CA2010350A1 - Desulfurizing agent and process of producing it - Google Patents
Desulfurizing agent and process of producing itInfo
- Publication number
- CA2010350A1 CA2010350A1 CA002010350A CA2010350A CA2010350A1 CA 2010350 A1 CA2010350 A1 CA 2010350A1 CA 002010350 A CA002010350 A CA 002010350A CA 2010350 A CA2010350 A CA 2010350A CA 2010350 A1 CA2010350 A1 CA 2010350A1
- Authority
- CA
- Canada
- Prior art keywords
- desulfurizing agent
- ash
- pelletized
- producing
- calcium hydroxide
- 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
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28004—Sorbent size or size distribution, e.g. particle size
-
- 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
- B01D53/50—Sulfur oxides
- B01D53/508—Sulfur oxides by treating the gases with solids
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
- B01J20/041—Oxides or hydroxides
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3007—Moulding, shaping or extruding
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
- C10L10/00—Use of additives to fuels or fires for particular purposes
- C10L10/02—Use of additives to fuels or fires for particular purposes for reducing smoke development
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/42—Materials comprising a mixture of inorganic materials
Landscapes
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Inorganic Chemistry (AREA)
- Combustion & Propulsion (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Environmental & Geological Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Treating Waste Gases (AREA)
- Solid Fuels And Fuel-Associated Substances (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
ABSTRACT
Desulfurizing agent and Process of Producing It A desulfurizing agent is described, which con-sists of 3 to 10% by weight brown coal ash, balance calcium hydroxide, and is used in pelletized form. The pellets are 0.? to 3 mm, preferably 0.5 to 1 mm, in diameter. A process of producing that desulfurizing agent is also described.
Desulfurizing agent and Process of Producing It A desulfurizing agent is described, which con-sists of 3 to 10% by weight brown coal ash, balance calcium hydroxide, and is used in pelletized form. The pellets are 0.? to 3 mm, preferably 0.5 to 1 mm, in diameter. A process of producing that desulfurizing agent is also described.
Description
-~ 2010350 3~-SCRITION
This invention rzlates to a desulfurizing agent ~hich is used to remove the oxides of sulfur from combusticn exh2ust Gases. Thz invention relates als3 to a process of ~rDducinq the ~esulfurizino a~ent and to the us- af the de-sulfurizinq aoent.
ossil fuels (true c~al, brown coal, oeat, pztrc-leum~ contain sulfur comoounds in various a~Dunts. Qs the fuels 3re combustod, oreferentially ~C2 and a s~all amount of ~33 are fnrmed from said sulfur comoounds. ~s a result, the exhaust qases ~raduce~ ~y the combustion of fossil fuels con-tain as much as 10,C~0 mo SC? per s~3 (S~3 = standard cubic ete~r). In the Fz~sral QenlJ~lic of ~er~any the 3vera~e C5z con-te~nt oF the conbusti~n axhaust nas~s ~ay 3e assu~ed to a~ount to~betl~ein 10CC an~ zOao ~0 ~G7 02r s~3. 9ecause the oxides af -~
sulfu~r a~re tOXlC ~to the znvironment .~lhen they enter the atmos~
~Z~ p~ere, the oxides of sulfur must ~e re~Dve~ fro~ the com~ustion -xhaust~gas~es~3s~cc~ple~tely as possible, particularly because x ~ ~ very~sub5t~antlal quantltles of fossil fuels arP combusted ~or ~m ~ o~o~zr~oraduction~
It is '~nown to contact combustiGn exhaust gases with~solid ~ès'ulfuri;zina aoents so that ~the Gxides ofl sulfur react~ ith the ~esulfurl~zlnD, aqent ~ith formation oF soli~ sul~
f~a-tes and sulfltes. ~articularly calcium oxide, calcium hydrox-e~an~d oal~ium carbonat- are used as solid desulfurizina aGent :~ :
Z0~0350 ano rea_t with SO7 and ~C3 3t elevate~ temDeratures in the nresence oF oxygen to For~ preferentially calciu~ sulfate. '~ut calcium sulfite is 31so for~eo by an undesire~ secon~ary re-ac.,ion in variDus amounts, which deoand on the reaction con-d~ti2ns. The re~cti~/ity of the ~esulfurizinq anents is parti-culerly dP~ermine~ by their Darticle size, crystal structure an~ ~erhanical strennth. ~'hereas so~e deâulfurizinn a~ents (suoh aà li~estone) arz directiy fed to the co~bustion cha~ber, other ~esulfurizing aoents are reactPd llith the sulfur nxide5 of th2 ca~bustion exhaust ~aszs in a soli~-gas reaction which uCo2~ds the ca~bustion. The ~a~ which is containz~ in the fuel ash will also rzact ~JIith the sulfur oxi~es contained in the 2 x ~ a u s t .. 2 s - s .
Tha oroportioning of the solid d2sulfurizing aoents use~ ~o oind the oxi~es of sulfur in a eas-solid reaction is roblz~atic because it is often necessa,y to usz the desulfur~
izi~nq aoent in a finely ~ivided stzte to orovi~ the require~
r~eactivity out that âtate involves an undasired beha\/ior as renards Flow 8nd a~glo~eration. ~or this reason, nu~erous atte~pts have been ~3de to use the ~esulfurizino ~nt in lu~p ~ -nr nellet sor~ ~lthcu~h this results in nu~orous cases in a decr~'aso of t~e reactiv ty bacalJse it isl oft~n nccess3rl/ tu .
use tho activz inqre~ient of the ~esul~urizino sqent in a three-fo~d over stoinchio~ztric surPlus in relation to thz sulfur oxide cont2nt nf the exhaust nases.
For this re~.cion it is an object of the invention tp nrs\/i~o 3 desulfurizinn anent Jhich h3s a hinh r2astivitv ,!hon it is used in lu~p for~ and ~,~hich has a hinh ~echanica strenoth. It is also an object of the inventian to orovi~e orooess cf orr~ucino ~he desulfurizino agont.
The 3b~ct un5erlyinn the invertion is accomPlishe~
in th3t the ~esulflJrizinq anent consists Df 3 to 10,c by weiqht 3ro~n coal ash, 5alance calciu~ hy~.roxide, and is !Jsed in a oelletized fPr~ as pellets l~hish are L7.? to 3 ~m, preFerably : . :
G.5 to ~ ~, in ~iameter. Curorisingly it has boen foun~ that bro~lln caal ash cn~oosed of 5 to 15~ by weirht silica, L to ~C, by llJeiqht alu~ina, ?0 to 57:J by ~ei~ht (total) calciu~ oxi~e, . ~ ~.
.5 to 5'. by weisht maqnesia, 7 to ?5~. by weinht sulfat2, cal~
su13t3d 2s CC3, and 3 to :15~' by l~eioht free calciu~ oxide, ~.Ji oermit a oDlletizino of calsiu~ hydroxi~o if s~i~ bro~n coal 3gh is cnrtaine~ in an 3mount from ~i to 102.~' by wziqht in cal~
ciu~ hy.1roxido sellets. The oellets h2ve 3 hioh reastivity and ere i.~ to } ~m in di3mct2r an~ owinn to their hioh ~echanical strsn.th can readily be suDolied to tho -o~bust~on chamber, in whish~ore than 50,~ of their s~lsiu~ hydroxide cont2nt are ;~
convert2d to salciu~ sulfat2 3nd no s21ciu~ sulfite is for~e~
T~is.~eans that Ithe ine!lliets have a qaod,dosulfurizijno activity at a rsaction te~oerztur2 fro~ 75C to 'J5~C. :
The ob~2st underlyinq the inv2ntion is zlso ac-co~plishod by a orocess of oroducinq the desulfurizinc agent :~. -: ::
in ~Ihich fine-qrained calcium hydroxide havinc a ~nartisle . .~ "~ :
diameter helow 50 u~ are ~ixed, that ~lixturP i5 o~ tizPr1 ~ith 2n 2ddition pf 15 to 43,~ Dy weioht, preforably 7~ ~0 3,~, by wQiaht, ~ater, an~l the areen Dellots arz ~rie~ at 70 to 1~L._ Far 3~ to ~30 ~inutos. The oelletized dPsulfurizina agent ~.Jhic:~ .
iq oroduced by the orocos5 in a-cor~ance with 'he invention : .
~as a '!io~ ~eshani_al strenath and 3 high reacti~/ity and can -asily hr orooo~tiona~. .qnv variatiDn of the water content D~ the -zlciu~ hv~r_xi~e us~d to Droduce the desulfurizinq anent is co~pensat~d bv ~ v3riation of the rate of the Llater ~ ~
requirPd fcr Pzllotizinn- ~ :
In a-_cordance l,)ith the invention it has ~roved parti~ularly [lesirabl2 to use the hydratert li~e forned by thz reaction of c21cium carbirie 2nd water as a fin~-grained ral-ciu~ hydroxi~ie, That hydrater' li~ne cpntains calziu~ hydroxido as its ~2in cDnstituent and o~lins to its s~all narticl2 qize :. :~
can well ~e ~ixed Wittl the brown caal ash.
In acsordance with the invention it is also con-temDl3t~ri to usP tha desulfurizin~l .er,ent for a dssulfurization : -of com~ustion exhaust 03sos which are ~sr~erl by the co~hustion oF sulfur-c~ntaininq Fuels in 3 circulatino rluidizert bed, wheroin the oell~'iz2d dnsulfurizin3 alent is intrsduced inta ;~
thP rC~actcr tdnP~hrfr~ ith the Fuel anr! ils ~'is_harne,d fr~ the reaztor tar!eth~r with the ash and t~e sulfur zontaineri in the :fuel i3 al!nost entirely container.~. as calciu~ sulfate in tn- ~-:.~ - :
~ixed 90ll ds sonsistinn of ash anc! ~izsulfurizinq aoent. It ~as ~: :
.
C
surprisinnly ~ezn found that the oellzts have su_h a hioh strenath that the wear and disintearation of the oPllets ~,!ill be slrw z\/on under the con~itions in a circulatina Fluidizsd ~ed so that the dosulfurizinn a~ent and its reacti3n products ~ill bz s3ntaine~l in the ash in a finelv ~ivido~ sta~e rather ~ -than as ~ust. r-esi~ie3, in a circulatinq fluidi~ed -Jod~ which is o~-r3t-~ at z co~bustion te~loeraturo fr3~ 33~ to 953C a hioh dzqrzz ~f ~2sulfurization olinn to a ~o~naratively hi~h reac- -tivity of the ~esulfurizinn aqent will be achievad ~zcauae Torz than a!~; of thz calciu~ hydroxi~2 which is c~ntained in the desLIlfurizinr agent are almost entirely reacted to fcr~ cal-cium sulfate. This shows that the desulfurizin~ agent which ha3 the nztur2 definad 3y the invention and has be2n nrodIlced in accordancz Ilth the invrntion will have a ozrticularly desirabla effoct !L~ en it is use~ to desulfuriza the combustion exhauât as2s fro~ a 13roo fuzl-firinn ol~n' LIhich ia ooerated 2S a circulatino fluidized bed.
; Thz subject metter 3f t~z in~ention will now be einf~d ~ore in detail with refqrencr- to ~n ex2m~1e~
The hy~rated li~e ~L!~ich i3 formo~ .Sy the dry n-sification of calcium szrbi~z and s3ntzined 4 to 5,- oy L~einht ater in~ 5 i~o lC;;i'i~iv w!~ioht drv ~attar, ~lIhish ~rV ~atter scn-3isted of ~.5 to 1,~ by weighL saL-ium c~r30n3tz as an im3uritV, balance c31ciu~ hydroxide, was ~ixed L~ith 5; by I,lei~ht brown c031 fLy ash, moistene~ ILlith water and pqll2ti~e~. The averagz article diametzr of the hydrate~ e amounted to 75 um and zol~3sn that nf the brown coal -sh 3~l0unted to 7G om. .~5 ~o u~.er ~as added o~r kq of ~ixed Fuels. Tha ~ixin~ an~ moistanino ooerations w~re perfor~ed in a olur31ity of s anes. ~ufFi-ciently 3trons ~reen oell~ts were oro~uced by the oelletizin~.
Th2 brolJn cosl flv ash supJlied cnnsisted oF e,.s; oy weight silica, 1~.3;~ oy Leinht alu~ina, 45.3 ay l~aisht calciu~ oxid~
and 17.5 oy ~eicht C03 The fly 3sh rontained alss 7 by wPinh unco~!lbuste~ carbon end aoout 15.k; bv ~,~eioht of freP
calcium oxide. The areen oellats were ~ried at 133r for J~
minutes cn a travelino ~rate. The ~ear of the ~ried nellets is very s~all an~ wes tested in that pellet sa~ol2s were vibrate~
on a sieve tower or aO ~ninuteS. In exDariments carr-ed out in - fuel-firinn pl3nt oDeratnd 25 3 circulatino fluidized bed it ~35 found that the ~ried qra~n oallets ~o not disintagr3t2 0 3 03rticla Siza llhich is smaller th3n that of tha circulat-inn solids (ash). The desulfurizati.n rate or the driad graen z112ts ~- i.a. the nercentaoe rate of the calciu~n hydroxi~2 hich is raacted with sulfur oxi~e3 - is hioher t~an the c'esul~
furization rate of unnellntizad hy~rate~ 2 ~hich has oeen recover~d fron calciu~ _arbide. Fcr ins ance 4~/ oF the cal-cium hy~roxi~e cont2nt of unpelletize~ hy~rat-d lime are con-verte~ within 170 ~Ih~ereas 50" of the calciu~ hydrox!idP which is contain~ in the dr e~ ~re~n oellets in accordanc2 llith th2 in-vention are converted within th~t time. ucnvPrsiDns of 55' and ~ -)5;~, r~spectively, were ~easur2d ~ithin ~ reaction ti~e of 1g3 ninutes.
This invention rzlates to a desulfurizing agent ~hich is used to remove the oxides of sulfur from combusticn exh2ust Gases. Thz invention relates als3 to a process of ~rDducinq the ~esulfurizino a~ent and to the us- af the de-sulfurizinq aoent.
ossil fuels (true c~al, brown coal, oeat, pztrc-leum~ contain sulfur comoounds in various a~Dunts. Qs the fuels 3re combustod, oreferentially ~C2 and a s~all amount of ~33 are fnrmed from said sulfur comoounds. ~s a result, the exhaust qases ~raduce~ ~y the combustion of fossil fuels con-tain as much as 10,C~0 mo SC? per s~3 (S~3 = standard cubic ete~r). In the Fz~sral QenlJ~lic of ~er~any the 3vera~e C5z con-te~nt oF the conbusti~n axhaust nas~s ~ay 3e assu~ed to a~ount to~betl~ein 10CC an~ zOao ~0 ~G7 02r s~3. 9ecause the oxides af -~
sulfu~r a~re tOXlC ~to the znvironment .~lhen they enter the atmos~
~Z~ p~ere, the oxides of sulfur must ~e re~Dve~ fro~ the com~ustion -xhaust~gas~es~3s~cc~ple~tely as possible, particularly because x ~ ~ very~sub5t~antlal quantltles of fossil fuels arP combusted ~or ~m ~ o~o~zr~oraduction~
It is '~nown to contact combustiGn exhaust gases with~solid ~ès'ulfuri;zina aoents so that ~the Gxides ofl sulfur react~ ith the ~esulfurl~zlnD, aqent ~ith formation oF soli~ sul~
f~a-tes and sulfltes. ~articularly calcium oxide, calcium hydrox-e~an~d oal~ium carbonat- are used as solid desulfurizina aGent :~ :
Z0~0350 ano rea_t with SO7 and ~C3 3t elevate~ temDeratures in the nresence oF oxygen to For~ preferentially calciu~ sulfate. '~ut calcium sulfite is 31so for~eo by an undesire~ secon~ary re-ac.,ion in variDus amounts, which deoand on the reaction con-d~ti2ns. The re~cti~/ity of the ~esulfurizinq anents is parti-culerly dP~ermine~ by their Darticle size, crystal structure an~ ~erhanical strennth. ~'hereas so~e deâulfurizinn a~ents (suoh aà li~estone) arz directiy fed to the co~bustion cha~ber, other ~esulfurizing aoents are reactPd llith the sulfur nxide5 of th2 ca~bustion exhaust ~aszs in a soli~-gas reaction which uCo2~ds the ca~bustion. The ~a~ which is containz~ in the fuel ash will also rzact ~JIith the sulfur oxi~es contained in the 2 x ~ a u s t .. 2 s - s .
Tha oroportioning of the solid d2sulfurizing aoents use~ ~o oind the oxi~es of sulfur in a eas-solid reaction is roblz~atic because it is often necessa,y to usz the desulfur~
izi~nq aoent in a finely ~ivided stzte to orovi~ the require~
r~eactivity out that âtate involves an undasired beha\/ior as renards Flow 8nd a~glo~eration. ~or this reason, nu~erous atte~pts have been ~3de to use the ~esulfurizino ~nt in lu~p ~ -nr nellet sor~ ~lthcu~h this results in nu~orous cases in a decr~'aso of t~e reactiv ty bacalJse it isl oft~n nccess3rl/ tu .
use tho activz inqre~ient of the ~esul~urizino sqent in a three-fo~d over stoinchio~ztric surPlus in relation to thz sulfur oxide cont2nt nf the exhaust nases.
For this re~.cion it is an object of the invention tp nrs\/i~o 3 desulfurizinn anent Jhich h3s a hinh r2astivitv ,!hon it is used in lu~p for~ and ~,~hich has a hinh ~echanica strenoth. It is also an object of the inventian to orovi~e orooess cf orr~ucino ~he desulfurizino agont.
The 3b~ct un5erlyinn the invertion is accomPlishe~
in th3t the ~esulflJrizinq anent consists Df 3 to 10,c by weiqht 3ro~n coal ash, 5alance calciu~ hy~.roxide, and is !Jsed in a oelletized fPr~ as pellets l~hish are L7.? to 3 ~m, preFerably : . :
G.5 to ~ ~, in ~iameter. Curorisingly it has boen foun~ that bro~lln caal ash cn~oosed of 5 to 15~ by weirht silica, L to ~C, by llJeiqht alu~ina, ?0 to 57:J by ~ei~ht (total) calciu~ oxi~e, . ~ ~.
.5 to 5'. by weisht maqnesia, 7 to ?5~. by weinht sulfat2, cal~
su13t3d 2s CC3, and 3 to :15~' by l~eioht free calciu~ oxide, ~.Ji oermit a oDlletizino of calsiu~ hydroxi~o if s~i~ bro~n coal 3gh is cnrtaine~ in an 3mount from ~i to 102.~' by wziqht in cal~
ciu~ hy.1roxido sellets. The oellets h2ve 3 hioh reastivity and ere i.~ to } ~m in di3mct2r an~ owinn to their hioh ~echanical strsn.th can readily be suDolied to tho -o~bust~on chamber, in whish~ore than 50,~ of their s~lsiu~ hydroxide cont2nt are ;~
convert2d to salciu~ sulfat2 3nd no s21ciu~ sulfite is for~e~
T~is.~eans that Ithe ine!lliets have a qaod,dosulfurizijno activity at a rsaction te~oerztur2 fro~ 75C to 'J5~C. :
The ob~2st underlyinq the inv2ntion is zlso ac-co~plishod by a orocess of oroducinq the desulfurizinc agent :~. -: ::
in ~Ihich fine-qrained calcium hydroxide havinc a ~nartisle . .~ "~ :
diameter helow 50 u~ are ~ixed, that ~lixturP i5 o~ tizPr1 ~ith 2n 2ddition pf 15 to 43,~ Dy weioht, preforably 7~ ~0 3,~, by wQiaht, ~ater, an~l the areen Dellots arz ~rie~ at 70 to 1~L._ Far 3~ to ~30 ~inutos. The oelletized dPsulfurizina agent ~.Jhic:~ .
iq oroduced by the orocos5 in a-cor~ance with 'he invention : .
~as a '!io~ ~eshani_al strenath and 3 high reacti~/ity and can -asily hr orooo~tiona~. .qnv variatiDn of the water content D~ the -zlciu~ hv~r_xi~e us~d to Droduce the desulfurizinq anent is co~pensat~d bv ~ v3riation of the rate of the Llater ~ ~
requirPd fcr Pzllotizinn- ~ :
In a-_cordance l,)ith the invention it has ~roved parti~ularly [lesirabl2 to use the hydratert li~e forned by thz reaction of c21cium carbirie 2nd water as a fin~-grained ral-ciu~ hydroxi~ie, That hydrater' li~ne cpntains calziu~ hydroxido as its ~2in cDnstituent and o~lins to its s~all narticl2 qize :. :~
can well ~e ~ixed Wittl the brown caal ash.
In acsordance with the invention it is also con-temDl3t~ri to usP tha desulfurizin~l .er,ent for a dssulfurization : -of com~ustion exhaust 03sos which are ~sr~erl by the co~hustion oF sulfur-c~ntaininq Fuels in 3 circulatino rluidizert bed, wheroin the oell~'iz2d dnsulfurizin3 alent is intrsduced inta ;~
thP rC~actcr tdnP~hrfr~ ith the Fuel anr! ils ~'is_harne,d fr~ the reaztor tar!eth~r with the ash and t~e sulfur zontaineri in the :fuel i3 al!nost entirely container.~. as calciu~ sulfate in tn- ~-:.~ - :
~ixed 90ll ds sonsistinn of ash anc! ~izsulfurizinq aoent. It ~as ~: :
.
C
surprisinnly ~ezn found that the oellzts have su_h a hioh strenath that the wear and disintearation of the oPllets ~,!ill be slrw z\/on under the con~itions in a circulatina Fluidizsd ~ed so that the dosulfurizinn a~ent and its reacti3n products ~ill bz s3ntaine~l in the ash in a finelv ~ivido~ sta~e rather ~ -than as ~ust. r-esi~ie3, in a circulatinq fluidi~ed -Jod~ which is o~-r3t-~ at z co~bustion te~loeraturo fr3~ 33~ to 953C a hioh dzqrzz ~f ~2sulfurization olinn to a ~o~naratively hi~h reac- -tivity of the ~esulfurizinn aqent will be achievad ~zcauae Torz than a!~; of thz calciu~ hydroxi~2 which is c~ntained in the desLIlfurizinr agent are almost entirely reacted to fcr~ cal-cium sulfate. This shows that the desulfurizin~ agent which ha3 the nztur2 definad 3y the invention and has be2n nrodIlced in accordancz Ilth the invrntion will have a ozrticularly desirabla effoct !L~ en it is use~ to desulfuriza the combustion exhauât as2s fro~ a 13roo fuzl-firinn ol~n' LIhich ia ooerated 2S a circulatino fluidized bed.
; Thz subject metter 3f t~z in~ention will now be einf~d ~ore in detail with refqrencr- to ~n ex2m~1e~
The hy~rated li~e ~L!~ich i3 formo~ .Sy the dry n-sification of calcium szrbi~z and s3ntzined 4 to 5,- oy L~einht ater in~ 5 i~o lC;;i'i~iv w!~ioht drv ~attar, ~lIhish ~rV ~atter scn-3isted of ~.5 to 1,~ by weighL saL-ium c~r30n3tz as an im3uritV, balance c31ciu~ hydroxide, was ~ixed L~ith 5; by I,lei~ht brown c031 fLy ash, moistene~ ILlith water and pqll2ti~e~. The averagz article diametzr of the hydrate~ e amounted to 75 um and zol~3sn that nf the brown coal -sh 3~l0unted to 7G om. .~5 ~o u~.er ~as added o~r kq of ~ixed Fuels. Tha ~ixin~ an~ moistanino ooerations w~re perfor~ed in a olur31ity of s anes. ~ufFi-ciently 3trons ~reen oell~ts were oro~uced by the oelletizin~.
Th2 brolJn cosl flv ash supJlied cnnsisted oF e,.s; oy weight silica, 1~.3;~ oy Leinht alu~ina, 45.3 ay l~aisht calciu~ oxid~
and 17.5 oy ~eicht C03 The fly 3sh rontained alss 7 by wPinh unco~!lbuste~ carbon end aoout 15.k; bv ~,~eioht of freP
calcium oxide. The areen oellats were ~ried at 133r for J~
minutes cn a travelino ~rate. The ~ear of the ~ried nellets is very s~all an~ wes tested in that pellet sa~ol2s were vibrate~
on a sieve tower or aO ~ninuteS. In exDariments carr-ed out in - fuel-firinn pl3nt oDeratnd 25 3 circulatino fluidized bed it ~35 found that the ~ried qra~n oallets ~o not disintagr3t2 0 3 03rticla Siza llhich is smaller th3n that of tha circulat-inn solids (ash). The desulfurizati.n rate or the driad graen z112ts ~- i.a. the nercentaoe rate of the calciu~n hydroxi~2 hich is raacted with sulfur oxi~e3 - is hioher t~an the c'esul~
furization rate of unnellntizad hy~rate~ 2 ~hich has oeen recover~d fron calciu~ _arbide. Fcr ins ance 4~/ oF the cal-cium hy~roxi~e cont2nt of unpelletize~ hy~rat-d lime are con-verte~ within 170 ~Ih~ereas 50" of the calciu~ hydrox!idP which is contain~ in the dr e~ ~re~n oellets in accordanc2 llith th2 in-vention are converted within th~t time. ucnvPrsiDns of 55' and ~ -)5;~, r~spectively, were ~easur2d ~ithin ~ reaction ti~e of 1g3 ninutes.
Claims (6)
1. A desulfurizing agent, characterized in that it consists of 3 to 10% by weight brown coal ash, balance calcium hydroxide, and is used in a pelletized form as pellets which are 0.2 to 3mm, in diameter.
2. A desulfurizing agent according to claim 1, wherein the pellets are 0.5 to 1mm in diameter.
3. A process of producing a desulfurizing agent characterized in the fine-grained calcium hydroxide having a particle diameter below 50 µm and 3 to 10% by weight brown coal ash having a particle diameter below 50 µm are mixed, that mixture is pelletized with an addition of 15 to 40% by weight, water, and the green pellets are dried at 20 to 100 degrees C for 30 to 300 minutes.
4. A process of producing a desulfurizing agent characterized in that fine-grained calcium hydroxide having a particle diameter below 50 µm and 3 to 10% by weight brown coal ash having a particle diameter below 50 µm are mixed, that mixture is pelletized with an addition of 20 to 30% by weight, water, and the green pellets are dried at 20 to 100 degrees C for 30 to 300 minutes.
5. A process according to claim 2, characterized in that hydrated lime resulting form the reaction of calcium carbide and water is used as a fine-grained calcium hydroxide.
6. Use of the desulfurizing agent according to claim 1 for the desulfurization of combustion exhaust gases which are formed by the combustion of sulfur-containing fuels in a circulating fluidized bed, wherein the pelletized desulfurizing agent is introduced into the reactor together with the fuel and is discharged from the reactor together with the ash and the sulfur contained in the fuel is almost entirely contained as calcium sulfate in the mixed solids consisting of ash and desulfurizing agent.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3908019A DE3908019C1 (en) | 1989-03-11 | 1989-03-11 | |
| DEP3908019.6 | 1989-03-11 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2010350A1 true CA2010350A1 (en) | 1990-09-11 |
Family
ID=6376169
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002010350A Abandoned CA2010350A1 (en) | 1989-03-11 | 1990-02-19 | Desulfurizing agent and process of producing it |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0387928A3 (en) |
| AU (1) | AU5117690A (en) |
| CA (1) | CA2010350A1 (en) |
| DE (1) | DE3908019C1 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2063890C (en) * | 1991-03-27 | 2007-03-13 | Masami Miura | Mutant aox2 promoter, microorganism carrying same, method of preparation thereof and production of heterologous protein using such microorganism |
| DE19607026A1 (en) * | 1996-02-24 | 1997-08-28 | Abb Research Ltd | Flue gas cleaning process for municipal refuse incineration plants |
| CN1099314C (en) * | 1998-06-26 | 2003-01-22 | 林石英 | Active calcium and active carbon mixed absorbent, producing method thereof and use for purifying coal gas |
| DE102009045278B4 (en) | 2009-10-02 | 2011-12-15 | Dirk Dombrowski | Mineral granular desulphurising agent based on calcium hydroxide, process for its preparation and its use |
| DE102011112657B4 (en) * | 2011-09-06 | 2015-02-12 | Fels-Werke Gmbh | Gas absorption granules and its use |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4230460A (en) * | 1978-10-31 | 1980-10-28 | Maust Jr Edwin E | Method for enhancing the utilization of powdered coal |
| DE2944989A1 (en) * | 1979-11-07 | 1981-05-21 | Deutsche Kommunal-Anlagen Miete GmbH, 8000 München | Purificn. of gases from pyrolysis of wastes - with reduced pollution from disposal of used absorbents |
| DE3128903C2 (en) * | 1981-07-22 | 1983-09-08 | L. & C. Steinmüller GmbH, 5270 Gummersbach | "Method for introducing additive into a reaction gas stream" |
| HU200361B (en) * | 1987-12-28 | 1990-05-28 | Gyoergy Vamos | Composition and process for reducing slagging of boiler furnaces and sulfur emission |
| DK153888A (en) * | 1988-03-21 | 1989-09-22 | Fls Miljoe A S | PROCEDURE FOR DISPOSAL OF WASTE |
-
1989
- 1989-03-11 DE DE3908019A patent/DE3908019C1/de not_active Expired - Lifetime
-
1990
- 1990-01-13 EP EP19900200089 patent/EP0387928A3/en not_active Withdrawn
- 1990-02-19 CA CA002010350A patent/CA2010350A1/en not_active Abandoned
- 1990-03-09 AU AU51176/90A patent/AU5117690A/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| AU5117690A (en) | 1990-09-13 |
| EP0387928A3 (en) | 1990-12-27 |
| DE3908019C1 (en) | 1990-06-13 |
| EP0387928A2 (en) | 1990-09-19 |
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