WO2016000060A1 - Valorisation d'un matériau hydrocarboné - Google Patents

Valorisation d'un matériau hydrocarboné Download PDF

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Publication number
WO2016000060A1
WO2016000060A1 PCT/CA2014/000915 CA2014000915W WO2016000060A1 WO 2016000060 A1 WO2016000060 A1 WO 2016000060A1 CA 2014000915 W CA2014000915 W CA 2014000915W WO 2016000060 A1 WO2016000060 A1 WO 2016000060A1
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WO
WIPO (PCT)
Prior art keywords
fraction
hydrocarbon material
feed
upgraded
olefin
Prior art date
Application number
PCT/CA2014/000915
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English (en)
Inventor
Nestor Gregorio Zerpa Reques
Arno DE CLERK
Yuhan Xia
Ayyub Abduljawad Omer
Original Assignee
Nexen Energy Ulc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from PCT/CA2014/000541 external-priority patent/WO2015000061A1/fr
Application filed by Nexen Energy Ulc filed Critical Nexen Energy Ulc
Priority to CA2953853A priority Critical patent/CA2953853C/fr
Priority to CN201480081537.3A priority patent/CN106661466B/zh
Priority to US15/323,658 priority patent/US20170152451A1/en
Publication of WO2016000060A1 publication Critical patent/WO2016000060A1/fr

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Classifications

    • 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
    • C10G47/22—Non-catalytic cracking in the presence of hydrogen
    • 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
    • C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
    • C10G21/003—Solvent de-asphalting
    • 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
    • C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
    • C10G29/20—Organic compounds not containing metal atoms
    • C10G29/205—Organic compounds not containing metal atoms by reaction with hydrocarbons added to the hydrocarbon oil
    • 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
    • C10G57/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one cracking process or refining process and at least one other conversion process
    • C10G57/005—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one cracking process or refining process and at least one other conversion process with alkylation
    • 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
    • C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils

Definitions

  • the present disclosure relates to the upgrading of hydrocarbon materials, including the upgrading of heavy hydrocarbon materials.
  • One upgrading approach involves the chemical processing of the heavy oil and/or bitumen by a suitable combination of conversion and separation steps.
  • Most chemical processing for converting heavy oil and/or bitumen into transportable oil are cracking based systems and usually include at least one form of cracking, e.g. thermal cracking, and at least one form of hydro-processing.
  • the cracking step is employed to reduce the viscosity and density of the heavy oil and/or bitumen.
  • the hydro-processing step is employed to reduce the olefin and di-olefin content of the heavy oil and/or bitumen.
  • a disadvantage of these processes is the production of cracked material comprising olefins and di-olefins.
  • olefins and more particularly the more reactive conjugated C 4 and C 5 di-olefins (i.e. butadiene, 1,3-pentadiene, 2-methyl- 1,3 -butadiene) may react with each other, with oxygen (such as oxygen in the air) or other reactive compounds (e.g. organic acids, carbonyls, amines, etc.), to form long chain polymers (polymerization reaction) commonly referred to as gums. Gums of this nature are known to foul process equipment. It has been reported in U.S.
  • Patent 6,210,560 assigned to Exxon Research and Engineering Company, that these polymerization reactions occur at a significant rate for petroleum oils having a di-olefins value per UOP-326 of 4 grams iodine/110 grams oil or greater in the temperature range of 232°C to 324°C; particularly 260°C to 304°C. Below this temperature range, the reaction rate is too slow for significant polymerization formation to occur and above this temperature range the chemical bonds are broken thermally faster than they are formed. It has also been reported in U.S. Patent Application Publication No. 2012/0273394 Al assigned to UOP LLC, that the fouling tendencies of oils having a di-olefins value per UOP-326 of less than about 2 grams iodine/1 10 grams oil are deemed acceptable.
  • a process for upgrading a hydrocarbon material comprising: treating a hydrocarbon material-comprising feed, wherein the treating includes cracking a hydrocarbon material-comprising feed, such that an upgraded intermediate is produced; and in the absence, or the substantial absence, of adscititious diatomic hydrogen, reducing the content of olefinic material within at least a fraction of the upgraded intermediate such that an olefinic material content-reduced product is produced.
  • a process for upgrading a hydrocarbon material comprising: treating a hydrocarbon material-comprising feed, wherein the treating includes cracking the hydrocarbon material-comprising feed within a reaction zone, such that an upgraded intermediate is produced; separating a feed material into at least an olefin-comprising treatment fraction and a treatment bypass fraction, wherein the feed material includes at least a fraction of the upgraded intermediate reducing the content of olefinic material within the olefin- comprising treatment fraction such that an olefin-depleted intermediate is produced; separating the treatment bypass fraction into a heavier hydrocarbon material-comprising fraction and a lighter hydrocarbon material-comprising fraction; combining at least the lighter hydrocarbon material-comprising fraction and the olefin-depleted intermediate such that an olefinic material content-reduced product is produced; producing an upgraded product including the olefinic material content-reduced product; and supplying at least a
  • a process for upgrading a hydrocarbon material comprising: treating a hydrocarbon material-comprising feed, wherein the treating includes cracking the hydrocarbon material-comprising feed within a reaction zone, such that an upgraded intermediate is produced; separating a feed material into at least an olefin-comprising treatment fraction, a heavier hydrocarbon material-comprising fraction, and a lighter
  • hydrocarbon material-comprising fraction wherein the feed material includes at least a fraction of the upgraded intermediate reducing the content of olefinic material within the olefin- comprising treatment fraction such that an olefin-depleted intermediate is produced; combining at least the lighter hydrocarbon material-comprising fraction and the olefin-depleted
  • a process for upgrading a hydrocarbon material comprising: treating a hydrocarbon material-comprising feed, wherein the treating includes cracking the hydrocarbon material-comprising feed, such that an upgraded intermediate is produced; separating a feed material into at least a light olefin-comprising treatment fraction and a treatment bypass fraction, wherein the feed material includes at least a fraction of the upgraded intermediate; reducing the content of light olefinic material within the olefin- comprising treatment fraction such that a light olefinic material-depleted intermediate is produced; combining the light olefinic material-depleted intermediate and the treatment bypass fraction so as to produce a light olefinic material content-reduced product; and producing an upgraded product including the light olefinic material content-reduced product.
  • a process for upgrading a hydrocarbon material comprising: supplying a hydrogen donor material to a reaction zone; supplying a hydrocarbon material-comprising feed to the reaction zone; treating the hydrocarbon material- comprising feed, wherein the treating includes cracking the hydrocarbon material-comprising feed in the presence of a hydrogen donor material within the reaction zone, such that an upgraded hydrocarbon material is produced.
  • Figure 1 is a process flow diagram of a process according to one embodiment
  • Figure 1A is a process flow diagram of a process according to another embodiment
  • Figure 2 is a process flow diagram of a process according to another embodiment
  • Figure 3 is a process flow diagram of a process according to another embodiment
  • Figure 4 is a process flow diagram of a process according to another embodiment
  • Figure 5 is a process flow diagram of a process according to another embodiment
  • Figure 5A is a process flow diagram of a process according to another
  • Figure 6 is a process flow diagram of a process according to another embodiment
  • Figure 7 is a process flow diagram of a process according to another embodiment
  • Figure 8 is a process flow diagram of a process according to another
  • Figure 9 is a process flow diagram of a process according to another embodiment.
  • Figure 10 is a process flow diagram of a process according to another
  • Figure 1 1 is a process flow diagram of a process according to another embodiment.
  • Figure 12 is a process flow diagram of a process according to another embodiment.
  • the present disclosure relates to the upgrading of hydrocarbon material.
  • the upgrading is of heavy hydrocarbon material.
  • Exemplary embodiments may relate to heavy hydrocarbon materials, but it is understood, unless the context suggests otherwise, that such embodiments are also applicable to hydrocarbon materials, generally.
  • Hydrocarbon is an organic compound consisting primarily of hydrogen and carbon, and, in some instances, may also contain heteroatoms such as sulfur, nitrogen and oxygen.
  • Hydrocarbon material is a material consisting of at least one hydrocarbon.
  • Heavy hydrocarbon material is, in some embodiments, for example, hydrocarbon material that includes at least 10 weight percent of hydrocarbon material that boils above 500°C.
  • the heavy hydrocarbon material is a hydrocarbon material that includes at least 20 weight percent of hydrocarbon material that boils above 500°C.
  • the heavy hydrocarbon material is a hydrocarbon material includes at least 40 weight percent of hydrocarbon material that boils above 500°C.
  • the heavy hydrocarbon material is a hydrocarbon material includes at least 60 weight percent of hydrocarbon material that boils above 500°C.
  • the heavy hydrocarbon material is a hydrocarbon material includes at least 80 weight percent of hydrocarbon material that boils above 500°C. In some of these embodiments, for example, the heavy hydrocarbon material is a hydrocarbon material that boils above 500°C. [0038] In some embodiments, for example, the heavy hydrocarbon material is a hydrocarbon material having an API (American Petroleum Institute) gravity of less than 22°. In some embodiments, for example, the heavy hydrocarbon material is a hydrocarbon material having an API gravity of less than 20°. In some embodiments, for example, the heavy hydrocarbon material is a hydrocarbon material having an API gravity of less than 15°.
  • API American Petroleum Institute
  • the heavy hydrocarbon material is a hydrocarbon material having an API gravity of less than 10°. In some embodiments, for example, the heavy hydrocarbon material has an API gravity of less than 5°. In some embodiments, for example, the heavy hydrocarbon material is a hydrocarbon material having an API gravity of less than 0°. In some embodiments, for example, the heavy hydrocarbon material is a hydrocarbon material having an API gravity of less than -5°.
  • the heavy hydrocarbon material includes, or in some embodiments, consists of, residuum or resid.
  • Exemplary residuum includes various heavy crude and refinery fractions.
  • the heavy hydrocarbon material includes, or in some embodiments, consists of, fresh resid hydrocarbon feeds, a bottoms stream from any refinery process, such as petroleum atmospheric tower bottoms, vacuum tower bottoms, or a bottoms stream from a coker or a thermal cracking unit, or a bottoms stream from a fluid catalytic cracking (“FCC”) unit operation or a resid fluid catalytic cracking (RFCC) unit operation, hydrocracked atmospheric tower, vacuum tower, FCC, or RFCC bottoms, straight run vacuum gas oil, hydrocracked vacuum gas oil, fluid catalytically cracked slurry oils or cycle oils, as well as other similar hydrocarbon materials, or any combination thereof, each of which may be straight run,
  • FCC fluid catalytic cracking
  • RFCC fluid catalytic
  • the heavy hydrocarbon material includes, or in some embodiments, consists of, a crude, such as an heavy and/or an ultra-heavy crude.
  • Crude refers to hydrocarbon material which have been produced and/or retorted from hydrocarbon- containing formations and which has not yet been distilled and/or fractionally distilled in a treatment facility to produce multiple components with specific boiling range distributions, such as atmospheric distillation methods and/or vacuum distillation methods.
  • Exemplary crudes include coals, bitumen, oil sands, heavy oil or crude oil.
  • the heavy hydrocarbon material is included within an asphaltene-comprising heavy hydrocarbon-comprising material includes an asphaltene content of less than 40 weight %, based on the total weight of the heavy hydrocarbon material.
  • the asphaltene-comprising heavy hydrocarbon- comprising material includes an asphaltene content of less than 20 weight %, based on the total weight of the heavy hydrocarbon material.
  • the asphaltene-comprising heavy hydrocarbon-comprising material includes an asphaltene content of less than 15 weight %, based on the total weight of the heavy hydrocarbon material.
  • asphaltenes refers to the heaviest and most polar molecules component of a carbonaceous material such as crude oil, bitumen or coal and are defined as a solubility class of materials that are insoluble in an n-alkane (usually npentane or n- heptane) but soluble in aromatic solvents such as toluene.
  • n-alkane usually npentane or n- heptane
  • aromatic solvents such as toluene.
  • SARA saturated and aromatic hydrocarbons and resins
  • Asphaltenes consist primarily of carbon, hydrogen, nitrogen, oxygen, and sulfur, as well as trace amounts of vanadium and nickel.
  • the density is approximately 1.2 g/cc and the hydrogen to carbon atomic ratio is approximately 1.2, depending on the asphaltenes source and the solvent used for extraction.
  • the asphaltenes fraction is also responsible for a large percentage of the contaminants contained in the bitumen (for example Athabasca bitumen is typically 72%-76% w/w of the metals, 53%-58% w/w of coke precursors, and 26%-31% w/w of the heteroatoms - sulphur, nitrogen and oxygen), making bitumen very challenging to process into clean and valuable products.
  • the heavy hydrocarbon material is included within deasphalted heavy hydrocarbon-comprising material.
  • an asphaltene-comprising heavy hydrocarbon-comprising material is deasphalted.
  • Deasphalting effects production of the deasphalted heavy hydrocarbon- comprising material, such that the asphaltene content of the deasphalted heavy hydrocarbon- comprising material is less than the asphaltene content of the asphaltene-comprising heavy hydrocarbon-comprising material.
  • the deasphalting is effected by at least a solvent extraction process.
  • the deasphalting is effected by at least a reactive process.
  • the deasphalting is effected by solvent extraction, as is well known in the art, and is described in, and amongst other sources, the article by Billon and others published in 1994 in Volume 49, No. 5 of the journal of the French Petroleum Institute, pages 495 to 507, in the book "Raffinage et conversion des wall prises du petrole [Refining and Conversion of Heavy Petroleum Products]" by J. F. Le Page, S. G. Chatila, and M. Davidson, Edition Technip, pages 17-32.
  • the solvent material is a supercritical fluid at the operating conditions of the zone within which the solvent material is separated (for recycling and re-use) from the heavy hydrocarbon material which it has previously extracted.
  • Olefin means an unsaturated hydrocarbon containing one or more carbon- carbon double bonds that are not part of an aromatic ring, and, for greater certainty, includes di- olefins and cyclo-olefins.
  • Olefinic material means a material consisting of one or more olefins.
  • Light olefinic material means any one or both of the following:
  • Peline specification refers to a characteristic of an oil that effects whether it can be transported by pipeline, and varies from jurisdiction to jurisdiction. In Canada, for example, there are three critical specifications that must be met by an oil to be acceptable for pipeline transport: The viscosity should be below the maximum viscosity limit (e.g. ⁇ 350 cSt at the pipeline reference temperature, which could be as low as 7.5°C during the winter months);
  • the density should be below the maximum density limit (e.g. ⁇ 940 kg.m at 15.6°C, or >19°API);
  • the olefins content should be below the maximum limit (e.g. ⁇ 1 wt% as 1- decene equivalent) per CAPP olefins in crude oil by proton NMR test.
  • fraction of, with reference to a material means, depending on the context, one of (a) a portion of the material with the same, or substantially the same, composition as the material as a whole, or (b) a portion of the material that is compositionally different than the material as a whole, or either one of (a) or (b).
  • the upgrading of the heavy hydrocarbon material includes cracking of the heavy hydrocarbon material.
  • Cracking refers to any process for breaking down heavier hydrocarbon molecules into lighter hydrocarbon molecules.
  • Exemplary methods of cracking include thermal cracking, steam cracking, catalytic cracking, and coking.
  • Thermal cracking refers to an example of a cracking process that uses heat to perform such breaking of heavier molecules into smaller ones.
  • Exemplary thermal cracking processes include visbreaking.
  • the cracking is effected within a cracking unit operation.
  • the cracking unit operation effects visbreaking, and includes a heater and a soaker.
  • the process includes treating a heavy hydrocarbon material-comprising feed 112.
  • the treating is such that an upgraded product 200 is produced.
  • the treating includes cracking the heavy hydrocarbon material-comprising feed 112 within a reaction zone 11 1.
  • the reaction zone 1 1 1 is disposed at a temperature of at least 300 degrees Celsius, such as, for example, at least 350 degrees Celsius.
  • the heavy hydrocarbon material-comprising feed may be derived from a heavy hydrocarbon material-comprising supply stream 1012 from which a portion has bypassed the process as bypass stream 1014 and then combined with the upgraded product 200.
  • cracking of the heavy hydrocarbon material-comprising feed produces olefinic material within an upgraded intermediate product 1 14.
  • the process further includes, within a reaction zone 120, effecting a reduction in content of olefinic material within the upgraded intermediate 1 14.
  • a reduction of the content of olefinic material within the upgraded intermediate 1 14 is then effected to produce an olefinic material content-reduced product 1 15.
  • An upgraded product 200 is produced including the olefinic material content-reduced product 115.
  • the process further includes creating conditions which suppress the formation of olefinic material during the cracking within the reaction zone 111.
  • the upgraded intermediate 1 14, prior to supplying the upgraded intermediate to the reaction zone 120 may be useful to pre-treat the upgraded intermediate 1 14, prior to supplying the upgraded intermediate to the reaction zone 120, such as by effecting a reduction in the content of di-olefins within the upgraded intermediate.
  • di-olefins and, particularly, the conjugated diolefins
  • the pre-treatment may include, for example, catalytic conversion, adsorption, precipitation, or extraction.
  • the catalyst material being used for the pre-treatment may be different than the catalyst material that is used for effecting, in the absence, or the substantial absence, of adscititious diatomic hydrogen, the reducing of the content of olefinic material within at least a fraction of the upgraded intermediate. If the pre- treatment is effected, in the absence, or the substantial absence, of adscititious diatomic hydrogen, and results in the reducing of the content of olefinic material within at least a fraction of the upgraded intermediate, then the pre-treatment is considered to be included within the step of reducing the content of olefinic material within at least a fraction of the upgraded intermediate in the absence, or the substantial absence, of adscititious diatomic hydrogen.
  • the reducing of the content of olefinic material within at least a fraction of the upgraded intermediate 1 14 is effected in the absence, or the substantial absence, of adscititious diatomic hydrogen (H 2 ).
  • the reducing of the content of olefinic material within at least a fraction of the upgraded intermediate 1 14 is effected within a reaction zone 120, and the ratio of the weight of adscititious diatomic hydrogen within the reaction zone 120 to the weight of olefinic material within at least a fraction of the upgraded intermediate within the reaction zone is less than 0.25, such as, for example, less than 0.1, and includes zero or substantially zero.
  • adscititious diatomic hydrogen is absent, or substantially absent within the reaction zone 120.
  • the reduction of the content of olefinic material within at least a fraction of the upgraded intermediate 1 14 is effected by alkylating one or more aromatic compounds, that are present within the at least a fraction of the upgraded intermediate, with the olefinic material.
  • aromatic compounds are typically present within heavy hydrocarbon material, and are, therefore, available to effect conversion of the olefinic material such that the content of olefinic material within the at least a fraction of the upgraded intermediate is reduced.
  • the one or more aromatic compounds with which the olefinic material participates in the alkylation reaction is present within the heavy hydrocarbon material being upgraded.
  • the one or more aromatic compounds are present within the bitumen or heavy oil from which the heavy hydrocarbon material, being upgraded, is derived.
  • the alkylation reaction is a reaction comprising the addition of an olefmic group to an aromatic group (e.g. the aromatic group is essentially the alkyl acceptor and would be available within the hydrocarbon feed).
  • the olefins-aromatics alkylation reaction produces an alkylated aromatic compound and effects a reduction in olefinic material content of the upgraded intermediate.
  • the reaction can occur without the use of an external source of olefins, di-olefins, aromatics and/or hydrogen and, without substantial loss of the volume of material as compared to the hydrocarbon feed.
  • the difference between the volume of the reaction product and the volume of the upgraded intermediate, whose olefinic material content is being reduced, is about 0.1% to 10% v/v.
  • the volume of the product is substantially similar to the original feed.
  • the exact volume decrease or increase is dependent on the olefinic material content of the upgraded intemediate and other reaction conditions.
  • the olefinic group that takes part in the reaction may be a sole olefin, or it may be attached to and/or form part of a molecule containing at least one other functional group.
  • the aromatic group may be a sole aromatic hydrocarbon or may be attached to, and/or form part of a molecule that contains at least one other functional group.
  • the alkylation is conducted within a reaction zone 120 (such as, for example, within a reactor 121) at a pressure and temperature which facilitates olefin alkylation with aromatics (olefins-aromatics alkylation).
  • a fraction of the upgraded intermediate 1 14, produced by the cracking of the heavy hydrocarbon material-comprising feed 1 12 within the cracking unit operation 1 10, is supplied to the reaction zone 120 so as to effect olefin alkylation with aromatics.
  • the temperature within the reaction zone is below about 380°C.
  • the temperature within the reaction zone ranges from about 50°C to about 380°C, such as, for example, from about 150°C to about 350°C.
  • the pressure within the reaction zone 200 is such that the reactants and resultant reaction product are disposed in a liquid, or substantially liquid, state. While the transition phase from liquid to vapour is pressure and temperature dependent, the methods disclosed herein can be carried out within a reaction zone at a pressure from about 0 to about 8 MPa, such as for example, from about 2 MPa to about 5 MPa.
  • the alkylation has a weight hourly space velocity of from about 0.01 to about 20 h_1 , such as, for example, from about 0.02 to about 20 h_1 .
  • the alkylation is catalyzed with a catalyst material disposed within the reaction zone 120.
  • the catalyst material includes at least one acid catalyst, and the reaction zone 120 is disposed at a temperature below around 380 °C and at a pressure sufficient for the reactants and resultant product to be disposed in a liquid, or substantially liquid, state.
  • the catalyst material, operating conditions, and reactor are selected to allow this process to achieve desirable olefins content reduction. It is possible to select different combinations of the reactor, catalyst material and operating conditions that will convert the olefins in the feed to a sufficient degree to meet the desired operating and/or pipeline specifications objective(s).
  • the catalyst material is selected such that the catalyst material can catalyze the reaction without being poisoned or otherwise inhibited to an extent that the reaction cannot occur. In practice, this means that if the catalyst material includes an acid catalyst, the reaction conditions are chosen such that the acid catalyst would not become irreversibly poisoned with basic compounds present in the feed.
  • the temperature can be chosen to prevent the acid catalyst from reacting with basic compounds, or at least, from becoming irreversibly bound to the basic compounds.
  • the upgraded intermediate 1 14 would generally be produced as a result of an upgrading process, such as an upgrading process for the processing of heavy oils, the upgraded intermediate 114 may have species that include heteroatoms such as sulfur, nitrogen and oxygen. These types of heteroatoms can sometimes be problematic for acid catalysis because strong bonds or strong adsorption can be formed between the compounds in the feed and the acid sites on the catalyst material, thereby rendering the catalyst material neutralized or inactive.
  • the acid strength of the catalyst material is selected in such a way that the compounds in the feed adsorb to form a bond with the acid sites that do not persist at the operating temperature of the catalyst material and hence the catalyst material is not rendered inactive.
  • the acid strength of the catalyst material is within the range of strength characterized by temperature programmed ammonia desorption within the temperature range of 150 degrees Celsius to 350 degrees Celsius.
  • the catalyst material may be a heterogeneous catalyst material selected from the group consisting of supported liquid phase catalyst material, solid catalyst materials, and supported homogeneous catalyst materials.
  • the supported liquid phase catalyst material includes Bransted acids (e.g. H 2 S0 4 , HF) and Lewis acids (e.g. BF 3 ).
  • Bransted acids e.g. H 2 S0 4 , HF
  • Lewis acids e.g. BF 3
  • the heterogeneous catalyst material has a particle size and particle morphology suitable for use in a packed bed may be used.
  • Catalyst materials that are suitable for use in packed bed reactors are known in the art. Such catalyst materials have a smaller chance of contaminating the hydrocarbon product as the catalyst material-product separation tends to be easier, allowing for simpler reactor and operating configurations. This may be advantageous when used in a field upgrading application (e.g. when the upgrading occurs on site), as such field upgrading applications are most economical when there is less complex equipment set-up.
  • the heterogeneous catalyst material includes large pore catalyst materials that can accommodate bulky olefin and the potentially bulky aromatics.
  • the desirable pore size mainly depends on the size of the molecules being treated and the size of the materials being produced.
  • the catalyst material includes a pore network with a pore diameter of greater than 0.5 nanometres.
  • the pore diameter is within the range of 0.5 to ten (10) nanometres. If the pore diameter is too small, larger molecules will not be able to travel through the pore network.
  • large pore diameter reduces the available surface area for catalyst activity, and also compromises mechanical integrity of the catalyst structure.
  • the catalyst material has acidic properties and, therefore, includes at least one acid catalyst.
  • the acid catalyst may be promoted with metals, even though metal promoters are not specifically required by the processes disclosed herein.
  • the acid catalyst has sufficient acid strength to catalyze the olefins-aromatics alkylation reaction, as well as an acid strength distribution to retain sufficient activity in contact with the basic compounds that are present in the upgraded intermediate.
  • the temperature and acid catalyst are selected such that an optimal combination of olefins-aromatics alkylation activity and smallest amount of catalyst inhibition by compounds that are strongly adsorbing, or are basic in nature in the reaction product (with reduced olefins levels) is achieved.
  • heterogeneous catalysts are catalytically active materials for liquid phase aromatic alkylation:
  • Acidic resins such as sulfonated styrene-divinylbenzene copolymers (e.g.
  • an amorphous silica-alumina catalyst, material or a crystalline silica-alumina catalyst material may be used in this process.
  • the silica- alumina catalyst material may have a Si0 2 to A1 2 0 3 ratio of 0-99 wt% for example, but in some circumstances, it may be appropriate to use a catalyst having a Si0 2 to A1 2 0 3 ratio ratio of 5-75 wt%.
  • the silica-alumina catalyst material is generally activated by calcination at a temperature in the range 500 to 600 degrees Celsius.
  • catalyst type is based on accessibility and performance in the presence of basic compounds, such as pyridine, which may be acid catalyst poisons.
  • Basic nitrogen compounds are typically present in most hydrocarbon feed materials that have not been hydro-processed.
  • the type of catalyst material affects the selection of the reactor and operating conditions.
  • the operating conditions are selected to match the catalyst employed. There are a number of guiding principles in selecting appropriate operating conditions. These are as follows:
  • the temperature range depends on the catalyst selected and the contaminants present in the hydrocarbon feed. Olefin-aromatic alkylation reactions are favored thermodynamically by low temperature. However, the contaminants present in the hydrocarbon feed, in particular basic nitrogen species, tend to deactivate the acid sites in the catalyst and render it ineffective after a short exposure time. It has been found however, that operating the catalyst at higher temperatures the catalyst can perform the reaction without being poisoned or otherwise inhibited to an extent that the reaction cannot occur. If too high a temperature is used however the rate of olefins polymerization reactions that promote fouling and catalyst deactivation will prevail.
  • the operating temperature needs to consider the rate of catalytic or thermal cracking such that the amount of olefins produced during the cracking process does not exceed the target olefins concentration at the outlet of the reactor.
  • the maximum operating temperature is in the range of about 320 to 380 degrees Celsius for silica- alumina catalysts.
  • the lower operating temperature limit is determined by the activity of the catalyst in the presence of basic heteroatom feed contaminants, where below this point olefin- aromatic alkylation reactions are too slow for significant olefins conversion to occur.
  • the minimum operating temperature In order to perform acid catalysis at an industrially meaningful rate, the minimum operating temperature must be sufficiently high to avoid excessive catalyst poisoning by irreversible adsorption of compounds.
  • the minimum operating temperature is in the range of from about 200 to 300 degrees Celsius for silica-alumina catalysts.
  • the temperature conditions appropriate for acidic resin and SPA catalysts are from about 50 to 380 degrees Celsius, and more particularly, from about 150 to 350 degrees Celsius.
  • the pressure should be sufficient to keep most of the hydrocarbon feed material in the liquid phase at the operating temperature. This limits the amount of light olefins that may be present in the vapour phase and that may pass through the reactor unconverted.
  • a typical operating pressure is in the range 0-8 MPa. For operating temperatures in the range of about 300 to 380 degrees Celsius, which is typical for silica-alumina catalysts, the pressure range is about 2-5 MPa.
  • the flow rate is determined by the olefins conversion requirements for the selected combination of catalyst and operating conditions.
  • the range of weight hourly space velocity (WHSV) is 0.01 to 20 h "1 .
  • the WHSV range is generally in the range of 0.02 to 2 h "1 .
  • Optimum conditions for olefins conversion are adjusted to meet final product specifications and may be determined empirically, depending on changes in feed composition, selected catalyst types (i.e. one or more catalyst types used in conjunction) and aging, number of reactor beds (i.e. single vs. multiple with interstage cooling) and other unit constraints. Process operating conditions can be optimized using strategies known in the art.
  • the process may be conducted in a conventional packed bed reactor.
  • the catalyst is contained and retained in a process vessel that is designed according to principles known in the art.
  • a single adiabatic packed bed (fixed bed) reactor is employed.
  • the use of multiple catalyst beds within the reactor, the use of inter-bed quench feed stream, the use of more than one reactor and product recycling may all be considered.
  • the adiabatic temperature increase should be controlled.
  • Aromatic alkylation with olefins and olefins dimerization (a possible side-reaction) are both exothermic.
  • Implementation of heat management strategies in the reactor design is known in the art.
  • the reactor may be operated either in down flow or up flow configuration.
  • the operation of the reactor in an up flow configuration with a liquid filled catalyst bed improves heat transfer and catalyst wetting, and maximizes liquid holdup.
  • This configuration also facilitates removal of heavy products (gums) typical of di-olefms reactions from the catalyst by dissolving it in the liquid product, as described in patents related to the buildup of fouling agents (e.g. U.S. Patent No. 4,137,274).
  • the operation of the reactor in a down flow configuration facilitates maintenance and catalyst replacement, since the contaminated portion of the catalyst will be concentrated at the top of the reactor where it is easier to access and replace.
  • the reactor may further be designed for easy maintenance and catalyst replacement in the field.
  • the olefinic material may include one or more cyclo-olefins, and the reducing of the content of olefinic material within the at least a fraction of the upgraded intermediate is effected by dehydrogenation of the one or more cyclo-olefins.
  • the dehydrogenation of a cyclo-olefin produces an aromatic.
  • the cyclo-olefin includes one or more heteroatoms
  • the dehydrogenation is effected within a reaction zone 120 disposed at a temperature of from about 100 degrees Celsius to about 300 degrees Celsius, such as, for example, from about 125 degrees Celsius to about 275 degrees Celsius.
  • the cyclo-olefin is a five-membered ring or a six-membered ring, and may include one or more heteroatoms.
  • the reaction zone 120 includes a catalyst material (including a supported catalyst material) that is active for hydrogenation- dehydrogenation, and includes catalysts that are active for hydrogenation-dehydrogenation in the presence of heteroatom-containing cyclo-olefins (e.g. Ni/Al 2 0 3 , Ni/Si0 2 , NiMo/Al 2 0 3 , CoMo/Al 2 0 3 , FeS, or MoS 2 ).
  • heteroatom-containing cyclo-olefins e.g. Ni/Al 2 0 3 , Ni/Si0 2 , NiMo/Al 2 0 3 , CoMo/Al 2 0 3 , FeS, or MoS 2 .
  • the catalyst material for the dehydrogenation includes large pore catalyst materials that can accommodate bulky olefin and the potentially bulky aromatics.
  • the desirable pore size mainly depends on the size of the molecules being treated and the size of the materials being produced.
  • the catalyst material includes a pore network with a pore diameter of greater than 0.5 nanometres.
  • the pore diameter is within the range of 0.5 to ten (10) nanometres. If the pore diameter is too small, larger molecules will not be able to travel through the pore network.
  • large pore diameter reduces the available surface area for catalyst activity, and also compromises mechanical integrity of the catalyst structure.
  • the olefinic material includes one or more cyclo-olefins
  • the reducing of the content of the olefinic material within the at least a fraction of the upgraded intermediate is effected by hydrogen disproportionation of the one or more cyclo-olefins.
  • the hydrogen disproportionation converts the one or more cyclo-olefins to cyclo- paraffin structures or aromatic structures.
  • the hydrogen disproportionation is effected within the reaction zone 1 11.
  • the temperature within the reaction zone 111 is at least 300 degrees Celsius.
  • the heavy hydrocarbon material-comprising feed that is the subject of the treating that includes cracking of the heavy hydrocarbon material-comprising feed, includes at least a fraction of a heavier hydrocarbon material-comprising fraction 134A that has been, along with a lighter hydrocarbon material- comprising fraction 134B, separated from a feed material 150.
  • a feed material 150 is provided, and the feed material 150 is separated (for example, by a separator 130, such as a fractionator) into at least the heavier hydrocarbon material-comprising fraction 134A and the lighter hydrocarbon material-comprising fraction 134B.
  • the heavier hydrocarbon material- comprising fraction 134A has a weight average molecular weight that is greater than that of the lighter hydrocarbon material-comprising fraction 134B.
  • the separation is effected based on differences in volatilities between the heavier hydrocarbon material-comprising fraction 134A and the lighter hydrocarbon material-comprising fraction 134B.
  • Suitable separation processes that are based on differences in volatilities between the heavier hydrocarbon material-comprising fraction 134 A and the lighter hydrocarbon material- comprising fraction 134B include stripping and distillation.
  • the heavier hydrocarbon material-comprising fraction 134A has a higher boiling point than the lighter hydrocarbon material-comprising fraction 134B. In some embodiments, for example, at a predetermined temperature at which the separation is effected, the heavier hydrocarbon material- comprising fraction 134A has a lower vapour pressure than the lighter hydrocarbon material- comprising fraction 134B.
  • the vapour pressure of the heavier hydrocarbon material- comprising fraction 134A is less than 90% (such as, for example, less than 80%, such as, for example, less than 70%, such as, for example, less than 60%, such as, for example, less than 50%) of the vapour pressure of the lighter hydrocarbon material-comprising fraction 134B.
  • the additional incremental cost in configuring a cracking unit operation 1 10 for effecting the cracking of lighter hydrocarbon material may not be justified, having regard to the fact that, relative to heavier hydrocarbon material, cracking of lighter hydrocarbon material is not pronounced and does not significantly contribute to the production of a hydrocarbon material having a pipeline specification
  • the lighter hydrocarbon material-comprising fraction 134B is combined with at least a fraction of the olefinic material content-reduced product 115, such that the upgraded product 200 is produced.
  • the reducing of the content of olefinic material within the upgraded intermediate 1 14 is effected by separating at least a fraction of the upgraded intermediate 114 into at least an olefin-comprising treatment fraction 132 and a treatment bypass fraction 134.
  • the separating is effected within a separator 130, such as a fractionator.
  • the separation is effected based on differences in volatilities between the olefin-comprising treatment fraction 132 and the treatment by-pass fraction 134.
  • Suitable separation processes that are based on differences in volatilities between the olefin-comprising treatment fraction 132 and the treatment by-pass fraction 134 include stripping and distillation. In some embodiments, for example, at a predetermined temperature at which the separation is effected, the olefin-comprising treatment fraction 132 has a higher vapour pressure than the treatment by-pass fraction 134.
  • the vapour pressure of the treatment by-pass fraction 134 is less than 90% (such as, for example, less than 80%, such as, for example, less than 70%, such as, for example, less than 60%, such as, for example, less than 50%) of the vapour pressure of the olefin-comprising treatment fraction 132.
  • the content of olefinic material within the olefin-comprising treatment fraction 132 is reduced such that an olefin depleted intermediate 136 is produced.
  • the reducing of the content of olefinic material within the olefin- comprising treatment fraction 132 includes effecting conversion of the olefinic material within the olefin-comprising treatment fraction 132, such as by the processes effected within the reaction zone 120, as explained above, including, in particular, those which are carried out in the absence, or the substantial absence, of adscititious diatomic hydrogen.
  • the treatment by-pass fraction 134 may then be combined with at least the olefin-depleted intermediate 136 to produce the olefinic material content-reduced product 1 15, which then may be produced as at least a part of the upgraded product 200.
  • the upgraded intermediate 114 may not have been sufficiently cracked by a single pass through the cracking unit operation 110, such that excessive amounts of heavy hydrocarbon material remain present within the upgraded intermediate 114. It may be desirable, therefore, to recycle a fraction of the upgraded intermediate 1 14 through the cracking unit operation 110 so as to further reduce the content of heavy hydrocarbon material within the upgraded intermediate 114.
  • the treatment by-pass fraction 134 is separated into at least fractions 136A, 136B, with the fraction 136B being combined with the olefin-depleted intermediate, and the fraction 136A being supplied to the cracking unit operation.
  • the heavy hydrocarbon material-comprising feed includes a combination of the heavy hydrocarbon material-comprising supply stream 150 and the fraction 138A.
  • the recycling of at least a fraction of the upgraded intermediate 1 14 may be effected by separating the treatment by-pass fraction 134 from the upgraded intermediate 114, and then supplying a fraction 138 A of the treatment by-pass fraction 134 to the reaction zone 111 of the cracking unit operation 1 10 (see, for example, Figure 4).
  • the fraction 134 may include not an insubstantial content of lighter hydrocarbon material, whose recycling through the reaction zone 1 1 1 may not be justifiable, as it is recognized that additional incremental cost in configuring the cracking unit operation 1 10 for effecting the cracking of recycled lighter hydrocarbon material may not be justified, having regard to the fact that, relative to heavier hydrocarbon material, cracking of lighter hydrocarbon material is not pronounced and does not significantly contribute to the production of a hydrocarbon material having a pipeline specification. It is, therefore, desirable to separate, from the treatment by-pass fraction 134, at least a heavier hydrocarbon material-comprising fraction 134A and a lighter hydrocarbon material-comprising fraction 134B, and recycle only at least some material (i.e.
  • the upgraded intermediate 114 includes cyclo-olefins
  • cyclo-olefms being recycled within the fraction 138 A may undergo hydrogen disproportionation within the reaction zone 1 1 1 , thereby further reducing the olefmic content of the upgraded product 200 being produced.
  • the process includes supplying a heavy hydrocarbon material-comprising supply stream 150 to the cracking unit operation such that the intermediate upgraded product 114 is produced. At least a fraction of the intermediate upgraded product 114 is separated into a olefin-comprising treatment fraction 132 and a treatment by-pass fraction 134.
  • the separating is effected within a separator 130, such as a fractionator.
  • the separation is effected based on differences in volatilities between the olefm-comprising treatment fraction 132 and the treatment by-pass fraction 134.
  • Suitable separation processes that are based on differences in volatilities between the olefin-comprising treatment fraction 132 and the treatment by-pass fraction 134 include stripping and distillation. In some embodiments, for example, at a predetermined temperature at which the separation is effected, the olefin-comprising treatment fraction 132 has a higher vapour pressure than the treatment by-pass fraction 134.
  • the vapour pressure of the treatment by-pass fraction 134 is less than 90% (such as, for example, less than 80%, such as, for example, less than 70%, such as, for example, less than 60%, such as, for example, less than 50%) of the vapour pressure of the olefin-comprising treatment fraction 132.
  • the boiling point range of the olefin-comprising treatment fraction is between 25 degrees Celsius and 365 degrees Celsius, such as, for example, between 25 degrees Celsius and 200 degrees Celsius, such as, for example, 25 degrees Celsius and 100 degrees Celsius.
  • the content of olefmic material within the olefin-comprising treatment fraction is reduced such that an olefin-depleted intermediate 136 is produced.
  • the reducing of the content of olefinic material within the olefin-comprising treatment fraction 132 includes effecting conversion of the olefinic material within the olefm-comprising treatment fraction 132, such as by the processes effected within the reaction zone 120, as explained above, including, in particular, those which are carried out in the absence, or the substantial absence, of adscititious diatomic hydrogen.
  • the treatment by-pass fraction 134 is then separated (such as by the separator
  • the separation is effected based on differences in volatilities between the heavier hydrocarbon material-comprising fraction 134 A and the lighter hydrocarbon material-comprising fraction 134B.
  • Suitable separation processes that are based on differences in volatilities between the heavier hydrocarbon material-comprising fraction 134A and the lighter hydrocarbon material- comprising fraction 134B include stripping and distillation.
  • the heavier hydrocarbon material-comprising fraction 134A has a lower vapour pressure than that of the lighter hydrocarbon material-comprising fraction 134B.
  • the vapour pressure of the heavier hydrocarbon material-comprising fraction 134A is less than 90% (such as, for example, less than 80%, such as, for example, less than 70%, such as, for example, less than 60%, such as, for example, less than 50%) of the vapour pressure of the lighter hydrocarbon material-comprising fraction 134B.
  • the lighter hydrocarbon material-comprising fraction 134B has a lower vapour pressure than that of the olefin-comprising treatment fraction 132.
  • the vapour pressure of the lighter hydrocarbon material- comprising fraction 134B is less than 90% (such as, for example, less than 80%, such as, for example, less than 70%, such as, for example, less than 60%, such as, for example, less than 50%) of the vapour pressure of the olefin-comprising treatment fraction 132.
  • the boiling point range of the olefin-comprising treatment fraction 132 is between 25 degrees Celsius and 365 degrees Celsius (such as, for example, between 25 degrees Celsius and 200 degrees Celsius, such as, for example, 25 degrees Celsius and 100 degrees Celsius), and the boiling point range of the lighter hydrocarbon material-comprising fraction 134B is between 80 degrees Celsius and 450 degrees Celsius (such as, for example, 200 degrees Celsius and 450 degrees Celsius, such as, for example, between 360 degrees Celsius and 450 degrees Celsius).
  • the lighter hydrocarbon material-comprising fraction 134B includes hydrocarbon material that is equivalent to light vacuum gas oil.
  • the treating includes, separating at least a fraction of the upgraded intermediate into at least an olefin-comprising treatment fraction 132, a light hydrocarbon material-comprising fraction 134B, and a heavy hydrocarbon material-comprising fraction 134A.
  • the separating is effected within a separator 130, such as a fractionator.
  • the separation is effected based on differences in volatilities between the olefm-comprising treatment fraction 132, the light hydrocarbon material-comprising fraction 134B, and the heavy hydrocarbon material-comprising fraction 134 A.
  • Suitable separation processes that are based on differences in volatilities between these components include stripping and distillation.
  • the heavier hydrocarbon material-comprising fraction 134A has a lower vapour pressure than that of the lighter hydrocarbon material-comprising fraction 134B
  • the lighter hydrocarbon material-comprising fraction 134B has a lower vapour pressure than that of the olefin-comprising treatment fraction 132.
  • the vapour pressure of the heavier hydrocarbon material-comprising fraction 134A is less than 90% (such as, for example, less than 80%, such as, for example, less than 70%, such as, for example, less than 60%, such as, for example, less than 50%) of the vapour pressure of the lighter hydrocarbon material-comprising fraction 134B, and the vapour pressure of the lighter hydrocarbon material-comprising fraction 134B is less than 90% (such as, for example, less than 80%, such as, for example, less than 70%, such as, for example, less than 60%, such as, for example, less than 50%) of the vapour pressure of the olefin-comprising treatment fraction 132.
  • a fraction 138A of the produced heavier hydrocarbon material-comprising fraction 134A may be recycled through the cracking unit operation 1 10.
  • the lighter hydrocarbon material -comprising fraction 134B instead of being processed through the cracking unit operation 1 10, the lighter hydrocarbon material -comprising fraction 134B may be combined with at least the produced olefm-depleted intermediate 136 (and, in some embodiments, for example, a fraction 138B of the heavier hydrocarbon material- comprising fraction 134A) to create an olefinic material content-reduced product 1 15, which may then be produced as the upgraded product 200.
  • the heavy hydrocarbon material-comprising supply stream 150 may be combined with the upgraded intermediate 1 14 to form the feed to the separator 130.
  • the reducing of the content of olefinic material within the upgraded intermediate 114 is defined by a reduction in the content of light olefinic material within at least a fraction of the upgraded intermediate 1 14 such that the content of light olefinic material within the olefinic material content-reduced product is less than the content of light olefinic material within the at least a fraction of the upgraded intermediate 1 14.
  • the ratio of the weight of light olefinic material within the olefinic material content-reduced product to the total weight of the olefinic material content-reduced product is less than the ratio of the weight of light olefinic material within the upgraded intermediate 114 to the total weight of the upgraded intermediate 114.
  • the reducing of the content of light olefinic material within the at least a fraction of the upgraded intermediate 114 includes effecting conversion of the light olefinic material within at least a fraction of the upgraded intermediate 1 14, such as by the processes effected within the reaction zone 120, as explained above with respect to olefinic material generally, including, in particular, those processes which are carried out in the absence, or the substantial absence, of adscititious diatomic hydrogen.
  • the reducing of the content of olefinic material within the upgraded intermediate 1 14 is effected by separating at least a fraction of the upgraded intermediate 1 14 into at least a lighter olefin-comprising fraction 142 and a heavier fraction 144, and then effecting a reduction in the content of light olefinic material within the light olefin-comprising fraction 142 (such as by the processes effected within the reaction zone 120, as explained above with respect to olefinic material generally) such that a light olefm-depleted intermediate 146 is produced, and then combining the heavier fraction 144 with at least the light olefin-depleted intermediate 146 to produce a light olefinic material content-reduced product.
  • the ratio of the weight of light olefinic material within the lighter olefin-comprising fraction 142 to the total weight of the lighter olefin-comprising fraction 142 is greater than the ratio of the weight of light olefinic material within the heavier fraction 144 to the total weight of the heavier fraction 144.
  • An upgraded product 200 may be produced including the light olefin content material-reduced product.
  • the separation is effected within a separator 130, such as a fractionator.
  • the separation is effected based on differences in volatilities between the lighter olefin-comprising fraction 142 and the heavier fraction 144.
  • Suitable separation processes that are based on differences in volatilities of the lighter olefin-comprising fraction 142 and the heavier fraction 144 include stripping and distillation. In some embodiments, for example, at a predetermined temperature at which the separation is effected, the lighter olefin- comprising fraction 142 has a higher vapour pressure than the heavier fraction 144.
  • the vapour pressure of the heavier fraction 144 is less than 90% (such as, for example, less than 80%, such as, for example, less than 70%, such as, for example, less than 60%, such as, for example, less than 50%) of the vapour pressure of the lighter olefin-comprising fraction 142.
  • the reducing of the content of olefinic material within the upgraded intermediate 114 is effected by separating at least a fraction of the upgraded intermediate 1 14 into a more volatile fraction 162 and a less volatile fraction 164, wherein the more volatile fraction 164 has a boiling point range, at a pressure of one (1) atmosphere, of between 25 degrees Celsius and 200 degrees Celsius, such boiling point range being characteristic of a lighter olefinic material.
  • a reduction in the content of olefinic material within the more volatile fraction 164 such as by the processes effected within the reaction zone 120, as explained above with respect to olefinic material generally) such that an olefin-depleted intermediate 166 is produced, and then combining at least a fraction of the less volatile fraction 164 with at least the olefm-depleted intermediate 166 to produce an olefinic material content- reduced product 1 15.
  • An upgraded product 200 may be produced including the olefin content material -reduced product 115.
  • the separation is effected within a separator 130, such as a fractionator.
  • the separation is effected based on differences in volatilities between the more volatile fraction and the less volatile fraction.
  • Suitable separation processes that are based on differences in volatilities of the more volatile fraction and the less volatile fraction include stripping and distillation.
  • the treating of the heavy hydrocarbon material-comprising feed 1 12 includes cracking the heavy hydrocarbon material-comprising feed within the reaction zone 111, of the cracking unit operation 1 10, in the presence of a hydrogen donor material 108.
  • the hydrogen donor material 108 is another hydrocarbon material-comprising feed that has hydrogen transfer or hydrogen donor properties.
  • the treating is such that an upgraded product 200 is produced.
  • the presence of the hydrogen donor material 108 discourages the production of olefinic material, and thereby renders the upgraded product 200 of a quality that meets at least one pipeline specification or come closer to meeting at least one pipeline specification.
  • the hydrogen donor material 108 is supplied to the reaction zone 111.
  • the ratio of weight of hydrogen donor material supplied to the reaction zone 111 to weight of heavy hydrocarbon material is at least 1 :20. In some of these embodiments, for example, the ratio is at least 1 :5, such as, for example, at least 1 :4. In some embodiments, for example, the ratio is between 1 :20 and 4: 1, such as, for example, between 1 :6 and 1 :3.
  • the hydrogen donor material includes synthetic crude oil.
  • the hydrogen donor material includes (or, in some embodiments, for example, is defined by) one or more cycloalkanes, one or more naptheno-aromatics, or one or more cycloalkanes and one or more naptheno-aromatics.
  • the cycloalkane may be substituted or unsubstituted.
  • the naphtheno-aromatic may be substituted or unsubstituted.
  • the hydrogen donor material includes a hydrocarbon including a six-membered ring structure that is attached to an aromatic.
  • the hydrogen donor material is substantially free of five-membered ring structures that cannot form aromatic rings as a consequence of their hydrogen donor activity.
  • the hydrogen donor material includes tetralin (i.e. 1 ,2,3,4-tetrahydrohaphthalene).
  • the cracking of the heavy hydrocarbon material-comprising feed in the presence of a hydrogen donor material, that includes a cycloalkane (such as a five-membered cycloalkane, and also, in some embodiments, and to some extent, a six-membered cyclo-alkane) or a naphtheno-aromatic produces an intermediate product 1 14 including a cyclo-olefin material that includes one or more cyclo-olefins.
  • the treating further includes effective a reactive process, such that the intermediate product 1 14 participates within the reactive process as a reactant and is consumed within the reactive process.
  • the reactive process includes dehydogenation of an olefinic material within a reaction zone 170 (such as within a reactor 172) to produce an olefmic material content-reduced product 1 15.
  • the treating includes dehydrogenating at least a fraction of the cyclo- olefin material of the intermediate product 114.
  • the reactive process is effected within the reaction zone 170 disposed at a temperature that is thermodynamically more favourable to the dehydrogenation of cyclo-olefins than to the dehydrogenation of cyclo-alkanes.
  • the temperature of the reaction zone is from about 125 degrees Celsius and 275 degrees Celsius.
  • a suitable catalyst material that is active for dehydrogenation and hydrogenation, is disposed within the reaction zone 170.
  • the catalyst material may include a supported metal catalyst that is active for dehydrogenation and hydrogenation in the presence of heteroatom-comprising compounds (e.g. Ni/Al 2 0 3 , Ni/Si0 2 , NiMo/Al 2 0 3 , CoMo/Al 2 0 3 ).
  • the catalyst material includes a dispersed catalyst.
  • an upgraded product 200 is produced and includes the olefinic material content-reduced product 115.
  • the upgraded product 200 meets at least one pipelines specification.
  • the upgraded product 200 is supplied to a pipeline for transporting to a refinery.
  • the process also includes transporting the upgraded product 200, via the pipeleine, to the refinery.
  • feed material 150 that is derived, in part, from a deasphalting process.
  • the feed material 150 includes a deasphalted heavy hydrocarbon-comprising material.
  • an asphaltene-comprising heavy hydrocarbon-comprising material 300 is supplied to a separator 302 to effect phase separation of gaseous material 304 and aqueous material 306 from the raw asphaltene-comprising heavy hydrocarbon-comprising material such that a dewatered/degassed asphaltene-comprising heavy hydrocarbon-comprising material 308 is produced.
  • the material 308 is admixed with solvent material 310, 312 in mixers 314, 316 to produce a mixture 318.
  • the mixture 318 is separated, within a separator 320, into at least an asphaltene- depleted heavy hydrocarbon-comprising material fraction 322 and an asphaltene-enriched material fraction 324.
  • the asphaltene content of the asphaltene-depleted heavy hydrocarbon- comprising fraction 322 is less than the asphaltene content of the mixture 318.
  • the asphaltene- enriched material fraction 324 being denser than the asphaltene-depleted heavy hydrocarbon- comprising material fraction 322, is recovered as an underflow product, and the asphaltene- depleted heavy hydrocarbon-comprising material fraction is recovered as an overhead product in the form of the deasphalted heavy hydrocarbon-comprising material which defines the feed material 150.
  • the asphaltene-enriched material fraction 324 is admixed with solvent material 326 within a mixer 328 and then separated within a separator 330 into an overflow material mixture 332, including deasphalted heavy hydrocarbon- comprising material and solvent material, and an underflow asphaltene-enriched material fraction 334.
  • the material 332 is recycled to upstream of the separator 320 to increase recovery of the deasphalted heavy hydrocarbon-comprising material fraction.
  • the underflow asphaltene-enriched material fraction 334 is supplied to a separator 336, such as a fractionator, to effect separation of the asphaltene-enriched material fraction 334 into a gaseous solvent-enriched material fraction 338 and a further-enriched asphaltene material fraction 340.
  • the gaseous solvent-enriched material fraction 338 may be re-used within the process, while the further-enriched asphaltene material fraction 340 may be further treated to recover water.
  • the feed material 150 which includes at least a fraction of an upgraded intermediate 1 14 produced by the cracking unit operation 1 10, is supplied to a separator 130 (such as a fractionator), for effecting separation of at least the lighter hydrocarbon material-comprising fraction 134B (for example, in the form of a distillate).
  • a separator 130 such as a fractionator
  • the separator 130 additionally effects separation of the olefin-comprising treatment fraction 132 (such as, for example, the lighter olefinic material-comprising fraction) as a distillate.
  • the olefin-comprising treatment fraction 132 is converted into an olefm-depleted intermediate 136 (such as a light olefin material- depleted intermediate), such as by the processes effected within the reaction zone 120, as explained above with respect to olefinic material generally, namely, any one of, or any combination of alkylation and dehydrogenation (with incidental hydrogenation, as explained above).
  • the heavier bottoms product 134A is also recovered.
  • the fraction 138B of the bottoms product 134A is combined with both of the olefin-depleted intermediate 136 and the lighter hydrocarbon material-comprising fraction 134B to produce the upgraded product 200.
  • a fraction 138A of the bottoms product 134A is supplied to the cracking unit operation 1 10.
  • the cracking unit operation may comprise, in series, a heater 1 10a and a soaker 110b, which effects cracking of the bottoms product fraction 138A to produce the upgraded intermediate 1 14 which is then combined into the feed material 150.
  • at least a fraction of the upgraded intermediate 114 is recycled through the cracking unit operation 1 10 in the form of the fraction 138A of the bottoms product 134A.
  • the feed material 150 includes a deasphalted heavy hydrocarbon-comprising material
  • the feed material 150 also typically includes residual solvent material deriving from the deasphalting process, and most of the residual solvent material may be recovered as a top distillate product 308 from the separator 130.
  • steam stream 131 1 supplies steam to the separator to reduce partial pressure of hydrocarbon material, and thereby improve the separation between distillate cuts to optimize the yields of desired product from the separator 130.
  • solvent stream 133 is merged with the treatment material 132 for purging the solvent loop from olefins and also for adding diluent to the upgraded product 200.
  • the presence of olefinic material within the upgraded product 200 is minimized by mitigating formation of the olefinic material within the cracking unit operation 1 10.
  • a bottoms product 134A is recovered and a fraction 138B of the bottoms product 134A is combined with the lighter hydrocarbon material- comprising fraction 134B and the stream 312 to produce the upgraded product 200, while a fraction 138A of the bottoms product 134A is combined with a hydrogen donor material 310 (such as synthetic crude oil that includes cycloalkanes) to produce a cracking unit operation feed 3102, and is then supplied to the cracking unit operation 110.
  • a hydrogen donor material 310 such as synthetic crude oil that includes cycloalkanes
  • the cracking unit operation 110 may comprise, in series, a heater 1 10a and a soaker 110b, which effects cracking of the feed 3102 to produce the upgraded intermediate 1 14 which is then combined into the feed material 150.
  • at least a fraction of the upgraded intermediate 1 14 is recycled through the cracking unit operation in the form of the second fraction 306 of the bottoms product 134A.
  • the feed material 150 includes a deasphalted heavy hydrocarbon-comprising material
  • the feed material 150 also typically includes residual solvent material deriving from the deasphalting process, and most of the residual solvent material may be recovered as a top distillate product 308 from the separator 130.
  • the process embodiment illustrated in Figure 1 1 is modified such that the presence of olefinic material within the upgraded product 200 is further minimized by one or both of aromatic alkylation and dehydrogenation (with incidental hydrogenation), as described above.
  • the dehydrogenation is also helpful for converting cyclo- olefins that may be derived from the supplied hydrogen donor material (such as from five- membered cyclo-alkanes).
  • reaction zone 170 is configured such that, as the received treatment material 132 is conducted through the reaction zone 170, the treatment material 132 is contacted, sequentially, with a dehydrogenation/hydrogenation catalyst, and then with an olefin-aromatic alkylation catalyst.
  • the olefin treating unit 172 includes an inlet 174 for receiving the treatment material 132 and an outlet 176 for discharging the olefin-depleted intermediate 136, and the dehydrogenation/hydrogenation catalyst is disposed closer to the inlet 174 than the olefin-aromatic alkylation catalyst, and the olefin-aromatic alkylation catalyst is disposed closer to the outlet 136 than the dehydrogenation/hydrogenation catalyst.
  • a fraction 138A of the bottoms product 134A is combined with the hydrogen donor material 310 (such as synthetic crude oil that contains cycloalkanes) to produce a cracking unit operation feed 3102 which is then supplied to the cracking unit operation.

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  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

L'invention concerne un procédé pour valoriser un matériau hydrocarboné. Le procédé comprend : (a) le traitement d'une charge comprenant le matériau hydrocarboné, le traitement comprenant le craquage d'une charge comprenant le matériau hydrocarboné de façon à produire un intermédiaire valorisé ; et (b) en l'absence ou pratiquement en l'absence d'hydrogène diatomique superflu, la réduction de la teneur en le matériau oléfinique d'au moins une fraction de l'intermédiaire valorisé de façon à produire un produit à teneur réduite en matériau oléfinique.
PCT/CA2014/000915 2013-07-04 2014-12-23 Valorisation d'un matériau hydrocarboné WO2016000060A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CA2953853A CA2953853C (fr) 2013-07-04 2014-12-23 Valorisation d'un materiau hydrocarbone
CN201480081537.3A CN106661466B (zh) 2013-07-04 2014-12-23 烃材料的升级
US15/323,658 US20170152451A1 (en) 2013-07-04 2014-12-23 Upgrading of hydrocarbon material

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
PCT/CA2014/000541 WO2015000061A1 (fr) 2013-07-04 2014-07-04 Réduction d'oléfines d'une charge d'hydrocarbures par alkylation d'oléfines-composés aromatiques
CAPCT/CA2014/000541 2014-07-04

Publications (1)

Publication Number Publication Date
WO2016000060A1 true WO2016000060A1 (fr) 2016-01-07

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20170327751A1 (en) * 2016-05-16 2017-11-16 Meg Energy Corp. Direct olefin reduction of thermally cracked hydrocarbon streams
US11001762B2 (en) 2017-04-06 2021-05-11 Suncor Energy Inc. Partial upgrading of bitumen with thermal treatment and solvent deasphalting

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5290428A (en) * 1992-03-12 1994-03-01 Alberta Oil Sands Technology And Research Authority Superacid catalyzed hydrocracking of heavy oils and bitumens
CA2192524A1 (fr) * 1995-12-21 1997-06-22 Robert A. Ludolph Methode pour valoriser des fractions petrolieres renfermant des olefines et des aromatiques

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5290428A (en) * 1992-03-12 1994-03-01 Alberta Oil Sands Technology And Research Authority Superacid catalyzed hydrocracking of heavy oils and bitumens
CA2192524A1 (fr) * 1995-12-21 1997-06-22 Robert A. Ludolph Methode pour valoriser des fractions petrolieres renfermant des olefines et des aromatiques

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20170327751A1 (en) * 2016-05-16 2017-11-16 Meg Energy Corp. Direct olefin reduction of thermally cracked hydrocarbon streams
US10619109B2 (en) * 2016-05-16 2020-04-14 Suncor Energy Inc. Direct olefin reduction of thermally cracked hydrocarbon streams
US11001762B2 (en) 2017-04-06 2021-05-11 Suncor Energy Inc. Partial upgrading of bitumen with thermal treatment and solvent deasphalting

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