review article the hydrolysis of carbonyl sulfide at low...

Hindawi Publishing CorporationThe Scientific World JournalVolume 2013 Article ID 739501 8 pageshttpdxdoiorg1011552013739501

Review ArticleThe Hydrolysis of Carbonyl Sulfide atLow Temperature A Review

Shunzheng Zhao Honghong Yi Xiaolong Tang Shanxue Jiang Fengyu Gao Bowen ZhangYanran Zuo and Zhixiang Wang

Department of Environmental Engineering College of Civil and Environmental EngineeringUniversity of Science and Technology Beijing Beijing 100083 China

Correspondence should be addressed to Honghong Yi yihonghongtsinghuaorgcn

Received 16 May 2013 Accepted 19 June 2013

Academic Editors S Niranjan L Wang and Q Wang

Copyright copy 2013 Shunzheng Zhao et al This is an open access article distributed under the Creative Commons AttributionLicense which permits unrestricted use distribution and reproduction in any medium provided the original work is properlycited

Catalytic hydrolysis technology of carbonyl sulfide (COS) at low temperature was reviewed including the development of catalystsreaction kinetics and reaction mechanism of COS hydrolysis It was indicated that the catalysts are mainly involved metal oxideand activated carbon The active ingredients which can load on COS hydrolysis catalyst include alkali metal alkaline earth metaltransition metal oxides rare earth metal oxides mixed metal oxides and nanometal oxides The catalytic hydrolysis of COS is afirst-order reactionwith respect to carbonyl sulfide while the reaction order of water changes as the reaction conditions changeThecontrolling steps are also different because the reaction conditions such as concentration of carbonyl sulfide reaction temperaturewater-air ratio and reaction atmosphere are differentThe hydrolysis of carbonyl sulfide is base-catalyzed reaction and the force ofthe base site has an important effect on the hydrolysis of carbonyl sulfide

1 Introduction

With the rapid development of ecomy energy supply anddemand have become increasingly prominent the scien-tific use of high-sulfur energy received extensive attentionAmong the chemical raw material gases which are madefrom coal oil and natural gas sulfur compounds can gen-erally be divided into two major categories of organic sulfurand inorganic sulfur Organic sulfur contains carbonyl sulfide(COS) carbon disulfide (CS

2) thiophene mercaptan and

so forth [1] Inorganic sulfur is mainly hydrogen sulfide(H2S) COS accounted for approximately 80 to 90 of

the total organic sulfur is normally regarded as a significantpoison which can cause the deactivation of the industrialcatalyst Even only a trace amount of COS can result inthe deactivation of catalysts and can lead to corrosion ofreaction equipments [2ndash4] For instance as little as 4mgof sulfur per gram of catalyst on the surface of the Fe-Cu-K catalyst decreases the activity by ca 50 in the Fischer-Tropsch process [5] Furthermore not only does COS causeeconomic loss but also affects the environment COS is

thought to be the most abundant sulfur-containing gas inthe troposphere Apart from volcanic injection troposphericCOS is the main source of sulfur in the stratosphere leadingto the stratospheric sulfate layerThe reactions of H OH andO (3P) with COS are known as important chemical sinks forconsumption of this compound [6] It has been proved to bea major source of acid rain when oxidized to sulfur oxideand to promote photochemical reactions [7ndash9] In additionin the past decades much attention was drawn to the sourcesand sinks of carbonyl sulfide (COS) in the atmosphere due tothe important role of COS in the formation of stratosphericsulfate aerosols [10ndash15] Therefore the removal of carbonylsulfide is the main problem to solve in the process of feed gasdeep purification

Currently the principal methods of carbonyl sulfideremoval include hydrogenation hydrolysis absorption ad-sorption photolysis and oxidation [16ndash22] Hydrolysismethod which has the advantages of low reaction temper-ature no consumption of the hydrogen source and fewside effects attracts a lot of researches at home and abroadCarbonyl sulfide hydrolysis research mainly includes two

2 The Scientific World Journal

aspects (1) research and development of hydrolysis catalyst(2) research on reaction kinetics and mechanism The twocomplement each other andpromote each otherTheprepara-tion of the catalyst is to use a suitable carrier load on a certainamount of an active ingredient At present the carriers ofCOS hydrolysis catalysts mainly contain two categories (1)metallic oxides including a composite metal oxide such as120574-Al2O3 TiO2and manganese iron composite metal oxides

(2) nonmetallic oxides mainly refer to activated carbonActive ingredients which can load on the carrier includealkalimetal alkaline earthmetal transitionmetal oxides rareearth metal oxides mixed metal oxide and nanoscale metaloxides Some catalysts with relatively superior performancehave been researched and developed at home and abroad sofar

The researches on reaction kinetics and mechanism notonly can accelerate the development of hydrolysis catalystwith goodperformance andhigh activity but also can providea theoretical basis for the reactor design Consequentlydomestic and foreign researchers researched and developedcatalyst They also studied the carbonyl sulfide hydrolysisreaction kinetics and mechanism and made a number ofresearch achievements

In this paper the development of catalyst for carbonylsulfide catalytic hydrolysis reaction kinetics and reactionmechanism has been summarized systematically

2 Catalysts for COS Hydrolysis

21 Catalyst Carrier Great catalyst carrier should haveproper specific surface area good heat resistance andmechanical strength At themoment COS hydrolysis catalystcarrier basically has two kinds One is a delegate withAl2O3and TiO

2metal oxides Another kind of non-metallic

oxide is a delegate with activated carbon In addition withthe development of material science the researchers alsohave developed many new types of catalyst carrier such ascordierite

211 Metal Oxide Metallic oxide carrier of COS hydrolysiscatalyst refers mainly to Al

2O3and TiO

2 In addition Fe-

Mn metal oxides have obtained the good effect in COSremoval Among them the Al

2O3as the present study more

in-depth and widely used catalyst has some characteristicsof large specific surface area high surface activity goodthermal stability and so forth Al

2O3itself has a certain

activity for the hydrolysis of COS The patent CN1069673introduces a kind of Al

2O3catalyst in which COS hydrolysis

conversion rate would be 512 under the condition of notadding any additives [28 29] However this kind of catalystsulphate resistance is poorerWe increase surface alkali centernumber and intensity by dipping a certain amount of alkalinecomponents on the surface to that further improve the COShydrolysis activity and to improve the service life and thecatalytic properties such as resistance to poisoning [30]Al2O3itself is same as TiO

2to have COS hydrolysis function

and its sulfate resistance is better than Al2O3

The catalyst with TiO2as the carrier has a great activ-

ity and high mechanical strength at low temperature [31]

Metal cationOxygen atomHydrogen atom

Water moleculeCarbonate

Calcination

Basic site

COS + H2O CO2 + H2S

Figure 1 Hydrolysis of COS on the hydrotalcite-derived oxides

Although the specific surface area of TiO2is low the price

is high it is not an easy molding industry and the industrialapplications are chief based on A1

2O3catalyst However by a

small amount of TiO2modulation the A1

2O3catalyst ability

greatly enhanced resistance to sulfur poisoning Compositecarrier was found that it is of granular distribution and gooddispersion by scanning electron microscope

In recent years the mixed oxides derived from hydro-talcite-like compounds (HTLCs) as catalysts received muchattention in view of their unique properties [32] HTLCs alsoknown as layered double hydroxides (LDHs) are a family ofanionic clays The chemical composition can be representedby the following general formula [M(II)

1minus119909M(III)

119909(OH)2]119909+

(A119899minus)119909119899sdotmH2O where M(II) and M(III) are divalent and

trivalent cations in the octahedral positions within thehydroxide layers x is the molar ratio M(III)Mtotal and itsvalue ranges between 017 and 033 A119899minus is an exchangeableinterlayer anion [33 34] HTLCs calcined at high tempera-tures will lose crystal water and the interlayer anions andhydroxyl will be removed too Therefore the hydrotalcite-like layered structures will be destroyed the surface area willincrease and the metal oxides are obtained

In our previous studies we found that the mixed oxidederived from HTLCs is a kind of potential catalysts for thehydrolysis of COS at low temperature (Figure 1) The catalystperformance was strongly related to the synthesis of pH andcalcination temperature In general COS was hydrolyzed toH2S which is depending on the chemistry of the derived

oxidesThe end products of hydrolysis were simple substanceS and sulfate The presence of oxygen will accelerate theformation of the final product [35ndash43]

212 Activated Carbon Activated carbon has become to bean ideal catalyst carrier because of its high specific surfacearea the large pore volume the large variety of surfacefunctional groups and good electron conductivity Howeverthe activity to remove COS for unmodified activated carbon

The Scientific World Journal 3

is very low and its sulfur capacity is small therefore itmust be modified Activated carbon has not only excellentCOS conversion rate but also can remove H

2S effectevily

by using carbonates and other active ingredients to modify[44] The 3018 desulfurizer developed by Dalian Institute ofChemical Physics showed a better removal COS performanceat a temperature of about 80∘C the product was elementalsulfur [45 46]

In our previous study a series of microwave coal-basedactive carbon catalysts loaded by metal oxides were preparedby a sol-gel method and tested for the catalytic hydrolysisof COS at relatively low temperatures The influences ofpreparation conditions on catalytic activity were studiedwhich were the kinds and amount of additive calcinationtemperatures and types and content of alkali [47ndash51]

213 Special Carrier Yan et al have used honeycomb cor-dierite as the carrier in the experiment [52] The cordieritewas polished to form the pillar-shaped carrier the desul-furizer which was made by using the method of dippingto make Al

2O3slurry load cordierite exhibit good desul-

furization effect The result indicated the following COShydrolysis activity gradually increases with the increase ofthe loading of 120574-Al

2O3and La(OH)

3at low temperatures

airspeed has greater impact on the activity of the catalystLa-Alhoneycomb cordierite catalyst has good antioxidantproperties the presence of O

2made the single loaded 120574-

Al2O3catalyst lose some activation while the catalyst which

was combined with La-Al has not been affected it indicatedthat La(OH)

3is COS hydrolysis catalyst which has higher

antioxidant

22 Active Ingredients

221 AlkaliMetal andAlkaline EarthMetal Alkali metal andalkaline earth metal which are supported on 120574-Al

2O3can

modulate the distribution of the amount of alkali and baseintensity and they played slightly different roles the alkalimetal can modulate the amount of alkali apparently whilethe alkaline earthmetal canmodulate the distribution of baseintensity apparently

George et al found that a small amount of NaOH plays asignificant role in promoting the COS hydrolysis the initialrate of Co-MoAl

2O3catalyst which was impregnated by

39 NaOH can increase by 25 times at 230∘C [23] Li andTan et al and so forth prepared a series of catalysts byusing oxides which were impregnated with alkali metal andalkaline earth metal and they sorted the catalytic activity bydoing experiments Cs

2O120574-Al

2O3gt K2O120574-Al

2O3 BaO120574-

Al2O3gt Na2O120574-Al

2O3 and CaO120574-Al

2O3gtMgO120574-Al

2O3

The catalytic activity was also related to the amount of loadedmetal oxides and the activity reached the highest when themole fraction is about 5 [53 54]

222 Transition Metals Composite Metal Oxides andNanometals Tong associated the activity of Al

2O3catalyst

(a transition metal) with the position of transition metalpromoter M in the periodic table found the relationshipof catalyst activity and the combination ability of the MndashS

bond and concluded that Iron as the active component ofthe catalyst on the COS has the highest catalytic activity [55]West et al loaded a series of metal ions (Fe3+ Co2+ Ni2+Cu2+ and Zn2+) to the Al

2O3plate It was shown that Cu2+

has the catalyst activity only at the beginning of the reaction[56 57] In addition researchers found that loading a varietyof active components to the unified carrier can achieve betterresults Wang et al investigated a ferromanganese compositemetal oxide by the coprecipitation method It was shownthat this desulfurizer has high-precision removal of COSand larger sulfur capacity in a strong reducing atmosphereThey also found that the desulfurization accuracy of thecatalyst is greatly improved while the nickel oxide andcerium oxide are added The COS concentration of theoutlet was less than 01 times 10minus6 adding zinc oxide achieveda greater improvement of sulfur capacity [58] With thedevelopment of nanotechnology nanomaterials has began tobe applied to the development ofCOShydrolysis catalyst Gaoet al investigated catalyst with 120572-FeOOH nanoparticles asthe active ingredient which was prepared by homogeneousprecipitation method the ammonia titration They foundthat it has a good effect on the COS hydrolysis and a highactivity under the condition of low temperature and highspace velocity Two series of catalysts achieved the 100conversion of COS at the temperature of 60∘C and 40∘Cndash45∘C respectively [59 60]

223 Rare Earth Metal Oxides Colin Rhodesa et al studiedthe synergistic effects of rare earth elements and alkaline rareearth accelerator on the Al

2O3plate Through the analysis

of DRIFT spectrum it was shown that the role of hydroxylgroups on the surface composite catalyst is similar to pureAl2O3 and it was concluded that accelerator can provide

high stable cation to the catalyst [61] Zhang et al initiallyinvestigated the hydrolytic activity of the rare earth seriesof sulfur oxides and divided the rare earth oxides into threecategories according to hydrolytic activity of COS (1) highhydrolytic activity La Pr Nd and Sm (2) high hydrolyticactivity Eu (3) low hydrolytic activity Ce Gd Dy Ho andEr with the following order La asymp Pr asymp Nd asymp Sm gt Eu gtCe gt Gd asymp Ho gt Dy gt Er In addition rare earth sulfuroxides showed a good oxidation resistance Some researchersfound that increasing temperature is conducive to improvethe antioxidant capacity of the catalyst but a certain amountof SO

2will lead to a decrease in catalyst activity and it is a

reversible inactivation [62ndash64]

3 Reaction Kinetics of COS Hydrolysis

Researches on catalytic hydrolysis reaction kinetics of car-bonyl sulfide include establishing the kinetic equations ofchemical reactions and determining the controlling step ofhydrolysis Dynamic models reported in articles are differentbecause of the difference in research conditions

At present most researchers hold that the catalytichydrolysis of COS is a first-order reaction with respect tocarbonyl sulfide while the reaction order of water changes asthe reaction conditions changeThe controlling steps are also


different because the reaction conditions such as concentra-tion of carbonyl sulfide reaction temperature water-air ratioand reaction atmosphere are different

Fiedorow et al [65] studied the hydrolysis of carbonylsulfide on pure alumina and base modified alumina respec-tivelyThey concluded that the catalytic hydrolysis of carbonylsulfide is a first-order reactionwith respect to carbonyl sulfideand a zero-order reaction with respect to water George [66]also reached the same conclusion by studying the hydrolysisof carbonyl sulfide on Co-Mo-Al catalyst

Tong et al [67] studied the hydrolysis of carbonyl sulfideunder medium temperature conditions and concluded thatthe catalytic hydrolysis of carbonyl sulfide is a first-orderreaction with respect to carbonyl sulfide while the reactionorder of water is influenced by the partial pressure of waterWhen the partial pressure of water is 01ndash026 the reactionorder of water is 04 When the pressure is higher than 026the reaction order of water is minus06The controlling step underlow temperature is the adsorption of carbonyl sulfide or theformation of reaction intermediated by adsorbed carbonylsulfide and water Chan and Dalld [68] studied the hydrolysisof carbonyl sulfide on Kaiser Kas201 catalyst They adoptedthe single factor experiment method and drawn the sameconclusion as Miroslav et al [69] who studied the hydrolysisreaction kinetics of carbonyl sulfide on Co-Mo-Al catalystand Al

2O3catalyst They concluded that when the reaction

temperature is 150 centigrade and when the volume fractionof carbonyl sulfide hydrogen sulfides and carbon dioxideare 022 01 and 001 respectively the hydrolysis rateremains unchanged as the fraction of water vapour increasesfrom 02 to 25 Thus the reaction order of water is zero

Liang et al [70] studied the hydrolysis of carbonyl sulfideon TGH-2 catalyst and found that when the water-air ratiois greater than 80 the reaction order of water is negativeTheir explanation is that the micropore is blocked due to itscondensation so the reaction process cannot continue Linet al [71] studied the hydrolysis of carbonyl sulfide under theconditions of low reaction temperature high water-air ratioand low carbonyl sulfide concentration They concluded thatthe reaction order of carbonyl sulfide is 1 while the reactionorder of water isminus05 In otherwords when the concentrationof carbonyl sulfide is low it will impede the hydrolysisprocessTheir explanations are that the condensation of watervapor blocks the pore of the catalyst and the two reactionsites are competitive in which the adsorption of water onthe basic site results in the decrease of catalytic activity Theyheld that the adsorption of carbonyl sulfide is dissociative andthe adsorption isotherm corresponds with the Freundlichequation In other words the adsorption of carbonyl sulfideis the controlling step of the reaction

Guo et al [72] studied the hydrolysis of carbonyl sulfideon TGH-3Q catalyst and measured adsorption isothermof carbonyl sulfide and water under the temperature of20ndash70 centigrade They concluded that the adsorption ofcarbonyl sulfide is dissociative and the adsorption isothermcorresponds with the Freundlich equation The adsorptionisothermofwater also correspondswith the Freundlich equa-tion However the adsorption of carbonyl sulfide increasesas the temperature increases while the adsorption of water

decreases as the temperature increases The intrinsic kineticequation of the hydrolysis is as follows

119877 = 1198961198621

COS119862minus05

H2O times

1

1 + 119870119862CO2

119896 = 182 times 1014119890minus75800119877119879

119870 = 4861198906000119877119879

(1)

In the equation 119877 means reaction rate 119896 means constantof reaction rate 119870 means adsorption constant of carbondioxide 119862means concentration of reactants

The equation shows that the catalytic hydrolysis ofcarbonyl sulfide is a first-order reaction with respect tocarbonyl sulfide And the water is essential as the hydrolyticagent however excessive water will impede the reactionprocess Besides the hydrolysis speeds up as the temperatureincreases Finally the hydrolysis of carbonyl sulfide is con-trolled by surface adsorption

By adopting the inner-recycle nongradient reactor Lianget al [70] studied the catalytic hydrolysis of carbonyl sulfideand found that the possibility of carbonyl sulfide to beadsorbed increases due to the high cycle ratioTherefore theyconcluded that hydrolysis is determined by surface reactionBy adopting the inner-recycle non-gradient reactor underthe reducing atmosphere Li et al [73] studied the catalytichydrolysis of carbonyl sulfide on 120574-906 catalyst and foundthat the reaction orders of carbonyl sulfide and water are 066and 006 respectively They held that hydrolysis is controlledby both the internal diffusion and the chemical reaction

Williams et al [74] found that the reaction kineticsof carbonyl sulfide also corresponds with the Langmuir-Hinshelwood equation They held that the reactants areadsorbed on the surface of the catalyst and the reactionbetween adsorbed carbonyl sulfide and water is the control-ling step of the hydrolysis By doing significance analysisTong S found that the Eley-Ridealmodel ismore significant tothe result compared with the Langmuir-Hinshelwoodmodel

4 Reaction Mechanism of COS Hydrolysis

Themain hydrolysis reactionmechanism is shown as follows

COS +H2O 997888rarr CO

2+H2S (2)

At present it is widely believed that the hydrolysis of carbonylsulfide belongs to base-catalyzed reaction and the force of thebase site has an important effect on the hydrolysis of carbonylsulfide

Williams et al [74] have already studied the effect ofsurface alkalinity of alkali on the hydrolysis of carbonylsulfide They proposed the concerted mechanism to describethe hydrolysis of carbonyl sulfide (Figure 2) They held thathydroxyl and water exist on the surface of catalyst andcarbonyl sulfide is adsorbed due to ion-dipole interactionThe base site is the active site of carbonyl sulfidersquos hydrolysis

By adopting the IR spectrum method Rhodes et al [61]studied the hydrolysis of carbonyl sulfide on Co-Mo catalystand found that the surface of the catalyst is covered partly


O120575+C

120575minus

S S

S

O

O O

C

CCHOHO

HO(cat)

(cat)

Na+ HOminus HOH

+ HOH(ads)

SH(ads)

+ OH CO2(ads) + H2O + SH

SH + H2O H2S(ads) + OH

Figure 2 The concerted mechanism as proposed by George [23]

by hydroxyl due to the adsorption of water and the carbonylsulfide is adsorbed due to ion-dipole interaction Then theHydrogenThiocarbonate (HTC) is formed HTC is the inter-mediate product and will decompose into hydrogen sulfideand carbon dioxide In the adsorption process carbonylsulfide and water are competitive By adopting the insitu IRtechnology Laperdrix et al [75] studied the hydrolysis ofcarbonyl sulfide on Al

2O3catalyst and found that HTC is

formed by the reaction of carbonyl sulfide and hydroxyl isadsorbed on the surface of the catalyst which enhances thepolarization of carbonyl sulfide

By adopting the IR spectrummethod Fiedorow et al [65]found that the hydroxyl on the surface of Al

2O3can adsorb

carbonyl sulfide and the intermediate product is thiocar-bonate which will decompose rapidly into hydrogen sulfideand carbon dioxide Hydrogen sulfide and carbon dioxideare competitive in the adsorption process Furthermore theydiscovered that the activity of the catalyst decreases in acidicconditions while it increases in alkaline conditions Theyproposed the following reaction mechanism

H2O + Θ larrrarr H

2O sdot Θ

H2O sdot Θ + COS (g) larrrarr Η

2S sdot Θ + CO

2(g)

Η2S sdot Θ larrrarr Η

2S + Θ

Θ active site

(3)

Wang [76] studied the hydrolysis of carbonyl sulfide onmixed metal oxides and proposed the following hydrolysismechanism of carbonyl sulfide

COS + Θ = COS sdot Θ

H2O + Θ = H

2O sdot Θ

H2O sdot Θ + COS sdot Θ = H

2S sdot Θ + CO

2sdot Θ

H2S sdot Θ = H

2S + Θ

CO2sdot Θ = CO

2+ Θ

Θ active site(4)

Additionally researchers found that the base strength onthe surface of the catalyst has an important effect on thehydrolysis of carbonyl sulfide By adopting the FTIR spec-trum and quantum chemistry methods Hoggan et al [77]studied the hydrolysis of carbonyl sulfide on Al

2O3catalyst

and found that hydrolysis proceeds much easier on sodiummeta aluminate which does not have bronsted acid Theyconcluded that carbonyl sulfide ismainly adsorbed on the siteof weak base Li et al [78] studied the hydrolysis of carbonylsulfide on alkali-modified 120574-Al

2O3catalyst and found that

distribution of base strength on the surface of the catalystis related to the distribution of energy on the surface Theyconcluded that the effective range of base strength in thehydrolysis is between 48 and 98

By adopting the CO2-TPD Shangguan and Guo [79]

studied the properties of the alkaline site on three kinds ofAl2O3catalyst and studied the hydrolysis of carbonyl sulfide

and carbon disulfide They found that the kinds amountsand strength of alkaline sites are different The alkalescentsite is the active site of the carbonyl sulfidersquos hydrolysis Theamount and strength of alkalescent site can be increased bysupporting Pt and K

2O on the surface of the catalyst thus

the hydrolysis activity of the catalyst can be increasedHong Hersquos group conducted in-depth studies on the

reaction mechanism of the COS hydrolysis and they haveachieved good results By studying the oxygen toxicity mech-anism of catalyst they found that the hydroxyl on the surfaceof the catalyst plays an important role in the hydrolysis andthe intermediate product is thiocarbonateThey reported thatthe reaction mechanism of COS on mineral oxides can besummarized as shown in Figure 3

In Figure 3 gaseous carbon dioxide (CO2) hydrogen

sulfide (H2S) sulfur dioxide (SO

2) surface sulfite (SO

3

2minus)and sulfate (SO

4

2minus) were found to be the gaseous and surfaceproducts respectively Hydrogen thiocarbonate (HSCO

2

minus


HSO3

minus(s) + HCO3

minus(s)

[O]

[O]

[O]

[O]

OH(s)OH(s)OCS(ads) HSCO2

minus(s)or H2O(g)Mineral oxides

H2S(g) + CO2(g)

SO2SO4

2minus(s)

Figure 3The concertedmechanism as proposed byHe et al [9 24ndash27]

HTC) was proposed to be the crucial intermediate for boththe oxidation and the hydrolysis pathway [24ndash27 80]

5 Conclusions

At present the catalytic hydrolysis method is the mainmethod to remove carbonyl sulfide It has many advantagessuch as low energy consumption easy operation and lessside reaction The main task is to develop a new kind ofcatalyst which is highly active highly stable and highlyantipoisoning The catalyst carrier basically has two kindsOne is a delegate with Al

2O3and TiO

2metal oxides Another

kind of nonmetallic oxide is a delegate with activated carbonAlkali metal and alkaline earth metal which are supportedon 120574-Al

2O3can modulate the distribution of the amount

of alkali and base intensity Regarding the production ofcatalytic hydrolysis of COS the simple substance S andsulfate can be formed on the catalystrsquos surface and theactivity of the catalyst decreased when the SSO

4

2minus speciesaccumulated on the catalystrsquos surface With the introductionof stringent requirements to reduce the sulfur content inindustrial feed gas the fresh impetus is being given tomodifying and improving the existing preparation methodof the hydrolysis catalyst By studying the reaction kineticsand reaction mechanism researchers can find better waysto develop the catalyst and to establish the desulfurizationprocessTherefore the focus of reaction kinetics and reactionmechanism is to establish kinetic models under differentconditions and to determine the effect of various kinds offactors and to clarify the path of the reaction

Acknowledgment

This work is supported by National Natural Science Founda-tion (50908110)

References

[1] E C Rupp E J Granite and D C Stanko ldquoCatalytic formationof carbonyl sulfide during warm gas clean-up of simulated coal-derived fuel gas with Pd120574-Al

2O3sorbentsrdquo Fuel vol 92 no 1

pp 211ndash215 2012[2] P D N Svoronost and T J Bruno ldquoCarbonyl sulfide a review

of its chemistry and propertiesrdquo Industrial and EngineeringChemistry Research vol 41 no 22 pp 5321ndash5336 2002

[3] P D Vaidya and E Y Kenig ldquoKinetics of carbonyl sulfidereaction with alkanolamines a reviewrdquo Chemical EngineeringJournal vol 148 no 2-3 pp 207ndash211 2009

[4] A Ryzhikov V Hulea D Tichit et al ldquoMethyl mercaptanand carbonyl sulfide traces removal through adsorption andcatalysis on zeolites and layered double hydroxidesrdquo AppliedCatalysis A vol 397 no 1-2 pp 218ndash224 2011

[5] V Saheb M Alizadeh F Rezaei and S Shahidi ldquoQuantumchemical and theoretical kinetics studies on the reaction ofcarbonyl sulfide with H OH and O(3P)rdquo Computational andTheoretical Chemistry vol 994 pp 25ndash33 2012

[6] N E Tsakoumis M Roslashnning Oslash Borg E Rytter and A Hol-men ldquoDeactivation of cobalt based Fischer-Tropsch catalysts areviewrdquo Catalysis Today vol 154 no 3-4 pp 162ndash182 2010

[7] Y Liu H He and Y Mu ldquoHeterogeneous reactivity of carbonylsulfide on 120572-Al

2O3and 120574-Al

2O3rdquo Atmospheric Environment

vol 42 no 6 pp 960ndash969 2008[8] V Saheb M Alizadeh F Rezaei and S Shahidi ldquoQuantum

chemical and theoretical kinetics studies on the reaction ofcarbonyl sulfide with H OH and O(3P)rdquo Computational andTheoretical Chemistry vol 994 pp 25ndash33 2012

[9] Y Liu and H He ldquoExperimental and theoretical study ofhydrogen thiocarbonate for heterogeneous reaction of carbonylsulfide on magnesium oxiderdquo Journal of Physical Chemistry Avol 113 no 14 pp 3387ndash3394 2009

[10] P J Crutzen ldquoThe possible importance of CSO for the sulfatelayer of the stratosphererdquo Geophysical Research Letters vol 3pp 73ndash76 1976

[11] M Chin and D D Davis ldquoA reanalysis of carbonyl sulfide asa source of stratospheric background sulfur aerosolrdquo Journal ofGeophysical Research vol 100 no 5 pp 8993ndash9005 1995

[12] A J Kettle U Kuhn M Von Hobe J Kesselmeier and MO Andreae ldquoGlobal budget of atmospheric carbonyl sulfidetemporal and spatial variations of the dominant sources andsinksrdquo Journal of Geophysical Research D vol 107 no 22 article4658 2002

[13] S A Montzka P Calvert B D Hall et al ldquoOn the global distri-bution seasonality and budget of atmospheric carbonyl sulfide(COS) and some similarities to CO

2rdquo Journal of Geophysical

Research D vol 112 no 9 Article ID D9302 2007[14] S F Watts ldquoThe mass budgets of carbonyl sulfide dimethyl

sulfide carbon disulfide and hydrogen sulfiderdquo AtmosphericEnvironment vol 34 no 5 pp 761ndash779 2000

[15] T Ogawa K Noguchi M Saito et al ldquoCarbonyl sulfide hydro-lase from Thiobacillus thioparus strain THI115 is one of the 120573-carbonic anhydrase family enzymesrdquo Journal of the AmericanChemical Society vol 135 pp 3818ndash3825 2013

[16] M E Whelan D Min and R C Rhew ldquoSalt marsh vegetationas a carbonyl sulfide (COS) source to the atmosphererdquo Atmo-spheric Environment vol 73 pp 131ndash137 2013

[17] X Wang J Qiu P Ning et al ldquoAdsorptiondesorption of lowconcentration of carbonyl sulfide by impregnated activatedcarbon under micro-oxygen conditionsrdquo Journal of HazardousMaterials vol 229-230 pp 128ndash136 2012

[18] W Afzal M P Breil I Tsivintzelis A H Mohammadi GM Kontogeorgis and D Richon ldquoExperimental study andphase equilibriummodeling of systems containing acid gas andglycolrdquo Fluid Phase Equilibria vol 318 pp 40ndash50 2012

[19] K Sunanda B N Rajasekhar P Saraswathy and B N JagatapldquoPhoto-absorption studies on carbonyl sulphide in 30000ndash91000 cmminus1 region using synchrotron radiationrdquo Journal ofQuantitative Spectroscopy and Radiative Transfer vol 113 no 1pp 58ndash66 2012


[20] S Hattori J A Schmidt D W Mahler S O Danielache M SJohnson and N Yoshida ldquoIsotope effect in the carbonyl sulfidereaction with O(3P)rdquo Journal of Physical Chemistry A vol 116no 14 pp 3521ndash3526 2012

[21] J Zhang J Xiao Y Liu and X Wei ldquoSolubility of carbonylsulfide in aqueous solutions of ethylene glycol at temperaturesfrom (30815 K to 32315) Krdquo Journal of Chemical and Engineer-ing Data vol 55 no 11 pp 5350ndash5353 2010

[22] R G Zhang L X Ling and B J Wang ldquoDensity functionaltheory analysis of carbonyl sulfide hydrolysis effect of solvationand nucleophile variationrdquo Journal of Molecular Modeling vol18 pp 1255ndash1262 2012

[23] Z M George ldquoEffect of catalyst basicity for COS-SO2and COS

hydrolysis reactionsrdquo Journal of Catalysis vol 35 no 2 pp 218ndash224 1974


2O3and 120574-Al


vol 42 no 6 pp 960ndash969 2008[25] Y Liu H He W Xu and N Yu ldquoMechanism of heterogeneous

reaction of carbonyl sulfide on magnesium oxiderdquo Journal ofPhysical Chemistry A vol 111 no 20 pp 4333ndash4339 2007

[26] H He J Liu Y Mu Y Yu and M Chen ldquoHeterogeneousoxidation of carbonyl sulfide on atmospheric particles andaluminardquo Environmental Science and Technology vol 39 no 24pp 9637ndash9642 2005

[27] Y Liu H He and Q Ma ldquoTemperature dependence of theheterogeneous reaction of carbonyl sulfide on magnesiumoxiderdquo Journal of Physical Chemistry A vol 112 no 13 pp 2820ndash2826 2008

[28] J Shangguan Y Zhao H Fan L Liang F Shen and M MiaoldquoDesulfurization behavior of zinc oxide based sorbent modifiedby the combination of Al

2O3andK

2CO3rdquo Fuel vol 108 pp 80ndash

84 2013[29] L L Yu X L Tang H H Yi and P Ning ldquoMedium- and low-

temperature catalytic hydrolysis of carbonyl sulfiderdquo IndustrialCatalysis vol 17 pp 21ndash26 2009

[30] J Xiao Y Peng and A Xiao ldquoThe development on thetechnique of hydrolysis of carbonyl sulfide and carbon disulfideat low and ambient temperaturerdquo Hubei Chemical vol 20 pp7ndash9 2003

[31] Y B Chen ldquoInvestigation and preparation of NCT-1 1 organicsulfur hydrolystrdquo Journal of Chemical Industry amp Engineeringvol 18 pp 9ndash11 1997

[32] G Centi and S Perathoner ldquoCatalysis by layered materials areviewrdquo Microporous and Mesoporous Materials vol 107 no 1-2 pp 3ndash15 2008

[33] Y Wu Y Yu J Z Zhou et al ldquoEffective removal of pyrophos-phate by Ca-Fe-LDH and itsmechanismrdquoChemical EngineeringJournal vol 179 pp 72ndash79 2012

[34] F Li J Liu D G Evans and X Duan ldquoStoichiometric synthesisof pure MFe

2O4(M=Mg Co and Ni) spinel ferrites from tai-

lored layered double hydroxide (hydrotalcite-like) precursorsrdquoChemistry of Materials vol 16 no 8 pp 1597ndash1602 2004

[35] H Yi S Zhao X Tang P Ning H Wang and D He ldquoInflu-ence of calcination temperature on the hydrolysis of carbonylsulfide over hydrotalcite-derived ZnndashNindashAl catalystrdquo CatalysisCommunications vol 12 no 15 pp 1492ndash1495 2011

[36] S Zhao H Yi X Tang P Ning H Wang and D He ldquoEf-fect of Ce-doping on catalysts derived from hydrotalcite-likeprecursors for COS hydrolysisrdquo Journal of Rare Earths vol 28no 1 pp 329ndash333 2010

[37] H Wang H Yi X Tang et al ldquoCatalytic hydrolysis of cosover conial mixed oxides modified by lanthanumrdquo FreseniusEnvironmental Bulletin vol 20 no 3 pp 773ndash778 2011

[38] H Wang H Yi P Ning et al ldquoCalcined hydrotalcite-likecompounds as catalysts for hydrolysis carbonyl sulfide at lowtemperaturerdquo Chemical Engineering Journal vol 166 no 1 pp99ndash104 2011

[39] H Yi HWang X Tang et al ldquoEffect of calcination temperatureon catalytic hydrolysis of COS over CoNiAl catalysts derivedfrom hydrotalcite precursorrdquo Industrial and Engineering Chem-istry Research vol 50 no 23 pp 13273ndash13279 2011

[40] H Y Wang H H Yi X L Tang et al ldquoStudy of hydrolysisof carbonyl sulfide over mixed oxides from hydrotalcite-likecompoundsrdquoChinese Journal of Environmental Engineering vol6 pp 545ndash549 2012

[41] S Zhao H Yi X Tang et al ldquoCharacterization of ZnndashNindashFe hydrotalcite-derived oxides and their application in thehydrolysis of carbonyl sulfiderdquo Applied Clay Science vol 56 pp84ndash89 2012

[42] H Y Wang H H Yi X L Tang et al ldquoCatalytic hydrolysisof COS over calcined CoNiAl hydrotalcite-like compoundsmodified by ceriumrdquo Applied Clay Science vol 70 pp 8ndash132012

[43] S Z Zhao H H Yi X L Tang and C Y Song ldquoLow temper-ature hydrolysis of carbonyl sulfide using ZnndashAl hydrotalcite-derived catalystsrdquo Chemical Engineering Journal vol 226 pp161ndash165 2013

[44] X Wang L Ding Z Zhao W Xu B Meng and JQiu ldquoNovel hydrodesulfurization nano-catalysts derived fromCo3O4nanocrystals with different shapesrdquo Catalysis Today vol

175 no 1 pp 509ndash514 2011[45] L T Liang The Study on Modified Alumina Based Catalyst

for Hish Concentration Carbonyl Sulfide Hydrolysis TaiyuanUniversity of Technology Taiyuan China 2005

[46] J Zhang and X Li ldquoThe research of removing COS at lowtemperature by modified active carbonrdquo Liaoning ChemicalIndustry vol 3 pp 102ndash104 1998

[47] D He H Yi X Tang et al ldquoThe catalytic hydrolysis of carbondisulfide on FendashCundashNiAC catalyst at low temperaturerdquo Journalof Molecular Catalysis A vol 357 pp 44ndash49 2012

[48] D He H Yi X Tang P Ning H Wang and S Zhao ldquoCarbondisulfide hydrolysis over FendashCuAC catalystmodified by ceriumand lanthanum at low temperaturerdquo Journal of Rare Earths vol28 no 1 pp 343ndash346 2010

[49] N Ping Y Lili Y Honghong et al ldquoEffect of FeCuCe loadingon the coal-based activated carbons for hydrolysis of carbonylsulfiderdquo Journal of Rare Earths vol 28 no 2 pp 205ndash210 2010

[50] P Ning K Li H H Yi et al ldquoSimultaneous catalytic hydrol-ysis of carbonyl sul fide and carbon disulfide over modifiedmicrowave coal-based active carbon catalysts at low tempera-turerdquo The Journal of Physical Chemistry C vol 116 pp 17055ndash17062 2012

[51] H Yi D He X Tang H Wang S Zhao and K Li ldquoEffectsof preparation conditions for active carbon-based catalyst oncatalytic hydrolysis of carbon disulfiderdquo Fuel vol 97 pp 337ndash343 2012

[52] MYan Z Xiao andY Zhang ldquoReaction ofCOShydrolysis overLa-A1Cordierite honeycomb catalystrdquo Journal of East ChinaUniversity of Science and Technology vol 31 no 1 pp 7130ndash71322005


[53] W Li W Shudong and Y Quan ldquoRemoval of carbonyl sulideat low temperature experiment and modelingrdquo Fuel ProcessingTechnology vol 91 no 7 pp 777ndash782 2010

[54] S Tan C Li S Liang and H Guo ldquoCompensation effect incatalytic hydrolysis of carbonyl sulfide at lower temperaturecompensation effect in COS hydrolysisrdquo Catalysis Letters vol8 no 2ndash4 pp 155ndash168 1991

[55] S Tong Catalytic Hydrolysis of Carbon Disulfide and CarbonylSulifde University of Alderta Edmonton Canada 1992

[56] J West B P Williams N C Young C Rhodes and G JHutchings ldquoNew directions for COS hydrolysis low tempera-ture alumina catalystsrdquo Studies in Surface Science and Catalysisvol 119 pp 373ndash378 1998

[57] J West B P Williams N Young C Rhodes and G J Hutch-ings ldquoNi- and Zn-promotion of 120574-Al

2O3for the hydrolysis of

COS under mild conditionsrdquo Catalysis Communications vol 2no 3-4 pp 135ndash138 2001

[58] F Wang H Zhao D Zhang and J Gao ldquoDesulfurizationmechanism of iron-manganese compound oxide desulfurizerfor removal of COS from coal gasrdquo Journal of the China CoalSociety vol 2 pp 197ndash200 2008

[59] Z Gao L Yin C Li and K Xie ldquoStudy on simultaneousremoval of COS and H

2S by using 120572-FeOOH nanoparticlerdquo

Journal of Fuel Chemistry and Technology vol 31 no 3 pp 249ndash253 2003

[60] Z Gao and C Li ldquoThe effect of preparation condition of activecomponent on activity of COS hydrolysisrdquoCoal Conversion vol7 pp 91ndash95 1997

[61] C Rhodes S A Riddel J West B P Williams and G JHutchings ldquoLow-temperature hydrolysis of carbonyl sulfideand carbon disulfide a reviewrdquo Catalysis Today vol 59 no 3pp 443ndash464 2000

[62] Y Zhang Z Xiao and J Ma ldquoHydrolysis of earbonyl sulfideover sulfidized rare earth oxidesrdquo Joumal of Fudan Universityvol 42 pp 372ndash374 2003

[63] Y Zhang Z Xiao and J Ma ldquoHydrolysis of COS over rare earthoxysulfidesrdquo Chemical Research in Chinese Universities vol 25pp 721ndash724 2004

[64] Y Zhang Z Xiao and JMa ldquoEfect of O2an d SO

2on hydrolysis

of carbonyl sulfide over rare earth oxysulfidesrdquo Journal of FudanUniversity vol 42 pp 379ndash380 2003

[65] R Fiedorow R Leaute and I GD Lana ldquoA study of the kineticsand mechanism of COS hydrolysis over aluminardquo Journal ofCatalysis vol 85 no 2 pp 339ndash348 1984

[66] Z M George ldquoKinetics of cobalt-molybdate-catalyzed reac-tions of SO

2with H

2S and COS and the hydrolysis of COSrdquo

Journal of Catalysis vol 32 no 2 pp 261ndash271 1974[67] S Tong I G D Lana and K T Chuang ldquoKinetic modelling of

the hydrolysis of carbonyl sulfide catalyzed by either titania oraluminardquoCanadian Journal of Chemical Engineering vol 71 no3 pp 392ndash400 1993

[68] V Chan and G Dalld ldquoOn the catalytic hydrolysis of carbonylsulfide over gamma-aluminardquo Canadian Journal of ChemicalEngineering vol 56 pp 751ndash753 1978

[69] Z Miroslav ldquoHeterogenously catalyzed hydrolysis of carbonylsulfiderdquo Chemicky Prumysl vol 24 pp 549ndash552 1974

[70] M Liang C Li andH Guo ldquoStudy on reaction kinetics of COShydrolysis at lower temperaturerdquo Chinese Journal of Catalysisvol 23 pp 357ndash362 2002

[71] J Y LinH XGuo andKC Xie ldquoStudies on the deactivation ofcarbonyl sulfide hydrolysis catastrdquo Journal of NingxiaUniversityvol 22 pp 192ndash194 2001

[72] H X GuoMQMiao and Y Q Zhang ldquoperformance of TGH-3Q COS hydrolysis catalyst at ambient and low temperaturerdquoIndustrial Catalysis vol 5 pp 37ndash43 1999

[73] J W Li C Li and J Liu ldquoStudy on COS hydrolysis kinetics on120574-906 catalyst in reducing atmosphererdquo Industrial Catalysis vol2 pp 23ndash29 1996

[74] B P Williams N C Young J West C Rhodes and GJ Hutchings ldquoCarbonyl sulphide hydrolysis using aluminacatalystsrdquo Catalysis Today vol 49 no 1ndash3 pp 99ndash104 1999

[75] E Laperdrix I Justin G Costentin et al ldquoComparative studyof CS

2hydrolysis catalyzed by alumina and titaniardquo Applied

Catalysis B vol 17 no 1-2 pp 167ndash173 1998[76] H N Wang ldquoPreparetion of catalyst and research of kinetics

for carbonyl sulfide hydrolysis under moderate temperaturerdquoTaiyuan University of Technology vol 2 pp 23ndash29 1996

[77] P E Hoggan A Aboulayt A Pieplu P Nortier and J CLavalley ldquoMechanism of COS hydrolysis on aluminardquo Journalof Catalysis vol 149 no 2 pp 300ndash306 1994

[78] C H Li H X Guo and S S Tan ldquoStudy on the alkalized 120574-Al2O3catalyst for its base strength distribution and catalytic

activityrdquo Journal of Molecular Catalysis vol 8 pp 305ndash311 1994[79] J Shangguan and H X Guo ldquoThe surface basicity and catalysis

over the alumina based catalysts for COS and CS2hydrolysisrdquo

Journal of Molecular Catalysis vol 11 pp 337ndash342 1997[80] J Liu Y Yu Y Mu and H He ldquoMechanism of heterogeneous

oxidation of carbonyl sulfide on Al2O3 an in Situ diffuse

reflectance infrared fourier transform spectroscopy investiga-tionrdquo Journal of Physical Chemistry B vol 110 no 7 pp 3225ndash3230 2006

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Inorganic ChemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

International Journal ofPhotoenergy


Carbohydrate Chemistry

International Journal of


Journal of

Chemistry


Advances in

Physical Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom

Analytical Methods in Chemistry

Journal of

Volume 2014

Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

SpectroscopyInternational Journal of


The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Medicinal ChemistryInternational Journal of


Chromatography Research International


Applied ChemistryJournal of



Theoretical ChemistryJournal of


Journal of

Spectroscopy

Analytical ChemistryInternational Journal of


Journal of


Quantum Chemistry


Organic Chemistry International

ElectrochemistryInternational Journal of



CatalystsJournal of


aspects (1) research and development of hydrolysis catalyst(2) research on reaction kinetics and mechanism The twocomplement each other andpromote each otherTheprepara-tion of the catalyst is to use a suitable carrier load on a certainamount of an active ingredient At present the carriers ofCOS hydrolysis catalysts mainly contain two categories (1)metallic oxides including a composite metal oxide such as120574-Al2O3 TiO2and manganese iron composite metal oxides

(2) nonmetallic oxides mainly refer to activated carbonActive ingredients which can load on the carrier includealkalimetal alkaline earthmetal transitionmetal oxides rareearth metal oxides mixed metal oxide and nanoscale metaloxides Some catalysts with relatively superior performancehave been researched and developed at home and abroad sofar

The researches on reaction kinetics and mechanism notonly can accelerate the development of hydrolysis catalystwith goodperformance andhigh activity but also can providea theoretical basis for the reactor design Consequentlydomestic and foreign researchers researched and developedcatalyst They also studied the carbonyl sulfide hydrolysisreaction kinetics and mechanism and made a number ofresearch achievements

In this paper the development of catalyst for carbonylsulfide catalytic hydrolysis reaction kinetics and reactionmechanism has been summarized systematically

2 Catalysts for COS Hydrolysis

21 Catalyst Carrier Great catalyst carrier should haveproper specific surface area good heat resistance andmechanical strength At themoment COS hydrolysis catalystcarrier basically has two kinds One is a delegate withAl2O3and TiO

2metal oxides Another kind of non-metallic

oxide is a delegate with activated carbon In addition withthe development of material science the researchers alsohave developed many new types of catalyst carrier such ascordierite

211 Metal Oxide Metallic oxide carrier of COS hydrolysiscatalyst refers mainly to Al

2O3and TiO

2 In addition Fe-

Mn metal oxides have obtained the good effect in COSremoval Among them the Al

2O3as the present study more

in-depth and widely used catalyst has some characteristicsof large specific surface area high surface activity goodthermal stability and so forth Al

2O3itself has a certain

activity for the hydrolysis of COS The patent CN1069673introduces a kind of Al

2O3catalyst in which COS hydrolysis

conversion rate would be 512 under the condition of notadding any additives [28 29] However this kind of catalystsulphate resistance is poorerWe increase surface alkali centernumber and intensity by dipping a certain amount of alkalinecomponents on the surface to that further improve the COShydrolysis activity and to improve the service life and thecatalytic properties such as resistance to poisoning [30]Al2O3itself is same as TiO

2to have COS hydrolysis function

and its sulfate resistance is better than Al2O3

The catalyst with TiO2as the carrier has a great activ-

ity and high mechanical strength at low temperature [31]

Metal cationOxygen atomHydrogen atom

Water moleculeCarbonate

Calcination

Basic site

COS + H2O CO2 + H2S

Figure 1 Hydrolysis of COS on the hydrotalcite-derived oxides

Although the specific surface area of TiO2is low the price

is high it is not an easy molding industry and the industrialapplications are chief based on A1

2O3catalyst However by a

small amount of TiO2modulation the A1

2O3catalyst ability

greatly enhanced resistance to sulfur poisoning Compositecarrier was found that it is of granular distribution and gooddispersion by scanning electron microscope

In recent years the mixed oxides derived from hydro-talcite-like compounds (HTLCs) as catalysts received muchattention in view of their unique properties [32] HTLCs alsoknown as layered double hydroxides (LDHs) are a family ofanionic clays The chemical composition can be representedby the following general formula [M(II)

1minus119909M(III)

119909(OH)2]119909+

(A119899minus)119909119899sdotmH2O where M(II) and M(III) are divalent and

trivalent cations in the octahedral positions within thehydroxide layers x is the molar ratio M(III)Mtotal and itsvalue ranges between 017 and 033 A119899minus is an exchangeableinterlayer anion [33 34] HTLCs calcined at high tempera-tures will lose crystal water and the interlayer anions andhydroxyl will be removed too Therefore the hydrotalcite-like layered structures will be destroyed the surface area willincrease and the metal oxides are obtained

In our previous studies we found that the mixed oxidederived from HTLCs is a kind of potential catalysts for thehydrolysis of COS at low temperature (Figure 1) The catalystperformance was strongly related to the synthesis of pH andcalcination temperature In general COS was hydrolyzed toH2S which is depending on the chemistry of the derived

oxidesThe end products of hydrolysis were simple substanceS and sulfate The presence of oxygen will accelerate theformation of the final product [35ndash43]

212 Activated Carbon Activated carbon has become to bean ideal catalyst carrier because of its high specific surfacearea the large pore volume the large variety of surfacefunctional groups and good electron conductivity Howeverthe activity to remove COS for unmodified activated carbon



2S effectevily






2O3and La(OH)







antioxidant



2O3can





2O120574-Al

2O3gt K2O120574-Al

2O3 BaO120574-



2O3gtMgO120574-Al

2O3



2O3catalyst























119877 = 1198961198621

COS119862minus05

H2O times

1

1 + 119870119862CO2

119896 = 182 times 1014119890minus75800119877119879

119870 = 4861198906000119877119879

(1)








2+H2S (2)





O120575+C

120575minus

S S

S

O

O O

C

CCHOHO

HO(cat)

(cat)

Na+ HOminus HOH

+ HOH(ads)

SH(ads)








2O3can adsorb


H2O + Θ larrrarr H

2O sdot Θ


2S sdot Θ + CO

2(g)


2S + Θ

Θ active site

(3)



H2O + Θ = H

2O sdot Θ


2S sdot Θ + CO

2sdot Θ

H2S sdot Θ = H

2S + Θ

CO2sdot Θ = CO

2+ Θ

Θ active site(4)


2O3catalyst













3


4


2

minus


HSO3

minus(s) + HCO3

minus(s)

[O]

[O]

[O]

[O]



H2S(g) + CO2(g)

SO2SO4

2minus(s)



5 Conclusions


2O3and TiO





4


Acknowledgment


References










2O3and 120574-Al
























2O3and 120574-Al







2O3andK















































2on hydrolysis




2with H































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of



2S effectevily






2O3and La(OH)







antioxidant



2O3can





2O120574-Al

2O3gt K2O120574-Al

2O3 BaO120574-



2O3gtMgO120574-Al

2O3



2O3catalyst























119877 = 1198961198621

COS119862minus05

H2O times

1

1 + 119870119862CO2

119896 = 182 times 1014119890minus75800119877119879

119870 = 4861198906000119877119879

(1)








2+H2S (2)





O120575+C

120575minus

S S

S

O

O O

C

CCHOHO

HO(cat)

(cat)

Na+ HOminus HOH

+ HOH(ads)

SH(ads)








2O3can adsorb


H2O + Θ larrrarr H

2O sdot Θ


2S sdot Θ + CO

2(g)


2S + Θ

Θ active site

(3)



H2O + Θ = H

2O sdot Θ


2S sdot Θ + CO

2sdot Θ

H2S sdot Θ = H

2S + Θ

CO2sdot Θ = CO

2+ Θ

Θ active site(4)


2O3catalyst













3


4


2

minus


HSO3

minus(s) + HCO3

minus(s)

[O]

[O]

[O]

[O]



H2S(g) + CO2(g)

SO2SO4

2minus(s)



5 Conclusions


2O3and TiO





4


Acknowledgment


References










2O3and 120574-Al
























2O3and 120574-Al







2O3andK















































2on hydrolysis




2with H































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of










119877 = 1198961198621

COS119862minus05

H2O times

1

1 + 119870119862CO2

119896 = 182 times 1014119890minus75800119877119879

119870 = 4861198906000119877119879

(1)








2+H2S (2)





O120575+C

120575minus

S S

S

O

O O

C

CCHOHO

HO(cat)

(cat)

Na+ HOminus HOH

+ HOH(ads)

SH(ads)








2O3can adsorb


H2O + Θ larrrarr H

2O sdot Θ


2S sdot Θ + CO

2(g)


2S + Θ

Θ active site

(3)



H2O + Θ = H

2O sdot Θ


2S sdot Θ + CO

2sdot Θ

H2S sdot Θ = H

2S + Θ

CO2sdot Θ = CO

2+ Θ

Θ active site(4)


2O3catalyst













3


4


2

minus


HSO3

minus(s) + HCO3

minus(s)

[O]

[O]

[O]

[O]



H2S(g) + CO2(g)

SO2SO4

2minus(s)



5 Conclusions


2O3and TiO





4


Acknowledgment


References










2O3and 120574-Al
























2O3and 120574-Al







2O3andK















































2on hydrolysis




2with H































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


O120575+C

120575minus

S S

S

O

O O

C

CCHOHO

HO(cat)

(cat)

Na+ HOminus HOH

+ HOH(ads)

SH(ads)








2O3can adsorb


H2O + Θ larrrarr H

2O sdot Θ


2S sdot Θ + CO

2(g)


2S + Θ

Θ active site

(3)



H2O + Θ = H

2O sdot Θ


2S sdot Θ + CO

2sdot Θ

H2S sdot Θ = H

2S + Θ

CO2sdot Θ = CO

2+ Θ

Θ active site(4)


2O3catalyst













3


4


2

minus


HSO3

minus(s) + HCO3

minus(s)

[O]

[O]

[O]

[O]



H2S(g) + CO2(g)

SO2SO4

2minus(s)



5 Conclusions


2O3and TiO





4


Acknowledgment


References










2O3and 120574-Al
























2O3and 120574-Al







2O3andK















































2on hydrolysis




2with H































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


HSO3

minus(s) + HCO3

minus(s)

[O]

[O]

[O]

[O]



H2S(g) + CO2(g)

SO2SO4

2minus(s)



5 Conclusions


2O3and TiO





4


Acknowledgment


References










2O3and 120574-Al
























2O3and 120574-Al







2O3andK















































2on hydrolysis




2with H































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of








2O3and 120574-Al







2O3andK















































2on hydrolysis




2with H































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


















2on hydrolysis




2with H































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of










Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of

review article the hydrolysis of carbonyl sulfide at low...

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