EP0333554A1 - Thermische Behandlungsverfahren von Kohlenwasserstoffeinsätzen in Gegenwart von Polysulfiden und wasserstoffabgebenden Substanzen - Google Patents

Thermische Behandlungsverfahren von Kohlenwasserstoffeinsätzen in Gegenwart von Polysulfiden und wasserstoffabgebenden Substanzen Download PDF

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Publication number
EP0333554A1
EP0333554A1 EP89400625A EP89400625A EP0333554A1 EP 0333554 A1 EP0333554 A1 EP 0333554A1 EP 89400625 A EP89400625 A EP 89400625A EP 89400625 A EP89400625 A EP 89400625A EP 0333554 A1 EP0333554 A1 EP 0333554A1
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EP
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Prior art keywords
polysulfide
hydrogen
polysulfides
cuts
hydrogen donor
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EP89400625A
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English (en)
French (fr)
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EP0333554B1 (de
Inventor
Pierre Le Perchec
Bernard Fixari
Michel Thomas
Louis Lena
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IFP Energies Nouvelles IFPEN
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IFP Energies Nouvelles IFPEN
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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 heat 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 is noted, moreover, on reading the Table of 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 polysulfide used in the present invention is usually a compound of formula (I) R 1 - (S) n - R 2 in which R 1 and R 2 , identical or different, each represent a hydrogen atom or a hydrocarbon radical and n is a number between 2 and 20, limits included and preferably between 2 and 8, limits included.
  • R 1 and R 2 independently of one another represent a hydrogen atom, a linear or branched alkyl radical, an aryl radical, an aryl-alkyl (aralkyl) radical or a cycloalkyl radical.
  • polysulphides of formula (I) are used in which at least one of the radicals R 1 and R 2 represents a hydrocarbon radical and preferably those in which R 1 and R 2 , identical or different, each represent a saturated aliphatic radical or unsaturated, linear or branched or an alicyclic radical.
  • the particularly preferred organic polysulphides of formula (I) are those in which R 1 and R 2 , which are identical or different, each represent an alkyl radical; they are hereinafter called dialkyl-polysulfides.
  • dialkyl-polysulfides 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 R 1 and / or R 2 represent an aryl, aralkyl or 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 0 / o 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 thermal treatments of hydrocarbon feedstocks usually having a viscosity of between approximately 600 and 70,000 mPa x s at 100 ° C and most often between approximately 1000 and 30,000 mPaxs 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.
  • RSV vacuum 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 about 0.3 1 to 1250: 1, preferably about 1.87: 1 to 125: 1 and most often 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 the boiling point of which is approximately 500 ° C. From the point P2 the combustion rich in carbon is carried out. A calibration is also carried out using crude oil, the simulated distillation of which is known.
  • the pyrogram obtained ( Figure 2) delivers the C0 2 concentration as a function of the time and temperature of the oven. It is thus easy to split the pyrogram by integration of the signal between temperature values chosen 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 fraction F2 represents the fraction 500 ° C at the end 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 o / o. 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 14 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.
  • Example 12 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 (H 2 S + CH 4 ) deductible from the weight. of the total gas fraction 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.
  • 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 percentage 500 ° C- (% 500 ° C-) of the recipe contains the gases formed and the fraction 500 ° C- liquid 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.
  • 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
  • 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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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
EP19890400625 1988-03-14 1989-03-06 Thermische Behandlungsverfahren von Kohlenwasserstoffeinsätzen in Gegenwart von Polysulfiden und wasserstoffabgebenden Substanzen Expired - Lifetime EP0333554B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8803272A FR2628437B1 (fr) 1988-03-14 1988-03-14 Procede de traitement thermique de charges hydrocarbonees en presence de polysulfures et de donneurs d'hydrogene
FR8803272 1988-03-14

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EP0333554A1 true EP0333554A1 (de) 1989-09-20
EP0333554B1 EP0333554B1 (de) 1992-09-02

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DE (1) DE68902663T2 (de)
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2912757A1 (fr) * 2007-02-20 2008-08-22 Arkema France Additif de reduction du cokage et/ou du monoxyde de carbonne dans les reacteurs de craquage et les echangeurs thermiques, son utilisation

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4443330A (en) * 1981-06-01 1984-04-17 Hri, Inc. Catalyst activity in coal liquid upgrading
FR2555192A1 (fr) * 1983-11-21 1985-05-24 Elf France Procede de traitement thermique de charges hydrocarbonees en presence d'additifs qui diminuent la formation de coke
EP0175511A1 (de) * 1984-09-10 1986-03-26 Mobil Oil Corporation Verfahren zum Viskositätsabbau
EP0269515A1 (de) * 1986-11-25 1988-06-01 Institut Français du Pétrole Verfahren zur thermischen Umwandlung von schweren Erdölfraktionen oder Raffinationsrückständen in Anwesenheit von oxidierten Schwefel- oder Stickstoffverbindungen und diese Verbindungen enthaltende Zusammensetzungen

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4443330A (en) * 1981-06-01 1984-04-17 Hri, Inc. Catalyst activity in coal liquid upgrading
FR2555192A1 (fr) * 1983-11-21 1985-05-24 Elf France Procede de traitement thermique de charges hydrocarbonees en presence d'additifs qui diminuent la formation de coke
EP0175511A1 (de) * 1984-09-10 1986-03-26 Mobil Oil Corporation Verfahren zum Viskositätsabbau
EP0269515A1 (de) * 1986-11-25 1988-06-01 Institut Français du Pétrole Verfahren zur thermischen Umwandlung von schweren Erdölfraktionen oder Raffinationsrückständen in Anwesenheit von oxidierten Schwefel- oder Stickstoffverbindungen und diese Verbindungen enthaltende Zusammensetzungen

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2912757A1 (fr) * 2007-02-20 2008-08-22 Arkema France Additif de reduction du cokage et/ou du monoxyde de carbonne dans les reacteurs de craquage et les echangeurs thermiques, son utilisation
WO2008107622A1 (fr) * 2007-02-20 2008-09-12 Arkema France Additif de reduction du cokage et/ou du monoxyde de carbone dans les reacteurs de craquage et les echangeurs thermiques, son utilisation
US8791314B2 (en) 2007-02-20 2014-07-29 Arkema France Additive for reducing coking and/or carbon monoxide in cracking reactors and heat exhangers and use of same

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DE68902663T2 (de) 1993-03-25
DE68902663D1 (de) 1992-10-08
FR2628437B1 (fr) 1992-12-31
EP0333554B1 (de) 1992-09-02
FR2628437A1 (fr) 1989-09-15

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