WO1991004941A1 - Procede de production de soufre elementaire a partir de gaz contenant du soufre - Google Patents

Procede de production de soufre elementaire a partir de gaz contenant du soufre Download PDF

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Publication number
WO1991004941A1
WO1991004941A1 PCT/US1990/002765 US9002765W WO9104941A1 WO 1991004941 A1 WO1991004941 A1 WO 1991004941A1 US 9002765 W US9002765 W US 9002765W WO 9104941 A1 WO9104941 A1 WO 9104941A1
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WO
WIPO (PCT)
Prior art keywords
sulfur
gas stream
percent
containing gases
gases
Prior art date
Application number
PCT/US1990/002765
Other languages
English (en)
Inventor
Thomas P. Dorchak
Santosh K. Gangwal
Scott M. Harkins
Original Assignee
Research Triangle Institute
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 Research Triangle Institute filed Critical Research Triangle Institute
Publication of WO1991004941A1 publication Critical patent/WO1991004941A1/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
    • C01B17/04—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
    • C01B17/0456—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 the hydrogen sulfide-containing gas being a Claus process tail gas
    • 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
    • C01B17/0473—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by reaction of sulfur dioxide or sulfur trioxide containing gases with reducing agents other than hydrogen sulfide

Definitions

  • This invention relates to a method for converting gaseous sulfur to elemental sulfur and other specific sulfur compounds.
  • sulfur containing gases are mixed with a preselected secondary gas stream and contacted with a catalyst.
  • Elemental sulfur is a vital raw material which is used in various industrial processes.
  • the Stretford process is a low temperature, wet oxidative scrubbing process. However, the Stretford process has numerous
  • preconce ⁇ tration step is required.
  • the process then oxidizes a portion of the feed gas to sulfur dioxide and reacts it with the nonoxidized portion to yield sulfur and water.
  • Catalysts are used to ensure equilibrium at hourly gas space velocities limited to 700 to 1400 scf/cfh.
  • Still more complex are those regenerable processes such as the Wellman-Lord which converts a very dilute sulfur dioxide gas stream, for example from combustion flue gas, to sulfuric acid or elemental sulfur.
  • the Wellman-Lord process uses sodium sulfite to scrub the flue gas.
  • the bisulfite product is thermally decomposed to yield a concentrated SO 2 gas stream for sulfuric acid production. Partial reduction of the concentrated sulfur dioxide gas stream.
  • SO 2 can produce elemental sulfur using augmented Claus technology at the tail end of the process.
  • a further object of the present invention is to provide a method for producing elemental sulfur from sulfur-containing gases which operates at intermediate temperatures.
  • Yet another object of the present invention is to provide a method for producing elemental sulfur from sulfur-containing gases which operates efficiently where concentrations of gsseous sulfur in- the sulfur-containing feed gas are low.
  • Another object of the present invention is to provide a method for producing elemental sulfur from sulfur containing gases which can also be used to convert oxidized gaseous sulfur compounds to reduced sulfur compounds and vise versa. Disclosure of the Invention
  • the method generally comprises the mixing of a primary gas stream of
  • sulfur-containing gases with a secondary gas stream to produce a preselected stoichoimetry, and contacting the combined gas stream with a
  • the catalyst is selected from the group consisting of silica, alumina, other Claus-type catalysts, sodium/alumina, zinc ferrite, zinc titanate and other mixed metal oxides, and
  • contacting of the combined gas stream is preferably accomplished at temperatures in the range of about 300° C to 700° C depending on the composition of the gas and pressure.
  • the contacting of the combined gas stream with the catalyst is preferably accomplished at pressures in excess of approximately 20 atm, but lower pressures can be used at the cost of reduced sulfur yield.
  • Figure 1 illustrates a schematic diagram of a system for implementing the method of the present invention.
  • Figure 2 illustrates a schematic diagram of an alternative system for implementing the method of the present invention.
  • Figure 3 is a schematic diagram of a
  • the present invention provides a method for converting the sulfur in gas streams containing gaseous sulfur compounds such as hydrogen sulfide, carbonyl sulfide and sulfur dioxide to elemental sulfur.
  • gaseous sulfur compounds such as hydrogen sulfide, carbonyl sulfide and sulfur dioxide
  • the method of the present invention can be used, under alternative conditions, to convert oxidized gaseous sulfur compounds such as sulfur dioxide to reduced sulfur compounds such as hydrogen sulfide, and vice versa.
  • the discussion below is directed primarily to the method as applied to the production of elemental sulfur it will be understood that the present invention is not limited in use to the production of elemental sulfur.
  • the method of the present invention generally comprises the mixing of a primary gas stream of sulfur-containing gas with a secondary gas stream of selected composition, and contacting the resulting combined gas stream with a preselected catalyst at temperatures of about 300°C to 700°C.
  • the composition of the secondary gas stream will vary depending upon the composition of the primary gas stream, with the object being that the
  • the resulting combined stream have a stoichiometry conducive to substantially complete conversion of the sulfur gases to the desired product, whether it be elemental sulfur or reduced/oxidized sulfur gases.
  • the mixture of primary and secondary gas streams should have close to such stoichiometry that the sulfur gases can be
  • oxidizing gases such as steam and carbon dioxide in the secondary stream as lone as the secondary gas stream is overall reducing in nature.
  • the secondary gas stream will be oxidizing in nature, e.g. containing sulfur dioxide, oxygen, and/or air.
  • the primary gas stream already has close to the desired stoichiometry the
  • the method of the present invention can also be used to convert oxidized sulfur gases to reduced sulfur gases, and vice versa, this being accomplished by shifting the primary/secondary gas stream mixture stoichiometry toward the desired gas and by selection of the appropriate temperature for the desired
  • the catalyst used pursuant to the method of the present invention is selected from a group consisting of silica, alumina, and other
  • the catalyst is in the form of pellets and a reactor having a single fixed bed of sorbent is used. It will, however, be recognized by those skilled in the art that reactor modifications including multistage
  • moving-bed and fluidized-bed systems can also be used.
  • the primary gas stream having been mixed with a small flow of the appropriate
  • the preferred operating conditions under which the combined primary and secondary gas streams are contacted by the catalyst for recovery of elemental sulfur include temperatures on the order of 300°C to 700°C, and space velocities (in fixed beds) up to and greater than 10,000
  • temperatures below 300°C, and at pressures below 10 atm For example, approximately 23% conversion to elemental sulfur from SO 2 has been accomplished at 650°C, at 1.5 atm. Additionally, at times, elemental sulfur conversion has actually increased as temperatures decreased.
  • Example 4 An oxidizing gas-H 2 S combination containing, 1.5 percent H 2 S, 0.6 percent COS, 1.8 percent O 2 , and balance N 2 , flowing through a fixed bed of a specially prepared and presulfated sodium alumina catalyst at a space velocity of 1750 scc/(cc.h), resulted in a 88.2 percent conversion of the inlet sulfur to elemental sulfur at a temperature of 600°
  • reaction temperature was reduced to a temperature of 540°C at constant space velocity, and the conversion to elemental sulfur was 89.4 percent.
  • reaction temperature was reduced to a temperature of 500°C at constant space velocity, and the conversion to elemental sulfur was 87.6 percent.
  • Reaction temperature was reduced to a temperature of 489°C at constant space velocity, and the conversion to elemental sulfur was S4.5 percent. Reaction temperature was reduced to a temperature of 449°C at constant space velocity, and the conversion to elemental sulfur was 91.1 percent. Reaction temperature was reduced to a temperature of 392°C at constant space vel ocity, and the conversi on to el emental sulf ur was 75. 9 percent.
  • Example 12 A potentially reactive gas combination
  • the primary gas stream referenced at 12
  • the primary gas stream is depicted as regeneration off-gas which will be used as one preferred primary gas stream sources, typically provided at a temperature on the order of 700°C, at a pressure of approximately 25 atm, with SO 2 concentrations of approximately 2 mole %.
  • the secondary gas stream, referenced at 14, is depicted as coal gas, the secondary stream 14 being reducing in nature.
  • the primary and secondary gas streams are mixed at 16 and directed into the sulfur production reactor 18 to be contacted by the fixed bed of catalyst therein shown at 19.
  • H 2 S rich overhead produced from the SCOT process is recycled through line 23 to be mixed with the primary stream 12 such that the further conversion to elemental sulfur can be effected and the clean tail gases, having an environmentally safe sulfur content of less than
  • the system 10' is a multiple bed system including a sulfur production reactor 18' having a catalyst bed 19', an intercooler 20' and a tail-gas
  • polishing reactor 24 having a catalyst bed 25.
  • the second reactor 24 is used to effect further conversions of sulfur and thereby clean the tail gas being discharged from reactor 24 through line 26 so as to leave only traces of SO 2 .
  • the primary regeneration off-gas need not be concentrated.
  • Regeneration off-gases are typically within the preferred temperature range of the method, and the method is suitable for conversion to elemental sulfur even where SO 2 concentrations are verv small.
  • the method of the present invention is essentially a one step, continuous process which results in elemental sulfur conversion greater than 90%.
  • a second stage is only necessary if over 99%
  • the method operates over a wide range of temperatures.
  • the process is insensitive to catalyst properties deemed

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)
  • Exhaust Gas Treatment By Means Of Catalyst (AREA)

Abstract

On a mis au point un procédé de production de soufre élémentaire (21) et de composés de soufre réduits/oxydés à partir de gaz (12, 23) contenant du soufre. Le procédé consiste à mélanger un courant gazeux primaire (12) avec un courant gazeux secondaire (14) afin de produire un courant gazeux combiné ayant une stoechiométrie présélectionnée, et à mettre en contact le courant gazeux combiné avec un sorbant/catalyseur (19). Le sorbant/catalyseur (19) est sélectionné dans le groupe composé de silice, d'oxyde d'aluminium, et d'autres catalyseurs du type Claus, sodium/oxyde d'aluminium, ferrite de zinc, titanate de zinc, ainsi que d'autres oxydes métalliques mélangés, et leurs mélanges. Le sorbant/catalyseur (19) produit du soufre élémentaire (21), par exemple, par les réactions: SO2 + 2H2 ---> 2H2O + S, SO2 + 2CO ---> 2CO2 + S.
PCT/US1990/002765 1989-10-02 1990-05-25 Procede de production de soufre elementaire a partir de gaz contenant du soufre WO1991004941A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US41568089A 1989-10-02 1989-10-02
US415,680 1989-10-02

Publications (1)

Publication Number Publication Date
WO1991004941A1 true WO1991004941A1 (fr) 1991-04-18

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4280990A (en) * 1979-12-11 1981-07-28 Hudson's Bay Oil And Gas Company Limited High pressure process for recovery of sulphur from gases
JPS60258294A (ja) * 1984-06-04 1985-12-20 Jgc Corp 天然ガスの脱硫精製方法
US4608363A (en) * 1980-07-21 1986-08-26 Aluminum Company Of America Activated alumina Claus catalyst having increased sodium oxide content

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4280990A (en) * 1979-12-11 1981-07-28 Hudson's Bay Oil And Gas Company Limited High pressure process for recovery of sulphur from gases
US4608363A (en) * 1980-07-21 1986-08-26 Aluminum Company Of America Activated alumina Claus catalyst having increased sodium oxide content
JPS60258294A (ja) * 1984-06-04 1985-12-20 Jgc Corp 天然ガスの脱硫精製方法

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