US3748827A - Process for optimum absorption of elemental sulfur from natural gas by the use of mineral oil and similar liquid hydrocarbons - Google Patents

Process for optimum absorption of elemental sulfur from natural gas by the use of mineral oil and similar liquid hydrocarbons Download PDF

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Publication number
US3748827A
US3748827A US00092633A US3748827DA US3748827A US 3748827 A US3748827 A US 3748827A US 00092633 A US00092633 A US 00092633A US 3748827D A US3748827D A US 3748827DA US 3748827 A US3748827 A US 3748827A
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United States
Prior art keywords
mineral oil
natural gas
liquid
elemental sulfur
liquid hydrocarbon
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Expired - Lifetime
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US00092633A
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English (en)
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W Bulian
A Dittmar
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Wintershall AG
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Wintershall AG
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    • E—FIXED CONSTRUCTIONS
    • E21—EARTH OR ROCK DRILLING; MINING
    • E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
    • E21B43/34—Arrangements for separating materials produced by the well
    • E21B43/40—Separation associated with re-injection of separated materials
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/02—Preparation of sulfur; Purification
    • C01B17/021—Separation of sulfur from gases
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/11—Purification; Separation; Use of additives by absorption, i.e. purification or separation of gaseous hydrocarbons with the aid of liquids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00—Purifying combustible gases containing carbon monoxide
    • C10K1/08—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors
    • C10K1/16—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with non-aqueous liquids
    • C10K1/18—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with non-aqueous liquids hydrocarbon oils

Definitions

  • natural gas containing large amounts of elemental sulfur in the vapor phase is freed therefrom by introducing into a rising stream of natural gas, an ascending, annular current of a mineral oil or a similar liquid hydrocarbon.
  • the mineral oil may be diesel oil, spindle oil or light machine oil; and the liquid hydrocarbon may be benzene, toluene xylene, coal tar oil, etc.
  • the mineral oil or hydrocarbon have a viscosity of 2200 cP at 20C., and a vapor pressure of up to 3 X l mm Hg at 20C.
  • the annular flow of mineral oil or liquid hydrocarbon surrounds the rising flow of natural gas and completely wets the casing wall.
  • FIG. 1 is a schematic representation of the apparatus of the invention.
  • FIG. 2 is a schematic representation of a second embodiment of the apparatus.
  • the process comprises introducing into a rising column of natural gas (i.e., rising from a well bottom), an ascending annular current of a mineral oil fraction or similar liquid hydrocarbon having a viscosity of 2200, preferably -60 of at C. and a vapor pressure up to 3 X 10 mm Hg at 20C. running up the pipe wall in the two-phase system consisting of mineral oil fraction or liquid hydrocarbon and the natural gas having elemental sulfur dissolved therein in the vapor phase.
  • a rising column of natural gas i.e., rising from a well bottom
  • the mineral oil fraction may be any one of diesel oil, spindle oil, light machine oil, or any other mineral oil having the stated viscosity and vapor pressure.
  • the liquid hydrocarbon which may be used in place of the mineral oil may be benzene, toluene, xylene, coal tar oils, etc, so long as it meets the vapor pressure and viscosity requirements set forth above.
  • the ratio of mineral oil (liters/hr) to natural gas (Nm lhr) is in the range of I: about 4-20, the amount of sulfur present in the natural gas will determine more precisely the ratio.
  • the ratio of mineral oil fraction (liters/hr) to natural gas (Nm lhr) should be approximately 1 20; when the sulfur is present in amounts from 0.1 to l gm/Nm the ratio should be I 12; when the sulfur is present in amounts from I to 2 gm/Nm, the ratio should be I 8 and when the sulfur is present in amounts from 2 to 5 gm/Nm, the ratio should be I z 4.
  • a surface-active agent preferably a fatty amine having the formula CH -(CI-I,),,-CI-I -NH, or the hydrochloride thereof, wherein n is an integer from 6 to 20 such as stearyl amine, is added thereto in order to reduce the interfacial tension between the natural gas and the mineral oil fraction in amounts ranging from about to 2,000, preferably 300 to 1,000 parts per million.
  • the sulfur physically dissolved therein as a result of the transfer is removed by desulfurization using a liquid-liquid extraction with a l-l0 percent, preferably 25 percent aqueous, alkali-hydrogen sulfide solution such as a solution of NI LHS and/or NaI-IS.
  • surface-active media such as an ionic and/or a nonionic hydroxyalkylate, for example, from a glycol and an alkylene oxide or sulfo acids from esters of oxygenic and nitrogenous organic base molecules in amounts from approximately l002,000, preferably SOD-1,200, ppm are added to the alkalihydrogen sulfide solution.
  • the preferred surface-active medium is SeparoP', a product of BASF which is a polyethylenepropylene oxide having a molecular weight between 2,000 and 5,000.
  • the riser pipe 10 of a natural gas well delivering natural gas from gas reservoir 11 is connected, at the well bottom, with a second parallel or concentric line 12 for feeding mineral oil into an ascending stream of natural gas coming up from the well bottom under pressure.
  • Pipe 12 is provided with an injection flow regulator 13 through which the mineral oil coming down line 12 is introduced beneath packing 25 into the space 24 within which lines 10 and 12 both open. From space 24, the mineral oil trickles downward toward the opening of line 10 where it is entrained in the ascending stream of natural gas.
  • the natural gas mixed with mineral oil is led to high pressure separator 15 wherein the natural gas is separated from the mineral oil.
  • Natural gas, free of mineral oil and sulfur is removed via conduit 16 and the mineral oil containing sulfur is led via conduit 17 to closed tank 18 into which is fed via conduit 19, an aqueous solution of NaHS for aiding in the removal of the sulfur from the mineral oil by a liquid-liquid extraction.
  • the two phase mixture of mineral oil and aqueous NaHS solution is led via conduit 20 to separation tank 21 in which the two phases are separated by gravity.
  • the oil phase, free of sulfur is recycled, via conduit 22 to conduit 12 for reuse.
  • the aqueous phase is discarded via conduit 23.
  • FIG. 2 there is shown a second embodiment wherein the second line 12 is concentrically disposed with relation to riser pipe 10.
  • EXAMPLE 1 In a natural gas well delivering 10,000 Nm lhr and containing 6 percent of hydrogen sulfide and 1 gm/Nm of elemental sulfur dissolved in the gas, a mineral oil fraction of 12 cl viscosity at 20C. and a vapor pressure 2.4 X 10 mm Hg at 20C is measured in through an injection flow regulator 13 from a second line 12 in the well bottom.
  • the bottom hole temperature which amounted to 125C. establishes a temperature of about 80C. for the mineral oil fraction after the inflow at the well bottom.
  • the amount of the mineral oil fraction added comes to 800 l/hr and said fraction contains an initial 0.45 percent by weight of sulfur.
  • a fatty amine like stearyl amine in an amount of 1,000 ppm was added to the mineral oil fraction before introducing same into the flow of natural gas.
  • the mixture of mineral oil fraction and natural gas is separated by means of a high-pressure separator 15.
  • the natural gas issues from the separator practically free of elemental sulfur and mineral oil and after drying, the natural gas is taken for further processing or for use.
  • the mineral oil fraction is then flashed to atmospheric pressure and delivered to a closed tank 18.
  • This mineral oil fraction contains 1.90 percent sulfur by weight, which is removed from the mineral oil fraction by a liquid-liquid extraction with a NaHS solution down to a residual content of 0.5 percent by weight of organi cally combined sulfur.
  • the nature of the organically combined sulfur in the mineral oil fractions differs and depends on the source and manner of processing of the crude oil.
  • the NaHS solution is produced for example by introducing sour gas into a NaOl-l solution.
  • an aqueous sodium hydrogen sulfide solution of 2.5% NaHS is used, to which a nonionic hydroxyalkylate prepared from glycol and an alkylene oxide is added in proportions of 1,000 ppm as a surface-active agent for speeding and more perfect transfer of the elemental sulfur from the mineral oil phase to the aqueous phase.
  • the two liquid phases of mineral oil fraction and NaHS solution in which the surface-active agent is dissolved are mixed homogeneously together by pumping with a centrifugal pump to effect a quicker and more perfect transfer of the sulfur from the mineral oil fraction to the aqueous phase.
  • the mixture is conveyed to another tank 21, in which separation of the two phases is automatically and perfectly completed by gravity separation. After about 3 hours, the oil is free of the sulfur and water and is recycled again into circulation.
  • EXAMPLE 2 In a natural gas well delivering 15,000 Nm lhr of natural gas at a hydraulic pressure of 325 atmospheres and containing 1.65 gni/Nm of elemental sulfur in addition to 7.5 percent of H 8 dissolved in the gas, 1,500 liters of spindle oil are injected in order to dissolve the sulfur. After separation of gas and oil at the wellhead by means of a separator, the oil contains 16.5 gm/l of dissolved sulfur. To free the oil of the sulfur and to enable it to be again usable for recycling 3 m of oil are scrubbed with m of a 2.5 percent aqueous NaHS solution and thus freed of sulfur.
  • a process as claimed in claim 1 which further comprises desulfurizing the mineral oil or liquid hydrocarbon by a liquid-liquid extraction with a l to percent aqueous alkali-hydrogen sulfide solution in the presence of l002,000 ppm of a surface active agent for accelerating the transfer of the sulfur from the mineral oil or liquid-hydrocarbon to the aqueous phase and recycling the desulfurized mineral oil or liquid hydrocarbon.
  • alkali hydrogen sulfide is NH H'S and/or NaHS and the surface active agent is an ionic or nonionic hydroXylakylate based on a glycol and an alkyleneoxide or a sulfo acid from an ester of an oxygenic and nitrogenous organic base molecule.
  • a process as claimed in claim 7 which further comprises desulfurizing the mineral oil or liquid hydrocarbon by a liquid-liquid extraction with a l to 10 percent aqueous alkali-hydrogen sulfide solution in the presence of loo-2,000 ppm of a surface active agent for accelerating the transition of the sulfur from the mineral oil or liquid hydrocarbon to the aqueous phase and recycling the desulfurized mineral oil or liquid hydrocarbon.
  • alkali hydrogen sulfide is NHJ-IS and/or NaHS and the surface active agent is an ionic or nonionic hydroxyalkylate based on a glycol and an alkyleneoxide or a sulfo acid from an ester of an oxygenic and nitrogenous organic base molecule.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Mining & Mineral Resources (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Analytical Chemistry (AREA)
  • Environmental & Geological Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Fluid Mechanics (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Water Supply & Treatment (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Treating Waste Gases (AREA)
  • Industrial Gases (AREA)
US00092633A 1969-11-28 1970-11-25 Process for optimum absorption of elemental sulfur from natural gas by the use of mineral oil and similar liquid hydrocarbons Expired - Lifetime US3748827A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE1959827A DE1959827C3 (de) 1969-11-28 1969-11-28 Verfahren zur Absorption von elementarem Schwefel aus Erdgas durch Anwendung von Mineralöl und ähnlichen flüssigen Kohlenwasserstoffen

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US3748827A true US3748827A (en) 1973-07-31

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US (1) US3748827A (fr)
JP (1) JPS501121B1 (fr)
CA (1) CA922898A (fr)
DE (1) DE1959827C3 (fr)
FR (1) FR2068988A5 (fr)
GB (1) GB1336315A (fr)
NL (1) NL7005452A (fr)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3862335A (en) * 1972-04-10 1975-01-21 Inst Francais Du Petrole Process for producing sulfur from a gas containing hydrogen sulfide and sulfur dioxide
US3915674A (en) * 1973-12-26 1975-10-28 Northern Natural Gas Co Removal of sulfur from polyether solvents
US3920421A (en) * 1974-01-15 1975-11-18 Chemsoil Corp Removal of oxides of nitrogen from gas streams which also contain sulfur dioxide
US5242672A (en) * 1986-06-25 1993-09-07 Elf Atochem North America, Inc. Process for removing sulfur from organic polysulfides
US6017383A (en) * 1997-08-26 2000-01-25 Ohio University Contaminant removal in a translating slug flow
US7550033B2 (en) * 2002-01-21 2009-06-23 Conocophillips Company Process for removing sulfides
US20130263736A1 (en) * 2011-01-21 2013-10-10 International Business Machines Corporation Silicone-based chemical filter and silicone-based chemical bath for removing sulfur contaminants
US8900491B2 (en) 2011-05-06 2014-12-02 International Business Machines Corporation Flame retardant filler
US9186641B2 (en) 2011-08-05 2015-11-17 International Business Machines Corporation Microcapsules adapted to rupture in a magnetic field to enable easy removal of one substrate from another for enhanced reworkability
US9307692B2 (en) 2011-10-28 2016-04-12 International Business Machines Corporation Microcapsules adapted to rupture in a magnetic field
US9716055B2 (en) 2012-06-13 2017-07-25 International Business Machines Corporation Thermal interface material (TIM) with thermally conductive integrated release layer

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5463165A (en) * 1993-12-20 1995-10-31 Mobil Oil Corporation Scrubbing of oilfield waste gas in subterranean formations

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3097917A (en) * 1961-04-19 1963-07-16 Dev Ltd Method for high pressure selective absorption of gases
US3474028A (en) * 1967-07-10 1969-10-21 Wintershall Ag Process for the extraction of sulfur from a mineral oil-sulfur solution

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1173856B (de) * 1963-02-12 1964-07-16 Wintershall Ag Verfahren zur Vermeidung von Schwefel-abscheidungen aus Erdgas in Steigrohren von Gasbohrungen
DE1270512B (de) * 1963-09-27 1968-06-20 Wintershall Ag Verfahren zur Vermeidung von Schwefelabscheidungen aus Erdgas in Steigrohren von Gasbohrungen
US3531160A (en) * 1968-09-18 1970-09-29 Phillips Petroleum Co Production of sour gas-sulfur wells employing a sulfur solvent

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3097917A (en) * 1961-04-19 1963-07-16 Dev Ltd Method for high pressure selective absorption of gases
US3474028A (en) * 1967-07-10 1969-10-21 Wintershall Ag Process for the extraction of sulfur from a mineral oil-sulfur solution

Cited By (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3862335A (en) * 1972-04-10 1975-01-21 Inst Francais Du Petrole Process for producing sulfur from a gas containing hydrogen sulfide and sulfur dioxide
US3915674A (en) * 1973-12-26 1975-10-28 Northern Natural Gas Co Removal of sulfur from polyether solvents
US3920421A (en) * 1974-01-15 1975-11-18 Chemsoil Corp Removal of oxides of nitrogen from gas streams which also contain sulfur dioxide
US5242672A (en) * 1986-06-25 1993-09-07 Elf Atochem North America, Inc. Process for removing sulfur from organic polysulfides
US6017383A (en) * 1997-08-26 2000-01-25 Ohio University Contaminant removal in a translating slug flow
US7550033B2 (en) * 2002-01-21 2009-06-23 Conocophillips Company Process for removing sulfides
US9283514B2 (en) 2011-01-21 2016-03-15 International Business Machines Corporation Silicone-based chemical filter and silicone-based chemical bath for removing sulfur contaminants
US20130263736A1 (en) * 2011-01-21 2013-10-10 International Business Machines Corporation Silicone-based chemical filter and silicone-based chemical bath for removing sulfur contaminants
US9005338B2 (en) * 2011-01-21 2015-04-14 International Business Machines Corporation Silicone-based chemical filter and silicone-based chemical bath for removing sulfur contaminants
US9333454B2 (en) 2011-01-21 2016-05-10 International Business Machines Corporation Silicone-based chemical filter and silicone-based chemical bath for removing sulfur contaminants
US10112155B2 (en) 2011-01-21 2018-10-30 International Business Machines Corporation Removing sulfur contaminants from a fluid using a silicone-based chemical filter
US10124302B2 (en) 2011-01-21 2018-11-13 International Business Machines Corporation Removing sulfur contaminants from water using a silicone-based chemical filter
US10053473B2 (en) 2011-05-06 2018-08-21 International Business Machines Corporation Flame retardant filler
US9303047B2 (en) 2011-05-06 2016-04-05 International Business Machines Corporation Flame retardant filler
US8900491B2 (en) 2011-05-06 2014-12-02 International Business Machines Corporation Flame retardant filler
US10059727B2 (en) 2011-05-06 2018-08-28 International Business Machines Corporation Flame retardant filler
US9908902B2 (en) 2011-05-06 2018-03-06 International Business Machines Corporation Flame retardant filler
US10040807B2 (en) 2011-05-06 2018-08-07 International Business Machines Corporation Flame retardant filler
US9186641B2 (en) 2011-08-05 2015-11-17 International Business Machines Corporation Microcapsules adapted to rupture in a magnetic field to enable easy removal of one substrate from another for enhanced reworkability
US9434133B2 (en) 2011-08-05 2016-09-06 International Business Machines Corporation Microcapsules adapted to rupture in a magnetic field to enable easy removal of one substrate from another for enhanced reworkability
US9694337B2 (en) 2011-08-05 2017-07-04 International Business Machines Corporation Microcapsules adapted to rupture in a magnetic field to enable easy removal of one substrate from another for enhanced reworkability
US9307692B2 (en) 2011-10-28 2016-04-12 International Business Machines Corporation Microcapsules adapted to rupture in a magnetic field
US9313946B2 (en) 2011-10-28 2016-04-19 International Business Machines Corporation Microcapsules adapted to rupture in a magnetic field
US9307693B2 (en) 2011-10-28 2016-04-12 International Business Machines Corporation Microcapsules adapted to rupture in a magnetic field
US9716055B2 (en) 2012-06-13 2017-07-25 International Business Machines Corporation Thermal interface material (TIM) with thermally conductive integrated release layer
US11621210B2 (en) 2012-06-13 2023-04-04 International Business Machines Corporation Thermal interface material (TIM) with thermally conductive integrated release layer

Also Published As

Publication number Publication date
DE1959827B2 (de) 1973-03-29
DE1959827C3 (de) 1982-02-25
NL7005452A (fr) 1971-06-02
FR2068988A5 (fr) 1971-09-03
DE1959827A1 (de) 1971-06-09
CA922898A (en) 1973-03-20
JPS501121B1 (fr) 1975-01-16
GB1336315A (en) 1973-11-07
SU379073A3 (fr) 1973-04-18

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