WO2017026914A1 - Procédé de décomposition à basse température de sulfure d'hydrogène comprenant une dérivation d'hydrogène et de soufre - Google Patents

Procédé de décomposition à basse température de sulfure d'hydrogène comprenant une dérivation d'hydrogène et de soufre Download PDF

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Publication number
WO2017026914A1
WO2017026914A1 PCT/RU2015/000865 RU2015000865W WO2017026914A1 WO 2017026914 A1 WO2017026914 A1 WO 2017026914A1 RU 2015000865 W RU2015000865 W RU 2015000865W WO 2017026914 A1 WO2017026914 A1 WO 2017026914A1
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WO
WIPO (PCT)
Prior art keywords
hydrogen sulfide
sulfur
hydrogen
catalyst
temperature
Prior art date
Application number
PCT/RU2015/000865
Other languages
English (en)
Inventor
Oleg Petrovich Andreev
Magmedali Alievich OMAROV
Ramidin Akberbubaevich SARKAROV
Aleksei Borisovich YUMASHEV
Magomed Idrisovich AKHMEDOV
Vyacheslav Vasilyevich SELEZNEV
Original Assignee
Publichnoe Aktsionernoe Obschestvo "Gazprom"
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.)
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Application filed by Publichnoe Aktsionernoe Obschestvo "Gazprom" filed Critical Publichnoe Aktsionernoe Obschestvo "Gazprom"
Publication of WO2017026914A1 publication Critical patent/WO2017026914A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/02—Preparation of sulfur; Purification
    • C01B17/021—Separation of sulfur from gases
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/02—Preparation of sulfur; Purification
    • C01B17/04—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/02—Preparation of sulfur; Purification
    • C01B17/04—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides
    • C01B17/0495—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by dissociation of hydrogen sulfide into the elements
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/02—Preparation of sulfur; Purification
    • C01B17/04—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides
    • C01B17/0404—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by processes comprising a dry catalytic conversion of hydrogen sulfide-containing gases, e.g. the Claus process
    • C01B17/0426—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by processes comprising a dry catalytic conversion of hydrogen sulfide-containing gases, e.g. the Claus process characterised by the catalytic conversion
    • C01B17/0439—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by processes comprising a dry catalytic conversion of hydrogen sulfide-containing gases, e.g. the Claus process characterised by the catalytic conversion at least one catalyst bed operating below the dew-point of sulfur
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Definitions

  • the invention relates to gas and oil refining, in particular to methods of decomposition and disposal of hydrogen sulfide, and may be used for production of hydrogen and sulfur from hydrogen sulfide.
  • Hydrogen sulfide is the main side product of oil refining, and a large amount thereof is contained in formation fluid of oil, gas and condensate fields.
  • hydrogen sulfide at gas and oil refineries is recycled by the Claus method of thermal decomposition with derivation of sulfur.
  • the disadvantage of this method is high temperature of the process and impossibility of hydrogen derivation.
  • Solid material capable of activation of hydrogen sulfide at the temperature under 200°C is selected as the mentioned material, and regeneration is performed by running through regenerating gas that does not contain hydrogen sulfide or one that contains it in concentration that is lower than in initial sulfurous gas at the temperature not higher than 350°C.
  • the disadvantage of this method is necessity of frequent regeneration of solid material to remove sulfur.
  • the closest solution to the proposed technical one is the method of decomposition of hydrogen sulfide with derivation of hydrogen and sulfur (patent of the Russian Federation No. 2239594, cl. 7 C01 B 17/04, 3/06, pubd. on 10.1 1.2004) that includes contact of sulfurous gas through a layer of solid material capable of decomposing hydrogen sulfide with generation of hydrogen and formation of sulfurous compounds on the material surface, periodical regeneration of material by decomposition of the mentioned hydrogen sulfurous compounds, and generation of sulfur.
  • hydrogen sulfide decomposition is performed in a chemisorptive-catalytic mode at the temperature under the melting point of sulfur with derivation of hydrogen and surface chemisorbed compounds. Reactivation is performed at the temperature under the sulfur melting point, and regeneration is performed at the temperature over the sulfur melting point.
  • the disadvantage of the method is cyclically of the process associated with necessity both to reactivate and regenerate solid material of catalyst, and a low degree of hydrogen sulfide decomposition when performing the process in the nonstop mode.
  • the object of the present invention is creation of an efficient method of low- temperature decomposition of hydrogen sulfide with derivation of hydrogen and sulfur that provides for performance of the process in the non-stop mode.
  • Technical result achieved by implementation of the invention is increase of hydrogen sulfide conversion degree and prevention of catalyst contamination.
  • Technical result is achieved on the basis of the method of low-temperature decomposition of hydrogen sulfide with derivation of hydrogen and sulfur which includes running of hydrogen sulfide through a layer of catalyst; at the temperature 0-35°C hydrogen sulfide is run through layers of catalyst and sulfur sorbent loaded into sequentially installed modules.
  • stainless steel chips with thickness of 0.1-0.2 mm and length of 1.5-5.5 mm is used as catalyst, and the number of modules with catalyst and sulfur sorbent is 6-12 pes.
  • gas mixture generated in the last module is run through ethanolamine solution for purification of hydrogen from hydrogen sulfide residues with further desorption of hydrogen sulfide from ethanolamine solution, and desorption of sulfur from sulfur sorbent is performed with nitrogen at the temperature of 140-160°C.
  • ⁇ - ⁇ 1203 may be used as sulfur sorbent.
  • Desorbed hydrogen sulfide may be returned to the first module input.
  • modules with catalyst and sulfur sorbent totaling 6-12 pes ensures hydrogen content over 75 vol. % in gaseous phase. Sulfur from sulfur sorbent is desorbed with nitrogen during sulfur enrichment at the temperature of 140-160°C.
  • derived hydrogen that contains 12-25 vol. % of hydrogen sulfide may be used directly for production purposes, for instance, for hydrogen refining of oil products from sulfur-containing compounds.
  • sulfur sorbent enriched with sulfur can be used as modifying agent widely used in production of asphalt- concrete products.
  • the claimed method suggests a combination of low-temperature catalytic process of hydrogen sulfide decomposition on the surface of metal catalyst and further removal of gaseous sulfur from the volume of generated resultants with numerous repetition of the processes of hydrogen sulfide catalytic decomposition and adsorption of gaseous sulfur with sequential running of gaseous mixture through catalyst layers and sulfur sorbent.
  • Hydrogen sulfide is run through layers of catalyst and sulfur sorbent loaded into sequentially installed modules for 3-48 hours at the temperature of 0-35°C and speed of 1 1/h.
  • Stainless steel chips with thickness of 0.1-0.2 mm and length of 1.5- 5.5 mm is used as catalyst; ⁇ - ⁇ 1 2 ⁇ 3 is used as sulfur sorbent.
  • To purify hydrogen from sulfur the resultant gas mixture is run through ethanolamine solution, ethanolamine solution is regenerated by way of heating and desorption of hydrogen sulfide. Regenerated solution is returned to the stage of hydrogen purification from hydrogen sulfide. Desorbed hydrogen sulfide is returned to the first module input.
  • the number of modules with catalyst and sulfur sorbent is 6-12 pes.
  • sulfur enrichment sulfur sorbent is removed from the system, directed to regeneration for derivation of elemental sulfur.
  • Desorption of sulfur from sulfur sorbent is performed with nitrogen at the temperature of 140-160°C.
  • Regenerated sulfur sorbent is repeatedly used for sulfur sorption.
  • gaseous mixture is analyzed for hydrogen and hydrogen sulfide content before sending it for purification.
  • Hydrogen sulfide decomposition products are hydrogen and sulfur based on the suggested method. Decomposition of hydrogen sulfide as in the prior art using MoS 2 molybdenum disulfide and stainless steel chips as catalyst was performed for comparison. Hydrogen sulfide was run through for 3 hours.
  • Si0 2 and sibunite may also be used as sulfur sorbent.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Catalysts (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Exhaust Gas Treatment By Means Of Catalyst (AREA)

Abstract

La présente invention concerne le raffinage du pétrole et du gaz, en particulier des procédés de décomposition et d'élimination de sulfure d'hydrogène, et pouvant être utilisée pour la production d'hydrogène et de soufre à partir de sulfure d'hydrogène. Le procédé de décomposition à basse température de sulfure d'hydrogène comprend la circulation de l'hydrogène sulfuré à travers un catalyseur et des couches de sorbant de soufre chargées dans des modules installés de manière séquentielle à la température de 0 à 35 °C. Des copeaux d'acier inoxydable présentant une épaisseur de 0,1 à 0,2 mm et une longueur de 1,5 à 5,5 mm sont utilisés en tant que catalyseur, et le nombre de modules présentant un catalyseur et le sorbant de soufre est de 6 à 12 pcs. Le mélange de gaz produit dans le dernier module est mis à circuler dans une solution d'éthanolamine pour la purification d'hydrogène à partir de résidus de sulfure d'hydrogène puis par désorption supplémentaire du sulfure d'hydrogène provenant de la solution d'éthanolamine. La désorption du soufre à partir du sorbant de soufre est effectuée à l'aide d'azote à la température de 140 à 160 °C. L'invention revendiquée garantit l'augmentation du degré de conversion du sulfure d'hydrogène et la prévention de la contamination de catalyseur.
PCT/RU2015/000865 2015-08-13 2015-12-09 Procédé de décomposition à basse température de sulfure d'hydrogène comprenant une dérivation d'hydrogène et de soufre WO2017026914A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
RU2015133966/05A RU2600375C1 (ru) 2015-08-13 2015-08-13 Способ низкотемпературного разложения сероводорода с получением водорода и серы
RU2015133966 2015-08-13

Publications (1)

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WO2017026914A1 true WO2017026914A1 (fr) 2017-02-16

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Country Status (2)

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RU (1) RU2600375C1 (fr)
WO (1) WO2017026914A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110127602A (zh) * 2018-02-09 2019-08-16 中国石油化工股份有限公司 应用催化剂分解硫化氢的方法
EP4180386A1 (fr) 2021-11-16 2023-05-17 TotalEnergies OneTech Procédé de conversion continue de h2s en h2 et en soufre

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2725636C1 (ru) * 2019-12-09 2020-07-03 Акционерное общество "Газпромнефть - Омский НПЗ" (АО "Газпромнефть-ОНПЗ") Способ низкотемпературного разложения сероводорода с получением водорода и серы
WO2022149994A1 (fr) * 2021-01-11 2022-07-14 Анатолий Николаевич СТАРЦЕВ Catalyseur pour produire de l'hydrogène et du soufre gazeux di-atomique lors du processus de décomposition de sulfure d'hydrogène

Citations (8)

* Cited by examiner, † Cited by third party
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US3634028A (en) * 1966-10-27 1972-01-11 Metallgesellschaft Ag Process for removing sulfur from gases
US3962409A (en) 1973-10-29 1976-06-08 Agency Of Industrial Science & Technology Process for production of hydrogen and sulfur from hydrogen sulfide as raw material
US4610766A (en) * 1985-06-11 1986-09-09 Phillips Petroleum Company Photochemical production of hydrogen from hydrogen sulfide
WO1994013579A1 (fr) * 1992-12-16 1994-06-23 The Regents Of The University Of California Procede de recuperation de souffre a partir de gaz acides
RU2216506C1 (ru) 2002-02-26 2003-11-20 Институт катализа им. Г.К.Борескова СО РАН Способ получения водорода и элементарной серы из сероводорода
RU2239594C1 (ru) 2003-10-07 2004-11-10 Институт катализа им. Г.К. Борескова СО РАН Способ разложения сероводорода
US20060120948A1 (en) * 2002-06-04 2006-06-08 Agarwal Pradeep K Membrane for hydrogen recovery from streams containing hydrogen sulfide
US20070292337A1 (en) * 2004-04-01 2007-12-20 Startsev Anatolii N Method for Hydrogen Sulphide and/or Mercaptans Decomposition

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RU2099280C1 (ru) * 1991-07-27 1997-12-20 Солвей Интерокс Лимитед Способ получения элементарной серы из сероводорода и циклический способ получения перекиси водорода
RU2152353C1 (ru) * 1999-10-06 2000-07-10 Мелуа Аркадий Иванович Способ получения серы
CN102380311B (zh) * 2010-09-01 2013-12-25 中国石油化工股份有限公司 汽油吸附脱硫再生烟气处理方法及其尾气加氢催化剂制法
US8916117B2 (en) * 2012-08-07 2014-12-23 Exxonmobil Research And Engineering Company Corrosion control in acid gas removal equipment by the situ generation of polysulfide ions

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3634028A (en) * 1966-10-27 1972-01-11 Metallgesellschaft Ag Process for removing sulfur from gases
US3962409A (en) 1973-10-29 1976-06-08 Agency Of Industrial Science & Technology Process for production of hydrogen and sulfur from hydrogen sulfide as raw material
US4610766A (en) * 1985-06-11 1986-09-09 Phillips Petroleum Company Photochemical production of hydrogen from hydrogen sulfide
WO1994013579A1 (fr) * 1992-12-16 1994-06-23 The Regents Of The University Of California Procede de recuperation de souffre a partir de gaz acides
RU2216506C1 (ru) 2002-02-26 2003-11-20 Институт катализа им. Г.К.Борескова СО РАН Способ получения водорода и элементарной серы из сероводорода
US20060120948A1 (en) * 2002-06-04 2006-06-08 Agarwal Pradeep K Membrane for hydrogen recovery from streams containing hydrogen sulfide
RU2239594C1 (ru) 2003-10-07 2004-11-10 Институт катализа им. Г.К. Борескова СО РАН Способ разложения сероводорода
US20070292337A1 (en) * 2004-04-01 2007-12-20 Startsev Anatolii N Method for Hydrogen Sulphide and/or Mercaptans Decomposition

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* Cited by examiner, † Cited by third party
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DATABASE WPI Week 200506, Derwent World Patents Index; AN 2005-055508, XP002758285 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110127602A (zh) * 2018-02-09 2019-08-16 中国石油化工股份有限公司 应用催化剂分解硫化氢的方法
CN110127602B (zh) * 2018-02-09 2020-09-25 中国石油化工股份有限公司 应用催化剂分解硫化氢的方法
EP4180386A1 (fr) 2021-11-16 2023-05-17 TotalEnergies OneTech Procédé de conversion continue de h2s en h2 et en soufre

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