EP0068543B1 - Procédé pour la préparation d'un mélange d'hydrocarbures - Google Patents

Procédé pour la préparation d'un mélange d'hydrocarbures Download PDF

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Publication number
EP0068543B1
EP0068543B1 EP19820200689 EP82200689A EP0068543B1 EP 0068543 B1 EP0068543 B1 EP 0068543B1 EP 19820200689 EP19820200689 EP 19820200689 EP 82200689 A EP82200689 A EP 82200689A EP 0068543 B1 EP0068543 B1 EP 0068543B1
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Prior art keywords
rct
residue
experiments
catalytic hydrotreatment
reduction
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EP19820200689
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German (de)
English (en)
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EP0068543A2 (fr
EP0068543A3 (en
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Jacobus Eilers
Willem Hartman Jurriaan Stork
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Shell Internationale Research Maatschappij BV
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Shell Internationale Research Maatschappij BV
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Priority claimed from NL8103067A external-priority patent/NL8103067A/nl
Priority claimed from NL8103121A external-priority patent/NL8103121A/nl
Priority claimed from NL8103396A external-priority patent/NL8103396A/nl
Priority claimed from NL8103576A external-priority patent/NL8103576A/nl
Priority claimed from NL8104326A external-priority patent/NL8104326A/nl
Priority claimed from NL8104327A external-priority patent/NL8104327A/nl
Application filed by Shell Internationale Research Maatschappij BV filed Critical Shell Internationale Research Maatschappij BV
Publication of EP0068543A2 publication Critical patent/EP0068543A2/fr
Publication of EP0068543A3 publication Critical patent/EP0068543A3/en
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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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
    • C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/107—Atmospheric residues having a boiling point of at least about 538 °C

Definitions

  • the invention relates to a process for the preparation of a hydrocarbon mixture having a Ramsbottom Carbon Test Value (RCT) of a%w and an initial boiling point of T 1 °C.
  • RCT Ramsbottom Carbon Test Value
  • the RCT is an important parameter in the assessment of the suitability of heavy hydrocarbon mixtures as feed stocks for catalytic conversion processes, such as catalytic cracking, carried out in the presence or absence of hydrogen, for the preparation of light hydrocarbon distillates, such as gasoline and kerosine. According as the feed has a higher RCT, the catalyst will be deactivated more rapidly in these processes.
  • Residual hydrocarbon mixtures such as residues obtained in the distillation of a crude mineral oil and asphaltic bitumen separated in the solvent deasphalting of the said distillation residues or of residues obtained in the distillation of a hydrotreated residual fraction of a crude mineral oil generally have too high an RCT to be suitable without previous treatment for use as feeds for the above-mentioned catalytic conversion processes. Since the RCT of residual hydrocarbon mixtures is mainly determined by the percentage of asphaltenes present in the mixtures, a reduction of the RCT of these mixtures can be obtained by reducing the asphaltenes content. Basically, this may be achieved in two ways.
  • Part of the asphaltenes may be separated from the mixture by solvent deasphalting, or part of the asphaltenes may be converted by subjecting the mixture to a catalytic hydrotreatment.
  • the latter method is preferred, in the first place, because its yield of heavy product with a low RCT is higher and further because, in contrast to the former method, where asphaltic bitumen is obtained as a by-product, it yields a valuable C 5 + atmospheric distillate as a by-product.
  • yields are low
  • only the latter method is eligible for the preparation of heavy product with a low RCT from asphaltic bitumen or from mixtures of asphaltic bitumen and distillation residue.
  • a drawback to the latter method is that it gives rise to the formation of an undesirable C 4 - fraction which, moreover, contributes considerably to the hydrogen consumption of the process.
  • asphaltic bitumen may be separated by solvent deasphalting that a deasphalted atmospheric residue is obtained which has the desired RCT of a%w.
  • the atmospheric residue may be separated by distillation into a vacuum distillate and a vacuum residue, and from the vacuum residue so much asphaltic bitumen may be separated by solvent deasphalting that a deasphalted vacuum residue is obtained having an RCT which is such that, when this deasphalted vacuum residue is mixed with the previously separated vacuum distillate, an oil is obtained which has the desired RCT of a%w.
  • Go as well as the conditions at which G reaches a value between 1.5 x G e and 2.0 x Go may be read from a graph composed on the basis of a number of catalytic hydrotreatment scouting experiments with the asphaltenes-containing hydrocarbon mixture carried out at different severities and in which the occurring G's have been plotted against the severities applied.
  • the space velocity which is variable
  • the other conditions in the scouting experiments are kept constant and chosen equal to those which will be used when the process is applied in practice.
  • the present patent application therefore relates to a process for the preparation of a hydrocarbon mixture with an RCT of a%w and an initial boiling point of T 1 °C, in which an asphaltenes-containing hydrocarbon mixture is subjected to a catalytic hydrotreatment, the product obained being separated by distillation into an atmospheric distillate and an atmospheric residue having an initial boiling point of T 1 °C, in which either a deasphalted atmospheric residue having the desired RCT of a%w is obtained from the said atmospheric residue by solvent deasphalting, or in which the atmospheric residue is first separated by distillation into a vacuum distillate and a vacuum residue, from which vacuum residue asphaltic bitumen is separated by solvent deasphalting such that a deasphalted vacuum residue is obtained having an RCT such that, when this latter deasphalted vacuum residue is mixed with the said vacuum distillate, a mixture having the desired RCT of a%w is obtained, the catalytic hydrotreatment being carried out under such conditions that the C 4 - production per
  • the process according to the invention is a two-step process in which reduction of the RCT is attained through reduction of the asphaltenes content.
  • the asphaltenes content is reduced by converting part of the asphaltenes by means of a catalytic hydrotreatment.
  • the asphaltenes content is reduced by separating part of the asphaltenes by means of solvent deasphalting.
  • Asphaltenes containing hydrocarbon mixtures usually contain an appreciable percentage of metals, especially vanadium and nickel. When such mixtures are subjected to a catalytic treatment, e.g.
  • asphaltenes-containing hydrocarbon mixtures having a vanadium + nickel content of more than 50 ppmw should preferably be subjected to demetallization before being contacted with the RCT-reduction catalyst.
  • This demetallization may very suitably be carried out by contacting the mixture in the presence of hydrogen, with a catalyst consisting of more than 80%w of silica.
  • Very suitable demetallization catalysts are those which meet certain given requirements as regards their porosity and particle size and which are described in Netherlands Patent Application No. 7309387.
  • a catalytic demetallization in the presence of hydrogen is applied to the hydrocarbon mixture, this demetallization may be carried out in a separate reactor.
  • both processes may very suitably be carried out in the same reactor containing, successively, a bed of demetallization catalyst and a bed of RCT-reduction catalyst.
  • RCT reduction should be taken to be the total RCT reduction occurring in the catalytic hydrotreatment (i.e. including the RCT reduction occurring in a possible catalytic demetallization process).
  • Suitable catalysts for carrying out the catalytic RCT reduction are those which contain at least one metal chosen from the group formed by nickel and cobalt and, in addition, at least one metal chosen from the group formed by molybdenum and tungsten on a carrier, which carrier consists more than 40%w of alumina.
  • Very suitable RCT-reduction catalysts are those which comprise the metal combination nickel/ molybdenum or cobalt/molybdenum on alumina as the carrier.
  • the conditions to be used in a catalytic demetallization process in the presence of hydrogen to be carried out if necessary, the same preference applies as that stated hereinbefore for the catalytic RCT reduction.
  • the desired RCT reduction in the first step of the process according to the invention may, for instance, be achieved by application of the space velocity pertaining to that RCT reduction, which can be read from a graph composed on the basis of a number of catalytic hydrotreatment scouting experiments with the asphaltenes-containing hydrocarbon mixture carried out at different space velocities and in which the RCT reductions achieved have been plotted against the space velocities used.
  • the space velocity which is variable, the other conditions in the scouting experiments are kept constant and chosen equal to those which will be used when the process according to the invention is applied in practice.
  • the second step of the process according to the invention is a solvent deasphalting step applied to a residue from the distillation of the hydrotreated product of the first step.
  • the distillation residue to which the solvent deasphalting step is applied may be an atmospheric residue or a vacuum residue from the hydrotreated product.
  • a vacuum residue from the hydrotreated product is used for the purpose.
  • Suitable solvents for carrying out the solvent deasphalting are paraffinic hydrocarbons having 3-6 carbon atoms per molecule, such as n-butane and mixtures thereof, such as mixtures of propane with n-butane and mixtures of n-butane with n-pentane.
  • Suitable solvent/oil weight ratios lie between 7:1 and 1:1 and in particular between 4:1 and 2:1.
  • the solvent deasphalting is preferably carried out at a pressure between 20 and 100 bar.
  • the deasphalting is preferably carried out at a pressure of 35 ⁇ 45 bar and a temperature of 100-150 0 C.
  • the desired RCT of the deasphalted atmospheric residue may be attained, for instance, by using the deasphalting temperature pertaining to that RCT, which can be read from a graph composed on the basis of a number of deasphalting scouting experiments with the atmospheric residue carried out at different temperatures in which the RCT's of the deasphalted atmospheric residues obtained have been plotted against the temperatures applied.
  • the temperature which is variable, the other conditions in the scouting experiments are kept constant and chosen equal to those which will be used when the process according to the invention is applied in practice.
  • the RCT and the quantity of the deasphalted vacuum residue should be adjusted to the quantity and the RCT of the vacuum distillate as follows.
  • VD vacuum distillate
  • B pbw of deasphalted vacuum residue will have to be prepared, its RCT DVR being such that it obeys the relation: or, expressed otherwise,
  • the left-hand member is known.
  • RCT M is known.
  • a graph can be composed in which the term B(RCTo vR - RCT M ) has been plotted against the temperature used.
  • the temperature to be applied in the deasphalting in the second step of the process according to the invention may be read from this graph, this being the temperature at which the term B(RCT DVR - RCT M ) has the given value A(RCT M - RCT VD ).
  • the other conditions in the scouting experiments on deasphalting are kept constant and chosen equal to those which will be applied when the process according to the invention is used in practice.
  • the metal content is also an important parameter in assessing the suitability of heavy hydrocarbon oils as feeds for catalytic conversion processes, in the presence or absence of hydrogen, for the preparation of light hydrocarbon distillates, such as gasoline and kerosine. According as the feed has a higher metal content, the catalyst will be deactivated more rapidly in these processes. As a rule, residual feed mixtures have not only too high an RCT, but also too high a metal content to be suitable, without treatment, as feeds for the afore-mentioned catalytic conversion processes.
  • the product obtained in the process according to the invention is a deasphalted atmospheric residue or a mixture of a vacuum distillate and a deasphalted vacuum residue, which product, in addition to a low RCT, has a very low metal content.
  • This is due to a considerable extent to the fact that the metal-containing distillation residue which is subjected to solvent deasphalting has been catalytically hydrotreated.
  • the solvent deasphalting of such metal-containing residues shows a very high metal-removing selectivity.
  • asphaltenes-containing hydrocarbon mixtures As asphaltenes-containing hydrocarbon mixtures to be used as feed for the process according to the invention the following six are preferred:
  • a mixture of an asphaltic bitumen I separated in the solvent deasphalting of a residue obtained in the distillation of a crude mineral oil and an asphaltic bitumen II separated in the solvent deasphalting of a residue obtained in the distillation of a hydrotreated residual fraction of a crude mineral oil which mixture comprises less than 50 pbw of asphaltic bitumen II per 100 pbw of asphaltic bitumen I.
  • the average molecular weight M of the asphaltic bitumen I used as feed component in feed 6 as well as the average molecular weight M of the asphaltic bitumen used as feed 3 are determined by ASTM method D 3592-77 using toluene as solvent.
  • the relations 1-6 mentioned above offer an opportunity of determining whether, in view of the maximum acceptable value of G (corresponding to 2.0 x Go), it is possible by catalytic hydrotreatment alone, starting from the feeds 1-6, to prepare a product from which, by distillation, an atmospheric residue can be obtained which has a given initial boiling point of T 1 °C and a given RCT of a%w. If, according to the relations, this proves impossible and, therefore, the combination route has to be applied, the relations further indicate the limits between which, in the catalytic hydrotreatment of the combination route, the RCT reductions should be chosen to ensure optimum efficiency of the combination route.
  • the feeds 4 ⁇ 6 are composed of two blending components.
  • One of these blending components (blending component I) is selected from the group consisting of atmospheric residues obtained in the distillation of a crude mineral oil, vacuum residues obtained in the distillation of a crude mineral oil and asphaltic bitumen separated in the solvent deasphalting of a residue obtained in the distillation of a crude mineral oil.
  • the other blending component (blending component II) is an asphaltic bitumen separated in the solvent deasphalting of a residue obtained in the distillation of a hydrotreated residual fraction of a crude mineral oil. Examples of the latter residual fractions are atmospheric residues and vacuum residues obtained in the distillation of a crude mineral oil and asphaltic bitumen separated in the solvent deasphalting of these residues.
  • a very attractive embodiment of the process according to the invention in which one of the feeds 4-6 is used is that in which the blending component II used as a component of the feed for the first step is the asphaltic bitumen obtained in the solvent deasphalting in the second step.
  • the conditions for attaining the desired RCT reduction in the first step of the process, with recirculation of asphaltic bitumen may be determined as follows. The relation found is used to determine the RCT reduction to be employed in the catalytic hydrotreatment in order to ensure optimum efficiency in the combination process, when blending component I is the only feed used.
  • the space velocity to be used for the purpose is determined on the basis of a number of catalytic hydrotreatment experiments using blending component I as the feed.
  • an oil is prepared which has the desired RCT of a%w and the desired initial boiling point of T i °C, and an asphaltic bitumen (asphaltic bitumen A) is obtained as a by-product.
  • the relation found is used to determine the RCT reduction to be employed in the catalytic hydrotreatment in order to ensure optimum efficiency in the combination process when a mixture of blending component I, and asphaltic bitumen A having the desired ratio r is used as the feed.
  • the space velocity to be used for the purpose is determined on the basis of a number of catalytic hydrotreatment scouting experiments using the mixture of blending component I and asphaltic bitumen A as the feed.
  • Atmospheric residue A had an RCT of 10%w (determined by ASTM method D 524), a vanadium + nickel content of 70 ppmw and a percentage boiling below 520°C of 50%w.
  • Atmospheric residue B had an RCT of 15.6%w (determined by ASTM method D 524), a vanadium + nickel content of 500 ppmw and a percentage boiling below 520°C of 29.4%w.
  • atmospheric residue A was subjected to catalytic hydrotreatment in thirteen experiments.
  • the experiments were carried out in a 1000 ml reactor containing two fixed catalyst beds of a total volume of 600 ml.
  • the first catalyst bed consisted of a Ni/V/SiO 2 catalyst containing 0.5 pbw of nickel and 2.0 pbw of vanadium per 100 pbw of silica.
  • the second catalyst bed consisted of a Co/Mo/Al 2 O 3 catalyst containing 4 pbw of cobalt and 12 pbw of molybdenum per 100 pbw of alumina.
  • the weight ratio between the NiN/Si0 2 and Co/Mo/AI 2 0 3 catalysts was 1:3. All the experiments were carried out at a temperature of 390°C, a pressure of 125 bar and a H 2 /oil ratio of 1000 NI/kg. Various space velocities were used in the experiments. The results of Experiments 1-13 at run hour 450 are listed in Table A.
  • the table gives the space velocity used, the RCT reduction achieved and the corresponding C 4 - production (calculated as %w on feed).
  • Experiments 1-12 were carried out in pairs, the difference in space velocity between the two experiments of each pair being such as to achieve a difference in RCT reduction of about 1.0%.
  • the table further gives the C 4 - production per % RCT reduction (G) for each pair of experiments.
  • the 520°C + vacuum residue was deasphalted with n-butane at a temperature of 115°C, a pressure of 40 bar and a solvent/oil weight ratio of 3:1, and the deasphalted vacuum residue obtained was mixed with the vacuum distillate.
  • the results of this experiment No. 17 according to the invention are given hereinafter.
  • vacuum residue A was subjected to catalytic hydrotreatment in thirteen experiments in a similar way as described for Experiments 1-13, using the same catalysts in the weight ratio indicated.
  • the reaction conditions were: a temperature of 385°C, a pressure of 150 bar and a H 2 /oil ratio of 1000 NI/kg.
  • Various space velocities were used in the experiments.
  • the results of Experiments 18-30 at run hour 500 are listed in Table C.
  • a catalytic hydrotreatment alone is insufficient to prepare from vacuum residue B an oil with an initial boiling point of 370°C and an RCT of 3%w in view of the maximum permissible value of G.
  • a solvent deasphalting step has to be applied.
  • Vacuum residue B was subjected to a catalytic hydrotreatment to prepare an oil having an initial boiling point of 370°C and an RCT of 3.0%w from it.
  • the experiment No. 34 was carried out in a 1000 ml reactor containing a fixed catalyst bed of 600 ml volume of the same Co/Mo/Al 2 O 3 catalyst as used in Example 1. Reaction conditions were: a temperature of 390°C, a pressure of 125 bar, a space velocity of 1.0 g.g -3 .h -1 and a H 2 /oil ratio of 1000 NI/kg.
  • the RCT reduction was 35.5%.
  • the 520°C + vacuum residue obtained after vacuum distillation of the product of the catalytic hydrotreatment was deasphalted with n-butane at a temperature of 127°C, a pressure of 40 bar and a solvent/oil weight ratio of 3:1, and the deasphalted vacuum residue obtained was mixed with the 370°-520°C vacuum distillate.
  • the results of this experiment according to the invention are given hereinafter.
  • Asphaltic bitumen A had been obtained through deasphalting with propane of a vacuum residue from a crude mineral oil. It had an RCT of 25.4%w (computed from the CCT determined by ASTM method D 189), an average molecular weight of 1400 (determined by ASTM method D 3592/77, using toluene as the solvent) and a vanadium + nickel content of 250 ppmw.
  • Asphaltic bitumen B had been obtained by deasphalting with n-butane of a vacuum residue from a crude mineral oil. It had an RCT of 48.0%w (computed from the CCT determined by ASTM method D 189), an average molecular weight of 2000 (determined by ASTM method D 8592/77, using toluene as the solvent) and a vanadium + nickel content of 420 ppmw.
  • Asphaltic bitumen A was subjected to catalytic hydrotreatment in thirteen experiments to prepare atmospheric residues having an initial boiling point of 370°C and different RCT's (c).
  • the experiments were similar to those described for Experiments 1-13, the weight ratio between the NiN/Si0 2 and Co/Mo/AI 2 0 3 catalysts however being 1:2.
  • the reaction conditions were: a temperature of 400°C, a pressure of 145 bar and a H 2 /oil ratio of 1000 NI/kg, and varying space velocities.
  • the results of Experiments 35-46 at run hour 450 are listed in Table E.
  • a catalytic hydrotreatment alone is insufficient to prepare from asphaltic bitumen B an oil having an initial boiling point of 370°C and an RCT of 4%w in view of the maximum permissible value of G.
  • a solvent deasphalting step should be applied.
  • Asphaltic bitumen B was subjected to a catalytic hydrotreatment to prepare an oil having an initial boiling point of 370°C and an RCT of 4.0%w from it.
  • the experiment was similar to those described for Experiments 1-13, the weight ratio between the Ni/V/SiO 2 and Co/Mo/A1 2 0 3 catalysts however being 1:1.
  • Reaction conditions were: a temperature of 390°C, a pressure of 150 bar, a space velocity of 0.41 g.g -1 .h -1 and a H 2 /oil ratio of 1000 NI/kg.
  • the RCT reduction was 61.0%.
  • the 520°C + vacuum residue obtained after vacuum distillation of the product of the catalytic hydrotreatment was deasphalted with n-butane at a temperature of 120°C, a pressure of 40 bar and a solvent/oil weight ratio of 3:1, and the deasphalted vacuum residue obtained was mixed with the 370°-520°C vacuum distillate.
  • the results of this experiment according to the invention are given hereinafter.
  • Asphaltic bitumen B had an RCT of 9.8%w (determined by ASTM method D 524), and a vanadium + nickel content of 95 ppmw and boiled below 520°C to an extent of 50%w.
  • Asphaltic bitumen B had an RCT of 35%w (calculated from the CCT determined by ASTM method D 189) and a vanadium + nickel content of 110 ppmw.
  • Asphaltic bitumen B was obtained by solvent deasphalting with n-butane of a vacuum residue obtained in the distillation of a hydrotreated mineral oil vacuum residue.
  • a catalytic hydrotreatment alone is not sufficient to prepare from mixture AB an oil having an initial boiling point of 370°C and an RCT of 1.5%w in view of the maximum permissible value of G. Then, in addition to the catalytic hydrotreatment, a solvent deasphalting treatment should be applied.
  • relation 4 in the form:
  • a mixture AB was subjected to catalytic hydrotreatment in eleven experiments to prepare atmospheric residues having an initial boiling point of 370°C and different RCT's (e).
  • the experiments were similar to those described for Experiments 18-30, the weight ratio between the NiN/Si0 2 and Co/Mo/A1 2 0 3 catalysts however being 1:2.5.
  • the reaction conditions were: a temperature of 385°C, a pressure of 150 bar and a H 2 / oil ratio of 1000 NI/kg, with varying space velocities.
  • the results of Experiments 52-62 at run hour 425 are listed in Table G.
  • Atmospheric residue C obtained in the distillation of a crude mineral oil, had an RCT of 10%w (determined by ASTM method D 524) and a vanadium + nickel content of 70 ppmw, and boiled below 520°C to an extent of 50%w.
  • a heavy mixture AB was used which had been obtained by mixing 100 pbwof a vacuum residue A and 30 pbw of an asphaltic bitumen B.
  • Vacuum residue A had an RCT of 19 %w (determined by ASTM method D 524), a vanadium + nickel content of 180 ppmw and a 5% boiling point of 520°C.
  • Asphaltic bitumen B had an RCT of 35 %w (calculated from the CCT determined by ASTM method D 189) and a vanadium + nickel content of 110 ppmw. It was obtained by solvent deasphalting with n-butane of a vacuum residue obtained in the distillation of a hydrotreated mineral oil vacuum residue.
  • a catalytic hydrotreatment alone is not sufficient to prepare from mixture AB an oil having an initial boiling point of 370°C and an RCT of 2.5 %w in view of the maximum permissible value of G.
  • a solvent deasphalting treatment should be applied.
  • the mixture AB was subjected to catalytic hydrotreatment in eleven experiments to prepare atmospheric residues having an initial boiling point of 370°C and different RCT's (e).
  • the experiments were similarto those described for Experiments 1-13, the weight ratio between the NiN/Si0 2 and Co/MO/Al 2 O 3 catalysts however being 1:2.
  • the reaction conditions were: a temperature of 380°C, a pressure of 170 bar and a H 2 /oil ratio of 1000 NI/kg, varying space velocities being used.
  • the results of Experiments 69-79 at run hour 400 are listed in Table J.
  • the feed used in this experiment was a mixture AC obtained by mixing 100 pbw of vacuum residue A with pbw of asphaltic bitumen C obtained in the above Experiment 83.
  • Application of relation 5 shows that for optimum utilization of the combination process care should be taken that the RCT reduction in the catalytic hydrotreatment is between 38.4 and 50.4%.
  • the space velocity applied was 0.29 g.g -1 .h -1 and the RCT reduction achieved was 45%.
  • an asphaltic bitumen D was separated which had an RCT of 39 %w.
  • the feed used in this experiment was a mixture AD obtained by mixing 100 pbw of vacuum residue A with pbw of asphaltic bitumen D obtained in the above Experiment 84.
  • Application of relation 5 shows that for optimum utilization of the combination process care should be taken that the RCT reduction in the catalytic hydrotreatment is between 37.8 and 49.8%.
  • the space velocity applied was 0.28 g.g -1 .h -1 and the RCT reduction achieved was 44%.
  • an asphaltic bitumen E was separated which had an RCT of 39 %w. Since the RCT of asphaltic bitumen E is equal to that of asphaltic bitumen D, this is the moment when in recycling the asphaltic bitumen the process has reached its stationary state.
  • the results of Experiments 83-85 are listed in Table L.
  • Asphaltic bitumen A obtained by solvent deasphalting with propane of a mineral oil vacuum residue had an RCT of 25.4%w (calculated from the CCT determined by ASTM method D 189), a vanadium + nickel content of 250 ppmw and an average molecular weight of 1400.
  • Asphaltic bitumen B had an RCT of 40 %w (calculated from the CCT determined by ASTM method D 189) and a vanadium + nickel content of 125 ppmw. It was obtained by solvent deasphalting with n-butane of a vacuum residue obtained in the distillation of a hydrotreated asphaltic bitumen which latter asphaltic bitumen was obtained by solvent deasphalting of a mineral oil vacuum residue.
  • a catalytic hydrotreatment alone is not sufficient to prepare from mixture AB an oil having an initial boiling point of 370°C and an RCT of 3.0 %w in view of the maximum permissible value of G.
  • a solvent deasphalting treatment should be applied.
  • Application of relation 6 shows that for optimum utilization of the combination process care should be taken that the RCT reduction in the catalytic hydrotreatment is between 36.7 and 50.7%.
  • the residual feed mixture AB was subjected to catalytic hydrotreatment in eleven experiments to prepare atmospheric residues having an initial boiling point of 370°C and different RCT's (e).
  • the experiments were similar to those described for Experiments 18-30, the weight ratio between the NiN/ Si0 2 and Co/Mo/Al 2 O 3 catalysts however being 1:2. All other reaction conditions were identical.
  • the results of Experiments 86-96 at run hour 430 are listed in Table M.
  • the feed used in this experiment was asphaltic bitumen A of Example 7.
  • Application of relation 6 shows that for optimum utilization of the combination process care should be taken that the RCT reduction in the catalytic hydrotreatment is between 51.0 and 61.4%.
  • the space velocity applied was 0.22 g.g -1 .h -1 and the RCT reduction achieved was 56%.
  • an asphaltic bitumen C was separated which had an RCT of 36 %w.
  • the feed used in this experiment was a mixture AC obtained by mixing 100 pbw of asphaltic bitumen A with 25 pbw of asphaltic bitumen C obtained in the above Experiment 100.
  • Application of relation 6 shows that for optimum utilization of the combination process care should be taken that the RCT reduction in the catalytic hydrotreatment is between 41.0 and 54.0%.
  • the space velocity applied was 0.21 g.g -1 .h -1 , and the RCT reduction achieved was 47.5%.
  • an asphaltic bitumen D was separated which had an RCT of 36 %w.
  • a heavy mixture ABC was used which had been obtained by mixing 55 pbw of an atmospheric residue A with 30 pbw of a vacuum residue B and with 15 pbw of an asphaltic bitumen C.
  • Atmospheric bitumen A which was obtained in the distillation of a crude mineral oil, had an RCT of 10 %w (determined by ASTM method 524), a vanadium + nickel content of 70 ppmw and a percentage boiling below 520°C of 50 %w.
  • Vacuum residue B which was obtained in the distillation of a crude mineral oil, had an RCT of 20,6 %w (computed from the CCT determined by ASTM method D 189), a vanadium + nickel content of 170 ppmw and a 5 %w boiling point of 500°C.
  • Asphaltic bitumen C had been obtained in the deasphalting with propane of a mineral oil vacuum residue. It had an RCT of 25.4 %w (computed from the CCT determined by ASTM method D 189), an average molecular weight of 1400 (determined by ASTM method D 3592-77, using toluene as the solvent) and a vanadium + nickel content of 250 ppmw.
  • the mixture ABC had an RCT of 15.5 %w, a vanadium + nickel content of 127 ppmw and 29.5 %w of the mixture boiled below 520°C.
  • the mixture ABC with an RCT of 15.5 %w (b) was subjected to catalytic hydrotreatment in fifteen experiments to prepare atmospheric residues having an initial boiling point of 370°C and different RCT's (c).
  • the experiments were similar to those described for Experiments 1-13, the weight ratio between the Ni/V/ Si0 2 and Co/Mo/Al 2 O 3 catalysts however being 1:2.
  • the reaction conditions were: a temperature of 400°C, a pressure of 160 bar and a H 2 /oil ratio of 1500 Ni/kg, varying space velocities being used.
  • the results of Experiments 102-116 at run hour 250 are listed in Table P.
  • Experiments 111, 112 and 116 are experiments according to the invention. The other experiments have been included for reasons of comparison. As can be seen in Table P in Experiments 110-111 and 112-113, in which RCT reductions were achieved of about 60 and 70%, respectively, G was about 1.5 Go and 2.0 G c , respectively.

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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)

Claims (9)

1. Un procédé pour la préparation d'un mélange d'hydrocarbures ayant un RCT de a % en poids et un point initial d'ébullition de Ti°C, caractérisé en ce qu'un mélange d'hydrocarbures contenant des asphaltènes est soumis à un hydrotraitement catalytique pour réduction de son RCT, le produit obtenu étant séparé par distillation en un distillat atmosphérique et un résidu atmosphérique ayant un point initial d'ébullition de T,oC, que soit ur résidu atmosphérique désasphalté ayant le RCT désiré de a % en poids est obtenu à partir de ce résidu atmosphérique par désasphaltage au solvant, soit le résidu atmosphérique est d'abord séparé par distillation en un distillat sous vide et un résidu sous vide, un bitume asphaltique étant séparé du résidu sous vide par désasphaltage au solvant de façon qu'on obtienne un résidu sous vide désasphalté ayant un RCT tel que, quand ce résidu sous vide désasphalté est mélangé avec le distillat sous vide ci-dessus, on obtienne un mélange ayant le RCT désiré de a % en poids, l'hydrotraitement catalytique étant effectué dans des conditions telles que la production de C4 par % de réduction de RCT ("G") soit comprise entre 1,5 Go et 2,0 Go comme défini.
2. Un procédé selon la revendication 1, caractérisé en ce que dans l'hydrotraitement catalytique pour la réduction du RCT, on utilise un catalyseur qui comprend au moins un métal choisi dans le groupe formé par le nickel et le cobalt et en outre au moins un métal choisi dans le groupe formé par le molybdène et le tungstène sur un support, lequel support est constitué de plus de 40% en poids d'alumine.
3. Un procédé selon la revendication 2, caractérisé en ce que dans l'hydrotraitement catalytique pour la réduction du RCT, on utilise un catalyseur qui comprend la combinaison de métaux nickel-molybdène ou cobalt-molybdène sur de l'alumine comme support.
4. Un procédé selon les revendications 2-3, caractérisé en ce que le mélange d'hydrocarbures contenant des asphaltènes.a une teneur en vanadium + nickel de plus de 50 ppm en poids et que dans l'hydrotraitement catalytique ce mélange est mis en contact avec deux catalyseurs successifs, le premier catalyseur étant un catalyseur de démétallisation constitué de plus de 80% en poids de silice et le deuxième catalyseur étant un catalyseur de réduction du RCT comme décrit dans la revendication 2 ou 3.
5. Un procédé selon la revendication 4, caractérisé en ce que le catalyseur de démétallisation comprend la combinaison de métaux nickel-vanadium sur de la silice comme support.
6. Un procédé selon l'une quelconque des revendications 1-5, caractérisé en ce que l'hydrotraitement catalytique est effectué à une température de 300-500°C, une pression de 50-300 bars (5-30 MPa), une vitesse spatiale de 0,02-10 g.g-1.h-1 et un rapport H2/charge de 100-5000 1(TPN)/kg.
7. Un procédé selon la revendication 6, caractérisé en ce que l'hydrotraitement catalytique est effectué à une température de 350―450°C, une pression de 75-200 bars (7,5-20 MPa), une vitesse spatiale de 0,1-2 g.g-'.h-' et un rapport H2/charge de 500-2000 1(TPN)/kg.
8. Un procédé selon l'une quelconque des revendications 1-7, caractérisé en ce qu'on effectue le désasphaltage au solvant en utilisant du n-butane comme solvant, à une pression de 35-45 bars et à une température de 100-150°C.
9. Un Procédé selon l'une quelconque des revendications 1-8, caractérisé en ce qu'un bitume asphaltique séparé dans le désasphaltage au solvant d'un résidu obtenu dans la distillation d'une fraction résiduelle hydrotraitée d'une huile minérale brute, lequel bitume asphaltique est utilisé comme constituant de mélange dans la charge pour la première étape du procédé, provient du désasphaltage au solvant , effectué dans la deuxième étape du procédé.
EP19820200689 1981-06-25 1982-06-04 Procédé pour la préparation d'un mélange d'hydrocarbures Expired EP0068543B1 (fr)

Applications Claiming Priority (12)

Application Number Priority Date Filing Date Title
NL8103067A NL8103067A (nl) 1981-06-25 1981-06-25 Werkwijze voor de bereiding van een koolwaterstofmengsel.
NL8103121A NL8103121A (nl) 1981-06-29 1981-06-29 Werkwijze voor de bereiding van een koolwaterstofmengsel.
NL8103121 1981-06-29
NL8103396A NL8103396A (nl) 1981-07-17 1981-07-17 Werkwijze voor de bereiding van een koolwaterstof mengsel.
NL8103576A NL8103576A (nl) 1981-07-29 1981-07-29 Werkwijze voor de bereiding van een koolwaterstofmengsel.
NL8104326 1981-09-21
NL8103576 1981-09-21
NL8104326A NL8104326A (nl) 1981-09-21 1981-09-21 Werkwijze voor de bereiding van een koolwaterstofmengsel.
NL8104327 1981-09-21
NL8103396 1981-09-21
NL8104327A NL8104327A (nl) 1981-09-21 1981-09-21 Werkwijze voor de bereiding van een koolwaterstofmengsel.
NL8103067 1981-09-21

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EP0068543A2 EP0068543A2 (fr) 1983-01-05
EP0068543A3 EP0068543A3 (en) 1985-12-11
EP0068543B1 true EP0068543B1 (fr) 1988-09-21

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JP (1) JPH0631334B2 (fr)
AR (1) AR241922A1 (fr)
AU (1) AU543734B2 (fr)
CA (1) CA1182770A (fr)
DE (1) DE3279051D1 (fr)
FI (1) FI78496C (fr)
GB (1) GB2100748B (fr)
MX (1) MX170898B (fr)
SG (1) SG67784G (fr)

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NL8202827A (nl) * 1982-07-13 1984-02-01 Shell Int Research Werkwijze voor de bereiding van asfaltenenarme koolwaterstofmengsels.
NL8301352A (nl) * 1983-04-18 1984-11-16 Shell Int Research Werkwijze voor de bereiding van asfaltenenarme koolwaterstofmengsels.
JPS60152594A (ja) * 1984-01-23 1985-08-10 Kawasaki Heavy Ind Ltd 直接脱硫装置残渣油の脱硫方法
JPS60248421A (ja) * 1984-05-21 1985-12-09 Diesel Kiki Co Ltd 自動車用空気調和装置
JPS6133313A (ja) * 1984-07-25 1986-02-17 Diesel Kiki Co Ltd 自動車用空気調和装置
JPS6172410U (fr) * 1984-10-19 1986-05-16
CA1222471A (fr) * 1985-06-28 1987-06-02 H. John Woods Methode pour ameliorer le rendement des produits distillables dans le craquage a diluant donneur d'hydrogene
JPH03281570A (ja) * 1990-03-30 1991-12-12 Ube Ind Ltd アルキレンオキサイドグラフトポリアミド組成物
US8215306B2 (en) 2008-12-12 2012-07-10 Kimberly-Clark Worldwide, Inc. Respiratory access port assembly with push button lock and method of use
US8256422B2 (en) 2009-05-15 2012-09-04 Kimberly-Clark Worldwide, Inc Respiratory access port assembly with passive lock and method of use
CN102652169B (zh) * 2009-12-11 2015-06-10 环球油品公司 用于生产烃燃料和组合物的方法和设备
US9078987B2 (en) 2011-12-23 2015-07-14 Avent, Inc. Clutch brake assembly for a respiratory access port
US20170022433A1 (en) * 2015-07-24 2017-01-26 Exxonmobil Research And Engineering Company Fixed bed hydroprocessing of deasphalter rock

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US3549517A (en) 1968-07-23 1970-12-22 Hydrocarbon Research Inc High conversion level hydrogenation of residuum
US3723297A (en) 1971-10-18 1973-03-27 Universal Oil Prod Co Conversion of asphaltene-containing charge stocks
NL175732C (nl) * 1972-07-07 Shell Int Research Werkwijze voor het katalytisch demetalliseren van residuale koolwaterstofolien en het verder katalytisch omzetten van de hierbij verkregen olie.
NL7512090A (nl) * 1975-10-15 1977-04-19 Shell Int Research Werkwijze voor het omzetten van koolwaterstof- fen.
NL7612960A (nl) * 1976-11-22 1978-05-24 Shell Int Research Werkwijze voor het omzetten van koolwater- stoffen.
US4082648A (en) * 1977-02-03 1978-04-04 Pullman Incorporated Process for separating solid asphaltic fraction from hydrocracked petroleum feedstock
NL7702161A (nl) * 1977-03-01 1978-09-05 Shell Int Research Werkwijze voor het omzetten van koolwater- stoffen.
JPS541306A (en) * 1977-06-07 1979-01-08 Chiyoda Chem Eng & Constr Co Ltd Hydrogenation of heavy hydrocarbon oil
JPS5850636B2 (ja) * 1977-07-15 1983-11-11 千代田化工建設株式会社 重質炭化水素油の脱硫処理方法
NL7805421A (nl) * 1978-05-19 1979-11-21 Shell Int Research Werkwijze voor de bereiding van een voeding voor een katalytisch kraakproces.

Also Published As

Publication number Publication date
DE3279051D1 (en) 1988-10-27
AU8519682A (en) 1983-01-06
AU543734B2 (en) 1985-05-02
MX170898B (es) 1993-09-21
CA1182770A (fr) 1985-02-19
FI822278L (fi) 1982-12-26
GB2100748B (en) 1984-08-30
EP0068543A2 (fr) 1983-01-05
FI78496C (fi) 1989-08-10
SG67784G (en) 1985-03-15
JPS587486A (ja) 1983-01-17
AR241922A1 (es) 1993-01-29
FI822278A0 (fi) 1982-06-24
GB2100748A (en) 1983-01-06
FI78496B (fi) 1989-04-28
JPH0631334B2 (ja) 1994-04-27
EP0068543A3 (en) 1985-12-11

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