EP1575884A2 - Lit de sorption a composants multiples destine la desulfuration d'hydrocarbures - Google Patents

Lit de sorption a composants multiples destine la desulfuration d'hydrocarbures

Info

Publication number
EP1575884A2
EP1575884A2 EP03790238A EP03790238A EP1575884A2 EP 1575884 A2 EP1575884 A2 EP 1575884A2 EP 03790238 A EP03790238 A EP 03790238A EP 03790238 A EP03790238 A EP 03790238A EP 1575884 A2 EP1575884 A2 EP 1575884A2
Authority
EP
European Patent Office
Prior art keywords
catalyst
catalyst bed
nickel
copper
zinc
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP03790238A
Other languages
German (de)
English (en)
Inventor
Jon P. Wagner
Eric J. Weston
R. Steve Spivey
R. Scott Osborne
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sued Chemie Inc
Original Assignee
Sued Chemie Inc
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 Sued Chemie Inc filed Critical Sued Chemie Inc
Publication of EP1575884A2 publication Critical patent/EP1575884A2/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/12—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers
    • C07C7/13—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers by molecular-sieve technique
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/12—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers
    • 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

Definitions

  • the present invention relates to a catalyst bed for the desulfurization of a hydrocarbon feedstream.
  • the catalyst bed comprises at least two catalysts, each having an affinity for sulfur-containing compounds. When used in combination, the catalyst bed demonstrates significant reductions in the sulfur concentration in the feedstream.
  • a process for reducing the concentration of sulfur compounds in a hydrocarbon feedstream to a level of less than about 500 ppb is also disclosed.
  • Hydrocarbon feed streams such as natural gas (NG), liquified petroleum gas (LPG) and gasoline, are used as the starting materials for several chemical processes, many of which utilize catalysts in one or more reaction steps.
  • NG natural gas
  • LPG liquified petroleum gas
  • gasoline gasoline
  • Nickel catalysts, which are generally useful for in hydrogenation reactions, are especially sensitive to sulfur poisoning on their active surfaces.
  • precious metals which are used in a variety of catalysts, are sensitive to sulfur and can be easily poisoned by the presence of sulfur or sulfur- containing compounds.
  • activated carbon has a high capacity for ethyl mercaptans
  • manganese oxide is effective for dimethyl sulfoxide removal
  • zinc oxide can be used to remove hydrogen sulfide.
  • catalysts known to be effective in desulfurization processes include carbon, copper / zinc oxides, nickel-based sorbents, nickel oxides, zeolites, molecular sieves and faujasites, among others.
  • different methods have been used to reduce the sulfur level in feedstreams. The most commonly used procedure involves the application of a hydrogen recycle stage to convert the sulfur-containing compounds to H 2 S, and then the removal of the sulfur compounds in a separate step. This can be an arduous and time- consuming procedure. Thus, a better method for removal of sulfur-containing compounds is needed.
  • the present invention is for a novel hydrocarbon feedstream catalyst bed for the desulfurization of a gas or a liquid hydrocarbon feedstream.
  • the bed comprises at least two catalysts having different sulfur compound affinities and / or specificities thereby improving the overall amount of sulfur compound removal.
  • the catalyst bed is configured such that the feed stream has initial contact with a first catalyst that is more selective or that has the greater affinity for the sulfur compound that is present in relatively high concentration within the feedstream. As the feedstream passes over the first catalyst, the targeted sulfur compounds are removed generating a cleaner stream for reaction with a second catalyst.
  • the catalysts are mixed within the catalyst bed. As the feedstream passes over the catalyst bed, the sulfur compounds are adsorbed by the catalyst having the highest affinity for the particular sulfur compound.
  • the present development further describes a process comprising passing a hydrocarbon feedstream over a catalyst bed comprising at least two catalysts having different sulfur compound affinities and / or specificities thereby improving the overall amount of sulfur compound removal.
  • the process reduces the sulfur content in a gas hydrocarbon feedstream from up to about 300 ppm to less than about 500 ppb, and in a liquid hydrocarbon feedstream from up to about 3 % to less than about 500 ppb.
  • Figure 1 is a perspective view of a catalyst bed of a hydrocarbon feedstream desulfurization system wherein the catalyst bed is made in accordance with the present invention and the selective adsorbent section is positioned near the inlet port and the general adsorbent section is positioned near the exit port;
  • Figure 2 is a perspective view of a catalyst bed of a hydrocarbon feedstream desulfurization system wherein the catalyst bed is made in accordance with the present invention and the general adsorbent section is positioned near the inlet port and the selective adsorbent section is positioned near the exit port; and
  • Figure 3 is a perspective view of a catalyst bed of a hydrocarbon feedstream desulfurization system wherein the catalyst bed is made in accordance with the present invention and the general adsorbent is intermixed with the selective adsorbent to form the filter bed.
  • the present invention is for a catalyst bed that is intended to be used to remove contaminants from a gas or liquid hydrocarbon feedstream.
  • sulfur-containing compounds such as, but not limited to, hydrogen sulfide, carbonyl sulfide, sulfides, mercaptans, thiophenes, tert-butyl mercaptan, di-sulfides, dimethyl sulfide, tetrahydrothiophene, ethyl mercaptan, and benzothiophene.
  • a hydrocarbon feedstream desulfurization system 10 includes a catalyst bed reactor 12 having an inlet port 14 and an exit port 16.
  • the catalyst bed reactor 12 houses a catalyst bed 20.
  • a hydrocarbon feedstream, F enters the reactor 12 at the inlet port 14.
  • the hydrocarbon feedstream is in contact with the catalyst bed 20 for a predetermined residence time, determined by the dimensions of the bed 20 and the rate of flow of the feedstream.
  • the catalyst bed 20 can have a controlled temperature and pressure.
  • the feedstream F then exits the catalyst bed 20 through the exit port 16. As the feedstream F passes over the bed 20, contaminants are removed from the feedstream.
  • the hydrocarbon feedstream may be supplied as a gas or as a liquid.
  • the typical sulfur concentration of the raw gas-phase hydrocarbon feedstream can have a sulfur concentration of up to about 300 ppm and the liquid-phase feedstream can have a sulfur concentration of up to about 3 %.
  • the process of the present invention reduces the sulfur concentration to less than about 500 ppb.
  • the catalyst bed 20 comprises a first catalyst or a general adsorbent catalyst 22, and a second catalyst or a selective adsorbent catalyst 24, each having an affinity for sulfur-containing compounds.
  • the first catalyst 24 is positioned near the inlet port 14 of the bed 20.
  • the second catalyst 22 is positioned near the exit port 16 of the bed 20.
  • the first or selective adsorbent catalyst 24 is preferably selected based on the material's 24 specificity for a predetermined class of chemical compounds.
  • a non-limiting list of some selective catalyst materials 24 would include copper/zinc catalysts, zinc oxide catalysts, copper/zinc/molybdenum oxide catalsyts, nickel aluminas, nickel silicas or combinations thereof.
  • a "selective adsorbent catalyst” is a material that fails to adsorb at least one of the sulfur compounds - ethyl mercaptan, tert- butyl mercaptan, tetrahydrothiophene and dimethyl sulfide - at a temperature of about 38°C, a pressure of about 15 psig, and a feedstream space velocity of not less than about 3000 hr '1 . If desired, the relative degrees of specificity for a series of adsorbents can be graded by increasing the reaction temperature and / or decreasing the space velocity.
  • the second or general adsorbent catalyst 22 is preferably selected from a group of relatively materials which are capable of adsorbing sulfur constituents without a high degree of specificity.
  • a non-limiting list of some general adsorbent catalysts would include activated carbon, magnesium oxide, copper/manganese, silver on alumina, nickel silicates, nickel silica/magnesia/alumina, zeolites, molecular sieves, faujasites and combinations thereof, have been shown to be.
  • a "general adsorbent catalyst” is a material that adsorbs ethyl mercaptan, tert-butyl mercaptan, tetrahydrothiophene and dimethyl sulfide at a temperature of about 38°C, a pressure of about 15 psig, and a feedstream space velocity of not less than about 3000 hi '1 .
  • the hydrocarbons when the hydrocarbon feedstream passes over the catalyst bed 20, the hydrocarbons initially passes over the selective adsorbent 24 where the targeted sulfur-containing components are adsorbed by selective adsorbent material 24. The remaining hydrocarbons then pass over the general adsorbent 22 where other sulfur-containing components may be retained by the adsorbent material 22. The remaining hydrocarbons then exit the catalyst bed 20.
  • a catalyst bed 120 comprises a general adsorbent catalyst 122 positioned near an inlet port 114 and a selective adsorbent catalyst 124 positioned near an exit port 1 16.
  • the hydrocarbon feedstream first passes over the general catalyst 122, and then over the selective catalyst 124. If the selective adsorbent catalyst 124 is highly selective, it will be relatively unaffected by the presence of other sulfur-containing compounds.
  • FIG. 3 shows a second alternative embodiment for a catalyst bed 220.
  • a general adsorbent catalyst 222 is intermixed with a selective adsorbent catalyst 224 throughout the length of the catalyst bed 220.
  • selected sulfur-containing compounds are adsorbed preferentially onto the selective catalyst 224 leaving the general catalyst 222 available to adsorb other sulfur-containing compounds.
  • the bed 220 with the catalysts intermixed is most effective when each catalyst 222, 224 has an affinity for a particular class of sulfur- containing compounds.
  • each catalyst 222, 224 has an affinity for a particular class of sulfur- containing compounds.
  • the "general" catalyst preferentially adsorbs thiophenes
  • the "selective" catalyst preferentially adsorbs mercaptans
  • Figures 1 - 3 have been presented and described in terms of only two catalysts or adsorbents. However, more than one catalyst can be combined to form the "general adsorbent catalyst" and / or more than one catalyst can be combined to form the "selective adsorbent catalyst".
  • the catalyst bed may vary in design and equipment from what is illustrated herein.
  • the general adsorbent catalyst and the selective adsorbent catalyst may be optimized to a particular hydrocarbon feedstream or contamination mixture.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Analytical Chemistry (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Catalysts (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

L'invention concerne un nouveau lit de catalyseur à alimentation en flux d'hydrocarbures, destiné à la désulfuration d'un flux de gaz ou d'hydrocarbures liquides, et un procédé qui consiste à faire circuler un flux d'hydrocarbures au-dessus du lit de catalyseur. Le lit comprend au moins deux catalyseurs possédant des affinités de composants de soufre et/ou ses spécificités, ce qui a pour effet d'améliorer la quantité globale de composé de soufre évacué. Le procédé de l'invention permet de réduire la teneur en soufre du flux d'alimentation entre environ 300 parties par 10[6] jusqu'à environ 500 parties par 10[9], et dans un flux d'hydrocarbure liquide entre environ 3 % jusqu'à environ moins de 500 parties par 10[9].
EP03790238A 2002-12-24 2003-11-26 Lit de sorption a composants multiples destine la desulfuration d'hydrocarbures Withdrawn EP1575884A2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US328809 1999-06-09
US10/328,809 US20040118751A1 (en) 2002-12-24 2002-12-24 Multicomponent sorption bed for the desulfurization of hydrocarbons
PCT/US2003/038297 WO2004060840A2 (fr) 2002-12-24 2003-11-26 Lit de sorption a composants multiples destine la desulfuration d'hydrocarbures

Publications (1)

Publication Number Publication Date
EP1575884A2 true EP1575884A2 (fr) 2005-09-21

Family

ID=32594588

Family Applications (1)

Application Number Title Priority Date Filing Date
EP03790238A Withdrawn EP1575884A2 (fr) 2002-12-24 2003-11-26 Lit de sorption a composants multiples destine la desulfuration d'hydrocarbures

Country Status (7)

Country Link
US (1) US20040118751A1 (fr)
EP (1) EP1575884A2 (fr)
JP (1) JP2006512453A (fr)
KR (1) KR20050088206A (fr)
AU (1) AU2003293244A1 (fr)
CA (1) CA2509200A1 (fr)
WO (1) WO2004060840A2 (fr)

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US7427385B2 (en) * 2004-12-17 2008-09-23 Exxonmobil Research And Engineering Company Systems and processes for reducing the sulfur content of hydrocarbon streams
US7597798B2 (en) * 2005-06-17 2009-10-06 Exxonmobil Research And Engineering Company Method for reducing the amount of high molecular weight organic sulfur picked-up by hydrocarbon streams transported through a pipeline
US20070000385A1 (en) * 2005-07-01 2007-01-04 Stouffer Mark R Adsorbents for removing H2S, other odor causing compounds, and acid gases from gas streams and methods for producing and using these adsorbents
KR20090098967A (ko) * 2006-11-08 2009-09-18 큐빅 디자인 스튜디오스 엘엘씨 비대칭 섞임 키보드
US20090292132A1 (en) * 2007-05-18 2009-11-26 Wayne Errol Evans Reactor system and process for reacting a feed
TW200904523A (en) * 2007-05-18 2009-02-01 Shell Int Research A reactor system, and a process for preparing an olefin oxide, a 1,2-diol, a 1,2-diol ether, a 1,2-carbonate and an alkanolamine
US8142646B2 (en) * 2007-11-30 2012-03-27 Saudi Arabian Oil Company Process to produce low sulfur catalytically cracked gasoline without saturation of olefinic compounds
KR101635652B1 (ko) 2008-05-15 2016-07-01 셀 인터나쵸나아레 레사아치 마아츠샤피 비이부이 알킬렌 카보네이트 및/또는 알킬렌 글리콜의 제조방법
RU2506123C2 (ru) 2008-05-15 2014-02-10 Шелл Интернэшнл Рисерч Маатсхаппий Б.В. Способ получения алкиленкарбоната и алкиленгликоля
JP5469470B2 (ja) * 2010-01-22 2014-04-16 東京瓦斯株式会社 水蒸気改質器に供給する原燃料の高次脱硫装置及び高次脱硫方法
DE102010014890A1 (de) 2010-04-14 2011-10-20 Süd-Chemie AG Vorrichtung zur Adsorptionsbehandlung eines Fluids oder Fluidstroms, Verfahren zum Regenerieren und/oder Entsorgen, Befüllen und/oder Installieren einer Vorrichtung zur Adsorptionsbehandlung eines Fluids oder Fluidstroms und Verfahren zur Adsorptionsbehandlung eines Fluids oder Fluidstroms
DE202010016522U1 (de) 2010-04-14 2011-02-17 Süd-Chemie AG Vorrichtung zur Adsorptionsbehandlung eines Fluids oder Fluidstroms
US9149756B2 (en) 2010-04-14 2015-10-06 Clariant Produkte (Deutschland) Gmbh Device for the adsorption treatment of a fluid or fluid stream
JP6607387B2 (ja) * 2015-02-02 2019-11-20 パナソニックＩｐマネジメント株式会社 脱硫方法及び脱硫器
CN109331629A (zh) * 2018-11-06 2019-02-15 广州点蓝环保设备有限公司 低浓度有机废气浓缩催化净化装置及其使用方法
US11773338B1 (en) 2022-11-03 2023-10-03 Saudi Arabian Oil Company Methods of processing whole crude oils that include sulfur

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Also Published As

Publication number Publication date
WO2004060840A2 (fr) 2004-07-22
JP2006512453A (ja) 2006-04-13
WO2004060840A3 (fr) 2004-09-30
AU2003293244A8 (en) 2004-07-29
KR20050088206A (ko) 2005-09-02
AU2003293244A1 (en) 2004-07-29
CA2509200A1 (fr) 2004-07-22
US20040118751A1 (en) 2004-06-24

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