EP0333554B1 - Thermal-treatment process of hydrocarbon feeds in the presence of polysulfides and hydrogen donors - Google Patents
Thermal-treatment process of hydrocarbon feeds in the presence of polysulfides and hydrogen donors Download PDFInfo
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- EP0333554B1 EP0333554B1 EP19890400625 EP89400625A EP0333554B1 EP 0333554 B1 EP0333554 B1 EP 0333554B1 EP 19890400625 EP19890400625 EP 19890400625 EP 89400625 A EP89400625 A EP 89400625A EP 0333554 B1 EP0333554 B1 EP 0333554B1
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- polysulphide
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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
- C10G47/32—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions in the presence of hydrogen-generating compounds
- C10G47/34—Organic compounds, e.g. hydrogenated hydrocarbons
Definitions
- the present invention relates to a process for heat treatment of hydrocarbon feedstocks and more particularly heavy feedstocks in the presence of hydrogen polysulfides and / or organic polysulfides and hydrogen donors. It is particularly applicable to the petroleum refining industry and in particular to thermal conversion processes such as visbreaking and non-catalytic hydroviscoreduction, that is to say without adding metals or metal compounds having a catalytic action on the reactions which occur. during heat treatment of the load.
- the present invention applies to methods of heat treatment of hydrocarbon charges in which the overall H / C ratio of the recipe (of effluents) is not significantly different from that of the charge to be treated .
- Improvement of thermal treatment processes used in the petroleum industry, in particular for the refining of fossil organic materials rich in high-mass polyaromatic structures, coke promoters, such as heavy and related oils: bituminous shales, asphalt sands, etc. and the refining residues, implies a control of the radical transformation processes by the use of efficient solvents or additives.
- French patent FR-B-2555192 describes in particular the use of nickel naphthenate as an anti-coke additive optionally combined with dimethyldisulfide (DMDS).
- DMDS dimethyldisulfide
- This process makes it possible to reduce, at isoconversion, the amount of insoluble matter in xylene (coke). It is noted however that on the one hand there is still a significant amount of coke and that on the other hand the conversion is greatly reduced compared to a heat treatment carried out without additive. It can also be seen from reading the table in this document that the additional addition of DMDS to nickel naphthenate does not make it possible to improve the conversion (yield at 350 ° C.) or to reduce the amount of coke formed (insoluble in xylene) significantly.
- the addition of metal compounds, to the load usually imposes the need for a subsequent treatment of the effluent obtained after the heat treatment in order to separate and possibly recycle these compounds, which can be a major handicap for the process.
- the object of the invention is in particular to remedy the drawbacks indicated above.
- the invention relates to a process for the thermal conversion of a hydrocarbon feedstock, for example a heavy petroleum cut, a refining residue, or a heavy petroleum in which said feedstock is subjected to a heat treatment, said process being characterized in that the heat treatment is carried out in the presence of at least one polysulfide chosen from the group formed by hydrogen polysulfides and organic polysulfides and at least one hydrogen donor compound .
- the polysulphide employed in the present invention is usually a compound of formula (I) R1 - (S) n - R2 in which R1 and R2, identical or different, each represent a hydrogen atom or a hydrocarbon radical and n is a number included between 2 and 20, limits included and preferably between 2 and 8, limits included.
- R1 and R2 independently of one another represent a hydrogen atom, a linear or branched alkyl radical, an aryl radical, an aryl-alkyl (aralkyl) radical or a radical cycloalkyl.
- polysulphides of formula (I) are used in which at least one of the radicals R1 and R2 represents a hydrocarbon radical and preferably those in which R1 and R2, identical or different, each represent a linear saturated or unsaturated aliphatic radical or branched or an alicyclic radical.
- the particularly preferred organic polysulphides of formula (I) are those in which R1 and R2, identical or different, each represent an alkyl radical; they are hereinafter called dialkyl-polysulfides.
- organic polysulphides By way of example of organic polysulphides, mention may be made of aliphatic and / or alicyclic disulphides and more particularly dialkyl disulphides.
- the organic polysulfides of formula (I) used in the present invention usually have from 2 to 72 carbon atoms and preferably from 2 to 48 carbon atoms in their molecule.
- dialkylpolysulfides used advantageously have from 2 to 24 carbon atoms in their molecule and the organic polysulfides of formula (I) in which R1 and / or R2 represent a cycloalkyl radical, advantageously have from 6 to 48 carbon atoms and preferably from 10 to 32 carbon atoms in their molecule.
- DMDS dimethyldisulfide
- DEDS diethyldisulfide
- DTBDS ditertiobutyldisulfide
- TPS 32 ditertiobutylpolysulfide
- TPS 37 ELF A
- the hydrocarbon polysulphides can result, in a particularly advantageous manner, from the oxidation, under conditions known per se, of the mercaptans contained in LPG petroleum fractions and advantageously light essences, (attractive Merox process). These cuts, once oxidized, can be made to the load to be visbreaked.
- the amount of polysulphide used in the present invention expressed in gram atom of sulfur per 100 g of load to be treated is usually from 0.01 to 1 gram atom of sulfur, preferably from 0.05 to 0.5 atom -gram of sulfur and most often from 0.08 to 0.3 gram-atom of sulfur, which corresponds by weight of sulfur relative to the load at: 0.32% to 32%, preferably 1.6% at 16% and most often 2.56% at 9.6%.
- hydrogen-donating compounds By way of example of hydrogen-donating compounds, mention may be made of the at least partially hydrogenated derivatives of naphthalene, anthracene, pyrene, fluoranthene, benzoanthracene, dibenzoanthracene, coronene, perylene, benzopyrene, their nitrogen heterocyclic analogs and their analogs substituted by at least one lower alkyl radical having for example from 1 to 10 carbon atoms.
- LCO Light Cycle Oil
- HCO Heavy Cycle Oil
- cuts such as 180 - 365 ° C or 320 - 500 ° C cuts, for example from catalytic cracking, LCO cuts or HCO at least partially hydrogenated, and polyaromatic cuts possibly at least partially hydrogenated
- the hydrocarbon fractions used as hydrogen donor are usually those which contain at least 0.8% by weight and preferably at least 1.25% by weight of transferable (or transferable) hydrogen such as for example those mentioned in the patent US-A-4425224.
- hydrogen donor compounds examples include tetrahydronaphthalene or tetralin (TN), dihydroanthracenes, tetrahydroanthracenes, dihydrobenzoanthracenes and dihydrodibenzoanthracenes.
- the amount of hydrogen donor used is usually from 10 to 400% by weight, preferably from 30 to 200% by weight and most often from 40 to 150% by weight relative to the weight of the feed to be treated.
- the synergistic effect of the action of the polysulphide and of the hydrogen donor is particularly important when the quantity of polysulphide used expressed in weight percent of sulfur relative to the charge to be treated is from 2.56 to 9.6 % and that the amount of hydrogen donor is 30 to 200% by weight and more particularly 40 to 150% by weight relative to the charge to be treated.
- the invention applies to various heat treatments of hydrocarbon feedstocks usually having a viscosity of between approximately 600 and 70,000 mPa xs at 100 ° C and most often between approximately 1000 and 30,000 mPa xs at 100 ° C.
- the invention applies in particular to visbreaking and hydroviscoreduction of distillation residues, for example residues of vacuum distillation (RSV) or atmospheric distillation.
- the visbreaking is usually carried out at temperatures of about 350 to 500 ° C, preferably about 380 to 450 ° C and most often about 410 to 450 ° C and the hydroviscoreduction at temperatures of the same order of greatness.
- the total pressure is usually about 1 MPa to 20 MPa at processing temperatures and the residence time is usually about 1 minute to 3 hours.
- the heat treatment is usually carried out under an inert atmosphere, for example under argon, helium or nitrogen or under an atmosphere of water vapor or of a mixture of water vapor and inert gas.
- the heat treatment is carried out in the presence of hydrogen, preferably substantially pure, or a mixture of substantially pure hydrogen and inert gas, although it is also possible to use industrial hydrogen containing for example less than about 5% by volume of hydrogen sulfide and preferably less than about 2.5% by volume of hydrogen sulfide.
- the invention also relates to a composition for carrying out the process according to the present invention, comprising on the one hand at least one polysulfide as defined above and on the other hand at least one hydrogen donor compound.
- the weight ratio of the hydrogen donor to the polysulfide in said composition is usually from about 0.3: 1 to 1250: 1, preferably from about 1.87: 1 to 125: 1 and most often from about 4.2: 1 to 58.6: 1.
- the proportion by weight of the composition introduced into the filler to be subjected to the heat treatment is usually about 10.3 to 432 parts per 100 parts of the filler to be treated, consisting, for example, of a heavy fraction of petroleum, preferably of about 31.6 to 216 parts per 100 parts of said load and most often about 42.6 to 159.6 parts per 100 parts of said load.
- Examples 1 to 16 were carried out batchwise. Examples 1 to 8 relate to visbreaking, of a residue under vacuum, carried out under argon and Examples 9 to 16 relate to hydroviscoreduction, carried out in the presence of substantially pure hydrogen, of the same charge.
- the hydrocarbon feedstock used in the examples is a vacuum residue (RSV) 500 ° C. of SAFANIYA origin, the characteristics of which are given in Table 1 below.
- the point P1 corresponds to the standard n-alkane heated under the same conditions and whose boiling point is approximately 500 ° C. From point P2, the carbon rich residue is burned. A calibration is also carried out using crude oil, the simulated distillation of which is known.
- the pyrogram obtained ( Figure 2) delivers the CO2 concentration as a function of the time and temperature of the oven. We can thus easily split the pyrogram by integrating the signal between selected temperature values, for example according to the fractions below. In the case of the untreated vacuum residue, the percentages of the various fractions are indicated below:
- the F2 fraction represents the 500 ° C fraction at the end of distillation (FD).
- centesimal analysis of the charges subjected to hydroviscoreduction shows that the sum of the weights of C, H and S is always greater than or equal to 95%. Consequently, the simple addition of these weights makes it possible to obtain with sufficient precision the actual respective percentages of the various above fractions of the liquid fraction.
- concentrations by weight of polysulphides are such that the level of sulfur introduced with respect to the charge to be treated is equal to 0.2 gram atom of sulfur per 100 g of RSV SAFANIYA in examples 3 to 6,8,11 to 12B and 16.
- the petroleum charge (RSV SAFANIYA) after slight heating (100 -120 ° C) to make it less viscous, is introduced into the reactor which is a stainless steel autoclave in the case of examples 1 to 16. The whole is constantly restless. Any additives are added after cooling.
- concentrations chosen by way of example as a hydrogen donor diluent (DDH) are such that the weight ratio RSV / DDH is equal to 1.
- Coke is defined as the part insoluble in hot benzene. An assay is carried out for each test. The amount of liquid is calculated after determining the coke level.
- the gas, liquid and coke rates are expressed in relation to petroleum alone or in relation to the petroleum + DDH mixture, after deduction of the polysulfurized additives if applicable. It is therefore implicitly assumed that the additive, even if it undergoes significant modifications during pyrolysis, can be recovered mainly in the liquid fraction (case for example of tetralin, LCO and diphenyldisulfide) or in the gas phase (case dimethyldisulfide).
- the calculation of the overall conversion is detailed below in the case of Example 12. This calculation takes into account the complete conversion of the DMDS into a gaseous fraction (H2S + CH4) deductible from the weight of the fraction total gaseous obtained after the hydroviscoreduction treatment.
- the charge subjected to the hydroviscoreduction comprises 47.6 g of RSV SAFANIYA, 47.6 g of tetralin and 4.8 g of DMDS, ie 100 g of raw material subjected to the heat treatment.
- Y (% 500 ° C + load - (% 500 ° C + recipe) (% 500 ° C + charge) x 100
- the recipe consists of all of the products from visbreaking or hydroviscoreduction (gas + liquid + solid (coke)).
- the 500 ° C+ percentage (% 500 ° C+) of the recipe therefore contains the 500 ° C+ liquid fraction of the liquid part of the recipe and possibly the coke formed during the heat treatment.
- the 500 ° C ⁇ percentage (% 500 ° C ⁇ ) of the recipe contains the gases formed and the 500 ° C ⁇ liquid fraction of the liquid part of the recipe.
- Table 2 summarizes the results of Examples 1 to 8 carried out under an initial argon pressure of 5 MPa at 430 ° C (visbreaking).
- Table 3 summarizes the results of Examples 9 to 16 carried out under an initial hydrogen pressure of 5 MPa at 430 ° C (water reduction).
- Table 4 gives the characteristics of a non-hydrogenated LCO originating from the catalytic cracking used as hydrogen donor in Examples 7, 8, 15 and 16.
- Table 5 compares at a low conversion temperature the action of thiophenol and the action of dimethyldisulfide in the presence of hydrogen donor.
- Examples 12 A and 12 B show that the ditertiobutylpentasulfide gives in combination with tetralin a result substantially similar to that of Example 12, with a few points of conversion.
- Example 12 C and 12 D are given for comparison and show that Example 12 according to the invention gives better results than Example 12 D according to the prior art in the presence of dimethyldisulfide alone and molybdenum naphthenate as catalyst. .
- Examples 17 to 21 illustrate a conversion carried out on the same Safaniya residue under initial 5 MPa hydrogen pressure at 390 ° C. for 15 minutes.
- a comparative study is carried out between thiophenol (prior art), dimethyldisulfide and ditertiobutylpentasulfide (X) in the presence of tetrahydronaphthalene (TN) and presented in Table 5 where the symbols are the same as those used in the previous tables.
- TN tetrahydronaphthalene
- Examples 22 to 25 were carried out in a micropilot, under a pressure of 10 MPa of substantially pure hydrogen, continuously, under the following conditions: Temperature: 450 ° C Charge residence time: 1 hour Hydrogen flow: 1.1 l / minute at normal temperature and pressure Liquid charge flow: 5 ml / minute.
- the charge used is the same as that used in Examples 1 to 21.
- the analysis method used in Examples 22 to 25 is the same as that used in Examples 1 to 21.
- the concentrations by weight of polysulphides are such that the level of sulfur introduced with respect to the charge to be treated is equal to 0.2 gram-atom of sulfur per 100 g of RSV SAFANIYA in Example 19 and to 0.1 atom- gram of sulfur in Examples 23 and 25.
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Description
La présente invention concerne un procédé de traitement thermique des charges hydrocarbonées et plus particulièrement des charges lourdes en présence de polysulfures d'hydrogène et/ou de polysulfures organiques et de donneurs d'hydrogène. Elle est particulièrement applicable à l'industrie du raffinage du pétrole et notamment aux procédés de conversion thermique tels que viscoréduction et hydroviscoréduction non catalytique, c'est à dire sans ajout de métaux ou composés de métaux ayant une action catalytique sur les réactions qui se produisent lors du traitement thermique de la charge.The present invention relates to a process for heat treatment of hydrocarbon feedstocks and more particularly heavy feedstocks in the presence of hydrogen polysulfides and / or organic polysulfides and hydrogen donors. It is particularly applicable to the petroleum refining industry and in particular to thermal conversion processes such as visbreaking and non-catalytic hydroviscoreduction, that is to say without adding metals or metal compounds having a catalytic action on the reactions which occur. during heat treatment of the load.
En d'autres termes, la présente invention s'applique aux procédés de traitement thermique des charges d'hydrocarbures dans lesquels le rapport global H/C de la recette (des effluents) n'est pas sensiblement différent de celui de la charge à traiter.In other words, the present invention applies to methods of heat treatment of hydrocarbon charges in which the overall H / C ratio of the recipe (of effluents) is not significantly different from that of the charge to be treated .
L'amélioration des procédés de traitement thermique utilisés dans l'industrie pétrolière, notamment pour le raffinage des matières organiques fossiles riches en structures polyaromatiques de haute masse, promoteurs de coke, tels que les pétroles lourds et apparentés : schistes bitumeux, sables asphaltiques... et les résidus de raffinage, implique un contrôle des processus de transformations radicalaires par la mise en oeuvre de solvants ou additifs performants.Improvement of thermal treatment processes used in the petroleum industry, in particular for the refining of fossil organic materials rich in high-mass polyaromatic structures, coke promoters, such as heavy and related oils: bituminous shales, asphalt sands, etc. and the refining residues, implies a control of the radical transformation processes by the use of efficient solvents or additives.
De nombreux travaux ont été consacrés à la mise en oeuvre de solvants donneurs d'hydrogène (structures hydropolyaromatiques telles que la tétraline, le dihydroanthracène ou des coupes pétrolières partiellement hydrogénées), capables d'inhiber efficacement le développement des réactions radicalaires de polycondensation ou de polymérisation en chaîne (US-A-2796386, US-A-4425224).Numerous studies have been devoted to the use of hydrogen-donating solvents (hydropolyaromatic structures such as tetralin, dihydroanthracene or partially hydrogenated petroleum fractions), capable of effectively inhibiting the development of radical polycondensation or polymerization reactions. chain (US-A-2796386, US-A-4425224).
Toutefois, dans des conditions identiques, l'utilisation d'un donneur d'hydrogène efficace entraîne une conversion en fractions légères plus modérée dès lors que l'on élimine du milieu réactionnel des intermédiaires réactifs promoteurs des processus de fragmentation des chaînes. Cet aspect du problème a conduit à l'association d'additifs capables de réaliser ensemble la capture radicalaire et l'activation des fragmentations des agrégats polymoléculaires présents dans ces fractions lourdes.However, under identical conditions, the use of an efficient hydrogen donor leads to a more moderate conversion into light fractions when reactive intermediates which promote chain fragmentation processes are eliminated from the reaction medium. This aspect of the problem has led to the association of additives capable of carrying out together the radical capture and the activation of the fragments of the polymolecular aggregates present in these heavy fractions.
Différents travaux mentionnent l'effet de l'hydrogène sulfuré, présent lors des traitements des coupes pétrolières riches en soufre, comme composé susceptible d'un double rôle catalytique : d'une part, l'amélioration des cinétiques de transfert d'hydrogène donc de l'efficacité de capture des radicaux libres ; d'autre part, l'activation de réactions de fragmentation.Various studies mention the effect of hydrogen sulfide, present during the treatment of sulfur-rich petroleum fractions, as a compound capable of a double catalytic role: on the one hand, the improvement of the kinetics of hydrogen transfer therefore of the efficiency of free radical capture; on the other hand, the activation of fragmentation reactions.
Le brevet Français FR-B-2555192 décrit en particulier l'utilisation de naphténate de nickel comme additif anti-coke associé éventuellement à du diméthyldisulfure (DMDS). Ce procédé permet de diminuer, à isoconversion, la quantité d'insolubles dans le xylène (coke). On constate cependant que d'une part il se forme encore une quantité de coke non négligeable et que d'autre part la conversion est fortement diminuée par rapport à un traitement thermique effectué sans additif. On constate, par ailleurs, à la lecture du Tableau de ce document, que l'addition supplémentaire de DMDS au naphténate de nickel ne permet pas d'améliorer la conversion (rendement en 350 °C⁻) ni de réduire la quantité de coke formé (insoluble au xylène) de façon significative. L'addition de composés métalliques, à la charge, impose habituellement la nécessité d'un traitement postérieur de l'effluent obtenu après le traitement thermique en vue de séparer et éventuellement recycler ces composés, ce qui peut être un handicap important pour le procédé.French patent FR-B-2555192 describes in particular the use of nickel naphthenate as an anti-coke additive optionally combined with dimethyldisulfide (DMDS). This process makes it possible to reduce, at isoconversion, the amount of insoluble matter in xylene (coke). It is noted however that on the one hand there is still a significant amount of coke and that on the other hand the conversion is greatly reduced compared to a heat treatment carried out without additive. It can also be seen from reading the table in this document that the additional addition of DMDS to nickel naphthenate does not make it possible to improve the conversion (yield at 350 ° C.) or to reduce the amount of coke formed (insoluble in xylene) significantly. The addition of metal compounds, to the load, usually imposes the need for a subsequent treatment of the effluent obtained after the heat treatment in order to separate and possibly recycle these compounds, which can be a major handicap for the process.
Il est connu par ailleurs par le brevet EP-A-0.175.511, d'utiliser un composé soufré comme le thiophénol en présence d'un diluant donneur d'hydrogène, ce dernier devant être associé avec des composés ayant des propriétés se rapprochant de celles des hydrocarbures aromatiques (le thiophénol par exemple). De plus, le thiophénol est un composé cher qui grêverait l'économie de son procédé d'utilisation.It is also known from patent EP-A-0.175.511 to use a sulfur-containing compound such as thiophenol in the presence of a hydrogen-donor diluent, the latter having to be combined with compounds having properties approaching those of aromatic hydrocarbons (thiophenol for example). In addition, thiophenol is an expensive compound which would hamper the economy of its process of use.
D'autres types d'activants ont été préconisés dans l'art antérieur, tels que les générateurs de radicaux ; d'une façon générale, ces additifs présentent diverses insuffisances réactionnelles, notamment :
- le domaine thermique de formation des espèces réactives est trop limité à partir de générateurs tels que l'eau oxygénée, les hydroperoxydes et les peroxydes organiques. Cette température, inférieure en général à 200 °C, conduit à une stabilité insuffisante pour leur action efficace dans le milieu aux températures habituellement en vigueur.
- leur action consiste plutôt en une modification chimique préalable au traitement thermique proprement dit ; de plus, une mauvaise sélectivité est observée du fait de la décomposition souvent brutale et exothermique de ces composés.
- the thermal domain for the formation of reactive species is too limited from generators such as hydrogen peroxide, hydroperoxides and organic peroxides. This temperature, generally lower than 200 ° C., leads to insufficient stability for their effective action in the medium at the temperatures usually in force.
- rather, their action consists of a chemical modification prior to the actual heat treatment; in addition, poor selectivity is observed due to the often brutal and exothermic decomposition of these compounds.
L'invention a notamment pour objet de remédier aux inconvénients signalés ci-avant.The object of the invention is in particular to remedy the drawbacks indicated above.
On a effet découvert, de manière surprenante, que l'on pouvait obtenir lors d'un traitement thermique, non catalytique, d'une charge hydrocarbonée, une conversion élevée en fractions plus légères liquides et facilement valorisables, (par exemple en fuels industriels) et simultanément une nette diminution de la formation de coke, tout en restant dans la gamme de température usuelle pour de tels traitements.It has been discovered, surprisingly, that a non-catalytic heat treatment of a hydrocarbon feed can be obtained, a high conversion into lighter, liquid fractions which are easily recoverable (for example into industrial fuels). and simultaneously a clear reduction in the formation of coke, while remaining in the usual temperature range for such treatments.
La synergie observée lors de l'emploi concomitant de donneurs d'hydrogène et de polysulfures d'hydrogène et/ou de polysulfures organiques permet en outre de réaliser des traitements thermiques convertissants à des températures plus élevées et d'obtenir ainsi une plus forte conversion en limitant efficacement la formation de coke et de gaz. Elle permet également d'éviter avantageusement dans certains cas l'utilisation d'hydrogène moléculaire dans les procédés de viscoréduction.The synergy observed during the concomitant use of hydrogen donors and hydrogen polysulfides and / or organic polysulfides also makes it possible to carry out heat treatments which convert at higher temperatures and thus to obtain a higher conversion into effectively limiting the formation of coke and gases. It also makes it possible advantageously to avoid in certain cases the use of molecular hydrogen in visbreaking processes.
D'une manière générale, l'invention concerne un procédé de conversion thermique d'une charge hydrocarbonée, par exemple d'une coupe pétrolière lourde, d'un résidu de raffinage, ou d'un pétrole lourd dans lequel ladite charge est soumise à un traitement thermique, ledit procédé étant caractérisé en ce que le traitement thermique est effectué en présence d'au moins un polysulfure choisi dans le groupe formé par les polysulfures d'hydrogène et les polysulfures organiques et d'au moins un compose donneur d'hydrogène.In general, the invention relates to a process for the thermal conversion of a hydrocarbon feedstock, for example a heavy petroleum cut, a refining residue, or a heavy petroleum in which said feedstock is subjected to a heat treatment, said process being characterized in that the heat treatment is carried out in the presence of at least one polysulfide chosen from the group formed by hydrogen polysulfides and organic polysulfides and at least one hydrogen donor compound .
Le polysulfure employé dans la présente invention est habituellement un composé de formule (I) R¹ - (S)n - R² dans laquelle R¹ et R², identiques ou différents représentent chacun un atome d'hydrogène ou un radical hydrocarboné et n est un nombre compris entre 2 et 20, bornes incluses et de préférence entre 2 et 8, bornes incluses.The polysulphide employed in the present invention is usually a compound of formula (I) R¹ - (S) n - R² in which R¹ and R², identical or different, each represent a hydrogen atom or a hydrocarbon radical and n is a number included between 2 and 20, limits included and preferably between 2 and 8, limits included.
Parmi les radicaux hydrocarbonés on peut citer, à titre d'exemple, les radicaux aliphatiques saturés ou insaturés, linéaires ou ramifiés, les radicaux cycloaliphatiques et les radicaux aryles. Dans la formule (I) ci-avant, R¹ et R² représentent indépendamment l'un de l'autre un atome d'hydrogène, un radical alkyle linéaire ou ramifié, un radical aryle, un radical aryle-alkyle (aralkyle) ou un radical cycloalkyle.Mention may be made, among hydrocarbon radicals, by way of example, of saturated or unsaturated, linear or branched aliphatic radicals, cycloaliphatic radicals and aryl radicals. In formula (I) above, R¹ and R² independently of one another represent a hydrogen atom, a linear or branched alkyl radical, an aryl radical, an aryl-alkyl (aralkyl) radical or a radical cycloalkyl.
On emploie avantageusement des polysulfures de formule (I) dans laquelle l'un au moins des radicaux R¹ et R² représente un radical hydrocarboné et de préférence ceux dans lesquels R¹ et R², identiques ou différents, représentent chacun un radical aliphatique saturé ou insaturé, linéaire ou ramifié ou un radical alicyclique. Les polysulfures organiques de formule (I) particulièrement préférés sont ceux dans lesquels R¹ et R², identiques ou différents, représentent chacun un radical alkyle ; ils sont dénommés ci-après dialkyl-polysulfures.Advantageously, polysulphides of formula (I) are used in which at least one of the radicals R¹ and R² represents a hydrocarbon radical and preferably those in which R¹ and R², identical or different, each represent a linear saturated or unsaturated aliphatic radical or branched or an alicyclic radical. The particularly preferred organic polysulphides of formula (I) are those in which R¹ and R², identical or different, each represent an alkyl radical; they are hereinafter called dialkyl-polysulfides.
A titre d'exemple de polysulfures organiques on peut citer les disulfures aliphatique et/ou alicyclique et plus particulièrement les dialkyl-disulfures.By way of example of organic polysulphides, mention may be made of aliphatic and / or alicyclic disulphides and more particularly dialkyl disulphides.
Les polysulfures organiques de formule (I) employés dans la présente invention ont habituellement de 2 à 72 atomes de carbone et de préférence de 2 à 48 atomes de carbone dans leur molécule.The organic polysulfides of formula (I) used in the present invention usually have from 2 to 72 carbon atoms and preferably from 2 to 48 carbon atoms in their molecule.
Les dialkylpolysulfures employés ont avantageusement de 2 à 24 atomes de carbone dans leur molécule et les polysulfures organiques de formule (I) dans laquelle R¹ et/ou R² représentent un radical cycloalkyle, ont avantageusement de 6 à 48 atomes de carbone et de préférence de 10 à 32 atomes de carbone dans leur molécule.The dialkylpolysulfides used advantageously have from 2 to 24 carbon atoms in their molecule and the organic polysulfides of formula (I) in which R¹ and / or R² represent a cycloalkyl radical, advantageously have from 6 to 48 carbon atoms and preferably from 10 to 32 carbon atoms in their molecule.
A titre d'exemples spécifiques de polysulfures organiques, on peut citer le diméthyldisulfure (DMDS), le diéthyldisulfure (DEDS), les dipropyldisulfures, les dibutyldisulfures, en particulier le ditertiobutyldisulfure (DTBDS), le ditertiobutylpolysulfure (n = 5) et le ditertiododécylpolysulfure (n = 5) commercialisé par exemple par ELF AQUITAINE sous le nom TPS 32, notamment parce qu'il contient environ 32 % en poids de soufre et le ditertiononylpolysulfure (n = 5) commercialisé par exemple par ELF AQUITAINE sous le nom TPS 37.By way of specific examples of organic polysulfides, mention may be made of dimethyldisulfide (DMDS), diethyldisulfide (DEDS), dipropyldisulfides, dibutyldisulfides, in particular ditertiobutyldisulfide (DTBDS), ditertiobutylpolysulfide (n = 5) and ditertod n = 5) marketed for example by ELF AQUITAINE under the name TPS 32, in particular because it contains approximately 32% by weight of sulfur and the ditertiononylpolysulfide (n = 5) marketed for example by ELF AQUITAINE under the name TPS 37.
Les polysulfures hydrocarbonés peuvent résulter, de manière particulièrement avantageuse, de l'oxydation, dans des conditions connues en soi, des mercaptans contenus dans des coupes pétrolières LPG et essences avantageusement légères, (procédé Mérox attractif). Ces coupes, une fois oxydées, peuvent être apportées à la charge devant être viscoréduite.The hydrocarbon polysulphides can result, in a particularly advantageous manner, from the oxidation, under conditions known per se, of the mercaptans contained in LPG petroleum fractions and advantageously light essences, (attractive Merox process). These cuts, once oxidized, can be made to the load to be visbreaked.
La quantité de polysulfure, employée dans la présente invention, exprimée en atome-gramme de soufre pour 100 g de charge à traiter est habituellement de 0,01 à 1 atome-gramme de soufre, de préférence de 0,05 à 0,5 atome-gramme de soufre et le plus souvent de 0,08 à 0,3 atome-gramme de soufre, ce qui correspond en poids de soufre par rapport à la charge à : 0,32 % à 32 %, de préférence 1,6% à 16 % et le plus souvent 2,56 % à 9,6 %.The amount of polysulphide used in the present invention, expressed in gram atom of sulfur per 100 g of load to be treated is usually from 0.01 to 1 gram atom of sulfur, preferably from 0.05 to 0.5 atom -gram of sulfur and most often from 0.08 to 0.3 gram-atom of sulfur, which corresponds by weight of sulfur relative to the load at: 0.32% to 32%, preferably 1.6% at 16% and most often 2.56% at 9.6%.
A titre d'exemple de composés donneurs d'hydrogène, on peut citer les dérivés au moins partiellement hydrogénés du naphtalène, de l'anthracène, du pyrène, du fluoranthène, du benzoanthracène, du dibenzoanthracène, du coronène, du pérylène, du benzopyrène, leurs analogues hétérocycliques azotés et leurs analogues substitués par au moins un radical alkyle inférieur ayant par exemple de 1 à 10 atomes de carbone. On peut également citer à titre d'exemple les coupes LCO (Light Cycle Oil) ou HCO (Heavy Cycle Oil) telles que les coupes 180 - 365° C ou 320 - 500° C provenant par exemple du craquage catalytique, les coupes LCO ou HCO au moins partiellement hydrogénées, et les coupes polyaromatiques éventuellement au moins partiellement hydrogénées ; les coupes hydrocarbonées employées comme donneur d'hydrogène sont habituellement celles qui contiennent au moins 0,8 % en poids et de préférence au moins 1,25 % en poids d'hydrogène cessible (ou transférable) telles que par exemple celles mentionnées dans le brevet US-A-4425224.By way of example of hydrogen-donating compounds, mention may be made of the at least partially hydrogenated derivatives of naphthalene, anthracene, pyrene, fluoranthene, benzoanthracene, dibenzoanthracene, coronene, perylene, benzopyrene, their nitrogen heterocyclic analogs and their analogs substituted by at least one lower alkyl radical having for example from 1 to 10 carbon atoms. Mention may also be made, for example, of LCO (Light Cycle Oil) or HCO (Heavy Cycle Oil) cuts such as 180 - 365 ° C or 320 - 500 ° C cuts, for example from catalytic cracking, LCO cuts or HCO at least partially hydrogenated, and polyaromatic cuts possibly at least partially hydrogenated; the hydrocarbon fractions used as hydrogen donor are usually those which contain at least 0.8% by weight and preferably at least 1.25% by weight of transferable (or transferable) hydrogen such as for example those mentioned in the patent US-A-4425224.
Comme exemples spécifiques de composés donneur d'hydrogène on peut citer le tétrahydronaphtalène ou tétraline (TN), les dihydroanthracènes, les tétrahydroanthracènes, les dihydrobenzoanthracènes et les dihydrodibenzoanthracènes. La quantité de donneur d'hydrogène employée est habituellement de 10 à 400 % en poids, de préférence de 30 à 200 % en poids et le plus souvent de 40 à 150 % en poids par rapport au poids de la charge à traiter.As specific examples of hydrogen donor compounds, mention may be made of tetrahydronaphthalene or tetralin (TN), dihydroanthracenes, tetrahydroanthracenes, dihydrobenzoanthracenes and dihydrodibenzoanthracenes. The amount of hydrogen donor used is usually from 10 to 400% by weight, preferably from 30 to 200% by weight and most often from 40 to 150% by weight relative to the weight of the feed to be treated.
L'effet de synergie de l'action du polysulfure et du donneur d'hydrogène est particulièrement important lorsque la quantité de polysulfure employée exprimée en pour-cent poids de soufre par rapport à la charge à traiter est de 2,56 à 9, 6 % et que la quantité de donneur d'hydrogène est de 30 à 200 % en poids et plus particulièrement de 40 à 150 % en poids par rapport à la charge à traiter.The synergistic effect of the action of the polysulphide and of the hydrogen donor is particularly important when the quantity of polysulphide used expressed in weight percent of sulfur relative to the charge to be treated is from 2.56 to 9.6 % and that the amount of hydrogen donor is 30 to 200% by weight and more particularly 40 to 150% by weight relative to the charge to be treated.
L'invention s'applique à divers traitements thermiques de charges hydrocarbonées ayant habituellement une viscosité comprise entre environ 600 et 70 000 mPa x s à 100 °C et le plus souvent entre environ 1000 et 30 000 mPa x s à 100 °C. L'invention s'applique en particulier à la viscoréduction et à l'hydroviscoréduction de résidus de distillation, par exemple de résidus de distillation sous vide (RSV) ou de distillation atmosphérique. La viscoréduction est habituellement effectuée à des températures d'environ 350 à 500 °C, de préférence d'environ 380 à 450 °C et le plus souvent d'environ 410 à 450 °C et l'hydroviscoréduction à des températures du même ordre de grandeur.The invention applies to various heat treatments of hydrocarbon feedstocks usually having a viscosity of between approximately 600 and 70,000 mPa xs at 100 ° C and most often between approximately 1000 and 30,000 mPa xs at 100 ° C. The invention applies in particular to visbreaking and hydroviscoreduction of distillation residues, for example residues of vacuum distillation (RSV) or atmospheric distillation. The visbreaking is usually carried out at temperatures of about 350 to 500 ° C, preferably about 380 to 450 ° C and most often about 410 to 450 ° C and the hydroviscoreduction at temperatures of the same order of greatness.
La pression totale est habituellement d'environ 1 MPa à 20 MPa aux températures de traitement et le temps de séjour est habituellement d'environ 1 minute à 3 heures.The total pressure is usually about 1 MPa to 20 MPa at processing temperatures and the residence time is usually about 1 minute to 3 hours.
Dans le cas de la viscoréduction, le traitement thermique est habituellement effectué sous atmosphère inerte par exemple sous argon, hélium ou azote ou sous atmosphère de vapeur d'eau ou d'un mélange de vapeur d'eau et de gaz inerte.In the case of visbreaking, the heat treatment is usually carried out under an inert atmosphere, for example under argon, helium or nitrogen or under an atmosphere of water vapor or of a mixture of water vapor and inert gas.
Dans le cas de l'hydroviscoréduction le traitement thermique est effectué en présence d'hydrogène, de préférence sensiblement pur ou d'un mélange d'hydrogène sensiblement pur et de gaz inerte, bien qu'il soit également possible d'utiliser de l'hydrogène industriel contenant par exemple moins d'environ 5 % en volume d'hydrogène sulfuré et de préférence moins d'environ 2,5 % en volume d'hydrogène sulfuré.In the case of hydroviscoreduction, the heat treatment is carried out in the presence of hydrogen, preferably substantially pure, or a mixture of substantially pure hydrogen and inert gas, although it is also possible to use industrial hydrogen containing for example less than about 5% by volume of hydrogen sulfide and preferably less than about 2.5% by volume of hydrogen sulfide.
L'invention concerne également une composition pour la mise en oeuvre du procédé selon la présente invention, comprenant d'une part au moins un polysulfure tel que défini ci-avant et d'autre part au moins un composé donneur d'hydrogène.The invention also relates to a composition for carrying out the process according to the present invention, comprising on the one hand at least one polysulfide as defined above and on the other hand at least one hydrogen donor compound.
Le rapport pondéral du donneur d'hydrogène par rapport au polysulfure dans ladite composition est habituellement d'environ 0,3 : 1 à 1250 : 1, de préférence d'environ 1,87 : 1 à 125 : 1 et le plus souvent d'environ 4,2 : 1 à 58,6 : 1.The weight ratio of the hydrogen donor to the polysulfide in said composition is usually from about 0.3: 1 to 1250: 1, preferably from about 1.87: 1 to 125: 1 and most often from about 4.2: 1 to 58.6: 1.
La proportion pondérale de la composition introduite dans la charge devant subir le traitement thermique est habituellement d'environ 10,3 à 432 parties pour 100 parties de la charge à traiter consistant, par exemple, en une fraction lourde de pétrole, de préférence d'environ 31,6 à 216 parties pour 100 parties de ladite charge et le plus souvent d'environ 42,6 à 159,6 parties pour 100 parties de ladite charge.The proportion by weight of the composition introduced into the filler to be subjected to the heat treatment is usually about 10.3 to 432 parts per 100 parts of the filler to be treated, consisting, for example, of a heavy fraction of petroleum, preferably of about 31.6 to 216 parts per 100 parts of said load and most often about 42.6 to 159.6 parts per 100 parts of said load.
Les exemples suivants illustrent l'invention et ne doivent en aucune manière être considérés comme limitatifs.The following examples illustrate the invention and should in no way be taken as limiting.
Les exemples 1, 2, 3, 7, 9, 10, 11, et 15 sont donnés à titre comparatif et ne font pas partie de l'invention.Examples 1, 2, 3, 7, 9, 10, 11, and 15 are given for comparison and do not form part of the invention.
Les exemples 1 à 16 ont été réalisés en discontinu (batch). Les exemples 1 à 8 concernent la viscoréduction, d'un résidu sous vide, effectuée sous argon et les exemples 9 à 16 concernent l'hydroviscoréduction, effectuée en présence d'hydrogène sensiblement pur, de la même charge.Examples 1 to 16 were carried out batchwise. Examples 1 to 8 relate to visbreaking, of a residue under vacuum, carried out under argon and Examples 9 to 16 relate to hydroviscoreduction, carried out in the presence of substantially pure hydrogen, of the same charge.
La charge hydrocarbonée utilisée dans les exemples est un résidu sous vide (RSV) 500 °C⁺ d'origine SAFANIYA dont les caractéristiques sont données dans le Tableau 1 ci-après.
Le résidu sous vide non traité et la fraction liquide résultant de la viscoréduction ou de l'hydroviscoréduction ont été analysés par pyroanalyse. Cette méthode comprend les étapes suivantes :
- on chauffe l'échantillon sous atmosphère inerte jusqu'à une température T1, puis après un palier à la température T1, on chauffe l'échantillon jusqu'à une température T2 que l'on maintient un certain temps. On réalise une combustion des effluents de chauffage par un mélange de gaz (Hélium + 3 % d'oxygène en volume (He + 3 % O₂)) en présence d'un catalyseur d'oxydation (CuO) ; les composés d'oxydation, notamment CO₂, sont détectés par exemple par un détecteur à infrarouge ; et
- le résidu restant après chauffage en atmosphère inerte est à son tour oxydé avec le même mélange (He + 3 % O₂) jusqu'à une température T3 et, après passage sur un catalyseur CuO, les composés d'oxydation du résidu (carbone résiduel) sont détectés par le même type de détecteur et les signaux traités par un calculateur.
- the sample is heated under an inert atmosphere to a temperature T1, then after a plateau at the temperature T1, the sample is heated to a temperature T2 which is maintained for a certain time. Combustion of the heating effluents is carried out with a mixture of gases (helium + 3% oxygen by volume (He + 3% O₂)) in the presence of an oxidation catalyst (CuO); the oxidation compounds, in particular CO₂, are detected for example by an infrared detector; and
- the residue remaining after heating in an inert atmosphere is in turn oxidized with the same mixture (He + 3% O₂) up to a temperature T3 and, after passing through a CuO catalyst, the oxidation compounds of the residue (residual carbon) are detected by the same type of detector and the signals processed by a computer.
Le profil de température de chauffage illustré par la Figure 1 est le suivant :
VA = VC = 20 °C/minute ; VE = 150 °C/minute
tA = 11 minutes, tB = 10 minutes, tC = 14 minutes, tD = 10 minutes,
tE = 2 minutes et tF = 10 minutes.The heating temperature profile illustrated in Figure 1 is as follows:
VA = VC = 20 ° C / minute; VE = 150 ° C / minute
tA = 11 minutes, tB = 10 minutes, tC = 14 minutes, tD = 10 minutes,
tE = 2 minutes and tF = 10 minutes.
Le point P1 correspond au n-alcane étalon chauffé dans les mêmes conditions et dont le point d'ébullition est d'environ 500°C. A partir du point P2 s'effectue la combustion du résidu riche en carbone. Un étalonnage est également effectué à l'aide d'un pétrole brut dont on connait la distillation simulée.The point P1 corresponds to the standard n-alkane heated under the same conditions and whose boiling point is approximately 500 ° C. From point P2, the carbon rich residue is burned. A calibration is also carried out using crude oil, the simulated distillation of which is known.
Le pyrogramme obtenu (Figure 2) délivre la concentration en CO₂ en fonction du temps et de la température du four. On peut ainsi facilement fractionner le pyrogramme par intégration du signal entre des valeurs de température choisies par exemple selon les fractions ci-dessous. Dans le cas du résidu sous vide non traité les pourcentages des diverses fractions sont indiqués ci-après :
La fraction F2 représente la fraction 500 °C à fin de distillation (FD).The F2 fraction represents the 500 ° C fraction at the end of distillation (FD).
Par étalonnage de la réponse du détecteur il est facile d'obtenir les poids de carbone correspondant aux fractions ci-dessus. De la même manière, les pourcentages et poids d'hydrogène et de soufre contenus dans l'échantilon sont obtenus en simultanéité avec ceux du carbone.By calibrating the response of the detector it is easy to obtain the carbon weights corresponding to the above fractions. Similarly, the percentages and weights of hydrogen and sulfur contained in the sample are obtained simultaneously with those of carbon.
L'analyse centésimale des charges soumises à hydroviscoréduction montre que la somme des poids de C, H et S est toujours supérieure ou égale à 95 %. Par conséquent la simple addition de ces poids permet d'obtenir avec suffisamment de précision les pourcentages respectifs réels des diverses fractions ci-dessus de la fraction liquide.The centesimal analysis of the charges subjected to hydroviscoreduction shows that the sum of the weights of C, H and S is always greater than or equal to 95%. Consequently, the simple addition of these weights makes it possible to obtain with sufficient precision the actual respective percentages of the various above fractions of the liquid fraction.
Cette méthode d'analyse est utilisée pour tous les exemples 1 à 16.This analysis method is used for all examples 1 to 16.
Les concentrations en poids de polysulfures sont telles que le taux de soufre introduit par rapport à la charge à traiter est égal à 0,2 atome-gramme de soufre pour 100 g de RSV SAFANIYA dans les exemples 3 à 6,8,11 à 12B et 16.The concentrations by weight of polysulphides are such that the level of sulfur introduced with respect to the charge to be treated is equal to 0.2 gram atom of sulfur per 100 g of RSV SAFANIYA in examples 3 to 6,8,11 to 12B and 16.
La charge pétrolière (RSV SAFANIYA) après un léger chauffage (100 -120 °C) pour la rendre moins visqueuse, est introduite dans le réacteur qui est un autoclave en acier inox dans le cas des exemples 1 à 16. L'ensemble est constamment agité. Les additifs éventuels sont ajoutés après refroidissement.The petroleum charge (RSV SAFANIYA) after slight heating (100 -120 ° C) to make it less viscous, is introduced into the reactor which is a stainless steel autoclave in the case of examples 1 to 16. The whole is constantly restless. Any additives are added after cooling.
Tous les exemples 1 à 16 de viscoréduction et d'hydroviscoréduction ont été réalisés sous une pression initiale (à 20 °C) de 5 MPa, à forte sévérité, à 430 °C pendant 15 minutes, après un temps de montée à la température du traitement thermique de 25 minutes environ.All of the examples 1 to 16 of visbreaking and visbreaking were carried out under an initial pressure (at 20 ° C.) of 5 MPa, at high severity, at 430 ° C. for 15 minutes, after a time for the temperature to rise. heat treatment of approximately 25 minutes.
Les concentrations choisies à titre d'exemple en diluant donneur d'hydrogène (DDH) sont telles que le rapport pondéral RSV/DDH soit égal à 1.The concentrations chosen by way of example as a hydrogen donor diluent (DDH) are such that the weight ratio RSV / DDH is equal to 1.
En présence simultanément de DDH et de polysulfure, les concentrations pondérales de chacun de ses additifs par rapport au RSV sont identiques à celles utilisées avec les additifs seuls.In the presence of DDH and polysulphide simultaneously, the weight concentrations of each of its additives with respect to RSV are identical to those used with the additives alone.
Après le traitement de viscoréduction ou d'hydroviscoréduction, on obtient généralement un système susceptible d'être polyphasique :
- une phase solide, le coke,
- une phase liquide contenant une partie des produits initiaux ou des produits de craquage, et
- une phase gazeuse.
- a solid phase, coke,
- a liquid phase containing part of the initial products or of the cracking products, and
- a gas phase.
Les produits liquides et le coke éventuel sont recueillis directement ou par dissolution dans le benzène, cette opération étant suivie d'une évaporation ; les gaz ne sont pas récupérés mais sont calculés par différence entre les quantités introduites et recueillies.The liquid products and any coke are collected directly or by dissolution in benzene, this operation being followed by evaporation; the gases are not recovered but are calculated by difference between the quantities introduced and collected.
Le coke est défini comme étant la partie insoluble dans le benzène chaud. Un dosage est effectué pour chaque essai. La quantité de liquide est calculée après détermination du taux de coke.Coke is defined as the part insoluble in hot benzene. An assay is carried out for each test. The amount of liquid is calculated after determining the coke level.
Les taux de gaz, liquide et coke sont exprimés par rapport au pétrole seul ou par rapport au mélange pétrole + DDH, après déduction des additifs polysulfurés le cas échéant. On suppose donc implicitement que l'additif, même s'il subit des modifications importantes pendant la pyrolyse, peut être récupéré majoritairement dans la fraction liquide (cas par exemple de la tétraline, du LCO et du diphényldisulfure) ou dans la phase gazeuse (cas du diméthyldisulfure).The gas, liquid and coke rates are expressed in relation to petroleum alone or in relation to the petroleum + DDH mixture, after deduction of the polysulfurized additives if applicable. It is therefore implicitly assumed that the additive, even if it undergoes significant modifications during pyrolysis, can be recovered mainly in the liquid fraction (case for example of tetralin, LCO and diphenyldisulfide) or in the gas phase (case dimethyldisulfide).
A titre d'exemple le calcul de la conversion globale est détaillé ci-après dans le cas de l'exemple 12. Ce calcul tient compte de la conversion complète du DMDS en une fraction gazeuse (H₂S + CH₄) déductible du poids de la fraction gazeuse totale obtenue après le traitement d'hydroviscoréduction.As an example, the calculation of the overall conversion is detailed below in the case of Example 12. This calculation takes into account the complete conversion of the DMDS into a gaseous fraction (H₂S + CH₄) deductible from the weight of the fraction total gaseous obtained after the hydroviscoreduction treatment.
La charge soumise à l'hydroviscoréduction comprend 47,6 g de RSV SAFANIYA, 47,6 g de tétraline et 4,8 g de DMDS, soit 100 g de matière brute soumise au traitement thermique.The charge subjected to the hydroviscoreduction comprises 47.6 g of RSV SAFANIYA, 47.6 g of tetralin and 4.8 g of DMDS, ie 100 g of raw material subjected to the heat treatment.
Après traitement on isole 0,7 g de coke (insoluble au benzène de la fraction liquide) et 94,2 g de fraction liquide globale. Par différence à 100 g on déduit le poids de la fraction gazeuse globale soit 5,1 g. Le gaz est composé de H₂S et CH₄ provenant du DMDS soit 4,8 g, par conséquent le poids de la fraction gazeuse formée à partir du RSV est de 0,3 g.After treatment, 0.7 g of coke (insoluble in benzene from the liquid fraction) and 94.2 g of overall liquid fraction are isolated. By difference at 100 g, the weight of the overall gas fraction is deducted, ie 5.1 g. The gas is composed of H₂S and CH₄ from DMDS, ie 4.8 g, therefore the weight of the gaseous fraction formed from RSV is 0.3 g.
La fraction liquide pétrolière est constituée de tétraline et des effluents issus de l'hydroviscoréduction du RSV qui représentent donc 94,2 - 47,6 = 46,6 g.The petroleum liquid fraction consists of tetralin and effluents from the hydroviscoreduction of RSV which therefore represent 94.2 - 47.6 = 46.6 g.
La conversion (Y), donnée dans les tableaux ci-après, est calculée à l'aide de la formule suivante :
La recette est constituée par l'intégralité des produits issus de la viscoréduction ou de l'hydroviscoréduction (gaz + liquide + solide (coke)).The recipe consists of all of the products from visbreaking or hydroviscoreduction (gas + liquid + solid (coke)).
Le pourcentage 500 °C⁺ (% 500 °C⁺) de la recette contient donc la fraction 500 °C⁺ liquide de la partie liquide de la recette et éventuellement le coke formé lors du traitement thermique.The 500 ° C⁺ percentage (% 500 ° C⁺) of the recipe therefore contains the 500 ° C⁺ liquid fraction of the liquid part of the recipe and possibly the coke formed during the heat treatment.
Le pourcentage 500 °C⁻ (% 500 °C⁻) de la recette contient les gaz formés et la fraction 500 °C⁻ liquide de la partie liquide de la recette.The 500 ° C⁻ percentage (% 500 ° C⁻) of the recipe contains the gases formed and the 500 ° C⁻ liquid fraction of the liquid part of the recipe.
Si l'on désigne par G, L et C respectivement le pourcentage de gaz, de liquide et de coke de la recette (G + L + C = 100 % de la recette) la conversion Y s'exprime alors par la formule suivante :
L'analyse de la partie liquide de la recette est effectuée par pyroanalyse comme expliqué ci-avant.The analysis of the liquid part of the recipe is carried out by pyroanalysis as explained above.
Pour effectuer les calculs, il s'agit donc de convertir les différents pourcentages pondéraux en pourcentages de carbone. La différence entre le poids usuel et le poids de carbone est faible lorsque l'additif introduit contient une forte proportion de carbone (cas de la tétraline : teneur en carbone : 90,91 %) mais elle ne l'est plus lorsque l'on introduit un additif comme par exemple le diméthyldisulfure (DMDS : teneur en carbone 25,0 %).To perform the calculations, it is therefore a question of converting the various weight percentages into percentages of carbon. The difference between the usual weight and the weight of carbon is small when the additive introduced contains a high proportion of carbon (case of tetralin: carbon content: 90.91%) but it is no longer so when introduces an additive such as for example dimethyldisulfide (DMDS: carbon content 25.0%).
La composition en carbone de la charge de départ est ainsi calculée en déduisant le polysulfure introduit (cas de l'exemple 12 : DMDS) :
RSV = 47,6 % x 83,27 % = 39,64
Tétraline (TN) = 47, 6 % x 90,91 % = 43,27
soit une répartition en % poids de carbone pour la charge de :
RSV = 39,64/(39,64 + 43,27) = 47,8 %
TN = 43,27/(39,64 + 43,27)= 52,2 %.The carbon composition of the starting charge is thus calculated in deducing the polysulphide introduced (case of Example 12: DMDS):
RSV = 47.6% x 83.27% = 39.64
Tetralin (TN) = 47.6% x 90.91% = 43.27
or a distribution in% weight of carbon for the charge of:
RSV = 39.64 / (39.64 + 43.27) = 47.8%
TN = 43.27 / (39.64 + 43.27) = 52.2%.
La distribution en fractions 500 °C⁻, 500 °C⁺ distillable, et carbone résiduel du RSV non traité, analysé par pyroanalyse et exprimé en % poids de carbone est de :
500 °C⁻ : 6 %
500 °C⁺ distillable (FD) : 78 %
Carbone résiduel (R) = 16 %.The distribution in
500 ° C⁻: 6%
500 ° C⁺ distillable (FD): 78%
Residual carbon (R) = 16%.
La distribution de la charge en % poids de carbone dans le cas de l'exemple 12 est donc :
500 °C⁻ = 52,2 + 47,8 x 6 % = 55,1 %
500 °C⁺ (FD) = 47,8 x 78 % = 37,3 %
R = 47,8 x 16 = 7,6 %.The distribution of the charge in% weight of carbon in the case of Example 12 is therefore:
500 ° C⁻ = 52.2 + 47.8 x 6% = 55.1%
500 ° C⁺ (FD) = 47.8 x 78% = 37.3%
R = 47.8 x 16 = 7.6%.
L'analyse de la recette, dans le cas de l'exemple 12, par pyroanalyse fournit, en déduisant le DMDS les résultats suivants :
L'analyse de la partie liquide de la recette, dont les fractions représentent 100 % par pyroanalyse, donne les résultats suivants :
500 °C⁻ = 78,8 %
500 °C⁺ (FD) = 15,1 %
Carbone résiduel (R) = 6,1 %.The analysis of the liquid part of the recipe, whose fractions represent 100% by pyroanalysis, gives the following results:
500 ° C⁻ = 78.8%
500 ° C⁺ (FD) = 15.1%
Residual carbon (R) = 6.1%.
La conversion (Y) de la fraction 500 °C⁺ de la charge, dans le cas de l'exemple 12, en fraction 500 °C⁻ est donc de :
Le Tableau 2 résume les résultats des exemples 1 à 8 effectués sous une pression initiale d'argon de 5 MPa à 430 °C (viscoréduction).Table 2 summarizes the results of Examples 1 to 8 carried out under an initial argon pressure of 5 MPa at 430 ° C (visbreaking).
Le Tableau 3 résume les résultats des exemples 9 à 16 effectués sous une pression initiale d'hydrogène de 5 MPa à 430 °C (hydroviscoréduction).Table 3 summarizes the results of Examples 9 to 16 carried out under an initial hydrogen pressure of 5 MPa at 430 ° C (water reduction).
Le Tableau 4 donne les caractéristiques d'un LCO non hydrogéné provenant du craquage catalytique utilisé comme donneur d'hydrogène dans les exemples 7, 8, 15 et 16.Table 4 gives the characteristics of a non-hydrogenated LCO originating from the catalytic cracking used as hydrogen donor in Examples 7, 8, 15 and 16.
Le tableau 5 compare à une faible température de conversion l'action du thiophénol et l'action du diméthyldisulfure en présence de donneur d'hydrogène.Table 5 compares at a low conversion temperature the action of thiophenol and the action of dimethyldisulfide in the presence of hydrogen donor.
On constate à la lecture des résultats présentés dans les Tableaux 2 et 3 que l'association d'un polysulfure organique DMDS et d'un donneur d'hydrogène (TN ou LCO) permet d'obtenir (exemples 4, 8, 12 et 16) des quantités de coke très voisines de celles obtenues avec la tétraline comme seul additif (exemples 2 et 10) mais en ayant une conversion bien plus élevée (13 et 18 points de plus, respectivement dans le cas de l'exemple 2 comparé à l'exemple 4 et de l'exemple 10 comparé à l'exemple 12).It is noted on reading the results presented in Tables 2 and 3 that the combination of an organic polysulphide DMDS and a hydrogen donor (TN or LCO) makes it possible to obtain (examples 4, 8, 12 and 16 ) quantities of coke very close to those obtained with tetralin as the only additive (examples 2 and 10) but with a much higher conversion (13 and 18 points more, respectively in the case of example 2 compared to l (Example 4 and Example 10 compared to Example 12).
Les exemples 12 A et 12 B font apparaître que le ditertiobutylpentasulfure donne en association avec la tetraline un résultat sensiblement similaire à celui de l'exemple 12, avec quelques points de conversion en moins.Examples 12 A and 12 B show that the ditertiobutylpentasulfide gives in combination with tetralin a result substantially similar to that of Example 12, with a few points of conversion.
Les exemples 12 C et 12 D sont donnés à titre comparatif et montrent que l'exemple 12 selon l'invention donne de meilleurs résultats que l'exemple 12 D selon l'art antérieur en présence de diméthyldisulfure seul et de naphténate de molybdène comme catalyseur.Examples 12 C and 12 D are given for comparison and show that Example 12 according to the invention gives better results than Example 12 D according to the prior art in the presence of dimethyldisulfide alone and molybdenum naphthenate as catalyst. .
Ces résultats montrent bien l'intérêt de l'association d'un donneur d'hydrogène et d'un polysulfure organique qui permet lors de la conversion thermique de garder l'avantage obtenu par addition du donneur d'hydrogène à la charge (formation de coke réduite, voir exemples 2 et 10, tout en conservant la majeure partie de l'avantage obtenu par addition de polysulfure (conversion élevée) sans en avoir l'inconvénient (formation de coke très élevée, voir exemples 3 et 11).These results clearly show the advantage of the association of a hydrogen donor and an organic polysulfide which allows during the thermal conversion to keep the advantage obtained by adding the hydrogen donor to the charge (formation of reduced coke, see examples 2 and 10, while retaining most of the advantage obtained by adding polysulphide (high conversion) without having the disadvantage (very high coke formation, see examples 3 and 11).
Dans le cas de l'utilisation d'un LCO, non hydrogéné au préalable, on constate que l'emploi en association de ce LCO et d'un polysulfure organique (exemples 8 et 16) permet d'obtenir une conversion plus élevée que lors de l'emploi du même LCO seul (exemples 7 et 15). Cette utilisation simultanée ne conduit pas à une augmentation excessive de la formation de coke à laquelle on aurait pu s'attendre en raison de l'utilisation d'un polysulfure organique (voir exemple 3 et 11).
Les exemples 17 à 21 illustrent une conversion effectuée sur le même résidu Safaniya sous pression d'hydrogène 5 MPa initiale à 390° C pendant 15 minutes. Une étude comparative est réalisée entre le thiophénol (art antérieur), le diméthyldisulfure et le ditertiobutylpentasulfure (X) en présence de tétrahydronaphtalène (TN) et présentée dans le tableau 5 où les symboles sont les mêmes que ceux utilisés dans les tableaux précédents. L'association tétraline-polysulfures selon l'invention donne de meilleurs résultats.
Les exemples 22 à 25 ont été réalisés dans un micropilote, sous une pression de 10 MPa d'hydrogène sensiblement pur, en continu, dans les conditions suivantes :
Température : 450 °C
Temps de séjour de la charge : 1 heure
Débit d'hydrogène : 1,1 l/minute à température et pression normales
Débit de charge liquide : 5 ml/minute.Examples 22 to 25 were carried out in a micropilot, under a pressure of 10 MPa of substantially pure hydrogen, continuously, under the following conditions:
Temperature: 450 ° C
Charge residence time: 1 hour
Hydrogen flow: 1.1 l / minute at normal temperature and pressure
Liquid charge flow: 5 ml / minute.
La charge utilisée est la même que celle employée dans les exemples 1 à 21. La méthode d'analyse utilisée dans les exemples 22 à 25 est la même que celle utilisée dans les exemples 1 à 21.The charge used is the same as that used in Examples 1 to 21. The analysis method used in Examples 22 to 25 is the same as that used in Examples 1 to 21.
Les concentrations en poids de polysulfures sont telles que le taux de soufre introduit par rapport à la charge à traiter est égal à 0,2 atome-gramme de soufre pour 100 g de RSV SAFANIYA dans l'exemple 19 et à 0,1 atome-gramme de soufre dans les exemples 23 et 25.The concentrations by weight of polysulphides are such that the level of sulfur introduced with respect to the charge to be treated is equal to 0.2 gram-atom of sulfur per 100 g of RSV SAFANIYA in Example 19 and to 0.1 atom- gram of sulfur in Examples 23 and 25.
Les résultats obtenus sont présentés dans le Tableau 6 ci-après, ils confirment les résultats obtenus en batch dans les exemples 1 à 21 et montrent l'avantage obtenu par l'association de polysulfure et de donneur d'hydrogène permettant l'augmentation de la conversion par rapport au cas de l'utilisation d'un donneur d'hydrogène seul.
Claims (15)
- A process for the thermal conversion of a hydrocarbon charge characterised in that said charge is subjected to a heat treatment in the presence of at least one polysulphide selected from the group formed by hydrogen polysulphides, aliphatic polysulphides and alicyclic polysulphides, and at least one hydrogen donor selected from the group formed by at least partially hydrogenated derivatives of naphthalene, anthracene, pyrene, fluoranthene, benzoanthracene, dibenzoanthracene, coronene, perylene, benzopyrene, their analogue heterocyclic derivatives, their analogue derivatives which are substituted by at least one lower alkyl radical, LCO and/or HCO cuts, at least partially hydrogenated LCO and/or HCO cuts, polyaromatic cuts and at least partially hydrogenated polyaromatic cuts.
- A process according to claim 1 wherein the polysulphide is a compound of the formula (I) R¹ - (S)n - R² in which R¹ and R² which are identical or different each represent a hydrogen atom or a branched or straight chain saturated or unsaturated aliphatic hydrocarbon radical or an alicyclic hydrocarbon radical, and n is a number between 2 and 20 inclusive.
- A process according to claim 1 or claim 2 wherein the polysulphide comprises from 2 to 72 carbon atoms in its molecule.
- A process according to one of claims 1 to 3 wherein the polysulphide is an aliphatic and/or alicyclic disulphide.
- A process according to one of claims 1 to 4 wherein the polysulphide is a dialkyl disulphide having from 2 to 48 carbon atoms in its molecule.
- A process according to one of claims 1 to 4 wherein the polysulphide is selected from the group formed by dimethyldisulphide, diethyldisulphide, dipropyldisulphides, dibutyldisulphides, ditertiododecyclpolysulphide (n = 5), ditertiononylpolysulphide (n = 5) and ditertiobutylpolysulphide (n = 5).
- A process according to one of claims 1 to 6 wherein the polysulphides result from the oxidation of mercaptans contained in LPG petroleum cuts and gasoline.
- A process according to one of claims 1 to 7 wherein the amount of polysulphide used is from 0.32% to 32% by weight of sulphur with respect to the charge to be treated.
- A process according to one of claims 1 to 8 wherein the hydrocarbon cuts contain at least 0.8% by weight of hydrogen which is capable of being given.
- A process according to one of claims 1 to 9 wherein the hydrogen donor is selected from the group formed by tetrahydronaphthalene, dihydroanthracenes, tetrahydroanthracenes, dihydrobenzoanthracenes, dihydrodibenzoanthracenes and an LCO cut (180 - 365 °C).
- A process according to one of claims 1 to 10 wherein the amount of hydrogen donor used is from 10 to 400% by weight with respect to the charge to be treated.
- A process according to one of claims 1 to 11 characterised in that said heat treatment comprises viscoreduction or hydroviscoreduction.
- A composition which can be used for carrying out the process according to one of claim 1 to 12 characterised in that it comprises on the one hand at least one polysulphide selected from the group formed by hydrogen polysulphides and aliphatic or alicyclic hydrocarbon polysulphides and on the other hand at least one hydrogen donor compound selected from the group formed by the at least partially hydrogenated derivatives of naphthalene, anthracene, pyrene, fluoranthene, benzoanthracene, dibenzoanthracene, coronene, perylene, benzopyrene, their analogue heterocyclic derivatives, their analogue derivatives which are substituted by at least one lower alkyl radical, LCO and/or HCO cuts, at least partially hydrogenated LCO and/or HCO cuts, polyaromatic cuts and at least partially hydrogenated polyaromatic cuts, which cuts may contain at least 0.8% of hydrogen which is capable of being given.
- A composition according to claim 13 wherein the polysulphide is a dialkyl disulphide having from 2 to 48 carbon atoms in its molecule.
- A composition according to claim 13 or claim 14 wherein the weight ratio of the hydrogen donor compound to the polysulphide is about 0.3:1 to 1250:1.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR8803272 | 1988-03-14 | ||
FR8803272A FR2628437B1 (en) | 1988-03-14 | 1988-03-14 | PROCESS FOR THE HEAT TREATMENT OF HYDROCARBON CHARGES IN THE PRESENCE OF POLYSULFIDES AND HYDROGEN DONORS |
Publications (2)
Publication Number | Publication Date |
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EP0333554A1 EP0333554A1 (en) | 1989-09-20 |
EP0333554B1 true EP0333554B1 (en) | 1992-09-02 |
Family
ID=9364225
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP19890400625 Expired - Lifetime EP0333554B1 (en) | 1988-03-14 | 1989-03-06 | Thermal-treatment process of hydrocarbon feeds in the presence of polysulfides and hydrogen donors |
Country Status (3)
Country | Link |
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EP (1) | EP0333554B1 (en) |
DE (1) | DE68902663T2 (en) |
FR (1) | FR2628437B1 (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
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FR2912757B1 (en) | 2007-02-20 | 2010-11-19 | Arkema France | ADDITIVE FOR REDUCING COKAGE AND / OR CARBON MONOXIDE IN CRACK REACTORS AND HEAT EXCHANGERS, USE THEREOF |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
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US4443330A (en) * | 1981-06-01 | 1984-04-17 | Hri, Inc. | Catalyst activity in coal liquid upgrading |
FR2555192B1 (en) * | 1983-11-21 | 1987-06-12 | Elf France | PROCESS FOR THE HEAT TREATMENT OF HYDROCARBON FILLERS IN THE PRESENCE OF ADDITIVES THAT REDUCE COKE FORMATION |
AU580617B2 (en) * | 1984-09-10 | 1989-01-19 | Mobil Oil Corporation | Process for visbreaking resids in the presence of hydrogen- donor materials and organic sulfur compounds |
FR2607145B1 (en) * | 1986-11-25 | 1990-06-08 | Inst Francais Du Petrole | IMPROVED PROCESS FOR THE THERMAL CONVERSION OF HEAVY OIL FRACTIONS AND REFINING RESIDUES IN THE PRESENCE OF OXYGEN COMPOUNDS OF SULFUR, NITROGEN OR PHOSPHORUS |
-
1988
- 1988-03-14 FR FR8803272A patent/FR2628437B1/en not_active Expired - Fee Related
-
1989
- 1989-03-06 DE DE1989602663 patent/DE68902663T2/en not_active Expired - Fee Related
- 1989-03-06 EP EP19890400625 patent/EP0333554B1/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
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FR2628437B1 (en) | 1992-12-31 |
DE68902663D1 (en) | 1992-10-08 |
EP0333554A1 (en) | 1989-09-20 |
FR2628437A1 (en) | 1989-09-15 |
DE68902663T2 (en) | 1993-03-25 |
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