WO2013173087A1 - Utilisation de tampons acides à titre d'auxiliaires pour éliminer les métaux et les amines - Google Patents

Utilisation de tampons acides à titre d'auxiliaires pour éliminer les métaux et les amines Download PDF

Info

Publication number
WO2013173087A1
WO2013173087A1 PCT/US2013/039420 US2013039420W WO2013173087A1 WO 2013173087 A1 WO2013173087 A1 WO 2013173087A1 US 2013039420 W US2013039420 W US 2013039420W WO 2013173087 A1 WO2013173087 A1 WO 2013173087A1
Authority
WO
WIPO (PCT)
Prior art keywords
acid
buffer solution
acid buffer
contaminated stream
ppm
Prior art date
Application number
PCT/US2013/039420
Other languages
English (en)
Inventor
Cato Russell Mcdaniel
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
Publication of WO2013173087A1 publication Critical patent/WO2013173087A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G17/00—Refining of hydrocarbon oils in the absence of hydrogen, with acids, acid-forming compounds or acid-containing liquids, e.g. acid sludge
    • C10G17/02—Refining of hydrocarbon oils in the absence of hydrogen, with acids, acid-forming compounds or acid-containing liquids, e.g. acid sludge with acids or acid-containing liquids, e.g. acid sludge
    • 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
    • C10G31/00—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for
    • C10G31/08—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for by treating with water

Definitions

  • the present invention relates to the use of acid buffers to reduce contaminants in crude oil. More specifically, the acid buffers are used to reduce metals and amines from crude oil in a refinery desalting process.
  • Liquid hydrocarbon mediums such as crude oils and crude fractions, including naphtha, gasoline, kerosene, jet fuel, fuel oil, gas oil and vacuum residuals, often contain contaminants that can be deleterious to either refinery processing or product quality.
  • the contaminants can contribute to corrosion, heat exchanger fouling, furnace coking, catalyst deactivation and product degradation in refinery and other processes.
  • the contaminants are broadly classified as salts, bottom sediment and water, solids and metals. The amounts of these impurities vary depending upon the particular crude and its processing.
  • Desalting is a process that is used to remove contaminants, primarily inorganic salts, from crude oils prior to refining.
  • the desalting step is provided by adding and mixing with the crude a few volume percentages of fresh water to contact brine and salt.
  • Desalting provides benefits to the processing or refining of crude oils, including, reducing crude unit corrosion; reducing crude preheat system fouling; reducing the potential for distillation column damage; reducing energy costs; and reducing downstream process and product contamination.
  • metals include, but are not limited to, are those of Groups IA, IIA, VB, VIII, IIB, and IVA of the Periodic Table (CAS version).
  • Exemplary metals include, but are not limited to, calcium, iron, zinc, silicon, nickel, sodium, potassium, vanadium and combinations thereof.
  • In crude oil desalting, an emulsion of water in oil is intentionally formed with the water admitted being on the order of about four (4) to about ten (10) percent by volume based on the crude oil. Water is added to the crude and mixed intimately to transfer the impurities in the crude to the water phase. Separation of the phases occurs due to coalescence of the small water droplets into progressively larger droplets and eventual gravitational separation of the oil and underlying water phase.
  • Acids including citric acid, are frequently added to the wash water as a metals sequestering agent.
  • the wash water containing the metals is then separated in the desalter.
  • Citric acid forms a citrate salt with the calcium present in the caide oil.
  • Calcium citrate has limited solubility in water; therefore at concentrations above around 200 ppm as calcium, a dispersant is required.
  • the crude After leaving the desalter, the crude enters a distillation tower and subsequently, enters the condensers.
  • Water may be entrained in the hydrocarbons being processed and /or water added to the process for such purposes as steam stripping.
  • the acidity of the condensed water may be very high, leading to corrosion.
  • the high acidity is due to dissolved acids in the condensate, principally HCl, organic acids, H 2 S, and 3 ⁇ 4Ci3 ⁇ 4.
  • HCl the most troublesome corrosive material, is formed by hydrolysis of calcium and magnesium chlorides originally present in the brines.
  • Amines are frequently added at various points in hydrocarbon refining processes in an attempt to control the corrosiveness of condensed acidic materials.
  • Amines may be added in pure form or as an aqueous solution. Their high alkalinity serves to raise the pH of the initial condensate rendering it less corrosive. Optimally, the amines are added in amounts sufficient to raise the pH of the liquid at the point of initial condensation to above a pH of 6.0.
  • the process may comprise providing an acid buffer solution; providing a contaminated stream; and mixing the acid buffer solution with the contaminated stream.
  • the contaminated stream may be an aqueous or hydrocarbon stream, or a mixture thereof, in another embodiment, the desalter is in a crude oil refinery.
  • the acid buffer solution may further comprise at least one acid selected from the group consisting of citric acid, glycine, 2(N- mo ⁇ holi o)ethanesulfonic acid, methanesulfonic acid, acetic acid, formic acid, and phosphoric acid.
  • the acid buffer solution may comprise at least one counter-ion selected from the group consisting of lithium, sodium, potassium, rubidium, cesium, and ammonium.
  • the acid buffer solution may comprise citric acid and sodium citrate.
  • the acid buffer solution may have a pH ranging from about 3.0 to 7.4.
  • the pH may be about 6.5.
  • the acid buffer solution may be present in a range of from about 1 to about 6,000 ppm of the contaminated stream. In yet another embodiment, the acid buffer solution may be present in a range of from about 100 to about 4,000 ppm. Alternatively, the acid buffer solution may be present in a range of from about 500 to about 2,000 ppm. [0016] Another embodiment discloses a method wherein the contaminants reduced are metals and amines.
  • a process for reducing contaminants during a desalting process may comprise providing an acid buffer solution; providing a contaminated stream; and mixing the acid buffer solution with the contaminated stream.
  • This process is suitable for use in a variety of desalting applications, including, but not limited to, wastewater treatment and crude oil refining.
  • the contaminated stream may be an aqueous or hydrocarbon stream, or a mixture thereof.
  • the desalter is in a crude oil refinery.
  • the acid buffer solution may comprise at least one acid selected from the group consisting of citric acid, glycine, 2(N- morphol ino)ethanesul fon ic acid, methanesulfonic acid, acetic acid, formic acid, and phosphoric acid.
  • the acid buffer solution may comprise at least one ion to maintain electric neutrality; i.e., a counter-ion.
  • Suitable counter-ions include, but are not limited to, alkali metals or ammonium.
  • the acid buffer solution further comprises a counter-ion selected from the group consisting of lithium, sodium, potassium, rubidium, cesium, and ammonium.
  • the acid buffer solution may comprise citric acid and sodium citrate.
  • the acid buffer solution may have a pH ranging from about 3.0 to 7.4. Alternatively, the pH may be about 6.5. [ ⁇ 022] In another embodiment, the acid buffer solution may be present in a range of from about 1 to about 6,000 ppm of the contaminated stream. In yet another embodiment, the acid buffer solution may be present in a range of from about 100 to about 4,000 ppm. Alternatively, the acid buffer solution may be present in a range of from about 500 to about 2,000 ppm.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

Procédé permettant de réduire les contaminants lors d'un processus de dessalage, ledit procédé pouvant comprendre la préparation d'une solution de tampon acide ; l'utilisation d'un flux contaminé ; et le mélange de la solution de tampon acide avec le flux contaminé.
PCT/US2013/039420 2012-05-16 2013-05-03 Utilisation de tampons acides à titre d'auxiliaires pour éliminer les métaux et les amines WO2013173087A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US13/472,576 2012-05-16
US13/472,576 US20130306522A1 (en) 2012-05-16 2012-05-16 Use of acid buffers as metal and amine removal aids

Publications (1)

Publication Number Publication Date
WO2013173087A1 true WO2013173087A1 (fr) 2013-11-21

Family

ID=48428708

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2013/039420 WO2013173087A1 (fr) 2012-05-16 2013-05-03 Utilisation de tampons acides à titre d'auxiliaires pour éliminer les métaux et les amines

Country Status (2)

Country Link
US (1) US20130306522A1 (fr)
WO (1) WO2013173087A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20230081029A1 (en) * 2021-09-15 2023-03-16 Halliburton Energy Services, Inc. Organic Acid Surfactant Booster For Contaminant Removal

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5080779A (en) * 1990-08-01 1992-01-14 Betz Laboratories, Inc. Methods for removing iron from crude oil in a two-stage desalting system
WO2006053350A1 (fr) * 2004-11-10 2006-05-18 Sasol Technology (Pty) Ltd Traitement de courants d'hydrocarbures de masse molaire elevee
FR2937563A1 (fr) * 2008-10-23 2010-04-30 Ge Energy Products France Snc Procede de traitement d'une phase organique comprenant au moins un compose metallique
US20110100877A1 (en) * 2009-11-04 2011-05-05 Assateague Oil Ilc Method and device for automated control of enhanced metal and amine removal from crude oil
WO2012018976A2 (fr) * 2010-08-05 2012-02-09 Baker Hughes Incorporated Procédé permettant d'extraire des métaux multivalents d'une huile brute

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7497943B2 (en) * 2002-08-30 2009-03-03 Baker Hughes Incorporated Additives to enhance metal and amine removal in refinery desalting processes

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5080779A (en) * 1990-08-01 1992-01-14 Betz Laboratories, Inc. Methods for removing iron from crude oil in a two-stage desalting system
WO2006053350A1 (fr) * 2004-11-10 2006-05-18 Sasol Technology (Pty) Ltd Traitement de courants d'hydrocarbures de masse molaire elevee
FR2937563A1 (fr) * 2008-10-23 2010-04-30 Ge Energy Products France Snc Procede de traitement d'une phase organique comprenant au moins un compose metallique
US20110100877A1 (en) * 2009-11-04 2011-05-05 Assateague Oil Ilc Method and device for automated control of enhanced metal and amine removal from crude oil
WO2012018976A2 (fr) * 2010-08-05 2012-02-09 Baker Hughes Incorporated Procédé permettant d'extraire des métaux multivalents d'une huile brute

Also Published As

Publication number Publication date
US20130306522A1 (en) 2013-11-21

Similar Documents

Publication Publication Date Title
RU2552651C2 (ru) Усовершенствованный способ удаления металлов и аминов из сырой нефти
US4992210A (en) Crude oil desalting process
EP1530620B1 (fr) Additifs permettant d'accroitre l'elimination de metaux et amines dans des processus de raffinage-dessalement
US5114566A (en) Crude oil desalting process
CN1066208C (zh) 使用胺掺混物抑制湿烃冷凝系统中氯化物腐蚀的方法
CA2917168A1 (fr) Inhibiteurs de corrosion a base de disulfure organique
US8226819B2 (en) Synergistic acid blend extraction aid and method for its use
WO2013130123A1 (fr) Additifs pour générateur de vapeur destinés à minimiser l'encrassement et la corrosion dans des tours de brut
WO2013173087A1 (fr) Utilisation de tampons acides à titre d'auxiliaires pour éliminer les métaux et les amines
EP0600606B1 (fr) Neutralisation d'amines avec un potentiel bas de précipitation de sels
US20190119580A1 (en) Process for controlling corrosion in petroleum refining units
EP1285045B1 (fr) Neutralisation de phase vapeur dans un processus integre de desasphaltage par solvant et de gazeification
US10767116B2 (en) Method and composition for neutralizing acidic components in petroleum refining units
WO2015107539A2 (fr) Système et procédé de traitement de vapeurs partielles cédées à une colonne de distillation de pétrole brute
KR20030016264A (ko) 통합된 용매의 탈아스팔트 공정 및 기화 공정에서의증기상 중화 방법

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: 13722255

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 13722255

Country of ref document: EP

Kind code of ref document: A1