Ammonia Cire STET Update 2015

Needham Technical Center

Ana cire ammonia daga Fly Ash

J. Bittner, S. Gasiorowski, da kuma F. Hrach

rabuwa Technologies, LLC 101 Hampton Avenue, Needham, Massachusetts, USA

Tsokaci

Da wadata da gardama ash samuwa don amfani a matsayin pozzolan a kankare iya mai tsanani tasiri da sakamakon ingancin iska dokokin a kan mai amfani shuka ayyukan. musamman, yadda shafi ragi a NOx, particulate, Say mai3 dauke da aerosol watsi da matakan da ake sa ran bukatar shigarwa na kula da tsarin wanda zai iya amfani da ammonia a matsayin reagent. Dangane da matakin da ammonia ba a cikin flue iskar gas a naúrar precipitators, da tattara gardama ash iya dauke da gurbata da ammonia da farko kamar yadda ammonium sulfate salts.

ST Boats & Technology LLC (STET) Ya ɓullo da wani tsari da ta kawar da ammonia daga gardama ash. A tsari recovers 100% na gardama ash bi da kuma sakamakonsa na ash hadu da dukan bayani dalla-dalla don amfani a kankare. ST ta ammonia kau tsari za a iya amfani da shi kadai ko kuma a hade tare da kamfanin ta carbon rabuwa fasahar. A carbon rabuwa tsari ne ba ta shafa gaban ammonia a kan gardama ash. Wannan ire m offers da mafi ƙasƙanci kudin bayani ga zalunta in ba haka ba unusable gardama ash.

A ST ammonia kau tsarin da aka gudanar a biyu wurare a cikin Amurka da kuma daya a Turai. A ammonia matakan da untreated gardama ash sun bambanta tsakanin 200 da kuma 3000 MG NH3 / kg ash (kashi da miliyan da taro, ko ppm). A ST tsari ya samu nasarar rage ash ammonia matakin zuwa kasa 50 MG NH3 / kg ash. Fiye 500,000 ton na gardama ash an sayar wa shirye mix kankare kera daga ST ta ammonia kau tsari.

Ammonia gurbata Fly Ash

Da wadata da gardama ash samuwa don amfani a matsayin pozzolan a kankare iya mai tsanani tasiri da sakamakon ingancin iska dokokin a kan mai amfani shuka ayyukan.1 musamman, yadda shafi ragi a NOx , particulate, Say mai3 dauke da aerosol watsi da matakan da ake sa ran bukatar shigarwa na kula da tsarin wanda zai iya amfani da ammonia a matsayin reagent. Dangane da matakin da ammonia ba a cikin flue iskar gas a electrostatic precipitators, da tattara gardama ash iya dauke da gurbata da ammonia da farko kamar yadda ammonium sulfate salts 1,2. Domin NOx iko, da flue iskar gas ammonia matakin za a kafa da adadin ammonia "slip‿, i.e. unreacted ammonia ba bayan da SCR ko SNCR naúrar. Don rage particulate ko SO3 aerosol watsi, ammonia ne allura a cikin flue iskar gas kafin da precipitators kuma za a ajiye a kan gardama ash. A mataki wanda wannan ya auku ne dogara a kan SO3 ciki, tashi ash sulfur abun ciki, alkalinity na gardama ash, da ammonia taro, kuma ash loading a flue iskar gas.

Amfani da tashi ash a cikin kankare yana buƙatar tokar kuda tana da takamaiman kaddarorin jiki da sinadarai3. A pozzolanic Properties na ash aka kunna a cikin kankare ta ƙarni na sosai alkaline free lemun tsami daga hydration na siminti. Lokacin da gardama ash ƙunshi ammonia, wannan ammonia ne 'yanci a matsayin gas da mataki na sosai alkaline bayani na kankare. A alkalinity canjawa da ma'auni na ammonium ion a warware kwayoyin ammonia bisa ga wadannan lissafi:

NH4+(AQ) + OH–(AQ) ↔ NH3(AQ) + H2A

A narkar da kwayoyin ammonia ne sauƙi saki daga bayani kamar yadda free ammonia gas.

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Ammonia ne mai karfi da ƙanshi a fili cewa daukawa connotation na barnyards, taki da kuma fitsari. A karfi wari na ammonia ne unacceptable ga kankare m, da kwangila aiki tare da kankare, da na ƙarshe kankare mai amfani.4

A ƙãre Properties na kankare ba adversely shafi lokacin amfani da ammonia gurbata gardama ash, amma wari ne unacceptable, musamman idan kankare da ake amfani a karkashin kasa ko kewaye sarari.5,6,7 Dangane da ƙayyadaddu na wuri, ciki har da adadin sabo iska wurare dabam dabam, ammonia wari da aka samu ba ya zama ƙyãmã lokacin amfani da gardama toka dauke da 100 to 200 MG na NH3 / kg (kashi da miliyan da taro, ko ppm). Domin tabbatar da cewa babu matsaloli suna ci karo da, da ammonia abun ciki na gardama ash ya kamata ba mafi girma daga 100 ppm2,8.

Duk da haka, Bugu da kari na ammonia a da ikon tsara shuka zai iya haifar da gardama ash ammonia abinda ke ciki na 200 to 2500 ppm, Rendering da gardama ash unacceptable don amfani a kankare.8 Kamar wancan, rage ingancin iska da matsaloli da iko da iska watsi da ikon shuke-shuke qara wani m sharar gida dashi matsala kuma qara CO2 greenhouse watsi da kara adadin ciminti amfani a kankare samarwa. Kau da ammonia daga gardama ash haka da cewa ana iya amfani da a kankare za ta amfana da mai amfani da guje wa m sharar gida dashi, da kankare m, mai amfani, kuma na ƙarshe mai zuwa ragewan da kudin na kayan da kuma kara samfurin quality, da kuma yanayi ta rage watsi da greenhouse gas daga ciminti samarwa.

The adadin ammonia da ammonium salts samu a gardama ash aka alaka da adadin ammonia ba a cikin flue iskar gas. Ga wani hali pulverized ci naúrar ta amfani da gabashin bituminous kwal da wani babban dumama darajar 12,000 BTU / laba (6667 kcal / kg), da flue iskar gas zuwa kwal taro rabo ne kamar 8 to 9.5. Lokacin da ash abun ciki na ci ne 10%, da kuma 80% na ash a ci an gano yadda gardama ash (20% zuwa kasa ash), da flue iskar gas / ash rabo ne kamar 100. Idan duk na ammonia jinsunan ba a cikin flue iskar gas da aka ajiye ko adsorbed a kan gardama ash, da maida hankali da ammonia a cikin ash zai zama kamar 50 sau fi a flue iskar gas a wani taro akai, e.g. wani ammonia “zamewa” na 2 ppm da kundinta zai haifar da wani ash dauke da 100 MG / kg (ppm da wt.) ammonia. Actual ma'aunai nuna wannan dangantaka zama daidai.9 A taro na ammonia a kan gardama ash zai bambanta tsakanin aiki da raka'a dogara a kan ash abun ciki na ci da gardama ash zuwa kasa ash rabo, kazalika da sauran abubuwan.

Ammonia allura zuwa electrostatic precipitators (Esp) don inganta yadda ya dace da kuma rage plume shirin hana haske na iya haifar da sosai high matakan da ammonia a gardama ash. Matsayin har zuwa 2500 ppm ammonia a ash an sami irin wannan tsarin. SNCR ayyukan yawanci aiki tare da ammonia zamewa yawa na 5 to 20 ppm, tare da ash gurbata zuwa matakin na 200 to 1000 ppm ammonia. SCR tsarin kullum an tsara aiki a matsakaicin ammonia zamewa matakan 2 ko 5 ppm, dangane da ƙayyadaddu na shigarwa.10 Kullum, da girma NH3/NOx rabo, da girma NOx rage wanda zai iya samu, tare da hakan ammonia zamewa sakamakon. Duk da haka, ammonia zamewa mafi girma daga 2 ppm na iya haifar da abun cikin ash-ammonia fiye da 100 ppm, samar da wani unmarketable ash.11 Mutane da yawa ikon shuke-shuke a Japan da Jamus aiki SCR raka'a tsara don wani 2 ppm iyakar zamewa gani kadan tasiri a kan marketability na gardama ash.1,5 Duk da haka, wasu SCR ta duniya da aka tsara don 5 ppm ammonia zamewa. Operation wadannan raka'a a wannan high zamewa matakin zai fi yiwuwa sakamakon a mafi girma daga 100 ppm na ammonia a kan gardama ash.

Sarrafa ammonia zamewa to low matakan ma rage plugging da kuma lalata da nisa da tushe kayan aiki saboda shaida na ammonium sulfates.1,10 Guje wa iska preheater plugging saboda wannan sabon abu ne sa ran ya zama ma fi muhimmanci a naúrar aiki a lokacin da kona high sulfur, Amurka garwashin. Kamar wancan, management na ammonia zamewa rage naúrar outage lokaci zai zama mafi girma damuwa fiye da iko da ammonia matakin na gardama ash. A sakamakon

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iya zama cewa babu wani gagarumin matsalar tasowa domin yin amfani da ash a wasu shafukan mai amfani, dangane da takamaiman zane da kuma aiki da watsi kula da tsarin.

A STET Tsari

STET ya ɓullo da wani tsari da ta kawar da ammonia daga gardama ash.12 A tsari recovers 100% na gardama ash bi da kuma sakamakonsa na ash hadu da dukan bayani dalla-dalla don amfani a kankare. STET ta ammonia kau tsari za a iya amfani da shi kadai ko kuma a hade tare da kamfanin ta carbon rabuwa fasahar. A carbon rabuwa tsari ne ba ta shafa gaban ammonia. Wannan ire m offers da mafi ƙasƙanci kudin bayani ga zalunta in ba haka ba unusable gardama ash.

Don cire ammonia a matsayin gas daga gardama ash, da STET aiwatar utilizes guda muhimman hakkokin sinadaran dauki cewa results a ammonia saki a kankare. Liberation of ammonia daga gardama ash bukatar cewa ammonium ion

–kwayoyin ammonia ma'auni a canja a cikin ni'imar ammonia ta gaban Alkali. Tashi toka da ta halitta high alkalinity bukatar wani ƙarin Alkali. Ga kasa alkaline toka, wani karfi Alkali za su bauta. A mafi arha tushen Alkali ne lemun tsami (Cao). A dauki ammonium salts da lemun tsami fede ammonia ne karfi da falala a kansu da sinadaran ma'auni. A sinadaran dauki auku hanzari da zarar da mahadi ake narkar.

A overall dauki za a iya jimlace su kamar yadda:

(NH4)2SO4(s) + Cao(s) → 2NH3(g) + CaSO4(s) + H2A(g)

Duk da haka, da tururi matsin lamba na daskararru ne quite low kuma dauki ba zai iya faruwa a cikin gas ko m zamani. Ammonium sulfate ne sosai narkewa a cikin ruwa da kuma dissociates zuwa ammonium ions da kuma sulfate ions.

(NH4)2SO4(AQ) → 2NH4+(AQ) + SO42-(AQ)

Lemun tsami ne sosai m a kan daukan hotuna zuwa ruwa, na fi son wani sosai exothermic dauki fiye da aka sani a matsayin “slaking”, samar da alli hydroxide ko hydrated lemun tsami.

Caos +H2Ya → Ca(OH)2(s)

A hydrated lemun tsami ne kawai ƙwauro, mai narkewa a cikin ruwa, samar da alli da hydroxide ions.

kamar yadda(OH)2(s) ↔ kamar yadda2+(AQ) + 2 OH–(AQ)

Alli sulfate ne ma ƙwauro narkewa, don haka kamar yadda alli ions aka sanya samuwa ta rushe da hydrated lemun tsami, suna da farko ta cinye hazo da alli sulfate.

kamar yadda2+(AQ) + SO42-(AQ) → CaSO4(s)

A karshe, wani ma'auni wanzu tsakanin ammonium ions da kuma ammonia narkewa a cikin ruwa.

NH4+(AQ) + OH–(AQ) ↔ NH3(AQ) + H2A

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A mataki wanda ammonium ions suna tuba zuwa kwayoyin ammonia ne dogara a kan PH daga cikin ruwa-ruwa tsarin, mafi girma PH ta fi samuwar kwayoyin ammonia. Wannan ma'auni ne da aka sani.13

A key siffa daga cikin STET tsari ne da yin amfani da wani m yawa na ruwa (1 to 4%, yawanci 2%) kuma kadan yawa Alkali (< 2%). Manyan yawa na ruwa ne detrimental ga aiwatar, inda hakan cikin kudi na ammonia saki. PH daga cikin sakamakon ash / lemun tsami / ruwa cakuda ya zama mafi girma daga PH 10.0. Very kananan yawa Alkali suna kara da cewa don tabbatar da wannan PH, dangane da halitta PH na ash. yawanci, kasa da 1% kamar yadda(OH)2 ake bukata, ko da tare da gardama ash tare da sauƙi acidic PH. Alli dangane alkalis ana amfani da sakamakon a kadan canji na gardama ash sunadarai. A tsari aka yi a yanayi zazzabi.

Tun da kudin na Alkali da kuma kudin da bushewa da samfurin ne babbar aiki kudi da kuma sizing da hadawa da bushewa da kayan aiki ne manyan aka gyara na babban birnin kudin, hankali da aunawa da reagent bukatun ga wani takamaiman ash wajibi ne don inganta tattalin arziki da aiwatar.

A tsari kwarara zane don ci gaba da aiki na STET tsari da aka gabatar a Figure 1. Ash, ruwa da Alkali a sarrafawa rabbai an metered zuwa mahautsini. Don tabbatar da m hadawa da kuma uniform watsawa na kara ruwa da Alkali, wani babban tsanani mahautsini da ake amfani da. A wurin zama lokaci a cikin irin wannan mahautsini ne sosai low, a kan tsari na daya na biyu. Ammonia ne nan da nan saki amma cikakken juyin bukatar hadawa sau na 3 to 4 minti don ba da damar for taro kai na gas daga girma na ash don ba da damar for taro kai na gas daga girma na ash.

Don samun wannan hadawa lokaci da kuma tabbatar da kyau kai da ammonia daga girma na ash, mai low tsanani na'urar kamar wani pug niƙa aka yi amfani da matsayin na biyu mahautsini. Tun lokacin da danshi abun ciki na ash ne sosai low, da kayan gudana ta hanyar wannan mahautsini a matsayin mai matuƙar agitated bushe foda. Ammonia gas tattara a duka biyu da high da kuma low gudun mixers ne ko dai sake yin fa'ida ga sa naúrar flue ko ya tuba zuwa nitrogen a wani biyu- mataki catalytic naúrar.

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Figure 1: STET ammonia kau tsari Flow zane

A deammoniated ash ya bushe da isar da kayan ta flash drier cire wuce haddi ruwa. Saboda da kadan adadin ruwan kara, ruwa cinyewa a cikin samuwar hydrated alli sulfate kan dauki tare da narkewa sulfate a cikin ash, da kuma asarar ruwa a lokacin low tsanani hadawa mataki, kawai karamin adadin ruwa bukatar a cire ta drier. Wannan minimizes da makamashi bukatar da bushewa mataki. Karshe ash yanayin zafi na kimanin 150daF sun isa don samar da cikakkiyar kyauta mai gudana, samfurin gardama ash tare da danshi abinda ke ciki da kyau a kasa da ASTM C 618 jaddadawa na 3 wt. %.3

Cikakken aikace-aikacen farko na tsarin cire ammonia na STET ya fara aiki a ciki 2003 a ST ta ash aiki da makaman a Jacksonville Electric Authority St. Johns River Power Park a Jacksonville, Florida. Wannan kasuwanci sikelin aiki iyawa up to 40 ton a kowace sa'a guda daga gurbata ash, rage ammonia abun ciki zuwa kasa 30 ppm. Ammonia matakan da shigowa gardama ash dabam daga ~ 200 zuwa 900 ppm. A tsari ne sosai robust, sakamakon a 90+% ammonia kau karkashin dukkan fitina saituna, samar ash da kyau a kasa mu manufa na matsakaicin 50 ppm ammonia. Karshe danshi abinda ke ciki ne <0.3%. Wakilin sakamakon da aka jera a Table 2. Fiye 250,000 tons of ammonia-contaminated ash has been successfully processed at the Jacksonville facility.

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Table 2: Hankula kasuwanci sikelin ammonia tsarin sakamako

Tashi ash a Big Bend Station a Tampa, Florida aka gurbata da ammonia saboda da allura daga ammonia a cikin ikon shuka ta Esp tsarin sarrafa da watsi da SO3 aerosol generated da SCR NOx kula da tsarin. A sauran ikon shuke-shuke, ammonia samu kuma ya auku tare da SNCR NOx iko da kuma yin amfani da ammonia inganta barbashi tarin a Esp tsarin. A Big Bend, da gardama ash ammonia matakai domin raka'a tare da ammonia allura kewayon daga 750 to 3360 ppm ammonia. Saboda haka, da gardama ash yi nufi ga kankare samarwa dole ne a bi ta ST ammonia kau tsari.

The zane na STET ammonia kau tsari shigar a Big Bend (Figure 2) shi ne na biyu cikakken sikelin da kafuwa da kuma ya hada da mutane da yawa tacewa. Material handling kayan aiki da aka inganta su da damar aiki a mafi girma rates. A bushewa tsarin da aka rage yawan ma'aikata daga baya zane da kuma ya hada da Juyin zafi gas don rage overall makamashi da bukatun na tsarin. A ƙarshe, the ammonia released in the process is fed to a two-stage catalytic unit where the collected ammonia gas is converted into nitrogen. A zafi generated da wannan dauki da aka gano da kuma amfani da himma da kwazo don samar da makamashi da ake bukata na gardama ash flash bushewa tsarin. The use of the two-stage catalytic system results in minimal NOx emissions. A tsari recovers 100% na gardama ash bi da kuma sakamakonsa na ash hadu da dukan bayani dalla-dalla don amfani a kankare.

Wannan kasuwanci sikelin aiki zai iya rike har zuwa 52 ton a kowace sa'a guda daga gurbata ash, rage ammonia abun ciki zuwa kasa 75 MG / kg. A tsari ne sosai robust, sakamakon a 97+% ammonia kau, samar ash da kyau a kasa mu manufa na matsakaicin 100 MG / kg ammonia. Karshe danshi abinda ke ciki ne <0.5%.

An STET ammonia kau tsari ya kasance a cikin aiki a RWE npower Aberthaw tashar ash aiki wurare a UK tun 2008. Aberthaw ƙara da ammonia inganta Esp tarin yadda ya dace tare da ammonia matakan a kan ash hankula 200 ppm da kuma aiwatar da aka tsara don 500 matsakaicin ppm.

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Figure 2: Ammonia kau tsarin a Big Bend Station, Tampa Florida

A Product Ash

A low ammonia gardama ash samfurin gana dukkan sinadaran da jiki da bukatun na ASTM C 618 misali da sakamakon kankare Properties ne m to ash ba hõre da ammonia kau tsari. Table na kwantanta hankula Properties na ash daga daya sa tashar tare da kaddarorin da shuka ash rage a ammonia abun ciki daga 250 MG / kg zuwa 20 MG / kg ta ci gaba da aiwatar ST. Lura cewa kewayon alli oxide ciki lura ga ash daga wannan tushen ne 1.4 to 12%. Bugu da kari na zuwa 1% kamar yadda(OH)2 (0.75% kamar yadda Cao) zai haifar da kawai qananan canje-canje a cikin ash sunadarai, Fadada canzawa insignificantly.

Kankare gwaji yi a kan deammoniated ash nuna shi ya zama mai kyau pozzolanic abu. Compressive ƙarfi ci gaba da amfani da wannan ash ne kamar yadda mai kyau a matsayin ko mafi alhẽri daga unammoniated ash daga wannan tushen. Dogon lokaci kankare karko Properties ne ma kyau kwarai, ciki har da inganta lalata juriya, sulfate juriya, chloride permeability, da lemun tsami shrinkage.

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Table na: Tashi Ash jiki da kuma sinadaran Properties.

Takaitacciyar

A mataki wanda mai kyau ingancin gardama ash za a damuwa a matsayin sakamakon NOx ko particulate watsi da tsarin a nan gaba za su dogara a kan fasahar zabi sanya ta utilities don rage NOx, particulate al'amari watsi da plume shirin hana haske. Duk da haka, STET ta ammonia kau tsari za a iya amfani don cire ammonia daga gurbata ash, samar da wani high darajar abu don yin amfani a kankare samarwa. Gano ammonia za a iya sake yin fa'ida ga sa naúrar for reutilization. This ammonia removal process can be installed as a stand-alone system or can be used in conjunction with STET’s successful fly ash carbon removal system.

1Stewart, B.R., Niyya Gurbin EPA ta Recent lemar sararin samaniya sufuri Rule, aikace-aikace, 1999 Taro kan Zaɓaɓɓen Catalytic da Rage Ragewar Ragewar Rashin Kataliya don sarrafa NOx, Mayu 1999, pp.9-10.

2Sloss, L. L., Hjalmarsson, A-K, kotu, H.N., Campbell, L.M., Stone, D.K., Sharif, G.S., Emmel, T., Naebodi, M., Livengood, C.D., Markussen, J. Nitrogen oxides Control Technology Gaskiya Littafi, Noyes Data Corporation, pp. 94-95, 1992

3“Standard Musammantawa for Coal Fly Ash kuma Raw ko Calcined Halitta Pozzolan for Amfani matsayin Ma'adinai admixture a Kankare”, ASTM C 618, American Society for Testing da Materials, Philadelphia, PA.

4Majors, R.K., Hill, R., McMurry, R., Thomas, S., A Nazarin Tasirin ammonia Allura a kan marketable Fly Ash ciki har da Quality Control Laifuka, aikace-aikace, 1999 Taron zababben catalytic da kuma Non-catalytic Rage ga NOx iko, Mayu 1999, pp.11-13.

5Daga can Brugghen, F.W., bako, C.H., Van den Berg, J.W., Kuiper, W.H., Visser, R., Matsaloli ci karo da lokacin da amfani da Ammonium gurbata Fly Ash. aikace-aikace: EPRI / EPA 1995 Hadin gwiwa Taro kan Station konewa NOx Control, Mayu 16-19, 1995. littafi 4, Zama 8A, pp. 1-16.

6Van den Berg, J.W., Cornelissen, H.A.W. ,Effect na low NOx Technologies a kan Fly Ash Quality, aikace-aikace: 13th International Taro kan Amfani da Management of Coal konewa Products, 1999, pp. 29-1 – 29-11.

7Koch, H-J., Prenzel, H., Gwaje-gwaje a kan wari aukuwa a Gyare na wani Kankare Screed – Yin amfani da NH3-Gurbataccen Fly Ash, Kankare Precasting Shuka kuma Technology, Vol 11, 1989 pp. 72-75.

8Fisher, B.C., Blackstock, T. Fly Ash Beneficiation amfani da ammonia yanã fizge tufarsu Tsari, 12th Taron Taro na Ƙasashen Duniya kan Gudanar da Konewar Kayayyakin Kayayyaki da Amfani, 1997 pp. 65-1 – 65-8.

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9Larrimore, L., Dodgen, D., Monroe, L., Faye hali na ammonia Gurbin kan Ash da Evaluation na Cire Hanyar, aikace-aikace: 13th International Taro kan Amfani da Management of Coal konewa Products, 1999, pp. 16-1 – 16-15.

10Control nitrogen oxide watsi: Zababben catalytic raguwa (SCR), Tsabta Coal Technology, Topical Report Number 9. U.S. Ma'aikatar Kula da Makamashi da kuma Kudancin Company Services, Inc. Yuli, 1997.

11O'Connor, D., Larrimore, L, Dodgen, D., Monroe, L., Tasirin Rage NOx na tushen Ammoniya akan Fly Ash: Ammonia adsorption a kan Ash, aikace-aikace, EPRI-DOE-EPA Combined Utility iska Control Taro: A Mega Taro, Agusta, 1999, takarda # 16.

12Gasiorowski, S.A., kuma Hrach, F.J., Hanyar for Ana cire ammonia daga ammonia gurbata Fly Ash, United States Patent Number 6,077,494, Yuni 20, 2000.

13Thurston, R.V., Russo, R.C., Emerson, K., Mai ruwa-ruwa ammonia ma'auni – Taswirar Kashi na Ammoniya mara ionized, United States kare muhalli, EPA-600 / 3-79-091, Agusta, 1979.

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