KR101937401B1 - Heavy oil reforming apparatus equipped with screws and heavy oil reforming method using the same - Google Patents

Abstract

The present invention relates to a heavy oil reforming apparatus provided with a screw, a method for operating the same, and a method for reforming heavy oil using the apparatus in the reforming of heavy oil using hydrocracking reaction. The heavy oil reforming apparatus provided with the screw of the present invention can supply a new catalyst into a reaction unit through the rotation of the screw and simultaneously discharge the waste catalyst used to the outside of the reaction unit. As a result, the catalyst can be continuously replaced without stopping the process, and the activity of the hydrocracking reaction catalyst can be continuously and excellently maintained. Therefore, the quality of the final product is remarkably enhanced, and at the same time, the present invention has a useful effect of continuously producing high quality products even in long-term operation of the apparatus.

Description

[0001] The present invention relates to a heavy oil reforming apparatus equipped with a screw and a heavy oil reforming apparatus equipped with the screw,

TECHNICAL FIELD The present invention relates to a heavy oil reforming apparatus equipped with a screw, a method of operating the screw, and a method for reforming heavy oil using the apparatus in the reforming of heavy oil using hydrocracking reaction.

Currently, countries around the world are facing the risk of resource problems due to heavy crude oil and a decrease in their reserves. As a result, high - priced technologies are emerging through the hardening of heavy oil. In particular, demand for low boiling liquid products such as gasoline, kerosene, diesel, intermediate distillate and naphtha products produced by high-cost technologies is steadily increasing. Recently, attention has been focused on hydrocracking as a method of decomposing heavy oil and obtaining light oil. According to the hydrogenolysis, intermediate distillation products such as kerosene and diesel can be obtained as well as gasoline, and the yield of produced oil can be changed according to the operating conditions. Also, .

Currently, continuous hydrocracking techniques using various reactor types are being used to modify heavy oil. Fixed-bed reactors, in which the reaction proceeds in the fixed state of the catalyst, are advantageous in that the initial installation cost is low and the operation process is simple. However, the catalyst layer can not be replaced during the reaction. In order to overcome such disadvantages, a process including a pretreatment process (patent document 2) has been developed, but it has a disadvantage that additional costs are incurred. The use of a catalytic fluidized bed reactor has the advantage of a high conversion rate, but as the reaction progresses, the catalyst is aggregated and sinks due to the residual carbon and coke formation. This phenomenon causes hot spots in the reactor and makes it difficult to maintain certain operating conditions (temperature, pressure, contact time of catalyst and reactants, catalyst flow). In order to maintain the quality of the product, there is a disadvantage that expensive catalyst exchanges must be frequently performed. In the case of the slurry bed reactor, it is possible to modify raw materials containing a large amount of asphaltenes and impurities contained in the heavy oil (Non-Patent Document 1), but the reaction-completed catalyst remains in the reactor together with unreacted residues and coke It is difficult to reuse the catalyst.

As described above, the hydrocracking reaction technology of heavy oil using various reactors has been developed. However, the technology capable of producing highly economical products (gasoline, diesel, and middle distillate) Development is needed.

The present inventors have made efforts to devise a method capable of continuously achieving excellent reforming efficiency by managing the catalyst efficiency during the reaction in the heavy oil reforming process using the catalyst, The apparatus can improve the efficiency of the reforming of the heavy oil due to the low cost and the consumption of the catalyst by continuously rotating the screw and enabling the new catalyst supply and the used catalyst exhaust during the reaction to be simultaneously performed. The present invention has been completed based on this finding.

Korean Patent No. 10-1555000 U.S. Patent No. 7517446B2

M. J. Angels et al., Catalysis Today, 220, (2014) 274-294

It is an object of the present invention to provide a process for the hydrocracking reaction of heavy oil which is capable of exchanging the catalyst without interruption of the process and which can maintain the catalytic activity excellently while maintaining the quality of the final product produced therefrom, And to provide a reforming apparatus.

Another object of the present invention is to provide a method for modifying heavy oil using the heavy oil reforming apparatus.

In order to achieve the above object,

The present invention relates to a fuel cell system comprising: a heavy oil and a hydrogen supply unit;

A catalyst supply unit;

A reaction part connected to the heavy oil and the hydrogen supply part and the catalyst supply part and equipped with a screw to cause hydrocracking reaction of the heavy oil; And

And a product collecting part connected to the reaction part and collecting the product. The present invention also provides a heavy oil reforming apparatus using the hydrocracking reaction.

The present invention also relates to a process for producing a catalyst comprising the steps of: (1) supplying heavy oil, hydrogen and a catalyst to a reaction vessel equipped with a screw;

A step of hydrocracking the heavy oil in the reaction part equipped with the screw (step 2); And

Comprising the step of collecting the product obtained after the reaction of step 2, step 3,

And a new catalyst is supplied into the reaction part by rotating the screw mounted on the reaction part.

The heavy oil reforming apparatus equipped with a screw according to the present invention can discharge new catalysts into the reaction part and simultaneously exhaust the waste catalysts used outside the reaction part through the rotation of the screw, And can also maintain the catalytic activity of the hydrocracking reaction continuously, thereby remarkably improving the quality of the final product, and at the same time, producing useful products capable of continuously producing high-quality products even in long-term operation of the apparatus .

1 is a graph showing the boiling point content of products according to the elapsed days of hydrocracking reaction of DAO (De Asphalted Oil) using the apparatus of the present invention.
2 is a graph showing the boiling point content of products according to the elapsed days of hydrocracking reaction of DAO (De Asphalted Oil) using the apparatus of Example 1 of the present invention.
3 is a graph showing the boiling point content of products according to the elapsed days of hydrocracking reaction of reduced-pressure residues using the apparatus of Example 2 of the present invention.
4 is a schematic view of a screw-mounted heavy oil reforming apparatus according to an embodiment of the present invention.
5 is a schematic view of a screw element mounted in a reaction part according to an embodiment of the present invention.
6 is a detailed enlarged view of a screw element to be attached to a reaction part according to an embodiment of the present invention.
7 is a schematic view of a screw element mounted on a catalyst supply of an embodiment of the present invention.

Hereinafter, the present invention will be described in detail.

The following description is provided to assist the understanding of the invention, and the present invention is not limited to the following description.

The present invention relates to a fuel cell system comprising: a heavy oil and a hydrogen supply unit;

A catalyst supply unit;

A reaction part connected to the heavy oil and the hydrogen supply part and the catalyst supply part and equipped with a screw to cause hydrocracking reaction of the heavy oil; And

And a product collecting part connected to the reaction part and collecting the product. The present invention also provides a heavy oil reforming apparatus using the hydrocracking reaction.

Hereinafter, the heavy oil reforming apparatus of the present invention will be described in detail with each constituent unit.

In the heavy oil reforming apparatus according to the present invention, the heavy oil and the hydrogen supplier supply heavy oil and hydrogen, which are reactants of the heavy hydrocracking decomposition reaction, to the reaction section.

Here, the heavy oil may contain only a pure heavy hydrocarbon component, but may be a heavy oil containing a heavy hydrocarbon as a main component, for example, impurities such as sulfur impurities and metal impurities, and generally at least 0.2 (VD), deasphalted oil (De Asphalted oil), and the like, which can be obtained from, for example, vacuum distillation. And may be a heavy oil having a boiling point of 350 DEG C or higher, 370 DEG C or higher, 500 DEG C or higher, or 530 DEG C or higher, as exemplified by boiling point distribution.

The heavy oil may contain at least 10 wt%, 20 wt%, 30 wt%, 40 wt%, 50 wt%, 60 wt%, 70 wt%, 80 wt% heavy hydrocarbons, , At least 90 wt.%, At least 95 wt.%, At least 97 wt.%, At least 99 wt.%, Preferably at least 50 wt.% Of heavy hydrocarbons.

Further, the heavy oil may be supplied with no solvent or with a solvent at the time of feeding, and examples of the usable solvent include benzene, toluene, xylene, tetra-hydrofuran, di- Chloromethane, n-hexane, n-pentane, tridecane, mixtures thereof and the like can be used, and any of them can be used without limitation as long as they can be used to supply the heavy oil to the reaction part.

The hydrogen may be a hydrogen gas or a high-pressure hydrogen gas. The hydrogen gas may be a pure hydrogen gas, but may be a mixed hydrogen gas containing hydrogen as a main component. The hydrogen gas may be a mixed gas containing impurities, For example, the impurities may include other gases other than hydrogen gas such as nitrogen, oxygen, and the like.

The hydrogen or the hydrogen-containing mixed gas supplied to the supply unit may contain at least 10 vol%, at least 20 vol%, at least 30 vol%, at least 40 vol%, at least 50 vol%, at least 60 vol% At least 70 vol%, at least 80 vol%, at least 90 vol%, at least 95 vol%, at least 97 vol%, at least 99 vol%, and preferably at least 95 vol% .

On the other hand, in supplying the heavy oil and hydrogen of the supply part, it may be supplied to the reaction part through a separate path or may be supplied to the reaction part through one path.

In addition, the heavy oil and hydrogen supplier of the apparatus of the present invention is not limited thereto, but may further include a heavy oil injection vessel 11 and a pump 12, for example, as schematically shown in FIG. 4 of the present invention, A booster pump 13 for storing and flowing high-pressure hydrogen, a storage pressure vessel 14, and a flow rate control device 15. Here, the flow control device 15 can be adjusted to regulate the hydrogen introduced into the device, and preferably to continuously introduce hydrogen.

[0030] In the meantime, it is possible to further include a heating means for precisely controlling the temperature deviation between the heavy oil and the hydrogen inside the reactor on the inlet side of the feed portion to be supplied into the reaction portion. For example, 16).

The heavy oil and hydrogen supplier may further include a measuring unit for continuously measuring the weight and pressure characteristics of the heavy oil.

In the apparatus for reforming heavy oil according to the present invention, the catalyst supply unit supplies a catalyst for promoting hydrocracking reaction of heavy oil. In particular, in the reaction unit equipped with the screw of the present invention, a new catalyst is supplied, Can be designed to discharge spent catalyst outside the reactor.

More specifically, in the reaction part equipped with the screw of the present invention, the catalyst is supplied into the reaction part through the rotation of the screw, and after the start of the operation and the filling of the catalyst is completely finished, The spent catalyst is discharged to the outside of the reaction part, so that the catalyst can be continuously exchanged even during the reaction.

4, the catalyst supply unit 20 may further include at least one storage container for storing the catalyst, and may include, for example, a first catalyst storage vessel 21 and a second catalyst storage vessel 22).

Further, if the catalyst supply portion is designed to be rotatable with the screw 31 in the reactor, or not at the same time as the catalyst supply, for example, the catalyst supply portion may also be provided with the screw 23 And can be designed to be connected organically so that the rotation of the screw 23 of the catalyst supply part and the rotation of the screw 31 of the reaction part are simultaneously performed.

That is, the screw of the catalyst supply part is rotated to allow the catalyst to flow into the reaction part, and the screw of the reaction part can be rotated simultaneously with the rotation of the screw of the catalyst supply part, so that the introduced catalyst flows into the reaction part along the screw And at the same time, the waste catalyst may be designed to be discharged to the outside of the reaction part on the other side of the reaction part screw.

In addition, the screw 23 of the catalyst supply unit can be designed to be manually or automatically rotated, and the length of one pitch of the screw is not particularly limited. However, the operation of the supplied catalyst is not unexpected It is desirable that the pitch length is appropriately shortened so as not to be supplied into the reaction part so that the amount of the catalyst to be supplied and the amount of the waste catalyst to be discharged can be finely adjusted even at as many revolutions as possible.

However, when the pitch length is excessively short, the catalyst may be clogged or clogged between the screws, resulting in malfunction. As a result, the pitch length can be appropriately adjusted in consideration of the shape and size of the catalyst, On the other hand, when the pitch length is excessively long, there is a problem that the catalyst can not be controlled arbitrarily, such as gravity, or that the catalyst can move unexpectedly by force. It is therefore preferable to select the pitch length appropriately in consideration of the above- .

As the screw used in the catalyst supply part of the present invention, a screw as shown in Fig. 7 can be used, though not limited thereto. 7 may have a ratio of 8 to 14, 9 to 12, 10 to 11, or 11.3 when the center axis diameter is in the range of 3 to 6, 4 to 5, or about 4.8. Here, the screw pitch period may be set at a ratio of 4 to 8, 5 to 7, or 6.6 per pitch, and the total number of pitches of the central axis is not particularly limited, but may be 10 to 30, 15 to 25, And may have a pitch number of 20 to 25. [ Alternatively, each of the pitches may be the same and may have different pitch lengths, but preferably those having the same pitch length can be used. On the other hand, it can be understood that a portion of the screw of the catalyst supply portion may not be a screw, and the portion other than the screw may be a handle portion or a screw rotation operation portion.

On the other hand, the material of the screw is not particularly limited, but may be appropriately selected in consideration of the size of the catalyst used, the shape of the catalyst, the components of the catalyst, and the like. For example, a material having an appropriate roughness may be used as a screw material so that the catalyst does not slide along the screw, and a material that does not affect the catalyst component may be selected and used.

However, the catalyst can be used without limitation as long as it is known as a catalyst for hydrocracking reaction of heavy oil, and all of the hydrocracking catalysts conventionally used in the technical field can be used. More preferably, the catalyst is disclosed in Korean Patent No. 10-1555000 A catalyst confirmed to be applicable to hydrocracking reaction of heavy oil can be used. For example, a 1% Ni-4.5% Mo / Goethite catalyst may be used as in the following embodiments of the present invention.

In the heavy oil reforming apparatus according to the present invention, the reaction unit equipped with the screw is connected to the heavy oil and the hydrogen supply unit and is connected to the catalyst supply unit.

In this connection, the form is not particularly limited, but may be, for example, a form in which the catalyst supply portion is preferably connected in the direction from the upper end to the lower end in order to easily supply the non-gaseous catalyst to the reactor, The heavy oil and the hydrogen supply unit may be connected to each other from the upper end to the lower end, but they may be connected at the side.

In addition, since the reaction part adopts screw mounting, unlike the conventional heavy oil reforming device, the supply and discharge of the catalyst can be easily controlled without stopping the apparatus. In particular, new catalyst is supplied into the reaction part in accordance with the rotation of the screw, The used spent catalyst on the other side can also be discharged sequentially out of the reaction part.

Thus, the catalytic activity in the reactor can be controlled through the rotation of the reaction part screw, and as a result, the production efficiency of the produced product can be maintained excellent by controlling the heavy hydrogenolysis reaction.

Particularly, in a conventional fixed bed or a reactor using a catalyst in the form of a slurry, the catalyst can not be exchanged during the reaction, and the reaction is stopped at a time when the catalyst efficiency is significantly lowered only after a relatively long period of time , All of the used catalysts must be replaced, and there is a disadvantage in that the catalyst is wasted and the cost is wasted.

In addition, there is no method and means for controlling the quality of the product produced during the operation of the apparatus and the reaction efficiency of the catalyst. Conventionally, the quality of the catalyst deteriorates as the use time elapses, .

On the other hand, through the rotation of the screw of the apparatus of the present invention, the catalyst that has been used for the longest time at the screw end portion of the catalyst among all the catalysts in the reaction portion, that is, the spent catalyst with the lowest activity, can be preferentially discharged to the outside, It is possible to finely control the activity of the catalyst in the reaction part by controlling the number of the catalysts, and thus it is advantageous especially in product quality control.

Meanwhile, in the reaction part of the present invention, a screw is mounted, and the reaction part may include a housing having an outer wall, and one or more further housings may be provided inside the outer wall. Here, a screw may be located in the outer wall of the housing, preferably in the center of the housing. Further, the screw may be continuously positioned from the top of the housing to the bottom, or only a portion of the interior of the housing may be a screw, or one or both of the top and bottom of the screw may protrude out of the housing. Meanwhile, it is possible to further include a separate adjusting means for rotating the screw in the housing, or to project the screw to the outside of the housing, or to project only the central shaft of the screw to the outside of the housing, .

On the other hand, the central shaft of the screw or the outwardly protruding screw can be brought into contact with the other screw of the catalyst supply unit so as to be rotatable in connection with each other, or a separate connecting means can be provided, The screw can be connected to rotate organically.

On the other hand, the screw pitch length in the reaction part is not particularly limited, but it is preferable that the catalyst in which the pitch length is loaded on the screw is shortened so that it flows or does not move due to an uncontrolled force or action such as gravity . However, when the pitch length is excessively shortened, the catalyst may be clogged or clumped between the screws, which may be suitably adjusted in consideration of the above.

On the other hand, there is an advantage that the pitch length can be shortened, and the more the screw in the reaction part is, the finer the catalyst supply and discharge can be controlled.

Further, it can be understood that the screw rotates to discharge the waste catalyst to the lower end of the reaction part, and at the same time, a new catalyst is supplied to the upper end. In another embodiment, And at the same time a new catalyst can be supplied from the lower end.

In addition, the screw may be vertically erected and may optionally be shaped at 10, 20, 30, 40, 50, 60, or 70 degrees or more. As another example, it is possible to feed the catalyst in the left, right, or right and left directions by rotating the screw horizontally, and at the same time, to discharge the spent catalyst.

Such a design change can be changed in consideration of the gap between the screw and the housing in the reaction section, and is included in the scope of the present invention without limitation if the design change is such that the catalyst does not clog, for example, clogging between the screws.

For example, the screw used in the reaction part of the present invention may be a screw as shown in FIG. 5 and FIG. 6, though it is not limited thereto. 5, when the total length of the reaction part screw is about 800 to 1000, 700 to 900, 800 to 900, or 840, the total pitch number of the screw is 50 to 100, 60 to 90, 70 to 80 , Or a pitch number of 70, and one pitch length may be a ratio of, for example, 8 to 16, 10 to 14, or 12. Alternatively, each of the pitches may be the same and may have different pitch lengths, but preferably those having the same pitch length can be used. On the other hand, the reaction part screw may have a non-screw part, which may be a length ratio of about 150 to 200, 160 to 190, or 184 in length. It should be understood that some or all of these lengths may be handles or operating parts of the screw, and on the other hand, they may be handles or operating parts in a length ratio of 10 to 30 or 21. On the other hand, a non-screw portion may be designed to be associated with the screw of the catalyst supply portion, or the screw portion may be designed to be associated with the screw of the catalyst supply portion, . 6, it can be seen that the preferable pitch length of one screw is 12, and the thickness of the screw portion may have a ratio of about 0.6 to 1, or 0.7 to 0.9, or 0.85 . In addition, the outermost screw diameter in relation to the central axis diameter may be set at a ratio of about 10 to 20: 15 to 30, and may be a ratio of 14: 20.2 as shown in the figure.

4, the reaction unit 30 may include a plurality of thermocouples in addition to the screw 31 installed therein, and the reaction unit 30 may include a plurality of thermocouples, The internal temperature can be maintained at a high temperature. Further, the reaction section may further include additional heating means or pressure holding means so that the hydrocracking reaction can be maintained at the most preferable temperature and pressure.

The hydrocracking reaction of the heavy oil in the reaction part can be performed at 350 to 500 ° C, 360 to 490 ° C, 370 to 480 ° C or 380 to 480 ° C, 70 to 200 bar, 75 to 190 bar, or 80 to 170 bar, and the liquid hourly space velocity (LHSV) may be performed under the condition of 0.15 to 0.55 hr ^-1 , The reaction conditions of the heavy hydrocracking reaction (hydrogenation reaction) may differ depending on the parameters such as the feedstock, the reactor, the catalyst, and the like, and the hydrocracking reaction is performed to lower the boiling point of the heavy oil, In particular, the present invention is intended to provide a heavy oil reforming apparatus, in which a screw-type half- (Reactor), and it is intended to attain a remarkably elevated efficiency. It will be understood by those of ordinary skill in the art that the different reaction conditions of the hydrocracking reaction itself are included in the scope of the present invention It can be easily understood.

In the heavy oil reforming apparatus according to the present invention, the product collecting unit is connected to the reaction unit and collects the product obtained by the heavy hydrocracking reaction.

The product collecting unit may be, for example, a product collecting unit 40 as shown in FIG. 4 of the present invention, and the product collecting unit may include one or two or more collecting containers. In the case of two or more collecting containers, Lt; RTI ID = 0.0 > a < / RTI > For example, the product collecting portion includes a first collecting container 41 and a second collecting container 42, and on the other hand, a static pressure maintaining regulator 43, a pressure vessel, and a booster pump .

Meanwhile, the first collecting container 41 and the second collecting container 42 may include a valve therebetween, and after the pressure is shut off by using the valve, the product in the second collecting container may be collected. Thereafter, the gas in the pressure vessel is supplied to the second collecting vessel to maintain it at the same pressure as the entire reaction system, and the valve between the first collecting vessel and the second collecting vessel can be opened again to maintain the initial state.

On the other hand, the product collecting part may have a filtration part separately for separating the product and the waste catalyst mixed therewith, or may include filtration means in the collection container of the product collecting part.

Here, the filtration unit or the filtration means is a means for separating only the light oil, which is industrially useful and has a low boiling point, from the product immediately after the reaction, from the impurities including the waste catalyst, or the separation means . The filtration means includes a filtration membrane in the form of a mesh, and generally includes all the filtration devices used for separating the useful component of the liquid component and the impurity of the solid component. For example, as shown in FIG. 4, May be included in each of the first collecting container and the second collecting container.

In addition, the heavy oil reforming apparatus of the present invention may further include an operation unit for analyzing the product collected by the product collecting unit.

Here, the operation unit may analyze the boiling point distribution of the product, further measure the rate of change by comparing the boiling point of the product with the initial product boiling point, and further measure the relative decrease rate of the catalyst activity. When it is deduced that the rate of change of the boiling point distribution derived from performing this calculation process falls to a predetermined range, for example, 5%, 10%, 20%, 30%, 40%, 50% Or when the rate of change of the catalytic activity is deduced to fall to a predetermined range, for example, 5%, 10%, 20%, 30%, 40%, 50% or more of the initial catalytic activity, To supply a new catalyst, and to discharge the spent catalyst.

Further, the operation unit may further include a function of instructing the catalyst supply unit to supply a catalyst to the reaction unit, or may further include another device capable of performing this function.

On the other hand, the manager may experimentally confirm the simply collected product without any separate operation unit to arbitrarily operate the catalyst supply unit, or the catalyst may be operated at a predetermined time interval from the setting time of the initial apparatus, Catalyst exchange may also be accomplished by a method of automatically setting to be supplied.

Here, the present invention aims at achieving the discharge of the spent catalyst at the same time as the supply of the catalyst to the reaction part without stopping the reaction or stopping the operation of the apparatus, and adopting the screwed reaction part (reactor) It can be easily understood by those skilled in the art that the time for exchanging the catalyst can be set or changed in consideration of the quality of the produced product and the production efficiency (catalyst efficiency) And the present invention encompasses all of these categories.

Preferably, in the following experimental examples, the product obtained by the product collecting unit of the apparatus was analyzed by GC-SIMDIS to determine the non-point distribution of the product. Preferably, the product was collected at a certain point in time, for example, , 5 days, or 7 days after the start of the test, and the change in the boiling point of the product was analyzed by analyzing the time points at 1 hour, 2 hours, 3 hours, 5 hours, 7 hours, 12 hours, 18 hours, And if the rate of change obtained from this is analyzed to determine that the product boiling point is high, the screw in the screw can be rotated to exchange the catalyst in the reactor and manage the overall catalytic activity in the reactor.

In the following experimental example of the present invention, it was confirmed that a product having a relatively low boiling point, that is, an excellent quality, can be provided as compared with the conventional reactor, and the screw type apparatus of the present invention was continuously operated for more than 26 days (See Examples and Experimental Examples described below). ≪ tb > < TABLE >

Further, the present invention relates to a method for producing a catalyst, comprising the steps of: (1) supplying heavy oil, hydrogen and a catalyst to a reaction vessel equipped with a screw;

A step of hydrocracking the heavy oil in the reaction part equipped with the screw (step 2); And

Comprising the step of collecting the product obtained after the reaction of step 2, step 3,

And a new catalyst is supplied into the reaction part by rotating the screw mounted on the reaction part.

Hereinafter, the heavy oil reforming method of the present invention will be described in detail for each step.

In the heavy oil reforming method according to the present invention, step 1 is a step of supplying heavy oil, hydrogen and a catalyst to a reaction unit equipped with a screw.

Here, the heavy oil and hydrogen can be understood as reactants for hydrocracking reaction, and the catalyst is a catalyst for hydrocracking reaction (hydrogenation reaction).

The heavy oil is, by way of non-limiting example, a heavy oil or heavy hydrocarbon of all categories recognized in the art, or a mixture comprising it as a major component, for example a mixture containing impurities such as sulfur impurities and metal impurities And may generally be a heavy hydrocarbon oil fraction containing at least 0.2, 0.3, or 0.5 weight ppm of metal, and preferably may be obtained from reduced pressure distillation, such as reduced pressure oil (VD), reduced pressure residues (De Asphalted oil, etc., and may be a heavy hydrocarbon having a boiling point of 350 ° C or more, 370 ° C or more, 500 ° C or more, or 530 ° C or more,

Further, the heavy oil may be supplied with no solvent or with a solvent at the time of feeding, and examples of the usable solvent include benzene, toluene, xylene, tetra-hydrofuran, di- Chloromethane, n-hexane, n-pentane, tridecane, mixtures thereof and the like can be used, and any of them can be used without limitation as long as they can be used to supply the heavy oil to the reaction part.

Meanwhile, the hydrogen may be a pure hydrogen gas or a mixed gas containing the same, for example, a hydrogen gas, or a mixture of other gases such as nitrogen and oxygen, wherein the hydrogen gas is the main component in the mixed gas For example, 50% by volume, 60% by volume, 70% by volume, 80% by volume, 90% by volume, 95% by volume, 97% by volume, 98% by volume, , 99% by volume or more.

On the other hand, the supply of the heavy oil and the hydrogen may be supplied into the reactor through separate routes, respectively, or may be supplied together or sequentially in one route. Further, in the supply of the heavy oil and hydrogen, it is preferable to further include a step of heating to a high temperature before the supply so that the hydrocracking reaction can proceed easily in the reactor, so that it can be supplied after heating, , And may be supplied after pressurization.

On the other hand, the catalyst may be fed into the reactor before the heavy oil and hydrogen feed and prefilled, or may be fed at the same time as the heavy oil and hydrogen feed, or after the feed. The catalyst to be fed may be any hydrocracking reaction catalyst. For example, a catalyst disclosed in Korean Patent No. 10-1555000 may be used. For example, a 1% Ni-4.5% Mo / Goethite catalyst may be used as in the present invention.

Further, in supplying the catalyst, it is preferable to perform the operation so that the screw in the reactor can rotate together with the catalyst supply, or the catalyst can be supplied to the screw rotation in the reactor. Here, The catalyst can be easily exchanged without interruption of the apparatus during the reaction simply by manipulating the rotation of the reactor screw.

Thus, the supply of the catalyst can be carried out using an apparatus that is organically connected to the screw in the reactor, for example, another screw (threaded screw).

In the heavy oil reforming method according to the present invention, the step 2 is a step of hydrocracking the heavy oil in the reaction part equipped with the screw.

Here, the hydrocracking reaction of the heavy oil is a reaction for cracking heavy oil and is a reaction for converting a relatively high boiling point hydrocarbon to a low boiling point hydrocarbon.

For example, heavy hydrocarbons having a boiling point of 350 ° C or more, 360 ° C or more, 370 ° C or more, 500 ° C or more, 510 ° C or more and 520 ° C or more are heated to 380 ° C or less, 370 ° C or less, C or less, 340 캜 or less, 300 캜 or less, 200 캜 or less, 150 캜 or less, 140 캜 or less, 100 캜 or less, 90 캜 or less, 80 캜 or less, 70 캜 or less, 50 캜 or less, , Or a light hydrocarbon having a low boiling point at room temperature.

In particular, it is an object of the present invention to provide a process for the production of a low boiling hydrocarbon which can be used industrially and which can be used in low boiling point liquid products such as gasoline, kerosene, diesel, intermediate distillate, ≪ / RTI >

In order to convert the heavy oil supplied in the step 1 into the light oil preferably with excellent efficiency, the catalyst disclosed in Korean Patent No. 10-1555000 was used as the catalyst employed in the present invention, Any catalyst used as a catalyst for the addition reaction, that is, hydrocracking reaction, can be used without limitation.

On the other hand, the screw in the reactor may be formed throughout the reactor, preferably from the top of the reactor to the bottom of the reactor, or may be formed in one section of the interior of the reactor. Alternatively, the screw may protrude to the outside through the top, bottom, or both of the reactors, or only the central axis of the screw may protrude out of the reactor. In addition, the reactor may be a single housing including a screw, and the housing may further include one or more housings. Further, it may further include an additional means for maintaining a high temperature and a high pressure in the reactor so that the hydrocracking reaction in the reactor can proceed smoothly inside or outside the housing that covers the screw.

On the other hand, the screw of the reactor can be rotated by manipulating or manipulating the central axis of the screw projecting outwardly, or can be designed as a screw rotating organically in the catalyst supply.

On the other hand, the gap between the outer wall of the reactor and the screw is not limited to this, but even if there is little or no clearance, the catalyst of the screw thread can be made so that it can not pass through.

Further, the rotation of the screw may be rotated at a time when catalyst supply or exhaustion of a spent catalyst is required, may be arbitrary through manual operation, or may be set to be continuously rotated, or may be adjusted to be rotated at a predetermined time interval .

On the other hand, only the catalyst may be supplied until the catalyst is initially completely filled in the reactor, and after the catalyst is completely filled, the catalyst may be discharged together with the catalyst.

Preferably, the screw is rotated in consideration of catalyst efficiency, product quality, and the like. That is, when the product quality and the catalyst efficiency fall below a specific range, the catalyst is rotated, and when the product quality and the catalyst efficiency reach the specific range or more, the rotation can be stopped and the catalyst exchange can be stopped.

In the heavy oil reforming method according to the present invention, the step 3 is a step (step 3) of collecting the obtained product after the reaction of the step 2.

Here, the product collecting step is a step of collecting a product discharged to an outlet provided in the reactor, for example, in addition to the discharged product, other impurities such as spent catalyst, coke and the like may be contained. Thus, the step of collecting the product may further comprise the step of separating or filtering the further discharged product from the impurities. For example, in order to remove solid impurities such as waste catalysts, a mash-type filtration means can be used, and filtration or separation means used for separating solid liquid can be used without limitation. Preferably, in order to obtain the product in pure form, the collecting step may be carried out one or more times or it may be carried out repeatedly to improve the purity of the product obtained earlier, It is possible to further apply the means for further separating the useful component, and then to add them later.

Further, after the step 3, it may further include analyzing the product collected in the step 3.

The analysis of the product collected by the product collecting unit may be to analyze the boiling point distribution of the product, and further, it may be compared with the boiling point of the original product to determine the rate of change. Further, can do. When the rate of change of the boiling point distribution resulting from performing this analysis is deduced to be reduced to a predetermined range, for example, 5%, 10%, 20%, 30%, 40%, 50% Or when the rate of change of the catalytic activity is deduced to fall to a predetermined range, for example, 5%, 10%, 20%, 30%, 40%, 50% or more of the initial catalytic activity, A new catalyst is supplied and the spent catalyst is discharged.

The exchange of such a catalyst may be performed simply by experimentally confirming the collected product by the administrator and arbitrarily determining the catalyst supply, or may be performed at a predetermined time interval from the start of the start of the step or continuously To achieve catalyst exchange.

Here, the present invention aims at achieving the discharge of the spent catalyst at the same time as the supply of the catalyst to the reaction part without stopping the reaction or stopping the operation of the apparatus, and adopting the screwed reaction part (reactor) It can be easily understood by those skilled in the art that the time for exchanging the catalyst can be set or changed in consideration of the quality of the produced product and the production efficiency (catalyst efficiency) And the present invention encompasses all of these categories.

Preferably, in the following experimental examples, the product obtained by the product collecting unit of the apparatus was analyzed by GC-SIMDIS to determine the non-point distribution of the product. Preferably, the product was collected at a certain point in time, for example, , 5 days, or 7 days after the start of the test, and the change in the boiling point of the product was analyzed by analyzing the time points at 1 hour, 2 hours, 3 hours, 5 hours, 7 hours, 12 hours, 18 hours, And if the rate of change obtained from this is analyzed to determine that the product boiling point is high, the screw in the screw can be rotated to exchange the catalyst in the reactor and manage the overall catalytic activity in the reactor.

In the following experimental example of the present invention, it was confirmed that a product having a relatively low boiling point, that is, an excellent quality, can be provided as compared with the conventional reactor, and the screw type apparatus of the present invention can be operated continuously for 26 days or more It was confirmed that the product could still be produced at the same level as the first (see Examples and Experimental Examples described below).

In the heavy oil reforming method according to the present invention, the reaction part equipped with the screw is operated to supply a new catalyst to the reaction part. After the catalyst is filled in the reactor, the spent catalyst is discharged to the outside of the reaction part The catalyst is exchanged as much as possible.

Here, the catalyst supply or exchange may be selectively operated at any time, and the product of step 3 may be analyzed to perform, for example, GC-SIMDIS analysis to utilize the boiling point distribution of the product, , Or by analyzing the activity of the catalyst, it may be determined that the average boiling point relative to the initial product quality rises below a predetermined range, for example, 5%, 10%, 15%, 20% or 30% The catalyst may be exchanged by rotating the reactor screw only when it is lowered to 98%, 95%, 90%, 80%, 70%, 60%, or 50% or less of the catalyst activity in the final reactor.

The present invention adopts a reaction unit equipped with the screw, so that a new catalyst can be introduced into the reactor at any desired time, at a desired time, or after a predetermined elapsed time or after a certain period of time, And at the same time, the used spent catalyst at the end of the reactor screw can be discharged to the outside of the reactor by the rotation. As a result, there is an advantage that the catalyst can be easily exchanged, and only a part of the spent catalyst can be exchanged in the catalyst in the reactor, so that the catalyst consumption is small and the reaction management is easy. Further, since the product quality control is easy, it is industrially useful.

Hereinafter, the heavy oil reforming apparatus and the heavy oil reforming method according to the present invention will be described in detail. It should be understood, however, that the following examples and experimental examples are illustrative of the invention and are not to be construed as limitations thereof.

A method of operating the heavy oil reforming apparatus according to the present invention will be described. The catalyst charged in the reaction part 30 is stored in the storage container 22 and filled in the reactor by the rotation of the catalyst supply screw 23. [ The reaction temperature is heated and maintained at 460 DEG C through the furnace and the plurality of thermocouples mounted in the reaction section 30. [ The hydrogen stored in the pressure vessel 14 by the booster pump 13 is supplied to the inside of the reactor through the flow rate control device 15. Hydrogen supplied constantly after reaching the reaction pressure (130 bar) is discharged to the outside through the constant pressure maintaining regulator (43), so that continuous hydrogen supply is performed during the hydrogenolysis reaction. When the catalyst filling, the reaction temperature, and the pressure are stabilized through the above process, the heavy oil as a raw material is fed into the reactor 11 through the metering pump 12. The product of the hydrocracking reaction which proceeds through this process is stored in the second product collecting container 42. A valve that connects the first product collection container 41 and the second product collection container 42 is used to block the pressure between the second product collection container and the entire system for real-time collection of the product. The pressure of the second product collecting vessel is kept at the same pressure as the pressure of the entire reaction system by the hydrogen stored in the pressure vessel after taking the product stored in the second product collecting vessel. The valve between the first product collecting container 41 and the second product collecting container 42 is opened to bring the same state as before the product collecting. When the decrease in catalytic activity is confirmed through the analysis of the product collected in real time, the screw 31 in the reaction part 30 is rotated to discharge the catalyst having low activity, and at the same time, The catalyst is injected.

< Example > Modification of Heavy Oil Using Heavy Oil Modification Apparatus of the Invention

The reforming reaction of the heavy oil according to Table 1 was carried out using the heavy oil reforming apparatus equipped with the screw according to the present invention. The general operation method is as described above.

(DAO (De Asphalted oil) and decompression residue) having the same composition and physical properties as those shown in Table 1 below were used. The hydrocracking reaction catalyst was subjected to hydrolysis of heavy oil in a registered patent (Korean Patent No. 10-1555000) 1% Ni-4.5% Mo / Goethite catalyst, which was confirmed to be applicable to the reaction, was extruded and each product obtained was subjected to GC-SIMDIS (Gas Chromatography - SIMulatedDistilization) And to determine the appropriate catalyst addition (exchange) point through analysis.

The amount of the catalyst which can be filled in the apparatus used in the experiment was about 50-60 g, and the operation was started after filling about 6 g of the initial catalyst. The analysis of the boiling point distribution of the obtained product was carried out, And

division Decompression residue DAO
Elemental analysis unit weight% C 84 85.4 H 10.71 12.5 S 4.84 2.6 N 0.14 0.0 Other 0.31 0.0 Sum 100 100
Metal analysis
(ICP analysis) unit ppm Ni 36.4 0.0 V 151 0.0 Fe 38.3 0.0 Si 198 0.4
SARA analysis
(TLC-FID analysis) unit weight% Saturate 4 36 Aromatic 61 51 Resin 18 13 Asphaltene 17 0 Sum 100 100
Fractional distillation unit weight% Room temperature to 70 ° C 0.0 0.0 70 to 370 DEG C 0.0 11.0 370 SIMILAR 530 DEG C 14.0 15.2 > 530 ° C 86.0 73.8

< Example  1> DAO  Hydrocracking reaction In  Pulse type operation

Continuous hydrocracking reaction of DAO heavy oil was performed and operation of adding catalyst in pulse form was carried out.

First, in the DAO hydrocracking reaction, when the boiling point of the product is lowered to a certain level or lower and the catalytic activity is lowered after the product boiling point is measured for the operation of the reactor and the process optimization, a new catalyst is introduced into the reactor by rotating the reactor screw The operation was carried out so as to maintain the catalytic activity in the whole reactor, and the results are shown in Fig.

Referring to FIG. 1, when the boiling point distribution of the product at 70 to 370 ° C was lowered to about 60 wt% or less based on the total product weight, the catalyst screw was rotated to feed the catalyst. Weight percent. &Lt; tb &gt; &lt; TABLE &gt; The initial catalyst loading time was 8 days, the second loading time was 12 days, and the third catalyst loading time was 21 days. It is confirmed that the total boiling point distribution is stable through the total of 3 times of catalyst input. Here, the fresh catalyst added at each exchange time was about 6 g in each case.

FIG. 2 is a graph showing the results of analysis after 6 days with the exception of the point of time when the activity is lowered as shown in FIG. 1 at the time of catalyst exchange. As shown in FIG. 2, It can be confirmed that a remarkably stable boiling point distribution appears.

Therefore, the apparatus for reforming a heavy oil according to the present invention, which is equipped with a screw, can arbitrarily change the catalyst by rotating the screw, and can set the catalyst change point at predetermined time intervals through analysis of boiling point, It is possible to produce the desired low boiling point product with excellent quality such as the first time, and it is found that the present invention apparatus is very useful in the modification of the heavy oil using the hydrogenolysis reaction compared to the conventional apparatus .

< Example  2> Decompression Residue  Hydrocracking reaction In  Continuous operation

The hydrogenolysis reaction was carried out in the same manner as in Example 1, but the catalyst was continuously added. The decompression residue was diluted with tridecane in a ratio of about 1: 1 to 1: 2 and used as a raw material for the decompression residue and as a raw material for the supply.

On the other hand, unlike the above-described pulse exchange method of the catalyst, on the basis of the results obtained by the DAO test in the decompression residue hydrocracking reaction, the catalyst is continuously fed to keep the hydrocracking reaction activity constant throughout the reactor .

Specifically, the screw was rotated finely and continuously so that the catalyst was put into the reactor at 0.042 g / hour after the start of the reaction by introducing about 6 g of the catalyst at the beginning, and the resulting product was subjected to a boiling point analysis, 3 is shown.

3 shows that the boiling point distribution of the product is maintained constant and the desired low boiling point product is produced even when the initial boiling point distribution and the reaction time point of 6 days are compared.

Therefore, the heavy oil reforming apparatus equipped with the screw of the present invention is a remarkably superior invention in the reforming of heavy oil, which can maintain the activity of the whole reactor constantly by adjusting the rate of catalyst input according to process conditions (LHSV, H ₂ / Able to know.

< Comparative Example  1> Fixed bed  Using a Fixed-Bed Of DAO  Hydrocracking reaction

In order to compare with the heavy oil reforming apparatus according to the present invention, the heavy oil reforming reaction was carried out using a conventional fixed bed reactor. Using the same DAO and catalyst as in Example 1, the remainder of the reaction conditions were the same as in Example 1 except for the reforming apparatus.

The fixed-bed reactor used was a tubular reactor capable of filling about 6 g of catalyst, filled with about 6 g of catalyst that could be packed in the reactor, and then fastened to the feed pump, furnace, and static pressure holding device. When the reaction temperature (470 ° C) and the reaction pressure (130 bar) are reached, the raw material is injected into the reactor through the feed pump. The product was stored in a collection container connected to the static pressure holding device and the supplied hydrogen was discharged to the outside. In addition, the obtained products were analyzed in the same manner as in the above examples.

< Comparative Example  2> Fixed bed  Decompression using a reactor Residual  Hydrocracking reaction

The hydrocracking reaction was carried out in the same manner as in Comparative Example 1, except that the raw material (vacuum residue) as in Example 2 was used.

< Experimental Example  1> Comparative analysis according to heavy oil reformer

The boiling point distributions of the products obtained from the screw-mounted heavy oil reforming apparatus and the conventional fixed bed catalyst type heavy oil reforming apparatus according to the present invention were analyzed to evaluate the product quality obtained for each apparatus and the catalyst efficiency in the reactor.

Specifically, for each product obtained, the boiling point distribution was analyzed by GC-SIMDIS (Gas Chromatography - SIMulated Description) using the HT750 method, and the results are shown in Table 2. The results of the analysis up to 4 days were compared for comparison.

Reaction time
(hr) The boiling point distribution of the product (% by weight) IBP - 70 ℃ 70 - 370 ° C 370 - 530 ° C > 530 ° C
Example 1 24 14.2 76.8 9.0 0.0 48 10.7 81.4 7.9 0.0 96 11.7 78.5 9.8 0.0
Comparative Example 1 24 0.0 62.0 35.0 3.0 48 0.0 64.0 33.0 3.0 96 0.0 60.8 36.2 3.0
Example 2 24 8.7 82.6 7.4 1.3 48 14.8 78.9 5.5 0.8
Comparative Example 2 24 0 51.6 45.3 3.1 48 0 48.5 48.2 3.2

As can be seen in Table 2, the products of Examples 1 and 2 using the screw-mounted heavy oil reforming apparatus of the present invention were the products of Comparative Example 1 and Comparative Example 2 using the apparatus of the fixed bed type at the same reaction time It can be confirmed that the content of the material having a lower boiling point is higher.

In particular, as the reaction time was prolonged, the low boiling point content of Comparative Examples 1 and 2 was decreased and the high boiling point content was increased, while the low boiling point content of the products produced in Examples 1 and 2 was increased or maintained constant.

Therefore, when the heavy oil reforming apparatus equipped with the screw according to the present invention is used, not only the product having a low boiling point as compared with the conventional fixed bed apparatus can be excellently produced even at the initial stage of the reaction, The apparatus is capable of continuous catalytic exchange, which allows it to produce low-boiling products at the same level of consistency from the constantly superior catalytic efficiency, while conventional fixed bed apparatus continually reduces reactor efficiency and low-boiling product weight percent.

Accordingly, the present invention is not only an excellent apparatus in the modification of the heavy oil using hydrocracking reaction but also is industrially useful since it is the only apparatus that can continuously operate the apparatus by exchanging the catalyst during the reaction .

10: Heavy oil and hydrogen supplier
11: Heavy oil injection container
12: Pump
13: Booster pump
14: Storage pressure vessel
15: Flow control device
16: Preheating device
20:
21: First catalyst storage container
22: a second catalyst storage container
23: Screw
30: Reaction part
31: Screw
32: Housing
40:
41: first product collecting container
42: Second product collecting container
43: Static pressure maintaining regulator
44: Booster pump
45: Storage pressure vessel

Claims (12)

Heavy oil and hydrogen supply;
A catalyst supply unit;
A reaction part connected to the heavy oil and the hydrogen supply part and the catalyst supply part and equipped with a screw to cause hydrocracking reaction of the heavy oil; And
And a product collecting part connected to the reaction part and collecting a product, wherein the device is a heavy oil reforming device using hydrocracking reaction,
Wherein the new catalyst is sequentially supplied into the reaction part according to the rotation of the screw, and the used catalyst is discharged to the outside of the reaction part in the order of supply.
delete The method according to claim 1,
Wherein the catalyst supply unit is a catalyst supply unit equipped with a screw.
The method according to claim 1,
Wherein the product collecting unit further comprises a separating means for separating the product and the discharged spent catalyst.
The method according to claim 1,
Wherein the product collecting portion includes one or more product collecting containers, at least one of the collecting containers including a static pressure holding portion.
The method according to claim 1,
Wherein the heavy oil and the hydrogen supply unit further include a heating means for heating the heavy oil and the hydrogen before supplying the heavy oil and the hydrogen to the reaction portion.
The method according to claim 1,
Wherein the catalyst supply unit is a continuous catalyst supply unit.
The method according to claim 1,
Wherein the product collecting portion is a continuous product collecting portion.
Supplying the heavy oil, hydrogen and the catalyst to a reaction part equipped with a screw (step 1);
A step of hydrocracking the heavy oil in the reaction part equipped with the screw (step 2); And
Comprising the step of collecting the product obtained after the reaction of step 2, step 3,
And a new catalyst is sequentially supplied into the reaction part by rotating the screw attached to the reaction part, and the used spent catalyst is discharged to the outside of the reaction part in the order of the supply.
10. The method of claim 9,
Further comprising the step of analyzing the product collected in step 3 above.
10. The method of claim 9,
Hydrocracking reaction of step 2 is normally 380 to 480 ℃ temperature, from 80 to 170 bar hydrogen pressure, and a liquid hourly space velocity (liquid hourly space velocity; LHSV) is being carried out under conditions of from 0.15 to 0.55 hr ^-1 A heavy oil reforming method.
A heavy oil reforming method for performing heavy oil reforming through hydrocracking reaction using the heavy oil reforming apparatus according to claim 1.

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