EP1343857A1 - Method for hydrotreatment of a heavy hydrocarbon fraction with switchable reactors and reactors capable of being shorted out - Google Patents
Method for hydrotreatment of a heavy hydrocarbon fraction with switchable reactors and reactors capable of being shorted outInfo
- Publication number
- EP1343857A1 EP1343857A1 EP00990056A EP00990056A EP1343857A1 EP 1343857 A1 EP1343857 A1 EP 1343857A1 EP 00990056 A EP00990056 A EP 00990056A EP 00990056 A EP00990056 A EP 00990056A EP 1343857 A1 EP1343857 A1 EP 1343857A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- guard
- catalyst
- zone
- section
- during
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING 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
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
- C10G65/04—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
- C10G2300/1048—Middle distillates
- C10G2300/1059—Gasoil having a boiling range of about 330 - 427 °C
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/107—Atmospheric residues having a boiling point of at least about 538 °C
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1074—Vacuum distillates
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/205—Metal content
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/205—Metal content
- C10G2300/206—Asphaltenes
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/30—Physical properties of feedstocks or products
- C10G2300/301—Boiling range
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4081—Recycling aspects
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/44—Solvents
Definitions
- the present invention relates to the refining and conversion of heavy fractions of hydrocarbons containing inter alia sulfur and metallic impurities, such as distillates or atmospheric residues, vacuum residues, deasphalted oils, vacuum distillates, pitches, asphalts mixed with an aromatic distillate, carbon hydrogenates, heavy oils of all origins and in particular from tar sands or shales. It relates in particular to the treatment of liquid charges. It would not be departing from the scope of the present invention if the liquid charge also contains asphaltenes.
- the fillers which can be treated according to the invention usually contain at least 0.5 ppm by weight of metals (nickel and / or vanadium), at least 0.5% by weight of sulfur.
- the objective of the catalytic hydrotreatment of these feeds is both to refine, that is to say to significantly reduce their content of metals, sulfur and other impurities while improving the hydrogen to carbon ratio (H / C) and while transforming them more or less partially into lighter cuts, the different effluents thus obtained can serve as bases for the production of good quality fuel oil, diesel and petrol, or fillers for other units such as cracking residue or cracked residue from vacuum distillates.
- the process of the present invention is an improvement on the processes of the prior art, in particular processes in fixed beds or bubbling beds of catalyst.
- the charge circulates through several reactors, preferably with a fixed bed or a bubbling bed arranged in series, the first reactor (s) being used to especially carry out hydrodetallization of the charge therein (so-called step HDM) as well as part of the hydrodesulfurization, the last reactor (s) being used to carry out deep refining of the feedstock, and in particular hydrodesulfurization (so-called HDS step).
- step HDM hydrodetallization of the charge therein
- the last reactor (s) being used to carry out deep refining of the feedstock, and in particular hydrodesulfurization (so-called HDS step).
- the effluents are withdrawn from the last HDS reactor.
- the ideal catalyst must be capable of treating fillers which may be rich in asphaltenes, while having a high demetallizing power combined with a high metal retention capacity and great resistance to coking.
- the Applicant has developed such a catalyst on a particular macroporous support (with a "sea urchin" structure) which gives it precisely the qualities sought in this step (patents EP-B-113297 and EP-B-113284):
- the ideal catalyst must have a strong hydrogenating power in order to achieve a deep refining of the products: desulphurization, further demetallization, lowering of the Conradson carbon and possibly of the asphaltenes content.
- the applicant has developed such a catalyst (patents EP-B-113297 and EP-B-113284) which is particularly well suited to the treatments of this type of filler.
- the disadvantage of this type of catalyst with high hydrogenating power is that it deactivates quickly in the presence of metals or coke.
- the advantage of fixed bed processes is that high refining performance is obtained thanks to the high catalytic efficiency of fixed beds.
- a certain metal content of the feed for example from 50 to 150 ppm
- the reactors in particular the first HDM reactor
- the temperatures are increased, which promotes the formation of coke and the increase in pressure drops; moreover, it is known that the first catalytic bed is liable to clog up fairly quickly because of the asphaltenes and sediments contained in the charge or following an operational incident.
- the unit has to be shut down at least every 2 to 6 months to replace the first deactivated or clogged catalytic beds, this operation being able to last up to 3 weeks, thereby reducing the factor unit operative.
- the advantage of the bubbling bed processes is that high conversion performance is obtained thanks to the possibility of working at high temperature.
- the applicant has developed such a process well suited to the treatment of conventional and heavy loads (patent CA 2,171,894 - French patent application FR-98 / 00.530)
- this guard reactor does not ensure strong demetallization of the feedstock and therefore poorly protects the main HDM reactors against the deposition of metals in the case of feedstocks rich in metals (for example more than 100 ppm ). It follows an accelerated deactivation of these reactors leading to too rapid shutdowns of the unit, therefore to always insufficient operating factors.
- hydrodetallization section the charge of hydrocarbons and hydrogen is passed under hydrodetallization conditions over a hydrodemetallization catalyst, then in a second subsequent section, hydrodesulfurization conditions, the effluent from the first section on a hydrodesulfurization catalyst.
- the hydrodetallization section comprises one or more hydrodemetallization zones, preferably in fixed beds, preceded by at least two hydrodetallization guard zones, also preferably in fixed beds, arranged in series to be used in a cyclic manner consisting of the successive repetition of steps b) and c) defined below: a) a step, in which the guard zones are used together for a duration at most equal to the deactivation and / or clogging time of one of them, b) a step , during which the deactivated and / or clogged guard zone is short-circuited and the catalyst that it contains is regenerated and / or replaced by fresh catalyst, and c) a step, during which the guard zones are used all together , the guard zone whose catalyst was regenerated during the previous step being reconnected and said step being continued for a duration at most equal to the deactivation and / or clogging of one of the guard zones.
- This process allows a cycle time in general of at least 11 months for the main HDM and HDS reactors with high refining and conversion performances while maintaining the stability of the products.
- the global desulfurization is of the order of 90% and the overall demetallization of the order of 95%.
- the disadvantage of this technology is the difficulty of obtaining performance in overall desulfurization greater than approximately 90% and / or in overall demetallization greater than approximately 95%, as well as the difficulty of obtaining cycle times greater than 11 months a few or the level of performance. It has surprisingly been found that bypassing one or more reactors of the hydrodemetallization section and / or of the hydrodesulfurization section makes it possible to maintain the catalytic activity for each of the stages and / or to improve the cycle time.
- the present invention thus relates to the possibility of short-circuiting one or more reactors when the catalyst is deactivated and / or clogged with sediment or coke to be regenerated and / or replaced by fresh or regenerated catalyst. This invention relates to reactors in the hydrodemetallization section as well as those in the hydrodesulfurization section.
- reactors of the hydrodemetallization and / or hydrodesulfurization section are for example short-circuited every 6 months to replace the deactivated or clogged catalytic beds, this operation improves the operating factor of the unit.
- the invention consists of a process for hydrotreating a heavy fraction of hydrocarbons in a first hydrodemetallization section, then in a second hydrodesulfurization section through which the effluent from the first section is passed.
- the hydrodetallization section is preceded by at least one guard zone.
- the method of the present invention makes it possible to very significantly reduce the viscosity of liquid effluents, hence a significant reduction in pressure losses in the reactors, better operation of the recycling compressor and obtaining a higher hydrogen pressure. It is thus possible to obtain a greater overall desulfurization and a diesel fraction having a much lower sulfur content, meeting current specifications and directly usable in the diesel (storage) tank of the refinery. Furthermore, the method according to the invention makes it possible to obtain a better functioning of the preheating ovens thanks to a better heat transfer and therefore a lower skin temperature of these ovens which goes in the direction of a lifetime. of these ovens more important and is therefore a favorable factor allowing to decrease the operating cost of the unit.
- the process according to the invention which combines the high performance of the reactors preferably in a fixed bed or bubbling bed, with a high operating factor for the treatment of feedstocks with high metal contents (1 to 1500 ppm but most often from 100 to 1000 and preferably 150 to 350 ppm) can be defined in one of its variants as a hydrotreatment process in at least two sections, of a heavy fraction of hydrocarbons containing sulfur impurities and metallic impurities, in which in a first so-called hydrodetallization section, the hydrocarbon and hydrogen charge is passed under hydrodetallization conditions over a hydrodetallization catalyst, then in a second subsequent section, the effluent from the first section is passed, under hydrodesulfurization conditions, over a hydrodesulfurization catalyst, and in which the hydrodemetallization section comprises one or more hydrodemetallization zones, preferably in fixed beds or bubbling beds, preceded by at least one, or possibly two hydrodetallization guard zones, also preferably in fixed beds or bubbling beds, arranged in series to be used
- the method according to the invention in the case where it involves two guard zones is therefore a hydrotreatment method comprising: a) a step, in which the guard zones are used all together for a duration at most equal to the time deactivation and / or clogging of one of them, b) a step, during which the deactivated and / or clogged guard zone is short-circuited and the catalyst which it contains is regenerated and / or replaced by fresh or regenerated catalyst, c) a step, during which the guard zones are used together, the guard zone whose catalyst has been regenerated and / or replaced during the previous step being reconnected and said step being continued for a duration at most equal to the deactivation and / or clogging time of one of the guard zones, d) a step in which at least one of the reactors of the hydrodemetallization section and / or of the hydrodesulfurization section can be short-circuited during the cycle when the catalyst is deactivated and / or clogged in order to be regenerated
- Another variant of the process according to the invention consists of a process for hydrotreating in at least two sections, a heavy fraction of hydrocarbons containing sulfur impurities and metallic impurities in which in a first section called hydrodemetallization, passing, under hydrodetallization conditions, the charge of hydrocarbons and hydrogen over a hydrodemetallization catalyst, then in a second subsequent section, the effluent from the first stage is passed under hydrodesulfurization conditions on a hydrodesulfurization catalyst, and in which the hydrodemetallization section comprises one or more hydrodemetallization zones preceded by at least one hydrodemetallization guard zone, the hydrodemetallization and / or hydrodesulfurization sections being composed of '' one or more reactors which can be short-circuited separately or not according to step d) defined above after, said hydrotreatment process comprising: a) a step, in which the guard zone is used for a duration at most equal to the deactivation and / or clogging time of said zone, b) a step, during which the zone
- the charge of said process is a heavy fraction of hydrocarbons containing sulfur impurities and metallic impurities, in general at least 0.5 ppm by weight of metals, for example a fraction obtained by distillation vacuum also called vacuum distillate (DSV).
- DSV vacuum distillate
- an amount of average distillate generally representing from 0.5% to 80% by weight is introduced at the entry of the first guard zone in operation, at the same time as the charge relative to the weight of the hydrocarbon charge.
- the amount of middle distillate introduced represents approximately 1% to approximately 50% and very preferably approximately 5% to approximately 25% by weight relative to the hydrocarbon charge.
- the atmospheric distillate which is introduced with the hydrocarbon feedstock is a direct distillation gas oil.
- the product resulting from the hydrodesulfurization step is sent to an atmospheric distillation zone. from which an atmospheric distillate is recovered, at least part of which is recycled at the entrance to the first guard zone in operation and an atmospheric residue.
- the diesel cut that we recycle is most often a cut whose initial boiling point is around 140 ° C ° C and the final boiling point around 400 ° C. Most often this cut is a 150 ° C-370 ° C, or 170-350 ° C cut.
- a gas oil coming from a unit operating according to the HYVAHL process or else a fraction of light gas oil coming from a catalytic cracking unit, most often called by a person skilled in the art under the initials LCO (from the English term Light Cylcle Oil) with an initial boiling point generally between approximately 140 ° C and approximately 220 ° C and with a final boiling point generally between approximately 340 ° C and about 400 ° C.
- LCO from the English term Light Cylcle Oil
- the amount of atmospheric distillate and / or of diesel that is recycled represents, by weight relative to the feed, approximately 1 to 50%, preferably 5 to 25% and more preferably approximately 10 to 20%.
- At least part of the atmospheric residue from the atmospheric distillation zone is sent to a vacuum distillation zone from which a vacuum distillate is recovered, at least part of which is recycled at the inlet of the first guard zone in operation and a vacuum residue which can be sent to the fuel oil storage zone of the refinery.
- At least part of the atmospheric residue and / or of the vacuum distillate is sent to a catalytic cracking unit, preferably a catalytic cracking unit in a fluidized bed, for example a unit such as that using the process developed by the applicant called R2R.
- a catalytic cracking unit preferably a catalytic cracking unit in a fluidized bed, for example a unit such as that using the process developed by the applicant called R2R.
- an LCO fraction and an HCO fraction are recovered in particular, which can be at least partly either one or the other, or a mixture of the two add to the fresh charge which is sends in the hydrotreatment process according to the present invention.
- a diesel fraction, a petrol fraction and a gaseous fraction are also most often recovered. At least part of this diesel fraction can optionally be recycled at the entrance to the first guard zone in operation.
- the catalytic cracking step can be carried out in a conventional manner known to those skilled in the art, under the appropriate residue cracking conditions, with a view to producing hydrocarbon products of lower molecular weight.
- Descriptions of operation and of catalysts which can be used in the context of cracking in a fluidized bed are described, for example, in patent documents US-A-4,695,370, EP-B-1,84517, US-A-4,959,334, EP-B-323,297, US -A-4965232, US-A-5120691, US-A-5344554, US-A-5449496, EP-A-485259, US-A-5286690, US-A-5324696 and EP-A-699224 whose descriptions are considered incorporated herein by the mere fact of this mention.
- the catalytic cracking reactor in a fluidized bed can operate with rising current or with falling current. Although this is not a preferred embodiment, it is also conceivable to carry out catalytic cracking in a moving bed reactor.
- Particularly preferred catalytic cracking catalysts are those which contain at least one zeolite usually in admixture with a suitable matrix such as, for example, alumina, silica, silica-alumina.
- the implementation of the method according to the invention comprises a particular variant in which during step c) the guard zones are used all together, the guard zone whose catalyst was regenerated during step b) being reconnected so that its connection is identical to that which it had before it was short-circuited during the step b).
- the implementation of the method according to the invention comprises another variant, which constitutes a preferred embodiment of the present invention, comprising the following steps: a) a step, in which the guard zones are used all together for a period of time at most equal to the deactivation and / or clogging time of the guard zone furthest upstream from the overall direction of circulation of the treated charge, b) a step, during which the charge penetrates directly into the guard zone located immediately after that which was most upstream during the previous stage and during which the guard zone which was most upstream during the previous stage is short-circuited and the catalyst which it contains is regenerated and / or replaced by fresh or regenerated catalyst, c) a step, during which the guard zones are used together, the guard zone whose catalyst has been regulated neutralized and / or replaced during the previous step being reconnected so as to be downstream of all the guard zones and said step being continued for a duration at most equal to the deactivation and / or clogging time of the guard zone which is, during this stage, the most up
- the guard zone furthest upstream in the overall direction of flow of the charge is progressively charged with metals, coke, sediments and other various impurities and is disconnected as soon as desired, but most often when the catalyst qu 'it contains is practically saturated with metals and various impurities.
- a particular conditioning section which allows these guard zones to be switched on, that is to say without stopping the operation of the unit: firstly, a system which operates at moderate pressure (from 1 MPa to 5 MPa but preferably from 1.5 MPa to 2.5 MPa) allows the following operations to be carried out on the disconnected guard reactor: washing, stripping, cooling, before discharging the spent catalyst; then heating and sulfurization after loading the fresh or regenerated catalyst; then another system of pressurization / depressurization and of gate valves of appropriate technology effectively makes it possible to permute these guard zones without stopping the unit, that is to say without affecting the operating factor, since all the washing operations, stripping, unloading of spent catalyst, recharging of fresh or regenerated catalyst, heating, sulfurization are carried out on the reactor or disconnected guard zone.
- moderate pressure from 1 MPa to 5 MPa but preferably from 1.5 MPa to 2.5 MPa
- VVH hourly space velocities
- VVH (h-1) VVH (h " 1 ) wide range preferred
- a preferred mode consists in operating the guard zones or reactors in service at a global VVH of approximately 0.1 to 4.0 h -1 and most often of approximately 0.2 to 1.0 h -1 , at Unlike other methods using smaller guard reactors, in particular that described in US Pat. No. 3,968,026, where smaller guard reactors are used.
- the VVH value of each guard reactor in operation is preferably around 0.5 to 8 hr "" 1 and most often around 1 to 2 hr -1 .
- the overall VVH value of the guard reactors and that of each reactor are chosen so as to achieve the maximum hydrodemetallization (HDM) while controlling the reaction temperature (limitation of exothermicity).
- the unit will include a conditioning section, not shown in the figures, provided with adequate circulation, heating, cooling and separation means operating independently of the reaction section, allowing by means of pipes and valves to carry out the operations for preparing the fresh or regenerated catalyst contained in the guard reactor and or the reactor short-circuited just before being connected, unit in operation, namely: preheating of the reactor during permutation or short-circuited , sulfurization of the catalyst it contains, setting to the required pressure and temperature conditions.
- a conditioning section not shown in the figures, provided with adequate circulation, heating, cooling and separation means operating independently of the reaction section, allowing by means of pipes and valves to carry out the operations for preparing the fresh or regenerated catalyst contained in the guard reactor and or the reactor short-circuited just before being connected, unit in operation, namely: preheating of the reactor during permutation or short-circuited , sulfurization of the catalyst it contains, setting to the required pressure and temperature conditions.
- this same section will also make it possible to carry out the operations of conditioning the spent catalyst contained in the reactor just after disconnection of the reaction section , namely: washing and stripping of the spent catalyst under the required conditions, then cooling before proceeding with the unloading operations of this spent catalyst, then replacement with fresh or regenerated catalyst More preferably, these catalysts are those described in the patents of the applicant EP-B-98764 and the French patent filed under the national registration number 97/07149.
- They contain a support and from 0.1 to 30% by weight, counted as metal oxides, of at least one metal or metal compound of at least one of groups V, VI and VIII of the periodic table of the elements and in the form of a plurality of juxtaposed agglomerates each formed of a plurality of needle-like plates, the plates of each agglomerate being oriented generally radially with respect to each other and with respect to the center of the agglomeration.
- the present patent application relates more particularly to the treatment of heavy oils or heavy petroleum fractions, with the aim of converting them into lighter fractions, more easily transportable or treatable by the usual refining processes.
- Coal hydrogenation oils can also be processed.
- the use of bubble bed reactors will be preferred.
- the invention solves the problem of transforming a non-transportable, viscous heavy oil, rich in metals, sulfur and containing more than 50% of constituents with normal boiling point above 520 ° C. into a stable hydrocarbon product. , easily transportable, of low content of metals and sulfur and having only a reduced content, for example less than 20% by weight, of constituents with normal boiling point greater than 520 ° C.
- the atmospheric residue or the vacuum residue can be subjected to deasphalting using a solvent, for example a hydrocarbon solvent or a mixture of solvents.
- a solvent for example a hydrocarbon solvent or a mixture of solvents.
- the most frequently used hydrocarbon solvent is a paraffinic, olefinic or cyclanic hydrocarbon (or mixture of hydrocarbons) having 3 to 7 carbon atoms.
- This treatment is generally carried out under conditions making it possible to obtain a deasphalted product containing less than 0.05% by weight of asphaltenes precipitated by heptane according to the AFNOR NF T 60115 standard.
- This deasphalting can be carried out by following the procedure described in patent US-A-4715946 in the name of the applicant.
- the volumetric solvent / charge ratio will most often be approximately 3: 1 to approximately 4: 1 and the elementary physicochemical operations that make up the overall deasphalting operation (mixing-precipitation, decantation of the asphaltenic phase, washing-precipitation of the asphaltic phase) will most often be carried out separately.
- the deasphalted product is then usually at least partially recycled at the entrance to the first guard zone in operation.
- the asphaltic phase washing solvent is the same as that used for precipitation.
- the mixture between the charge to be deasphalted and the deasphalting solvent is most often produced upstream of the exchanger which adjusts the temperature of the mixture to the value required to achieve good precipitation and good decantation.
- the charge-solvent mixture preferably passes through the tubes of the exchanger and not on the shell side.
- the residence time of the charge-solvent mixture in the precipitation mixing zone is generally from approximately 5 seconds (s) to approximately 5 minutes (min), preferably from approximately 20 s to approximately 2 min.
- the residence time of the mixture in the settling zone is usually from about 4 min to about 20 min.
- the residence time of the mixture in the washing zone generally remains between approximately 4 min and approximately 20 min.
- the upward speeds of the mixtures both in the settling zone and in the washing zone will most often be less than approximately 1 cm per second (cm / s), and preferably less than approximately 0.5 cm / s.
- the temperature applied in the washing zone will most often be lower than that applied in the settling zone.
- the temperature difference between these two areas will usually be about 5 ° C to about 50 ° C.
- the mixture from the washing zone will most often be recycled in the decanter and advantageously upstream of the exchanger located at the entrance to the decantation zone.
- the solvent / asphaltene phase ratio recommended in the washing zone is approximately 0.5: 1 to approximately 8: 1 and preferably approximately 1: 1 to approximately 5: 1.
- the deasphalting may include two stages, each stage including the three basic phases of precipitation, decantation and washing.
- the temperature recommended in each phase of the first stage is preferably on average about 10 ° C. to about 40 ° C. lower than the temperature of each corresponding phase of the second stage.
- the solvents that are used can also be of the phenol, glycol or C1 to C6 alcohols type. However, paraffinic and / or olefinic solvents having 3 to 6 carbon atoms will be very advantageously used.
- one of the variants of the process according to the invention consists of a process for hydrotreating in at least two sections, of a heavy fraction of hydrocarbons containing sulfur impurities and metallic impurities in which in a first section called hydrodemetallization, the hydrocarbon and hydrogen charge is passed under hydrodetallization conditions over a hydrodemetallization catalyst, then the effluent from the hydrodemetallization is passed, under hydrodesulfurization conditions the first step on a hydrodesulfurization catalyst, and in which the hydrodemetallization section comprises one or more hydrodemetallization zones preceded by at least two hydrodemetallization guard zones arranged in series to be used in a cyclic manner consisting of the successive repetition of steps b) and c) defined below, the hydrodemetallization sections and / o u of hydrodesulfurization being composed of one or more reactors which can be short-circuited separately or not according to step d) defined below, said hydrotreatment process comprising: a) a step, in which the guard zones are used together for
- Another variant of the process according to the invention consists of a process for hydrotreating in at least two sections, a heavy fraction of hydrocarbons containing sulfur impurities and metallic impurities in which in a first section called hydrodemetallization, passing, under hydrodetallization conditions, the charge of hydrocarbons and hydrogen over a hydrodemetallization catalyst, then in a second subsequent section, the effluent from the first stage is passed under hydrodesulfurization conditions on a hydrodesulfurization catalyst, and in which the hydrodemetallization section comprises one or more hydrodemetallization zones preceded by at least one hydrodemetallization guard zone, the hydrodemetallization and / or hydrodesulfurization sections being composed of '' one or more reactors which can be short-circuited separately or not according to step d) defined above after, said hydrotreatment process comprising: a) a step, in which the guard zone is used for a duration at most equal to the deactivation and / or clogging time of said zone, b) a step, during which the zone
- Another variant of the process according to the invention consists of a process for hydrotreating in at least two sections, a heavy fraction of hydrocarbons containing sulfur impurities and metallic impurities in which in a first section called hydrodemetallization, passing, under hydrodetallization conditions, the charge of hydrocarbons and hydrogen over a hydrodemetallization catalyst, then in a second subsequent section, the effluent from the first stage is passed under hydrodesulfurization conditions on a hydrodesulfurization catalyst, and in which the hydrodemetallization section comprises one or more hydrodemetallization zones preceded by at least two hydrodemetallization guard zones comprising one or more reactors, preferably in fixed beds or in bubbling beds , arranged in series to be used cyclically consisting of the successive repetition of the steps b) and c) defined below, the hydrodemetallization and / or hydrodesulfurization sections being composed of one or more reactors which can be short-circuited separately or not according to step d) defined below, said hydrotreatment process comprising:
- an amount of average distillate representing from 0.5% to 80% by weight is introduced at the entrance to the first guard zone in operation, at the same time as the charge.
- the weight of the hydrocarbon charge More preferably, the atmospheric distillate which is introduced with the hydrocarbon feedstock is a direct distillation gas oil.
- the product resulting from the hydrodesulfurization step is preferably sent to an atmospheric distillation zone from which an atmospheric distillate is recovered, at least part of which is preferably recycled at the inlet. of the first guard zone in operation, and an atmospheric residue. More preferably, at the entrance of the first guard zone in operation, at least part of a diesel fraction from the atmospheric distillation which follows the hydrodesulfurization step is recycled.
- the recycled diesel fraction is a fraction with an initial boiling point of approximately 140 ° C. and a final boiling point of approximately 400 ° C.
- the quantity of atmospheric distillate and / or of diesel introduced at the entry of the first guard zone in operation, at the same time as the charge preferably represents by weight relative to the charge approximately 1 to 50 %.
- a variant consists in preferably sending at least part of the atmospheric residue and / or the distillate under vacuum in a catalytic cracking unit from which an LCO fraction and an HCO fraction are recovered and sent to the less in part either one or the other, or a mixture of the two fractions at the entrance to the first guard zone in operation.
- the guard zones are used all together, the guard zone whose catalyst was regenerated during step b) being reconnected so as to that its connection is identical to the one it had before it was short-circuited during step b).
- the conditioning zone or zones is associated with a conditioning section which allows the short-circuiting or the permutation of said zone or zones of guard on operation, without stopping the operation of the unit, said section being adjusted so as to condition the catalyst contained in the guard zone which is not in operation, at a pressure of between 1 MPa and 5 MPa.
- the feedstock in order to treat a feedstock consisting of a heavy oil or a heavy oil fraction containing asphaltenes, the feedstock is first subjected to hydroviscoreduction conditions , mixed with hydrogen, before sending the charge to the guard zone (s).
- the atmospheric residue obtained at the end of the optional atmospheric distillation step is subjected to deasphalting using a solvent or a mixture of solvent and the deasphalted product is at least partly recycled at the entrance to the first guard zone in operation.
- the vacuum residue obtained at the end of the optional vacuum distillation step is subjected to deasphalting using a solvent or a mixture of solvent and the deasphalted product is at least partly recycled at the entrance to the first guard zone in operation.
- all the reactors are in a fixed bed.
- at least one reactor of the guard zones and / or the hydrodematallation and / or hydrodesulfurization sections is a bubbling bed reactor.
- the reactors in the guard zones are in a fixed bed, and all the reactors in the hydrodesulfurization zone are in a bubbling bed.
- all the reactors in the guard zones are in a fixed bed, and all the reactors in the hydrodemetallization zone are in a bubbling bed, and possibly very preferably all the reactors in the hydrodesulfurization zone are also in a bubbling bed. It is also possible to operate the process according to the invention with only bubbling bed reactors in the guard zones and in the hydrodemetallization and hydrodesulfurization sections.
- FIG. 1 briefly explains the invention by way of illustration.
- the load arrives in the guard guard zones, designated 1A and 1B by the line 1 and leaves these zones via the line 13, via the lines 23 and / or 24.
- the load leaving the guard zone (s) arrives by the line 13 in the section of HDM which is represented here by a reaction section 2 consisting of one or more reactor (s), each of the reactors being provided with its own short circuit.
- the effluent from section 2 is withdrawn through line 14, then sent to a hydrodesulfurization section 3, which may include one or more reactors optionally in series, and optionally provided with their own short circuit.
- the effluent from section 3 is withdrawn through line 15
- a medium distillate is introduced via line 55 which mixes with the hydrocarbon charge in line 1.
- the guard zone comprises 2 reactors
- the method in its preferred embodiment, will comprise a series of cycles each comprising four successive periods: - a first period during which the load passes successively zone 1A then zone 1 B and in which the fraction diesel from atmospheric distillation which is recycled is introduced with the feed into zone 1A.
- the charge is introduced via line 1 and line 21, which has a valve 31 open, to the guard reactor 1A.
- the valves 32, 33 and 35 are closed.
- the effluent from zone 1A is sent to the guard reactor 1 B via line 23, line 26 which has a valve 34 open, and line 22.
- the effluent from zone 1 B is sent to section 2 of HDM through line 24 which has an open valve 36 and line 13 which has an open valve 37.
- step b) of the process the valves 31, 33, 34 and 35 are closed and the charge is introduced by line 1 and line 22, which includes a valve 32 open, in zone 1 B.
- the effluent from zone 1 B is sent to section 2 of HDM via line 24, which comprises an open valve 36, and line 13 which comprises an open valve 37.
- step c) of the process the valves 31, 34 and 36 are closed and the valves 32, 33 and 35 are open.
- the charge is introduced via line 1 and line 22 to zone 1 B.
- the effluent from zone 1 B is sent via line 24, line 27 and line 21 into the guard reactor 1A.
- the effluent from zone 1A is sent to section 2 of HDM via line 23 and line 13, which has a valve 37 open.
- a fourth period during which the charge only crosses the guard zone 1A and in which the diesel fraction from the atmospheric distillation which is recycled is introduced with the charge in the zone 1A.
- the number of cycles performed for the guard reactors is a function of the duration of the operating cycle of the entire unit and the average frequency of permutation of zones 1A and 1 B.
- the valves 32, 33, 34 and 36 are closed and the valves 31, and 35 are open.
- the charge is introduced via line 1 and line 21 to zone 1A.
- the effluent from zone 1A is sent to section 2 of HDM via line 23 and line 13 which includes a valve 37 open.
- the hydrodemetallization section can comprise one or more reactors, each or more of these reactors can be temporarily isolated for periodic renewal of the catalyst (s) [step d) of the process].
- the method will comprise, in its preferred embodiment, a series of cycles each comprising three successive periods:
- the effluent from zone 1 A is sent to the guard zone 1 B via line 23, line 26 which has a valve 34 open and line 22.
- the effluent from zone 1 B is sent to section 2 of HDM via line 24, which includes an open valve 36, and line 13 which includes an open valve 37.
- the effluent from section 2 is sent to section 3 of HDS via line 14 which has two open valves 42 and 39.
- the effluent from section 3 is then sent to a fractionation unit not represented by line 15 which has a valve 40 open.
- the effluent from section 3 is then sent to a fractionation unit not shown, via line 15 , which has a valve 40 open. During this period, the HDM catalyst is renewed, then said catalyst is conditioned according to the method described in this invention. This conditioning is particularly necessary if the catalyst is in oxide form.
- the hydrodesulfurization section 3 can comprise one or more reactors, each or more of these reactors can be temporarily isolated for periodic catalyst renewal [step d) of the process].
- the method will comprise, in its preferred embodiment, a series of cycles each comprising three successive periods:
- the diesel fraction from atmospheric distillation which is recycled is introduced with the feed into zone 1 B.
- the valves 32, 33, 35, 38, 39 and 40 are closed.
- the charge is introduced into zone 1A via line 1 and line 21.
- the effluent from zone 1A is sent to zone 1B via line 23, line 26 which has a valve 34 open, and the line 22.
- the effluent from zone 1 B is sent to section 2 of HDM via line 24, which comprises an open valve 36, and line 13 which comprises an open valve 37.
- the effluent from section 2 is then sent to a fractionation unit not represented by line 14, which comprises an open valve 42, and line 16, which comprises an open valve 41.
- the catalyst or the catalysts of section 3 are renewed, then the catalyst (s) are conditioned according to the method described in this invention, this conditioning is particularly necessary when the catalyst is in oxide form.
Abstract
Description
Claims
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PCT/FR2000/003472 WO2002048288A1 (en) | 2000-12-11 | 2000-12-11 | Method for hydrotreatment of a heavy hydrocarbon fraction with switchable reactors and reactors capable of being shorted out |
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EP1343857A1 true EP1343857A1 (en) | 2003-09-17 |
EP1343857B1 EP1343857B1 (en) | 2006-07-26 |
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US (1) | US20040055934A1 (en) |
EP (1) | EP1343857B1 (en) |
JP (1) | JP4697571B2 (en) |
KR (1) | KR100783448B1 (en) |
CN (1) | CN1322097C (en) |
AU (1) | AU2001226863A1 (en) |
BR (1) | BR0017384B1 (en) |
CA (1) | CA2432022A1 (en) |
DE (1) | DE60029645T2 (en) |
MX (1) | MXPA03005072A (en) |
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Publication number | Priority date | Publication date | Assignee | Title |
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CN109453667B (en) * | 2018-10-31 | 2021-08-06 | 四川大学 | Regeneration method of desulfurization catalyst and ammonium sulfate preparation method and equipment using same |
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Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3910834A (en) * | 1972-08-29 | 1975-10-07 | Universal Oil Prod Co | Moving bed reactor conversion process for particulate containing hydrocarbons such as shale oil and tar-sands oil |
US3876533A (en) * | 1974-02-07 | 1975-04-08 | Atlantic Richfield Co | Guard bed system for removing contaminant from synthetic oil |
US4017382A (en) * | 1975-11-17 | 1977-04-12 | Gulf Research & Development Company | Hydrodesulfurization process with upstaged reactor zones |
US4118310A (en) * | 1977-06-28 | 1978-10-03 | Gulf Research & Development Company | Hydrodesulfurization process employing a guard reactor |
NL191022C (en) * | 1978-01-20 | 1994-12-16 | Shell Int Research | Device suitable for the catalytic hydrotreating of heavy hydrocarbon oils. |
US4925554A (en) * | 1988-02-05 | 1990-05-15 | Catalysts & Chemicals Industries Co., Ltd. | Hydrotreating process for heavy hydrocarbon oils |
FR2660322B1 (en) * | 1990-03-29 | 1992-06-19 | Inst Francais Du Petrole | PROCESS FOR HYDROTREATING AN OIL RESIDUE OR HEAVY OIL WITH A VIEW TO REFINING THEM AND CONVERTING THEM INTO LIGHTER FRACTIONS. |
FR2681871B1 (en) * | 1991-09-26 | 1993-12-24 | Institut Francais Petrole | PROCESS FOR HYDROTREATING A HEAVY FRACTION OF HYDROCARBONS WITH A VIEW TO REFINING IT AND CONVERTING IT TO LIGHT FRACTIONS. |
FR2784687B1 (en) * | 1998-10-14 | 2000-11-17 | Inst Francais Du Petrole | PROCESS FOR HYDROTREATING A HEAVY HYDROCARBON FRACTION WITH PERMUTABLE REACTORS AND INTRODUCING A MEDIUM DISTILLATE |
CN1119395C (en) * | 1999-03-19 | 2003-08-27 | 中国石油化工集团公司 | Two-stage fraction oil hydrogenating and arene eliminating process |
-
2000
- 2000-12-11 BR BRPI0017384-3A patent/BR0017384B1/en not_active IP Right Cessation
- 2000-12-11 DE DE60029645T patent/DE60029645T2/en not_active Expired - Lifetime
- 2000-12-11 AU AU2001226863A patent/AU2001226863A1/en not_active Abandoned
- 2000-12-11 KR KR1020037007692A patent/KR100783448B1/en active IP Right Grant
- 2000-12-11 EP EP00990056A patent/EP1343857B1/en not_active Expired - Lifetime
- 2000-12-11 US US10/450,127 patent/US20040055934A1/en not_active Abandoned
- 2000-12-11 MX MXPA03005072A patent/MXPA03005072A/en active IP Right Grant
- 2000-12-11 JP JP2002549807A patent/JP4697571B2/en not_active Expired - Fee Related
- 2000-12-11 WO PCT/FR2000/003472 patent/WO2002048288A1/en active IP Right Grant
- 2000-12-11 CA CA002432022A patent/CA2432022A1/en not_active Abandoned
- 2000-12-11 CN CNB008201358A patent/CN1322097C/en not_active Expired - Lifetime
-
2003
- 2003-06-10 NO NO20032620A patent/NO332312B1/en not_active IP Right Cessation
Non-Patent Citations (1)
Title |
---|
See references of WO0248288A1 * |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2013057389A1 (en) | 2011-10-20 | 2013-04-25 | IFP Energies Nouvelles | Method of converting petroleum feedstocks comprising a step of ebullated-bed hydroconversion and a step of fixed-bed hydroprocessing for producing fuels with a low sulphur content |
WO2013083883A1 (en) | 2011-12-07 | 2013-06-13 | IFP Energies Nouvelles | Method for the hydroconversion of petroleum feedstocks in fixed beds for the production of fuel oils having a low sulphur content |
WO2014096704A1 (en) | 2012-12-20 | 2014-06-26 | IFP Energies Nouvelles | Process with separation for treating petroleum feedstocks for the production of fuel oils with a low sulphur content |
WO2014096703A1 (en) | 2012-12-20 | 2014-06-26 | IFP Energies Nouvelles | Integrated process for treating petroleum feedstocks for the production of fuel oils with a low sulphur content |
FR3014897A1 (en) * | 2013-12-17 | 2015-06-19 | IFP Energies Nouvelles | NEW INTEGRATED PROCESS FOR THE TREATMENT OF PETROLEUM LOADS FOR THE PRODUCTION OF LOW SULFUR AND SEDIMENT FIELDS |
WO2015091033A1 (en) * | 2013-12-17 | 2015-06-25 | IFP Energies Nouvelles | Novel integrated process for treating petroleum feedstocks for the production of fuel oils having a low content of sulphur and of sediments |
US9650580B2 (en) | 2013-12-17 | 2017-05-16 | IFP Energies Nouvelles | Integrated process for the treatment of oil feeds for the production of fuel oils with a low sulphur and sediment content |
EA032845B1 (en) * | 2013-12-17 | 2019-07-31 | Ифп Энержи Нувелль | Novel integrated process for the treatment of oil fractions for the production of fuel oils with a low sulphur and sediments |
Also Published As
Publication number | Publication date |
---|---|
WO2002048288A1 (en) | 2002-06-20 |
NO20032620L (en) | 2003-08-08 |
KR100783448B1 (en) | 2007-12-07 |
CN1484684A (en) | 2004-03-24 |
CN1322097C (en) | 2007-06-20 |
AU2001226863A1 (en) | 2002-06-24 |
NO20032620D0 (en) | 2003-06-10 |
BR0017384A (en) | 2004-03-02 |
JP4697571B2 (en) | 2011-06-08 |
NO332312B1 (en) | 2012-08-27 |
DE60029645D1 (en) | 2006-09-07 |
MXPA03005072A (en) | 2004-05-24 |
EP1343857B1 (en) | 2006-07-26 |
BR0017384B1 (en) | 2011-04-05 |
CA2432022A1 (en) | 2002-06-20 |
JP2004519533A (en) | 2004-07-02 |
DE60029645T2 (en) | 2006-11-30 |
KR20030059837A (en) | 2003-07-10 |
US20040055934A1 (en) | 2004-03-25 |
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