WO2017093012A1 - Adsorption et élimination de soufre régénérable - Google Patents

Adsorption et élimination de soufre régénérable Download PDF

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Publication number
WO2017093012A1
WO2017093012A1 PCT/EP2016/077689 EP2016077689W WO2017093012A1 WO 2017093012 A1 WO2017093012 A1 WO 2017093012A1 EP 2016077689 W EP2016077689 W EP 2016077689W WO 2017093012 A1 WO2017093012 A1 WO 2017093012A1
Authority
WO
WIPO (PCT)
Prior art keywords
adsorbent
steam
sulfur
removal
zinc oxide
Prior art date
Application number
PCT/EP2016/077689
Other languages
English (en)
Inventor
Poul Erik Højlund NIELSEN
Birgitte HAMMERSHØI
Burcin TEMEL MCKENNA
Original Assignee
Haldor Topsøe A/S
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 Haldor Topsøe A/S filed Critical Haldor Topsøe A/S
Publication of WO2017093012A1 publication Critical patent/WO2017093012A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/34—Regenerating or reactivating
    • B01J20/3433—Regenerating or reactivating of sorbents or filter aids other than those covered by B01J20/3408 - B01J20/3425
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/34—Regenerating or reactivating
    • B01J20/345—Regenerating or reactivating using a particular desorbing compound or mixture
    • B01J20/3458—Regenerating or reactivating using a particular desorbing compound or mixture in the gas phase
    • B01J20/3466—Regenerating or reactivating using a particular desorbing compound or mixture in the gas phase with steam
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/112—Metals or metal compounds not provided for in B01D2253/104 or B01D2253/106
    • B01D2253/1124—Metal oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/30—Sulfur compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/40—Further details for adsorption processes and devices
    • B01D2259/40083—Regeneration of adsorbents in processes other than pressure or temperature swing adsorption
    • B01D2259/40088—Regeneration of adsorbents in processes other than pressure or temperature swing adsorption by heating
    • B01D2259/4009—Regeneration of adsorbents in processes other than pressure or temperature swing adsorption by heating using hot gas
    • 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
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/48—Sulfur compounds

Definitions

  • the present invention relates to regenerable zinc oxide based sorbents. More specifically, the invention concerns a method for the removal of sulfur from a sulfide adsorbent, said method comprising the following steps:
  • Sulfur is both an environmental hazard when it is present as a contaminant in fuel for combustion and, as mentioned, a poison for several catalytic materials when it is present in electrochemical systems such as fuel cells.
  • Supported metal catalysts are widely used to produce high purity hy ⁇ drogen in fuel processing systems via processes such as catalytic reforming, water gas shift (WGS) and oxidation of carbon monoxide, and they are also used as electrode mate ⁇ rials in fuel cells.
  • the metals in supported metal catalysts have a very low sulfur tolerance (of the order 0.1 to 10 ppmv) , but unfortunately typical sulfur concentrations in fuels may be as high as 3000 ppmw.
  • US 6.350.422 Bl discloses sorbent composi ⁇ tions comprising zinc oxide, at least one silica component, at least one colloidal metal oxide and optionally at least one pore generating component.
  • the sorbent composition can be regenerated with oxygen or an oxygen-containing gas.
  • US 6.951.635 B2 describes zinc oxide-based sorbents and processes for making and using them.
  • the active zinc compo ⁇ nent is a two-phase material consisting essentially of a zinc oxide phase and a zinc aluminate phase, each charac- terized by a small crystallite size of typically less than 500 A (Angstrom) .
  • Regenerable sorbents for removal of sulfur from hydrocarbon feedstocks are disclosed in US 2008/0251423 Al . These sorbents contain zinc aluminate, free alumina as well as iron oxide.
  • US 5.703.003 Al describes sorbent pellets for removing sul ⁇ fide from a coal gasification stream at an elevated temperature, comprising contacting a zinc oxide sorbent with a 3 ⁇ 4S containing gas, thereby desulfurizing the gas and sul- fiding the sorbent.
  • the sulfide sorbent can be regenerated.
  • Durable zinc oxide containing sorbents for coal gas desul- furization are also described in CA 2.145.250 Al .
  • a process for removing or recovering sulfur from a gas stream using a Claus-type reactor followed by contact with a regenerable sorbent and recycle of SO 2 from the sorbent regeneration to the Claus- type reactor feed.
  • the sorbent comprises zinc oxide, ex ⁇ panded perlite, alumina and a promoter metal, said promoter metal being at least one metal selected from Ni, Co, Fe, Mn, W, Ag, Au, Cu, Pt, Zn, Sn, Ru, Mo, Sb, V, Ir, Cr and Pd.
  • US 2010/0170394 Al describes a silicate-resistant desulfu- rization sorbent composition
  • a support component in the form of one or more silicate-resistant silica-con ⁇ taining that have been treated with one or more silicate- inhibiting metals selected from the group consisting of Sr, Ba, La and combinations thereof.
  • the sorbent compositions exhibit a surprisingly low in-situ silicate generation rate when exposed to oxidative regeneration conditions.
  • WO 03/053579 Al describes how a deactivated sorbent compo ⁇ sition is reactivated by contacting the deactivated
  • sorbent which comprises a promoter metal and at least about 2 wt% sulfur as sulfates, with a hydrogen-containing stream under activation conditions sufficient to reduce the valence of the promoter metal and reduce the amount of sul ⁇ fates associated with said deactivated sorbent, thereby providing an activated sorbent.
  • applicant's older PCT application WO 90/14876 dis ⁇ closes the removal of sulfides from gas streams while using a solid adsorbent containing Sn, Sn-oxides or mixtures thereof and optionally a stabilizing component consisting of Ni, Cu, Co, Fe or oxides thereof, said removal taking place by contacting the sulfide-containing gas stream with the solid adsorbent, which is expediently in the form of a carrier with the Sn-component and the stabilizing compo ⁇ nent.
  • the adsorbent is sulfided and the gas stream is desulfurized. Subsequently the sulfided adsorbents are regenerated by contact with steam.
  • the regeneration process employed is substantially thermoneutral , so that superheat ⁇ ing and consequently sintering of the adsorbent is avoided. Moreover, it is not necessary to operate at low tempera ⁇ tures, whereby the formation of sulfates as by-products is avoided.
  • the feed gas typically contains 600-800 ppmv 3 ⁇ 4S which is a much higher concentration than that foreseen in the present invention.
  • the goal underlying the present invention has been to demonstrate that it is possible to strip off sulfur from zinc sulfide (ZnS) by treating it with steam or steam en- riched with oxygen, thereby regenerating the sulfided ad ⁇ sorbent by converting it back to ZnO. The ZnO can then be used to adsorb sulfur again.
  • the adsorbent is used to capture sulfur in the feed stream for a certain period of time. Then the sulfidized adsorbent is regener ⁇ ated with steam and minor amounts of oxygen in the feed, especially in a swing operation. After the regeneration, the adsorbent can be turned in for the sulfur adsorption process again.
  • the method according to the invention for the removal of sulfides from a gas stream may be a de ⁇ sirable option. This is because the sulfur concentrations in connection with thermal gasification of biomass are in the 100 ppm range, which means that the traditional way of removing sulfur by using an acid gas removal (AGR) unit will become a rather expensive and thus not attractive pos ⁇ sibility.
  • AGR acid gas removal
  • SK-501 and HTZ-5 refer to the names of products sold by Haldor Topsoe. HTZ-5 is used in cleaning sulfur from various feeds. SK-501 is used for high temperature water gas shift operations. It contains a surplus of ZnO and may be regarded as a prototype of a supported ZnO guard.
  • ZnS + 3H 2 0 ⁇ > ZnO + 3H 2 + S0 2 towards right.
  • H 2 O 2 in water plus 2 was used, which corre ⁇ sponds to 50% steam and 0.5-1% O 2 from H 2 O 2 decomposition, the balance being N 2 , at various temperatures, i.e. 500 to 600°C.
  • the sulfur content decreased from 3.8 wt% to 0.3 wt%.
  • the results of the experiments show that it is possible to remove sulfur from an adsorbent with steam or with steam and 0 2 , depending on the regeneration conditions.
  • the re ⁇ generation method of the invention has the advantage that the same batch of adsorbent can be used many times with this method.
  • the examples are divided into two parts, dealing with the SK-501 (>30 wt% ZnO, supported) adsorbent and an HTZ-5 (un- supported) adsorbent, respectively.
  • Example 3 10 g of sulfided SK-501 was loaded as halved pellets into a tubular reactor. The regeneration took place first with only steam + 2 at 550°C. After 24 hours, the regeneration condition was switched to 1 vol% H2O2 in steam + N 2 . After 48 hours, 1 g of spent catalyst was taken out from the top of the catalyst bed, and it was found to contain 0.8 wt% sulfur. The regeneration test was continued as Example 3 below .
  • Example 3 10 g of sulfided SK-501 was loaded as halved pellets into a tubular reactor. The regeneration took place first with only steam + 2 at 550°C. After 24 hours, the regeneration condition was switched to 1 vol% H2O2 in steam + N 2 . After 48 hours, 1 g of spent catalyst was taken out from the top of the catalyst bed, and it was found to contain 0.8 wt% sulfur. The regeneration test was continued as Example 3 below .
  • Example 3 10 g of sulfided SK
  • the SO 2 that was formed during regeneration was partly cap ⁇ tured in the exit condensate and partly lost to the vapor phase over the low pressure separator.
  • the condensate anal ⁇ ysis involved oxidizing SO 2 further to SO 4 ions by H 2 O 2 and analyzing SO 4 by ion chromatography.
  • the amount of oxygen in the steam mixture is a critical pa ⁇ rameter.
  • 0.5 to 1 vol% O 2 was used, and the amount of sulfur remaining on the catalyst was 0.3 wt% which probably is in the form of ZnSC ⁇ .

Landscapes

  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Inorganic Chemistry (AREA)
  • Industrial Gases (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

L'invention concerne un procédé pour l'élimination de soufre d'un adsorbant de sulfures comprenant l'entrée en contact du flux gazeux contenant des sulfures avec un adsorbant à base d'oxyde de zinc, la désulfuration du flux gazeux lors de la sulfuration de l'adsorbant et la régénération de l'adsorbant sulfuré par un traitement avec de la vapeur ou de la vapeur enrichie en oxygène à une température élevée. De cette manière, l'adsorbant est reconverti en oxyde de zinc.
PCT/EP2016/077689 2015-12-02 2016-11-15 Adsorption et élimination de soufre régénérable WO2017093012A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DKPA201500774 2015-12-02
DKPA201500774 2015-12-02

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WO2017093012A1 true WO2017093012A1 (fr) 2017-06-08

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110721692A (zh) * 2018-07-16 2020-01-24 中国石油化工股份有限公司 汽油吸附脱硫催化剂及其制备方法和应用
CN110917876A (zh) * 2019-11-15 2020-03-27 湖南环达环保有限公司 一种氧化锌脱硫剂的再生方法
USD889325S1 (en) 2018-09-20 2020-07-07 Bayerische Motoren Werke Aktiengesellschaft Radiator grille for a vehicle

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4442078A (en) * 1982-07-07 1984-04-10 The United States Of America As Represented By The United States Department Of Energy Method of removing hydrogen sulfide from gases utilizing a zinc oxide sorbent and regenerating the sorbent
US4732888A (en) * 1986-05-15 1988-03-22 Amax Inc. Durable zinc ferrite sorbent pellets for hot coal gas desulfurization
US5693588A (en) * 1996-08-16 1997-12-02 The United States Of America As Represented By The Department Of Energy Reduction of spalling in mixed metal oxide desulfurization sorbents by addition of a large promoter metal oxide
US5703003A (en) * 1994-03-23 1997-12-30 United States Department Of Energy Durable regenerable sorbent pellets for removal of hydrogen sulfide from coal gas
US20080271602A1 (en) * 2007-05-01 2008-11-06 Auburn University Doped supported zinc oxide sorbents for regenerable desulfurization applications
WO2013065007A1 (fr) * 2011-11-03 2013-05-10 Indian Oil Corporation Ltd. Adsorbant nanostructuré pour éliminer le soufre des carburants de type diesel et essence et son procédé de préparation

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4442078A (en) * 1982-07-07 1984-04-10 The United States Of America As Represented By The United States Department Of Energy Method of removing hydrogen sulfide from gases utilizing a zinc oxide sorbent and regenerating the sorbent
US4732888A (en) * 1986-05-15 1988-03-22 Amax Inc. Durable zinc ferrite sorbent pellets for hot coal gas desulfurization
US5703003A (en) * 1994-03-23 1997-12-30 United States Department Of Energy Durable regenerable sorbent pellets for removal of hydrogen sulfide from coal gas
US5693588A (en) * 1996-08-16 1997-12-02 The United States Of America As Represented By The Department Of Energy Reduction of spalling in mixed metal oxide desulfurization sorbents by addition of a large promoter metal oxide
US20080271602A1 (en) * 2007-05-01 2008-11-06 Auburn University Doped supported zinc oxide sorbents for regenerable desulfurization applications
WO2013065007A1 (fr) * 2011-11-03 2013-05-10 Indian Oil Corporation Ltd. Adsorbant nanostructuré pour éliminer le soufre des carburants de type diesel et essence et son procédé de préparation

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110721692A (zh) * 2018-07-16 2020-01-24 中国石油化工股份有限公司 汽油吸附脱硫催化剂及其制备方法和应用
CN110721692B (zh) * 2018-07-16 2023-01-13 中国石油化工股份有限公司 汽油吸附脱硫催化剂及其制备方法和应用
USD889325S1 (en) 2018-09-20 2020-07-07 Bayerische Motoren Werke Aktiengesellschaft Radiator grille for a vehicle
CN110917876A (zh) * 2019-11-15 2020-03-27 湖南环达环保有限公司 一种氧化锌脱硫剂的再生方法
CN110917876B (zh) * 2019-11-15 2021-09-28 湖南环达环保有限公司 一种氧化锌脱硫剂的再生方法

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