[go: up one dir, main page]

WO2019094328A1 - Élimination de produits chimiques contenant du silicium de flux d'hydrocarbures - Google Patents

Élimination de produits chimiques contenant du silicium de flux d'hydrocarbures Download PDF

Info

Publication number
WO2019094328A1
WO2019094328A1 PCT/US2018/059196 US2018059196W WO2019094328A1 WO 2019094328 A1 WO2019094328 A1 WO 2019094328A1 US 2018059196 W US2018059196 W US 2018059196W WO 2019094328 A1 WO2019094328 A1 WO 2019094328A1
Authority
WO
WIPO (PCT)
Prior art keywords
petroleum
less
wppm
silicon
silicon content
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/US2018/059196
Other languages
English (en)
Inventor
Mustafa Al-Sabawi
Lindsay A. MITCHELL
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ExxonMobil Technology and Engineering Co
Original Assignee
ExxonMobil Research and Engineering Co
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
Application filed by ExxonMobil Research and Engineering Co filed Critical ExxonMobil Research and Engineering Co
Priority to CA3077234A priority Critical patent/CA3077234A1/fr
Publication of WO2019094328A1 publication Critical patent/WO2019094328A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

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
    • C10G31/00—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for
    • C10G31/09—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for by filtration
    • 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
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/002—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal in combination with oil conversion- or refining processes
    • 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
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/02—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by distillation
    • 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
    • C10G53/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes
    • C10G53/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only
    • 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
    • C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
    • C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
    • C10G67/14—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including at least two different refining steps in the absence 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
    • C10G7/00—Distillation of hydrocarbon oils
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/205—Metal content

Definitions

  • the present disclosure relates to methods for removing silicon-containing compounds, such as anti-foaming agents, from petroleum-based streams to simplify refinery and/or further treatment, optionally to ultimately form a fuel or lubricant product.
  • Anti-foaming agents are one type of chemical used to mitigate such problems. These agents, which are typically oil-soluble silicon-containing chemicals such as polysiloxanes (e.g. , PDMS), when present in crude oil, pose issues for refiners because some silicon-containing chemicals can degrade the quality of refinery products, including gasoline and distillates. Moreover, silicon is a known poison for catalysts in refinery reactors/units. Thus, removal of these silicon-containing chemicals can be important for mitigating issues in refineries and downstream operations.
  • PDMS polysiloxanes
  • polysiloxane anti-foaming agents can readily thermally decompose, for example at about 300-350°C, into lighter cyclic products (e.g. , hexamethyl-cyclotrisiloxane) that have similar boiling point ranges to fuels and fuel precursors, such as naphtha, jet fuel, and diesel. These decomposition products are generally considered detrimental to catalysts, catalytic processes, and fuels products.
  • refinery desalter technology may remove some silicon-containing chemicals, others typically remain in the oil-phase after the desalting process. These chemicals can typically decompose at high temperatures, such as in refinery furnaces, crude towers, and cokers. The decomposition products may then be distributed across wide boiling-point distribution range refinery streams, becoming a threat to catalysts, processing, and finished products.
  • the present invention proposes filtration as an effective technology to remove silicon- based additives (i.e. organic silicon) from crude oil and refinery streams. It has been found that these chemicals may be only partially soluble in hydrocarbons, even though they are not effectively removed by refinery desalters. Consequently, utilization of conventional solids removal methods, such as filtration, allows for removal of silicon-based chemicals.
  • silicon- based additives i.e. organic silicon
  • One aspect of the invention involves a method of removing organosilicon compounds from a petroleum-based feedstream.
  • the method can comprise: providing a petroleum-based feedstream having a first silicon content of at least 1.0 wppm; and filtering the petroleum-based feedstream to yield a permeate having a second silicon content lower than the first silicon content.
  • the second silicon content is at least 25% lower than the first silicon content, the second silicon content is less than 1.0 wppm, or both.
  • the second silicon content is less than 1.0 wppm and at least 50% lower than the first silicon content.
  • Examples of the petroleum-based feedstream can include, but are not necessarily limited to, a bituminous crude oil, a diluted heavy crude oil, an at least partially deasphalted heavy crude oil, a diluted and at least partially deasphalted heavy crude oil, a fracked crude oil, a tight oil, a bottoms stream from a refinery distillation separator, an off-spec fuel stream, an off- spec lubricant stream, and combinations thereof.
  • the petroleum-based feedstream can exhibit one or more (e.g., two or more, three or more, four or more, or all five) enumerated characteristics: a solids content of at least 0.5 wt%; an insolubility number (IN) of at least 18; a solubility blending number (SBN) of 80 or less; a difference between SBN and IN of at least 20; and a silicon content of at least 1.3 wppm.
  • the petroleum-based feedstream can exhibit one or more (e.g., two or more, three or more, four or more, or all five) enumerated characteristics: a solids content of at least 0.5 wt%; an insolubility number (IN) of at least 18; a solubility blending number (SBN) of 80 or less; a difference between SBN and IN of at least 20; and a silicon content of at least 1.3 wppm.
  • the petroleum-based feedstream can exhibit one or more (e.g.
  • the method can further comprise adding solids (e.g. , comprising silica, alumina, a silicate, an aluminosilicate, sand, a silicon-containing clay, an aluminum-containing clay, hydrocarbon conversion catalyst fines, at least partially spent hydrocarbon conversion catalyst fines, a zeolite, or a combination thereof) to the petroleum-based feedstream to form a solids-enriched petroleum-based feedstream before the filtering step, which then filters the solids-enriched petroleum-based feedstream.
  • solids e.g. , comprising silica, alumina, a silicate, an aluminosilicate, sand, a silicon-containing clay, an aluminum-containing clay, hydrocarbon conversion catalyst fines, at least partially spent hydrocarbon conversion catalyst fines, a zeolite, or a combination thereof
  • the solids-enriched petroleum- based feedstream can have a solids content of at least 0.5 wt%, and optionally the permeate from the filtering step can additionally exhibit a solids content of 0.2 wt% or less.
  • the method can further comprise blending the petroleum-based feedstream with a petroleum-based blendstock to form a petroleum-based blended stream before the filtering step, which then filters the petroleum-based blended stream.
  • the petroleum-based blended stream can retain a silicon content of at least 1.3 wppm and can exhibit one or more (e.g., two or more, three or more, or all four) enumerated characteristics: a solids content of at least 0.5 wt%; an insolubility number (IN) of at least 18; a solubility blending number (SBN) of 80 or less; and a difference between SBN and IN of at least 20.
  • the permeate from the filtering step can additionally exhibit a solids content of 0.2 wt% or less.
  • the filtering step can utilize a porous solid filter made of a material that has substantially no catalytic activity for hydrocarbon conversion (e.g., comprising a polymer with repeat units comprising an amine, an amide, an ester, an ether, an imine, a urethane, a urea, a siloxane, polymerized ethylene, polymerized propylene, a polymerized styrenic, a polymerized diene, a polymerized acrylate, a polymerized acetate, or a combination thereof) and having a pore size of 1 micron or less.
  • a porous solid filter made of a material that has substantially no catalytic activity for hydrocarbon conversion (e.g., comprising a polymer with repeat units comprising an amine, an amide, an ester, an ether, an imine, a urethane, a urea, a siloxane, polymerized ethylene, polymerized propylene,
  • the filtering step is conducted at a temperature between 0°C and 225°C, at a pressure between 50 kPaa and 2.2 MPaa, or both.
  • the organosilicon compounds accounting for at least 10% of the first silicon content have a high molecular weight corresponding to a viscosity of at least 25000 cPs, e.g. , between 50000 cPs and 1000000 cPs.
  • the method can further comprise a distilling step before the filtering step, wherein the distilling step yields the petroleum-based feedstream as a side draw or as a bottoms stream.
  • the permeate is further subject to one or more catalytic hydrocarbon conversion refinery processes to form an unadditized fuel/lubricant product or blendstock selected from the group consisting of motor gasoline, diesel fuel, kerosene, jet fuel, avgas, Group I lubricant, Group II lubricant, Group III lubricant, Group IV lubricant, Group V lubricant, a biofuel, a biolubricant, and combinations thereof.
  • an unadditized fuel/lubricant product or blendstock selected from the group consisting of motor gasoline, diesel fuel, kerosene, jet fuel, avgas, Group I lubricant, Group II lubricant, Group III lubricant, Group IV lubricant, Group V lubricant, a biofuel, a biolubricant, and combinations thereof.
  • Typical decomposition products can include, but are by no means limited to, cyclic siloxanes, organosilanes, and partially or completely oxidized silicon-containing compounds. Cyclic siloxanes can comprise a majority of the decomposition products of the organosilicon compounds, with some of the most problematic including those species having boiling points in the motor gasoline, jet fuel, kerosene, and/or diesel fuel ranges. For example, select cyclic siloxane decomposition products can have boiling points of about 134°C, about 176°C, about 210°C, and about 245°C.
  • An aspect of the present invention therefore involves a method of removing silicon- containing compounds, such as organosilicon compounds, from a petroleum-based feedstream.
  • the method may include providing a petroleum-based feedstream having a first silicon content of at least 1.0 wppm (e.g., at least 1.3 wppm, at least 1.6 wppm, at least 2.0 wppm, at least 2.5 wppm, at least 3.0 wppm, at least 3.5 wppm, at least 4.0 wppm, at least 4.5 wppm, at least 5.0 wppm, at least 6.0 wppm, at least 7.0 wppm, at least 8.0 wppm, at least 9.0 wppm, at least 10 wppm, at least 15 wppm, at least 20 wppm, at least 25 wppm, at least 30 wppm, at least 35 wppm, at least 40 wppm, at least 45 wppm, or at
  • the method may also include filtering the petroleum-based feedstream to yield a permeate having a second silicon content lower than the first silicon content.
  • the second silicon content can be (i) at least 25% lower than the first silicon content (e.g., at least 30% lower, at least 35% lower, at least 40% lower, at least 45% lower, at least 50% lower, at least 55% lower, at least 60% lower, at least 65% lower, at least 70% lower, at least 75% lower, at least 80% lower, at least 85% lower, at least 90% lower, or at least 95% lower), (ii) less than 1.0 wppm (alternatively, less than 2.0 wppm, less than 1.8 wppm, less than 1.6 wppm, less than 1.4 wppm, less than 1.3 wppm, less than 1.2 wppm, or less than 1.1 wppm), based on the weight of the permeate, or (iii) both (i) and (ii).
  • the second silicon content can be up to 99% lower than the first silicon content (e.g., up to 97% lower, up to 95% lower, up to 90% lower, up to 85% lower, up to 80% lower, up to 75% lower, up to 70% lower, up to 65% lower, up to 60% lower, up to 55% lower, up to 50% lower, up to 45% lower, or up to 40% lower).
  • the second silicon content can be less than 1.0 wppm and at least 50% lower than the first silicon content.
  • the filtering step may additionally yield a retentate having a third silicon content higher than the first silicon content.
  • the retentate may be recycled as a portion of a feedstream to a delayed coker, for example as a delayed coker antifoam additive (due to its content of organosilicon).
  • Silicon content in compositions such as the petroleum-based feedstreams/permeates of the methods according to the invention can be measured and/or calculated using any reasonable technique.
  • One example technique includes an inductively coupled plasma (ICP) instrument, which usually works in tandem with one or more other instruments, such as atomic emission spectroscopy (AES), optical emission spectroscopy (OES), mass spectrometry (MS), x- ray fluorescence (XRF), or the like.
  • ICP inductively coupled plasma
  • ASTM 5815 can be used, along with ICP-AES analysis, to attain silicon contents of various streams/compositions.
  • the silicon-containing compounds to be removed from the petroleum-based feedstream can include organosilicon compounds, such as antifoaming agents, that have a relatively high molecular weight, as indicated by a relatively high viscosity.
  • organosilicon compounds may be all, most, or a portion of the silicon-containing compounds in the hydrocarbon compositions of various streams herein.
  • the organosilicon compounds accounting for at least 5 wt% of the first silicon content can have a molecular weight corresponding to a viscosity of at least about 15000 cPs (e.g., at least 10 wt%, at least 20 wt%, at least 30 wt%, at least 40 wt%, at least 50 wt%, more than 50 wt%, at least 60 wt%, at least 70 wt%, at least 75 wt%, at least 80 wt%, at least 85 wt%, at least 90 wt%, at least 95 wt%, at least 97 wt%, at least 98 wt%, at least 99 wt%, or approximately 100 wt%) can have a molecular weight corresponding to a viscosity of at least about 15000 cPs (e.g.
  • the organosilicon compounds accounting for at least 10 wt% of the first silicon content can have a molecular weight corresponding to a viscosity of between 50000 cPs and 1000000 cPs. In another particular embodiment, the organosilicon compounds accounting for at least 75 wt% of the first silicon content can have a molecular weight corresponding to a viscosity of between 50000 cPs and 1000000 cPs.
  • the filtering step may be effective in removing many silicon-containing compounds from the feedstream (thus creating a reduced silicon content in the permeate), one focus of the filtering step is to specifically remove organosilicon compounds. That is not to say that removing inorganic silicon-containing compounds is unimportant.
  • inorganic silicon-containing compounds can tend not to be highly soluble in feedstreams such as the petroleum-based (organic) feedstreams being input into the filtering step.
  • the efficacy of filtration to remove largely insoluble silicon-containing compounds is well-documented. Nevertheless, the efficacy of filtration to remove somewhat soluble organosilicon compounds from petroleum-based (organic) feedstreams is not believed to be well-known.
  • the organosilicon compounds can comprise polysiloxanes having the following structure:
  • n can represent the number of siloxane repeat units, which can be measured by a variety of methods (viscosity being described hereinabove, in which case “n” would be described by the number of repeat units needed to attain a given viscosity/range).
  • the pendant groups R' and R" for each repeat unit may independently or collectively be similar or different amongst each polysiloxane repeat unit and may comprise or be a hydrocarbonaceous moiety optionally containing one or more oxygen, nitrogen, or sulfur atoms.
  • R' and/or R" may be inorganic moieties, such as -OH, -NH 2 , -SH, or the like, such functionality is typically not intentionally sought. It is typically present via oxidation or some other minor thermochemical side reaction, and typically encompasses less than about 2 wt% of all R'+R" groups, e.g. , less than about 1 wt%, less than about 0.5 wt%, or less than about 1 wt%.
  • R' and R" can each individually comprise or be a C1-C40 hydrocarbon moiety (e.g., C1-C30, C1-C20, C1-C12, or Ci-C 6 ), optionally containing one or more heteroatoms comprising O, N, and/or S.
  • most or substantially all of the R' and R" pendant groups can be -CH3, such that the polysiloxane can be polydimethylsiloxane or a copolymer containing predominantly dimethylsiloxane repeat units.
  • the filtration step can be carried out at any convenient temperature and pressure. However, because certain silicon-containing chemicals (such as antifoaming agents) can begin decomposing into highly undesirable by-products at temperatures as low as about 300°C at approximately atmospheric pressure (about 0 psig or about 0 kPag), the temperature and pressure of the filtration step may be limited accordingly.
  • silicon-containing chemicals such as antifoaming agents
  • the filtering step can be conducted at a temperature of about 280°C or less, e.g., about 270°C or less, about 260°C or less, about 250°C or less, about 240°C or less, about 230°C or less, about 220°C or less, about 210°C or less, about 200°C or less, about 180°C or less, about 165°C or less, about 150°C or less, about 135°C or less, about 120°C or less, about 105°C or less, about 90°C or less, about 80°C or less, about 70°C or less, about 60°C or less, about 50°C or less, about 40°C or less, or about 30°C or less.
  • a temperature of about 280°C or less e.g., about 270°C or less, about 260°C or less, about 250°C or less, about 240°C or less, about 230°C or less, about 220°C or less, about 210°C
  • the filtering step can be conducted at a temperature of at least about -80°C, at least about -65°C, at least about -50°C, at least about -35°C, at least about - 20°C, at least about -10°C, at least about 0°C, at least about 5°C, at least about 10°C, at least about 15°C, at least about 20°C, at least about 25°C, at least about 30°C, at least about 40°C, at least about 50°C, at least about 60°C, at least about 70°C, at least about 80°C, at least about 90°C, at least about 105°C, at least about 120°C, at least about 135°C, or at least about 150°C.
  • the filtering step can be conducted at a pressure of about 20 MPaa or less, e.g. , about 15 MPaa or less, about 10 MPaa or less, about 5.1 MPaa or less, about 3.1 MPaa or less, about 2.2 MPaa or less, about 1.7 MPaa or less, about 1.2 MPaa or less, about 800 kPaa or less, about 500 kPaa or less, about 300 kPaa or less, about 200 kPaa or less, or about 100 kPaa or less.
  • the filtering step can be conducted at a pressure of at least about 5 kPaa, at least about 10 kPaa, at least about 25 kPaa, at least about 50 kPaa, at least about 75 kPaa, at least about 100 kPaa, at least about 200 kPaa, at least about 300 kPaa, at least about 500 kPaa, or at least about 800 kPaa.
  • the filtering step can be conducted at a temperature between 0°C and 225°C and/or at a pressure between 50 kPaa and 2.2 MPaa.
  • the filtering step can utilize a porous solid filter made of a material that has substantially no catalytic activity for hydrocarbon conversion.
  • the filtering step can utilize a filter that is distinct from a guard bed (alternatively termed a silicon trap). This is not to say that a guard bed (or silicon trap) cannot be used in addition to the filter - the porous solid filter material described herein should merely be understood to be distinct from a guard bed (or silicon trap).
  • the porous solid filter can include or be made from a polymer with repeat units comprising an amine, an amide, an ester, an ether, an imine, a urethane, a urea, a siloxane, polymerized ethylene, polymerized propylene, a polymerized styrenic, a polymerized diene, a polymerized acrylate, a polymerized acetate, or a combination thereof.
  • the porous solid filter can have a pore size of 1.5 microns or less, e.g. , 1.3 microns or less, 1.1 microns or less, 1 micron or less, 0.9 microns or less, 0.8 microns or less, 0.7 microns or less, 0.6 microns or less, 0.5 microns or less, 0.4 microns or less, or 0.3 microns or less.
  • the porous solid filter can have a pore size of at least 0.1 microns, at least 0.2 microns, at least 0.3 microns, at least 0.4 microns, at least 0.5 microns, at least 0.6 microns, at least 0.7 microns, at least 0.8 microns, or at least 0.9 microns.
  • the petroleum-based feedstreams from which organosilicon compounds may be desirably removed may include varieties of crude oils into which silicon-containing compounds, such as antifoaming agents, were added to assist in production; varieties of crude oils that have been contaminated by exposure to silicon-containing compounds (e.g. , via storage or transport, such as in a tank, through a pipeline, or the like); refinery streams (including distilled fractions, converted hydrocarbon streams, treated hydrocarbon streams, recycle streams, or the like, or combinations thereof) that have been contaminated by exposure to silicon-containing compounds; off-specification (off-spec) products, or the like.
  • silicon-containing compounds such as antifoaming agents
  • the petroleum-based feedstream can include, but need not be limited to, a bituminous crude oil, a diluted heavy crude oil, an at least partially deasphalted heavy crude oil, a diluted and at least partially deasphalted heavy crude oil, a fracked crude oil, a tight oil, a bottoms stream from a refinery distillation separator, a kerosene boiling range stream, a jet fuel boiling range stream, an off-spec fuel stream, an off-spec lubricant stream, or a combination thereof.
  • the filtering step may optionally be preceded by a distilling step.
  • the distilling step can yield the petroleum-based feedstream as a product, for example, as a bottoms stream, as a side draw, or as some combination thereof.
  • the petroleum-based feedstream is a whole crude oil or a wide boiling fraction of a crude oil (e.g.
  • the filtering step may be followed by one or more refinery distillation steps, (hydro)conversion steps, (hydro)treatment or (hydro)processing steps, blending steps, or other desired activity to be carried out on the permeate.
  • the permeate may be further subject to one or more catalytic hydrocarbon conversion refinery processes to form an unadditized fuel/lubricant product or blendstock selected from the group consisting of motor gasoline, diesel fuel, kerosene, jet fuel, avgas, Group I lubricant, Group II lubricant, Group III lubricant, Group IV lubricant, Group V lubricant, a biofuel, a biolubricant, and combinations thereof.
  • the retentate may be further treated to reduce its silicon content or may be recycled with little or no treatment as a portion of a feedstream to a delayed coker, for example as a delayed coker antifoam additive (due to its content of organosilicon).
  • properties and characteristics can define the petroleum- based feedstream prior to the filtering step. Indeed, some properties and characteristics can indicate a likelihood of a very successful method of organosilicon removal, such as the percentage reduction in silicon content between permeate and feedstream and/or the absolute reduction in silicon content from the permeate to the feedstream below a desired level. In situations indicative of a high likelihood of success in organosilicon removal, no silicon-related treatment steps may be needed or conducted prior to the filtration step. In situations not indicative of a high likelihood of success in organosilicon removal, or even in the occasional case indicating a high likelihood of success, it may be desired to take additional steps in order to raise the likelihood of success in organosilicon removal. Nevertheless, in order to distinguish between the two types of situations, it can be useful to categorize the properties and/or characteristics of petroleum-based feedstreams that tend toward and away from high likelihood of success in organosilicon removal.
  • petroleum-based feedstreams exhibiting one or more (e.g., two or more, three or more, four or more, or all) of the following enumerated properties can have a relatively high likelihood of success: a solids content of at least 0.5 wt% (e.g.
  • an insolubility number (IN) of at least 10 e.g., at least 12, at least 15, at least 17, at least 20, at least 22, at least 25, at least 27, at least 30, or at least 32
  • a solubility blending number (SBN) of 90 or less e.g.
  • a difference between SBN and IN of at least 15 e.g., at least 20, at least 25, at least 30, or at least 35
  • a silicon content of at least 1.3 wppm (e.g., at least 1.5 wppm, at least 1.7 wppm, at least 1.9 wppm, at least 2.1 wppm, at least 2.3 wppm, at least 2.5 wppm, or at least 2.8 wppm).
  • wppm e.g., at least 1.5 wppm, at least 1.7 wppm, at least 1.9 wppm, at least 2.1 wppm, at least 2.3 wppm, at least 2.5 wppm, or at least 2.8 wppm.
  • petroleum-based feedstreams exhibiting one or more (e.g., two or more, three or more, four or more, or all) of the following enumerated properties may not have a relatively high likelihood of success: a solids content of less than 3.0 wt% (e.g. , less than 2.5 wt%, less than 2.0 wt%, less than 1.5 wt%, less than 1.0 wt%, less than 0.9 wt%, less than 0.8 wt%, less than 0.7 wt%, less than 0.6 wt%, or less than 0.5 wt%); an insolubility number (IN) of less than 30 (e.g.
  • a solubility blending number SBN of greater than 70 (e.g. , greater than 75, greater than 80, greater than 85, or greater than 90); a difference between SBN and IN of less than 25 (e.g., less than 20, less than 18, or less than 15); and a silicon content of at least 1.3 wppm (e.g., at least 1.5 wppm, at least 1.7 wppm, at least 1.9 wppm, at least 2.1 wppm, at least 2.3 wppm, at least 2.5 wppm, or at least 2.8 wppm) .
  • SBN solubility blending number
  • the method may include adding solids to a petroleum-based feedstream, for example a feedstream having any of the enumerated properties discussed above, to form a solids-enriched petroleum-based feedstream before the filtering step.
  • the filtering step can then filter the solids-enriched petroleum-based feedstream instead of merely the petroleum-based feedstream.
  • the solids-enriched petroleum-based feedstream to be sent to the filtering step can exhibit a solids content of at least 0.5 wt% (e.g., at least 0.6 wt%, at least 0.7 wt%, at least 0.8 wt%, at least 0.9 wt%, or at least 1.0 wt%), and the permeate obtained from the filtering step can exhibit a solids content of 0.2 wt% or less (e.g., 0.15 wt% or less, 0.1 wt% or less, 0.05 wt% or less, 0.01 wt% or less, 50 wppm or less, or 20 wppm or less).
  • the added solids may contain or be formed from silica, alumina, a silicate, an aluminosilicate, sand, a silicon-containing clay, an aluminum-containing clay, hydrocarbon conversion catalyst fines, at least partially spent hydrocarbon conversion catalyst fines, a zeolite, or a combination thereof.
  • insoluble portions of the filtration feedstream can provide an alternatively miscible environment for the silicon-containing compounds, which can thus lead to enhanced filtration efficacy.
  • insoluble portions of the feedstream may comprise or be highly inorganic silicon-containing solids (e.g. , silica and/or metallosilicate particulates such as aluminosilicates), other highly organic insoluble compounds (e.g.
  • those compounds having increased heteroatom content and/or aromatic character, relative to the remainder of the feedstream, such as asphaltenes) can additionally or alternatively provide a more miscible environment for organosilicon-type compounds.
  • the organosilicon-type compounds can therefore be more easily removed from the feedstream, rendering the permeate following filtration not only considerably lower in solids content but also advantageously lower in silicon content, preferably having a silicon content at or below the desired specification (e.g. , about 1.0 wppm).
  • a feedstream does not contain enough solids/insolubles and/or exhibits too high a miscibility for silicon-containing compounds (e.g., organosilicon-type compounds such as anti- foaming agents), the effectiveness of the filtration may undesirably decrease.
  • silicon-containing compounds e.g., organosilicon-type compounds such as anti- foaming agents
  • the method may include blending the petroleum-based feedstream with a petroleum-based blendstock to form a petroleum-based blended stream before the filtering step.
  • the filtering step can then filter the petroleum-based blended stream instead of merely the petroleum-based feedstream.
  • the petroleum-based blended stream to be sent to the filtering step can retain a silicon content of at least 1.3 wppm and can exhibit one or more of the following enumerated characteristics: a solids content of at least 0.5 wt% (e.g., at least 0.6 wt%, at least 0.7 wt%, at least 0.8 wt%, at least 0.9 wt%, or at least 1.0 wt%); an insolubility number (IN) of at least 10 (e.g.
  • SBN solubility blending number
  • the permeate from the filtering step can exhibit a solids content of 0.2 wt% or less (e.g., 0.15 wt% or less, 0.1 wt% or less, 0.05 wt% or less, 0.01 wt% or less, 50 wppm or less, or 20 wppm or less).
  • insolubility number can correspond to n-heptane insoluble compounds, as can be characterized using ASTM D6560.
  • n-heptane insoluble compounds e.g., asphaltenes
  • ASTM D6560 n-heptane insoluble compounds
  • Such n-heptane insoluble compounds can typically be understood as compounds insoluble in n-heptane while typically being soluble in toluene, under the conditions set forth in ASTM D6560.
  • ASTM D6560 According to the ASTM standard, if less than 0.5 mass % of a sample yields insoluble solids in n-heptane at the appropriate conditions, the test outcome is noted to be completely n-heptane soluble (IN ⁇ 0).
  • certain petroleum-based compounds e.g., asphaltenes or asphaltene- type compounds
  • Such alternative solvents can include, but are not limited to, other C3-C7 alkanes, toluene, or combinations thereof.
  • the insolubility number of a fuel oil sample can be characterized directly, such as by using ASTM D6560, other methods of characterization can additionally or alternatively be used.
  • another method for characterizing a petroleum-based feedstreams can be based on a Micro Carbon Residue (MCR) test, such as according to ISO 10370.
  • MCR Micro Carbon Residue
  • ISO 10370 ISO 10370.
  • MCR test about 4 grams of a sample can be put into a weighed glass bulb. The sample in the bulb can then be heated in a bath at about 553°C for about 20 minutes. After cooling, the bulb can be weighed again and the difference noted.
  • An additional/alternative method of characterizing the solubility properties of a petroleum-based feedstreams can correspond to the toluene equivalence (TE) of a fuel oil, based on the toluene equivalence test as described, for example, in U.S. Patent No. 5,871,634, which is incorporated herein by reference with regard to the definitions for and descriptions of toluene equivalence, solubility number (SBN), and insolubility number (IN).
  • TE toluene equivalence
  • SBN solubility number
  • IN insolubility number
  • the above test method for the toluene equivalence test can be expanded to allow for determination of a solubility number (SBN) and an insolubility number (IN) for a petroleum- based feedstream sample. If it is desired to determine SBN and/or IN for a petroleum-based feedstream sample, the toluene equivalence test described above can be performed to generate a first data point corresponding to a first volume ratio Rl of petroleum-based composition to test liquid at a first percent of toluene Tl in the test liquid at the TE value. After generating the TE value, one option can be to determine a second data point by a similar process but using a different feedstream to test liquid mixture volume ratio.
  • SBN solubility number
  • IN insolubility number
  • a percent toluene below that determined for the first data point can be selected and that test liquid mixture can be added to a known volume of the petroleum-based feedstream until certain highly organic compounds (e.g., asphaltenes) just begin to precipitate.
  • the volume ratio of feedstream to test liquid mixture, R2 at the selected percent toluene in the test liquid mixture, T2 can be used as the second data point.
  • one option for the second test liquid mixture can be to use a test liquid containing 0% toluene or 100% n-heptane. This type of test for generating the second data point can be referred to as the heptane dilution test.
  • the insolubility and solubility numbers for a sample can be calculated based on Equations (2) and (3) in U.S. Patent Application Publication Number 2017/0044451, the contents of which are incorporated by reference herein, particularly regarding aspects of alternative miscibility testing such as toluene equivalence, heptane dilution, etc.
  • alternative methods are available for determining the solubility number of a petroleum-based feedstream that has an insolubility number of zero or approximately zero.
  • feedstream density can be an additional or alternative factor in establishing or determining the miscibility of a feedstream or blend. For instance, by blending in components containing a distinctly higher or lower density, or a blendstock containing them, it is believed that phase separation/immiscibility can be more easily induced in the resulting blend, thereby (again, counterintuitively) enhancing filtration effectiveness and efficiency for silicon-containing compounds.
  • the petroleum-based blendstock may comprise or be: a whole or partial crude oil, whether including a measurable content of silicon-containing compounds (such as antifoaming agents) or not; a refinery stream (including any distilled fraction or portion thereof, converted hydrocarbon stream, treated hydrocarbon stream, recycle stream, or the like, or a combination thereof), whether including a measurable content of silicon-containing compounds or not; off-specification (off-spec) products, whether including a measurable content of silicon-containing compounds or not; on-specification (on-spec) products, which are typically but not necessarily unadditized; or the like.
  • Converted and/or treated (hydroprocessed) hydrocarbon refinery streams may have been subject to hydrotreatment, hydrocracking, dewaxing/isomerization, hydrofinishing, or the like, or combinations thereof.
  • Hydrotreatment can typically include catalysts.
  • catalysts used for hydrotreatment can include conventional hydroprocessing catalysts, such as those that comprise at least one Group VIII non-noble metal (from Columns 8-10 of IUPAC periodic table), for example Fe, Co, and/or Ni (such as Co and/or Ni), and at least one Group VIB metal (from Column 6 of IUPAC periodic table), for example Mo and/or W.
  • Such hydroprocessing catalysts can optionally include transition metal sulfides. These catalytically active metals or mixtures of metals can typically be present as oxides, sulfides, or the like, on supports such as refractory metal oxides.
  • Suitable metal oxide supports can include low acidic oxides such as silica, alumina, titania, silica-titania, and titania-alumina, inter alia.
  • Suitable aluminas can include porous aluminas (such as gamma or eta) having: average pore sizes from about 50 A to about 200 A, e.g., from about 75 A to about 150 A; a (BET) surface area from about 100 m 2 /g to about 300 m 2 /g, e.g., from about 150 m 2 /g to about 250 m 2 /g; and a pore volume from about 0.25 cmVg to about 1.0 cmVg, e.g., from about 0.35 cmVg to about 0.8 cmVg.
  • the supports are, in certain embodiments, preferably not promoted with a halogen such as fluorine, as this can undesirably increase the acidity of the support.
  • the at least one Group VIII non-noble metal can typically be present in an amount ranging from about 2 wt% to about 40 wt%, for example from about 4 wt% to about 15 wt%.
  • the at least one Group VIB metal, as measured in oxide form can typically be present in an amount ranging from about 2 wt% to about 70 wt%, for example from about 6 wt% to about 40 wt% or from about 10 wt% to about 30 wt%. These weight percents are based on the total weight of the catalyst.
  • Suitable catalysts can include CoMo (e.g.
  • NiMo e.g., -1-10% Ni as oxide, -10-40% Mo as oxide
  • NiW e.g. , -1-10% Ni as oxide, -10-40% W as oxide
  • the hydrotreating catalyst can include or be a bulk metal catalyst, or can include a combination of stacked beds of supported and bulk metal catalyst.
  • bulk metal it is meant that the catalyst particles are unsupported and comprise about 30-100 wt% of at least one Group VIII non-noble metal and at least one Group VIB metal, based on the total weight of the bulk catalyst particles, calculated as metal oxides, which bulk catalyst particles can also have a (BET) surface area of at least 10 m 2 /g.
  • a bulk catalyst composition can include one Group VIII non-noble metal and two Group VIB metals.
  • the molar ratio of Group VIB to Group VIII non-noble metals can range generally from about 10: 1 to about 1 : 10.
  • the ratio of the different Group VIB metals is generally not critical. The same can hold when more than one Group VIII non-noble metal is present. Nevertheless, in embodiments where molybdenum and tungsten are present as Group VIB metals, the Mo:W ratio can preferably be in the range from about 9: 1 to about 1 :9.
  • a bulk metal hydrotreating catalyst can have a surface area of at least 50 m 2 /g, for example at least 100 m 2 /g. Additionally or alternately, bulk metal hydrotreating catalysts can have a pore volume of about 0.05 ml/g to about 5 ml/g, for example about 0.1 ml/g to about 4 ml/g, about 0.1 ml/g to about 3 ml/g, or about 0.1 ml/g to about 2 ml/g, as determined by nitrogen adsorption. Bulk metal hydrotreating catalyst particles can additionally or alternatively have a median diameter of at least about 50 nm, e.g.
  • the median particle diameter can be in the range of about 0.1 ⁇ to about 50 ⁇ , preferably about 0.5 ⁇ to about 50 ⁇ .
  • hydrotreating conditions can include: temperatures of about 200°C to about 450°C, for example about 315°C to about 425°C; pressures of about 250 psig (-1.8 MPag) to about 5000 psig (-35 MPag), for example about 300 psig (-2.1 MPag) to about 3000 psig (-21 MPag); liquid hourly space velocities (LHSV) of about 0.1 hr 1 to about 10 hr "1 ; and hydrogen treat gas rates of about 200 scf/B (-36 m /m 3 ) to about 10000 scf/B (-1800 m /m 3 ), for example about 500 scf/B (-90 m /m 3 ) to about 10000 scf/B (-1800 m /m 3 ).
  • hydrocracking catalysts can contain sulfided base metals on acidic supports, such as amorphous silica-alumina, cracking zeolites, or other cracking molecular sieves such as USY or acidified alumina.
  • acidic supports such as amorphous silica-alumina, cracking zeolites, or other cracking molecular sieves such as USY or acidified alumina.
  • a hydrocracking catalyst can include at least one molecular sieve, such as a zeolite. Often these acidic supports can be mixed and/or bound with other metal oxides such as alumina, titania, and/or silica.
  • Non-limiting examples of supported catalytic metals for hydrocracking catalysts can include combinations of Group VIB and/or Group VIII non-noble metals, including Ni, NiCoMo, CoMo, NiW, NiMo, and/or NiMoW.
  • Support materials which may be used can comprise a refractory oxide material such as alumina, silica, alumina-silica, kieselguhr, diatomaceous earth, magnesia, zirconia, or combinations thereof, with alumina, silica, and/or silica-alumina being the most common (and preferred, in some embodiments).
  • the at least one Group VIII non-noble metal as measured in oxide form, can be present in an amount typically ranging from about 2 wt% to about 40 wt%, e.g. , from about 4 wt% to about 15 wt%.
  • the at least one Group VIB metal as measured in oxide form, can additionally or alternatively be present in an amount typically ranging from about 2 wt% to about 70 wt%, e.g., for supported catalysts from about 6 wt% to about 40 wt% or from about 10 wt% to about 30 wt%. These weight percents are based on the total weight of the catalyst.
  • suitable hydrocracking catalyst active metals can include NiMo, NiW, or NiMoW, typically supported.
  • hydrocracking catalysts with noble metals can be used.
  • noble metal catalysts can include those based on Pt and/or Pd.
  • the amount of the noble metal can be at least about 0.1 wt%, based on the total weight of the catalyst, for example at least about 0.5 wt% or at least about 0.6 wt%.
  • the amount of the noble metal can be about 5.0 wt% or less, based on the total weight of the catalyst, for example about 3.5 wt% or less, about 2.5 wt% or less, about 1.5 wt% or less, about 1.0 wt% or less, about 0.9 wt% or less, about 0.75 wt% or less, or about 0.6 wt% or less.
  • a hydrocracking catalyst can include a large pore molecular sieve selective for cracking of branched hydrocarbons and/or cyclic hydrocarbons.
  • Zeolite Y such as ultrastable zeolite Y (USY)
  • USY ultrastable zeolite Y
  • the silica to alumina ratio (Si/ Ah, measured as oxides) in a USY zeolite can be at least about 10, for example at least about 15, at least about 25, at least about 50, or at least about 100.
  • the unit cell size for a USY zeolite can be about 24.50 A or less, e.g., about 24.45 A or less, about 24.40 A or less, about 24.35 A or less, or about 24.30 A.
  • a variety of other types of molecular sieves can be used in a hydrocracking catalyst, such as zeolite Beta and/or ZSM-5.
  • Still other categories of suitable molecular sieves can include molecular sieves having 10-member ring pore channels and/or 12-member ring pore channels.
  • Examples of molecular sieves having 10-member ring pore channels and/or 12-member ring pore channels can include molecular sieves having one or more of the following zeolite framework types: MRE, MTT, EUO, AEL, AFO, SFF, STF, TON, OSI, ATO, GON, MTW, SFE, SSY, and VET.
  • the conditions selected for hydrocracking can depend on the desired level of conversion, the level of contaminants in the input feed to the hydrocracking stage, and potentially other factors.
  • Suitable hydrocracking conditions can include temperatures of about 450°F ( ⁇ 232°C) to about 840°F ( ⁇ 449°C), for example about 450° F.
  • the conditions can include temperatures in the range of about 500°F ( ⁇ 260°C) to about 815°F ( ⁇ 435°C), for example about 500°F ( ⁇ 260°C) to about 750°F ( ⁇ 399°C) or about 500°F ( ⁇ 260°C) to about 700°C ( ⁇ 371°C); hydrogen partial pressures from about 500 psig (-3.5 MPag) to about 3000 psig (-21 MPag); liquid hourly space velocities from about 0.2 hr 1 to about 5 hr "1 ; and hydrogen treat gas rates from about 210 m /m 3 (-1200 scf/B) to about 1100 m 3 /m 3 (-6000 scf/B).
  • a dewaxing catalyst can be used for dewaxing of a potential fuel oil.
  • Suitable dewaxing catalysts can include molecular sieves such as crystalline aluminosilicates (zeolites).
  • the molecular sieve can comprise, consist essentially of, or be ZSM-5, ZSM-22, ZSM-23, ZSM-35, ZSM-48, zeolite Beta, ZSM-57, or a combination thereof (e.g. , ZSM-23 and/or ZSM-48, or ZSM-48 and/or zeolite Beta).
  • molecular sieves selective for isomerization/dewaxing as opposed to cracking can be used, such as ZSM-48, zeolite Beta, and/or ZSM-23, inter alia.
  • the molecular sieve can comprise, consist essentially of, or be a 10-member ring 1-D molecular sieve, such as EU-1, ZSM-35 (or ferrierite), ZSM-11, ZSM-57, NU-87, SAPO-11, ZSM-48, ZSM-23, and/or ZSM-22.
  • the dewaxing catalyst can include EU-2, EU-11, ZBM-30, ZSM-48, ZSM-23, isostructural versions thereof (e.g.
  • the dewaxing catalyst can include a binder, such as alumina, titania, silica, silica-alumina, zirconia, or a combination thereof (e.g., alumina and/or titania or silica and/or zirconia and/or titania).
  • a binder such as alumina, titania, silica, silica-alumina, zirconia, or a combination thereof (e.g., alumina and/or titania or silica and/or zirconia and/or titania).
  • such dewaxing catalysts when dewaxing catalysts are used, such dewaxing catalysts can have a low ratio of silica to alumina.
  • the ratio of silica to alumina in the zeolite can be less than about 200: 1, for example less than about 110: 1, less than about 100: 1, less than about 90: 1, or less than about 80: 1, optionally at least about 30: 1, at least about 50: 1, at least about 60: 1, or at least about 70: 1.
  • the ratio of silica to alumina in the dewaxing catalyst can be from about 30: 1 to about 200: 1, about 60: 1 to about 110: 1, or about 70: 1 to about 100: 1.
  • the catalysts in these processes can (further) include a metal hydrogenation component, which can typically include/be a Group VIB and/or Group VIII metal. Suitable combinations can include Ni/Co/Fe with Mo/W, e.g. , NiMo or NiW.
  • the amount of metal (from the metal hydrogenation component) in/on the catalyst can be at least about 0.1 wt% based on catalyst, e.g. , at least about 0.15 wt%, at least about 0.2 wt%, at least about 0.25 wt%, at least about 0.3 wt%, or at least about 0.5 wt%, based on catalyst weight.
  • the amount of metal (from the metal hydrogenation component) in/on the catalyst can be about 20 wt% or less, based on catalyst weight, e.g. , about 10 wt% or less, about 5 wt% or less, about 2.5 wt% or less, or about 1 wt% or less.
  • Effective processing conditions in a catalytic dewaxing zone can include a temperature of about 200°C to about 450°C, e.g., about 270°C to about 400°C, a hydrogen partial pressure of about 1.8 MPag to about 35 MPag (-250 psig to -5000 psig), e.g., about 4.8 MPag to about 21 MPag, and a hydrogen treat gas rate of about 36 m /m 3 (-200 scf/B) to about 1800 m /m 3 (-10000 scf/B), e.g.
  • the conditions can include temperatures in the range of about 600°F ( ⁇ 343°C) to about 815°F ( ⁇ 435°C), hydrogen partial pressures of about 500 psig (-3.5 MPag) to about 3000 psig (-21 MPag), and hydrogen treat gas rates of about 210 m /m 3 (-1200 scf/B) to about 1100 m /m 3 (-1200 scf/B).
  • the LHSV can be from about 0.1 hr 1 to about 10 hr 1 , such as from about 0.5 hr 1 to about 5 hr 1 and/or from about 1 hr 1 to about 4 hr "1 .
  • the methods for organosilicon removal disclosed herein can be used to make improved products with reduced silicon contents.
  • the silicon contents of the products can enable them to be exposed to further treatments using certain hydrocarbon conversion catalysts for which organosilicon compounds can be strong poisons or deactivators. While such methods may not completely remove the organosilicon compounds from the feedstreams and/or blended streams, they may advantageously reduce the silicon content low enough for the certain hydrocarbon conversion catalysts to have a reasonable lifetime of activity, even with a relatively low rate of organosilicon poisoning/deactivation.
  • the reduced silicon content products can be further treated to provide end-use compositions for fuels, fuel blendstocks, lubricants, and lubricant blendstocks, among other things.
  • Cn means hydrocarbon(s) having n carbon atom(s) per molecule, wherein n is a positive integer.
  • hydrocarbon means a class of compounds containing hydrogen bound to carbon, and encompasses (i) saturated hydrocarbon compounds, (ii) unsaturated hydrocarbon compounds, and (iii) mixtures of hydrocarbon compounds (saturated and/or unsaturated), including mixtures of hydrocarbon compounds having different values of n.
  • ring atom means an atom that is part of a cyclic ring structure.
  • a benzyl group has six ring atoms and tetrahydrofuran (THF) has 5 ring atoms.
  • THF tetrahydrofuran
  • ring atoms need not be only carbon atoms - they can include one or more heteroatoms such as N, O, and/or S.
  • heteroatom can described by the ring name, even if the cyclic structure has a substituted ring structure.
  • the furanyl oxygen describes the sole oxygen in the THF ring
  • the piperidinyl nitrogen describes the sole nitrogen in a piperidinyl ring
  • the morpholinyl nitrogen and the morpholinyl oxygen describe the sole nitrogen and the sole oxygen, respectively in a morpholinyl ring.
  • the piperazinyl nitrogen because of the ambiguity, it would not be proper to characterize either of the two nitrogens in a piperazinyl ring as "the piperazinyl nitrogen.”
  • substituted means that a hydrogen group has been replaced with a heteroatom, or a heteroatom containing group.
  • a “substituted hydrocarbon” is a hydrocarbon made of carbon and hydrogen where at least one carbon (and attendant hydrogen(s)) and/or at least one hydrogen is replaced by a heteroatom or heteroatom containing group.
  • a heterocyclic ring is a ring having a heteroatom in the ring structure as opposed to a heteroatom substituted ring where a hydrogen on a ring atom is replaced with a heteroatom.
  • tetrahydrofuran is a heterocyclic ring and 4-N,N-dimethylamino-phenyl is a heteroatom substituted ring.
  • isomers of a named group exist (for alkyl, e.g., n- butyl, iso-butyl, sec-butyl, and tert-butyl) reference to one member of the group (e.g., n-butyl) shall expressly disclose the remaining isomers (e.g., iso-butyl, sec-butyl, and tert-butyl) in the family.
  • references to an isomeric group without specifying a particular isomer expressly discloses all isomers (e.g., n-butyl, iso-butyl, sec-butyl, and tert-butyl).
  • polymer is used herein to refer to homopolymers, copolymers, interpolymers, terpolymers, etc.
  • a copolymer may refer to a polymer comprising at least two monomers, optionally with other monomers.
  • a "homopolymer” is a polymer having all mer units that are the same.
  • a "copolymer” is a polymer having two or more types of mer units that are distinct or different from each other.
  • terpolymer is a polymer having three types of mer units that are distinct or different from each other.
  • Me is methyl
  • Et is ethyl
  • Pr is propyl
  • cPr is cyclopropyl
  • nPr is n-propyl
  • iPr is isopropyl
  • Bu is butyl
  • nBu is normal butyl
  • iBu is isobutyl
  • sBu is sec-butyl
  • tBu is tert-butyl
  • Oct octyl
  • Ph is phenyl
  • Bz is benzyl
  • OH (or - OH) is hydroxyl
  • RT is room temperature (and is between about 20°C and about 25°C, unless otherwise indicated).
  • the present invention can additionally or alternatively include one or more of the following embodiments.
  • Embodiment 1 A method of removing organosilicon compounds from a petroleum- based feedstream, the method comprising: providing a petroleum-based feedstream having a first silicon content of at least 1.0 wppm; and filtering the petroleum-based feedstream to yield a permeate having a second silicon content lower than the first silicon content, wherein the second silicon content is at least 25% lower than the first silicon content, the second silicon content is less than 1.0 wppm, or both.
  • Embodiment 2 The method of embodiment 1 , wherein the petroleum-based feedstream comprises a bituminous crude oil, a diluted heavy crude oil, an at least partially deasphalted heavy crude oil, a diluted and at least partially deasphalted heavy crude oil, a fracked crude oil, a tight oil, a bottoms stream from a refinery distillation separator, an off-spec fuel stream, an off-spec lubricant stream, or a combination thereof.
  • the petroleum-based feedstream comprises a bituminous crude oil, a diluted heavy crude oil, an at least partially deasphalted heavy crude oil, a diluted and at least partially deasphalted heavy crude oil, a fracked crude oil, a tight oil, a bottoms stream from a refinery distillation separator, an off-spec fuel stream, an off-spec lubricant stream, or a combination thereof.
  • Embodiment 3 The method of embodiment 1 or embodiment 2, wherein the petroleum-based feedstream exhibits one or more enumerated characteristics: a solids content of at least 0.5 wt%; an insolubility number (IN) of at least 10; a solubility blending number (SBN) of 90 or less; a difference between SBN and IN of at least 15; and a silicon content of at least 1.3 wppm.
  • Embodiment 4 The method of embodiment 3, wherein the petroleum-based feedstream exhibits at least four of the enumerated characteristics.
  • Embodiment 5 The method of embodiment 1 or embodiment 2, wherein the petroleum-based feedstream exhibits one or more enumerated characteristics: a solids content less than 0.5 wt%; an insolubility number (IN) less than 10; a solubility blending number (SBN) of greater than 90; a difference between SBN and IN of less than 15; and a silicon content of at least 1.5 wppm.
  • a solids content less than 0.5 wt%
  • an insolubility number (IN) less than 10
  • SBN solubility blending number
  • Embodiment 6 The method of embodiment 5, wherein the petroleum-based feedstream exhibits at least three of the enumerated characteristics.
  • Embodiment 7 The method of any of the preceding embodiments, further comprising adding solids to the petroleum-based feedstream to form a solids-enriched petroleum-based feedstream before the filtering step, which then filters the solids-enriched petroleum-based feedstream.
  • Embodiment 8 The method of embodiment 7, wherein the added solids comprise silica, alumina, a silicate, an aluminosilicate, sand, a silicon-containing clay, an aluminum- containing clay, hydrocarbon conversion catalyst fines, at least partially spent hydrocarbon conversion catalyst fines, a zeolite, or a combination thereof.
  • Embodiment 9 The method of embodiment 7 or embodiment 8, wherein the solids- enriched petroleum-based feedstream has a solids content of at least 0.5 wt%, and wherein the permeate from the filtering step additionally exhibits a solids content of 0.2 wt% or less.
  • Embodiment 10 The method of any of the preceding embodiments, further comprising blending the petroleum-based feedstream with a petroleum-based blendstock to form a petroleum-based blended stream before the filtering step, which then filters the petroleum- based blended stream, wherein the petroleum-based blended stream retains a silicon content of at least 1.3 wppm and exhibits one or more enumerated characteristics: a solids content of at least 0.5 wt%; an insolubility number (IN) of at least 10; a solubility blending number (SBN) of 90 or less; and a difference between SBN and IN of at least 15.
  • a solids content of at least 0.5 wt% an insolubility number (IN) of at least 10
  • SBN solubility blending number
  • Embodiment 11 The method of embodiment 10, wherein the permeate from the filtering step additionally exhibits a solids content of 0.2 wt% or less.
  • Embodiment 12 The method of any of the preceding embodiments, wherein the second silicon content is less than 1.0 wppm and at least 50% lower than the first silicon content.
  • Embodiment 13 The method of any of the preceding embodiments, wherein the filtering step utilizes a porous solid filter made of a material that has substantially no catalytic activity for hydrocarbon conversion and having a pore size of 1 micron or less.
  • Embodiment 14 The method of embodiment 13, wherein the porous solid filter comprises a polymer with repeat units comprising an amine, an amide, an ester, an ether, an imine, a urethane, a urea, a siloxane, polymerized ethylene, polymerized propylene, a polymerized styrenic, a polymerized diene, a polymerized acrylate, a polymerized acetate, or a combination thereof.
  • Embodiment 15 The method of any of the preceding embodiments, wherein the filtering step is conducted at a temperature between 0°C and 225°C, at a pressure between 50 kPaa and 2.2 MPaa, or both.
  • Embodiment 16 The method of any of the preceding embodiments, wherein the organosilicon compounds accounting for at least 10% of the first silicon content have a high molecular weight corresponding to a viscosity of at least 25000 cPs.
  • Embodiment 17 The method of embodiment 16, wherein the molecular weight of the organosilicon compounds corresponds to a viscosity between 50000 cPs and 1000000 cPs.
  • Embodiment 18 The method of any of the preceding embodiments, further comprising a distilling step before the filtering step, wherein the distilling step yields the petroleum-based feedstream as a side draw or as a bottoms stream.
  • Embodiment 19 The method of any of the preceding embodiments, wherein the permeate is further subject to one or more catalytic hydrocarbon conversion refinery processes to form an unadditized fuel/lubricant product or blendstock selected from the group consisting of motor gasoline, diesel fuel, kerosene, jet fuel, avgas, Group I lubricant, Group II lubricant, Group III lubricant, Group IV lubricant, Group V lubricant, a biofuel, a biolubricant, and combinations thereof.
  • an unadditized fuel/lubricant product or blendstock selected from the group consisting of motor gasoline, diesel fuel, kerosene, jet fuel, avgas, Group I lubricant, Group II lubricant, Group III lubricant, Group IV lubricant, Group V lubricant, a biofuel, a biolubricant, and combinations thereof.
  • Example 1 shows the effect of filtration on a number of crude oil samples containing an undesirably high silicon content, believed to be from the presence of polymeric silicon- containing antifoaming agents used in their production.
  • a first aliquot ( ⁇ 5 mL to -100 mL) of each provided sample was analyzed by ICP-AES according to ASTM 5185 to determine silicon content (pre-filtration).
  • each sample was filtered using a ⁇ 0.45-micron nylon filter.
  • From each permeate a second aliquot was taken and analyzed a second time (again by ICP-AES according to ASTM 5185) to determine silicon content (post-filtration).
  • the results are shown below in Table 1, along with pre-filtration characteristics of solubility blending number (SBN) and insolubility number (IN).
  • the filtering reduced the Si content for all Samples A-G by at least 23% (Sample G) to at least 84% (Sample A), and possibly up to 100%, depending upon the actual post-filtration Si content, which can be anywhere below 1.0 wppm and down to ⁇ 0 wppm (but which value would have to be measured by a different method, having accuracy below 1.0 wppm).
  • Example 2 shows the effect of solids content in the efficacy of using filtration to remove silicon-containing species from several crude oil samples.
  • crude oil sample HI was pre-filtered using a -0.45 -micron nylon filter, which, as shown in Example 1, should remove both silicon-containing species and particulate matter larger than the filter.
  • two pre-filtered permeates, HI and H2 were spiked with a -60000 cSt organosilicon polymeric composition (EC9019ATM, commercially available from Nalco), with the aim of attaining approximately 30-40 wppm in the permeate, on a silicon-basis.
  • Samples Jl and J2 were treated similarly to samples HI and H2, with the following exceptions: Samples Jl and J2 were not pre-filtered a first time to remove solids (meaning that solids, and thus any residual silicon-containing compounds, were present during spiking; and samples Jl and J2 were spiked with the organosilicon polymeric composition with the aim of attaining approximately 8-9 wppm on a silicon-basis. Samples K and L were treated similarly to HI and Jl, respectively, with the following exceptions: samples K and L were taken from a different crude source than samples HI and Jl ; and sample L was spiked to attain approximately 15 wppm instead of -8-9 wppm.
  • sample M shows that removal of organosilicon compounds by filtration can be problematic for compositions with high SBN values, low IN values, and/or low solids contents (spiked toluene contained no intentionally added solids).
  • This observation appears to be corroborated by the relative difficulty observed in organosilicon removal in samples HI, H2, and K, all of which had their solids contents reduced to near 0% by the pre-spiking filtration step, as compared to samples Jl, J2, and L in Example 2, as well as to samples A-F in Example 1, all of which did not undergo an initial (pre-spiking) filtration step.

Landscapes

  • 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)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

L'invention concerne des procédés d'élimination de composés contenant du silicium (d'organosilicium) de flux de départ à base de pétrole. Les procédés peuvent comprendre l'utilisation d'un flux de départ à base de pétrole ayant une première teneur en silicium d'au moins 1,0 ppm en poids et la filtration du flux de départ à base de pétrole pour produire un perméat ayant une seconde teneur en silicium inférieure à la première teneur en silicium, la seconde teneur en silicium étant au moins 25 % inférieure à la première teneur en silicium ou la seconde teneur en silicium étant inférieure à 1,0 ppm en poids, ou les deux.
PCT/US2018/059196 2017-11-13 2018-11-05 Élimination de produits chimiques contenant du silicium de flux d'hydrocarbures Ceased WO2019094328A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CA3077234A CA3077234A1 (fr) 2017-11-13 2018-11-05 Elimination de produits chimiques contenant du silicium de flux d'hydrocarbures

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201762585037P 2017-11-13 2017-11-13
US62/585,037 2017-11-13

Publications (1)

Publication Number Publication Date
WO2019094328A1 true WO2019094328A1 (fr) 2019-05-16

Family

ID=64572472

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2018/059196 Ceased WO2019094328A1 (fr) 2017-11-13 2018-11-05 Élimination de produits chimiques contenant du silicium de flux d'hydrocarbures

Country Status (3)

Country Link
US (1) US20190144763A1 (fr)
CA (1) CA3077234A1 (fr)
WO (1) WO2019094328A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111612649B (zh) * 2020-05-23 2021-03-19 上海轻叶能源股份有限公司 一种储运油品移动大数据管理系统
US20220235284A1 (en) * 2021-01-27 2022-07-28 Phillips 66 Company Decreasing refinery fouling and catalyst deactivation
CN117323993A (zh) * 2022-06-23 2024-01-02 中国科学院大连化学物理研究所 一种用于催化臭氧氧化的催化剂及其制备方法和应用

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5871634A (en) 1996-12-10 1999-02-16 Exxon Research And Engineering Company Process for blending potentially incompatible petroleum oils
US20060231462A1 (en) * 2005-04-15 2006-10-19 Johnson Raymond F System for improving crude oil
US20140262955A1 (en) * 2013-03-14 2014-09-18 Russell Evan Cooper Process, Method, and System for Removing Heavy Metals from Fluids
US20160168485A1 (en) * 2014-12-12 2016-06-16 Exxonmobil Research And Engineering Company Membrane fabrication methods using organosilica materials and uses thereof
US20170044451A1 (en) 2015-08-13 2017-02-16 Exxonmobil Research And Engineering Company Modification of fuel oils for compatibility
WO2017109639A1 (fr) * 2015-12-21 2017-06-29 Sabic Global Technologies B.V. Procédés et systèmes pour produire des oléfines et des composés aromatiques à partir de naphta de cokéfaction

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5871634A (en) 1996-12-10 1999-02-16 Exxon Research And Engineering Company Process for blending potentially incompatible petroleum oils
US20060231462A1 (en) * 2005-04-15 2006-10-19 Johnson Raymond F System for improving crude oil
US20140262955A1 (en) * 2013-03-14 2014-09-18 Russell Evan Cooper Process, Method, and System for Removing Heavy Metals from Fluids
US20160168485A1 (en) * 2014-12-12 2016-06-16 Exxonmobil Research And Engineering Company Membrane fabrication methods using organosilica materials and uses thereof
US20170044451A1 (en) 2015-08-13 2017-02-16 Exxonmobil Research And Engineering Company Modification of fuel oils for compatibility
WO2017109639A1 (fr) * 2015-12-21 2017-06-29 Sabic Global Technologies B.V. Procédés et systèmes pour produire des oléfines et des composés aromatiques à partir de naphta de cokéfaction

Also Published As

Publication number Publication date
CA3077234A1 (fr) 2019-05-16
US20190144763A1 (en) 2019-05-16

Similar Documents

Publication Publication Date Title
KR102447300B1 (ko) 선박용 연료들의 제조를 위한 고정층 수소화 처리, 수소화 처리된 잔사유 분획물의 분리 및 접촉 분해 스텝을 포함하는 전환 프로세스
EP3360949B1 (fr) Modification d'huiles de carburant pour la compatibilité
JP6392774B2 (ja) ３００℃より高い沸点と−２５℃以下の流動点を有する炭化水素溶媒の製造方法
DK2788458T3 (en) PROCEDURE FOR HYDRO-CONVERSION OF RAW OIL CHARGES IN FIXED RENTS FOR THE PREPARATION OF FUEL OIL WITH A LOW SULFUR CONTENT
US9605218B2 (en) Integrated hydrocracking and slurry hydroconversion of heavy oils
US10570342B2 (en) Deasphalting and hydroprocessing of steam cracker tar
KR20150032815A (ko) 수소처리 단계를 채용하는, ｈｃｏ 또는 슬러리 타입의 촉매 크래킹으로부터 기원하는 탄화수소-함유 컷 유래의 황 함량이 낮은 선박 연료 제조 방법
JP2016503821A5 (fr)
US20180134972A1 (en) Processing of challenged fractions and cracked co-feeds
CN109937246A (zh) 从加氢处理过的催化油浆生产碳黑和树脂
EP3209753B1 (fr) Procédé d'hydrocraquage intégré avec un procédé de distillation sous vide et un procédé de déparaffinage par solvant pour réduire l'accumulation d'hydrocarbures lourds aromatiques polycycliques
US20210207042A1 (en) Modified ultra-stable y (usy) zeolite catalyst for improving cold flow properties of distillates
WO2014205178A1 (fr) Hydroconversion de boues et cokéfaction d'huiles lourdes
WO2019094328A1 (fr) Élimination de produits chimiques contenant du silicium de flux d'hydrocarbures
US11473024B2 (en) Processing pyrolysis tar particulates
JP5406629B2 (ja) 高芳香族炭化水素油の製造方法
AU2018329532A1 (en) Reactor staging for slurry hydroconversion of polycyclic aromatic hydrocarbon feeds
CA2899496A1 (fr) Production d'huile lourde de faible point de trouble
WO2010004127A2 (fr) Procede de conversion comprenant une viscoreduction de residu puis un desasphaltage et une hydroconversion
EP4013837A1 (fr) Processus pour améliorer les rendements en huile de base
JP6548223B2 (ja) 燃料油基材の製造方法
US20240084204A1 (en) Process for making bright stock base oil products
KR20230131234A (ko) 색 안정성이 향상된 기유의 제조 방법
JP2024506820A (ja) 重質グレード基油製品を製造するプロセス
CN118525073A (zh) 蒸汽裂化含砷烃进料

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18812440

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 3077234

Country of ref document: CA

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18812440

Country of ref document: EP

Kind code of ref document: A1