EP0629683B1 - Process for upgrading a hydrocarbonaceous feedstock - Google Patents

Process for upgrading a hydrocarbonaceous feedstock Download PDF

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Publication number
EP0629683B1
EP0629683B1 EP19940201673 EP94201673A EP0629683B1 EP 0629683 B1 EP0629683 B1 EP 0629683B1 EP 19940201673 EP19940201673 EP 19940201673 EP 94201673 A EP94201673 A EP 94201673A EP 0629683 B1 EP0629683 B1 EP 0629683B1
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EP
European Patent Office
Prior art keywords
isoparaffins
separated
fraction
mono
normal paraffins
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EP19940201673
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German (de)
English (en)
French (fr)
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EP0629683A1 (en
Inventor
Marius Gerardus Frederikus Peutz
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Shell Internationale Research Maatschappij BV
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Shell Internationale Research Maatschappij BV
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Priority to EP19940201673 priority Critical patent/EP0629683B1/en
Publication of EP0629683A1 publication Critical patent/EP0629683A1/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
    • C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
    • C10G25/02—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents with ion-exchange material
    • C10G25/03—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents with ion-exchange material with crystalline alumino-silicates, e.g. molecular sieves
    • 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
    • C10G61/00—Treatment of naphtha by at least one reforming process and at least one process of refining in the absence of hydrogen
    • C10G61/02—Treatment of naphtha by at least one reforming process and at least one process of refining in the absence of hydrogen plural serial stages only
    • C10G61/06—Treatment of naphtha by at least one reforming process and at least one process of refining in the absence of hydrogen plural serial stages only the refining step being a sorption process
    • 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
    • C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
    • C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
    • C10G69/08—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one step of reforming naphtha

Definitions

  • the present invention relates to a process for upgrading a hydrocarbonaceous feedstock substantially boiling in the gasoline range, to produce a gasoline blending pool having an enhanced octane content and a reduced aromatics content.
  • One of the main objects in nowaday's oil refining is to produce gasolines fulfilling the increasing environmental demands on product quality and having a high octane number.
  • EP-A-0 553 931 describes one such process already proposed for obtaining an octane-enhanced gasoline.
  • Object of the present invention is to provide a process for the preparation of gasolines fulfilling both the increasing environmental demands on product quality and the high octane requirement.
  • gasolines can be produced having a high octane number and a considerably reduced aromatics content, in particular benzene, when use is made of an upgrading process comprising a specific sequence of process steps.
  • the present invention relates to a process for producing a gasoline blending pool having an enhanced octane content and a reduced aromatics content, which process comprises:
  • the two hydrocarbon feed streams which are derived from the feedstock in step a) can suitably be obtained by distillation.
  • the two hydrocarbon feed streams are adjacent fractions obtained by distillation. Depending, of course, on the sharpness of the cutting points of the fractions chosen in the distillation some overlap may occur among the adjacent fractions.
  • the separation treatment in step a) is carried out in such a way that the first hydrocarbon feed stream substantially comprises C 5 and smaller hydrocarbons. If the first hydrocarbon feed stream substantially comprises C 5 and smaller hydrocarbons said feed stream does not need to be subjected to an isomerisation process but can advantageously directly be introduced in the gasoline blending pool.
  • at least part of the feedstock to be upgraded can be subjected to the hydrogenation in step e) before being subjected to the separation treatment in step a).
  • the hydrocarbonaceous feedstock boiling in the gasoline range can suitably be obtained by distillation of crude or by catalytic cracking although it may be obtained by other cracking processes such as thermal cracking, delayed coking, visbreaking and flexicoking.
  • Such gasoline feedstocks usually contain unacceptable levels of sulphur and nitrogen and benefit from a hydrotreatment before they are subjected to the process according to the present invention.
  • the process according to the present invention is carried out in such a way that in step b) both the normal paraffins and mono-isoparaffins (mono-branched paraffins) are separated from the di-isoparaffins (di-branched paraffins).
  • This is suitably established by passing at least part of the second hydrocarbon feed stream to a separation zone comprising a shape-selective separatory molecular sieve having a pore size intermediate 5.5 x 5.5 to 4.5 x 4.5 ⁇ , but excluding 4.5 x 4.5 ⁇ , the pore size being sufficient to permit entry of normal paraffins and mono-isoparaffins but restrictive to prohibit entry of di-isoparaffins, other multi-branched paraffins, cyclic paraffins and aromatic hydrocarbons.
  • the first separation effluent stream comprising both normal paraffins and mono-isoparaffins and the second separation effluent stream comprising di-isoparaffins can be recovered.
  • first separation effluent is subjected to the reforming step.
  • substantially the entire first separation effluent stream is subjected to the reforming stream, although also part thereof may be used as a preferred chemical feedstock.
  • a feedstock for a highly selective (dehydro)cyclization process is particularly preferred.
  • the normal paraffins are firstly separated from the mono-isoparaffins and di-isoparaffins, whereas the mono-isoparaffins are subsequently separated from the di-isoparaffins.
  • use can be made of a multiple select adsorbent molecular sieve system having particular separatory qualities.
  • the multiple separatory sieve system to be used comprises a first molecular sieve having a pore size of 4.5 x 4.5 ⁇ or smaller and being shaped to permit adsorption of normal paraffins in a selective manner vis-a-vis mono-isoparaffins, di-isoparaffins, other multi-branched paraffins, cyclic paraffins and aromatic hydrocarbons and a second molecular sieve having a pore size intermediate 5.5 x 5.5 to 4.5 x 4.5 ⁇ , but excluding 4.5 x 4.5 ⁇ , being selected to permit adsorption of mono-isoparaffins (and any remaining normal paraffins) in deference to di-isoparaffins, other multi-branched paraffins, cyclic paraffins and aromatic hydrocarbons which can be passed directly to a refinery gasoline blending pool.
  • At least part of the second hydrocarbon feed stream is firstly contacted with the first shape-selective separatory molecular sieve as defined hereinabove to produce a first separation effluent stream comprising the normal paraffins and a second separation effluent stream comprising both mono- and di-isoparaffins.
  • the latter separation effluent stream is subsequently contacted with the second shape-selective separatory molecular sieve as described hereinabove.
  • a third separation effluent stream comprising mono-isoparaffins can be recovered and a fourth separation effluent stream comprising di-isoparaffins can be recovered. At least part of the first and third separation effluents can be subjected to the reforming step.
  • substantially the entire first and third separation effluent streams are subjected to the reforming step.
  • at least part of the first and third separation effluent streams may suitably be used as a preferred chemical feedstock as mentioned hereinbefore.
  • the multiple select adsorbent molecular sieve system as described hereinabove comprises at least two molecular sieves. These can be arranged in separate vessels, or they can be arranged in a stacked flow scheme within one vessel.
  • This first molecular sieve can be a calcium 5 ⁇ zeolite or any other sieve of similar pore dimensions. It is not necessary to size the first sieve to adsorb all of the normal paraffins, but it is preferred so that the second molecular sieve does not have to function as a normal paraffin adsorption sieve.
  • the second molecular sieve in this process sequence is exemplified by a molecular sieve which has eight and ten member rings and pore dimensions intermediate 5.5 x 5.5 and 4.5 x 4.5 ⁇ , but excluding 4.5 x 4.5 ⁇ .
  • the preferred second molecular sieve of this invention is exemplified by a ferrierite molecular sieve. It is preferred that the ferrierite sieve be present in a hydrogen form, but it alternatively can be exchanged with a cation of an alkali metal, or alkaline earth metal or transition metal cation.
  • the second molecular sieves of this invention include ferrierite and other analogous shape-selective materials with pore openings intermediate in dimensions to those of the calcium 5 ⁇ zeolite and ZSM-5.
  • Other examples of crystalline sieves include aluminophosphates, silicoaluminophosphates, and borosilicates.
  • the aluminophosphate, silicoaluminophosphate and borosilicate molecular sieves which can be used as a second molecular sieve will have a pore opening intermediate 5.5 x 5.5 and 4.5 x 4.5 ⁇ , but excluding 4.5 x 4.5 ⁇ .
  • the second molecular sieve comprises a large pore zeolite that has been ion exchanged with cations to diminish the effective pore size of the sieve to within the aforementioned range of dimensions.
  • the respective sieves applied in a multiple select adsorbent molecular sieve system should be arranged in a process sequence to first provide adequate adsorption of the normal paraffin hydrocarbons, and then, adsorption of the mono-isoparaffins.
  • Each of these respective sieves can be provided with a common desorbent stream or each sieve may have its own desorbent stream.
  • the desorbent is preferably a gaseous material such as a hydrogen gas stream.
  • At least part of the reformate obtained in step d) is subjected to a separation treatment from which a light fraction comprising C 6 and smaller hydrocarbons and a heavy fraction comprising C 6 and greater hydrocarbons are recovered.
  • step e At least part of the light fraction and optionally at least part of the heavy fraction are subjected to the hydrogenation in step e).
  • C 5 and smaller hydrocarbons are separated from the light fraction before the latter is subjected to the hydrogenation in step e).
  • any conventional hydrogenation catalyst can be applied.
  • a catalyst comprising at least one component of a Group VIII and/or Group VIb metal on a silica-alumina-containing carrier.
  • a platinum component on an amorphous silica-alumina carrier.
  • the hydrogenation step can suitably be carried out under conventional hydrogenation conditions. Typically the hydrogenation is carried out at a temperature between 150 to 300 °C and a partial hydrogen pressure of between 10 to 30 bar.
  • At least part of the light and heavy fraction is recovered.
  • at least part of the light and heavy fraction is subjected to a separation treatment wherein normal paraffins and optionally mono-isoparaffins are separated from di-isoparaffins, and whereby a first hydrocarbon product stream comprising normal paraffins and optionally mono-isoparaffins and a second hydrocarbon product stream comprising di-isoparaffins is recovered.
  • At least part of the first hydrocarbon product stream may be used as preferred chemical feedstock as mentioned hereinbefore.
  • the separation treatment is carried out in such a way that both the normal paraffins and mono-isoparaffins are separated from the di-isoparaffins.
  • This is suitably established by passing at least part of the light and heavy fraction to a separation zone comprising a shape-selective separatory molecular sieve having a pore size intermediate 5.5 x 5.5 to 4.5 x 4.5 ⁇ but excluding 4.5 x 4.5 ⁇ , the pore size being sufficient to permit entry of normal paraffins and mono-isoparaffins but restrictive to prohibit entry of di-isoparaffins.
  • a first hydrocarbon product stream comprising both normal paraffins and mono-isoparaffins and a second hydrocarbon product stream comprising di-isoparaffins can be recovered.
  • the separation treatment is carried out in such a way that the normal paraffins are firstly separated from the mono-isoparaffins and di-isoparaffins, whereas the mono-isoparaffins are subsequently separated from the di-isoparaffins.
  • a multiple select adsorbent molecular sieve system as described hereinbefore.
  • a multiple select adsorbent molecular sieve system is applied both upstream and downstream the reforming step.
  • the separation treatments upstream and downstream of the reforming step wherein the normal paraffins and optionally the mono-isoparaffins are separated from di-isoparaffins are preferably carried out in the same separation zone.
  • the light fraction comprising C 6 and smaller hydrocarbons and the heavy fraction comprising C 6 and greater hydrocarbons have been obtained from the reformate by means of distillation.
  • the light and the heavy fraction are adjacent fractions obtained by distillation.
  • some overlap may occur among the adjacent fractions.
  • the reformate obtained in step d) is firstly subjected to a separation treatment wherein a gaseous fraction is separated from a liquid fraction, whereafter the liquid fraction is separated into the light fraction comprising C 6 and smaller hydrocarbons and the heavy fraction comprising C 6 and greater hydrocarbons.
  • any conventional reforming catalyst can be applied.
  • a catalyst is applied having a substantial (dehydro)cyclization selectivity.
  • a catalyst is a platinum-containing catalyst with platinum present in for instance a range of 0.005 wt% to 10.0 wt%.
  • the catalytic metals associated with the reforming function are preferably noble metals from Group VIII of the Periodic Table of elements, such as platinum and palladium.
  • the reforming catalyst can be present per se or it may be mixed with a binder material.
  • noble metal(s)-containing reforming catalysts normally requires a pretreatment in the form of a catalytic hydrotreatment of the feedstock to be upgraded. In this way nitrogen-compounds and sulphur-compounds can be removed from the feedstock which compounds would otherwise reduce the performance of the reforming catalyst considerably.
  • the reforming step can suitably be carried out under conventional reforming conditions. Typically the process is carried out at a temperature from 450 to 550 0 C and a pressure of 3 to 20 bar.
  • the reaction section in which the reforming step is to be performed can suitably be separated into several stages or reactors.
  • a process according to the present invention is carried out in accordance with the flow diagram as schematically shown in Figure 1.
  • a hydrocarbonaceous feedstock substantially boiling in the gasoline range and having the properties as set out in Table 1 is introduced via a line 1 and a line 1a into a distillation column 2 in which the feedstock is separated into two hydrocarbon feed streams.
  • a first hydrocarbon feed stream comprising C 5 and smaller hydrocarbons is withdrawn via a line 3 and introduced into a gasoline blending pool 4.
  • a second hydrocarbon feed stream comprising C 5 and greater hydrocarbons is withdrawn via a line 5, and passed to a separation zone 6 which contains two molecular sieves 7 and 8.
  • Molecular sieve #1 (7) is a commercial zeolite having a pore size from 4.5 to 4.5 ⁇ or smaller.
  • molecular sieve #2 has a pore size of 5.5 x 5.5 to 4.5 x 4.5 ⁇ , but excludes 4.5 x 4.5 ⁇ .
  • the first molecular sieve 7 selectively adsorbs normal paraffins in preference to mono-isoparaffins, di-isoparaffins, other multi-branched paraffins, cyclic paraffins and aromatic hydrocarbons.
  • a fraction comprising normal paraffins is withdrawn via a line 9 and introduced into a reforming reactor 10.
  • the separation effluent stream substantially freed from normal paraffins is withdrawn via a line 11 and contacted with molecular sieve #2(8).
  • the reformate obtained is subsequently withdrawn via a line 14 and introduced into a distillation column 15.
  • the distillation column 15 the reformate is separated into a gaseous fraction and a liquid fraction.
  • the gaseous fraction is withdrawn via a line 16
  • the liquid fraction is withdrawn via a line 17.
  • the liquid fraction is subsequently passed to a distillation column 18.
  • the distillation column 18 the liquid fraction is separated into a first fraction comprising C 5 and smaller hydrocarbons, a second fraction comprising C 6 and C 7 hydrocarbons and a third fraction comprising C 7 and greater hydrocarbons.
  • the first fraction is withdrawn from the distillation column 18 via a line 19 and introduced into the gasoline blending pool 4.
  • the second fraction is passed to a hydrogenation unit 20 via line 21.
  • a hydrogen stream is introduced into the hydrogenation unit 20 via a line 22.
  • the hydrogenated product obtained from the hydrogenation unit 20 is then co-processed with the feedstock to be upgraded via lines 23 and 1a.
  • the third fraction is withdrawn from the distillation column 18 via a line 24 and introduced into the gasoline blending pool 4.

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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)
  • Crystallography & Structural Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Hydrogen, Water And Hydrids (AREA)
EP19940201673 1993-06-15 1994-06-10 Process for upgrading a hydrocarbonaceous feedstock Expired - Lifetime EP0629683B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP19940201673 EP0629683B1 (en) 1993-06-15 1994-06-10 Process for upgrading a hydrocarbonaceous feedstock

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP93201716 1993-06-15
EP93201716 1993-06-15
EP19940201673 EP0629683B1 (en) 1993-06-15 1994-06-10 Process for upgrading a hydrocarbonaceous feedstock

Publications (2)

Publication Number Publication Date
EP0629683A1 EP0629683A1 (en) 1994-12-21
EP0629683B1 true EP0629683B1 (en) 1998-12-09

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP19940201673 Expired - Lifetime EP0629683B1 (en) 1993-06-15 1994-06-10 Process for upgrading a hydrocarbonaceous feedstock

Country Status (5)

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EP (1) EP0629683B1 (da)
CA (1) CA2125737C (da)
DE (1) DE69415084T2 (da)
DK (1) DK0629683T3 (da)
ES (1) ES2126053T3 (da)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2131909C1 (ru) * 1998-07-01 1999-06-20 Открытое акционерное общество "Ново-Уфимский нефтеперерабатывающий завод" Способ получения экологически чистого высокооктанового бензина
RU2139911C1 (ru) * 1999-03-23 1999-10-20 ЗАО "Рязанская нефтеперерабатывающая компания" Способ получения нефтепродуктов
RU2180679C2 (ru) * 2000-05-22 2002-03-20 Открытое акционерное общество "Нижнекамскнефтехим" Растворитель и способ его получения
US8808534B2 (en) * 2011-07-27 2014-08-19 Saudi Arabian Oil Company Process development by parallel operation of paraffin isomerization unit with reformer
US11072748B2 (en) * 2019-12-09 2021-07-27 Saudi Arabian Oil Company Selective reforming process to produce gasoline blending components and aromatics

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1208231A (fr) * 1957-05-01 1960-02-22 Exxon Research Engineering Co Procédé perfectionné de reformage des naphtas
US2935539A (en) * 1958-04-25 1960-05-03 Exxon Research Engineering Co Hydrocarbon separation process using metallic amine complex substituted molecular sieves
US3012961A (en) * 1959-05-14 1961-12-12 Socony Mobil Oil Co Inc Production of jet fuel
GB1106044A (en) * 1965-07-05 1968-03-13 Universal Oil Prod Co Production of jet and motor fuel
GB9013566D0 (en) * 1990-06-18 1990-08-08 Shell Int Research Process for producing gasoline components
DK0553931T3 (da) * 1992-01-30 1997-09-22 Shell Int Research Fremgangsmåde til opgradering af et carbonhydridholdigt råmateriale.

Also Published As

Publication number Publication date
CA2125737A1 (en) 1994-12-16
ES2126053T3 (es) 1999-03-16
DE69415084T2 (de) 1999-06-24
CA2125737C (en) 2005-02-22
DE69415084D1 (de) 1999-01-21
DK0629683T3 (da) 1999-08-16
EP0629683A1 (en) 1994-12-21

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