US20200109337A1 - Process and apparatus for treating mercaptans in a naphtha boiling range feed - Google Patents

Process and apparatus for treating mercaptans in a naphtha boiling range feed Download PDF

Info

Publication number
US20200109337A1
US20200109337A1 US16/545,001 US201916545001A US2020109337A1 US 20200109337 A1 US20200109337 A1 US 20200109337A1 US 201916545001 A US201916545001 A US 201916545001A US 2020109337 A1 US2020109337 A1 US 2020109337A1
Authority
US
United States
Prior art keywords
naphtha
stream
mercaptan
compounds
boiling range
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.)
Abandoned
Application number
US16/545,001
Other languages
English (en)
Inventor
Zunqing Alice He
Stephen Edward LEICHTY
Cameron Adams McCORD
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.)
Chevron USA Inc
Original Assignee
Chevron USA Inc
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 Chevron USA Inc filed Critical Chevron USA Inc
Priority to US16/545,001 priority Critical patent/US20200109337A1/en
Assigned to CHEVRON U.S.A. INC. reassignment CHEVRON U.S.A. INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: LEICHTY, STEPHEN EDWARD, MCCORD, CAMERON ADAMS, HE, ZUNQING ALICE
Publication of US20200109337A1 publication Critical patent/US20200109337A1/en
Abandoned legal-status Critical Current

Links

Images

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
    • C10G35/00—Reforming naphtha
    • C10G35/04—Catalytic reforming
    • C10G35/06—Catalytic reforming characterised by the catalyst used
    • 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
    • C10G53/14—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only including at least one oxidation step
    • 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
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • 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
    • C10G27/00—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation
    • C10G27/04—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1025—Natural gas
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1037—Hydrocarbon fractions
    • C10G2300/104—Light gasoline having a boiling range of about 20 - 100 °C
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1037—Hydrocarbon fractions
    • C10G2300/1044—Heavy gasoline or naphtha having a boiling range of about 100 - 180 °C
    • 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
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P
    • 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
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4018—Spatial velocity, e.g. LHSV, WHSV

Definitions

  • the present disclosure generally relates to processes and apparatuses for treating petroleum fractions. More particularly, the field relates to an improved process and apparatus for removing mercaptan compounds from petroleum fractions such as naphtha.
  • Hydroprocessing such as hydrotreating
  • hydrotreating can be effective for reducing the sulfur content of a naphtha boiling range fraction to a desired sulfur level.
  • the existing hydrotreating assets do not have sufficient available hydraulic capacity to process the petrochemical naphtha stream and building a grass roots hydrotreater for this purpose is a very expensive option.
  • Sweetening of petroleum fractions such as naphtha boiling range hydrocarbons or other liquid hydrocarbons, that contain mercaptans (or sour petroleum fractions) are well-developed commercial processes commonly used in many petroleum refineries.
  • mercaptans contained in the feed hydrocarbon stream e.g., sour hydrocarbon stream
  • disulfide compounds that remain in the hydrocarbon stream (e.g., sweetened hydrocarbon stream).
  • sweetening processes therefore, do not remove sulfur from the hydrocarbon stream but rather convert the sulfur to an acceptable form.
  • the sweetening process involves an admixture of an oxygen-containing stream to the sour hydrocarbon stream to supply the required oxygen.
  • the admixture of hydrocarbons and oxygen contacts an oxidation catalyst in an aqueous alkaline environment to oxidize the mercaptans.
  • a caustic e.g., an aqueous caustic solution
  • the sour hydrocarbon stream to create the aqueous alkaline environment.
  • at least a portion of the caustic is carried with the sweetened hydrocarbon stream and can be problematic for further downstream processing.
  • Current approaches for removing caustic from sweetened hydrocarbon streams often require additional downstream equipment and can be costly and/or are relatively inefficient.
  • a process for treating a naphtha boiling range stream containing mercaptan compounds comprising: (a) oxidizing mercaptan compounds in the naphtha boiling range stream to provide a mercaptan-depleted naphtha stream rich in disulfide compounds; (b) passing the mercaptan-depleted naphtha stream rich in disulfide compounds to a naphtha splitter column; and (c) fractionating at least a portion of the mercaptan-depleted naphtha stream rich in disulfide compounds into at least two streams, a light naphtha stream lean in disulfide compounds and a heavy naphtha stream rich in disulfide compounds.
  • an apparatus for treating a naphtha boiling range stream containing mercaptan compounds comprising: (a) an oxidation unit to provide a mercaptan-depleted naphtha stream rich in disulfide compounds; and (b) a naphtha splitter column in downstream communication with the oxidation unit to provide a light naphtha stream lean in disulfide compounds in a naphtha splitter overhead line and a heavy naphtha stream rich in disulfide compounds in a naphtha splitter bottoms line.
  • FIG. 1 s a process flow diagram illustrating an exemplary process and apparatus of the present disclosure.
  • naphtha or “naphtha boiling range” refers to hydrocarbons boiling in a range of about 25° C. to 190° C. atmospheric equivalent boiling point (AEBP), as determined by any standard gas chromatographic simulated distillation method such as ASTM D2887, and can include one or more C 5 -C 10 hydrocarbons.
  • AEBP atmospheric equivalent boiling point
  • light naphtha refers to hydrocarbons boiling in a range of about 25° C. to 85° C., and can include one or more C 5 -C 6 hydrocarbons.
  • heavy naphtha refers to hydrocarbons boiling in the range of about 85° C. to 190° C. (e.g., 110° C. to 170° C.), and can include one or more C 6 -C 10 hydrocarbons.
  • straight-run naphtha and its acronym “SRN” which accordingly refers to “naphtha” defined above that is derived directly from the atmospheric distillation unit, optionally subjected to steam stripping, as is well known.
  • Straight-run naphtha may also be derived from natural gas condensates.
  • the term “rich” refers to a stream exiting a vessel that has a concentration of one or more compounds exceeding a stream entering the vessel.
  • lean refers to a stream exiting a vessel that has a concentration of one or more compounds less than a stream entering the vessel.
  • depleted is synonymous with reduced from originally present. For example, removing a substantial portion of a material from a stream would produce a material-depleted stream that is substantially depleted of that material.
  • mercaptan means thiol compounds of the formula R—SH where R is a hydrocarbon group, such as an alkyl or aryl group, that is saturated or unsaturated and optionally substituted,
  • diisulfide means compounds having the molecular formula R—S—S—R′ where R and R′ are each, independently, a hydrocarbon group, such as an alkyl or aryl group, that is saturated or unsaturated and optionally substituted.
  • R and R′ are each, independently, a hydrocarbon group, such as an alkyl or aryl group, that is saturated or unsaturated and optionally substituted.
  • CS 2 carbon disulfide
  • C x means hydrocarbon molecules that have “x” number of carbon atoms
  • C x means hydrocarbon molecules that have “x” and/or more than “x” number of carbon atoms
  • C x- means hydrocarbon molecules that have “x” and/or less than “x” number of carbon atoms.
  • communication means that material flow is operatively permitted between enumerated components.
  • downstream communication means that at least a portion of material flowing to the subject in downstream communication may operatively flow from the object with which it communicates.
  • upstream communication means that at least a portion of the material flowing from the subject in upstream communication may operatively flow to the object with which it communicates.
  • process flow lines in the FIGURE can be referred to interchangeably as, for example, lines, pipes, feeds, gases, products, discharges, parts, portions, conduits or streams.
  • FIGURE has been simplified by the deletion of a large number of apparatuses customarily employed in a process of this nature, such as vessel internals, temperature and pressure control systems, flow control valves, recycle pumps, etcetera which are not specifically required to illustrate the performance of the invention.
  • a feed 2 that is a crude oil or a natural gas condensate stream containing a range of hydrocarbons is passed to a distillation unit 10 where the feed is separated into a light stream 3 , a naphtha boiling range stream 5 , and/or one or more heavier or bottoms fractions.
  • the distillation unit 10 may be an atmospheric distillation unit.
  • the distillation unit 10 may be a natural gas condensate splitter.
  • the feed in line 2 may be dried and/or pre-treated to reduce and/or remove one or more of undesired components such as carbon dioxide, mercury, and water prior to fractionation.
  • Naphtha boiling range streams typically contain one or more mercaptan compounds.
  • the mercaptans occurring in naphtha boiling range streams are generally C 1 -C 10 mercaptans (e.g., C 1 -C 6 mercaptans).
  • the mercaptans are generally concentrated in the light fractions of the naphtha and more precisely in the fraction with a boiling point of less than 120° C.
  • the mercaptan sulfur may be present in the naphtha boiling range stream in an amount ranging from about 2 ppm to 300 wppm or more, depending on the particular stream to be treated.
  • the mercaptan-containing naphtha boiling range stream 5 is passed to an oxidation unit 20 where mercaptan compounds in the naphtha stream are converted to disulfide compounds.
  • the flow direction in oxidation unit 20 can be down flow or up flow.
  • the naphtha stream 5 is mixed with an air or other oxygen-containing gas stream 7 supplied at a rate that supplies at least the stoichiometric amount of oxygen necessary to oxidize the mercaptan compounds in the naphtha boiling range stream 5 to disulfide compounds.
  • the mole ratio of oxygen to mercaptan sulfur may range from about 1:4 to 10:1 (e.g., about 1:1 to 10:1, or about 1:1 to 3:1).
  • the oxidation of the mercaptan compounds is promoted through the presence of a catalytically effective amount of an oxidation catalyst capable of functioning at the conditions found in the oxidation unit 20 .
  • the oxidation unit 20 may be configured in a packed bed configuration to ensure adequate mixing between the naphtha boiling range feed, the catalyst, and the oxygen.
  • the oxidation unit 20 may comprise a cylindrical fixed bed of catalyst through which the reactants move in a vertical direction.
  • the oxidation conditions utilized in oxidation unit 20 may include a pressure of from about 101 to 2068 kPa (gauge) (15 to 300 psig), such as from 172 to 689 kPa (gauge) (25 to 100 psig); a temperature of from 35° C. to 200° C. (e.g. 50° C. to 150° C.); and a liquid hourly space velocity of from 1 to 10 h ⁇ 1 (e.g., 1 to 5 h ⁇ 1 ).
  • mercaptan compounds are depleted in the naphtha boiling range stream in the substantial absence of any caustic solvent, such as an aqueous solution of alkali metal hydroxide (e.g., sodium hydroxide, potassium hydroxide).
  • alkali metal hydroxide e.g., sodium hydroxide, potassium hydroxide
  • Suitable oxidation catalysts are any known conventional catalysts for oxidizing mercaptans to disulfides and can include those which are comprised of a Group 5-12 metal component (e.g., one or more of vanadium, chromium, manganese, cobalt, nickel, copper, zinc) retained on a refractory inorganic oxide support.
  • a Group 5-12 metal component e.g., one or more of vanadium, chromium, manganese, cobalt, nickel, copper, zinc
  • the inorganic oxide binder of the catalyst may comprise materials such as alumina, silica, zirconia, titania, thoria, boria, magnesia, chromia, stannic oxide, and the like as well as combinations and composites thereof, for example silica-alumina, alumina-zirconia, alumina-titania, aluminum phosphate, and the like.
  • Alumina is a preferred refractory inorganic oxide binder.
  • a precursor of the desired refractory inorganic oxide may be used to form, bind, and/or otherwise prepare the catalyst.
  • Such binder precursors or sources may be converted into a refractory inorganic oxide binder, for example, by calcination.
  • the alumina may be any of the various aluminum oxides, hydroxides, and gels, including boehmite, pseudo-boehmite, gibbsite, bayerite, and the like, especially transition and gamma aluminas. Suitable aluminas are commercially available, for example, under the trade names CATAPAL ⁇ B and VERSALTM 250.
  • the metal component of the catalyst may comprise a metal selected from the group consisting of vanadium, chromium, manganese, cobalt, nickel, copper, zinc, and combinations thereof. In one embodiment, the metal component comprises copper.
  • the metal content of the catalyst can range from 10 to 40 wt. % (e.g., 15 to 30 wt. %) as the metal based upon the total weight of the catalyst.
  • the metal component may be incorporated into the catalyst in any suitable manner such as co-mulling, co-precipitation or co-gellation with the carrier material, ion exchange, or impregnation.
  • the metal component may exist within the final catalyst as a compound such as an oxide, sulfide, halide, or oxyhalide, in chemical combination with one or more of the other ingredients of the composite, or as an elemental metal.
  • the metal component is copper
  • the metal component may be present as copper metal, copper, oxide, copper sulfide, or a combination thereof.
  • the catalyst is most preferably used in particulate form, for example as pellets, extrudate, spheres or granules, although other solid forms also are suitable.
  • Particle size of the catalyst is selected such that a bed of catalyst particles is easily maintained in a suitable reactor for the oxidation process but permits flow of the naphtha boiling range through the bed without undesirable pressure drop.
  • Preferred average particle sizes are such that catalyst particles pass through a 2-mesh screen but are retained on a 24-mesh screen (U.S. Sieve Series) and more preferably pass through a 4-mesh screen but are retained on a 12-mesh screen.
  • the oxidation catalyst may have a BET surface area in a range of 30 to 300 m 2 /g (e.g., 50 to 200 m 2 /g).
  • the oxidation catalyst may be a fresh or spent sulfur sorbent having application in eliminating residual sulfur from conventionally desulfurized reformer or isomerization feed streams, such as described in U.S. Pat. No. 4,259,213.
  • the effluent from oxidation unit 20 comprises a mercaptan-depleted naphtha stream rich in disulfide compounds.
  • Organic disulfides have higher boiling points than those of their mercaptan precursors.
  • mercaptans that typically boil in a light naphtha fraction are converted in the oxidation unit 20 into disulfides that typically boil in a heavy naphtha fraction.
  • the mercaptan-depleted naphtha stream rich in disulfide compounds in line 11 is passed to a naphtha splitter column 30 in which it is fractionated to provide a light naphtha stream lean in disulfide compounds in a naphtha splitter overhead line 13 and a heavy naphtha stream rich in disulfide compounds in a naphtha splitter bottoms line 23 .
  • the light naphtha stream typically a C 5 -C 6 or a C 5 -C 7 stream, with reduced sulfur content may be condensed and separated in a receiver with a portion of the condensed liquid being sent in line 19 for blending to the gasoline pool.
  • Any light ends may be vented to an appropriate combustion destination such as a furnace burner of a flare equipped for streams with high levels of oxygen via line 17 .
  • the heavy naphtha stream typically comprising C 7+ naphtha, is rich in disulfide compounds, and may be taken from a bottoms outlet in the naphtha splitter bottoms line 23 for further processing.
  • the naphtha splitter column 30 may be operated with a top pressure of 69 to 448 kPa (gauge) (10 to 65 psig) and a bottom temperature of 121° C. to 232° C. (250° F. to 450° F.). Alternatively, the naphtha splitter column 30 may be operated at a vacuum.
  • the naphtha splitter column 30 may include a reboiler at a bottom of the column to vaporize and send a portion of the heavy naphtha stream back to the bottom of the column.
  • the heavy naphtha stream rich in disulfide compounds in line 23 may be passed to a hydroprocessing unit to convert organic disulfides in the stream to hydrocarbons and hydrogen sulfide.
  • a heavy naphtha stream lean in disulfide compounds can be recovered and routed as desired by the refiner.
  • a mercaptan-containing whole straight-run naphtha (boiling range of 30° F.-330° F.; API gravity of 62.5) mixed with a selected air rate was flowed continuously through a 10 mL reactor bed loaded with a spent copper-containing oxidation catalyst that was previously used as an adsorbent in a sulfur guard bed for a refinery process.
  • the catalyst contained about 30 wt. % copper and was prepared by co-mulling and impregnating an alumina support with copper, as described in U.S. Pat. No. 4,259,213.
  • the unit was operated at various temperatures and liquid hourly space velocities (LHSV) at a pressure of 65 psig. The results are summarized in Table 1.
  • the treated naphtha products in Runs 1-5 contained less than 1 ppm mercaptans.
  • a treated naphtha product prepared as described in Example 1 was then distilled into light (200° F. ⁇ ) and heavy (200° F.+) naphtha cuts.
  • the physical properties and composition of the light and heavy naphtha cuts are summarized in Tables 2.
  • ASTM D4814 requires that fuels for automotive spark engines have a copper strip corrosion maximum of 1.
  • a silver strip rating of 1 indicates slight tarnish.
  • ASTM D4814 requires that fuels for automotive spark engines have a silver strip corrosion maximum of 1.
  • ASTM D4814 requires that fuels for automotive spark engines have a maximum solvent-washed gum content of 5 mg/100 mL.
  • Hydrocarbon class distribution was analyzed via detailed hydrocarbon analysis using gas chromatography (GC-DHA) by a method derived from the ASTM D6729 method. To improve identifications of GC species, 60 meter high resolution dual columns (one polar column and one non-polar column) were used. Those peaks that were not identified were grouped in the “Unclassified” category.
  • the thermal stability of disulfides in the light and heavy naphtha cuts was determined at the naphtha splitter bottom temperature. Disulfides are products from mercaptan oxidation and can convert reversibly back to mercaptans at higher temperature. Each cut was heated to 350° F. in a Parr bomb type reactor for one and four hours. Sulfur speciation studies using gas chromatography sulfur chemiluminescence detection (GC-SCD) indicated no detectable reappearance of any mercaptans in the light and heavy naphtha cuts.
  • GC-SCD gas chromatography sulfur chemiluminescence detection
  • Example 1 was repeated except that the whole straight-run naphtha feed was a 300° F. ⁇ cut from a blend of Canadian condensates CFT and CRW.
  • the feed contained 90.4 wppm of C 1 -C 9 mercaptans including cyclic and aromatic mercaptans.
  • the mercaptan conversion results for this “tough feed” are summarized in Table 3.
  • a treated naphtha product was then distilled into light (200° F. ⁇ ) and heavy (200° F.+) naphtha cuts. Both cuts were tested for their thermal stability at 302° F. GC-SCD indicated no detectable reappearance of any mercaptans in the light and heavy naphtha cuts.
  • Example 1 was repeated except that a fresh copper-containing oxidation catalyst was used.
  • the test was conducted on a conventional whole straight-run naphtha under the following conditions:

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)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
US16/545,001 2018-10-08 2019-08-20 Process and apparatus for treating mercaptans in a naphtha boiling range feed Abandoned US20200109337A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US16/545,001 US20200109337A1 (en) 2018-10-08 2019-08-20 Process and apparatus for treating mercaptans in a naphtha boiling range feed

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201862742603P 2018-10-08 2018-10-08
US16/545,001 US20200109337A1 (en) 2018-10-08 2019-08-20 Process and apparatus for treating mercaptans in a naphtha boiling range feed

Publications (1)

Publication Number Publication Date
US20200109337A1 true US20200109337A1 (en) 2020-04-09

Family

ID=70051987

Family Applications (1)

Application Number Title Priority Date Filing Date
US16/545,001 Abandoned US20200109337A1 (en) 2018-10-08 2019-08-20 Process and apparatus for treating mercaptans in a naphtha boiling range feed

Country Status (3)

Country Link
US (1) US20200109337A1 (ko)
KR (1) KR20200040184A (ko)
SG (1) SG10201907657WA (ko)

Also Published As

Publication number Publication date
SG10201907657WA (en) 2020-05-28
KR20200040184A (ko) 2020-04-17

Similar Documents

Publication Publication Date Title
KR101441129B1 (ko) 옥탄가 손실이 적은 크래킹 가솔린의 심도 탈황 방법
US6843905B2 (en) Low-sulfur fuel
US20060151359A1 (en) Naphtha desulfurization process
US20200332201A1 (en) Process for fluidized catalytic cracking of disulfide oil to produce ethylene used for metathesis to produce propylene
RU2665701C2 (ru) Способ получения бензина с малым количеством серы и меркаптанов
CA2486670C (en) Multi-stage hydrodesulfurization of cracked naphtha streams with a stacked bed reactor
AU2002227310A1 (en) Low-sulfur fuel
CA2467879C (en) Multi-stage hydrodesulfurization of cracked naphtha streams with interstage fractionation
US10968400B2 (en) Process to remove olefins from light hydrocarbon stream by mercaptanization followed by MEROX removal of mercaptans from the separated stream
US20200109337A1 (en) Process and apparatus for treating mercaptans in a naphtha boiling range feed
US3126331A (en) Purifying hydrocarbons
US11180432B1 (en) Process for fluidized catalytic cracking of disulfide oil to produce BTX
US20050011811A1 (en) Desulfurization of a naphtha gasoline stream derived from a fluid catalytic cracking unit
US20230220287A1 (en) Hydrocarbon Pyrolysis of Feeds Containing Mercury
US9822317B2 (en) Process and apparatus for selectively hydrogenating naphtha
US9393538B2 (en) Process and apparatus for selectively hydrogenating naphtha
US6802959B1 (en) Separation of olefinic hydrocarbons from sulfur-containing hydrocarbons by use of a solvent
US10731090B2 (en) Process and apparatus for treating mercaptans
Greenwood et al. Sulfur removal from gasoline and diesel: Reaching low levels without sacrificing fuel quality or quantity
Imran AL–Mansuriya gas fields associated liquid and its role to increase the potential capacity of gasoline fuel in Daura oil refinery
CA2780480C (en) Improved selective cracked naphtha desulfurization using arsenic trap catalysts
US20060124508A1 (en) Method of converting saturated sulfur compounds of a hydrocarbon cut containing few or no olefins
Dragomir et al. Upgrading of the FCC Gasoline Quality

Legal Events

Date Code Title Description
AS Assignment

Owner name: CHEVRON U.S.A. INC., CALIFORNIA

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:HE, ZUNQING ALICE;LEICHTY, STEPHEN EDWARD;MCCORD, CAMERON ADAMS;SIGNING DATES FROM 20190729 TO 20190806;REEL/FRAME:050096/0466

STPP Information on status: patent application and granting procedure in general

Free format text: RESPONSE TO NON-FINAL OFFICE ACTION ENTERED AND FORWARDED TO EXAMINER

STPP Information on status: patent application and granting procedure in general

Free format text: NON FINAL ACTION MAILED

STPP Information on status: patent application and granting procedure in general

Free format text: FINAL REJECTION MAILED

STPP Information on status: patent application and granting procedure in general

Free format text: RESPONSE AFTER FINAL ACTION FORWARDED TO EXAMINER

STPP Information on status: patent application and granting procedure in general

Free format text: ADVISORY ACTION MAILED

STPP Information on status: patent application and granting procedure in general

Free format text: RESPONSE TO NON-FINAL OFFICE ACTION ENTERED AND FORWARDED TO EXAMINER

STPP Information on status: patent application and granting procedure in general

Free format text: DOCKETED NEW CASE - READY FOR EXAMINATION

STPP Information on status: patent application and granting procedure in general

Free format text: NON FINAL ACTION MAILED

STPP Information on status: patent application and granting procedure in general

Free format text: RESPONSE TO NON-FINAL OFFICE ACTION ENTERED AND FORWARDED TO EXAMINER

STPP Information on status: patent application and granting procedure in general

Free format text: FINAL REJECTION MAILED

STCV Information on status: appeal procedure

Free format text: NOTICE OF APPEAL FILED

STCV Information on status: appeal procedure

Free format text: APPEAL BRIEF (OR SUPPLEMENTAL BRIEF) ENTERED AND FORWARDED TO EXAMINER

STCV Information on status: appeal procedure

Free format text: EXAMINER'S ANSWER TO APPEAL BRIEF MAILED

STCV Information on status: appeal procedure

Free format text: ON APPEAL -- AWAITING DECISION BY THE BOARD OF APPEALS

STCV Information on status: appeal procedure

Free format text: BOARD OF APPEALS DECISION RENDERED

STCB Information on status: application discontinuation

Free format text: ABANDONED -- AFTER EXAMINER'S ANSWER OR BOARD OF APPEALS DECISION