WO2004074178A1 - A single step removal of hydrogen sulfide from gases - Google Patents

A single step removal of hydrogen sulfide from gases Download PDF

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Publication number
WO2004074178A1
WO2004074178A1 PCT/US2003/018909 US0318909W WO2004074178A1 WO 2004074178 A1 WO2004074178 A1 WO 2004074178A1 US 0318909 W US0318909 W US 0318909W WO 2004074178 A1 WO2004074178 A1 WO 2004074178A1
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WO
WIPO (PCT)
Prior art keywords
solid
oxidant
gas
sulfur
regenerated
Prior art date
Application number
PCT/US2003/018909
Other languages
French (fr)
Inventor
Yongchun Tang
Mark Haught
Original Assignee
Sheeta Global Technology Corporation
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Filing date
Publication date
Application filed by Sheeta Global Technology Corporation filed Critical Sheeta Global Technology Corporation
Priority to AU2003245510A priority Critical patent/AU2003245510A1/en
Publication of WO2004074178A1 publication Critical patent/WO2004074178A1/en

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Classifications

    • 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
    • B01D53/52—Hydrogen sulfide
    • 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
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/81—Solid phase processes
    • 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
    • C01B17/48—Sulfur dioxide; Sulfurous acid
    • C01B17/50—Preparation of sulfur dioxide
    • C01B17/501—Preparation of sulfur dioxide by reduction of sulfur compounds
    • 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
    • C01B17/48—Sulfur dioxide; Sulfurous acid
    • C01B17/50—Preparation of sulfur dioxide
    • C01B17/508—Preparation of sulfur dioxide by oxidation of sulfur compounds

Definitions

  • the present invention relates to the field of gas treatment. Particularly, the
  • present invention relates to the removal of hydrogen sulflde from hydrogen sulfide
  • Hydrogen sulfide (H 2 S) is a major contaminant in natural gas. H 2 S is
  • This concentrated H 2 S-containing gas is then combusted to produce a gas with a H 2 S to
  • sulfur dioxide (SO 2 ) ratio of 2 to 1 in a Claus furnace This is followed by up to three rounds of Claus reaction at temperatures of around 250-280°C over an alumina catalyst to recover elemental sulfur.
  • the Claus reaction is exothermic and equilibrium limited.
  • reaction is conducted in up to three reaction stages
  • the Claus tail gas contains sulfur that must be further treated in an expensive tail
  • liquid adsorption such as amines
  • alkyline solution a metal ion-containing organic composition
  • solid phase adsorption
  • H 2 S can be removed through a liquid adsorption process.
  • Patent No. 6, 531 , 103 discloses a process in which H 2 S is contacted with a liquid
  • the liquid absorbent includes a metal ion-containing organic composition.
  • United States Patent No. 4, 647, 397 discloses a process and composition for removing
  • United States Patent No. 4, 889, 700 describes a ,
  • Patent No. 4, 539, 189 teaches a process and composition for removing H 2 S and like sulfides from gas streams by contact with a substituted aromatic nitrile having an electron-
  • H 2 S may be removed through solid phase adsorption.
  • the solid phase may be removed through solid phase adsorption.
  • metal-containing nanoparticles being selected from the group consisting of metal oxides, metal hydroxides and combination
  • precursors can be selectively absorbed from gas streams by contacting the gas stream at
  • a regenerative sorbent comprising a supported or unsupported
  • United States Patent No. 4, 489,047 describes a
  • 3,935,294 discloses a method for the separation of one component or more from a vapor or
  • United States Patent No. 5,306,476 teaches a continuous process for the removal of hydrogen sulfide from a gas stream using a membrane
  • the solid adsorption process only removes H 2 S from natural gas stream and the
  • post adsorption gas requires further treatment, preferably by the Claus process.
  • the use of solid adsorption is limited since the efficiency of solid adsorption is typically
  • H 2 S can be removed by a gas phase H 2 S reaction with gas oxidants (O, and
  • Patent No. 4,088,743 discloses a process for the conversion of H 2 S to SO 2 in a feed gas
  • the oxidation is conducted in the presence of an extremely stable oxidation
  • the multi-component catalyst includes an antimony-containing
  • Patent No. 4,623,533, 6,372,193, 6,299,851, 6,235,259, and 6,207,127 teach various combinations
  • phase reaction can not be directly applied to a H 2 S containing gas. Often it requires H 2 S is
  • H 2 S may be removed through a liquid phase reactant.
  • No. 5,215,728 discloses a method and apparatus for a hydrothermal treatment of a catalytic polyvalent metal redox absorption solution, after absorption of the H 2 S from an
  • Patent No. 5,122,351 teaches a catalytic polyvalent metal redox solution, which can be
  • United States Patent No. 4,202,864 teaches a method by contacting a flow of the steam with aqueous liquid reactant media consisting essentially of one or more reactive
  • No. 6,432,375 discloses a process of using sulfuric acid for removing hydrogen sulfide
  • 5,180,572 discloses a process where the hydrogen sulfide gas is contacted with a quinone
  • H 2 S may be removed by high temperature H 2 S dissociation or
  • One aspect of the present invention is directed to an unexpected discovery that a solid oxidant can directly oxidize H 2 S into element sulfur and/or sulfur dioxide without the need of introducing a gas oxidant or a liquid oxidant into the reaction.
  • Another aspect of the present invention is directed to a method of removing an H 2 S from a H 2 S containing gas.
  • the method comprises a) contacting the H 2 S containing gas with a solid oxidant; b) reacting the H 2 S with the solid oxidant to form a reduced solid oxidant and an elemental sulfur and/or a sulfur dioxide; and c) separating the element sulfur and/or the sulfur dioxide from a post-reaction gas.
  • Another aspect of the present invention is directed to a method of removing an H,S from a H 2 S containing gas comprising, a) introducing the H 2 S containing gas into a solid oxidant reactor containing a solid reactant, wherein the solid reactant comprises a solid oxidant; b) reacting the H,S with the solid oxidant to form a reduced solid oxidant and an element sulfur and/or a sulfur dioxide; and c) separating the element sulfur and/or the sulfur dioxide from a post-reaction gas at an outlet of the container.
  • Another aspect of the present invention is directed to a composition which
  • Another aspect of the present invention is directed to a composition which
  • Another aspect of the present invention is directed to a container which
  • the solid oxidant reactor tlirough the inlet, and a solid oxidant which is contained in the reactor and oxidizes H 2 S to form element sulfur and/or sulfur dioxide.
  • Figure 1 shows a reaction scheme for H,S removal using a solid oxidant. As a hydrogen sulfide containing gas is contacted with the solid oxidant, H 2 S is oxidized
  • Figure 2 shows an example of H 2 S removal using MgSO 4 as a solid oxidant.
  • MgSO 4 in the presence of a gas or liquid oxidant.
  • [O] refers to a gas oxidant including but not limited to air, O 2 , SO 3 , and NO 2 , or a liquid oxidant including but not limited to H,O 2
  • Figure 3 shows an apparatus used for H 2 S removal and post-reaction gas
  • Valve A is used to inter-
  • an inert gas such as Helium for the purpose of reactor conditioning
  • Valve B is used to choose the
  • valve B is to divert H 2 S containing gas into the reactor. In the non-H 2 S
  • valve A directs the inert gas to pass the reactor for solid oxidant dehydration or the gas oxidant to pass the reactor for solid oxidant regeneration.
  • reactor which contain a solid oxidant or a solid reactant is typically about 12
  • center meters and it is constructed using 7 mm I.D. medium wall quartz tubing.
  • reactor is maintained by using a heating tape and temperature can be varied in the range from room temperature up to 700 degree Celsius, preferably up to 500 degree Celsius.
  • the outlet D may also contain a glass trap (the U-
  • the sampling valve (labeled as E) is to
  • the gas chromatograph is equipped with a capillary column with a broad range of gas
  • the post-reaction gas For example, at the 100% conversion at which the post reaction gas
  • H 2 S free or containing less than about 4ppm H 2 S 100% of H 2 S is oxidized into S and/or SO 2 .
  • 40% conversion 40% of the H 2 S in the H 2 S containing gas is oxidized
  • the conversion rate is about 100%.
  • the conversion rate declines as
  • MgSO 4 gradually is reduced to MgSO 3 .
  • the reaction temperature is about 330°C.
  • Figure 5 shows the formation of element sulfur (S) after a H 2 S gas passes
  • Figure 6 shows the removal of H,S from a H 2 S containing gas over reaction
  • reaction temperature is 330°C.
  • Figure 7 shows the removal of H 2 S from a H 2 S containing gas over reaction
  • Figure 8 shows the removal of H 2 S from a H 2 S containing gas over reaction
  • Al 2 (SO 4 ) 3 is used in a H 2 S
  • Al 2 (SO 4 ) 3 is then regenerated to Al 2 (SO 4 ) 3 through oxidation by oxygen or air at 400°C.
  • Figure 9 shows the removal of H 2 S from, a H 2 S containing gas over reaction
  • Figure 10 shows the removal of H 2 S from a H 2 S containing gas over
  • Figure 11 shows sets of reactors containing a solid oxidant being used
  • a set of reactors (Set A) is used for H 2 S removal.
  • another set of reactors (Set B) undergoes regeneration for the
  • One aspect of the present invention is directed to an unexpected discovery
  • a solid oxidant can directly oxidize H 2 S into element sulfur and/or sulfur dioxide without the need of introducing a gas oxidant or a liquid oxidant into the reaction (See
  • Another aspect of the present invention is directed to a method of removing
  • the method comprises a) contacting the H 2 S
  • Another aspect of the present invention is directed to a method of removing
  • an H 2 S from a H 2 S containing gas comprising, a) introducing the H 2 S containing gas into a
  • solid oxidant reactor containing a solid reactant, wherein the solid reactant comprises a solid oxidant; b) reacting the H 2 S with the solid oxidant to form a reduced solid oxidant
  • Another aspect of the present invention is directed to a composition which
  • H,S comprises H,S and a solid oxidant wherein the solid oxidant oxidizes H,S to form element sulfur and/or sulfur dioxide.
  • Another aspect of the present invention is directed to a composition which
  • Another aspect of the present invention is directed to a container which
  • H 2 S containing gas refers to a gas that contains
  • H 2 S containing gases includes, but are not limited to, (1) a natural gas,
  • coal gasification process (4) a refinery hydrogen desulfurization gas, (5) an industrial
  • exhaust gas for example, a power plant exhaust gas that must meet the environmental H 2 S
  • solid oxidant used herein refers to a solid that is capable of
  • characteristics of a solid oxidant include 1) that the solid oxidant can react with H 2 S at a
  • H 2 S is converted or oxidized to form elemental sulfur and/or sulfur dioxide.
  • the solid oxidant after oxidizing H 2 S into elemental sulfur and/or sulfur dioxide be able to be re-oxidized or regenerated either by a gas oxidant (such as air O 2 , SO 3 , and
  • a solid oxidant can be dehydrated
  • the solid oxidant used herein can be a solid sulfate oxidant or a solid non-
  • the solid sulfate oxidant is a salt of sulfate (SO 4 2" ) capable of being
  • solid sulfate oxidants include, but are not limited to, MgSO 4 , CaSO 4 , SrSO 4 , BaSO 4 , Al 2 (SO 4 ) 2 , FeSO 4 , K.SO,, and Na 2 SO 4 .
  • the solid non-sulfate oxidants include, but are not limited to, MgSO 4 , CaSO 4 , SrSO 4 , BaSO 4 , Al 2 (SO 4 ) 2 , FeSO 4 , K.SO,, and Na 2 SO 4 .
  • sulfate oxidant is a solid metal oxide or a solid non-metal oxide which includes a solid
  • a solid non-sulfate oxidant is in an
  • Example of solid polymer-based oxidants include, but are not limited to, Polystyrene based pyrazolinium Cr[IV], Polyacenaphthylene supported t-
  • solid of interest is indeed a solid oxidant, the solid of interest can be placed in a solid
  • solid of interest is a preferred solid oxidant.
  • the gas oxidant is an oxidant in gas phase and includes but is not limited to O 2 , NO 2 , SO 3 or air.
  • the liquid oxidant is an oxidant in liquid phase and includes but is not limited to
  • the reduced form of the solid oxidant or the reduced solid oxidant refers to
  • MgSO 4 a solid oxidant
  • MgSO 3 a reduced solid oxidant
  • a reduced solid oxidant can be any suitable solid oxidant.
  • a gas oxidant such as O 2 , NO 2 , SO 3 and air
  • a liquid oxidant such as H 2 O 2
  • reaction gas are known to an ordinary skilled artisan.
  • SO 2 can be separated
  • SO 2 can also be separated through solid absorption in, for example,
  • the separated SO can be applied to a number of
  • Element sulfur is in a liquid
  • a post reaction temperature is below the melting point of elemental sulfur (about 110°C),
  • a solid oxidant reactor's outlet is kept at a post reaction temperature
  • element sulfur is separated from the post reaction gas,as a
  • the outlet contains a collection trap that holds
  • temperature applied to the outlet is between about 120°C and about 220°C, the element
  • the water-free element sulfur is a desirable
  • post-reaction gas refers to a reacted gas from a H 2 S
  • the post-reaction gas contain remaining or residual H 2 S
  • the residual H 2 S is less than the progenitor gas. In another preferred embodiment, the residual H 2 S is less than the progenitor gas. In another preferred embodiment, the residual H 2 S is less than the progenitor gas. In another preferred embodiment, the residual H 2 S is less than the progenitor gas. In another preferred embodiment, the residual H 2 S is less than the progenitor gas. In another preferred embodiment, the residual H 2 S is less than the progenitor gas. In another preferred embodiment, the residual H 2 S is less than the progenitor gas. In another preferred embodiment, the residual H 2 S is less than the progenitor gas. In another preferred embodiment, the residual H 2 S is less than the progenitor gas. In another preferred embodiment, the residual H 2 S is less than the progenitor gas. In another preferred embodiment, the residual H 2 S is less than the progenitor gas. In another preferred embodiment, the residual H 2 S is less than the progenitor gas. In another preferred embodiment, the residual H 2 S is less than the progenitor gas
  • lOOppm in the post-reaction gas preferably less than lOppm, more preferably less
  • the gas can be viewed as a post reaction gas substantially
  • the post-reaction gas can be reintroduced into a reactor for one or more rounds of H 2 S reaction or conversions to render a final post-reaction gas with H 2 S of
  • reactor or "solid oxidant reactor” used herein refers to a
  • the reactor usually has one inlet and one
  • the reactor may have various shapes, for example, cylindrical shape or
  • coaxial reactor It is preferred that the reactor is cylindrical.
  • the reactor can be placed in
  • the reactor is place vertically with an inlet at the top of the reactor and an outlet at the bottom of the
  • both sets can be used for H 2 S reaction or conversion at the same time
  • solid material or “solid reactant” used herein refers to a solid
  • the solid reactant must contain a solid
  • the solid reactant may further contain a solid catalyst.
  • the solid catalyst is
  • transition metals such as Co and Ni
  • base metal such as Aluminum and Magnesium
  • transition metals may improve the H,S conversion.
  • solid catalysts also include
  • Fe/MgO See, Jung KD et al., APPLIED CATALYSIS
  • a solid catalyst may facilitate the speed or kinetics of a
  • MgSO 4 is used as a solid oxidant, H 2 O is produced as one of the end products (See Figure
  • a solid reactant may further comprise a solid medium that supports a solid
  • the solid medium is a material with various shape or porousness on which a
  • solid oxidant may be mounted. It is contemplated that the surface area of the solid oxidant
  • solid oxidants of various types are present in various embodiments. Accordingly, in a preferred embodiment, solid oxidants of various types.
  • zeolite a solid medium
  • zeolite a solid medium
  • reaction temperature refers to a temperature applied to an H 2 S conversion or reaction. It is preferred that a reaction temperature is between
  • the temperature is between about 100°C and about 700°C. It is more preferred that the temperature is between about 100°C and about 700°C. It is more preferred that the temperature is between about 100°C and about 700°C. It is more preferred that the temperature is between about 100°C and about 700°C. It is more preferred that the temperature is between about 100°C and about 700°C. It is more preferred that the temperature is between about 100°C and about 700°C. It is more preferred that the temperature is between about
  • a preferred reaction temperature may depend on the choice of a
  • reaction temperature for MgSO4 ranges from about 200°C to about 400°C, preferably from about 300°C to 350°C.
  • reaction temperature for MgSO4 ranges from about 200°C to about 400°C, preferably from about 300°C to 350°C.
  • SrSO4 ranges from about 250°C to about 450°C, preferably from about 330°C to about
  • reaction temperature for Al,(SO4) 3 ranges from about 150°C to about 350°C
  • reaction temperature preferably from about 220°C to about 300°C.
  • the adjustment and optimization of a reaction temperature are within the skills of an ordinary artisan.
  • post reaction temperature is a temperature applied to a post
  • reaction gas to separate element sulfur and/or sulfur dioxide from the post reaction gas.
  • the post reaction temperature is applied at the outlet of a reactor.
  • reaction temperature to separate element sulfur ranges from about 25°C to about 250°C.
  • the post reaction temperature is preferably at a temperature where water is in a gas phase. In this case, a preferred post reaction
  • the post reaction temperature ranges from about 120°C to about 200°C.
  • flow rate refers to a volume of a gas in a given time
  • the flow rate of a gas depends on, for
  • present invention significantly lower the cost of removing H,S from a H,S containing gas
  • H 2 S removal in the present invention can be
  • EXAMPLE I An apparatus has been constructed to conduct a H,S
  • the apparatus has been constructed H,S removal as shown in FIG 3.
  • the first valve (labeled as A in FIG 3) is for a switch between oxygen (or other gas oxidants, such as air, SO 3 and fuming sulfuric acid)
  • This valve is used for the regeneration of the solid oxidant in the reactor by
  • the second valve (labeled as B) is to divert a carrier gas (for example Helium: "He" as
  • C (labeled as C) is typically about 12 center meters long and 7 mm I.D. in a medium wall
  • temperature can be maintained by using a heating tape and temperature can be varied in
  • An outlet is connected to the end of the reactor.
  • the outlet also contains a
  • the glass trap (labeled as D in FIG 3) to condense both elemental sulfur and water.
  • the dual- loop sampling valve (labeled as E in FIG 3) is to divert reactor effluent (a post reaction .
  • the gas chromatograph (F in FIG 3) is equipped with a capillary column
  • the thermal conductivity detector was used to detect and analyze all gas
  • EXAMPLE II Solid oxidant MgSO 4 oxidizes H 2 S in a H 2 S containing gas.
  • FIG 4 shows the plot of H 2 S conversion
  • the reduced form of MgSO 4 can be regenerated by a gas oxidant to a liquid oxidant
  • EXAMPLE III Solid oxidant SrSO4 oxidizes H 2 S in a H 2 S containing gas.
  • the reactor Prior to the H 2 S conversion, the reactor was heated to 330 degree Celsius with helium gas
  • the reduced form of SrSO 4 can be regenerated by a gas oxidant to a liquid oxidant
  • EXAMPLE V Al 2 (SO 4 ) 3 can be regenerated by oxygen or air.
  • FIG 8 shows that during the first 20 minutes 100% H 2 S was converted in the
  • EXAMPLE VI Al 2 (SO 4 ) 3 can be regenerated by SO 3 .
  • FIG 10 shows the H 2 S conversion versus time using the regenerated

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Abstract

The present invention is directed to methods of removing H2S from a H2S containing gas by reacting H2S with a solid oxidant directly without the need of introducing a gas oxidant into the reaction. When H2S is reacted with the solid oxidant, H2S is oxidized into element sulfur and/or sulfur dioxide, both of which can be easily purified and separated from a post reaction gas substantially free of H2S. Therefore, the invented methods provided by the present invention offer significant advantages in removing H2S from H2S containing gases as well as recovering element sulfur and/or sulfur dioxide from H2S.

Description

A SINGLE STEP REMOVAL OF HYDROGEN STJLFIDE
FROM GASES
RELATED APPLICATION
[0001] This application claims the benefit of U.S. Provisional Application No.
60/447,503, filed February 19, 2003, which is hereby incorporated by reference in its
entirety including drawings as fully set forth herein.
FIELD OF THE INVENTION [0002] The present invention relates to the field of gas treatment. Particularly, the
present invention relates to the removal of hydrogen sulflde from hydrogen sulfide
containing gases.
KGROU D OF THE INVENTION [0003] Hydrogen sulfide (H2S) is a major contaminant in natural gas. H2S is
corrosive, toxic, and even deadly, posing serious environmental hazard and health risks.
Therefore, H2S must be removed during a gas process before gas can be utilized in both
domestic and industrial settings.
[0004] A traditional method for H2S removal, commonly known as the Claus
process, involves a number of steps including amine scrubbing at a low temperature
followed by amine regeneration using steam to produce a concentrated H2S-containing gas.
This concentrated H2S-containing gas is then combusted to produce a gas with a H2S to
sulfur dioxide (SO2) ratio of 2 to 1 in a Claus furnace. This is followed by up to three rounds of Claus reaction at temperatures of around 250-280°C over an alumina catalyst to recover elemental sulfur. The Claus reaction is exothermic and equilibrium limited. To
circumvent equilibrium limitations, the reaction is conducted in up to three reaction stages
with interstage cooling/ sulfur condensation followed by interstage re-heating. However,
even with three stages, the reaction is not complete due to thermodynamic limitations at
250°C. The Claus tail gas contains sulfur that must be further treated in an expensive tail
gas treatment plant before discharge. Thus, overall H2S removal and sulfur recovery using
the Claus process is extremely cumbersome, equipment intensive, and expensive.
[0005] Other approaches have been developed to remove H2S from gas. In
general, these approaches can be classified as (1) liquid adsorption, such as amines,
alkyline solution, a metal ion-containing organic composition; (2) solid phase adsorption;
(3) gas phase H2S reaction with a gas oxidant (O2 and/or SO3) using solid phase catalysis;
(4) liquid phase reaction (such as FeSO4 and H2SO4); and (5) high temperature H2S
dissociation or thermal cracking.
[0006] H2S can be removed through a liquid adsorption process. United States
Patent No. 6, 531 , 103 discloses a process in which H2S is contacted with a liquid
absorbent. The liquid absorbent includes a metal ion-containing organic composition.
The H2S and the liquid absorbent form sulfur-metal cation coordination complexes in
which the oxidation state of the sulfur and the metal ion remains essentially unchanged.
United States Patent No. 4, 647, 397 discloses a process and composition for removing
H2S and like sulfides from gas streams by contact with a substituted aromatic nitrile
having an electron-attracting substituent on the aromatic ring at least as strong as halogen
(e.g., isophthalonitrile) and an organic tertiary amine in an inert organic solvent such as N- methyl-2-pyrrolidone. United States Patent No. 3, 941, 875 describes a process for
treating a hydrogen sulfide-containing gas in a closed loop system wherein the gas is
passed through and absorbed by an alkaline aqueous absorbent containing an alkali
carbonate and an oxidation catalyst. United States Patent No. 4, 889, 700 describes a ,
method and devices for the selective removal of H2S from an H2S-containing gas by
contacting the gas in an absoiption column with an H2S-selective absorbent liquid. United
States Patent No. 4, 844, 876 teaches a method for the selective removal of H2S from a
H2S-containing gas by operating in a single column comprising an upper absorption zone
and a lower regeneration zone separated by a medial enrichment zone. United States
Patent No. 4, 539, 189 teaches a process and composition for removing H2S and like sulfides from gas streams by contact with a substituted aromatic nitrile having an electron-
attracting substituent on the aromatic ring at least as strong as halogen (e.g.,
isophthalonitrile) and an organic tertiary amine in an inert organic solvent such as N- methyl-2-pyrrolidone. However, the liquid adsorption process only removes H2S from
natural gas stream and the post adsorption gas requires further treatment, preferably the
Claus process. Overall, the application of liquid adsorption is limited since liquid
adsorption is not suitable for H2S-containing gas with high concentration of H,S.
[0007] H2S may be removed through solid phase adsorption. The solid phase
adsorption processes is primarily involved in physical adsorption of H2S onto a solid
absorbent. For example, United States Patent No. 6,447,577 discloses a method for
removing H2S from hydrocarbon streams by using metal-containing nanoparticles being selected from the group consisting of metal oxides, metal hydroxides and combination
thereof, whereby the nanoparticles absorb the contaminants from the stream. United States Patent No. 3, 974, 256 describes a process where hydrogen sulfide and its
precursors can be selectively absorbed from gas streams by contacting the gas stream at
elevated temperatures with a regenerative sorbent comprising a supported or unsupported
lanthanum or rare earth metal component. United States Patent No. 4, 489,047 describes a
process for removing hydrogen sulfide using solid acceptors. United States Patent No.
3,935,294 discloses a method for the separation of one component or more from a vapor or
gas mixture which involves the step of reacting the component to form a complex or thermally decomposable molecule by reaction with a compound adsorbed or otherwise
deposited on a solid carrier. United States Patent No. 5,306,476 teaches a continuous process for the removal of hydrogen sulfide from a gas stream using a membrane
comprising a metal oxide deposited on a porous support. Similar to the liquid adsorption
process, the solid adsorption process only removes H2S from natural gas stream and the
post adsorption gas requires further treatment, preferably by the Claus process. In general, the use of solid adsorption is limited since the efficiency of solid adsorption is typically
lower than liquid adsorption.
[0008] H2S can be removed by a gas phase H2S reaction with gas oxidants (O, and
SO3) using solid phase catalysis. This process uses a solid reactant and it also converts
H2S into elemental sulfur in. the presence of a gas oxidant such as O2 and SO3. The Claus
process can be viewed as one example of this type of process. In addition, United States
Patent No. 4,088,743 discloses a process for the conversion of H2S to SO2in a feed gas
containing H2S through oxidation with air or oxygen at temperatures between 300 °F. and
900 °F.. The oxidation is conducted in the presence of an extremely stable oxidation
catalyst comprising an oxide and/or sulfide of vanadium supported on a non-alkaline porous refractory oxide. United States Patent No. 6,251 ,359 discussed a method for
I selectively oxidizing hydrogen sulfide to elemental sulfur in the presence of a multi-
component catalyst. The multi-component catalyst includes an antimony-containing
substance and a vanadium-and-magnesium-coήtaining material. The hydrogen sulfide ,with
oxygen and nitrogen reacts on the catalyst to form sulfur. Furthermore, United States
Patent No. 4,623,533, 6,372,193, 6,299,851, 6,235,259, and 6,207,127 teach various
processes whereby H2S-containing gases are desulfurized by direct catalytic oxidation of
the H2S to elemental sulfur in the presence of an oxygen-containing gas. However, gas
phase reaction can not be directly applied to a H2S containing gas. Often it requires H2S is
first separated from a H2S containing gas by, for example, the Claus process, and the separated H,S is oxidized by a gas phase reaction.
[0009] H2S may be removed through a liquid phase reactant. United States Patent
No. 5,215,728 discloses a method and apparatus for a hydrothermal treatment of a catalytic polyvalent metal redox absorption solution, after absorption of the H2S from an
H2S containing gas stream, to avoid substantial buildup of thiosulfate salts, cyanide salts,
and cyanide complexes in the catalytic polyvalent metal redox solution. United States
Patent No. 5,122,351 teaches a catalytic polyvalent metal redox solution, which can be
recovered and re-used in a catalytic polyvalent metal redox solution for H2S-removal.
United States Patent No. 4,202,864 teaches a method by contacting a flow of the steam with aqueous liquid reactant media consisting essentially of one or more reactive
compounds of certain metals which form solid metal sulfide reaction products and are
electropositive with respect to hydrogen. United States Patent No. 5,167,940 teaches a
method for converting H2S to sulfur in a catalytic polyvalent metal redox absorption solution. United States Patent No. 4,332,781 teaches that hydrogen sulfide and carbonyl
sulfide can be removed from a gas stream in a staged procedure characterized by
conversion of the hydrogen sulfide to produce sulfur in an aqueous solution, hydrolysis of
the carbonyl sulfide remaining in the gas stream to produce hydrogen sulfide and carbon
dioxide, and removal of the hydrogen sulfide from the gas stream. United States Patent
No. 6,432,375 discloses a process of using sulfuric acid for removing hydrogen sulfide
from a gas stream, such as sour natural gas, with the formation of elemental sulfur as a by¬
product. United States Patent No. 5,698,171 teaches that H2S is contacted with an aqueous
scavenging mixture which includes a scavenging compound. United States Patent No.
5,180,572 discloses a process where the hydrogen sulfide gas is contacted with a quinone
in an aqueous solvent containing a sulfur complexing agent to yield sulfur and the
corresponding hydroquinone. United States Patent No. 4,693,881 teaches the conversion of H,S into sulfur by allowing the H,S mixture to contact with an acidic iron sulfate
solution. However, it is often difficult to obtain desirable end products, for example,
element sulfur, in liquid reaction. Separation of element sulfur from liquid further increases the cost of operation.
[0010] Finally, H2S may be removed by high temperature H2S dissociation or
thermal cracking. This process requires high temperature to decompose H2S into sulfur
and hydron (See, for example, United States Patent No. 6,403,051). However, usually the
temperature for these processes usually is greater than 900°C and limits practical
application. [0011] Overall, existing H2S removal processes often require multiple steps, multiple components, high pressure, high temperature, and high capital or operation cost. Therefore, there is a need for a more simplified and cost effective method of removing H2S from H2S-containing gases. ' (
SUMMARY OF THE INVENTION
[0012] One aspect of the present invention is directed to an unexpected discovery that a solid oxidant can directly oxidize H2S into element sulfur and/or sulfur dioxide without the need of introducing a gas oxidant or a liquid oxidant into the reaction.
[0013] Another aspect of the present invention is directed to a method of removing an H2S from a H2S containing gas. The method comprises a) contacting the H2S containing gas with a solid oxidant; b) reacting the H2S with the solid oxidant to form a reduced solid oxidant and an elemental sulfur and/or a sulfur dioxide; and c) separating the element sulfur and/or the sulfur dioxide from a post-reaction gas.
[0014] Another aspect of the present invention is directed to a method of removing an H,S from a H2S containing gas comprising, a) introducing the H2S containing gas into a solid oxidant reactor containing a solid reactant, wherein the solid reactant comprises a solid oxidant; b) reacting the H,S with the solid oxidant to form a reduced solid oxidant and an element sulfur and/or a sulfur dioxide; and c) separating the element sulfur and/or the sulfur dioxide from a post-reaction gas at an outlet of the container. [0015] Another aspect of the present invention is directed to a composition which
comprises H2S and a solid oxidant wherein the solid oxidant oxidizes H2S to form element
sulfur and/or sulfur dioxide.
[0016] Another aspect of the present invention is directed to a composition which
comprises a H2S containing gas and a solid oxidant wherein the solid oxidant oxidizes H2S
to form element sulfur and/or sulfur dioxide.
[0017] Another aspect of the present invention is directed to a container which
comprises a reactor with an inlet and an outlet, a H2S containing gas which is introduced to
the solid oxidant reactor tlirough the inlet, and a solid oxidant which is contained in the reactor and oxidizes H2S to form element sulfur and/or sulfur dioxide.
BRIEF DESCRIPTION OF THE DRAWINGS
[0018] Figure 1 shows a reaction scheme for H,S removal using a solid oxidant. As a hydrogen sulfide containing gas is contacted with the solid oxidant, H2S is oxidized
to form element sulfur (S) and/or sulfur dioxide (SO2). Simultaneously, the solid oxidant
is reduced to a reduced form of the solid oxidant which can be regenerated in the presence
of gas oxidants or liquid oxidants.
[0019] Figure 2 shows an example of H2S removal using MgSO4 as a solid oxidant.
In the reaction, hydrogen sulfide is oxidized to form element sulfur and/or sulfur dioxide
and the solid oxidant MgSO4 is reduced to become MgSO3. MgSO3.can be regenerated to
MgSO4.in the presence of a gas or liquid oxidant. [O] refers to a gas oxidant including but not limited to air, O2, SO3, and NO2, or a liquid oxidant including but not limited to H,O2
and H2SO4.
[0020] Figure 3 shows an apparatus used for H2S removal and post-reaction gas
testing. There are two three-way valves (A and B) in the figure. Valve A is used to inter-
change between an inert gas (such as Helium for the purpose of reactor conditioning) and a
gas oxidant (such as air, O2, SO3 and fuming sulfuric acid). Valve B is used to choose the
operation either at the H2S removal mode or at the non-H2S removal mode. In the H2S
removal mode, the valve B is to divert H2S containing gas into the reactor. In the non-H2S
removal mode, the valve A directs the inert gas to pass the reactor for solid oxidant dehydration or the gas oxidant to pass the reactor for solid oxidant regeneration. The •
reactor (labeled as C) which contain a solid oxidant or a solid reactant is typically about 12
center meters and it is constructed using 7 mm I.D. medium wall quartz tubing. The
advantage of use quartz tubing is to minimize any H2S absorption. The temperature at the
reactor is maintained by using a heating tape and temperature can be varied in the range from room temperature up to 700 degree Celsius, preferably up to 500 degree Celsius. A
gas is introduced into the reactor through an inlet (See the Metering Valve) and released to
an outlet of the reactor (See region D). The outlet D may also contain a glass trap (the U-
shape gas trap) to condense both elemental sulfur. The sampling valve (labeled as E) is to
divert a post reaction gas either to a vent or to a gas clrromatograph (labeled as F in FIG
3). The gas chromatograph is equipped with a capillary column with a broad range of gas
analysis (called GS GasPro from J& W Scientific) and the thermal conductivity detector
(TCD) in the gas chromatograph is used to analyze all gases. [0021] Figure 4 shows the removal of H2S from a H2S containing gas over reaction
time in the presence of a solid oxidant MgSO4. A H2S containing gas containing about
10% H2S in argon continuously passes through a solid oxidant reactor as shown in Figure
3 and the post-reaction gas is analyzed by gas chromatography.. The conversion value
represents the amount of H2S in the H2S containing gas that is oxidized into element sulfur
(S) and/or sulfur dioxide (SO2) and is inversely related to the remaining amount of H2S in
the post-reaction gas. For example, at the 100% conversion at which the post reaction gas
is either H2S free or containing less than about 4ppm H2S, 100% of H2S is oxidized into S and/or SO2. At the 40% conversion, 40% of the H2S in the H2S containing gas is oxidized
to S and/or SO2 and 60% remains in the post-reaction gas. The figure shows that during
the first 25 minutes, the conversion rate is about 100%. The conversion rate declines as
MgSO4 gradually is reduced to MgSO3. The reaction temperature is about 330°C.
[0022] Figure 5 shows the formation of element sulfur (S) after a H2S gas passes
through solid oxidant MgSO4. Element sulfur is visibly deposited at the outlet of a solid oxidant reactor.
[0023] Figure 6 shows the removal of H,S from a H2S containing gas over reaction
time in the presence of solid oxidant SrSO4. The reaction temperature is 330°C.
[0024] Figure 7 shows the removal of H2S from a H2S containing gas over reaction
time in the presence of solid oxidant Al2(SO4)3. Figure 7(a) shows the conversion value or
rate over reaction time. Figure 7(b) shows the formation and deposit of element sulfur at
the outlet of the solid oxidant reactor. The reaction temperature is 250°C. [0025] Figure 8 shows the removal of H2S from a H2S containing gas over reaction
time in the presence of regenerated solid oxidant Al2(SO4)3. Al2(SO4)3 is used in a H2S
removal reaction and reduced to a reduced form of Al2(SO4)3. The reduced form of
Al2(SO4)3 is then regenerated to Al2(SO4)3 through oxidation by oxygen or air at 400°C.
[0026] Figure 9 shows the removal of H2S from, a H2S containing gas over reaction
time in the presence of regenerated solid oxidant Al,(SO4)3. The reduced form of Al2(SO4)3
is regenerated to Al2(SO4)3 through oxidation by SO3 at 250°C.
[0027] Figure 10 shows the removal of H2S from a H2S containing gas over
reaction time in the presence of regenerated solid oxidant Al2(SO4)3. The reduced form of Al2(SO4)3 is regenerated to Al,(SO4)3 through oxidation by 97% H,SO4 at 250°C and
residual H,SO4 is expelled at 400°C for 2 hours.
[0028] Figure 11 shows sets of reactors containing a solid oxidant being used
parallelly for H,S removal reaction and regeneration. A set of reactors (Set A) is used for H2S removal. Concurrently, another set of reactors (Set B) undergoes regeneration for the
reduced solid oxidant by a gas oxidant or a liquid oxidant. After the solid oxidant in Set A
is exhausted or reduced and Set B is regenerated, H2S containing gas is switched to the
reactors of Set B for H2S removal, and simultaneously the gas oxidant or the liquid oxidant
is switched to the reactors of Set A for regeneration.
DETAILED DESCRIPTION OF THE INVENTION
[0029] One aspect of the present invention is directed to an unexpected discovery
that a solid oxidant can directly oxidize H2S into element sulfur and/or sulfur dioxide without the need of introducing a gas oxidant or a liquid oxidant into the reaction (See
Figure 1).
[0030] Another aspect of the present invention is directed to a method of removing
an H,S from a H2S containing gas. The method comprises a) contacting the H2S
containing gas with a solid oxidant; b) reacting the H2S with the solid oxidant to form a
reduced solid oxidant and an element sulfur and/or a sulfur dioxide; and c) separating the
element sulfur and/or the sulfur dioxide from a post-reaction gas.
[0031] Another aspect of the present invention is directed to a method of removing
an H2S from a H2S containing gas comprising, a) introducing the H2S containing gas into a
solid oxidant reactor containing a solid reactant, wherein the solid reactant comprises a solid oxidant; b) reacting the H2S with the solid oxidant to form a reduced solid oxidant
and an element sulfur and/or a sulfur dioxide; and c) separating the element sulfur and/or
the sulfur dioxide from a post-reaction gas at an outlet of the container.
[0032] Another aspect of the present invention is directed to a composition which
comprises H,S and a solid oxidant wherein the solid oxidant oxidizes H,S to form element sulfur and/or sulfur dioxide.
[0033] Another aspect of the present invention is directed to a composition which
comprises a H2S containing gas and a solid oxidant wherein the solid oxidant oxidizes H2S
to form element sulfur and/or sulfur dioxide.
[0034] Another aspect of the present invention is directed to a container which
comprises a reactor with an inlet and an outlet, a H2S containing gas which is introduced to the solid oxidant reactor through the inlet, and a solid oxidant which is contained in the •
reactor and oxidizes H2S to form element sulfur and/or sulfur dioxide.
[0035] The term "H2S containing gas" used herein refers to a gas that contains
from about 0.001 % to about 100% of H2S, preferably from about 0.01 % to about 20%' qf
H2S. Examples of H2S containing gases includes, but are not limited to, (1) a natural gas,
(2) a refinery process stream gas, (3) a synthetic gas from sulfur containing coal from a
coal gasification process, (4) a refinery hydrogen desulfurization gas, (5) an industrial
exhaust gas, for example, a power plant exhaust gas that must meet the environmental H2S
standard, (6) an oil and gas refinery waste stream, (7) a residual gas from a sulfur plant, (8) a gas after treatment of sulfur dioxide containing fuel gas, (9) a H2S gas generated due to
steam injection of heavy oil recovery, (10) a heavy oil upgrading gas, (11) a shale oil
recovery gas, (12) a vent gas from, for example, oil-gas production, chemical processing,
storage tanks, wastewater treatment, control systems and laboratories, (13) a gas from wet wells, (14) a landfill gas, (15) a municipal and industrial biogas, and (16) a geothermal
natural gas.
[0036] The term "solid oxidant" used herein refers to a solid that is capable of
oxidizing H2S to form element sulfur (S) and/or sulfur dioxide (SO2) or oxidizing H2S in a
H2S containing gas to form element sulfur (S) and/or sulfur dioxide (SO,). The identifying
characteristics of a solid oxidant include 1) that the solid oxidant can react with H2S at a
temperature below about 700°C, preferably between about 100°C and about 700°C, and 2)
that H2S is converted or oxidized to form elemental sulfur and/or sulfur dioxide.
Preferably, the solid oxidant after oxidizing H2S into elemental sulfur and/or sulfur dioxide be able to be re-oxidized or regenerated either by a gas oxidant (such as air O2, SO3, and
NO2) and/or a liquid oxidant (such as H2SO4 and H2O2). A solid oxidant can be dehydrated
or hydrated. It is further contemplated that a plurality of solid oxidants can be used in the same H2S conversion.
[0037] The solid oxidant used herein can be a solid sulfate oxidant or a solid non-
sulfate oxidant. The solid sulfate oxidant is a salt of sulfate (SO4 2") capable of being
thermally reduced. Examples of solid sulfate oxidants include, but are not limited to, MgSO4, CaSO4, SrSO4, BaSO4, Al2(SO4)2, FeSO4, K.SO,, and Na2SO4. The solid non-
sulfate oxidant is a solid metal oxide or a solid non-metal oxide which includes a solid
polymer-based oxidant. Like a solid sulfate oxidant, a solid non-sulfate oxidant is in an
oxidation state and capable of being thermally reduced. Examples of solid metal oxides
include, but are not limited to, CuO, MnO2, Fe2O3, Fe3O4, KMnO4, and Peroxide (such as
Percarbonate and Perborate). Example of solid polymer-based oxidants include, but are not limited to, Polystyrene based pyrazolinium Cr[IV], Polyacenaphthylene supported t-
butyl chromates, Poly[N-[2-aminoethyl]acrylamido] triethylammoniumpolyhalides,
Polystyrene based pyrazolinium permanganates, and 1,4-Butanediol dimethacrylate crosslinked polyacenaphthylene.
[0038] To examine or determine whether a solid suspected to be a solid oxidant (a
solid of interest) is indeed a solid oxidant, the solid of interest can be placed in a solid
oxidant reactor as shown in Figure 3. A H2S containing gas is allowed to pass through the
reactor containing the solid of interest and a post-reaction gas is analyzed by gas
chromatography. An indication of H2S conversion in the post-reaction gas suggests that the solid of interest is capable of oxidizing H2S and the solid of interest can be regarded, as
a solid oxidant. After the reaction, the solid of interest is further treated with a gas oxidant
or a liquid oxidant for regeneration and then is reacted with a H2S containing gas. If the
regenerated solid of interest demonstrates a reproducible capability of oxidizing H2S, the
solid of interest is a preferred solid oxidant.
[0039] The term "reaction", "H2S reaction", "H2S conversion", or "conversion"
used herein refers to a chemical reaction wherein a solid oxidant is contacted with H2S and
undergoes an oxidization and reduction process at a temperature below about 700°C. While a H2S containing gas is introduced in the reaction for H2S to contact with a solid
oxidant, it is not necessary to introduce a gas oxidant or a liquid oxidant into the reaction.
The gas oxidant is an oxidant in gas phase and includes but is not limited to O2, NO2, SO3 or air. The liquid oxidant is an oxidant in liquid phase and includes but is not limited to
H2O2 and H2SO4.
[0040] The reaction between a solid oxidant and H2S gives rise to a reduced form
of the solid oxidant (a reduced solid oxidant) and element sulfur and/or sulfur dioxide. A
H2S containing gas after the reaction becomes a post reaction gas.
[0041] The reduced form of the solid oxidant or the reduced solid oxidant refers to
a reduction product of the solid oxidant after being reduced in a reaction. As an example,
after a H2S reaction, MgSO4, a solid oxidant, is reduced to MgSO3, a reduced solid oxidant.
In a preferred embodiment of the present invention, a reduced solid oxidant can be
regenerated or oxidized back to the solid oxidant, or a regenerated solid oxidant that has
the identifying characteristics of the original solid oxidant. Methods for regenerating reduced oxidants are well known in the art. It is preferred that a reduced solid oxidant is
regenerated by a gas oxidant such as O2, NO2, SO3 and air, or a liquid oxidant such as H2O2
and H2SO4.
[0042] A H2S reaction under methods described herein converts H2S into element
sulfur and/or sulfur dioxide. It is observed that whether a reaction results element sulfur
alone, or sulfur dioxide alone, or both depends on the reaction conditions such as gas flow
rate, reaction temperature, amount of H2S in the H2S containing gas, and the type of solid
oxidant used. For example, in a reaction using MgSO4 as a solid oxidant with 10% H2S in
the H2S containing gas using the apparatus as shown in Figure 3, when a reaction
temperature is about 330°C and a flow rate of the gas is about 1.5ml/minute, no SO2 is observably formed. However, when the flow rate is slower than 1.5ml/minute, SO2 is
detected.
[0043] Methods for separating element sulfur and/or sulfur dioxide from a post-
reaction gas are known to an ordinary skilled artisan. For example, SO2 can be separated
from a post-reaction gas by liquid absorption such as absorption through an alkaline
aqueous solution. SO2 can also be separated through solid absorption in, for example,
carbon black, lime or limestone. The separated SO, can be applied to a number of
applications including, for example, the formation of H2SO4. Element sulfur is in a liquid
or solid phase in the post-reaction gas can be separated through temperature discrepancy
between the reaction and the post-reaction temperatures. For example, a post reaction
temperature can be applied at an outlet of a reactor so that the post reaction temperature is
sufficient enough for element sulfur to form a liquid or a solid. In a preferred embodiment, a post reaction temperature is below the melting point of elemental sulfur (about 110°C),
element sulfur will become a solid depositing at the outlet of a reactor. In another
preferred embodiment, a solid oxidant reactor's outlet is kept at a post reaction temperature
between about 120°C to 200°C, element sulfur is separated from the post reaction gas,as a
liquid and deposits in the outlet. Preferably, the outlet contains a collection trap that holds
the separated element sulfur. In another preferred embodiment, when a post reaction
temperature applied to the outlet is between about 120°C and about 220°C, the element
sulfur separated from the post reaction gas is water free since the element sulfur is in a
liquid phase and water is in a gas phase. The water-free element sulfur is a desirable
product in many industrial applications such as the fertilizer industry.
[0044] The term "post-reaction gas" used herein refers to a reacted gas from a H2S
containing gas in which H,S is converted through a reaction. In comparison to its
progenitor H2S containing gas, the post-reaction gas contain remaining or residual H2S
which is 80%) lower than that in the progenitor H,S containing gas. It is preferred that residual H,S is 90% lower than the progenitor gas. It is more preferred that residual H2S is
95% lower the progenitor gas. It is even more preferred that residual H2S is 99% lower
than the progenitor gas. In another preferred embodiment, the residual H2S is less than
about lOOppm in the post-reaction gas, preferably less than lOppm, more preferably less
than about 4ppm, most preferably less than about lppm. When a post reaction gas
contains less than 4ppm H,S, the gas can be viewed as a post reaction gas substantially
free of H2S or a H2S free gas. It is contemplated that if the post-reaction gas contains more
than about 4ppm H2S, the post-reaction gas can be reintroduced into a reactor for one or more rounds of H2S reaction or conversions to render a final post-reaction gas with H2S of
less than about 4ppm
[0045] The term "reactor" or "solid oxidant reactor" used herein refers to a
container where the reaction of converting H2S to element sulfur and/or sulfur dioxide in
the presence of a solid oxidant takes place. The reactor usually has one inlet and one
outlet, wherein the inlet is used for the introduction of a gas into the reactor and outlet is
used for the release of a gas outside of the reactor. It is within the scope of the present
invention that the reactor may have various shapes, for example, cylindrical shape or
coaxial reactor. It is preferred that the reactor is cylindrical. The reactor can be placed in
various positions, for example, horizontally or vertically. It is preferred that the reactor is place vertically with an inlet at the top of the reactor and an outlet at the bottom of the
reactor. It is further contemplated that a first set of reactors (Set A which includes reactors
A„ A,, — An, wherein "n" is an integer and n > 1) to which a H,S containing gas is introduced can be used for H,S conversion process. In the same time, a second set o
reactors to which a oxidant gas or liquid is introduced (Set B which includes reactors B„
B,, — Bn, wherein "n" is an integer and n > 1) is used for the solid oxidant regeneration
process. See, Figure 11. When the solid oxidants in the first set (Set A) are exhausted or
become reduced solid oxidants and the solid oxidants in the second set (Set B) have been
regenerated, the H2S containing gas is switched to the second set of reactors for H,S
reaction and the oxidant gas/liquid is introduced to the first set for regeneration. It is also
contemplated that both sets can be used for H2S reaction or conversion at the same time,
and both sets can be regenerated at the same time. It is within the scope of the present ' ' '
invention that a number of set As and Bs can be simultaneously used in removing H2S ■
from a H2S containing gases.
[0046] The term "solid material" or "solid reactant" used herein refers to a solid
used in a H2S reaction or placed in a reactor. The solid reactant must contain a solid
oxidant. The solid reactant may further contain a solid catalyst. The solid catalyst is
capable of lowering the S-H bond activation energy barrier. It is known in the art that
certain transition metals, such as Co and Ni, and base metal, such as Aluminum and Magnesium, may lower the S-H bond activation energy barrier. Accordingly, these
transition metals may improve the H,S conversion. Examples of solid catalysts also
include, but are not limited to, (1) Fe/MgO (See, Jung KD et al., APPLIED CATALYSIS
A-GENERAL, 240 (1-2): 235-241 (2003)); (2) SiC supported NiS2-based catalysts (See,
Keller N et al, Applied Catalysis A- General, 234 (1-2): 191-205 (2002)); (3) Vanadium
based catalyst (See, Kalinkin et al., REACTION KINETICS AND CATALYSIS
LETTERS 74 (1): 177-184 (2001)); and (4) iron oxide (See, Cantrell et al, ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 222: 64-GEOC Part 1
(2001)). It is contemplated that a solid catalyst may facilitate the speed or kinetics of a
H2S reaction by absorbing or removing end-products of the reaction. For example, when
MgSO4 is used as a solid oxidant, H2O is produced as one of the end products (See Figure
2). Absorption or removal of H2O by a hydroscopic salt may enhance the kinetics of the
reaction. Accordingly, it is within the scope of the present invention that solid catalysts
include hydroscopic salts. Examples of hydroscopic salts include, but are not limited to CaSO4, CaCl2, MgCl2, and A1C3. [0047] A solid reactant may further comprise a solid medium that supports a solid
oxidant. The solid medium is a material with various shape or porousness on which a
solid oxidant may be mounted. It is contemplated that the surface area of the solid oxidant
plays a role in the rate of an H2S reaction. It is observed that for the same weight mount of
the solid oxidant used the capacity and rate of the H2S reaction is inversely related to the
size of a solid oxidant. Accordingly, in a preferred embodiment, solid oxidants of various
sizes are mounted onto a porous solid medium. An example of a solid medium is zeolite.
[0048] The term "reaction temperature" used herein refers to a temperature applied to an H2S conversion or reaction. It is preferred that a reaction temperature is between
about 100°C and about 700°C. It is more preferred that the temperature is between about
200°C and about 500°C. A preferred reaction temperature may depend on the choice of a
solid oxidant. For example, the reaction temperature for MgSO4 ranges from about 200°C to about 400°C, preferably from about 300°C to 350°C. The reaction temperature for
SrSO4 ranges from about 250°C to about 450°C, preferably from about 330°C to about
430°C. The reaction temperature for Al,(SO4)3 ranges from about 150°C to about 350°C,
preferably from about 220°C to about 300°C. The adjustment and optimization of a reaction temperature are within the skills of an ordinary artisan.
[0049] The term "post reaction temperature" is a temperature applied to a post
reaction gas to separate element sulfur and/or sulfur dioxide from the post reaction gas. It
is preferred that the post reaction temperature is applied at the outlet of a reactor. The post
reaction temperature to separate element sulfur ranges from about 25°C to about 250°C. If
a water free element sulfur is desired, the post reaction temperature is preferably at a temperature where water is in a gas phase. In this case, a preferred post reaction
temperature ranges from about 120°C to about 200°C. The post reaction temperature to
separate sulfur dioxide from the post reaction gas using a liquid absoiption ranges from
about 25°C to about 100°C. I
[0050] The term "flow rate" used herein refers to a volume of a gas in a given time
introduced into a reactor. As known in the art, the flow rate of a gas depends on, for
example, H2S concentration in a gas, gas pressure, temperature, the nature of a solid
oxidant, the solid medium, porousness, size of an outlet of a reactor, or the ratio between
the sizes of an outlet and an inlet. The range of the flow rate is within the knowledge of an ordinary skilled artisan.
[0051] The embodiments disclosed in the present invention offer significant advantages not heretofore present in the art. For example, the methods provided in the
present invention significantly lower the cost of removing H,S from a H,S containing gas
by simplifying reactions into a single step. The methods pose no environmental hazards
since all resulting products or end products can be separated and utilized and therefore are
environmentally desirable. The methods convert H,S in a H2S containing gas directly to element sulfur and/or sulfur dioxide and therefore do not require the separation of H2S
from H2S containing gases first. In addition, H2S removal in the present invention can be
easily deployed on site at a location a H2S containing gas releases due to the simplicity of
reaction. The methods are also applicable to all H2S containing gases, regardless of the
H2S concentration. Moreover, the resulting products, such element sulfur, or water-free element sulfur, and/or sulfur dioxide, all have substantial commercial value and
application, let alone the value of H2S-free post reaction gas.
[0052] Having generally described the present invention, the same will be better
understood by reference to certain specific examples, which are set forth herein for the
purpose of illustration.
[0053] EXAMPLES
[0054] EXAMPLE I. An apparatus has been constructed to conduct a H,S
conversion reaction for the removal of H2S from a H2S containing gas.
[0055] The apparatus has been constructed H,S removal as shown in FIG 3. There
are two three-way valves in the drawing. The first valve(labeled as A in FIG 3) is for a switch between oxygen (or other gas oxidants, such as air, SO3 and fuming sulfuric acid)
and helium. This valve is used for the regeneration of the solid oxidant in the reactor by
introducing a gas oxidant into the solid oxidant reactor after the solid oxidant is reduced.
The second valve (labeled as B) is to divert a carrier gas (for example Helium: "He" as
labeled) and a H,S containing gas into the reactor. The actual heating zone of the reactor
(labeled as C) is typically about 12 center meters long and 7 mm I.D. in a medium wall
quartz tube. Quartz tubing minimizes surface adsoiption of H2S in the reactor. The reaction
temperature can be maintained by using a heating tape and temperature can be varied in
the range from room temperature up to 450 degree Celsius.
[0056] An outlet is connected to the end of the reactor. The outlet also contains a
glass trap (labeled as D in FIG 3) to condense both elemental sulfur and water. The dual- loop sampling valve (labeled as E in FIG 3) is to divert reactor effluent (a post reaction .
gas) either to the vent or to a gas chromatograph (labeled as F in FIG 3). There are dual
100 micro liter sampling-loops attached to the valve,
[0057] The gas chromatograph (F in FIG 3) is equipped with a capillary column
with a broad range of gas analysis (called GS GasPro from J&W Scientific). After the
capillary column, the thermal conductivity detector was used to detect and analyze all gas
components in the post reaction gas.
[0058] EXAMPLE II. Solid oxidant MgSO4 oxidizes H2S in a H2S containing gas.
[0059] In this embodiment, a H,S containing gas containing about 10% H,S in argon passed through the solid oxidant reactor in Figure 3 at the flow rate of 1 to 1.5
ml/minutes. The reactor was packed with about 4 gram of MgSO4. A reaction scheme for
H,S removal by MgSO4 is shown in Figure 2. Prior to the reaction, the reactor was heated
to 330 degree Celsius with helium gas flowing for about 3-4 hours to dehydrate MgSO4 in the reactor. Once the MgSO4 became dried, the H,S containing gas was allowed to pass
through the reactor. The conversion of H2S in the post reaction gas was measured based
on the H2S/Ar ratio of the H,S containing gas. FIG 4 shows the plot of H2S conversion
percentage versus time. At a slow flow rate less than 1.5ml/minute ( for example, about
0.5 ml/minute), SO, was detected in the post reaction gas. SO2 diminished when flow rate
increases. At a flow rate of 1.5 ml/minute, there was no observable SO,. Furthermore, during the first 25 minutes, the H,S conversion rate was 100%> . The conversion rate
declined when MgSO4 was gradually reduced. Element sulfur was separated from the post
reaction gas and deposited on the inner surface at the outlet of a reactor as shown in Figure 5. The reduced form of MgSO4can be regenerated by a gas oxidant to a liquid oxidant
(Figure 2).
[0060] EXAMPLE III Solid oxidant SrSO4 oxidizes H2S in a H2S containing gas.
[0061] In this embodiment, a H2S containing gas containing about 10%o H2S was
passed through the reactor at a flow rate of about 1 to about 1.5 ml/minutes in the
apparatus as shown in Figure 3. The reactor was loaded with about 6 grams of SrSO4.
Prior to the H2S conversion, the reactor was heated to 330 degree Celsius with helium gas
flowing for about 3-4 hours to dehydrate the SrSO4 in the reactor. The H2S containing gas was allowed to pass the reactor and the post reaction gas was detected and analyzed. The
plot of H2S percentage conversion versus time is shown in Figure 6. During the first 25
minutes, the H2S conversion rate was 100%) . The conversion rate declined when SrSO4
was gradually reduced. The reduced form of SrSO4 can be regenerated by a gas oxidant to a liquid oxidant
[0062] EXAMPLE IV. Solid oxidant Al,(SO4)3 oxidizes H,S in a H,S containing
gas.
[0063] In this experiment, the reactor was loaded with about 6g of Al2(SO4)3 and
prepared for reaction as described in Example II & III. The reactor was dehydrated for 4
hrs. at 350°C. A H2S containing gas containing about 10%> H2S was passed through the
reactor at the flow rate of 1 to 1.5 ml/minutes. Figure 7(a) shows the plot of H2S
percentage conversion versus time. During the first 15 minute, H2S conversion rate kept at 100%. Figure 7(b) shows that elemental sulfur was separated from the post reaction gas
and deposited at the outlet of the reactor.
[0064] EXAMPLE V. Al2(SO4)3 can be regenerated by oxygen or air.
I
[0065] This example shows that a solid oxidant can be regenerated after the solid
oxidant is reduced to a reduced solid oxidant after a H2S reaction. After two one-hour
reactions as described in Example IV, the Al2(SO4)3 in the reactor lost its ability to convert
H2S into elemental sulfur and/or sulfur dioxide due to the reduction of Al2(SO4)3. The
reactor was then applied to a temperature of about 400 degree Celsius and air was
introduced into the reactor. The reduced form of Al,(SO4)3 was re-oxidized by air for about
1.5 hours. After regeneration, the reactor temperature was reduced to 250 degree Celsius.
As soon as the temperature stabilized, a H2S containing gas was flowed through the reactor. FIG 8 shows that during the first 20 minutes 100% H2S was converted in the
presence of the regenerated Al,(SO4)3. The conversion over time plot appears to be the
same as the plot using a new Al,(SO4)3(comparing Figure 7 and Figure 8). This clearly
indicates that regeneration through air can be readily achieved.
[0066] EXAMPLE VI. Al2(SO4)3 can be regenerated by SO3.
[0067] This example shows that Al,(SO4)3 can also be regenerated by SO3. The
regeneration procedure was as described in Example V except that the SO3 passed the
reduced Al,(SO4)3 at a temperature of 250°C. Figure 9 shows H2S conversions over time
in the presence of regenerated Al2(SO4)3. Figure 9 also shows that the duration to keep
100% conversion rate (about 25 minutes) by using a regenerated Al2(SO4)3 appears longer ' (
than the original Al2(SO4)3 (about 20 minutes). The increase of Al2(SO4)3 conversion
capacity may be due to the oxidation of impurities in the original Al2(SO4)3.
[0068] EXAMPLE VII. Al2(SO4)3 can be regenerated by H2SO4.
[0069] This example shows that a solid oxidant can be regenerated by a liquid
oxidant. After Al2(SO4)3 in the reactor is completely reduced, concentrated H2SO4 is
loaded into at an inlet of the reactor at 250°C. The reactor was tilted upward with a helium
flow to force the H2SO4 into the reactor for 1 hr. The reactor was then heated to 400°C for
1 hr. with oxygen flowing to force out any water and residual H2SO4. The reactor was
cooled back down to 250°C and H2S removal began with a 10%H,S containing argon flowing at 1.5ml/min. FIG 10 shows the H2S conversion versus time using the regenerated
Al,(SO4)3.
[0070] Papers and patents cited in the disclosure are expressly incorporated by
reference in their entirety. It is to be understood that the description, specific examples, and figures, while indicating preferred embodiments, are given by way of illustration and
exemplification and are not intended to limit the present invention. Various changes and modifications within the present invention will become apparent to the skilled artisan from
the disclosure contained herein. Therefore, the spirit and scope of the appended claims
should not be limited to the description of the preferred versions contained herein.

Claims

What is claimed is:
1. A method of converting a H2S into an element sulfur and/or a sulfur dioxide
comprising reacting the H2S with a solid oxidant. ' ,
2. The method of claim 1 wherein the solid oxidant is a solid sulfate oxidant
or a solid non-sulfate oxidant.
3. The method of claim 2 wherein the solid sulfate oxidant is selected from
the group consisting of MgSO4, CaSO4, SrSO4, BaSO4, Al2(SO4)2, FeSO4, K.SO, and
Na2SO4.
4. The method of claim 2 wherein the solid non-sulfate oxidant is a solid metal oxidant or a solid polymer based oxidant.
5. The method of claim 4 wherein the solid metal oxidant is selected from CuO, MnO2, Fe2O3, Fe3O4. KMnO4, Peroxide, Percarbonate, and Perborate.
6. The method of claim 4 wherein the solid polymer based oxidant is selected from Polystyrene based pyrazolinium Cr[IV], Polyacenaphthylene supported t-butyl chromates, Poly[N-[2-aminoethyl]acrylamido] triethylammoniumpolyhalides, Polystyrene based pyrazolinium permanganates, and 1 ,4-Butanediol dimethacrylate crosslinked polyacenaphthylene.
7. The method of claim 1 wherein the solid oxidant is added with a solid
catalyst.
8. The method of claim 7 wherein the solid catalyst is selected from the group
consisting of a transition metal, a base metal, a Fe/MgO, a SiC supported NiS2-based
catalyst, a vanadium based catalyst, an iron oxide, and a hydroscopic salt.
9. The method of claim 1 wherein the solid oxidant is regenerated after
reacting with the H2S.
10. The method of claim 9 wherein the solid oxidant is regenerated by a gas
oxidant or a liquid oxidant. ' ,
11. The method of claim 10 the gas oxidant is selected from the group
consisting of air, O2, SO3, and NO2.
12. The method of claim 10 wherein the liquid oxidant is selected from the
group consisting of H2O2 and H,SO4.
13. The method of claim 1 wherein the H2S is reacted with the solid oxidant at
a reaction temperature between about 100°C and about 700°C.
14. The method of claim 1 wherein the reaction temperature is between about
200°C and 500°C. . .
15. A method of removing a H,S from a H,S containing gas comprising the
steps of: a) contacting the H,S containing gas with a solid oxidant;
b) reacting the H,S with the solid oxidant to form a reduced solid oxidant and
an element sulfur and/or a sulfur dioxide;
c) separating the element sulfur and/or the sulfur dioxide from a post-reaction
gas.
16. The method of claim 15 wherein the solid oxidant is a solid sulfate oxidant
or a solid non-sulfate oxidant.
17. The method of claim 16 wherein the solid sulfate oxidant is selected from
the group consisting of MgSO4, CaSO4, SrSO4, BaSO4, Al2(SO4)2, FeSO4, K.SO, and
Na2SO4. '
18. The method of claim 16 wherein the solid non-sulfate oxidant is a solid
metal oxidant or a solid polymer based oxidant.
19. The method of claim 18 wherein the solid metal oxidant is selected from CuO, MnO2, Fe2O3, Fe3O4. KMnO4, Peroxide, Percarbonate, and Perborate.
20. The method of claim 18 wherein the solid polymer based oxidant is selected from Polystyrene based pyrazolinium Cr[IV], Polyacenaphthylene supported t- butyl chromates, Poly[N-[2-aminoethyl]acrylamido] triethylammoniumpolyhalides, Polystyrene based pyrazolinium permanganates, and 1,4-Butanediol dimethacrylate crosslinked polyacenaphthylene.
21. The method of claim 15 wherein the solid oxidant is added with a solid catalyst.
22. The method of claim 21 wherein the solid catalyst is selected from the
group consisting of a transition metal, a base metal, a Fe/MgO, a SiC supported NiS2-
based catalyst, a vanadium based catalyst, an iron oxide, and a hydroscopic salt.
23. The method of claim 15 wherein the reduced solid oxidant is regenerated.
24. The method of claim 23 wherein the solid oxidant is regenerated by the gas
oxidant or a liquid oxidant.
25. The method of claims 24 wherein the gas oxidant is selected from the group
consisting of air, O2, SO3, and NO2.
26. The method of claims 24 wherein the liquid oxidant is selected from the .
group consisting of H2O2 and H2SO4.
27. The method of claim 15 wherein the H2S is reacted with the solid oxidant at
a reaction temperature between about 100°C and about 700°C.
28. The method of claim 15 wherein the reaction temperature is between about
200°C and about 500°C.
29 The method of claim 15 wherein the post reaction gas contains less than
about 100 ppm H2S.
30 The method of claim 15 wherein the post reaction gas contains less than about 10 ppm H2S .
31 The method of claim 15 wherein the post reaction gas is substantially free
of H2S.
32 The method of claim 15 wherein the element sulfur is separated from the
post reaction gas through a post reaction temperature.
33. The method of claim 32 the post reaction temperature is between about
25°C and about 250°C.
34. The method of claim 15 wherein the post reaction temperature is between
about 120°C and about 250°C and the element sulfur is a water-free sulfur.
35. The method of claim 15 wherein the sulfur dioxide is separated from the
post reaction gas through a liquid absoiption or a solid absorption.
36. The method of claim 35 wherein the liquid absoiption is an alkaline
aqueous absoiption.
37 The method of claim 35 wherein the solid absorption is a carbon black
absoiption, a lime absoiption, or a limestone absorption.
38. The method of claim 15 wherein the sulfur dioxide is used to form H2SO4.
39. T he method of claim 15 wherein the solid oxidant is mounted onto a solid
medium.
40. The method of claim 39 wherein the solid medium is porous.
41. A method of removing an H2S from a H2S containing gas comprising the
steps of:
a) introducing the H2S containing gas into a reactor containing a solid reactant, wherein the solid material comprises a solid oxidant;
b) reacting the H2S with the solid oxidant to form a reduced solid oxidant and
an element sulfur and/or a sulfur dioxide;
c) separating the element sulfur and/or the sulfur dioxide from a post-reaction gas at an outlet of the container.
42. The method of claim 41 wherein the solid oxidant is a solid sulfate oxidant
or a solid non-sulfate oxidant.
43. The method of claim 42 wherein the solid sulfate oxidant is selected from
the group consisting of MgSO4, CaSO4, SrSO4, BaSO4, Al,(SO4)2, FeSO4, K,SO4 and
Na2SO4.
44. The method of claim 42 wherein the solid non-sulfate oxidant is a solid metal oxidant or a solid polymer based oxidant.
45. The method of claim 44 wherein the solid metal oxidant is selected from CuO, MnO,, Fe2O3, Fe3O4. KMnO4, Peroxide, Percarbonate, and Perborate.
46. The method of claim.44 wherein the solid polymer based oxidant is selected from Polystyrene based pyrazolinium Cr[IV], Polyacenaphthylene supported t- butyl chromates, Poly[N-[2-aminoethyl]acrylamido] triethylammoniumpolyhalides, Polystyrene based pyrazolinium permanganates, and 1,4-Butanediol dimethacrylate crosslinked polyacenaphthylene. '
47. The method of claim 41 wherein the solid reactant further comprising a solid catalyst.
48. The method of claim 47 wherein the solid catalyst is selected from the group consisting of a transition metal, a base metal, a Fe/MgO, a SiC supported NiS2-
based catalyst, a vanadium based catalyst, an iron oxide, and a hydroscopic salt.
49. The method of claim 41 wherein the reduced solid oxidant is regenerated.
50. The method of claim 49 wherein the solid oxidant is regenerated by the gas
oxidant or a liquid oxidant.
51. The method of claims 50 wherein the gas oxidant is selected from the group
consisting of air, O2, SO3, and NO .
52. The method of claims 50 wherein the liquid oxidant is selected from the
group consisting of H2O2 and H,SO4.
53. The method of claim 41 wherein the H,S is reacted with the solid oxidant at
a reaction temperature between about 100°C and about 700°C.
54. The method of claim 41 wherein the reaction temperature is between about
200°C and about 500°C.
55 The method of claim 41 wherein the post reaction gas contains less than about 100 ppm H2S.
56 The method of claim 41 wherein the post reaction gas contains less than
about 10 ppm H2S.
57 The method of claim 41 wherein the post reaction gas is substantially free
ofH-S.
58 The method of claim 41 wherein the element sulfur is separated from the post reaction gas at a post reaction temperature.
59. The method of claim 41 the post reaction temperature is between about
25°C and about 250°C.
60. The method of claim 41 wherein the post reaction temperature is between about 120 °C and about 250°C and the element sulfur is a water-free sulfur.
61. The method of claim 41 wherein the sulfur dioxide is separated from the post reaction gas through a liquid absorption or a solid absoiption.
62. The method of claim 61 wherein the liquid absoiption is an alkaline aqueous absorption.
63 The method of claim 61 wherein the solid absoiption is a carbon black absoiption, a lime absorption, or a limestone absorption.
64. The method of claim 41 wherein the sulfur dioxide is used to form H,SO4.
65. The method of claim 41 wherein the solid reactant further comprises a solid
medium.
66. The method of claim 65 wherein the solid medium is porous.
67. The method of claim 65 wherein the solid oxidant is mounted onto the solid
medium.
68. The method of claim 41 further comprising a step of simultaneously
regenerating a second reduced solid oxidant in a second reactor to a second regenerated
solid oxidant.
69. The method of claim 68 wherein the second regenerated solid oxidant is
reacted with the H2S and the reduced solid oxidant simultaneously is regenerated.
70. The method of claim 68 wherein both the solid oxidant and the second
regenerated solid oxidant are reacted with H2S and then regenerated.
71. A composition comprising:
H2S, and a solid oxidant, wherein the solid oxidant oxidizes H2S to form element
sulfur and/or a sulfur dioxide.
72. A composition comprising: a H2S containing gas, and
a solid oxidant wherein the solid oxidant oxidizes H2S to form element
sulfur and/or sulfur dioxide.
73. A container comprising:
a reactor with an inlet and an outlet,
a H2S containing gas which is introduced to the reactor tlirough the inlet,
and
a solid oxidant which is contained in the reactor and oxidizes H2S to form
element sulfur and/or sulfur dioxide.
PCT/US2003/018909 2003-02-19 2003-06-16 A single step removal of hydrogen sulfide from gases WO2004074178A1 (en)

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CN111094175A (en) * 2017-08-18 2020-05-01 土耳其石油炼油厂图普拉斯股份公司 System and method for decomposing gaseous hydrogen sulfide into hydrogen gas and elemental sulfur
CN115382522A (en) * 2022-08-24 2022-11-25 重庆赛迪热工环保工程技术有限公司 Blast furnace gas desulfurizer regeneration system and method
CN117443154A (en) * 2023-09-28 2024-01-26 昆明理工大学 Natural gas desulfurizing agent and preparation method and application thereof
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101607172B (en) * 2008-06-16 2011-07-27 中国科学院过程工程研究所 Desulfurizer for desulfurization of smoke and method for preparing same
CN111094175A (en) * 2017-08-18 2020-05-01 土耳其石油炼油厂图普拉斯股份公司 System and method for decomposing gaseous hydrogen sulfide into hydrogen gas and elemental sulfur
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CN117443154A (en) * 2023-09-28 2024-01-26 昆明理工大学 Natural gas desulfurizing agent and preparation method and application thereof

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