JP2004519533A - Method for hydrotreating heavy hydrocarbon cuts using sortable and shortable reactors - Google Patents

Method for hydrotreating heavy hydrocarbon cuts using sortable and shortable reactors Download PDF

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JP2004519533A
JP2004519533A JP2002549807A JP2002549807A JP2004519533A JP 2004519533 A JP2004519533 A JP 2004519533A JP 2002549807 A JP2002549807 A JP 2002549807A JP 2002549807 A JP2002549807 A JP 2002549807A JP 2004519533 A JP2004519533 A JP 2004519533A
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guard
catalyst
zone
section
step
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JP4697571B2 (en
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ステファン クレスマン
パスカル トロムール
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アンスティテュ フランセ デュ ペトロール
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G65/00Treatment of hydrocarbon oils by two or more hydrotreatment processes only
    • C10G65/02Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
    • C10G65/04Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10Feedstock materials
    • C10G2300/1037Hydrocarbon fractions
    • C10G2300/1048Middle distillates
    • C10G2300/1059Gasoil having a boiling range of about 330 - 427 °C
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10Feedstock materials
    • C10G2300/107Atmospheric residues having a boiling point of at least about 538 °C
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10Feedstock materials
    • C10G2300/1074Vacuum distillates
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20Characteristics of the feedstock or the products
    • C10G2300/201Impurities
    • C10G2300/202Heteroatoms content, i.e. S, N, O, P
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20Characteristics of the feedstock or the products
    • C10G2300/201Impurities
    • C10G2300/205Metal content
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20Characteristics of the feedstock or the products
    • C10G2300/201Impurities
    • C10G2300/205Metal content
    • C10G2300/206Asphaltenes
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20Characteristics of the feedstock or the products
    • C10G2300/30Physical properties of feedstocks or products
    • C10G2300/301Boiling range
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40Characteristics of the process deviating from typical ways of processing
    • C10G2300/4081Recycling aspects
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40Characteristics of the process deviating from typical ways of processing
    • C10G2300/44Solvents

Abstract

The present invention provides a process for hydrotreating a heavy hydrocarbon fraction using a first hydrodemetallization section and then a second hydrodesulfurization section that passes the effluent from the first section. Consists of processes. At least one guard zone is provided before this hydrodemetallization section. The hydrotreating process includes the following steps: a) using a guard zone in the meantime; b) meanwhile operating bypassing the guard zone to regenerate and / or replace the catalyst therein. C) reconnecting the guard zone during which the internal catalyst has been regenerated and / or replaced; d) meanwhile bypassing at least one of the reactors in the hydrodemetallization section and / or hydrodesulfurization section. Regenerating and / or replacing the catalyst therein.

Description

[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention is particularly directed to heavy hydrocarbon fractions containing sulfur and metal impurities, such as atmospheric distillation bottoms, vacuum distillation bottoms, deasphalted oils, pitch, asphalt containing aromatics, coal hydrocracking And refining and conversion of heavy oils from products, various feedstocks, and especially bituminous shale or bituminous sand. Specifically, the present invention relates to the treatment of liquid feedstock. Asphaltene which is also included in the liquid feedstock is also included in the scope of the present invention.
[0002]
[Prior art]
The feed which can be treated according to the invention usually contains at least 0.5 ppm by weight of metals (nickel and / or vanadium) and at least 0.5% by weight of sulfur.
[0003]
The catalytic hydrotreating of such feeds has two purposes: refining, ie, substantially reducing the content of metals, sulfur and other impurities contained therein, and at the same time converting them. By increasing its hydrogen-to-carbon ratio (H / C) as a lighter or lesser fraction, the resulting altered effluent will be of high quality fuel, gas oil and gasoline. Can be used as a basic raw material for producing the same or as a raw material for other units such as a residual oil cracking unit and a cracking vacuum distillation distillate unit.
[0004]
The cause of problems when catalytically hydrotreating such a feedstock is that such impurities gradually accumulate on the catalyst in the form of metal or coke and rapidly reduce the activity of the catalyst system. In such a case, it is necessary to stop the operation to replace the catalyst.
[0005]
Therefore, this type of hydrotreating the feedstock must be designed to obtain the longest possible operating cycle without shutting down the unit, and achieve an operating cycle of at least one year. Is the goal.
[0006]
There are various methods for treating this type of feedstock. To date, such processing has been implemented in one of the following ways:
A method using a fixed catalyst bed (for example, the HYVAHL-F method of Institut Francais du Petrole), or
A method comprising at least one reactor capable of quasi-continuous catalyst exchange (eg HYVAHL-M moving bed method from Institut Francais du Petrole) ).
[0007]
The process of the present invention is an improvement over prior art processes, especially fixed bed or ebullated bed processes. In such a process, the feed circulates through a plurality of reactors arranged in series, preferably a fixed bed or ebullated bed reactor, while the first (single or multiple) reactor is In particular, it is used to carry out hydrodemetallation (HDM) of the feed and partially hydrodesulfurization, the last reactor (s) being used for deep refining of the feed, in particular Used to perform hydrodesulfurization (HDS step). The effluent of this process is withdrawn from the last HDS reactor.
[0008]
Such a method typically employs a specific catalyst adapted to each step, but the average operating conditions are a pressure of about 5 MPa to about 25 MPa, preferably about 10 MPa to about 20 MPa, and a temperature of about 340 MPa. C. to 440C, preferably 370C to 420C.
[0009]
In the case of the HDM step, ideal catalysts are suitable for treating asphaltene-rich feedstocks, yet have high metal removal capacity due to large metal holding capacity and high resistance to coking. Must. The present applicant has developed a catalyst supported on a specific porous carrier (sea urchin-like structure), and the carrier has obtained the following properties which are desirable for this step (Patent Document 1 and Patent Document 1). 2).
[0010]
The degree of demetallation in the HDM step is at least 10% to 90%;
The metal holding capacity exceeds 10% based on the weight of the new catalyst, so that a longer operating cycle can be achieved,
High coking resistance even at temperatures above 390 ° C., resulting in longer cycle periods often limited by increased pressure drop and reduced activity due to coke formation Which indicates that most of the heat conversion reactions are taking place in this step.
[0011]
In the case of the HDS step, the ideal catalyst must have a high hydrogenation capacity, which allows for extreme purification of the product, such as desulfurization, subsequent demetallization, reduction of Conradson carbon and possibly asphaltenes. Be able to do it. The Applicant has also developed such a catalyst (see US Pat. Nos. 5,059,009 and 5,049,037), which are particularly suitable for treating feedstocks of this type.
[0012]
A disadvantage of such high hydrogenation catalysts is the rapid loss of activity due to the presence of metal or coke. For this reason, a suitable HDM catalyst capable of performing most of the conversion and demetallization at relatively high temperatures and a relatively low temperature due to its protection from metals and other impurities. When combined with a suitable HDS catalyst that can be extremely hydrogenated and does not easily cause coking, its purification performance can be reduced by the performance obtained by using a single catalyst system and the temperature. Eventually higher performance than can be obtained using a similar HDM / HDS combination, where the pattern of increasing causes rapid coking on the HDS catalyst.
[0013]
The significance of the fixed bed method is that a high purification performance can be obtained due to the high catalytic efficiency of the fixed bed. In contrast, if the amount of metal in the feed is higher than a certain level (e.g., 50-150 ppm), even if a high performance catalyst is used, its performance, especially the uptime in such a method Is insufficient, and the reactor (especially the first stage HDM reactor) rapidly accumulates metal and decreases its activity. When the temperature is increased to compensate for the decrease in activity, coke formation is promoted. The pressure drop increases, and moreover, the first-stage catalyst bed is often clogged very quickly due to asphaltenes and settling substances contained in the feed or as a result of operational problems.
[0014]
As a result, the unit must be shut down at least every 2 to 6 months and the first stage deactivated or plugged catalyst bed must be replaced, which can take up to 3 weeks Therefore, the operating coefficient of the unit is further reduced.
[0015]
The significance of the ebullated bed method lies in its high conversion performance because it can be operated at high temperatures. The applicant has developed a method which is very suitable for treating normal and heavy feeds (see Patent Documents 5 and 6).
[0016]
Even with an optimal catalyst system, operating times can be reduced due to operational problems and / or use that is not suitable for the feedstock. Then the unit will shut down depending on the amount of coke present in the reactor. We have continued our efforts to address these operational and catalyst use challenges.
[0017]
The inventors have also attempted to overcome the shortcomings of fixed bed arrangements from another perspective.
[0018]
As a result, one or more moving bed reactors have been proposed to be installed before the HDM step (see US Pat. Such a moving bed may operate in either a co-current mode (eg, the HYCON method of SHELL) or a counter-current mode (eg, the HYVAHL-M method of the present applicant). Can be. In this way, a reactor, for example a fixed-bed reactor, can be protected by performing a part of the demetallization and sieving out particles which may be present in the feedstock and which may cause blockages. Furthermore, by quasi-continuous catalyst replacement in one or more of these moving bed reactors, the unit does not have to be shut down every three to six months.
[0019]
The disadvantage of such moving bed technology is that its overall performance and efficiency is much worse than that of a fixed bed of the same volume, causing attrition to move the catalyst, and consequently downstream. Under fixed operating conditions where the flow in fixed beds is impeded and the operating conditions are high, the danger of coking and the formation of catalyst agglomerates cannot be neglected in the case of heavy feedstocks, especially in the event of problems. become. The formation of such lumps hinders the movement of the catalyst in the reactor and in the catalyst extraction pipe after use, and finally the operation of the unit must be stopped to clean the reactor and the extraction pipe. Occurs.
[0020]
Install a guard reactor, preferably a fixed bed reactor (space velocity, HSV = 2-4) prior to the HDM reactor to maintain excellent performance while maintaining acceptable operating coefficients (See Patent Documents 9 and 10). Typically, this guard reactor can be short-circuited by using a special isolation valve. In this way, the main reactor is protected from the risk of blockage during the moment. If a guard reactor becomes blocked, it will short it out, which may cause the next main reactor to be blocked instead, forcing the unit to shut down. Furthermore, if the size of the guard reactor is small, the metal-rich (for example, 100 ppm or more) raw material cannot be sufficiently demetallized, so that the main HDM reactor cannot be metalized. Can no longer be adequately protected from deposition. Eventually, in these reactors, activity reduction is promoted, and the unit must be stopped frequently, and the operation coefficient becomes unsatisfactory.
[0021]
Patent Document 11 describes a system having both a good fixed bed performance and a high operation coefficient for treating a charged material having a high metal content (1-1500 ppm, usually 100-1000 ppm, preferably 150-350 ppm). But it consists of a hydrotreatment carried out in at least two steps to hydrotreat a heavy hydrocarbon fraction containing sulfur and metal impurities, where the hydrogenation in the first section is carried out. In demetallization, the hydrocarbon feed and hydrogen are passed under hydrodemetallization conditions over a hydrodemetallization catalyst, and then in a second step, the effluent from the first section is hydrodesulfurized. It passes under the hydrodesulfurization catalyst below. In this method, the hydrodemetallization section preferably comprises one or more hydrodemetallization zones of a fixed bed, but prior to it at least two hydrodemetallization zones which are also preferably fixed beds. It has a metal guard zone and is arranged in series to allow cyclic use consisting of successive repetitions of steps b) and c) shown below:
a) using the guard zone simultaneously, during which time one of the guard zones deactivates and / or closes;
b) operating with a short circuit in the deactivated and / or closed guard zone during that time, and regenerating and / or replacing the catalyst inside it; and
c) reconnecting the guard zones during which the catalyst has been regenerated during the previous step and using all of the guard zones simultaneously, until the time when one of the guard zones deactivates and / or closes; Perform the above steps.
[0022]
In this manner, the main HDM and HDS reactors generally have a high purification and conversion performance and can produce a stable product while having a cycle period of at least 11 months. Total desulfurization is on the order of 90% and total demetallation is on the order of 95%.
[0023]
[Patent Document 1]
EP-B-0113297.
[0024]
[Patent Document 2]
European Patent No. B-0113284.
[0025]
[Patent Document 3]
EP-B-0113297.
[0026]
[Patent Document 4]
European Patent No. B-0113284.
[0027]
[Patent Document 5]
Canadian Patent No. 2171894.
[0028]
[Patent Document 6]
French Patent Application No. 98/00530.
[0029]
[Patent Document 7]
U.S. Pat. No. A-3910834.
[0030]
[Patent Document 8]
British Patent No. B-2124252.
[0031]
[Patent Document 9]
U.S. Pat. No. 4,118,310.
[0032]
[Patent Document 10]
U.S. Pat. No. 3,968,026.
[0033]
[Patent Document 11]
French Patent No. B1-2681871.
[0034]
[Problems to be solved by the invention]
Disadvantages of this technique are that it is difficult to achieve an overall desulfurization performance of greater than about 90% and / or an overall demetalization performance of greater than about 95%, and, regardless of the performance level, It can be difficult to make the cycle time longer than 11 months. Surprisingly, it has been found that short-circuiting one or more reactors of the hydrodemetallation and / or hydrodesulfurization section can maintain the catalyst activity at each step and / or improve the cycle time. Was done.
[0035]
[Means for Solving the Problems]
The present invention provides for short-circuiting of one or more reactors (i.e., when the catalyst is deactivated and / or plugged by settling materials or coke and regenerated and / or replaced with fresh or regenerated catalyst). Bypass). The present invention relates to both a reactor in the hydrodemetallation section and a reactor in the hydrodesulfurization section.
[0036]
Accordingly, the reactor in the hydrodemetallization section and / or hydrodesulfurization section is shorted, for example, every six months, and the deactivated or plugged catalyst bed is replaced by a new one, this operation This results in an improvement in the unit availability factor.
[0037]
The present invention provides a process for hydrotreating a heavy hydrocarbon fraction using a first hydrodemetallization section and then a second hydrodesulfurization section that passes the effluent from the first section. The method consists of: At least one guard zone is provided before this hydrodemetallization section. The above hydrotreating method includes the following steps:
a) using a guard zone in the meantime;
b) short circuiting the guard zone in the meantime and regenerating and / or replacing the catalyst inside it;
c) reconnecting the guard zone during which the internal catalyst has been regenerated and / or replaced with a new one;
d) meanwhile, at least one of the reactors of the hydrodemetallization section and / or the hydrodesulfurization section can be short-circuited, and the catalyst therein is regenerated and / or replaced with a new one.
[0038]
A method for improving the performance of a fixed bed, summarized below, is also described in French patent A-2 784 687 by the applicant. The concept there can be applied to the present invention.
[0039]
However, the pressure loss in the reactor is high due to the high viscosity of the feedstock and the liquid effluent as a whole, and it is difficult to operate the circulating compressor, and the hydrogen pressure is low. There are problems such as that metal or good hydrodesulfurization cannot be obtained. Furthermore, it is known that the resulting gas oil fractions cannot normally be used directly, because of their unacceptably high sulfur content in current specifications.
[0040]
Therefore, it is desirable and possible to improve the performance of the method as described in Applicant's French patents B1-2 681 871 and A-2 784 687. Specifically, the method of the present invention allows the viscosity of the liquid effluent to be substantially reduced substantially, so that the pressure loss inside the reactor is substantially reduced and the circulation compressor Improved operation results in higher hydrogen pressure. This generally improves the desulfurization level and greatly reduces the sulfur content of the gas oil fraction, so that it meets current standards and can be added directly to the gas oil pool of a refinery. In addition, the method of the present invention improves the heat transfer and improves the efficiency of the preheating furnace, thereby allowing the furnace wall temperature to be reduced, thereby increasing the life of the furnace and contributing to lower unit operating costs. Will do.
[0041]
The process of the present invention combines high performance reactors, preferably fixed bed reactors or ebullated bed reactors, with high operating coefficients, high metal content (1-1500 ppm, usually 100-1000 ppm, preferably 150-1000 ppm). A process for hydrotreating a heavy hydrocarbon fraction containing sulfur and metal impurities in at least two sections. Can be defined as
There, in a first hydrodemetallization section, the hydrocarbon feed and hydrogen are passed over the hydrodemetallation catalyst under hydrodemetallization conditions,
The effluent from the first section is then passed under hydrodesulfurization conditions over a hydrodesulfurization catalyst in a subsequent second section;
Here, the hydrodemetallization section comprises one or more hydrodemetallization zones (preferably fixed or ebullated bed zones), before which at least one or possibly two. Placing a hydrodemetallation guard zone (also preferably a fixed bed or ebullating bed zone) in series so that it can be used in a cycle consisting of repeating steps b) and c) defined below,
Said hydrodemetallation and / or hydrodesulfurization section comprises one or more reactors (preferably fixed bed or ebullated bed reactors), either separately or according to step d) as defined below. , It is possible to short circuit. When two guard zones are used, the method of the present invention is a hydrotreating method comprising the following steps:
a) using all of the guard zones at the same time, at the same time, at most until the time of deactivation and / or closure of one of the guard zones;
b) short-circuiting the deactivated and / or closed guard zone in the meantime and regenerating the catalyst therein and / or replacing it with fresh or regenerated catalyst;
c) meanwhile, the step of simultaneously using the guard zone, which is a regeneration and / or replacement of the internal catalyst during the preceding step, which is reconnected and the step Performing at most equal time between the time when one of the zones deactivates and / or closes; and
d) During the cycle, when the catalyst is deactivated and / or clogged and needs to be regenerated and / or replaced with a new or regenerated catalyst, during which the reaction of the hydrodemetallization section and / or the hydrodesulfurization section A step capable of shorting at least one of the vessels.
[0042]
A further variant of the process according to the invention comprises a process for hydrotreating a heavy hydrocarbon fraction containing sulfur impurities and metal impurities in at least two sections,
There, in a first hydrodemetallization section, the hydrocarbon feed and hydrogen are passed over the hydrodemetallation catalyst under hydrodemetallization conditions,
The effluent from the first step is then passed under hydrodesulfurization conditions over a hydrodesulfurization catalyst in a subsequent second section, wherein the hydrodemetallation section is preceded by at least one hydrodesulfurization section. Comprising one or more hydrodemetallization zones having a hydrodemetallization guard zone;
Said hydrodemetallation and / or hydrodesulphurization section comprises one or more reactors, which can be short-circuited separately or according to step d) as defined below.
[0043]
The hydrotreating method comprises the following steps:
a) using a guard zone during which time is at least equal to the time of deactivation and / or closure of said zone;
b) short-circuiting the deactivated and / or closed guard zone in the meantime and regenerating the catalyst therein and / or replacing it with fresh or regenerated catalyst;
c) reconnecting the guard zone, during which the internal catalyst has been regenerated and / or replaced during the preceding step, until said time until one of the guard zones deactivates and / or closes; Performing for at most equal time;
d) During the cycle, when the catalyst is deactivated and / or clogged and needs to be regenerated and / or replaced with a new or regenerated catalyst, during which the reaction of the hydrodemetallization section and / or the hydrodesulfurization section A step capable of shorting at least one of the vessels.
[0044]
In one variant of the process according to the invention, the feed for the process is a heavy hydrocarbon cut containing sulfur and metal impurities, generally at least 0.5 ppm by weight of metal, for example, , A fraction obtained from vacuum distillation and called a vacuum distillation distillate (VD).
[0045]
In the process of the present invention, the middle distillate in an amount generally represented by about 0.5% to about 80% by weight, based on the weight of the hydrocarbon feed, is added to the first functional guard zone. Is preferably introduced.
[0046]
The amount of middle distillate introduced is preferably about 1% to about 50% by weight, more preferably about 5% to about 25% by weight, based on the weight of the hydrocarbon feed.
[0047]
In a specific embodiment, the atmospheric distillate introduced with the hydrocarbon feed is a straight run gas oil.
[0048]
In a further embodiment, the product from the hydrodesulfurization step is sent to an atmospheric distillation zone from which atmospheric distillate is recovered and at least a portion thereof is recycled to the inlet of the first functional guard zone. Circulate and recover atmospheric distillation bottoms.
[0049]
In one particular variation, at least a portion of the gas oil fraction from atmospheric distillation is recycled. In this case, the gas oil fraction to be recycled is usually a fraction having an initial boiling point of about 140 ° C. and an end point of about 400 ° C. This fraction is usually a 150-370 ° C fraction or a 170-350 ° C fraction.
[0050]
In a further variation possible in the process of the invention, gas oil from a unit operating using the HYVAHL method or light gas oil from a catalytic cracking unit, commonly known as LCO (light cycle oil). It is possible to recycle those whose initial boiling point is usually in the range of about 140 ° C. to about 220 ° C. and whose final boiling point is usually in the range of about 340 ° C. to about 400 ° C. It is a heavy gas oil fraction from catalytic cracking and is generally known as HCO (heavy cycle oil). Its initial boiling point is in the range of about 340 ° C to about 380 ° C, and its end point is usually about 350 ° C. Those in the range of about 550 ° C can also be recycled.
[0051]
The amount of atmospheric distillate and / or gas oil to be recycled is from about 1% to 50%, preferably from 5% to 25%, more preferably from about 10% to 20% by weight, based on the feedstock. It is.
[0052]
In a further variation, at least a portion of the atmospheric distillation resid from the atmospheric distillation zone is sent to a vacuum distillation zone, from which the vacuum distillate is recovered, and at least a portion thereof is provided to a first functional guard. It can be recirculated to the inlet of the zone and the vacuum distillation bottoms can also be recovered and sent to the essential oil fuel pool.
[0053]
In a further variant, at least a portion of the atmospheric distillation bottoms and / or the vacuum distillate is converted into a catalytic cracking unit, preferably a fluidized bed catalytic cracking unit, for example using the R2R process developed by the applicant. To a unit like that. From this catalytic cracking unit, the LCO fraction and in particular the HCO fraction is recovered, and at least a part of one or the other or a mixture of the two can be added to a fresh charge, which is converted to the hydrogen of the present invention. To the chemical processing method. Usually, a gas oil fraction, a gasoline fraction and a gas fraction are also recovered. At least a portion of the gas oil fraction can optionally be recycled to the inlet of the first functional guard zone.
[0054]
The catalytic cracking step can be carried out under suitable resid cracking conditions using conventional methods well known in the art to produce lower molecular weight hydrocarbon-containing products. Operating conditions and catalysts that can be used in fluidized bed cracking are described in the following patents: That is, U.S. Pat. No. A-4695370, EP-B-0 184 517, U.S. Pat. No. A-4959 334, EP-B-0 323 297, and U.S. Pat. No. 4,965,232. U.S. Pat. No. A-5 120 691, U.S. Pat. No. A-5 344 554, U.S. Pat. No. A-5 449 496, European Patent A-0 485 259, U.S. Pat. No. 5,286,690. U.S. Patent No. A-5 324 696 and European Patent No. A-0 699 224, the descriptions of which are incorporated herein by reference.
[0055]
This fluidized bed catalytic cracking reactor may be used in either an upward flow system or a downward flow system. Although not a preferred embodiment of the present invention, it is also possible to carry out the catalytic cracking in a moving bed reactor. Particularly preferred catalytic cracking catalysts contain at least one zeolite and are usually used in admixture with a suitable matrix such as alumina, silica or silica-alumina.
[0056]
The method of the invention also includes certain variants, in which during step c) all guard zones are used simultaneously, but when the catalyst guard zone regenerated during step b) is reconnected The connection is then made in the same way as before the short circuit during step b).
[0057]
The method of the present invention includes further variations that constitute a preferred embodiment of the present invention, including the following steps:
a) during which all guard zones are used at the same time, at least equal to the time at which the most upstream zone, based on the overall flow direction of the treated feed, is deactivated and / or closed. Steps;
b) meanwhile, the step of passing the charge directly through the guard zone located immediately behind the most upstream guard zone during the previous step, during which the most during the previous step Short-circuiting the upstream guard zone to regenerate the catalyst therein and / or replacing it with fresh or regenerated catalyst; and
c) meanwhile, the step of simultaneously using all of the guard zones, wherein the guard zones in which the internal catalyst has been regenerated and / or replaced during the previous step have been reconnected to be downstream of the set of guard zones. Wherein said step is at least equal to the time during which the most upstream zone is deactivated and / or closed based on the overall flow direction of the treated feed during this step. Continued use steps;
d) meanwhile, short-circuiting at least one of the reactors of the hydrodemetallization section and / or the hydrodesulphurization section, during which the deactivated and / or plugged catalyst is regenerated and / or fresh catalyst or Or a step of replacing with a regenerated catalyst.
[0058]
In a preferred embodiment of the present method, the guard zone located upstream in the circulating flow direction of the entire charge gradually contains metal, coke, sedimentable substances, and various other impurities, so that the desired timing The catalyst is usually separated at a timing when the catalyst inside the catalyst is substantially saturated with metals and various impurities.
[0059]
In a preferred embodiment, a specific conditioning section is used so that these guard zones can be reordered during operation, ie without shutting down the unit. First, the following operations are performed on a disconnected guard reactor using a system operated at moderate pressure (1-5 MPa, preferably 1.5-2.5 MPa); Washing, stripping, and cooling prior to charging; then charging the fresh catalyst followed by heating and sulfidation; then, using appropriate operating techniques, by further pressurization / decompression and cock / valve operation. The guard zone is effectively replaced without stopping the unit and thus without affecting the operating coefficient, but the washing, stripping, discharging, refilling of new catalyst, heating and sulfurization of these spent catalysts All are performed on disconnected reactors or guard zones.
[0060]
The reactor of this hydrotreating unit is usually operated at the space velocity (HSV) indicated below.
[0061]
In a preferred manner, the overall HSV in the guard reactor or zone is about 0.1-4.0 h. -1 , Usually about 0.2-1.0h -1 Other methods using smaller guard reactors, such as those described in U.S. Pat. No. 3,968,026 using smaller guard reactors, There is a difference from the method. The value of the HSV in the guard reactors, each of which plays a role, is preferably about 0.5 to 8 h. -1 , Usually about 1-2h -1 It is. The HSV values of the guard reactor and of each reactor are selected so as to maximize the performance of hydrodemetallation (HDM) while controlling the reaction temperature (with limited exotherm).
[0062]
In an advantageous embodiment, the unit comprises a conditioning section (not shown) with circulating means, heating means, cooling means and suitable separating means which function independently of the reaction section, whereby the piping By operating the valves and the valve, the operation of preparing a new or regenerated catalyst in the guard reactor and the operation for the short-circuited reactor immediately before connection to the operating unit can be performed, i.e. The guard reactor during the short circuit is preheated, the catalyst of its contents is sulphided and the guard reactor is adjusted to the required pressure and temperature conditions. When the guard reactor is rearranged or short-circuited by performing a series of necessary valve operations, the same catalyst is used to condition the spent catalyst in the guard reactor immediately after disconnection from the reaction section. The washing and stripping of the spent catalyst under the required conditions, followed by cooling, then withdrawing this spent catalyst and replacing it with a new or regenerated catalyst I do.
[0063]
Also preferred for these catalysts are those described in EP-B-0 098 764 and FR-A-97 / 07149 filed by the applicant. These catalysts comprise a support and 0.1% to 30% by weight, expressed as metal oxide, of a compound of at least one metal or at least one metal of groups V, VI and VIII of the periodic table. The shape is a plurality of parallel-arranged lump each formed from a plurality of needle-like plate-like crystallites, and the plate-like crystallites of each lump are generally relative to each other. And radially to the center of the mass.
[0064]
More specifically, the present invention relates to the processing of heavy petroleum or petroleum fractions, converting them to lighter fractions to facilitate the processing used in transportation and conventional refining processes. It is aimed at. The oil obtained from coal hydrocracking can also be treated. In that case, it is preferred to use an ebullated bed reactor.
[0065]
More specifically, the present invention relates to a difficult-to-transport, high-viscosity heavy oil containing 50% or more of a component having a high metal and sulfur content and usually having a boiling point of more than 520 ° C. The present invention solves the problem of conversion to a stable hydrocarbon-containing product in which components having a boiling point higher than 520 ° C. are reduced and become, for example, less than 20% by weight.
[0066]
In a specific embodiment, prior to sending the charge to the guard reactor, it is first mixed with hydrogen and subjected to hydride visbreaking conditions.
[0067]
In a further embodiment, the atmospheric or vacuum resid may be deasphalted with a solvent, for example a hydrocarbon-containing solvent or solvent mixture. The most frequently used hydrocarbon-containing solvents are paraffinic, olefinic or alicyclic hydrocarbons (or hydrocarbon mixtures) having 3 to 7 carbon atoms. This treatment is usually carried out under the condition that the product after deasphalting contains less than 0.05% by weight of asphaltene by sedimentation with heptane according to the AFNOR NF T60115 standard. This deasphalting can be carried out using the method described in Applicant's U.S. Pat. No. 4,715,946. The volume ratio of the solvent to the charge is usually about 3: 1 to about 4: 1, and physicochemical elementary operations (mixing-sedimentation, decantation of asphalt phase, Washing-sedimentation of the asphalt phase) is usually carried out separately. The deasphalted product is then usually at least partially recirculated to the entrance of the first functional guard zone.
[0068]
The solvent used to wash the asphaltene phase is usually the same as the solvent used to settle.
[0069]
A mixture of the raw material for deasphalting and the solvent for deasphalting is usually set on the upstream side of the heat exchanger, but this heat exchanger has an appropriate sedimentation so that good decantation is possible. To adjust the mixture to the required temperature.
[0070]
The charge-solvent mixture is preferably flowed to the tube side of the heat exchanger, but not to the shell side.
[0071]
The residence time of the feed-solvent mixture in the mixture settling zone is generally from about 5 seconds to about 5 minutes, but is preferably from about 20 seconds to about 2 minutes.
[0072]
The residence time of the mixture in the decantation zone is typically from about 4 minutes to about 20 minutes.
[0073]
The residence time of the mixture in the wash zone is generally between about 4 minutes and about 20 minutes.
[0074]
The rate of rise of the mixture in the decantation and washing zones is typically less than about 1 cm / sec, preferably less than about 0.5 cm / sec.
[0075]
The temperature applied in the wash zone is usually lower than the temperature applied in the decantation zone. The temperature difference between the two zones is typically between about 5C and about 50C.
[0076]
The mixture from the washing zone is usually recycled to the decanter, preferably upstream of the heat exchanger located at the entrance of the decantation zone.
[0077]
The ratio of solvent to asphaltenes in the wash zone may be from about 0.5: 1 to about 8: 1, preferably from about 1: 1 to about 5: 1.
[0078]
The deasphalting can be in two stages, each stage including three elementary operations: sedimentation, decantation and washing. In cases where this stringency is required, the temperature in each operation of the first stage is reduced by an average of about 10 ° C. to about 40 ° C. compared to the temperature in each operation corresponding to that of the second stage. Is good.
[0079]
The solvent used is a C1-C6 alcohol or phenol or glycol-based solvent. However, it is particularly advantageous to use paraffinic and / or olefinic solvents having 3 to 6 carbon atoms.
[0080]
In summary, in one variation, the method of the present invention comprises a method for hydrotreating heavy hydrocarbons containing sulfur and metal impurities in at least two sections;
There, in a first hydrodemetallization section, the hydrocarbon feed and hydrogen are passed over the hydrodemetallation catalyst under hydrodemetallization conditions,
The effluent from the first stage is then passed under hydrodesulfurization conditions over a hydrodesulfurization catalyst in a subsequent second section,
Wherein said hydrodemetallization section comprises one or more hydrodemetallization zones, prior to which at least two hydrodemetallization guard zones are arranged in series, wherein b ) And c) can be used in a cycle consisting of successive repetitions,
Said hydrodemetallation and / or hydrodesulfurization section comprises one or more reactors, which can be short-circuited separately or according to step d) as defined below;
The hydrotreating method includes the following steps:
a) using all of the guard zones at the same time, at most equal to the time before one of the guard zones deactivates and / or closes;
b) short-circuiting the deactivated and / or closed guard zone in the meantime and regenerating the catalyst therein and / or replacing it with fresh or regenerated catalyst;
c) meanwhile, the step of simultaneously using all of the guard zones, wherein the guard zone is a regeneration and / or replacement of the internal catalyst during the preceding step, which is reconnected and said step Performing at most equal time between the time when one of the is deactivated and / or the time when it is closed;
d) During the cycle, when the catalyst is deactivated and / or clogged and needs to be regenerated and / or replaced with a new or regenerated catalyst, during which the reaction of the hydrodemetallization section and / or the hydrodesulfurization section A step capable of shorting at least one of the vessels.
[0081]
In a further variation, the method of the invention comprises a method for hydrotreating a heavy hydrocarbon fraction containing sulfur and metal impurities in at least two sections,
There, in a first hydrodemetallization section, the hydrocarbon feed and hydrogen are passed over the hydrodemetallation catalyst under hydrodemetallization conditions,
The effluent from the first stage is then passed under hydrodesulfurization conditions over a hydrodesulfurization catalyst in a subsequent second section,
Wherein the hydrodemetallization section comprises one or more hydrodemetallization zones preceded by at least one hydrodemetallization guard zone;
Said hydrodemetallation and / or hydrodesulfurization section comprises one or more reactors, which can be short-circuited separately or according to step d) as defined below;
The hydrotreating method includes the following steps:
a) using a guard zone during which time is at least equal to the time of deactivation and / or closure of said zone;
b) short-circuiting the deactivated and / or closed guard zone in the meantime and regenerating the catalyst therein and / or replacing it with fresh or regenerated catalyst;
c) meanwhile, reconnecting the guard zone in which the internal catalyst has been regenerated and / or replaced during the preceding step, until said one of the guard zones deactivates and / or closes. Performing for a time at least equal to
d) During the cycle, when the catalyst is deactivated and / or clogged and needs to be regenerated and / or replaced with a new or regenerated catalyst, during which the reaction of the hydrodemetallization section and / or the hydrodesulfurization section A step capable of shorting at least one of the vessels.
[0082]
In a further variation, the method of the invention comprises a method for hydrotreating a heavy hydrocarbon fraction containing sulfur and metal impurities in at least two sections,
There, in a first hydrodemetallization section, the hydrocarbon feed and hydrogen are passed over the hydrodemetallation catalyst under hydrodemetallization conditions,
The effluent from the first section is then passed under hydrodesulfurization conditions over a hydrodesulfurization catalyst in a subsequent second section;
Wherein the hydrodemetallization section comprises one or more hydrodemetallization zones and, prior to it, at least two reactors, preferably at least two reactors comprising fixed or ebullated bed zones. Placing the hydrodemetallation guard zones in series so that steps b) and c) as defined below can be used in a cycle consisting of continuous repetition,
Said hydrodemetallation and / or hydrodesulfurization section comprises one or more reactors, which can be short-circuited separately or according to step d) as defined below;
The hydrotreating method includes the following steps:
a) during which all guard zones are used at the same time, at least equal to the time at which the most upstream zone, based on the overall flow direction of the treated feed, is deactivated and / or closed. Steps;
b) meanwhile, the step of passing the charge directly through the guard zone located immediately behind the most upstream guard zone during the previous step, during which the most during the previous step Short-circuiting the upstream guard zone to regenerate the catalyst therein and / or replace it with fresh catalyst; and
c) meanwhile, the step of simultaneously using all of the guard zones, wherein the guard zones in which the internal catalyst has been regenerated and / or replaced during step b) are reconnected to be downstream of the set of guard zones. And said step lasts at least as long as the time during which the most upstream zone deactivates and / or closes relative to the overall flow direction of the treated feed during this step Steps;
d) During the cycle, at least one of the reactors in the hydrometallization section and / or the hydrodesulfurization section is short-circuited, during which the deactivated and / or clogged catalyst is regenerated and / or fresh catalyst Or or replacing with a regenerated catalyst.
[0083]
In the process of the present invention, a middle distillate in an amount generally represented by 0.5% to 80% by weight, based on the weight of the hydrocarbon feed, is introduced into the inlet of the first functional guard zone. Is preferred. It is more preferable that the atmospheric distillation distillate introduced at the same time as the hydrocarbon feed is a straight-run gas oil.
[0084]
In the process of the present invention, the product from the hydrodesulfurization step is preferably sent to an atmospheric distillation zone from which atmospheric distillate is recovered, preferably at least a portion thereof, of the first functional distillate. Recirculate to the guard zone inlet to recover atmospheric distillation bottoms. More preferably, at least a portion of the gas oil fraction from the atmospheric distillation step after the hydrodesulfurization step is recycled to the inlet of the first functional guard zone.
[0085]
In a preferred variant of the process of the invention, the recirculated gas oil fraction is a fraction with an initial boiling point of about 140 ° C. and an end point of about 400 ° C.
[0086]
In these preferred variants, the amount of atmospheric distillate and / or gas oil introduced simultaneously with the feed to the inlet of the first functional guard zone is from about 1% to 50%, based on the feed. Preferably, it is weight%.
[0087]
It is also possible to send at least a portion of the atmospheric distillation bottoms from the atmospheric distillation zone to a vacuum distillation zone, where the vacuum distillate is recovered and at least a portion thereof is passed to a first functional guard zone. Recirculation to the inlet of the vacuum distillation also recovers the vacuum distillation bottoms. In this case, a preferred variant is that at least part of the atmospheric distillation bottoms and / or the vacuum distillation distillate is sent to a catalytic cracking unit, where the LCO and HCO fractions are recovered and the two fractions One or the other or at least a portion of the mixture to the entrance of the first functional guard zone.
[0088]
In a preferred manner in the process according to the invention, the guard zones are all used simultaneously during step c), but the guard zones which have regenerated the internal catalyst in step b) have their connections short-circuited during step b). The connection is made in the same way as before.
[0089]
In a further preferred embodiment of the method according to the invention, a conditioning section is associated with one or more guard zones, which, during operation, allow the said single or multiple guard zones without stopping the unit. The zones can be shorted and re-arranged, but the above sections are adjusted to condition the catalyst in the inactive guard zone so that the pressure is in the range of 1-5 MPa. I do.
[0090]
In a preferred mode of the process of the present invention, the feed is first treated with hydrogen prior to feeding the feed to one or more guard zones in order to treat the feed comprising heavy oil or a heavy oil fraction containing asphaltenes. Place under conditions of mixing and hydride visbreaking.
[0091]
In a preferred mode of the process of the present invention, the atmospheric distillation residue obtained in any atmospheric distillation step is subjected to deasphalting using a solvent or a mixture of solvents, and at least a part of the product after deasphalting is subjected to the first step. Recirculate to the entrance of the functional guard zone.
[0092]
In a preferred mode of the method of the present invention, the vacuum distillation resid obtained in any vacuum distillation step is subjected to deasphalting using a solvent or solvent mixture, and at least a part of the product after deasphalting has a first function. Recirculate to the entrance of the sex guard zone.
[0093]
In a further preferred variant of the process according to the invention, all reactors are fixed-bed reactors. In a further preferred variant, at least one of the guard reactor and / or the hydrodemetallation section and / or the hydrodesulfurization section is an ebullated bed reactor. In a further preferred variant, the reactor for the guard zone is a fixed bed reactor and all reactors in the hydrodesulfurization zone are ebullated bed reactors.
[0094]
In a further preferred variant, all reactors in the guard zone are fixed bed reactors, all reactors in the hydrodemetallization zone are ebullated bed reactors, and optionally but preferably All of the reactors in the desulfurization zone are ebullated bed reactors. It is also possible to operate the process of the present invention only in an ebullated bed reactor in the guard zone and in the hydrodemetallation and hydrodesulfurization sections.
[0095]
BEST MODE FOR CARRYING OUT THE INVENTION
The present invention will be briefly described with reference to FIG.
[0096]
The charged materials reach the guard zones 1A and 1B via the pipe 1, and exit from these zones via the pipe 23 and / or the pipe 24 and the pipe 13. The feed leaving the guard zone or zones reaches the HDM section via line 13, which is indicated here as reaction section 2 and is carried out in one or more reactors. Although configured, each of the reactors is provided with a dedicated short circuit channel. The effluent from section 2 is withdrawn via line 14 and sent to hydrodesulfurization section 3, which has one or more reactors, which are arranged in series. Alternatively, a dedicated short-circuit channel may be provided for each of them. The effluent from section 3 is withdrawn via line 15.
[0097]
In FIG. 1, the middle distillate is introduced via a pipe 55 and mixed with a hydrocarbon feedstock in the pipe 1.
[0098]
In the case shown in FIG. 1, there are two reactors in the guard zone, but in a preferred embodiment, the method comprises a series of cycles, each of which comprises four consecutive periods. ) Is divided into:
• During the first phase, the feed passes continuously through zone 1A and then zone 1B, where the gas oil fraction recycled from atmospheric distillation is introduced into zone 1A along with the feed. . During this first phase (step a) of the method), the charge is introduced into the guard reactor 1A via the pipe 1 and the pipe 21 (the valve 31 is open). During this period, valves 32, 33 and 35 are closed. The effluent from zone 1A is sent to guard reactor 1B via line 23, line 26 (valve 34 is open) and line 22. The effluent from zone 1B is sent to HDM section 2 via line 24 (valve 36 is open) and line 13 (valve 37 is open).
[0099]
-During the second phase, the feed passes only through zone 1B and the gas oil fraction recycled from atmospheric distillation is introduced into zone 1B along with the feed. During this second phase (step b of the method)), valves 31, 33, 34 and 35 are closed and the charge is introduced into zone 1B via lines 1 and 22 (valve 32 is open). . During this phase, the effluent from zone 1B is sent to HDM section 2 via line 24 (valve 36 is open) and line 13 (valve 37 is open).
[0100]
-During the third phase, the feed passes continuously through zone 1B and then zone 1A, where the gas oil fraction recycled from atmospheric distillation is introduced into zone 1B along with the feed. During this third phase (method step c)), valves 31, 34 and 36 are closed and valves 32, 33 and 35 are open. The charged raw material is introduced into the zone 1B via the pipe 1 and the pipe 22. The effluent from zone 1B is sent to guard reactor 1A via pipes 24, 27 and 21. The effluent from zone 1A is sent to HDM section 2 via pipe 23 and pipe 13 (valve 37 is open).
[0101]
• During the fourth period, the charge passes only through guard zone 1A and the gas oil fraction recycled from atmospheric distillation is introduced into zone 1A along with the charge.
[0102]
The number of cycles performed for the guard reactor is a function of the duration of the operating cycle of all units and the average frequency of permutation of zones 1A and 1B. During the fourth period, valves 32, 33, 34 and 36 are closed and valves 31 and 35 are open. The charge is introduced into the zone 1A via the pipe 1 and the pipe 21. During this period, the effluent from zone 1A is sent to HDM section 2 via line 23 and line 13 (valve 37 is open).
[0103]
In the case shown in FIG. 1, the hydrodemetallation (HDM) section 2 can be provided with one or more reactors. Each or more of these reactors can be temporarily disconnected in order to periodically (step d) of the catalyst). In its preferred embodiment, the method comprises a series of cycles, each divided into three consecutive phases:
-During the first phase, the charge is passed continuously through guard zones 1A, 1B and HDM section 2 and finally to HDS section 3. During this period, the gas oil fraction recycled from atmospheric distillation is introduced into guard zone 1A along with the feed. During this period, valves 32, 33, 35, 38 and 41 are closed. The charged raw material is introduced into the zone 1A via the pipe 1 and the pipe 21. The effluent from the zone 1A is sent to the guard zone 1B via the pipe 23, the pipe 26 (the valve 34 is open) and the pipe 22. The effluent from zone 1B is sent to HDM section 2 via line 24 (valve 36 is open) and line 13 (valve 37 is open). The effluent from section 2 is sent to HDS section 3 via line 14 (two valves 42 and 39 open). The effluent from section 3 is then sent via line 15 (valve 40 open) to a fractionation unit (not shown).
[0104]
-During the second phase, the feed passes continuously through guard zones 1A and 1B and then through HDS section 3. During this period, the gas oil fraction recycled from atmospheric distillation is introduced into zone 1B along with the feed. During this operation, valves 32, 33, 35, 37, 41 and 42 are closed. The charged raw material is introduced into the zone 1A via the pipe 1 and the pipe 21. The effluent from the zone 1A is sent to the guard zone 1B via the pipe 23, the pipe 26 (the valve 34 is open) and the pipe 22. The effluent from zone 1B is sent to HDS section 3 via line 24 (valve 36 is open) and line 25 (two valves 38 and 39 are open). The effluent from section 3 is then sent via line 15 (valve 40 open) to a fractionation unit (not shown). During this phase, the HDM catalyst is replaced with a new one, and the catalyst is then conditioned using the method described in the present invention. This conditioning is particularly necessary if the catalyst is in the form of an oxide.
[0105]
During the third phase, the feed is passed continuously through guard zones 1A and 1B and HDM section 2 and then to HDS section 3. During this period, the gas oil fraction recycled from the atmospheric distillation step is introduced into the guard zone 1B along with the feed. The conditions here are the same as in the first stage, and the reactor containing the replaced new catalyst should be placed in the same position in the flow path system as compared to that described for the first stage. Can be.
[0106]
In the case shown in FIG. 1, the hydrodesulfurization section 3 can be provided with one or more reactors, each or more of which replace the catalyst periodically with new ones ( For step d)) of the method, it can be temporarily disconnected. In its preferred embodiment, the method comprises a series of cycles, each divided into three consecutive phases:
During the first phase, the feed is passed continuously through guard zones 1A, 1B and HDM section 2 and then to HDS section 3. During this period, the gas oil fraction recycled from atmospheric distillation is introduced into guard zone 1A along with the feed. During this period, valves 32, 33, 35, 38 and 41 are closed. The charged raw material is introduced into the guard zone 1A via the pipe 1 and the pipe 21. The effluent from the guard zone 1A is sent to the guard zone 1B via the pipe 23, the pipe 26 (the valve 34 is open) and the pipe 22. The effluent from the guard zone 1B is sent to the HDM section 2 via the pipe 24 (the valve 36 is open) and the pipe 13 (the valve 37 is open). The effluent from section 2 is sent to section 3 via line 14 (two valves 42 and 39 open). The effluent from section 3 is then sent via line 15 (valve 40 open) to a fractionation unit (not shown).
[0107]
-During the second phase, the feed passes continuously through guard zones 1A and 1B and then through HDM section 2. During this period, the gas oil fraction recycled from atmospheric distillation is introduced into zone 1B along with the feed. During this operation, valves 32, 33, 35, 38, 39 and 40 are closed. The charged raw material is introduced into the zone 1A via the pipe 1 and the pipe 21. The effluent from the zone 1A is sent to the zone 1B via the pipe 23, the pipe 26 (the valve 34 is open) and the pipe 22. The effluent from zone 1B is sent to HDM section 2 via line 24 (valve 36 is open) and line 13 (valve 37 is open). The effluent from section 2 is then sent via line 14 (valve 42 open) and line 16 (valve 41 open) to a fractionation unit (not shown). During this phase, the catalyst or catalysts from section 3 are replaced with new ones, and then the catalyst or catalysts are conditioned using the method described in the present invention. This conditioning is particularly necessary if the catalyst is in the form of an oxide.
[0108]
During the third phase, the feed is passed continuously through guard zones 1A and 1B and HDM section 2 and then to HDS section 3. During this period, the gas oil fraction recycled from the atmospheric distillation step is introduced into zone 1B along with the feed. The conditions here are the same as in the first phase, the reactor containing the new catalyst can be placed in the feed line system at the same position as described for the first phase.
[Brief description of the drawings]
FIG. 1 is a flow sheet showing an example of the present invention.

Claims (20)

  1. A method for hydrotreating a heavy hydrocarbon fraction containing sulfur and metal impurities in at least two sections, comprising:
    Wherein, in a first hydrodemetallation section, the hydrocarbon feed and hydrogen are passed over the hydrodemetallation catalyst under hydrodemetallation conditions;
    The effluent from the first stage is then passed into a subsequent second section under hydrodesulfurization conditions over a hydrodesulfurization catalyst,
    Wherein said hydrodemetallization section comprises one or more hydrodemetallization zones, prior to which at least two hydrodemetallization guard zones are arranged in series, wherein b ) And c) can be used in a cycle consisting of successive repetitions,
    The hydrodemetallation and / or hydrodesulfurization section comprises one or more reactors which can be short-circuited separately or according to step d) as defined below;
    a) using all of the guard zones simultaneously, at most equal to the time until one of the guard zones deactivates and / or closes;
    b) short-circuiting the underactive and / or closed guard zone and regenerating the catalyst therein and / or replacing it with fresh or regenerated catalyst;
    c) using all of the guard zones simultaneously, reconnecting the guard zones in which the internal catalyst has been regenerated and / or replaced during the preceding step, the step being carried out for a time and / or when one of the guard zones is deactivated. Or performing a time equal to or longer than the time before the closing time; and
    d) when the catalyst is deactivated and / or clogged during the cycle and needs to be regenerated and / or replaced with a fresh or regenerated catalyst, the reactor of the hydrodemetallization section and / or Capable of shorting at least one unit.
  2. A method for hydrotreating a heavy hydrocarbon fraction containing sulfur and metal impurities in at least two sections, comprising:
    Wherein, in a first hydrodemetallation section, the hydrocarbon feed and hydrogen are passed over the hydrodemetallation catalyst under hydrodemetallation conditions;
    The effluent from the first stage is then passed under hydrodesulfurization conditions over a hydrodesulfurization catalyst in a subsequent second section,
    Wherein the hydrodemetallization section comprises one or more hydrodemetallization zones preceded by at least one guard zone;
    The hydrodemetallation and / or hydrodesulfurization section comprises one or more reactors which can be short-circuited separately or according to step d) as defined below;
    a) using the guard zone for at least as long as the time before the zone deactivates and / or closes;
    b) short-circuiting the underactive and / or closed guard zone and regenerating the catalyst therein and / or replacing it with fresh or regenerated catalyst;
    c) reconnecting the guard zone in which the internal catalyst has been regenerated and / or replaced during a preceding step, said step being extended until the time of deactivation and / or closing of one of the guard zones. Using a time equal to
    d) when the catalyst is deactivated and / or clogged during the cycle and needs to be regenerated and / or replaced with a fresh or regenerated catalyst, the reactor of the hydrodemetallization section and / or Capable of shorting at least one unit.
  3. A method for hydrotreating a heavy hydrocarbon fraction containing sulfur and metal impurities in at least two sections, comprising:
    Wherein, in a first hydrodemetallation section, the hydrocarbon feed and hydrogen are passed over the hydrodemetallation catalyst under hydrodemetallation conditions;
    The effluent from the first stage is then passed under hydrodesulfurization conditions over a hydrodesulfurization catalyst in a subsequent second section,
    Wherein the hydrodemetallization section comprises one or more hydrodemetallization zones, before which at least two or more reactors, preferably fixed bed or ebullated bed reactors. Placing the hydrodemetallation guard zones in series so that steps b) and c) as defined below can be used in a cycle consisting of continuous repetition,
    The hydrodemetallation and / or hydrodesulfurization section comprises one or more reactors which can be short-circuited separately or according to step d) as defined below;
    a) using all of the guard zones at the same time, at most equal to the time of deactivation and / or closing of the zone located upstream, based on the overall flow direction of the treated feed;
    b) during the previous step the feed is passed directly through the guard zone located immediately behind the most upstream guard zone, during which the most upstream during the previous step Short-circuiting the existing guard zone, regenerating its internal catalyst and / or replacing it with fresh catalyst; and c) simultaneously using all of the guard zones, during step b) the internal catalyst Regenerating and / or replacing the guard zone so that it is downstream of the set of guard zones, wherein said step is most often performed during this step with reference to the overall flow direction of the treated feedstock. Continuing for a time at most equal to the time before the upstream zone deactivates and / or closes;
    d) short-circuiting at least one of the reactors in the hydrodemetallation section and / or the hydrodesulfurization section, during which the deactivated and / or plugged catalyst is regenerated and / or with fresh or regenerated catalyst Permuting.
  4. 4. An intermediate effluent in an amount represented by 0.5% to 80% by weight, based on the weight of the hydrocarbon feed, is introduced into the inlet of the first guard zone in operation. The method according to any one of claims 1 to 4.
  5. 5. The process according to claim 4, wherein the atmospheric distillate introduced simultaneously with the hydrocarbon feed is a straight run gas oil.
  6. The product from the hydrodesulfurization step is sent to an atmospheric distillation zone from which atmospheric distillate is recovered and at least a portion thereof is recycled to the inlet of the first functional guard zone, The method according to any one of claims 1 to 5, wherein the pressure distillation residue is also recovered.
  7. 7. The method of claim 6, wherein at least a portion of the gas oil fraction from the atmospheric distillation step after the hydrodesulfurization step is recycled to an inlet of a first functional guard zone.
  8. The method according to claim 5 or 7, wherein the recycle gas oil fraction has an initial boiling point of about 140 ° C and an end point of about 400 ° C.
  9. 5. The amount of said atmospheric distillate and / or gas oil introduced into the inlet of the first functional guard zone at the same time as the feed is from about 1% to 50% by weight, based on the feed. The method according to any one of claims 1 to 8.
  10. At least a portion of the atmospheric resid from the atmospheric distillation zone is sent to a vacuum distillation zone, where the vacuum distillate is recovered and at least a portion is recycled to the inlet of the first functional guard zone. The method according to claim 6 or 7, wherein the circulation is carried out, and the vacuum distillation residue is also recovered.
  11. At least a portion of the atmospheric distillation bottoms and / or vacuum distillation distillate is sent to a catalytic cracking unit where LCO and HCO fractions are recovered, and one, the other or a mixture of the two fractions. 11. The method of claim 10, wherein at least a portion is sent to an entrance of the first functional guard zone.
  12. During step c), the guard zones are all used simultaneously, and the guard zones, which have regenerated the internal catalyst in step b), are connected in the same way as before the short circuit during step b) The method according to claim 1, wherein the method is performed.
  13. A conditioning section is associated with one or more guard zones, by means of which said one or more guard zones can be short-circuited or rearranged during operation without stopping the operation of the unit. 13. Any one of the preceding claims, wherein the section is adjusted such that the pressure is in the range of 1 to 5 MPa for conditioning the catalyst in the inactive guard zone. The method described in.
  14. In order to treat a feed consisting of a heavy oil or a heavy oil fraction containing asphaltenes, the feed is first mixed with hydrogen before the feed is sent to one or more guard zones and hydrogenated visbreaking. 14. The method according to any one of the preceding claims, wherein the method is subject to conditions.
  15. 8. The atmospheric distillation bottoms are subjected to deasphalting using a solvent or solvent mixture, and at least a portion of the deasphalted product is recycled to an inlet of a first functional guard zone. 12. The method according to any one of 10 or 11.
  16. 12. The vacuum distillation resid is subjected to deasphalting using a solvent or solvent mixture and at least a portion of the deasphalted product is recycled to the inlet of the first functional guard zone. The method described in.
  17. 17. The method according to any one of the preceding claims, wherein all of the reactors are fixed bed reactors.
  18. 18. The method according to any of the preceding claims, wherein at least one of the guard zone and / or hydrodemetallation section and / or hydrodesulfurization section reactor is an ebullated bed reactor.
  19. 19. The method according to claim 18, wherein the reactors for the guard zone are fixed bed reactors and all reactors in the hydrodesulfurization zone are ebullated bed reactors.
  20. 20. A process according to claim 18 or claim 19, wherein the reactors for the guard zone are fixed bed reactors and all reactors in the hydrodemetallation zone are ebullated bed reactors.
JP2002549807A 2000-12-11 2000-12-11 Method for hydrotreating heavy hydrocarbon fractions using a sortable reactor and a reactor that can be shorted Expired - Fee Related JP4697571B2 (en)

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