US2657175A - Desulfurization of heavy petroleum oils - Google Patents

Desulfurization of heavy petroleum oils Download PDF

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Publication number
US2657175A
US2657175A US195939A US19593950A US2657175A US 2657175 A US2657175 A US 2657175A US 195939 A US195939 A US 195939A US 19593950 A US19593950 A US 19593950A US 2657175 A US2657175 A US 2657175A
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Prior art keywords
sulfur
residua
feed
product
catalyst
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Expired - Lifetime
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US195939A
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English (en)
Inventor
Mason Ralph Burgess
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Standard Oil Development Co
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Standard Oil Development Co
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Publication date
Priority to NL84440D priority Critical patent/NL84440C/xx
Application filed by Standard Oil Development Co filed Critical Standard Oil Development Co
Priority to US195939A priority patent/US2657175A/en
Priority to US196156A priority patent/US2640011A/en
Priority to GB22818/51A priority patent/GB736072A/en
Priority to FR1048630D priority patent/FR1048630A/fr
Application granted granted Critical
Publication of US2657175A publication Critical patent/US2657175A/en
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/14Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing with moving solid particles
    • C10G45/16Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing with moving solid particles suspended in the oil, e.g. slurries
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06Halogens; Compounds thereof
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used

Definitions

  • the present invention relates to the treatment of sulfur-containing organic materials, in particular, sulfur-bearing hydrocarbon material, to desulfurize the same. More particularly, the present invention relates to the desulfurization of sulfur-containing petroleum fractions, parcharacteristics. Sulfur is objectionable in fuel oils of any kindbecause it burns to form SO2 which is obnoxious and corrosive.
  • - Sulfur occurs in petroleum stocks generally in two main forms, as mercaptans and as part of a more or less substituted ring, of which thiophene is the prototype.
  • the former type is .generally found in the lower boiling fractions, in the naphtha, kerosene, and light gas oil material, whereas the ring-sulfur compounds form the bulk of the sulfur-bearing material of the high boiling petroleum fractions.
  • a high boiling product such as a residuum that contains about 3%Yof sulfur is estimated to consist extensively of molecules containing sulfur, and so extraction of sulfur-containing material is no longer feasible, inasmuch as the bulk of the extracted material is in the extract and m 2 lost, unless a means is present for removing sulfur from this extract.
  • an object of the present invention to provide an improved method of desulfurizing sulfur-bearing organic hydrocarbon material, in particular desulfurizing high boiling stocks such as residua.
  • a further object of the invention is to provide an improved means of refining petroleum fractions to separate therefrom, sulfur and undesirable sulfur compounds.
  • a still further objectof the present invention is to provide a cheap method for upgrading heavy stocks such as residua.
  • a still further object of the present invention is to ⁇ disclose a novel means of hydrodesulfurizing in the absence of a xed catalyst bed whereby inactivation of catalyst is substantially avoided.
  • a homogeneous catalyst system is meant a system wherein the catalyst is always presenting a fresh surface" to the reactants, i. e., any system having a self-generating surface.
  • the catalyst is miscible in the material being treated, vor it is completely dispersed therethrough, and reaction products being precipitated, fresh surface is constantly provided.
  • boron halide complexes are particularly useful as homogeneous catalysts in reducing the sulfur content of reduced crudes and residua in the presence of hydrogen, and in upgrading such residua.
  • Residua are of little commercial value per se, because of their high coking characteristics and sulfur content, and because of their high ash and asphaltene content.
  • they may readily and economically be converted into useful products, such as feed stock for catalytic cracking, or for bunker and marine fuel, neither of which can tolerate high sulfur content.
  • sulfur content may be as high as 6%, corresponding to a mixture wherein the vast bulk of the molecules contain sulfur andare. of course, of high molecular weight.
  • high boiling high molecular weight petroleum fractions are treated in a hydrogenation zone with hydrogen at pressures from about 500-5000 p. s. i. g. and temperatures of 300-900 F., though preferably below 800 F., in the presence of one of the halides of boron, particularly boron fluoride-alcohol complexes, boron fluoride-ether complexes, boron fluoride-water complexes, etc. may be employed in the ratio of 100 to 2.5 parts hydrocarbon feed per part boron fluoride, and the complexing material may be present in the ratio of 0.25 to 6 parts boron fluoride per part complexing compound.
  • the boron fluoride complex is readily prepared by bubbling an excess of boron fluoride through the complexing material, such as water, at about 35 to 100 F. until a stoichiometric amount has been absorbed, and then subjecting the mixture to reduced pressure to remove the excess boron iiuoride.
  • the complexing material such as water
  • the petroleum stock is introduced through lines 2 and 6 into reactor lil, together with catalyst either from storage through lines 4 and 6, or in part from recycled catalyst as shown.
  • the mixture is contacted countercurrently with a hydrogen-containing gas introduced through line 8.
  • the hydrogenator l is suitably a packed tower, though other known means of obtaining intimate contact between liquids and gases may be employed.
  • the quantity of complex used may vary from 5 to 50% by weight of the feed, and the ratio of boron fluoride to the complex-forming material may be in the range of 0.25 to 6. The latter ratio depends considerably upon the molecular weight of the complexing material. Mol ratios of boron fluoride to complexing materials of l/1 and 2/1 and 0.5/1 are preferred.
  • the feed rates of 0.25 to 4 V./v./hr. may be employed, together with hydrogen feed rates of about 500 to 5000 standard cubic feet per barrel of liquid feed. Though commercial hydrogen is preferable, even hydro-v gen containing appreciable quantities of carbon monoxide may be employed.
  • Catalyst dispersed in the solid residue may advantageously be recovered by treating the solid with HF introduced through line I6.
  • the volatilized boron iiuoride is withdrawn overhead through line i8 and passed through lines 20, 5 and 6, back to the reactor.
  • reactor l 0 which may contain, besides hydrogen, also a certain amount of liquid hydrocarbons occurring as a result of cracking, and also, gases such as HzS and a small amount of boron uoride, may be passed to separator 24. Overhead therefrom, gas may be withdrawn and, if desired, recycled via lines 26 and 8 to the reactor. Any known means for removing H28 from this gas stream may be employed. when it is desired to free recycle gases from this material.
  • Liquid product from separator 24 may be withdrawn through line 2B and passed to scrubber 32, wherein it is combined with the main liquid fraction.
  • the scrubbed oil is passed via line 42 to fractionating system 44 equipped with suitable heating means.
  • Overhead through line 46 there is recovered a substantially sulfur-free naphtha, while through line 48 there are withdrawn gas and heating oils with very low sulfur content. Residue is withdrawn through line 49, and this may be recovered as such, as when it is desired to recover bunker fuel, or it may be recycled in part or in total to the process Via line 52.
  • Make-up boron fluoride or water or both, may be introduced as needed through line 4. Coke free of boron halide may be withdrawn from settlers I4 through line l l.
  • the catalyst instead of being the fluoride of boron, may be another halide. Recovery of fboron fluoride from the deposited solids need not take place in the settler, but may take place in auxiliary vessels. Under certain circumstances it may be desirable to pretreat the residua or reduced crude with hydrogen in the absence of a catalyst prior to homogeneously catalytically hydrodesulfurizing the same; appreciable reduction in amount of catalyst required may sometimes thus be realized.
  • boron halide catalyzed hydrodesulfurizing is advantageously employed in desulfurizing and upgrading other materials, such as gas oils, cycle oils, and heating oils, particularly these boiling above about 650 F.
  • N aptha 400 F- Wt. Percent of product 20. 5 14. 4 Wt. Percent sulfur 0. ll 0. 04 Gas Oil, 850 F. (600 F. 3
  • An improved process for preparing feed stock for a catalytic cracking process from high sulfur petroleum residua which comprises contacting said residu-a feed in a hydrogenation zone with hydrogen under conditions avoiding substantial cracking of said feed to naphtha, maintaining Within said zone elevated pressures, a temperature above about 300 F., but less than about 800 F., a feed rate suiicient to avoid substantial cracking of said residua, contacting said residua with a homogeneous hydrosulfurization catalyst comprising an addition product of boron fluoride and water, and recovering a catalytic cracking feed stock containing substantially less sulfur than said initial feed.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Catalysts (AREA)
US195939A 1950-11-16 1950-11-16 Desulfurization of heavy petroleum oils Expired - Lifetime US2657175A (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
NL84440D NL84440C (xx) 1950-11-16
US195939A US2657175A (en) 1950-11-16 1950-11-16 Desulfurization of heavy petroleum oils
US196156A US2640011A (en) 1950-11-16 1950-11-17 Desulfurization of heavy petroleum oils
GB22818/51A GB736072A (en) 1950-11-16 1951-10-01 Improvements in or relating to desulfurization of heavy petroleum fractions
FR1048630D FR1048630A (fr) 1950-11-16 1951-10-18 Procédé de désulfuration des huiles lourdes

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US195939A US2657175A (en) 1950-11-16 1950-11-16 Desulfurization of heavy petroleum oils
US196156A US2640011A (en) 1950-11-16 1950-11-17 Desulfurization of heavy petroleum oils

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US196156A Expired - Lifetime US2640011A (en) 1950-11-16 1950-11-17 Desulfurization of heavy petroleum oils

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FR (1) FR1048630A (xx)
GB (1) GB736072A (xx)
NL (1) NL84440C (xx)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2745792A (en) * 1951-12-06 1956-05-15 Shiah Chyn Duog Hydrocarbon treating process
US2834717A (en) * 1956-03-07 1958-05-13 Shiah Chyn Duog Process of desulfurizing hydrocarbons with a boron fluoride coordination compound followed by hydrofining with a hydrogen donor
US3117074A (en) * 1958-10-06 1964-01-07 Sinclair Research Inc Method of separating sludge from liquid hydrocracked products
US3371049A (en) * 1965-11-15 1968-02-27 Consolidation Coal Co Regeneration of zinc halide catalyst used in hydrocracking of polynuclear hydrocarbons
US6103773A (en) * 1998-01-27 2000-08-15 Exxon Research And Engineering Co Gas conversion using hydrogen produced from syngas for removing sulfur from gas well hydrocarbon liquids

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2578692C2 (ru) 2011-10-24 2016-03-27 Адитиа Бирла Нуво Лимитед Усовершенствованный способ производства углеродной сажи
WO2013175488A2 (en) 2012-03-30 2013-11-28 Aditya Birla Science And Technology Company Ltd. A process for obtaining carbon black powder with reduced sulfur content

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB301395A (xx) * 1927-11-29 1929-12-19 Fritz Hofmann

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE421858C (xx) *
US1814410A (en) * 1926-02-24 1931-07-14 Ig Farbenindustrie Ag Process for purifying and refining hydrocarbon oils

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB301395A (xx) * 1927-11-29 1929-12-19 Fritz Hofmann

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2745792A (en) * 1951-12-06 1956-05-15 Shiah Chyn Duog Hydrocarbon treating process
US2834717A (en) * 1956-03-07 1958-05-13 Shiah Chyn Duog Process of desulfurizing hydrocarbons with a boron fluoride coordination compound followed by hydrofining with a hydrogen donor
US3117074A (en) * 1958-10-06 1964-01-07 Sinclair Research Inc Method of separating sludge from liquid hydrocracked products
US3371049A (en) * 1965-11-15 1968-02-27 Consolidation Coal Co Regeneration of zinc halide catalyst used in hydrocracking of polynuclear hydrocarbons
US6103773A (en) * 1998-01-27 2000-08-15 Exxon Research And Engineering Co Gas conversion using hydrogen produced from syngas for removing sulfur from gas well hydrocarbon liquids

Also Published As

Publication number Publication date
GB736072A (en) 1955-08-31
FR1048630A (fr) 1953-12-23
NL84440C (xx)
US2640011A (en) 1953-05-26

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