EP1307527A1 - Procede d'hydrocraquage en 2 etapes de charges hydrocarbonees - Google Patents
Procede d'hydrocraquage en 2 etapes de charges hydrocarboneesInfo
- Publication number
- EP1307527A1 EP1307527A1 EP01956643A EP01956643A EP1307527A1 EP 1307527 A1 EP1307527 A1 EP 1307527A1 EP 01956643 A EP01956643 A EP 01956643A EP 01956643 A EP01956643 A EP 01956643A EP 1307527 A1 EP1307527 A1 EP 1307527A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- catalyst
- hydrocracking
- stage
- reactor
- zeolite
- 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.)
- Withdrawn
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
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
- C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
- C10G47/12—Inorganic carriers
- C10G47/16—Crystalline alumino-silicate carriers
- C10G47/20—Crystalline alumino-silicate carriers the catalyst containing other metals or compounds thereof
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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
- C10G65/12—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including cracking steps and other hydrotreatment 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
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/207—Acid gases, e.g. H2S, COS, SO2, HCN
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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
- C10G2300/30—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
- C10G2300/4018—Spatial velocity, e.g. LHSV, WHSV
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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
- C10G2300/4081—Recycling aspects
-
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
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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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/06—Gasoil
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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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/08—Jet fuel
Definitions
- the present invention relates to an improved process for hydrocracking hydrocarbon feedstocks, two-step process with intermediate separation, in which the second hydrocracking step is carried out in the presence of an added nitrogen content which is greater than 110 ppm by weight.
- the objective of the process is essentially the production of middle distillates, that is to say sections with an initial boiling point of at least 150 ° C and a final going up to before the initial boiling point of the residue. , for example less than 340 ° C, or even less than 370 ° C.
- Hydrocracking of heavy petroleum fractions is a very important refining process which makes it possible to produce, from excess heavy and little valorized charges, lighter fractions such as gasolines, jet fuels and light gas oils which the refiner seeks to adapt its production to the structure of demand.
- Certain hydrocracking processes also make it possible to obtain a highly purified residue which can provide excellent bases for oils.
- the advantage of catalytic hydrocracking is to provide middle distillates, jet fuels and diesel, of very good quality.
- the gasoline produced has a much lower octane number than that from catalytic cracking.
- Hydrocracking is a process which derives its flexibility from three main elements which are, the operating conditions used, the types of catalysts used and the fact that hydrocracking of hydrocarbon feedstocks can be carried out in one or two stages. Indeed, hydrocracking is a process which can be declined in different versions which are for the main ones:
- Hydrocracking in one step which comprises first and generally a thorough hydrotreatment which aims to achieve a hydrodenitrogenation and a desulfurization of the feed before it is sent to the hydrocracking catalyst itself , in particular in the case where this comprises a zeolite.
- This advanced hydrotreatment of the feed causes only a limited conversion of the feed, into lighter fractions, which remains insufficient and must therefore be completed on the more active hydrocracking catalyst.
- This version of the hydrocracking one step also called "Once Through” has a variant which presents a recycling of the unconverted fraction to the reactor for further conversion of the feed.
- Two-stage hydrocracking includes a first stage, which aims, as in the "one-step” process, to carry out the hydrorefining of the feedstock but also to achieve a conversion of the latter in the order of 40 at 60%.
- the effluent from the first stage then undergoes separation (distillation), most often called intermediate separation, which aims to separate the conversion products from the unconverted fraction.
- separation distillation
- intermediate separation only the fraction of the feedstock not converted during the first step is treated.
- This separation allows a two-step hydrocracking process to be more selective in diesel than a one-step process.
- the intermediate separation of the conversion products avoids their "over-cracking" into naphtha and gas in the second step on the hydrocracking catalyst.
- the unconverted fraction of the charge treated in the second step generally contains very low NH 3 contents as well as organic nitrogen compounds, generally less than 20 ppm by weight or even less than 10 ppm by weight.
- the 2-step process can be carried out with either an intermediate separation after the hydrorefining, in a process comprising a hydrorefining reactor and a hydrocracking reactor, or with an intermediate separation between the first and second reactor d hydrocracking in a process comprising in series the hydrorefining reactors, 1 st hydrocracking, 2 nd hydrocracking.
- the hydrocracking catalysts used in hydrocracking processes are all of the bifunctional type combining an acid function with a hydrogenating function.
- the acid function is provided by supports of large surfaces (150 to 800 m2.g-1. Generally) having a surface acidity, such as halogenated aluminas (chlorinated or fluorinated in particular), combinations of boron oxides and aluminum, amorphous silica-aluminas and zeolites.
- the hydrogenating function is provided either by one or more metals from group VIII of the periodic table, or by a combination of at least one metal from group VI B from the periodic table and at least one metal from group VIII.
- these catalysts are present downstream of the hydrotreatment catalyst in the one-stage hydrocracking processes or else in the second stage of the 2-stage hydrocracking processes. However, they can also be present in the first hydrocracking stage.
- a weak acid function and a strong hydrogenating function give catalysts which are not very active, working at generally high temperatures (greater than or equal to 390 ° C.), and at low space feed rates (the WH expressed in volume of charge at process per unit volume of catalyst and per hour is generally less than or equal to 2 h "1 ) but with very good selectivity for middle distillates.
- a strong acid function and a weak hydrogenating function give active catalysts but having poorer selectivities for middle distillates The search for a suitable catalyst will therefore be centered on a judicious choice of each of the functions to adjust the activity / selectivity couple of the catalyst.
- a first type of conventional catalytic hydrocracking catalyst is based on weakly acidic amorphous supports, such as amorphous silica-aluminas for example. These systems are more particularly used to produce middle distillates of very good quality, and also, when their acidity is very low, oil bases. These catalysts are generally used in two-step processes.
- catalysts comprising zeolite Y of structural type FAU, or beta type catalysts have a catalytic activity greater than that of amorphous silica-aluminas, but have selectivities for light products which are higher. These catalysts are generally used in one-step "ounce through” processes or with recycling of the unconverted fraction. They were also used in the second stage of a two-stage hydrocracking process.
- the invention describes a hydrocracking process, of hydrocarbon feedstocks, in 2 stages comprising a first stage including a hydrorefining, an intermediate separation of the converted products, and a second hydrocracking stage of at least part of the residue , said second step operating in the presence of ammonia in an amount corresponding to more than 110 ppm by weight of nitrogen.
- the amount of nitrogen is greater than 150 ppm and preferably greater than 200 ppm. Generally, it is at most 1000 ppm, or at most 800 ppm, or even at most 500 ppm.
- ammonia is obtained by direct injection of ammonia or by injection of a nitrogenous compound which decomposes into ammonia under the reaction conditions, the injection taking place directly in the reactor and for example at several points of the reactor, or preferably in the feed entering this reactor.
- Many nitrogen compounds can be used, for example aniline.
- a wide variety of fillers can be treated by the process according to the invention and generally they contain at least 20% by volume and often at least 80% by volume of compounds boiling above 340 ° C.
- the feed can be, for example, LCOs (light cycle oil), atmospheric distillates, vacuum distillates, for example gas oil obtained from the direct distillation of crude oil or from conversion units such as FCC, coker or visbreaking, as well as feedstocks coming from aromatic extraction units from the lubricating oil bases or coming from solvent dewaxing of the lubricating oil bases, or from distillates coming from desulphurization or hydroconversion of RAT (atmospheric residues) and / or RSV (vacuum residues), or the filler can be a deasphalted oil, or any mixture of the aforementioned fillers.
- LCOs light cycle oil
- atmospheric distillates for example gas oil obtained from the direct distillation of crude oil or from conversion units such as FCC, coker or visbreaking, as well as feedstocks coming from aromatic extraction units from the
- the nitrogen content is usually between 1 and 5000 ppm by weight, more generally between 200 and 3000 ppm by weight, and the sulfur content between 0.01 and 5% by weight, more generally between 0.2 and 4%.
- the feed undergoes in the first step at least one hydrorefining (hydrodesulfurization, hydrodenitrogenation, conversion).
- catalysts which contain at least one amorphous support and at least one hydro-dehydrogenating element (generally at least one element from groups VIB and VIII non-noble, and most often at least one element from group VIB and at least a non-noble element of group VIII)
- the feed to be treated is brought into contact in the presence of hydrogen, with a hydrorefining catalyst comprising at least one matrix, at least one hydro-dehydrogenating element chosen from the group formed by the elements of group VIB and group VIII of the periodic table, optionally at least one promoter element deposited on the catalyst and chosen from the group formed by phosphorus, boron and silicon, optionally at least one element from group VIIA (preferred chlorine, fluorine), and optionally at least one element from group VIIB (preferred manganese), optionally at least one element from group VB (preferred niobium).
- a hydrorefining catalyst comprising at least one matrix, at least one hydro-dehydrogenating element chosen from the group formed by the elements of group VIB and group VIII of the periodic table, optionally at least one promoter element deposited on the catalyst and chosen from the group formed by phosphorus, boron and silicon, optionally at least one element from group VIIA (preferred chlorine, fluorine), and optionally at least one element from group VIIB
- this catalyst contains boron and / or silicon as a promoter element, optionally with phosphorus as another promoter element.
- the boron, silicon, phosphorus contents are then 0.1-20%, preferably 0.1-15%, even more advantageously 0.1-10%.
- the matrices which can be used alone or as a mixture are, by way of nonlimiting example, alumina, halogenated alumina, silica, silica-alumina, clays (for example among natural clays such as - kaolin or bentonite), magnesia, titanium oxide, boron oxide, zirconia, aluminum phosphates, titanium phosphates, zirconium phosphates, carbon, aluminates. It is preferred to use matrices containing alumina, in all of these forms known to those skilled in the art, and even more preferably aluminas, for example gamma alumina.
- hydro-dehydrogenating function is preferably fulfilled by at least one metal or compound of metal from group VIII which is non-noble and VI preferably chosen from molybdenum, tungsten, nickel and cobalt.
- this role is ensured by the combination of at least one element of GVIII (Ni, Co) with at least one element of group VIB (Mo, W).
- This catalyst may advantageously contain phosphorus; in fact, it is known in the prior art that this compound provides two advantages to hydrotreatment catalysts: ease of preparation during in particular the impregnation of nickel and molybdenum solutions, and better hydrogenation activity.
- the total concentration of metal oxides of groups VI and VIII is between 5 and 40% by weight and preferably between 7 and 30% and the weight ratio expressed as metal oxide between metal (or metals) of the group VIB on metal (or metals) of group VIII is preferably between 20 and 1.25 and even more preferred between 10 and 2.
- the concentration of phosphorus oxide P2O5 will be less than 15% by weight and preferably at 10% by weight .
- Another preferred catalyst which contains boron and / or silicon generally contains in% by weight relative to the total mass of the catalyst at least one metal chosen from the following groups and with the following contents :
- the catalyst also containing at least one support chosen from the following groups with the following contents:
- the said catalyst being characterized in that that it additionally contains, 0.1 to 20%, preferably 0.1 to 15% and even more preferably 0.1 to 10% of boron and / or 0.1 to 20%, preferably from 0.1 to 15% and even more preferably from 0.1 to 10% of silicon, and optionally,
- Such a catalyst has a higher activity in the hydrogenation of aromatic hydrocarbons and in hydrodenitrogenation and in hydrodesulfurization than the catalytic formulas without boron and / or silicon, and also has a higher activity and selectivity in hydrocracking than the catalytic formulas known in the art. prior art.
- the catalyst with boron and silicon is particularly interesting.
- the preferred catalysts are the NiMo and / or NiW catalysts on alumina, also the NiMo and / or NiW catalysts on alumina doped with at least one element included in the group of atoms formed by phosphorus, boron, silicon and fluorine, or else the NiMo and / or NiW catalysts on silica-alumina, or on silica-alumina-titanium oxide doped or not with at least one element included in the group of atoms formed by phosphorus, boron, fluorine and silicon .
- the 1 st stage hydrorefining catalyst contains:
- At least one non-noble element of groups VIB and VIII (% oxide) - 0-20% of at least one promoter element chosen from phosphorus, boron, silicon (% oxide), preferably 0.1-20%; advantageously boron and / or silicon are present, and optionally phosphorus.
- the catalysts described above are generally used to provide hydrorefining, also called hydrotreatment stage.
- This hydrorefining step can be followed by an intermediate separation (the unconverted effluent then goes to the second step), or else all of the effluent leaving the hydrorefining step is treated with a catalyst.
- hydrocracking 1 st step is generally used to provide hydrorefining, also called hydrotreatment stage.
- This first stage hydrocracking is carried out for example in another reactor or in an additional catalyst bed in the reactor where the hydrorefining takes place. A pre-cracking is thus obtained allowing the desired conversions to be achieved in the first step.
- the catalyst used has at least one hydro-dehydrogenating function, a higher acidity making it possible to complete the pre-cracking. This stronger acidity can be provided by an acid solid such as an amorphous silica-alumina or a zeolite.
- the hydrocracking catalyst is identical to that of the second stage (as described later) or different and is preferably zeolitic.
- the catalysts used in the process according to the present invention are preferably subjected beforehand to a sulphurization treatment making it possible to transform, at least in part, the metallic species into sulphide before they are brought into contact with the load to be processed.
- This activation treatment by sulfurization is well known to those skilled in the art and can be carried out by any method already described in the literature either in situ, that is to say in the reactor, or ex situ.
- a conventional sulfurization method well known to those skilled in the art consists in heating in the presence of hydrogen sulfide (pure or for example under a flow of a hydrogen / hydrogen sulfide mixture) to a temperature between 150 and 800 ° C., preferably between 250 and 600 ° C, generally in a reaction zone with a crossed bed.
- the charge is brought into contact, in the presence of hydrogen, with at least one catalyst as described above, at a temperature between 330 and 450 ° C, preferably 360-420 ° C, under a pressure comprised between 5 and 25 MPa, preferably less than 20 MPa, the space velocity being between 0.1 and 6 h, preferably 0.2-3 h ⁇ 1 , and the quantity of hydrogen introduced is such that the volume ratio of liter of hydrogen / liter of hydrocarbon is between 100 and 2000 l / l.
- the content of nitrogenous organic compounds in the effluent leaving the first stage is less than 20 ppm by weight and preferably less than 10 ppm by weight.
- This first step also makes it possible to pre-crack the feed to be treated.
- this adjustment can be made by varying the nature and the quality of the catalyst (s) used in the first step and / or the operating conditions of this first step.
- the conversion, during the first step, into products having boiling points below 340 ° C., and better still below 370 ° C. is greater than 20% and preferably greater than 30% and even more preferably between 40 and 60%.
- the effluent from this first step is sent to a separation means (separator flask, for example) which aims to separate the ammonia (NH3) and the hydrogen sulfide (H2S) produced during this first step.
- a separation means separation means (separator flask, for example) which aims to separate the ammonia (NH3) and the hydrogen sulfide (H2S) produced during this first step.
- the hydrocarbon effluent from this separation will undergo atmospheric distillation, and in some cases the combination of atmospheric distillation and vacuum distillation.
- the purpose of distillation is to separate the converted hydrocarbon products, i.e. generally having boiling points below 340 ° C (and better still below 370 ° C) and an unconverted liquid fraction (residue) .
- vacuum distillation can be added. This will be the case for example for distilling the diesel with better efficiency, or when we want out of the way in 2nd stage a heavy fraction of the residue.
- the liquid fraction, residue, containing products whose boiling point is higher than 340 ° C or even higher than 370 ° C and resulting from distillation is at least partly and preferably entirely introduced in the second stage of the method according to the invention.
- the residue fraction resulting from the intermediate separation and sent to the second stage is called "clean", that is to say that it contains less than 10 ppm by weight of organic nitrogen and less than 10 ppm by weight of organic sulfur, c i.e. nitrogen and sulfur included in organic compounds.
- clean that is to say that it contains less than 10 ppm by weight of organic nitrogen and less than 10 ppm by weight of organic sulfur, c i.e. nitrogen and sulfur included in organic compounds.
- at least one nitrogenous compound which is decomposable into ammonia under the conditions of the second stage or directly of ammonia is added to the charge or is injected into the second stage reactor.
- aromatic amines aniline for example
- aliphatic amines n-Butyl-amine for example
- pyroles pyridines
- ureas nitrated, nitrous or nitrosated derivatives
- primary, secondary or tertiary amines compounds with ammonium ...
- the amount of ammonia (NH 3 ) added to the reactor (s) of the second step of the hydrocracking process according to the invention is such that in the said reactor (s) the content by weight of nitrogen, expressed in ppm by weight (parts per million) relative to the charge entering said reactor (s) is greater than 110 ppm and preferably greater than 150 ppm and even more preferably greater than 200 ppm weight.
- the second stage catalyst being, for the reaction, sulfurized, it should be kept in contact with a partial pressure H 2 S sufficient to avoid its desulfurization in the presence of hydrogen and at reaction temperatures.
- H 2 S a partial pressure
- hydrogen sulphide or at least one sulfur compound decomposing into H 2 S is added to the feedstock or directly in the reactor, under the conditions of the second step.
- DMDS dimethyl disulphide
- CS 2 carbon disulphide
- organic polysulphides organic polysulphides
- mercaptans organic polysulphides
- sulphides disulphides
- oxygenated sulfur compounds oxygenated sulfur compounds
- the amount of hydrogen sulfide (H 2 S) added to the reactors of the second stage of the hydrocracking process according to the invention corresponds to a sulfur content by weight, expressed in ppm (parts per million) relative to the incoming feed in said (the said) reactor greater than 20 ppm and preferably greater than 50 ppm and even more preferably greater than 200 ppm.
- the NH 3 and H 2 S quantities are adjustable by the operator throughout the reaction.
- the addition takes place at the level of at least one reactor (in the feed or directly in the reactor).
- the ammonia (NH 3 ) and the hydrogen sulphide (H 2 S) injected in the second stage of the hydrocracking process according to the invention come from the recycling of at least part of the ammonia and of the hydrogen sulfide produced in the first step of the process and obtained during the intermediate separation.
- the ammonia produced in the first step and separated will be used as the ammonia supply. It can be the gas containing NH 3 , H 2 S, H 2 and the light hydrocarbons separated for example at the level of a gas-liquid separator.
- it can be a more purified gas obtained after washing with effluent from the first stage, separation of the aqueous phase and stripping of this aqueous phase so as to produce an ammonia gas containing little hydrogen and little light gases. This latter embodiment will be described later on from the figures.
- the operating conditions used in the second step of the process according to the invention are: a temperature above 200 ° C, often between 250- 480 ° C, advantageously between 320 and 450 ° C, preferably between 330 and 425 ° C , under a pressure greater than 0.1 MPa, often between 5 and 25 MPa, preferably less than 20 MPa and even more advantageously greater than 9 MPa or better still at 10 MPa, the space speed being between 0.1 and 20 h "1 and preferably 0.1 -6h " , preferably 0.2-3h "1 , and the quantity of hydrogen introduced is such that the volume ratio liter of hydrogen / liter of hydrocarbon is between 80 and 5000I / I and most often between 100 and 2000 l / l.
- These operating conditions used in the second step of the process according to the invention make it possible to achieve conversions by pass, into products having boiling points below 340 ° C, and better still below 370 ° C, above 30% and even more preferably between 40 and 60%.
- the second stage catalyst comprises at least one Y zeolite, at least one matrix and a hydro-dehydrogenating function.
- it can also contain at least one element chosen from boron, phosphorus and silicon, at least one element of G VIIA (chlorine, fluorine for example), at least one element of G VIIB (manganese for example), minus an element of G VB (niobium for example).
- the catalyst contains at least one porous or poorly crystallized mineral matrix of the oxide type. Mention may be made, by way of nonlimiting example, of aluminas, silicas, silica-aluminas, aluminates, alumina-boron oxide, magnesia, silica-magnesia, zirconia, titanium oxide, l clay, alone or in mixture.
- the hydro-dehydrogenating function is generally provided by at least one element from group VI B (for example molybdenum and / or tungsten) and / or at least one element from group VIII which is non-noble (for example cobalt and / or nickel) of the classification of the elements.
- group VI B for example molybdenum and / or tungsten
- group VIII which is non-noble (for example cobalt and / or nickel) of the classification of the elements.
- a preferred catalyst essentially contains at least one group VI metal, and / or at least one non-noble group VIII metal, zeolite Y and alumina.
- An even more preferred catalyst essentially contains nickel, molybdenum, a Y zeolite and alumina.
- the catalyst contains at least one element chosen from the group formed by boron, silicon and phosphorus.
- the catalyst optionally contains at least one element of group VIIA, preferably chlorine and fluorine, optionally at least one element of group VIIB (manganese for example), optionally at least one element of group GVB (niobium for example ).
- Boron, silicon and / or phosphorus can be in the matrix, the zeolite or are preferably deposited on the catalyst and then mainly located on the matrix.
- a preferred catalyst contains B and / or Si as a promoter element deposited with preferably in addition to the promoter phosphorus. The amounts introduced are 0.1 - 20% by weight of catalyst calculated as oxide.
- the element introduced, and in particular the silicon, mainly located on the matrix of the support can be characterized by techniques such as the Castaing microprobe (distribution profile of the various elements), transmission electron microscopy coupled with an X-ray analysis of the components of the catalysts, or else by establishing a distribution map of the elements present in the catalyst by electron microprobe.
- the catalyst of step 2 ee advantageously contains: - 0, 1 -80% by weight of zeolite Y
- the zeolite can optionally be doped with metallic elements such as, for example, the metals of the rare earth family, in particular lanthanum and cerium, or noble or non-noble metals of group VIII, such as platinum, palladium, ruthenium, rhodium, iridium, iron and other metals such as manganese, zinc, magnesium.
- metallic elements such as, for example, the metals of the rare earth family, in particular lanthanum and cerium, or noble or non-noble metals of group VIII, such as platinum, palladium, ruthenium, rhodium, iridium, iron and other metals such as manganese, zinc, magnesium.
- noble or non-noble metals of group VIII such as platinum, palladium, ruthenium, rhodium, iridium, iron and other metals such as manganese, zinc, magnesium.
- Different Y zeolites can be used.
- a particularly advantageous H-Y acid zeolite is characterized by different specifications: an overall Si ⁇ 2 / Al2 ⁇ 3 molar ratio of between approximately 6 and 70 and preferably between approximately 12 and 50: a sodium content of less than
- -10 -10 preferably between 24.38 x 10 m and 24.26 x 10 m; a CNa capacity for taking up sodium ions, expressed in grams of Na per 100 grams of modified zeolite, neutralized then calcined, greater than about 0.85; a specific surface area determined by the BET method greater than approximately 400 m 2 / g and preferably greater than 550 m ⁇ / g, a water vapor adsorption capacity at 25 ° C. for a partial pressure of 2.6 torrs (i.e.
- the zeolite has a porous distribution, determined by physisorption of nitrogen, comprising between 5 and 45% and preferably between 5 and 40% of the total pore volume of the zeolite contained in pores with a diameter between
- a preferred catalyst using this type of zeolite contains a matrix, at least one dealuminated Y zeolite and having a crystalline parameter comprised between 2,424 nm and 2,455 nm preferably between 2,426 and 2,438 nm, a higher overall Si0 2 / Al 2 0 3 molar ratio.
- nx M n + ) / AI a content of cations of alkaline earth or alkali metals and / or of cations of rare earths such that the atomic ratio (nx M n + ) / AI is less than 0.8, preferably less than 0.5 or even less than 0.1, a specific surface area determined by the BET method of 400 m 2 / g, preferably greater than 550m 2 / g, and a water adsorption capacity at 25 ° C to a value P / P 0, 2 greater than 6% by weight, said catalyst also comprising at least one hydro-dehydrogenating metal, and silicon deposited on the catalyst.
- a catalyst comprising a partially amorphous Y zeolite.
- partially amorphous Y zeolite means a solid having:
- A1 a peak rate which is less than 0.40 preferably less than about 0.30
- AU a crystalline fraction expressed relative to a reference zeolite Y in sodium form (Na) which is less than about 60%, preferably less than about 50%, and determined by X-ray diffraction.
- the partially amorphous, solid Y zeolites used in the composition of the catalyst according to the invention exhibit at least one (and preferably all) of the following other characteristics:
- -iv / a Si / Ai ⁇ v structure ratio greater than or equal to the overall Si / Ai ratio, -v / a pore volume at least equal to 0.20 ml / g of solid, a fraction of which is between 8% and 50% , is made up of pores with a diameter of at least 5 nm (nanometer) or 50 ⁇ .
- Peak rates and crystal fractions are determined by X-ray diffraction using a procedure derived from ASTM method D3906-97 "Determination of Relative X-ray Diffraction Intensifies of Faujasite-Type-Containing
- a diffractogram is composed of the lines characteristic of the crystallized fraction of the sample and a background, mainly caused by the diffusion of the amorphous or microcrystalline fraction of the sample (a weak diffusion signal is linked to the apparatus, air , sample holder, etc.)
- the peak rate of the sample will be compared to that of a reference considered to be 100% crystallized (NaY for example).
- the peak rate of a perfectly crystallized NaY zeolite is of the order of 0.55 to 0.60.
- the peak rate of a conventional USY zeolite is from 0.45 to 0.55, its crystalline fraction relative to a perfectly crystallized NaY is from 80 to 95%.
- the peak rate of the solid which is the subject of the present invention is less than 0.4 and preferably less than 0.35. Its crystalline fraction is therefore less than 70%, preferably less than 60%.
- the partially amorphous zeolites are prepared according to the techniques generally used for dealumination, from commercially available Y zeolites, that is to say which generally have high crystallinities (at least 80%). More generally, it will be possible to start from zeolites having a crystalline fraction of at least 60%, or at least 70%.
- the Y zeolites generally used in hydrocracking catalysts are manufactured by modification of commercially available Na-Y zeolite. This modification leads to so-called stabilized, ultra-stabilized or dealuminated zeolites. This modification is carried out by at least one of the dealumination techniques, and for example hydrothermal treatment, acid attack. Preferably, this modification is carried out by combination of three types of operations known to those skilled in the art: hydrothermal treatment, ion exchange and acid attack.
- Another particularly interesting zeolite is a globally non-dealuminated and highly acidic zeolite.
- zeolite By globally non-dealuminated zeolite is meant a Y zeolite (structural type FAU, faujasite) according to the nomenclature developed in "Atlas of zeolites structure types", WM Meier, DH Oison and Ch. Baerlocher, 4 th revised Edition 1996, Elsevier.
- the crystalline parameter of this zeolite may have decreased by extraction of the aluminum from the structure or framework during the preparation, but the overall SiO 2 / AI 2 0 3 ratio has not changed since the aluminum has not been chemically extracted.
- Such a globally non-dealuminated zeolite therefore has a silicon and aluminum composition expressed by the overall S1O 2 / AI 2 O 3 ratio equivalent to the starting non-dealuminated Y zeolite.
- the values of the parameters (SiO 2 / AI 2 0 3 ratio and crystalline parameter) are given below.
- This globally non-dealuminated Y zeolite can be in the hydrogen form or be at least partially exchanged with metal cations, for example using cations of alkaline earth metals and / or rare earth metal cations of atomic number 57 to 71 inclusive. We prefer a zeolite devoid of rare earths and alkaline earths, the same for the catalyst.
- the zeolite Y which is not globally dealuminated generally exhibits a crystalline parameter greater than 2.438 nm, an overall Si0 / Al 2 0 3 ratio less than 8, a Si0 2 / Al 2 0 3 molar ratio of framework less than 21 and greater than the Si0 2 ratio. / AI 2 O 3 overall.
- the generally non-dealuminated zeolite can be obtained by any treatment which does not extract the aluminum from the sample, such as for example treatment with water vapor, treatment with SiCI, etc.
- Another type of advantageous catalyst for hydrocracking contains an acidic amorphous oxide matrix of the alumina type doped with phosphorus, a globally non-dealuminated and highly acidic Y zeolite and optionally at least one element of group VIIA and in particular fluorine.
- the invention is not limited to the cited and preferred Y zeolites, but other types of Y zeolites can be used in this process.
- the catalyst Prior to the injection of the feedstock in the second step of the process according to the present invention, the catalyst is subjected to a sulfurization treatment making it possible to transform, at least in part, the metallic species into sulfide before they are brought into contact with the feedstock treat.
- This activation treatment by sulfurization is well known to those skilled in the art and can be carried out by any method already described in the literature either in situ, that is to say in the reactor, or ex situ.
- a conventional sulfurization method well known to those skilled in the art consists in heating in the presence of hydrogen sulfide (pure or for example under a flow of a hydrogen / hydrogen sulfide mixture) to a temperature between 150 and 800 ° C., preferably between 250 and 600 ° C, generally in a reaction zone with a crossed bed.
- the effluent leaving the second stage of the hydrocracking process according to the invention is subjected to a so-called final separation (for example by atmospheric distillation optionally followed by vacuum distillation), so as to separate the gases (such than ammonia (NH 3 ) and hydrogen sulfide (H 2 S), as well as the other light gases present, hydrogen and possibly conversion products ).
- a so-called final separation for example by atmospheric distillation optionally followed by vacuum distillation
- the gases such than ammonia (NH 3 ) and hydrogen sulfide (H 2 S)
- H 2 S hydrogen sulfide
- There is obtained at least one residual liquid fraction containing products whose boiling point is generally higher than 340 ° C. which is at least partly recycled at the level of the second stage of the process.
- the final separation is carried out with the means of the intermediate separation when these comprise an atmospheric distillation and possibly a vacuum distillation.
- the invention also relates to an installation for carrying out a hydrocracking process in 2 stages, the installation comprising:
- At least one first stage hydrorefining reactor (2) comprising at least one catalyst bed for hydrorefining the feed
- the first first stage reactor which is a hydrorefining reactor
- at least one line (3) for bringing hydrogen to said reactor and at least one line (4) at the outlet of the effluent from the last reactor in the first stage
- - at least one gas-liquid separator (5) for separating from the effluent leaving the first stage, at least one gas leaving through a pipe (6)
- At least one second stage hydrocracking reactor (14) comprising at least one bed of catalyst for carrying out hydrocracking, of at least part of said residue
- the installation comprises also
- the feed to be treated enters via line (1) into the first stage hydrorefining reactor (2) containing at least one bed of hydrorefining catalyst. It is mixed with the hydrogen supplied by a pipe (3). This may be make-up hydrogen and / or recycle hydrogen, as described in Figure 2.
- the gases are separated in a gas-liquid separator (5), a separator flask for example.
- the gases are recovered by a pipe (6) and the resulting liquid effluent by a pipe (7).
- the liquid effluent is then subjected to an intermediate separation, for example in a column (8) so as to separate the converted products which exit in FIG. 1 through the pipes (9) for light hydrocarbons (C1 -C4), (10) for petrol, (11) for kerosene, (12) for diesel.
- an intermediate separation for example in a column (8) so as to separate the converted products which exit in FIG. 1 through the pipes (9) for light hydrocarbons (C1 -C4), (10) for petrol, (11) for kerosene, (12) for diesel.
- the unconverted effluent (residue) which leaves the bottom of the column (8) via the pipe (13) is sent at least in part to the second stage reactor (14) containing at least one bed of hydrocracking catalyst.
- the gases (pipe 20) are separated in a gas-liquid separator (18).
- the resulting liquid, leaving via a pipe (19), is generally at least partly recycled in the 2-step process and preferably at the level of the column (8) so as to separate the products converted during the second stage. Another part of the liquid may not be recycled and has left the recycling loop, this is called "bleed" or purging.
- the separators (5) and (18) are supplied with water, and the 3 gas, aqueous and organic phases are then separated.
- the gas phase essentially comprises hydrogen and constitutes the recycling hydrogen which can very advantageously be used to supply the hydrogen to the first stage and second stage reactors.
- the aqueous phase the ammonium sulphide is dissolved, in this way NH3 and H 2 S are mainly eliminated from the recycling gas.
- the organic phase essentially contains the hydrocarbon products and is sent to column (8).
- the load which arrives by the pipe (1) (refer to FIG. 2 for the description which follows), is sent for example into a charge tank of the first step (22) to be taken up there by the charge pump 1 1st stage (23). It is mixed with up hydrogen supplied via line (24) and optionally at 1 st step recycle gas introduced through line (25) respectively compressed by the booster compressor (26) and the recycle compressor ( 27).
- the mixture is advantageously sent successively in a train of heat exchangers 1 st stage (28) and then into the furnace 1 ⁇ re step (29) to be brought to the reaction temperature.
- the reactor includes one or more fixed catalytic beds, possibly separated by injections of quench (coolant, generally hydrogen).
- quench coolant, generally hydrogen
- the mixture is cooled in the heat exchanger train (28) optionally followed by an air cooler, to be collected in a gas-liquid separator tank (34).
- a vapor phase which can be partially purged by a line (36), and at least part of which can be returned to the reactor by means of the recycling compressor (27) and the line (25), another part being able to be sent in the second step according to the method via line (44),
- the hydrocarbon liquid 37 is introduced into a distillation train 39.
- This train is composed of one or more columns to be distilled, and makes it possible to recover via the pipes 40a, 40b, 40c, and 40d respectively the gases, petrol, kerosene, diesel .
- the product not converted by the reaction (residue)
- it is recovered at the bottom of the column (39), and sent via the pipeline (41) to the 2nd stage charge flask (42) to be taken up there by the second stage load (43).
- this fluid is heated by an exchanger assembly (45), then an oven (46), finally be introduced through line (47) into the second stage reactor (48). Make-up hydrogen can also be introduced, if necessary.
- the effluent from this second stage reactor and leaving via the pipe (49) is at least partly cooled in the exchange train (45), and is sent to the separator tank (34) common to the two stages. It is thus obtained as valorized hydrocarbon products, middle distillates (kerosene, petrol, diesel) and possibly a heavier fraction recovered by a pipe (54) (bleed) on the pipe (41) leaving the final separation (here column (39) common to intermediate separation).
- the backup compressor (26), the recycling compressor (27) and the separator tank (34) are common to the two stages.
- a particular heat exchange system has been described by way of example in FIG. 2, but any other arrangement is suitable.
- secondary details may vary, such as the relative position of injection of the charge, the recycling gas and the make-up gas in hydrogen, the number and arrangement of the heat exchangers, or even the number of compressor or separator tank reactors.
- the two hydrocracking stages can have a common or separate recycling compressor and separator tank.
- FIG. 2 shows a single 1 st stage reactor which is therefore a hydrorefining reactor but several reactors can be used, which can include one or more hydrocracking reactors.
- ammonia can be made according to various methods.
- the required amount of ammonia is injected in the form of a liquid containing a nitrogenous compound.
- This compound is chosen so that, under the conditions of temperature and pressure prevailing inside the reactor, and in the presence of hydrogen, it undergoes decomposition into ammonia NH3.
- a compound decomposing completely into NH 3 and hydrocarbons is preferred.
- the nitrogenous compound is introduced into the reaction section.
- FIGS. 3A, 3B, 3C different modes of introduction have been shown, the other elements of the figures not shown below corresponding to those of FIG. 2.
- this gas is injected into the reaction section by a pipe (57), generally by means of a compressor (56), the gas being brought to the compressor by a pipe (58), a balloon gas (55) can be provided.
- the injection point can be placed at the intake of the recycling compressor (fig. 3A), at any point in the high pressure section (fig. 3B), and / or in the charge tank (fig. 3C).
- the latter method is preferred because it minimizes the cost of the ammonia compressor.
- the pipe (57) for introducing the ammonia opens into the pipe (44) recycling the gas coming from the gas-liquid separator in the hydrocracking reactor of the 2 nd step.
- Example 1 Preparation of a hydrocracking catalyst 2 nd step containing a zeolite Y
- a dealuminated zeolite USY with an overall Si / Ai molar ratio equal to 15.2, with a Si / Ai framework ratio 29, with a crystalline parameter at 24.29 A containing 0.03% by weight of Na, having a crystalline fraction of 85% is used in this example to prepare the hydrocracking catalyst.
- the support for the hydrocracking catalyst containing this zeolite Y is produced in the following manner: 20 grams of the zeolite Y described above are mixed with 80 grams of a matrix composed of ultrafine tabular boehmite or alumina gel sold under the name SB3 by the company Condéa Chemie Gmbh.
- This powder mixture was then mixed with an aqueous solution containing 66% by weight nitric acid and then kneaded for 15 minutes. At the end of this kneading, the dough obtained is passed through a die having cylindrical orifices with a diameter equal to 1.4 mm. The extrudates are then dried overnight at 120 ° C in air and then calcined at 550 ° C in air. The support extrudates, containing the Y zeolite, are impregnated to dryness with an aqueous solution of a mixture of ammonium heptamolybdate, nickel nitrate and orthophosphoric acid, dried overnight at 120 ° C. in air and finally calcined in air at 550 ° C. The oxide contents by weight of the NiMoPY catalyst obtained are shown in Table 1.
- the feed for the second step is produced by hydrotreating a vacuum distillate on an HR360 catalyst sold by Procatalyse in the presence of hydrogen, at a temperature of 395 ° C and at an hourly space speed of 0.55h-1.
- the conversion to 380 ° C products is approximately 50% by weight.
- the 380 ° C + fraction is collected and will serve as a feed for the second step.
- Example 3 Test in the presence of NHg according to the invention
- the filler prepared in Example 2 was injected into the test unit 2 ee hydrocracking step which comprises a fixed bed reactor with upward circulation of the charge ( "up-flow"), into which is introduced 50 ml of catalyst prepared in Example 1.
- the catalyst is sulfurized by a diesel + DiMethylDiSulfide (DMDS) + aniline mixture up to 350 ° C.
- DMDS DiMethylDiSulfide
- the catalytic performances obtained under these conditions are described in Table 4 of this example.
- the catalytic performances are expressed by the temperature to reach a gross conversion level of 70% and by the gross selectivity in middle distillates 150-380 ° C for this conversion. These catalytic performances are measured on the catalyst after a stabilization period, generally at least 48 hours, has been observed.
- Table 4 shows that the use of a catalyst comprising a Y zeolite, under the conditions of the two-stage hydrocracking process according to the invention, leads to iso-conversion of 70% by weight, to selectivities in middle distillates (cut 150-380 ° C) significantly improved compared to those recorded in a process not in accordance with the invention (100 ppm by weight of nitrogen) while making it possible to use reaction temperatures which are entirely compatible with industrial cycle times.
- the examples demonstrate that the addition of significant quantities of ammonia to the 2 nd stage reactor calms the crisp activity of zeolite Y and then makes it possible to increase the selectivities for middle distillates.
- the selectivities obtained are of the same order as those carried out with silica-aluminas but with greater activities.
- the method according to the invention then provides significant flexibility to the refiner between the naphtha maximized obtaining (low nitrogen content in 2 step ee and low conversion 1 st step) and diesel maximized obtaining (high nitrogen content 2 in step ee and high conversion to 1 st step). This flexibility was not obtained with silica-aluminas used in the 2nd stage.
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Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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FR0010095A FR2812302B1 (fr) | 2000-07-31 | 2000-07-31 | Procede d'hydrocraquage en 2 etapes de charges hydrocarbonees |
FR0010095 | 2000-07-31 | ||
PCT/FR2001/002447 WO2002010315A1 (fr) | 2000-07-31 | 2001-07-26 | Procede d'hydrocraquage en 2 etapes de charges hydrocarbonees |
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EP1307527A1 true EP1307527A1 (fr) | 2003-05-07 |
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EP01956643A Withdrawn EP1307527A1 (fr) | 2000-07-31 | 2001-07-26 | Procede d'hydrocraquage en 2 etapes de charges hydrocarbonees |
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US (1) | US7160436B2 (fr) |
EP (1) | EP1307527A1 (fr) |
KR (1) | KR100801120B1 (fr) |
BR (1) | BR0112831B1 (fr) |
FR (1) | FR2812302B1 (fr) |
MX (1) | MXPA03000372A (fr) |
TW (1) | TW589368B (fr) |
WO (1) | WO2002010315A1 (fr) |
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JP4013674B2 (ja) * | 2002-07-11 | 2007-11-28 | 松下電器産業株式会社 | プラズマドーピング方法及び装置 |
FR2863913B1 (fr) * | 2003-12-23 | 2006-12-29 | Inst Francais Du Petrole | Catalyseur zeolithique,support a base de matrice silico-aluminique et de zeolithe, et procede d'hydrocraquage de charges hydrocarbonees |
FR2900157B1 (fr) * | 2006-04-24 | 2010-09-24 | Inst Francais Du Petrole | Procede de desulfuration d'essences olefiniques comprenant au moins deux etapes distinctes d'hydrodesulfuration |
US9101853B2 (en) * | 2011-03-23 | 2015-08-11 | Saudi Arabian Oil Company | Integrated hydrocracking and fluidized catalytic cracking system and process |
US9101854B2 (en) * | 2011-03-23 | 2015-08-11 | Saudi Arabian Oil Company | Cracking system and process integrating hydrocracking and fluidized catalytic cracking |
FR2981659B1 (fr) * | 2011-10-20 | 2013-11-01 | Ifp Energies Now | Procede de conversion de charges petrolieres comprenant une etape d'hydroconversion en lit bouillonnant et une etape d'hydrotraitement en lit fixe pour la production de fiouls a basse teneur en soufre |
CN103059944B (zh) * | 2011-10-21 | 2015-04-01 | 中国石油化工股份有限公司 | 一种加工劣质原料的加氢裂化工艺方法 |
WO2013075850A1 (fr) * | 2011-11-22 | 2013-05-30 | Turkiye Petrol Rafinerileri A.S | Procédé et système de production de diesel |
CN103509599B (zh) * | 2012-06-29 | 2015-10-28 | 中国石油化工股份有限公司 | 一种生产中间馏分油的并流式加氢方法 |
CN103525461B (zh) * | 2012-07-06 | 2015-07-29 | 中国石油化工股份有限公司 | 一种加氢裂化方法 |
US20140034549A1 (en) * | 2012-08-03 | 2014-02-06 | Lummus Technology Inc. | Residue hydrocracking |
US9533293B2 (en) | 2014-04-16 | 2017-01-03 | King Fahd University Of Petroleum And Minerals | Modified zeolite second stage hydrocracking catalyst and use of thereof for hydrocarbon conversion |
CN105754649B (zh) * | 2014-12-20 | 2018-06-19 | 中国石油化工股份有限公司 | 一种提高加氢裂化装置运行安全性的方法 |
US11332678B2 (en) | 2020-07-23 | 2022-05-17 | Saudi Arabian Oil Company | Processing of paraffinic naphtha with modified USY zeolite dehydrogenation catalyst |
US11420192B2 (en) * | 2020-07-28 | 2022-08-23 | Saudi Arabian Oil Company | Hydrocracking catalysts containing rare earth containing post-modified USY zeolite, method for preparing hydrocracking catalysts, and methods for hydrocracking hydrocarbon oil with hydrocracking catalysts |
RU2758847C1 (ru) * | 2021-03-24 | 2021-11-02 | Публичное акционерное общество "Нефтяная компания "Роснефть" (ПАО "НК "Роснефть") | Способ получения зимних и арктических дизельных топлив из прямогонных дизельных фракций с содержанием серы до 5000 мг/кг и азота до 200 мг/кг |
US11618858B1 (en) | 2021-12-06 | 2023-04-04 | Saudi Arabian Oil Company | Hydrodearylation catalysts for aromatic bottoms oil, method for producing hydrodearylation catalysts, and method for hydrodearylating aromatic bottoms oil with hydrodearylation catalysts |
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US3702818A (en) * | 1968-05-23 | 1972-11-14 | Mobil Oil Corp | Hydrocracking process with zeolite and amorphous base catalysts |
GB1229432A (fr) * | 1968-07-11 | 1971-04-21 | ||
US3816296A (en) * | 1972-11-13 | 1974-06-11 | Union Oil Co | Hydrocracking process |
US4713167A (en) * | 1986-06-20 | 1987-12-15 | Uop Inc. | Multiple single-stage hydrocracking process |
US5190903A (en) * | 1991-03-31 | 1993-03-02 | Uop | Low acidity Y zeolite |
US5228979A (en) * | 1991-12-05 | 1993-07-20 | Union Oil Company Of California | Hydrocracking with a catalyst containing a noble metal and zeolite beta |
FR2778345B1 (fr) | 1998-05-06 | 2000-11-24 | Inst Francais Du Petrole | Catalyseur a base de zeolithe y contenant du bore et/ou du silicium, utilisable en hydrocraquage |
JP2007009807A (ja) * | 2005-06-30 | 2007-01-18 | Toyota Motor Corp | 内燃機関の制御装置 |
JP2007087001A (ja) * | 2005-09-21 | 2007-04-05 | Fuji Xerox Co Ltd | バックアップリストア装置、及びバックアップリストア方法 |
JP4873139B2 (ja) * | 2006-06-23 | 2012-02-08 | Nok株式会社 | ガスケットの製造方法 |
-
2000
- 2000-07-31 FR FR0010095A patent/FR2812302B1/fr not_active Expired - Lifetime
-
2001
- 2001-07-26 WO PCT/FR2001/002447 patent/WO2002010315A1/fr active Application Filing
- 2001-07-26 BR BRPI0112831-0A patent/BR0112831B1/pt not_active IP Right Cessation
- 2001-07-26 KR KR1020037001496A patent/KR100801120B1/ko not_active IP Right Cessation
- 2001-07-26 MX MXPA03000372A patent/MXPA03000372A/es active IP Right Grant
- 2001-07-26 EP EP01956643A patent/EP1307527A1/fr not_active Withdrawn
- 2001-07-26 US US10/343,218 patent/US7160436B2/en not_active Expired - Fee Related
- 2001-07-31 TW TW090118653A patent/TW589368B/zh not_active IP Right Cessation
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See references of WO0210315A1 * |
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US20040045869A1 (en) | 2004-03-11 |
FR2812302B1 (fr) | 2003-09-05 |
KR100801120B1 (ko) | 2008-02-05 |
MXPA03000372A (es) | 2004-02-26 |
KR20030020434A (ko) | 2003-03-08 |
BR0112831B1 (pt) | 2012-07-24 |
BR0112831A (pt) | 2003-06-24 |
TW589368B (en) | 2004-06-01 |
US7160436B2 (en) | 2007-01-09 |
FR2812302A1 (fr) | 2002-02-01 |
WO2002010315A1 (fr) | 2002-02-07 |
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