WO2012170034A1 - Systems and methods for removing elemental sulfur from a hydrocarbon fluid - Google Patents
Systems and methods for removing elemental sulfur from a hydrocarbon fluid Download PDFInfo
- Publication number
- WO2012170034A1 WO2012170034A1 PCT/US2011/040046 US2011040046W WO2012170034A1 WO 2012170034 A1 WO2012170034 A1 WO 2012170034A1 US 2011040046 W US2011040046 W US 2011040046W WO 2012170034 A1 WO2012170034 A1 WO 2012170034A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- adsorbent
- hydrocarbon fluid
- elemental sulfur
- hydrocarbon
- group
- Prior art date
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
- B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
- B01D53/06—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with moving adsorbents, e.g. rotating beds
-
- 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
- C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
-
- 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
- C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
- C10G25/003—Specific sorbent material, not covered by C10G25/02 or C10G25/03
-
- 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
- C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
- C10G25/02—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents with ion-exchange material
- C10G25/03—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents with ion-exchange material with crystalline alumino-silicates, e.g. molecular sieves
- C10G25/05—Removal of non-hydrocarbon compounds, e.g. sulfur compounds
-
- 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
- C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
- C10G25/06—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents with moving sorbents or sorbents dispersed in the oil
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
- C10G25/12—Recovery of used adsorbent
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
- C10G29/20—Organic compounds not containing metal atoms
-
- 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
- C10G75/00—Inhibiting corrosion or fouling in apparatus for treatment or conversion of hydrocarbon oils, in general
- C10G75/02—Inhibiting corrosion or fouling in apparatus for treatment or conversion of hydrocarbon oils, in general by addition of corrosion inhibitors
-
- 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
- C10K1/002—Removal of contaminants
- C10K1/003—Removal of contaminants of acid contaminants, e.g. acid gas removal
- C10K1/004—Sulfur containing contaminants, e.g. hydrogen sulfide
-
- 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
- C10K1/32—Purifying combustible gases containing carbon monoxide with selectively adsorptive solids, e.g. active carbon
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/10—Working-up natural gas or synthetic natural gas
- C10L3/101—Removal of contaminants
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/10—Working-up natural gas or synthetic natural gas
- C10L3/101—Removal of contaminants
- C10L3/102—Removal of contaminants of acid contaminants
- C10L3/103—Sulfur containing contaminants
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/10—Working-up natural gas or synthetic natural gas
- C10L3/101—Removal of contaminants
- C10L3/102—Removal of contaminants of acid contaminants
- C10L3/104—Carbon dioxide
-
- 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
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
- C10L2290/54—Specific separation steps for separating fractions, components or impurities during preparation or upgrading of a fuel
- C10L2290/542—Adsorption of impurities during preparation or upgrading of a fuel
Definitions
- the present invention generally relates to systems and methods for removing elemental sulfur from a hydrocarbon fluid. More particularly, the present invention relates to removing elemental sulfur from a hydrocarbon fluid using an adsorbent.
- sokbiSity of elemental sulfur in natural gas is depe.nile.ut on «ia «y factors including the hydrocarbon, -fluid coinposiiion, pressure and temperature of the fluid hi the formation, at pressure reduction and cooling systems in the production piping.
- the solubility of elemental sulfur is strongly dependent on die concentration of other sulfur species such as H 2 S, and the amount of liquid hydrocarbon associated with gas production. Additionally, solubility may be affected by the volume and salinity of any water produced and the concentration of carbon dioxide in the gas. Solubility of the sulfur may he reduced with reductions in pressure and temperature of the natural gas during movement from the formation into the production, transportation and processing equipment. Air contamination and Interaction of sulfide species with oxidized forms of iron may be associated with production of elemental sulfur and thereafter precipitation.
- Solvents used in these operations may be physical solvents (e.g. hydrocarbons or hydrocarbon mixtures, eofcer gas oil, kerosene/diesel, mineral oil and aromatic solvents such as benzene and toluene) or chemical solvents (e.g. amine based chemicals including aqueous ethyhmine and alky! amines m aromatic solvents, and disulfide based solvents (e.g. dimethyl disulfide)).
- physical solvents e.g. hydrocarbons or hydrocarbon mixtures, eofcer gas oil, kerosene/diesel, mineral oil and aromatic solvents such as benzene and toluene
- chemical solvents e.g. amine based chemicals including aqueous ethyhmine and alky! amines m aromatic solvents, and disulfide based solvents (e.g. dimethyl disulfide)
- the method of application and the amount of solvent are specifically designed or selected for each system.
- the application of these solvents is not without challenges.
- the solvents are produced with the gas to the gas plant.
- the specific gravity of the solvent loaded with elemental sulfur can be equal to or higher than the specific gravity of the water produced, resulting in separation and handling problems at the gas plant.
- Some of the solvents can also cause operational problems with the downstream processes.
- not adding enough solvent can result in the downstream precipitation of elemental sulfur as the production cools
- Each of the solvents has specific handling challenges.
- the disulfide based solvents have a noxious odor and are very difficult to handle.
- Coker gas oil has a bad odor and other solvents are linked to environmental, health and/or safety issues.
- the application of solvents is typically once through. This can result in a large expense associated with sulfur oiaoagemenf.
- the hydrogen sulfide product stream that was produced (manufactured) is cleaner after the sulfur and i hS, is removed.
- the filter media described in the '056 patent therefore, does not remove sulfur from naturally occurring or processed hydrocarbon fits ids but is removing it .from a manufactured hydrogen sulfide product stream.
- the present invention overcomes one or more of the prior art disadvantages by providing systems and methods for removing elemental sulfur from hydrocarbon tldds using an adsorbers!
- the present invention includes a system for removing elemental sulfur from a hydrocarbon fluid, apprising: i) a vessel lor Che hydrocarbon fluid; and it) an adsorbent for removing the elemental sulfur from the hydrocarbon IMd, the adsorbent selected from the group consisting of alumina, activated alumina, activated carbon, gamma-activated alumina and molecular sieves.
- the present invention includes a method for removing elemental sulfur from a hydrocarbon fluid, comprising: i) treating the hydrocarbon fl uid with an adsorbent selected from the group consisting of alumina, activated alumina, activated carbon, gamma-activated alumina and. molecular sieves; and ii) removing a substantial portion of the elemental sulfur from the hydrocarbon fluid.
- the present invention includes a method lor removing elemental sulfur from a hydrocarbon fluid, comprising; i) treating the hydrocarbon fluid with an adsorbent; and ii) removing a substantial portion of the elemental sulfur from a portion of the hydrocarbon fluid excluding manufactured hydrogen sulfide, [0016]
- FIG * 1A illustrates one embodiment of a system for implementing the present invention.
- FIG. I B illustrates another embodiment of a system for implementing the present invention.
- FIG. 2 illustrates one embodiment of a system for regeneration of the adsorbent according to the present invention.
- the present invent son. provides systems sod methods to prevent or reduce elemental sulfur deposition in conduits and equipment used in the oil and gas production, transportation, separation, and refining operations while the hydrocarbon fluids are being transported or processed in those conduits and equipment. While the following description refers to the oil and gas industry, the systems and methods of the present invention are not limited thereto and may also be applied in. other industries to achieve similar results.
- Swlfirr species suitable for treatment according to the present invention include elemestal. sulfur, polymeric sulfur and xero-va!ent polymeric sulfur collectively referred to herein as elemental, sulfur.
- elemental sulfur-containing fluids means hydrocarbon fluids containing elemental sulfur, which can be entrained, dissolved, solubtlked, or dispersed in the fluid and are prone to precipitation or deposition onto the surfaces of the transportation or processing equipment.
- Representative hydrocarbon fluids tnay include raw natural gas, processed natural gas, coal seam gas, oil shale gas, tar sands gas, synthesis gas, crude oils, distillates, condensate, and the like.
- Natural gas means a normally gaseous mixture of hydrocarbons, at least at ambient surface conditions of temperature and pressure, containing principally methane hut also containing other light hydrocarbons such as ethane, ethylene, propane, butane or even higher molecular weight hydrocarbons.
- the natural gas can also contain varying amounts of carbon dioxide, as well as hydrogen sulfide, e&rbonyl sulfide, mereapians and elemental sulfur.
- the hydrocarbon fluids may include,, without limitation pipeline quality natural gas, natural gas from a wei!4iea4 and a hydrocarbon based refinery stream.
- the condiuts and equipment to be protected may include those used is natural gas transmission and distribution, or in natural gas processing, and those used in hydrocarbon production facilities.
- the adsorbent may also be used in combination with other treatments used in the production and / or transportation of hydrocarbon .fluids.
- the size of the purification equipment to be used may he empirically determined based upon the weight of expected or pro ven elemental sulfur content of the fluid. Equipment size can also be determined as a trade-off between capitol funds available, plot space available, pressure available, and desired time between adsorbent change-outs / regenerations.
- the adsorbent may suitably be formed into exirudates, pellets or other shapes to permit the passage of hydrocarbon fluids over (e,g. around and through) the adsorbent.
- the active component of the adsorbent may consist of high internal surface area materials such as, for example, alumina, activated alumina, activated carbon, gamma-activated alumina and moleeular sieves, which may be matrixed, bound and/or impregnated with inactive inorganic material such as clays, silica and/or other metal (or their oxides) such as, titanium, copper, cobalt, and molybdenum.
- the components of the adsorbent may be either naturally occurring or in the form of gelatinous precipitates or gels including mixtures of silica and metals (or their oxides.) It may be desirable to provide at least a part of the foregoing materials in colloidal form so as to facilitate extrusion of the adsorbent.
- the relative proportions of acti ve material and matrix vary widely, with the active material content ranging from about I up to 100 percent by weight
- the temperature and pressure conditions may vary.
- the elemental sulfur reco very process may be conducted at a pressure of between about. 5 atmospheres (atm) and 400 aim, or may be conducted in t3 ⁇ 4e narrower pressure range of between about 20 aim and 100 aim.
- the elemental sulfur recovery process may be conducted at a temperature of between, about -5° P.. and about 300° F, or may be conducted in the narrow temperature range of between about 15° F and about 100 s F .
- the system 100 includes an adsorbent 184 where the adsorbent 104 is selected from the aforementioned groups.
- the system 100 may include an inlet ft Iteration system 11.4 having a particulate filter 106, typically steed to 1.0 microns, and, optionally, a spare particulate filter 108 through which, the hydrocarbon fluid first passes via an inlet 110 before passing to a vessel 1 12 containing the adsorbent 104,
- the vessel 112 may be provided In any orientation, including as a horizontal vessel depleted in FIG, I A or as & vertically aligned vessel depicted in FIG. I B.
- the vessel 112 may be used in any orientation, depending on plot area, pressure drop available, the quantity of sulfur to be removed, and the desired frequency of adsorbent, change- out. Moreover, the adsorbent.
- the system UN may also include an outlet filtration system 116 having a particulate filter 118, typically sked to 10 microns, and, optionally, a spare particulate filter 120 before exiting via an outlet 122,
- adsorbent 104 may be fully or partially bypassed, if necessary, via a bypass 124.
- the adsorbent may be employed in combination with a corrosion inhibitor to further reduce the effect of sulfur deposition and the corrosion of the internal surfaces of a pipeline and equipment through which a sulfur-containing fluid is passing or being processed. Corrosion inhibitors which may be selected are well known in the an.
- Representative corrosion inhibitors include, hut are not limited to, imidazolines, quaternary ammonium compounds, phosphate esters, and the like, in addition, multiple adsorbent beds may be installed directly in series, in parallel, or throughout the system to opiimfee the removal of elemental sulfur, As illustrated in FIG. 2, the adsorbent 104 may be regenerated to near original quality thus, avoiding discarding of the adsorbent. Regeneration may include using pressure letdown and/or circulation with heating and cooling of the circulating gas stream.
- the circulating gas stream may be the hydrocarbon, fluid or may he an inert gas such as nitrogen or carbon dioxide, This may be accomplished by positioning the vessel 112 in a loop following a circulation blower 202 and a heater-cooler 284, after which the output ts vented to a flare via a valve 206 or recycled to the vessel 112, Alternatively, the blower 202 and heater-cooler 284 may not be present since simple pressure reduction may be adequate to regenerate the adsorbent to proper quality.
- a .method for removing elemental suiftu from, a hydrocarbon, fluid may include treating the hydrocarbon fluid with m adsorbent selected from the foregoing group and removing a substantia! portion of the elemental sulfur from the hydrocarbon fluid wherein the structure of the vessel used in conjunction with the method may be of the character and structure described above in reference to FIG I A and FIG IB.
- a method for removing elemental sulfur from a hydrocarbon fluid may include treating the hydrocarbon fluid with an adsorbent selected from the foresom3 ⁇ 4 3 ⁇ 4roup and removing a substantial nortion of the elemental sulfur from a portion of the hydrocarbon fluid excluding manufactured hydrogen sulfide.
- the treatment may include moving the hydrocarbon fluid over the adsorbent or moving the adsorbent in the hydrocarbon fluid.
- the sulfur adsorbs onto the surface of the adsorbent or into the internal pores and interna! surface area of the adsorbent.
- the adsorbent Once saturated with elemental sulfur, the adsorbent may be disposed of in. an acceptable manner or regenerated by i) pressure reduction; i.i) heat addition; and/or Hi) the use of a fluid swept through the adsorbent bed.
- the treatment may feather include treating the hydrocarbon fluid with a corrosion inhibitor, which may be selected from the group consisting of imidazolines, quaternary ammonium, compounds and phosphate esters.
- a natural gas stream can contain from less than 1 part per billion to over 100,000 parts per billion of soluble elemental sulfur depending on the pressure, temperature, and gas composition.
- the gas stream is at its elemental sulfur saturation pressure and associated temperature, as the pressure is reduced and/or the temperature is reduced the elemental sulfur can desublimaie and deposit is the conduits and equipment
- An example gas stream of natural gas at 70 aim and 7S°f could contain about 20 parts per billion of elemental sulfur. If the pressure is reduced through a throttling valve, then the gas will also get cooler. Cioing from about 70 aim and 7S°F to a pressure of about 60 aim, the gas will cool to about 67*F (depending upon the composition ⁇ and the elemental sulfur saturation level of the gas will be reduced to about 7 parts per billion, ' The resultant reduction of solubility will cause the elemental sulfur to desublimate and deposit elemental sulfur. With a gas flow rate of 100 million cubic feel: per day, this represents 39 lbs per year of elemental sulfur depositee in the conduits and equipment.
- the elemental sulfur in the gas stream should be reduced from about 20 parts per billion to about 2 [1/10 of 20] parts per billion or less.
- the gas pressure is reduced from 70 aim to 60 «tra, the elemental sulfur will not desublimate and deposit in the conduits and equipment, since the available solubility of die elemental sul fur (about 7 parts per billion) in the gas is much greater than the elemental sulfur left in the gas streams after the adsorbent (about 2 parts per billion or less).
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)
- Combustion & Propulsion (AREA)
- Analytical Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Separation Of Gases By Adsorption (AREA)
Abstract
Description
Claims
Priority Applications (12)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BR112013031425A BR112013031425B8 (en) | 2011-06-10 | 2011-06-10 | DEVICE AND METHOD TO REMOVE ELEMENTARY SULFUR FROM HYDROCARBONIC FLUIDS |
PCT/US2011/040046 WO2012170034A1 (en) | 2011-06-10 | 2011-06-10 | Systems and methods for removing elemental sulfur from a hydrocarbon fluid |
AU2011370639A AU2011370639B2 (en) | 2011-06-10 | 2011-06-10 | Systems and methods for removing elemental sulfur from a hydrocarbon fluid |
RU2013142359/04A RU2571413C2 (en) | 2011-06-10 | 2011-06-10 | Device and methods for elemental sulphur removal from carbon fluid |
MX2013010792A MX369913B (en) | 2011-06-10 | 2011-06-10 | Systems and methods for removing elemental sulfur from a hydrocarbon fluid. |
CA2829090A CA2829090C (en) | 2011-06-10 | 2011-06-10 | Systems and methods for removing elemental sulfur from a hydrocarbon fluid |
US14/113,868 US10286352B2 (en) | 2011-06-10 | 2011-06-10 | Systems and methods for removing elemental sulfur from a hydrocarbon fluid |
EP11867356.5A EP2673339A4 (en) | 2011-06-10 | 2011-06-10 | Systems and methods for removing elemental sulfur from a hydrocarbon fluid |
CN201180070659.9A CN104039931A (en) | 2011-06-10 | 2011-06-10 | Systems and methods for removing elemental sulfur from a hydrocarbon fluid |
CN201710547821.0A CN107446638A (en) | 2011-06-10 | 2011-06-10 | System and method for removing elementary sulfur from hydrocarbon fluid |
ARP120102083 AR089642A1 (en) | 2011-06-10 | 2012-06-12 | SYSTEM AND METHOD FOR ELIMINATION OF ELEMENTARY SULFUR FROM A HYDROCARBON FLUID |
US16/367,839 US11040303B2 (en) | 2011-06-10 | 2019-03-28 | Systems and methods for removing elemental sulfur from a hydrocarbon fluid |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/US2011/040046 WO2012170034A1 (en) | 2011-06-10 | 2011-06-10 | Systems and methods for removing elemental sulfur from a hydrocarbon fluid |
Related Child Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US14/113,868 A-371-Of-International US10286352B2 (en) | 2011-06-10 | 2011-06-10 | Systems and methods for removing elemental sulfur from a hydrocarbon fluid |
US16/367,839 Continuation US11040303B2 (en) | 2011-06-10 | 2019-03-28 | Systems and methods for removing elemental sulfur from a hydrocarbon fluid |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2012170034A1 true WO2012170034A1 (en) | 2012-12-13 |
Family
ID=47296340
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2011/040046 WO2012170034A1 (en) | 2011-06-10 | 2011-06-10 | Systems and methods for removing elemental sulfur from a hydrocarbon fluid |
Country Status (10)
Country | Link |
---|---|
US (2) | US10286352B2 (en) |
EP (1) | EP2673339A4 (en) |
CN (2) | CN104039931A (en) |
AR (1) | AR089642A1 (en) |
AU (1) | AU2011370639B2 (en) |
BR (1) | BR112013031425B8 (en) |
CA (1) | CA2829090C (en) |
MX (1) | MX369913B (en) |
RU (1) | RU2571413C2 (en) |
WO (1) | WO2012170034A1 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
RU2553994C1 (en) * | 2014-08-12 | 2015-06-20 | Общество с ограниченной ответственностью "Алтайский центр прикладной химии" | Method for removal of organic sulphur compounds from liquid hydrocarbon fuel |
RU2610525C1 (en) * | 2015-12-09 | 2017-02-13 | Федеральное государственное бюджетное учреждение науки Институт катализа им. Г.К. Борескова Сибирского отделения Российской академии наук | Method for deasphalting and demetallizing heavy oil stock |
GB2613166A (en) * | 2021-11-25 | 2023-05-31 | Plastic Energy Ltd | A method for the removal of impurities from a pyrolysis oil |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10183267B2 (en) * | 2014-10-23 | 2019-01-22 | Ashley Day | Gas-to-liquids conversion process using electron beam irradiation |
CN104891057B (en) * | 2015-06-08 | 2017-07-04 | 西安长庆科技工程有限责任公司 | A kind of methyl alcohol is received and storage skid-mounted unit |
US10746659B2 (en) * | 2017-07-21 | 2020-08-18 | Exxonmobil Research And Engineering Company | Determination of organic silicon in hydrocarbonaceous streams |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5730860A (en) * | 1995-08-14 | 1998-03-24 | The Pritchard Corporation | Process for desulfurizing gasoline and hydrocarbon feedstocks |
US20030226786A1 (en) * | 2002-06-05 | 2003-12-11 | Feimer Joseph L. | Process to remove sulfur contaminants from hydrocarbon streams |
US20080108518A1 (en) * | 2006-11-02 | 2008-05-08 | Clark J Caleb | Method of removing dispersed sulfur from sulfur-containing fluids |
Family Cites Families (22)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2765914A (en) | 1953-08-14 | 1956-10-09 | Exxon Research Engineering Co | Process for removing sulfur from a liquefiable hydrocarbon of less than six carbon atoms |
US4329160A (en) * | 1974-07-08 | 1982-05-11 | Union Carbide Corporation | Suppression of COS formation in molecular sieve purification of hydrocarbon gas streams |
SU857230A1 (en) * | 1979-12-19 | 1981-08-23 | Институт физико-органической химии АН Белорусской ССР | Method of desulfurizing light hydrocarbons |
US4522793A (en) * | 1983-06-28 | 1985-06-11 | Phillips Petroleum Company | Removing H2 S from natural gas using two-stage molecular sieves |
US4795545A (en) * | 1987-09-17 | 1989-01-03 | Uop Inc. | Process for pretreatment of light hydrocarbons to remove sulfur, water, and oxygen-containing compounds |
US5200062A (en) | 1991-06-17 | 1993-04-06 | Exxon Research And Engineering Company | Process for removing elemental sulfur from fluids |
US5686056A (en) | 1996-02-05 | 1997-11-11 | Bechtel Group, Inc. | Methods and apparatus for purifying hydrogen sulfide |
US6248230B1 (en) * | 1998-06-25 | 2001-06-19 | Sk Corporation | Method for manufacturing cleaner fuels |
US6482316B1 (en) * | 1999-06-11 | 2002-11-19 | Exxonmobil Research And Engineering Company | Adsorption process for producing ultra low hydrocarbon streams |
US6531052B1 (en) * | 2000-10-05 | 2003-03-11 | Alcoa Inc. | Regenerable adsorbent for removing sulfur species from hydrocarbon fluids |
US6579444B2 (en) * | 2000-12-28 | 2003-06-17 | Exxonmobil Research And Engineering Company | Removal of sulfur compounds from hydrocarbon feedstreams using cobalt containing adsorbents in the substantial absence of hydrogen |
DE10106616A1 (en) | 2001-02-13 | 2002-08-22 | Siemens Ag | Method for controlling the amplification of a high-frequency signal |
EP1590425A1 (en) * | 2002-10-29 | 2005-11-02 | Shell Internationale Researchmaatschappij B.V. | Removal of sulphur compounds from hydrocarbon streams using adsorbents and regeneration of the loaded adsorbents |
US7309379B2 (en) * | 2002-11-08 | 2007-12-18 | Tw Environmental, Inc. | Moving bed adsorber/desorber and low flow (high yield) desorber devices and their methods of use |
JP3962919B2 (en) * | 2002-11-12 | 2007-08-22 | 栗田工業株式会社 | Metal anticorrosive, metal anticorrosion method, hydrogen chloride generation inhibitor and method for preventing hydrogen chloride generation in crude oil atmospheric distillation equipment |
US7144499B2 (en) | 2003-11-26 | 2006-12-05 | Lyondell Chemical Technology, L.P. | Desulfurization process |
US7311891B2 (en) * | 2005-03-09 | 2007-12-25 | Basf Catalysts Llc | Process for the recovery of sulfur from Claus tail gas streams |
EP2167429A4 (en) * | 2007-06-14 | 2015-04-08 | Exxonmobil Upstream Res Co | Process for purification of hydrocarbons |
CN101481627B (en) | 2008-01-09 | 2012-11-14 | 中国石油化工股份有限公司 | Hydrocarbon oil desulphurization adsorbing agent and use method thereof |
US8524073B2 (en) | 2009-03-23 | 2013-09-03 | General Electric Company | Surface modified sorbent |
CN101955794B (en) * | 2009-07-16 | 2013-09-25 | 中国石油化工股份有限公司 | Desulphurization method |
US20110253595A1 (en) * | 2010-04-20 | 2011-10-20 | Esam Zaki Hamad | Combined solid adsorption-hydrotreating process for whole crude oil desulfurization |
-
2011
- 2011-06-10 US US14/113,868 patent/US10286352B2/en active Active
- 2011-06-10 RU RU2013142359/04A patent/RU2571413C2/en active
- 2011-06-10 MX MX2013010792A patent/MX369913B/en active IP Right Grant
- 2011-06-10 BR BR112013031425A patent/BR112013031425B8/en active IP Right Grant
- 2011-06-10 CA CA2829090A patent/CA2829090C/en active Active
- 2011-06-10 EP EP11867356.5A patent/EP2673339A4/en active Pending
- 2011-06-10 WO PCT/US2011/040046 patent/WO2012170034A1/en active Application Filing
- 2011-06-10 CN CN201180070659.9A patent/CN104039931A/en active Pending
- 2011-06-10 CN CN201710547821.0A patent/CN107446638A/en active Pending
- 2011-06-10 AU AU2011370639A patent/AU2011370639B2/en active Active
-
2012
- 2012-06-12 AR ARP120102083 patent/AR089642A1/en active IP Right Grant
-
2019
- 2019-03-28 US US16/367,839 patent/US11040303B2/en active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5730860A (en) * | 1995-08-14 | 1998-03-24 | The Pritchard Corporation | Process for desulfurizing gasoline and hydrocarbon feedstocks |
US20030226786A1 (en) * | 2002-06-05 | 2003-12-11 | Feimer Joseph L. | Process to remove sulfur contaminants from hydrocarbon streams |
US20080108518A1 (en) * | 2006-11-02 | 2008-05-08 | Clark J Caleb | Method of removing dispersed sulfur from sulfur-containing fluids |
Non-Patent Citations (1)
Title |
---|
See also references of EP2673339A4 * |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
RU2553994C1 (en) * | 2014-08-12 | 2015-06-20 | Общество с ограниченной ответственностью "Алтайский центр прикладной химии" | Method for removal of organic sulphur compounds from liquid hydrocarbon fuel |
RU2610525C1 (en) * | 2015-12-09 | 2017-02-13 | Федеральное государственное бюджетное учреждение науки Институт катализа им. Г.К. Борескова Сибирского отделения Российской академии наук | Method for deasphalting and demetallizing heavy oil stock |
GB2613166A (en) * | 2021-11-25 | 2023-05-31 | Plastic Energy Ltd | A method for the removal of impurities from a pyrolysis oil |
WO2023094629A1 (en) | 2021-11-25 | 2023-06-01 | Plastic Energy Limited | A method for the removal of impurities from a pyrolysis oil |
Also Published As
Publication number | Publication date |
---|---|
CA2829090A1 (en) | 2012-12-13 |
RU2571413C2 (en) | 2015-12-20 |
BR112013031425B1 (en) | 2020-01-21 |
AU2011370639A1 (en) | 2013-09-19 |
AU2011370639B2 (en) | 2015-06-11 |
EP2673339A4 (en) | 2014-10-22 |
EP2673339A1 (en) | 2013-12-18 |
US20190217243A1 (en) | 2019-07-18 |
RU2013142359A (en) | 2015-03-27 |
CA2829090C (en) | 2016-06-07 |
US10286352B2 (en) | 2019-05-14 |
US11040303B2 (en) | 2021-06-22 |
AR089642A1 (en) | 2014-09-10 |
MX369913B (en) | 2019-11-26 |
MX2013010792A (en) | 2014-04-30 |
CN104039931A (en) | 2014-09-10 |
US20140165831A1 (en) | 2014-06-19 |
BR112013031425B8 (en) | 2022-08-02 |
CN107446638A (en) | 2017-12-08 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US11040303B2 (en) | Systems and methods for removing elemental sulfur from a hydrocarbon fluid | |
US5106507A (en) | Method for recovering hydrocarbon contaminants from wastewater | |
US4370236A (en) | Purification of hydrocarbon streams | |
AU2009211454B2 (en) | A process for regeneration of adsorbent beds | |
US8852427B2 (en) | Method and systems to remove polar molecules from refinery streams | |
EP2167429A1 (en) | Process for purification of hydrocarbons | |
Stewart et al. | Gas dehydration field manual | |
Saji | Research advancements in sulfide scavengers for oil and gas sectors | |
Hajilary et al. | Amine gas sweetening system problems arising from amine replacement and solutions to improve system performance | |
Mansoori et al. | HSS anions reduction combined with the analytical test of aqueous MDEA in South Pars gas complex | |
Manteghian et al. | Reduction of chloride in amine from gas sweetening unit using a continuous virtual countercurrent ion exchange setup | |
KR101613903B1 (en) | Removing unstable sulfur compounds from crude oil | |
RU2669360C2 (en) | Devices and methods for removing elementary sulfur from hydrocarbon fluid media | |
US20240109010A1 (en) | Pre-loading of filter media with contaminants for improved capture in process vessels | |
EP0871532B1 (en) | Process for removing heavier aromatic compounds from a light hydrocarbon gas stream | |
O’Brien et al. | Adjusting gas treatment strategies to resolve methanol issues | |
Waite et al. | Improve Amine Unit Reliability and Optimize Treating | |
Bright et al. | Gas Treaters need clean amines | |
US9670422B2 (en) | Process for the removal of mercury from hydrocarbon streams containing oxygen | |
Engel | Filtration and Separation In Solfur Recovery. | |
Syamsul et al. | Operating Experience to Extend Lifetime of Molecular Sieves at the Belanak Floating Production Storage Offloading (FPSO) Vessel, South Natuna Sea, Indonesia | |
le Grange et al. | HOW TO LIMIT AMINE SYSTEM FAILURES: A review of incident trends reveals ways to reduce risks to production. | |
Alexander | An Offshore Dehydration System For The Production Of The Norphlet Sour Gas In Mobile Bay | |
Ali | Oxidative Removal Of Hydrogen Sulfide From Kurdistan Region-Iraq Crude Oil | |
de Villiers et al. | DEA Treater Revamp Targets Foaming |
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: 11867356 Country of ref document: EP Kind code of ref document: A1 |
|
DPE2 | Request for preliminary examination filed before expiration of 19th month from priority date (pct application filed from 20040101) | ||
ENP | Entry into the national phase |
Ref document number: 2829090 Country of ref document: CA |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2011867356 Country of ref document: EP |
|
ENP | Entry into the national phase |
Ref document number: 2013142359 Country of ref document: RU Kind code of ref document: A |
|
ENP | Entry into the national phase |
Ref document number: 2011370639 Country of ref document: AU Date of ref document: 20110610 Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: MX/A/2013/010792 Country of ref document: MX |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 14113868 Country of ref document: US |
|
REG | Reference to national code |
Ref country code: BR Ref legal event code: B01A Ref document number: 112013031425 Country of ref document: BR |
|
REG | Reference to national code |
Ref country code: BR Ref legal event code: B01E Ref document number: 112013031425 Country of ref document: BR |
|
ENP | Entry into the national phase |
Ref document number: 112013031425 Country of ref document: BR Kind code of ref document: A2 Effective date: 20131206 |