WO2011087540A2 - Emulsification of hydrocarbon gas oils to increase efficacy of water based hydrogen sulfide scavengers - Google Patents

Emulsification of hydrocarbon gas oils to increase efficacy of water based hydrogen sulfide scavengers Download PDF

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Publication number
WO2011087540A2
WO2011087540A2 PCT/US2010/053457 US2010053457W WO2011087540A2 WO 2011087540 A2 WO2011087540 A2 WO 2011087540A2 US 2010053457 W US2010053457 W US 2010053457W WO 2011087540 A2 WO2011087540 A2 WO 2011087540A2
Authority
WO
WIPO (PCT)
Prior art keywords
heavy oil
scavenger
aqueous
hydrogen sulfide
processing equipment
Prior art date
Application number
PCT/US2010/053457
Other languages
English (en)
French (fr)
Other versions
WO2011087540A3 (en
Inventor
Larry John Karas
Craig Anderson
Original Assignee
General Electric Company
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 General Electric Company filed Critical General Electric Company
Priority to AU2010341783A priority Critical patent/AU2010341783A1/en
Priority to EP10770692A priority patent/EP2516596A2/en
Priority to RU2012127278/04A priority patent/RU2012127278A/ru
Priority to KR1020127019030A priority patent/KR20120123348A/ko
Priority to CN2010800646589A priority patent/CN102762696A/zh
Priority to SG2012047007A priority patent/SG181925A1/en
Priority to MX2012007493A priority patent/MX2012007493A/es
Priority to CA2785532A priority patent/CA2785532A1/en
Priority to JP2012545940A priority patent/JP2013515818A/ja
Priority to BR112012015563A priority patent/BR112012015563A2/pt
Publication of WO2011087540A2 publication Critical patent/WO2011087540A2/en
Publication of WO2011087540A3 publication Critical patent/WO2011087540A3/en

Links

Classifications

    • 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
    • C10G29/00Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
    • C10G29/20Organic compounds not containing metal atoms
    • C10G29/22Organic compounds not containing metal atoms containing oxygen as the only hetero atom
    • C10G29/24Aldehydes or ketones
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01FMIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F23/00Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
    • B01F23/40Mixing liquids with liquids; Emulsifying
    • 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
    • C10G2300/00Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20Characteristics of the feedstock or the products
    • C10G2300/201Impurities
    • C10G2300/207Acid gases, e.g. H2S, COS, SO2, HCN
    • 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
    • C10G2300/00Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40Characteristics of the process deviating from typical ways of processing
    • C10G2300/4075Limiting deterioration of equipment

Definitions

  • This invention relates generally to processing heavy oil, and more particularly, to methods for removing hydrogen sulfide in heavy oil with an aqueous- based scavenger/oil emulsion.
  • H 2 S hydrogen sulphide
  • Hydrogen sulfide scavengers can be used to remove hydrogen sulfide from heavy oil. It is known to be possible to reduce the hydrogen sulphide content present in aqueous mediums by using aqueous solutions of aldehydes such as formaldehyde, glyoxal, and glutaraldehyde (see for example the U.S. Pat. Nos. 4,680, 127 and 5,284,635). However, simple addition of water-based hydrogen sulfide scavengers to heavy oil provides poor results.
  • aldehydes such as formaldehyde, glyoxal, and glutaraldehyde
  • water-based scavengers such as glyoxal will eventually settle out of the heavy oil into an acidic aqueous phase and settle to the bottom of processing equipment.
  • This aqueous phase may run along the bottom of the processing or refinery equipment as small tributaries in pipelines or stagnate at the bottom of holding tanks.
  • This acidic aqueous phase is highly corrosive and can cause troughing in the processing or refinery equipment.
  • the invention is directed to a method for reducing the amount of hydrogen sulfide present in heavy oil and reducing the amount of corrosion in processing equipment contacting the heavy oil.
  • the method includes the steps of adding an aqueous-based scavenger containing one or more aldehydes to the heavy oil using a static mixer injection system and creating an aqueous-based scavenger/heavy oil emulsion using a high shear/high velocity pump.
  • the method further includes diverting a portion of the heavy oil into a scavenger addition branch, adding the aqueous-based scavenger to the portion of the heavy oil and forming the emulsion in the addition branch, and adding the aqueous-based scavenger/oil emulsion to the heavy oi l in the processing equipment.
  • the aqueous-based scavenger is glyoxal.
  • FIG. 1 is a schematic diagram of an aqueous-based scavenger addition system for use with hydrocarbon media processing equipment.
  • a hydrogen sulfide scavenger addition system 10 is fluidically connected to processing equipment 12 for hydrocarbon media.
  • the scavenger system 10 reduces the amount of hydrogen sulfide present in the hydrocarbon media, such as heavy oils, by adding an aqueous-based scavenger in a manner so as to desirably avoid causing significant corrosion to processing equipment 1 2.
  • Aqueous- based scavengers are useful for the elimination of hydrogen sulphide present in various fluids and notably are particularly effective at eliminating the hydrogen sulphide present in heavy oi ls which can ex ist in the form of water in oi l or oil in water emulsions.
  • the processing equipment 12 in contact with the heavy oi l may be any type of equipment that can be used for processing the hydrocarbon media, such as pipelines and holding tanks. Processing equipment 1 2 subject to corrosion is general ly processing equipment made of carbon steel, but any type of processing equipment may be protected.
  • the heavy oi l may be any type of heavy oi l containing hydrogen sulfide.
  • the heavy oil includes, but is not limited to, gas oi l, naphtha, FCC slurry, diesel fuel, fuel oi l, jet fuel, gasoline, kerosene or vacuum residua.
  • the heavy oil may be at an elevated temperature to aid in transport in the processing equipment 1 2. For example, the heavy oil may be at a temperature of from about ambient to about 1 50 °C. Typically, the temperatures required to move the heavy oil in the processing equipment 12 is about 80 °C.
  • a portion of the heavy oil flowing through the processing equipment 12 is diverted from the processing equipment 12 into the scavenger addition system 10 via a scavenger addition branch 14.
  • a static mixer 1 6 is used to initially mix the scavenger with the portion of heavy oil flowing through the system 10.
  • the static mixer 16 comprises an injection quill dispersion system 18.
  • the scavenger is added to the diverted heavy oil flow in a continuous manner with the injection quill 1 8 located generally at the center of the addition branch 14 in the direction of the heavy oil flow.
  • the injection quill 18 desirably has an open-ended tube (not shown) cut at about a 45° angle with a slot.
  • the scavenger injection rate is controlled with an injection pump 20 or shut-off valve 22 in addition line 24.
  • a suitable injection quill 1 8 is available from Metal Samples Corrosion Monitoring Systems of Munford, AL.
  • the scavenger may be injected into the heavy oil by any conventional inline injection system and may be injected at any point in-line suitable to allow the scavenger to mix with the heavy oil.
  • an aqueous-based scavenger/oil micro-emulsion is formed using a high shear/high velocity mixer or pump 30.
  • a high shear/high velocity mixer or pump 30 such as one available from Silverson Machines, Inc. of East Longmeadow, MA.
  • the diverted portion of the heavy oil flow in the scavenger addition system 10, now containing the micro-emulsion, is then returned to the heavy oil flow in the processing equipment 12.
  • the scavenger may be added to the heavy oil flowing through the processing equipment without diverting a portion of the flow such that the entire heavy oil flow flows through the scavenger addition system 10.
  • the scavenger is a dispersed aqueous phase containing about 20 to 70% of one or more aldehydes chosen from the group constituted by formaldehyde, glyoxal, glutaraldehyde, glycolaldehyde or glyoxylic acid.
  • the water-based scavenger added to the heavy oil to reduce the hydrogen sulfide is Glyoxal.
  • Glyoxal is a water-soluble aldehyde and may include oligomers of glyoxal.
  • Glyoxal is commercially available as a 40 weight percent aqueous solution.
  • the scavenger may also contain an enhancing additive to catalyze the reaction of actives with the hydrogen sulfide.
  • the enhancing catalyst is a quaternary ammonium salt.
  • the quaternary ammonium salt desirably is added in an amount of about 2.5 wt %.
  • the glyoxal is added to the heavy oil in an amount sufficient to reduce the levels of hydrogen sulfide in the heavy oil.
  • glyoxal may be added in an amount of from about I ppm to about 2000 ppm, and desirably between about I ppm and about 500 ppm by volume, based on the velocity of the heavy oil through the processing equipment and the concentration of hydrogen sulfide.
  • glyoxal may be added in an amount of from about 10 ppm to about 200 ppm by volume. Any amount of hydrogen sulfide in the heavy oil may be reduced and the actual amount of residual hydrogen sulfide will vary depending on the starting amount.
  • the hydrogen sulfide levels are reduced to 1 50 ppm by volume or less, as measured in the vapor phase, based on the volume of the heavy oil. In another embodiment, the hydrogen sulfide levels are reduced to 100 ppm by volume or less, as measured in the vapor phase, based on the volume of the heavy oil. In another embodiment, the hydrogen sulfide levels are reduced to 50 ppm by volume or less, as measured in the vapor phase, based on the volume of the heavy oil. In another embodiment, the hydrogen sulfide levels are reduced to 20 ppm by volume or less, as measured in the vapor phase, based on the volume of the heavy oil.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
PCT/US2010/053457 2009-12-23 2010-10-21 Emulsification of hydrocarbon gas oils to increase efficacy of water based hydrogen sulfide scavengers WO2011087540A2 (en)

Priority Applications (10)

Application Number Priority Date Filing Date Title
AU2010341783A AU2010341783A1 (en) 2009-12-23 2010-10-21 Emulsification of hydrocarbon gas oils to increase efficacy of water based hydrogen sulfide scavengers
EP10770692A EP2516596A2 (en) 2009-12-23 2010-10-21 Emulsification of hydrocarbon gas oils to increase efficacy of water based hydrogen sulfide scavengers
RU2012127278/04A RU2012127278A (ru) 2009-12-23 2010-10-21 Эмульгирование углеводородных газойлей для повышения эффективности поглотителя сероводорода на водной основе
KR1020127019030A KR20120123348A (ko) 2009-12-23 2010-10-21 수성 황화수소 소거제의 효능을 증가시키기 위한 탄화수소 가스 오일의 유화
CN2010800646589A CN102762696A (zh) 2009-12-23 2010-10-21 用于增加水基硫化氢清除剂效率的烃气油的乳化
SG2012047007A SG181925A1 (en) 2009-12-23 2010-10-21 Emulsification of hydrocarbon gas oils to increase efficacy of water based hydrogen sulfide scavengers
MX2012007493A MX2012007493A (es) 2009-12-23 2010-10-21 Emulsificacion de gasoleos de hidrocarburo para aumentar la eficacia de depuradores de sulfuro de hidrogeno con base acuosa.
CA2785532A CA2785532A1 (en) 2009-12-23 2010-10-21 Emulsification of hydrocarbon gas oils to increase efficacy of water based hydrogen sulfide scavengers
JP2012545940A JP2013515818A (ja) 2009-12-23 2010-10-21 水性硫化水素スカベンジャーの効果を高めるための炭化水素ガスオイルの乳化
BR112012015563A BR112012015563A2 (pt) 2009-12-23 2010-10-21 "emulsificação de gasóleos de hidrocarboneto para aumentar a eficácia de sequestrantes de sulfeto de hidrogênio á base de água"

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US12/646,432 US20110147272A1 (en) 2009-12-23 2009-12-23 Emulsification of hydrocarbon gas oils to increase efficacy of water based hydrogen sulfide scavengers
US12/646,432 2009-12-23

Publications (2)

Publication Number Publication Date
WO2011087540A2 true WO2011087540A2 (en) 2011-07-21
WO2011087540A3 WO2011087540A3 (en) 2011-11-17

Family

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Family Applications (1)

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PCT/US2010/053457 WO2011087540A2 (en) 2009-12-23 2010-10-21 Emulsification of hydrocarbon gas oils to increase efficacy of water based hydrogen sulfide scavengers

Country Status (15)

Country Link
US (1) US20110147272A1 (zh)
EP (1) EP2516596A2 (zh)
JP (1) JP2013515818A (zh)
KR (1) KR20120123348A (zh)
CN (1) CN102762696A (zh)
AR (1) AR079659A1 (zh)
AU (1) AU2010341783A1 (zh)
BR (1) BR112012015563A2 (zh)
CA (1) CA2785532A1 (zh)
CL (1) CL2012001711A1 (zh)
MX (1) MX2012007493A (zh)
RU (1) RU2012127278A (zh)
SG (1) SG181925A1 (zh)
TW (1) TW201137108A (zh)
WO (1) WO2011087540A2 (zh)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018062254A1 (ja) 2016-09-27 2018-04-05 株式会社クラレ 金属腐食の抑制方法
WO2018097108A1 (ja) 2016-11-22 2018-05-31 株式会社クラレ 含硫黄化合物除去用の組成物
US10119079B2 (en) 2014-03-17 2018-11-06 Kuraray Co., Ltd. Composition for removal of sulfur-containing compounds
US10294428B2 (en) 2015-01-29 2019-05-21 Kuraray Co., Ltd. Composition for removing sulfur-containing compounds

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DK2758347T3 (en) 2011-09-23 2017-03-27 Lonza Ag PROCEDURE FOR REMOVING HYDROGEN SULFIDE FROM INDUSTRIAL PROCESS FLUIDS
WO2013049027A1 (en) * 2011-09-27 2013-04-04 General Electric Company Hydrogen sulfide scavenger compositions, methods for making and processes for removing hydrogen sulfide from liquid hydrocarbon media
CA2880283C (en) * 2012-08-21 2020-07-21 Lonza, Inc. Method of scavenging hydrogen sulfide and/or sulfhydryl compounds
EP3362535B1 (en) 2015-10-14 2020-05-06 Haldor Topsøe A/S A process for removing sulphur compounds from process streams
US10513662B2 (en) * 2017-02-02 2019-12-24 Baker Hughes, A Ge Company, Llc Functionalized aldehydes as H2S and mercaptan scavengers
CN108732940B (zh) * 2017-04-24 2021-05-07 西门子(中国)有限公司 优化汽油柴油切割过程的催化裂化分馏塔的顶循环油流量的方法和系统
US11926797B2 (en) 2019-07-17 2024-03-12 Bl Technologies, Inc. Method of removal and conversion of amines in a refinery desalter
CN112710812B (zh) * 2020-11-17 2023-02-24 中国石油天然气股份有限公司 检测与处理油田产出原油中有毒气体的一体化工艺
WO2024081958A2 (en) * 2022-10-14 2024-04-18 Solugen, Inc. Compositions to control level of undesirable materials

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US5284635A (en) 1989-09-05 1994-02-08 Societe Francaise Hoechst Process for the elimination of hydrogen sulfide by using water-in-oil emulsions

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US4680127A (en) 1985-12-13 1987-07-14 Betz Laboratories, Inc. Method of scavenging hydrogen sulfide
US5284635A (en) 1989-09-05 1994-02-08 Societe Francaise Hoechst Process for the elimination of hydrogen sulfide by using water-in-oil emulsions

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10119079B2 (en) 2014-03-17 2018-11-06 Kuraray Co., Ltd. Composition for removal of sulfur-containing compounds
US10294428B2 (en) 2015-01-29 2019-05-21 Kuraray Co., Ltd. Composition for removing sulfur-containing compounds
WO2018062254A1 (ja) 2016-09-27 2018-04-05 株式会社クラレ 金属腐食の抑制方法
WO2018097108A1 (ja) 2016-11-22 2018-05-31 株式会社クラレ 含硫黄化合物除去用の組成物
US11434433B2 (en) 2016-11-22 2022-09-06 Kuraray Co., Ltd. Composition for removal of sulfur-containing compound

Also Published As

Publication number Publication date
CN102762696A (zh) 2012-10-31
EP2516596A2 (en) 2012-10-31
RU2012127278A (ru) 2014-01-27
CL2012001711A1 (es) 2013-04-12
KR20120123348A (ko) 2012-11-08
AU2010341783A1 (en) 2012-07-19
SG181925A1 (en) 2012-07-30
US20110147272A1 (en) 2011-06-23
AR079659A1 (es) 2012-02-08
WO2011087540A3 (en) 2011-11-17
BR112012015563A2 (pt) 2017-09-05
JP2013515818A (ja) 2013-05-09
TW201137108A (en) 2011-11-01
MX2012007493A (es) 2012-08-03
CA2785532A1 (en) 2011-07-21

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