CA2131987A1 - Method for removing sulfide with catalytic carbon - Google Patents
Method for removing sulfide with catalytic carbonInfo
- Publication number
- CA2131987A1 CA2131987A1 CA002131987A CA2131987A CA2131987A1 CA 2131987 A1 CA2131987 A1 CA 2131987A1 CA 002131987 A CA002131987 A CA 002131987A CA 2131987 A CA2131987 A CA 2131987A CA 2131987 A1 CA2131987 A1 CA 2131987A1
- Authority
- CA
- Canada
- Prior art keywords
- thc
- nitrogen
- char
- catalytically
- sulfides
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
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
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8603—Removing sulfur compounds
- B01D53/8606—Removing sulfur compounds only one sulfur compound other than sulfur oxides or 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
- B01D53/86—Catalytic processes
- B01D53/8603—Removing sulfur compounds
- B01D53/8612—Hydrogen sulfide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/02—Preparation of sulfur; Purification
- C01B17/04—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides
- C01B17/0404—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by processes comprising a dry catalytic conversion of hydrogen sulfide-containing gases, e.g. the Claus process
- C01B17/046—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by processes comprising a dry catalytic conversion of hydrogen sulfide-containing gases, e.g. the Claus process without intermediate formation of sulfur dioxide
- C01B17/0469—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by processes comprising a dry catalytic conversion of hydrogen sulfide-containing gases, e.g. the Claus process without intermediate formation of sulfur dioxide at least one catalyst bed operating below the dew-point of sulfur
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/336—Preparation characterised by gaseous activating agents
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Carbon And Carbon Compounds (AREA)
- Catalysts (AREA)
Abstract
An improved process is provided for the selective removal of sulfide from gas or liquid media containing oxygen and water by contacting said media with a catalytically-active carbonaceous char.
The improvement is provided by the use of a catalytically-active carbonaceous char prepared by low-temperature carbonization and oxidation of a bituminous coal or bituminous coal-like material followed by exposure to a nitrogen containing compound at high-temperatures during the initial calcination and/or activation of the oxidized material.
The improvement is provided by the use of a catalytically-active carbonaceous char prepared by low-temperature carbonization and oxidation of a bituminous coal or bituminous coal-like material followed by exposure to a nitrogen containing compound at high-temperatures during the initial calcination and/or activation of the oxidized material.
Description
' WO 9411C990 2 1 3 1 9 8 7 PCT~S94/0088~
..~
. . .
- Tm,~e -~ :
, MET~IOD FOR REMO~XNG SUL~IDE WIT~ CATALY I IC G~RBON
LD OF T~E lN~FNllON `; ` ` ~ ` `
Thc p~sent i~lVCDtiOD ~elates tO thc USC of a higSly colybcDlly ~ c c~s char for Ihe E~ rcmoval of sulfJdc ~om gâs~or~q~d media ~ osencc dODCygeD and~wa~cr. `' `~ :^ i :: BACKG~OU~DOFT~IN~'ENlION ~ ~ ~
VJ~rious mc~ of rcmo~ing H~S using a~s~ re hwwo. For e~ple, 1~ ~as been uscd for the ~emoval of hydFogcn ~ulfidc and vl~rious mn~sn~ a humidifiod, ~ng 10 gas~ous stream. ImptovemeD~s in thc~vai qrbilibe~ of ~l# C~35 ch~ hvcbccD realized by the addi~ion of a basc~ such as ~nunonia or hydroxi~ to tbc char w~c d~g the~:mov~;psocess. It hasbeenf~undths~ ~dditionofc~l-inhalogens~Dd~ransido~c~ali~c~schar substratcs also the l~movd of hydioge~ nd m_ ~m ~d air ~ums. Howcvcr, noneoftheseimplovcmu! ~edtheirhe~tplopQticsd~ ~entally 1 ~i responsible for lhe obscrvcd pbawmalon in the abscncc of promo~ wch as ~ y~idc, potassium iodide, or othcr compuulds. : :
Some implovcments iu thc po~e ~ze distribudon of ~cdvu~ cub~s hllve beeD dcsc~ibed wherein a high-~cm~alre cdvued cubon~ char is ~led~with ~ or mel mi~compwnd~and calcineda~high~ es. ChucFc~dinthis~m n~erhav~eD~edbyd~a~ biDdes;
20 bowever,: the ~ili~ of such chan to ~emo~c h~ u~lfidc by c~lytic <~do~ was not ~ or ~: ~eported. l~çptoductiond~c~uschar~ ~btbkf~chy~genwlfidco~cnhasbeeR~aught whclein a high-temp~#~re aeti~ bon colce i~ o~idi~d ~nd e~ed to a ni~conu~ning ammoruum salt al tcmpo~res abo~c 3S0 C.
wog41l6g902~31987 ~ . ;; PCT/US94/00884 Such prior an methods have c~rlain disadvantages which limit ~hcir applicaioa. The usc of commercially-availablc unimprcgnatui scdvn~cd carbons for cataly~ic hydroger1 ~utfide remova~ suffers from low rates of aemo~ral, ~nd conscqucntly, low hydrogc~ sulfidc b~a~through c~citics. T~c u5c of promotc~s in the p~escncc of ~2ch ~naceous ~s also entails cerlain di~advantagcs. For c~amplc, thc use of 5 ammonia roqlai~s added cost and ha~ard in thc ~ns~ion al~d co~trol ~3f measmed a~monia additio~. The usc of sodium hydm~ide a~d o~er mc~al ul~ ~Iso iD~rolva addcd costs ~ ~ell as ~ iDc~ascd dsk of thennal cxcursjo~ d~c to the 3Owenng of the char ignition tempcsa~e.
Accordin~ly, it is Ihe o~joct of ~hc p~e~t i~vention to p~dc ~ cut~ c~u which iscataly~ically activ~ for sulfidc and me~csptan removal in thc presencc of o~ygeD aDd water wbcl~ compased 10 to other unimprcgDated chars and ap~ *om t~se ac~ic parame~ h~own to affect ~ch removal. For cx~mplc, c~t insic p~uamete~ ca~ includc p~ticlc size di~ributioD, po~ volumc distJibudoo, and contact ~ime. It ~s further thc object of thc p-e~ent iovendon to produce a~d employ ~uch ~onsc~s chars at minimal cost ~nd hazard when comp~ed to pnor ar~ .
~ . . . .
SUMM~RY OF T~IE INVENlrlON
., I :`
Gcncrally~ the present inven~on co2np~scs the ~:moval of w~ldcs aDd mc~aptans from media containing oxygen and watcr by thc cataly~c action ~f aubonacoous chars. l~cse c~ars arc prcparcd by the low-tem~rc carbonization and oxitation of nit~cn p~r feedstocl~ Thc o~idizcd low-temperature c~ar is Ihcn subjected to a nitroge~tai~ng ~p~und at high tempa~res during thc initial ~alcination or calcination/acd-ation. Ln all cascs, bightall~ c~w cha~ re those p~aduced 20 by ~hennal ~mcn~ at tempa~tures gralterthan 700 C Low ~pC~E cubonacoous ch~ are those that havc no~ aspenenccd tempe~res ~ate~ Ihan 700 C.
The prefe~d ~trogen-~ feodstoclt i- a bi~minou~ coal or a bi~miwus co~l-lilce ma~ial such as thosc dcrivod from higher or loweT ~nlc bi~meDs, coals. or lipoocllulo~c m~ by various ehunical Iseatments. B~amples of higher ~ ooals include ~th~acite or scmi~ c coals, while c1samples of 25 lower ranlc coals include peatt lignitC~ and sub-bi~mi~ous oo~ls. E~amplc~ of lhe ehemieal treatment of these fecdstocks include all~ali metal trea~mcnt of thc high ~anlt ~ial6 aDd ZiD: chloride or phosplloric æid trcatment of thc low ~anlt matcrials. These typcs of treatmc~ts can slso be ~pplicd to lignocellulose matenals.
. . .
WO 94116990 2 1 3 1 9 8 7 ~ ; ~/US941008~
In a prcfened embodimcnt of llbi8 iDvention, thei feedstocl~ matsrial i~ aizcd, mixcd if necessary with small alslounts of a suitaUc binder such a~ pitch, briqucucd or o?Lherwiisci fonned, and sizcd. Thc sizcd matcnal is ?Ihen cxtensi~dy oxidized at tcDlpcrah~rcs Ics~ ~han 700 C, prcfe~ably les?ic than 400 C. The 5 oxida~ion is continucd UDlil additioDal ga D the catalytic acti~i~ty of thc fiDal prot?ua U~c 1~0 IOlSger eviden~.
Thc oxidation i c wcll bcyond lhat ~ically required to r~s~ove lhc col~ng proper~ of bi~ coals and pr~uces an optimally o~cidized ch~. Otl~e~ oo~vel icnt mcaD~ of o~ on c~ d60 be usod to cf~eGt thc low-tempe~ re oxidatioG and c~bonizatio~ of thc ~K m~ s ~:
~e oxi~zcd low-tcmp~re c~ char i~ thc~ a~po~ed to ~iall ~nounl~c of ~n 10 inexpe~ciYe~ abundar~ ~d sclativcly ~-toxic nilrogc~-contai~iDg compou~d ~uch as urca du~ing, no~ ahcr, thc initial calcination and co~on of she aubon ~ Thc amo~t~ of nilrogen-con~aiDing compounds uscd ase typically w~all, prcfe~ably Icsc tb~ S% by wcight of thc o~idizcd b~mpc~re carb~nacoous char`or ~uch ~ ddido~l guns i~ th~ cs~y~c ~tiv,ity Qf th~ al ~UCI `aré~no longer cvidcnt. Thc t-eatm_ is ca~Ti~ b~i hea~ng t} o~i~ rc char to bigh temp~res, 15 ~prcferably belween 8S0 C and 9S0 C, in the p~e of t~e nilrogen~onuining comp~nd. This hc~ting is preferably conductc~ undcr an ~mo~pherc Ibat is inert accept ~orthc ~asa and vapors atlributablc to the ch~r andfor the nitrogcn-containing compowld. The bcasin~ e and ~p~ efe ably selccscd such that addhional ~ns i~ the catalytic cti~iq of ~c final product l~se oo ~gcr cvidcnt. ~ ~
Thc nitrogcn~ ed high-tem~ c us cbt~r may then bc acdvated to ~hc desired 20 density at tempera~res sbove 700 C in ~tcam andfor c~bon dio~ nth or without thc addidon of otbcr gasifying agents wch as alr. Thc calcincd or calcined/acti~ated c s char is then cooled in an - oxygen-frce or olhe~wisc iDCrt ~Itmospberc to tempc~ Ic~s tbaD ~ C, p~fe~ably Icss thar 200 C.
Additional gains in alalylic actiYiq may bc ~lizod blr epcating t~c o~udation~ powrc lo nitrogcn-conlaini~g compouDds~calcina~on or calcin~tionf~lctiY~ Dert coding as m~my tuncs as may bc desircd.
25 Altcrna~iYely, any o~h~ mcthod ~ to genale cataly~ic ~iviq in high tempQ~e c~ceous chars may be applied IO the rcsultana product to fb~thar ~DhaDcc its a~talytic ~ctivity.
The cataly~c~y-utive c~ char p~d ~ocdLng to the above method is then contac~ed with a sulfide~ontai~g media in the prescnce of watcr ant o~ygen. Sulfide is rcmoved f~om the media by wo 941l69go2~.3 19 8~ Pcr/usg4/oo~
calalytic oxidation to primalily sulfates and clemen~l ~ ur. The o~ng tcmpuaturc is b~wecn ~1s ~1t O C and 300 C and pseferably bcswecn about 0 C and 100 C and morc preferably b~w~en about 2S C an~ 90 C.
PRESENTLY ~FERRED EMBOD~ENTS i -~; lheutili~o~ein~endo~isillustra~dbythefollo~qngtwoex~mple~. Incache%ample,oquivalent mcsh sizc fmctions of thc ca~bonaceous c~s wcrc evsl~cd t4 ~cgate any particlc sizc effec~ Thc chars used in thesc examples ha~e appFo~y the ulmc de~e~ and CCI, acdvities. Tbi~ Deat oguivalcnce indicates that the porc volumes of both chan ue nea~ly equivalen~ Thc~eforc ~c bcncfits of ~e prescnt i nvcntion ~rc cvidcnt as thc extrinsic propefie~ affccting clllfidc ~mt>val ue nc~rly oqui~alent for thcsc 10 samples. E~ple 1 temo ~hcH2Sremovalapaci~ofa~pcndcmesh~f~ionofacommacial . .." -"~ actiYa~ed ca~on. Examplc 2 dcmonstr~cs the 1~2S Doval capaciq o~he invcndon. Companson of lhesc . , .-two examples shows ~hat the perfonnance of the invendon grcady e~cceeds that of a typical acti~/atcd carbon.
~ -:
EXAMPLE 1 ~ . ~
A commerci~lly available sctivaled aubon, 8PL (~d by Cslgon CSUbOD Co~oration, 15 Pittsburgh PA~ was sizct to less than S ~ g~er than 6 mcsh (IJ.S. St ndard Serics sieYcs). When ~o sized this carbon showed an Apparent Density ( Test Method TM-7, Calpn Carbon Cpo~ion, Pi~sburgh PA) of OrS04 gTams per cc and a ca, Nwnber ( Tesl M~ TM-6, Calgon Cllrbon Corpo~ation, Pitlsburgh PA ) of 55.1%. The sizcd carbon was loadcd inlo a ~lum- having ao insite diamaer of ~ppro~umately 0.73 inches to gi fe a bcd depth of 9 inchcs. Column lo ding w~ done in ~uch a manneras to achieve a packinn 2Q density cquivalent to ~c Apparcnt Dalsity. A ~as strcam ba~g ~ relativc humidity of g~er than 50~fc, an oxygen content of g~ea~ than 17 vl~f*, and a howo H2S concenllYion of app~im~y I vh/% was passed through this eolumn al a flow rate of 1~50 ~ ~tc und ambicn~ dîdons. The cfflucnt from this column was monito~ nd the el~l time re~ui~d to chieve a 50 wm H2S breal~luough was measured. For this ea~on sample the elapsed timc piod w~s equal to 9 mi~utes.
~1~198~
WO ~4116990 ^ PCT/US94/008~4 . EXAMPLE 2 Bituminous coal was pulvaized, mLl~ed with ~ut 4 tc 6% coal t.ar pitch, and briquctIcd. The rcsul~ant briqueues were crushed and sized to producc ~ appro~imatcly less than 4 mcsh size and greatcr than 10 mesh sizc (U.S. Slandard Se~ies devcs) maserial. ID thc prcsc~cc of largc quan~ tics of e~ccss air, this material was o~idized by hcating from 100 C to 200 C a~ a ~ate of 200 C pcr hour, thCD from 200 C to 350 C at a rate of 100 C pa hour, then held at 3SO C for 4 ~ and fi~ally h:atcd from 3SO C to 450 C at - a ratc of 100 C per hour. The rcsult~nt o~cidi2ed matcrial was coolod to Dear ambicnt tcmp~us~s în a low o xygen content a~mosphere, sizcd to produce an #pp~o~atcly lc~ ~ S ~nd gteater Iban 6 mcsh ~izc (U.S.
Slandard Scrics si~res) n~serial, and ~ubscqucntl~ imprc~ with an aqueous ures soludon and dricd. Thc 10 ~uantity of urca ~oludon u~sed was sufficic~t to producc a 4% urea loading o~ a dry wcigh~ b~sis. Aftcr impregna~ion,portionsoftheo~udized,imp~ atedlow-~paaturccharwacrapidlybcatedto950Cunder . an incrt gas atmosphere. ~cdia~ely following this calcina~ion ~ nent thc resultant ma~erials wcre zctivaled with stcam at 950 C for a ~uffi~c~t pcriot of timc to acbievc ~he dcsired yidd. After activation, the materials werc coolcd ~o ambicnt ~em~ under a~ iDert ~plleYc. The catalyticaliy-aclive 15 ~ ivated ca~bonaccous chars ~o prQduccd, when combincd and dzed to less ~an S mesh (U.S. Standard &!~ies) and greater ~ 6 mcsh (U.S. St~ Scnes) exhibitot ~n Ap~t Dcnsity ~cst Mcthod TM-7, Calgon Car~on Colporation, Pittsburgh PA) of 0.49S g~ams per cc. Thc CC:I, Numbcr of the sizcd, combincd chars was SS.S%.
Thc H2S rcmoval ability of thc sizcd, catal~tically-~lc~ivc, activatcd high-tcmpcraturc carbonaceous 20 char prepared as described above was ~inul using conditions idcntical to thosc describcd in Example 1. For tbis sample of catalytically-activc activatcd car'oonacoous char the elapsed time pcriod ~cquired to achicvc a SO ppm H~S brcalcthrough was oqual to 326 minutcs.
While a prescntly prefe~ed embodiment of thc invcntion ha~ bCeD dcscribed, it may be otherwisc cmbodied within the scopc ~f tllc appeDded claims.
..~
. . .
- Tm,~e -~ :
, MET~IOD FOR REMO~XNG SUL~IDE WIT~ CATALY I IC G~RBON
LD OF T~E lN~FNllON `; ` ` ~ ` `
Thc p~sent i~lVCDtiOD ~elates tO thc USC of a higSly colybcDlly ~ c c~s char for Ihe E~ rcmoval of sulfJdc ~om gâs~or~q~d media ~ osencc dODCygeD and~wa~cr. `' `~ :^ i :: BACKG~OU~DOFT~IN~'ENlION ~ ~ ~
VJ~rious mc~ of rcmo~ing H~S using a~s~ re hwwo. For e~ple, 1~ ~as been uscd for the ~emoval of hydFogcn ~ulfidc and vl~rious mn~sn~ a humidifiod, ~ng 10 gas~ous stream. ImptovemeD~s in thc~vai qrbilibe~ of ~l# C~35 ch~ hvcbccD realized by the addi~ion of a basc~ such as ~nunonia or hydroxi~ to tbc char w~c d~g the~:mov~;psocess. It hasbeenf~undths~ ~dditionofc~l-inhalogens~Dd~ransido~c~ali~c~schar substratcs also the l~movd of hydioge~ nd m_ ~m ~d air ~ums. Howcvcr, noneoftheseimplovcmu! ~edtheirhe~tplopQticsd~ ~entally 1 ~i responsible for lhe obscrvcd pbawmalon in the abscncc of promo~ wch as ~ y~idc, potassium iodide, or othcr compuulds. : :
Some implovcments iu thc po~e ~ze distribudon of ~cdvu~ cub~s hllve beeD dcsc~ibed wherein a high-~cm~alre cdvued cubon~ char is ~led~with ~ or mel mi~compwnd~and calcineda~high~ es. ChucFc~dinthis~m n~erhav~eD~edbyd~a~ biDdes;
20 bowever,: the ~ili~ of such chan to ~emo~c h~ u~lfidc by c~lytic <~do~ was not ~ or ~: ~eported. l~çptoductiond~c~uschar~ ~btbkf~chy~genwlfidco~cnhasbeeR~aught whclein a high-temp~#~re aeti~ bon colce i~ o~idi~d ~nd e~ed to a ni~conu~ning ammoruum salt al tcmpo~res abo~c 3S0 C.
wog41l6g902~31987 ~ . ;; PCT/US94/00884 Such prior an methods have c~rlain disadvantages which limit ~hcir applicaioa. The usc of commercially-availablc unimprcgnatui scdvn~cd carbons for cataly~ic hydroger1 ~utfide remova~ suffers from low rates of aemo~ral, ~nd conscqucntly, low hydrogc~ sulfidc b~a~through c~citics. T~c u5c of promotc~s in the p~escncc of ~2ch ~naceous ~s also entails cerlain di~advantagcs. For c~amplc, thc use of 5 ammonia roqlai~s added cost and ha~ard in thc ~ns~ion al~d co~trol ~3f measmed a~monia additio~. The usc of sodium hydm~ide a~d o~er mc~al ul~ ~Iso iD~rolva addcd costs ~ ~ell as ~ iDc~ascd dsk of thennal cxcursjo~ d~c to the 3Owenng of the char ignition tempcsa~e.
Accordin~ly, it is Ihe o~joct of ~hc p~e~t i~vention to p~dc ~ cut~ c~u which iscataly~ically activ~ for sulfidc and me~csptan removal in thc presencc of o~ygeD aDd water wbcl~ compased 10 to other unimprcgDated chars and ap~ *om t~se ac~ic parame~ h~own to affect ~ch removal. For cx~mplc, c~t insic p~uamete~ ca~ includc p~ticlc size di~ributioD, po~ volumc distJibudoo, and contact ~ime. It ~s further thc object of thc p-e~ent iovendon to produce a~d employ ~uch ~onsc~s chars at minimal cost ~nd hazard when comp~ed to pnor ar~ .
~ . . . .
SUMM~RY OF T~IE INVENlrlON
., I :`
Gcncrally~ the present inven~on co2np~scs the ~:moval of w~ldcs aDd mc~aptans from media containing oxygen and watcr by thc cataly~c action ~f aubonacoous chars. l~cse c~ars arc prcparcd by the low-tem~rc carbonization and oxitation of nit~cn p~r feedstocl~ Thc o~idizcd low-temperature c~ar is Ihcn subjected to a nitroge~tai~ng ~p~und at high tempa~res during thc initial ~alcination or calcination/acd-ation. Ln all cascs, bightall~ c~w cha~ re those p~aduced 20 by ~hennal ~mcn~ at tempa~tures gralterthan 700 C Low ~pC~E cubonacoous ch~ are those that havc no~ aspenenccd tempe~res ~ate~ Ihan 700 C.
The prefe~d ~trogen-~ feodstoclt i- a bi~minou~ coal or a bi~miwus co~l-lilce ma~ial such as thosc dcrivod from higher or loweT ~nlc bi~meDs, coals. or lipoocllulo~c m~ by various ehunical Iseatments. B~amples of higher ~ ooals include ~th~acite or scmi~ c coals, while c1samples of 25 lower ranlc coals include peatt lignitC~ and sub-bi~mi~ous oo~ls. E~amplc~ of lhe ehemieal treatment of these fecdstocks include all~ali metal trea~mcnt of thc high ~anlt ~ial6 aDd ZiD: chloride or phosplloric æid trcatment of thc low ~anlt matcrials. These typcs of treatmc~ts can slso be ~pplicd to lignocellulose matenals.
. . .
WO 94116990 2 1 3 1 9 8 7 ~ ; ~/US941008~
In a prcfened embodimcnt of llbi8 iDvention, thei feedstocl~ matsrial i~ aizcd, mixcd if necessary with small alslounts of a suitaUc binder such a~ pitch, briqucucd or o?Lherwiisci fonned, and sizcd. Thc sizcd matcnal is ?Ihen cxtensi~dy oxidized at tcDlpcrah~rcs Ics~ ~han 700 C, prcfe~ably les?ic than 400 C. The 5 oxida~ion is continucd UDlil additioDal ga D the catalytic acti~i~ty of thc fiDal prot?ua U~c 1~0 IOlSger eviden~.
Thc oxidation i c wcll bcyond lhat ~ically required to r~s~ove lhc col~ng proper~ of bi~ coals and pr~uces an optimally o~cidized ch~. Otl~e~ oo~vel icnt mcaD~ of o~ on c~ d60 be usod to cf~eGt thc low-tempe~ re oxidatioG and c~bonizatio~ of thc ~K m~ s ~:
~e oxi~zcd low-tcmp~re c~ char i~ thc~ a~po~ed to ~iall ~nounl~c of ~n 10 inexpe~ciYe~ abundar~ ~d sclativcly ~-toxic nilrogc~-contai~iDg compou~d ~uch as urca du~ing, no~ ahcr, thc initial calcination and co~on of she aubon ~ Thc amo~t~ of nilrogen-con~aiDing compounds uscd ase typically w~all, prcfe~ably Icsc tb~ S% by wcight of thc o~idizcd b~mpc~re carb~nacoous char`or ~uch ~ ddido~l guns i~ th~ cs~y~c ~tiv,ity Qf th~ al ~UCI `aré~no longer cvidcnt. Thc t-eatm_ is ca~Ti~ b~i hea~ng t} o~i~ rc char to bigh temp~res, 15 ~prcferably belween 8S0 C and 9S0 C, in the p~e of t~e nilrogen~onuining comp~nd. This hc~ting is preferably conductc~ undcr an ~mo~pherc Ibat is inert accept ~orthc ~asa and vapors atlributablc to the ch~r andfor the nitrogcn-containing compowld. The bcasin~ e and ~p~ efe ably selccscd such that addhional ~ns i~ the catalytic cti~iq of ~c final product l~se oo ~gcr cvidcnt. ~ ~
Thc nitrogcn~ ed high-tem~ c us cbt~r may then bc acdvated to ~hc desired 20 density at tempera~res sbove 700 C in ~tcam andfor c~bon dio~ nth or without thc addidon of otbcr gasifying agents wch as alr. Thc calcincd or calcined/acti~ated c s char is then cooled in an - oxygen-frce or olhe~wisc iDCrt ~Itmospberc to tempc~ Ic~s tbaD ~ C, p~fe~ably Icss thar 200 C.
Additional gains in alalylic actiYiq may bc ~lizod blr epcating t~c o~udation~ powrc lo nitrogcn-conlaini~g compouDds~calcina~on or calcin~tionf~lctiY~ Dert coding as m~my tuncs as may bc desircd.
25 Altcrna~iYely, any o~h~ mcthod ~ to genale cataly~ic ~iviq in high tempQ~e c~ceous chars may be applied IO the rcsultana product to fb~thar ~DhaDcc its a~talytic ~ctivity.
The cataly~c~y-utive c~ char p~d ~ocdLng to the above method is then contac~ed with a sulfide~ontai~g media in the prescnce of watcr ant o~ygen. Sulfide is rcmoved f~om the media by wo 941l69go2~.3 19 8~ Pcr/usg4/oo~
calalytic oxidation to primalily sulfates and clemen~l ~ ur. The o~ng tcmpuaturc is b~wecn ~1s ~1t O C and 300 C and pseferably bcswecn about 0 C and 100 C and morc preferably b~w~en about 2S C an~ 90 C.
PRESENTLY ~FERRED EMBOD~ENTS i -~; lheutili~o~ein~endo~isillustra~dbythefollo~qngtwoex~mple~. Incache%ample,oquivalent mcsh sizc fmctions of thc ca~bonaceous c~s wcrc evsl~cd t4 ~cgate any particlc sizc effec~ Thc chars used in thesc examples ha~e appFo~y the ulmc de~e~ and CCI, acdvities. Tbi~ Deat oguivalcnce indicates that the porc volumes of both chan ue nea~ly equivalen~ Thc~eforc ~c bcncfits of ~e prescnt i nvcntion ~rc cvidcnt as thc extrinsic propefie~ affccting clllfidc ~mt>val ue nc~rly oqui~alent for thcsc 10 samples. E~ple 1 temo ~hcH2Sremovalapaci~ofa~pcndcmesh~f~ionofacommacial . .." -"~ actiYa~ed ca~on. Examplc 2 dcmonstr~cs the 1~2S Doval capaciq o~he invcndon. Companson of lhesc . , .-two examples shows ~hat the perfonnance of the invendon grcady e~cceeds that of a typical acti~/atcd carbon.
~ -:
EXAMPLE 1 ~ . ~
A commerci~lly available sctivaled aubon, 8PL (~d by Cslgon CSUbOD Co~oration, 15 Pittsburgh PA~ was sizct to less than S ~ g~er than 6 mcsh (IJ.S. St ndard Serics sieYcs). When ~o sized this carbon showed an Apparent Density ( Test Method TM-7, Calpn Carbon Cpo~ion, Pi~sburgh PA) of OrS04 gTams per cc and a ca, Nwnber ( Tesl M~ TM-6, Calgon Cllrbon Corpo~ation, Pitlsburgh PA ) of 55.1%. The sizcd carbon was loadcd inlo a ~lum- having ao insite diamaer of ~ppro~umately 0.73 inches to gi fe a bcd depth of 9 inchcs. Column lo ding w~ done in ~uch a manneras to achieve a packinn 2Q density cquivalent to ~c Apparcnt Dalsity. A ~as strcam ba~g ~ relativc humidity of g~er than 50~fc, an oxygen content of g~ea~ than 17 vl~f*, and a howo H2S concenllYion of app~im~y I vh/% was passed through this eolumn al a flow rate of 1~50 ~ ~tc und ambicn~ dîdons. The cfflucnt from this column was monito~ nd the el~l time re~ui~d to chieve a 50 wm H2S breal~luough was measured. For this ea~on sample the elapsed timc piod w~s equal to 9 mi~utes.
~1~198~
WO ~4116990 ^ PCT/US94/008~4 . EXAMPLE 2 Bituminous coal was pulvaized, mLl~ed with ~ut 4 tc 6% coal t.ar pitch, and briquctIcd. The rcsul~ant briqueues were crushed and sized to producc ~ appro~imatcly less than 4 mcsh size and greatcr than 10 mesh sizc (U.S. Slandard Se~ies devcs) maserial. ID thc prcsc~cc of largc quan~ tics of e~ccss air, this material was o~idized by hcating from 100 C to 200 C a~ a ~ate of 200 C pcr hour, thCD from 200 C to 350 C at a rate of 100 C pa hour, then held at 3SO C for 4 ~ and fi~ally h:atcd from 3SO C to 450 C at - a ratc of 100 C per hour. The rcsult~nt o~cidi2ed matcrial was coolod to Dear ambicnt tcmp~us~s în a low o xygen content a~mosphere, sizcd to produce an #pp~o~atcly lc~ ~ S ~nd gteater Iban 6 mcsh ~izc (U.S.
Slandard Scrics si~res) n~serial, and ~ubscqucntl~ imprc~ with an aqueous ures soludon and dricd. Thc 10 ~uantity of urca ~oludon u~sed was sufficic~t to producc a 4% urea loading o~ a dry wcigh~ b~sis. Aftcr impregna~ion,portionsoftheo~udized,imp~ atedlow-~paaturccharwacrapidlybcatedto950Cunder . an incrt gas atmosphere. ~cdia~ely following this calcina~ion ~ nent thc resultant ma~erials wcre zctivaled with stcam at 950 C for a ~uffi~c~t pcriot of timc to acbievc ~he dcsired yidd. After activation, the materials werc coolcd ~o ambicnt ~em~ under a~ iDert ~plleYc. The catalyticaliy-aclive 15 ~ ivated ca~bonaccous chars ~o prQduccd, when combincd and dzed to less ~an S mesh (U.S. Standard &!~ies) and greater ~ 6 mcsh (U.S. St~ Scnes) exhibitot ~n Ap~t Dcnsity ~cst Mcthod TM-7, Calgon Car~on Colporation, Pittsburgh PA) of 0.49S g~ams per cc. Thc CC:I, Numbcr of the sizcd, combincd chars was SS.S%.
Thc H2S rcmoval ability of thc sizcd, catal~tically-~lc~ivc, activatcd high-tcmpcraturc carbonaceous 20 char prepared as described above was ~inul using conditions idcntical to thosc describcd in Example 1. For tbis sample of catalytically-activc activatcd car'oonacoous char the elapsed time pcriod ~cquired to achicvc a SO ppm H~S brcalcthrough was oqual to 326 minutcs.
While a prescntly prefe~ed embodiment of thc invcntion ha~ bCeD dcscribed, it may be otherwisc cmbodied within the scopc ~f tllc appeDded claims.
Claims (6)
[received by the International Bureau on 16 July 1994 (16.07.94);
original claims 1, 2, 5 and 6 amended; original claim 3 deleted;
new claim 7 added; remaining claim 4 unchanged;
claims renumbered 1-6 (1 page)]
1. A process for the removal of sulfides from gas or liquid media which comprises contacting said media, in the presence of oxygen and water, with a catalytically-active carbonaceous char, said char being prepared from a bituminous coal or a coal having bituminous properties carbonized and oxidized at temperatures below 700° C and subjected thereafter to nitrogen-containing compounds while heating to temperatures greater than 700° C.
2. A process as set forth in Claim 1 wherein said catalytically-active carbonaceous char has been activated at temperatures above 700° C using at least one of steam, carbon dioxide, and oxygen.
3. The process of Claim 1 wherein the sulfide is hydrogen sulfide.
4. The process of Claim 1 wherein said process is operated at a temperature of between 0° C and 300° C to remove said sulfides.
5. The process of Claim 1 wherein said process is operated at a temperature of between about 25° C and 90° C to remove said sulfides.
6. A process as set forth in Claim 1 wherein said nitrogen-containing compounds are urea and nitrogen-containing compounds having at least one nitrogen-containing functionality in which the nitrogen exhibits a formal oxidation number less than that of elemental nitrogen.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US872393A | 1993-01-21 | 1993-01-21 | |
| US008,723 | 1993-01-21 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2131987A1 true CA2131987A1 (en) | 1994-08-04 |
Family
ID=21733292
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002131987A Abandoned CA2131987A1 (en) | 1993-01-21 | 1994-01-21 | Method for removing sulfide with catalytic carbon |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP2572206B2 (en) |
| CA (1) | CA2131987A1 (en) |
| WO (1) | WO1994016990A1 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5637232A (en) * | 1996-03-11 | 1997-06-10 | Calgon Carbon Corporation | Process for the catalytic oxidation of ferrous iron in liquid media |
| KR101439504B1 (en) | 2012-10-09 | 2014-09-15 | 주식회사 포스코 | Method of active carbon for removing hydrogen sulfide and active carbon manufactured by the same |
| KR101512562B1 (en) | 2013-08-20 | 2015-04-16 | 대전대학교 산학협력단 | A process for producing biomass adsorbent from platanus leaves |
| BR112017025946A8 (en) * | 2015-06-01 | 2023-02-07 | Calgon Carbon Corp | METHOD TO PURIFY BIOGAS AND BIOGAS PURIFICATION SYSTEM |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US737579A (en) * | 1902-12-06 | 1903-09-01 | Ernst Burschell | Process of purifying gas. |
| GB411918A (en) * | 1932-01-04 | 1934-06-18 | Franz Krczil | Improvements in the methods and means for producing active charcoal or for re-activating spent charcoal |
| US3630959A (en) * | 1969-06-04 | 1971-12-28 | Standard Oil Co Ohio | Carbonization of bituminous coals |
| JPS5220395A (en) * | 1975-08-08 | 1977-02-16 | Mitsubishi Petrochem Co Ltd | Process for producing porous carbonaceous particles |
| DE4109892C2 (en) * | 1991-03-26 | 1994-12-22 | Metallgesellschaft Ag | Process for removing hydrogen sulfide from gases using activated carbon |
-
1994
- 1994-01-21 CA CA002131987A patent/CA2131987A1/en not_active Abandoned
- 1994-01-21 WO PCT/US1994/000884 patent/WO1994016990A1/en active Application Filing
- 1994-01-21 JP JP6517278A patent/JP2572206B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| WO1994016990A1 (en) | 1994-08-04 |
| JP2572206B2 (en) | 1997-01-16 |
| JPH07505116A (en) | 1995-06-08 |
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