swine waste management

7/29/2019 Swine Waste Management

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R E N E W A B L E E N E R G Y F R O M S W I N E W A S T EBingjun He , Univers it y o f Idaho, Mo scow, ID 1

Yua nhui Zha ng, Ted L. Funk , U nivers i ty of I l linois , Urbana, IL 2Ger ald L. Riskow ski , Texas A &M Univers i ty , C ol lege Stat ion, TX 3

ABSTRACT: A t h e r m o c h e m i c a l c o n v e r s i o n ( T C C ) p r o c e s s w a s d e v e l o p e d a n d r e s e a r c h e d t or educe was te and to p roduc e r enewable energy from swine manure . Expe r imen ta l r e su lt sshowe d tha t opera t ing t em pera tu r e and r e t en tion t ime were the key pa ramete r s . I t i s c r i ti ca ltha t a p rocess gas , r educ ing o r non- r educ ing gases bu t no t wa te r vapor , be added to theprocess in o rder to y i e ld an o il p roduc t . The opera t ing t empe ra tu r e r anged f rom 275C to350C, co r r espond ing o pera t ing p r essu res ranged f rom 5 .5 to18 MPa . The in i ti a l p r essu reso f p rocess gases were 0 .34-2 .76 M Pa (50 to 400 ps i) . Oi l p roduc t was eva lua ted bye lementa l ana lys i s , hea t ing va lue , and benzene so lub il i ty . Oi l v i scos i ty and i ts change vs .s to r age time w ere a l so s tud ied . T yp ica l o i l y i e ld o f the TC C process r ange d f rom 60% to65% on the inpu t vo la t il e so l ids . The av erage e l ementa l com pos i t ion o f the r aw o i l p roduc t swas 71 .1% carbon , 8 .97% hydro gen , 4 .12% n i t rogen , 0 .2% su l fu r , and 3 .44% ash . The wa te rcon ten t o f r aw o i l va r i ed f rom 11 .3% to 15 .8%, which was l e ss depend en t on the opera t ingparamete r s . The average hea t ing va lue o f the o i l p roduc t s was 32 ,500 kJ /kg . Theseproper t i e s a r e comparab le to those o f l i quefac t ion o i l s f rom wood s ludge and o the r b iomass .When CO was as the p rocess gas , t he o i l v i scos i ty was a t t he l eve l o f 0 .5 Pa . s a t opera t ingtempera tu r es o f 315C-350 C. The v i sco s i ty inc r eased in the fi r s t 15d o f s to rage , and d id no tsubs tan t i a l ly change over the r es t o f t he 60d s to r age t ime . The TCC o i l con ta ins h igh su l fu rand n i t rogen con ten t . Fur the r inv es t iga t ion i s necessa ry to r educe the h igh n i t rogen and su l fu rcontent before the ful l u t i l izat ion of the oi l product can be achieved.

I n t r o d u c t i o n

The impac t o f l a rge conf inement opera t ions o f swine f a rms on the env i ronment has causeinc reas ing concerns f rom sc i en t if i c com mun i t i e s and governm ent agenc ies . Odo r emiss ion f rom tswine f ac il i ti e s has bec om e a ma jo r concern o f the r epub l ic . Regu la t ions on manure m anag em ent al ike ly to becom e s t r ingen t . Swine manure , on ce cons ide red a nu t r ien t - r i ch f er t il i ze r, has becom e expens ive burden to the pork indus t ry . On the o the r hand , swine m anure i s a p l en t i fu l source o f b iomatha t has the po ten t i a l t o be conver t ed in to r enewable energy th rough b io log ica l and /o r chemicprocesses . A the rmoch em ica l conver s ion (TC C) p rocess is a chem ica l r e fo rmin g p rocess in which tdepo lym er iza t ion and r e fo rming r eac t ions o f l i gno-ce l lu los ic com poun ds occur in a hea ted and f roxyge n-absen t enc losure . Based on the charac te r i s ti c s and the p roduc t s o f a p rocess , t he TC C processa r e fu r the r ca t egor i zed as pyro lys i s , gas i f i ca t ion , and l iquefac t ion . Among the TCC processes , d i r el iquefac t ion i s the mos t wide ly s tud ied b iomass conver s ion p rocess .

Di r ec t l i quefac t ion was h i s to r i ca l ly l i nked to hydrogena t ion and o the r h igh-p ressu re the rmdecompos i t ion p rocesses tha t employ r eac t ive hydrogen o r ca rbon monox ide (CO) to p roduce a l i qu

Bingjun (Brian) He, assistant professor, D epartm ent of Biological and A gricultural Engineering, U niversity of Idaho, M oscow, ID 8384Phone: 208.885.7714, fax : 208.885.7908, email: .2 Yuanhui Z hang, associate professor; Ted L . Funk, extension specialist and assistant professor; Departm ent of Agricultural E ngineering.3 Gerald L. Riskowski, professo r and head, D epartme nt of Biological and Agricultural E ngineering.1


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fu e l f ro m o rg an i c ma t t e r . Th e ca rb o n aceo u s ma te r i a l s a re co n v e r t ed t o l i q u e f i ed p ro d u c t s t h ro u g h co m p l ex seq u en ce o f ch an g e s i n p h y s i ca l s t ru c t u re an d ch emica l b o n d s (Ch o rn e t an d Ov e ren d , 1 9 8 5Su ch l i q u e fac t i o n p ro cesse s h ad b een u sed t o co n v e r t c e l l u lo s i c was t e s (Ap p e l l e t a l . , 1 9 8 0 ) , mu n ic ip asewag e s l u d g e (Kran i ch , 1 9 8 4 ) , an d man y o th e r h ig h -mo i s tu re b io mass feed s t o ck s (E l l i o t e t a l . , 1 9 8u s i n g ca r r i er o il s a s reac t i o n m ed ia . In mo s t o f t h e s tu d i e s, l i v e s to ck wa s t e was n o t i n c l u d ed a s a ma jb i o mass re so u rce fo r t h e d i rec t l i q u e fac t i o n p ro cess , a l t h o u g h i t was u sed a s feed s t o ck i n so me p y ro l y ss tud ies (Kre is , 1979) .

Sw i n e man u re i s a c a rb o n -en r i ch e d b io mass . I t h a s t h e p o ten t i a l to b e co n v e r t ed t o a l i q u id op ro d u c t t h ro u g h a TCC p ro cess . To av o id t h e i n t en se en e rg y req u i remen t o f p re -d ry i n g o f t h e swinma n u re a s in p y ro ly s i s , i t i s b en e f i c i a l t o p ro cess f re sh man u re d i rec t l y wi th o u t p re -d ry i n g . W e ex p lo reth e a l t e rn a t i v e mean s t o t r ea t swin e man u re f ro m in t en s i v e p ro d u c t i o n fac i l i t i e s , mean wh i l e , t o p ro d u cren ewab le en e rg y f ro m swin e was t e , b y a t h e rmo ch emica l co n v e rs i o n p ro cess , o r d i rec t l i q u e fac t i oTh i s p ap e r su mmar i ze s t h e o i l p ro d u c t i o n f ro m swin e was t e f ro m o u r p rev i o u s re sea rch an d d e t a i l et ech n i ca l d i scu ss io n s h a v e b een rep o r t ed e l sewh e re (H e e t a l. , 2 0 0 0 a ,b ; 2 0 0 1 a ,b , c ) .

M a t e r i a ls a n d M e t h o d s

T C C R e a c t o rA T C C p r o c e s s u si n g a b a t c h T C C r e a c t o r w a s d e s i g n e d an d d e v e lo p e d . T h e r e a ct o r w a s m a d

o f T3 1 6 s t a in l e s s s tee l wi th a cap ac i t y w as 1 .8 L (0.5 g a l) (Pa r r In s t ru men t s Co m p an y , M o l in e , IL ). co u ld o p e rat e at ex t rem e o p e ra t i o n co n d i t i o n s o f 3 7 5 C (7 0 0 F) an d 3 4 .5 M Pa (5 0 0 0 p s i) . Twag i t a ti o n p ro p e ll e r s 8 0 -m m (3 in ) ap a r t o n a sh a f t we re d r i v en b y a 2 0 0 W mag n e t i c d r iv e . Op e ra t i o n the reac tor was cont ro l led by a co nt ro l le r wh ich fea tured a th ree - te rm Proport ional -Integra l-Differen tialt emp era tu re co n t ro l wi th an accu rac y o f +_ 2C. A h ig h -p re ssu re cab l e t u b i n g c o n n ec t ed t o an in l e t o f tr eac t o r fo r p ro cess g a s i n t ro d u c t i o n . Th e reac to r u n it was h o u sed i n an en c lo sed ch a mb er wh e re ex h au s t f an p ro v id ed a s l i g h t l y n eg a t i v e p re ssu re i n t h e ch amb er t o en su re an y e scap in g g ase s f ro m tp ro cess b e in g ex h au s t ed o u t s i d e o f t h e o p e ra t i n g ro o m, a s i ll u s t rat ed i n f i g u re 1.

Controller 642 fl ~ ~ ]

SafetyHead

Relay

Powe r Supply

To Exhau~

~ TapWater

TCCReactor

~ Valve5Control alve5

~:~ Safety eadQ 5ensors/transduce~

( ~ (T~j Localnd,cat,on5~ ~ Remoteontrol

Fi g u re 1 . I l l u s tra t i o n o f t h e TC C p ro cess an d co n t ro l sch eme .


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FeedstockThe feedstock, f resh swine manure , was col lec ted f rom the par t ia l s lot ted f loor of a swinf in i she r room a t the Swine R esea rch Fa rm , Unive r s i ty of I ll ino is a t Urban a -Cham pa ign . The to tal so l id(TS) , vo la t il e so lids (VS) content s , and pH were 27 .4+1.4% wt , 87 .3+1.3% wt , and 6 .0+0.2 , re spec t ive lThe e lem enta l com pos i t ion w as , % wt dry bas is (m ean _+ SD), C 45.67 +1.1 2, H 6.45_+0.21, N 3.45 +0.3and S 0 .038+0.006. Feeds toc k was prepa red indiv idua l ly for each expe r iment by ad jus t ing the to tsol ids content with tap water to the des ired level .P rocess P arametersThe pa rame te r s in the TCC process inc luded the ope ra t ing t empera ture (T) , p rocess gas in i t i apressure (Pini. ), tota l sol ids con tent (TS ) , pH, and re tent ion t im e (RT). The temp era ture range in ths tudy was 275-35 0C . The cor re spon ding ope ra t ing pre ssure s were 5 .5-~18 M Pa (800-~2600 ps i ). Thprocess gase s inc luded the r educ ing gases of ca rbon monoxide (CO) and hydrogen (H2) and noreduc ing gases of n i t rogen (N2), carbo n dioxide (CO2), and a ir . Th e ini tia l pressu re of process gasranged f rom 0 .34 to 2 .76 M Pa (50 to 400 ps i ) . The e f fec t of pH on the f re sh manure was s tudied a t pH7, and 10. Retent io n t ime var ied f rom 5 to 180 ra in for dif ferent condi t ions . Beca use of the presence abundant m ine ral s and ca rbona te s , no ex t ra ca ta lys t was added throughout the expe r iments .Products Analysis

The TS and VS of the f eeds tock were measured by fo l lowing the procedure s desc r ibed in thStanda rd Me thod s for the Exam ina t ions of Wa te r and W as tewa te r (C le sce r i e t al ., 1989). The e lementana lyses , inc luding ca rbon, hydrog en, n i t rogen (CHN) , and su l fur (S) , we re pe r formed on the o il p roduby a ca rbon-hydrogen-ni t rogen ana lyze r (Mode l CE440, Exe te r Ana ly t ica l , Inc . , N . Che lmsford , Massand Induc t ive ly Coupled P la sm a (Pe rk in E lmer Norwa lk , Cont . ), r espec t ive ly . H igh hea t ing va lu(HHV) of o i l p roduc ts we re ca lcu la ted us ing an equa t ion based on the comple te oxida t ion of ca rbon anhydrogen e lements (He , 2000) :

H H V (kJ/kg) = f . ( 32 , 792 . C + 142 , 900 .H ) + 9 , 275 .S - 2 , 371 . N (Where C, H, S, and N are the weight f rac t ions of carbon, hydrogen, sulfur , and ni t rogen in th

raw oi l p roduc ts , r e spec t ive ly , and f i s a cor rec tion fac tor of oxyg en con tent on hea t ing va lues (1 > f > This equa t ion g ives sma l le r va r ia t ions than the Dulong ' s equa t ion (Sawayama e t a l . , 1996; Se lv ig anGibson, 1945). The low hea t ing va lue (LH V) i s ba sed on the de f in i tion by Rick and Vix (1991) a t tr e fe rence t em pera ture of 25C:

L H V (kJ/kg) = H H V - 2 1 7 . 9 H - 2 4 .4 2" W (where H i s the hyd rogen pe rcentage by w e ight and W i s the wa te r pe rcentage by we ight .Benzene so lubi l i ty content of the TCC oi l p roduc t was pe r formed re fe r r ing to the AST

s tanda rd me thod for pe t ro leum produc ts (A STM , 1999a ). The y ie ld and benzene so lubi l ity of r aw oproduct a re def ined as fol lows:

Oi l so l ub i l i ty (% )- (1 - so l id r e s idue (g ) ) x 100% (to ta l o i l s ample (g)tota l oi l p rodu ct (g)Oil yie ld (%) = x 100% (tota l vola t i le sol ids inpu t (g)

The wa te r content in the r aw TCC oi l p roduc ts was measured by so lvent r ec t i f i c a t ion fo l lowing thprocedure of AS TM Standa rd D95 (AS TM , 1999b) in a ba tch d i s t il l a tion a s sembly . Benzene (ACCert i f ied grade , Fisher Ch em icals) w as se lec ted as the solvent . The w ater con tent of the oi l produ cwas ca lcula ted as fol lows:


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W ater con ten t (%) - wa te r co l l ec t ed in r ece ive r (g ) x 100% (weigh t o f r aw o i l sample (g )

Viscos i ty o f t he r aw o i l p roduc t was measured us ing a Synchro-Lec t r i c v i scomete r (Brookf i eEng ineer ing Labora to r i es , S tough ton , Mass . ) accord ing to the ASTM S tandard D5018 (ASTM, 1999cThe v i scomete r was ca l ib r a t ed wi th g lycer in (Cer t i f i ed ACS grade , F i sher Chemica l s ) and the sp indspeed was se t a t 20 rpm. Sam ples w ere measured a t 65C m ain ta ined by a wa te r ba th .

R e s u l t s a n d D i s c u s s i o n sP roduct Di stri bution

The p roduc t s a f t e r the TC C process w ere d i s t r ibu ted in to four d i f fe r en t por t ions : r aw o i l p roducgaseous p roduc t , so l id p roduc t , and pos t -p rocessed wa te r . The am ount s and co mpo s i t ion o f the d i f f e rep roduc t s va r i ed accord ing to the opera t ing cond i t ions . The inpu t vo la t i le so l ids d i s t r ibu ted among afour p roduc t s a f t e r t he p rocess , and the amoun t va r ied wi th the opera t ing cond i t ions . A p rodud i s t ribu t ion based on the average o f 90 exper im en t s w i th CO as p rocess gas i s i l l u s tr a t ed in figu re 2.

( a )post - sol idw a t e r ~ ~ , ~8 2.9 % ~ i ~ ~ . ~ ~ 3 .3 %

~ N ~o il / ~ g a s

8 .9% 4 .9%

In oil62 .3%

16.9%

(b ) In post-wa te r13.0%~_ 1

Insol id7.8%

Fig ure 2 . P roduc t d i s tr ibu t ions . ( a ) t o t a l mass ba lance , and (b ) vo la t i l e so l ids ba lance .Even though the pe rcen tages in each por t ion va r i ed wide ly , t he majo r por t ion o f VS inpu t w

conver t ed in to r aw o i l p roduc t . The p or t ion o f VS in the gas p roduc t w as ma in ly in the fo rm of CO2.T C C O i l P r o d u c t i o n w i t h C O a s P r o c e s s G a s

The conver s ion p rocess o f swine manure to o i l i s s imi l a r t o o the r b iomass l i quefac t ion p rocessand to some ex ten t i t i s even eas i e r a s swine manure con ta ins l e ss l i gn in and the o rgan ic mat t e r waf ine ly "p re -p rocess ed" by the an imal d iges t ion p rocess . On the o the r hand , l e ss li gn in means l e ss energcon ten t and r esu l ts i n a lowe r o il y i e ld (Hum phrey , 1979; Glasse r , 1985) . Swine m anure has h igoxy gen to carbon rat io and low h ydro gen to carbon rat io (Zahn et a l ., 1997; Hru ban t e t a l ., 1978) . Thecharac te r i s ti c s a f fec t t he o il fo rma t ion e f f i c iency nega t ive ly . Af t e r the TCC process , swine manus lu r ry was co mple te ly c onver t ed in to d i f f e ren t p roduc t s . There fo re , t he conve r s ion r a t e was no t used asparam ete r to charac te r i ze the TC C proc ess as in o the r b ioma ss conver s ion p rocesses . Add i t ion o fr educ ing gas i s necessa ry in d i r ec t l i quefac tion . P re l iminary t e s t r e su l t s show ed tha t l i tt l e o r no o rgancarbon was conver t ed to o i l wi thou t the add i tion o f a p rocess . How ever , t he p rocess gas cou ld bereduc ing o r non- r educ ing ( see d i scuss ion on p rocess gas e f f ec t s be low) . Tempera tu r e had a subs tan t ie f f ec t on the o i l f o rmat ion . Depo lymer iza t ion r eac t ions would no t occur un t i l t he t empera tu r e r eachthe leve l where the ac t iva t ion energy i s overcom e. In th is s tudy , t he p r e f e r red o pera t ing cond i t ion f


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s u c c es s f u l f o r m a t i o n o f T C C o i l p r o d u c t w a s 2 8 5 C t o 3 0 5 C , a n d t h e c o r r e s p o n d i n g o p e r a t inpre s sure s we re 6 .8 to 11 . 5 M Pa (1 000 to 1650 ps i ). T he se c ond i t ions we re m uc h m i lde r c ompa re d to tr e por te d ope ra t ing c ond i t ions fo r o the r b ioma ss s tud ie s whe re the ope ra t ing te mpe ra tu re a nd p re s surwe re up to 400 C a nd 40 MPa (5800 ps i ) (E l l io t e t a l . , 1988 ; Kra n ic h , 1984 ; Appe l l e t a l . , 1980re spe c t ive ly .

T he typ ic a l o i l y ie ld o f the T CC proc e s s r a nge d f rom 60% to 65% on the vo la t i l e so l ids inpuT h i s w a s h i g h e r t h a n t h a t i n w o o d a n d m o i s t - b i o m a s s l i q u e f a c t i o n w h e r e i t w a s 2 5 % t o 3 5 % ( F i g u e r oe t a l. , 1982 ; E l l io t t e t a l ., 1988) . T he ra w T CC o i l wa s r e a d i ly s e pa ra te d by g ra v i ty f rom the posproc e s se d wa te r . Org a n ic so lve n t e x t ra c t ion , whic h i s usua l ly ne e de d fo r the r e c ove ry o f l ique fa c t ioo i l s f rom some b ioma ss c onve rs ion p roc e s se s (Booc oc k e t a l . , 1980 ; E l l io t t e t a l . , 1988) , wa s nne c e s sa ry in the T CC proc e s s .E lemental Composition and Heating Values

I t i s ne c e s sa ry tha t b ioma ss -de r ive d o i l s be c ha ra c te r iz e d in o rde r to u t i l i z e the m d i re c t ly a s fuo r f o r f u r th e r u p g r a d in g . T h e c h e m i c a l c o m p o s i t i o n s o f th e b i o m a s s - d e r i v e d o i ls a r e c o m p l i c a t e d a ne x te ns ive num be rs o f c om pou nd s ha v e be e n re por te d (P i skorz e t a l. , 1988 ; E l l io tt e t a l. , 1988 ; Pa kda nd Roy , 1988 ; Ma g gi a nd De lm on , 1994 ; S ip i la e t a l ., 1998) . T he c he m ic a l a nd phys ic a l s t ab i l i ty the b ioma ss -d e r ive d o i l s a re a l so impor ta n t fo r long- t im e s to ra ge o f the oi l s (Adja ye e t a l. , 1992) . In ths tudy , on ly the e le me nta l c ompos i t ion wa s a na lyz e d .

T he e le me nta l c ompos i t ion , the be nz e ne so lub i l i ty , a nd h igh he a t ing va lue s d id no t va ry a s muca s the r a w o i l p rodu c t y ie ld . T he a v e ra ge c a rbon a nd hyd roge n c o mp os i t ion in the r a w o i l p roduc t w71 .1%_+ 4.5% a nd 9 .0%_+ 0.5%, wi th the h ighe s t va lue s o f 77 . 9% a nd 9 . 8% , r e spe c t ive ly . T he a ve ra gn i t r o g en c o n t e n t i n t h e ra w o i l p r o d u c t w a s 4 . 1 % w i t h a st a n d a rd d e v i a t i o n o f 0 . 4 % . A b o u t 3 . 4 % o f tr a w o i l p rodu c t wa s a sh . T he ox yge n c on te n t , c a lc u la te d a s the d i f f e re nc e o f the o the r me nt ion ee le me nts a nd a sh , a ve ra g e d a bou t 12%. Mo is tu re c on te n t o f the r a w o i l p rodu c t r a nge d f rom 11 . 3% 15 . 8% a nd the a ve ra ge be nz e ne so lub i l i ty o f o i l p roduc t wa s a bou t 80%.

Compa r i son o f the a bove re su l t s to those o f typ ic a l pyro lys i s a nd l ique f ie d o i l s i s summa r iz e d ta b le 2 . T he e le me nta l c om pos i t ion o f T C C o i l s i s ve ry s imi la r to tha t o f l ique f ie d o i l ob ta ine d f roke lp (E l l io t t e t a l ., 1988) . T h is me a ns tha t bo th p roc e s se s und e rw e nt a s imi la r c he mic a l me c ha n ise xc e p t tha t the l ique f ie d o i l f rom ke lp wa s ob ta ine d unde r muc h ha r she r ope ra t ing c ond i t ions a nd the oy i e ld w a s m u c h l o w e r ( a b o u t 2 0 % ) . T h e T C C o i ls c o n t ai n e d h i g h e r ca r b o n a n d h y d r o g e n c o n t e n t alowe r n i t roge n c on te n t tha n pyro lys i s o i l s (Ric k a nd Vix , 1991) . T he wa te r a nd a sh c on te n t o f T C C owe re s imi la r to those o f pyro lys i s o i l s . Ho we v e r , the su l fu r c on te n t o f T C C o i l s wa s mu c h h ighe r due the h igh su l fu r c on te n t in the swine ma n ure , wh ic h wa s 0 . 38%. Fur the r t r e a tme nt i s ne e de d in o rde r u t i l i z e the T C C o i l d i r e c t ly a s fue l . T h is f a c to r shou ld a l so be c ons ide re d in s e le c t ing a n upgra d inproc e s s be c a use bo th n i t roge n a nd su l fu r in o i l s a re ma jor a i r po l lu t ion c onc e rns .

Effects o f Dif ferent Process G ases on the ProcessT he p roc e s s ga s e f fe c t s on e le me nta l c ompos i t ion o f the o i l p roduc ts a re summa r iz e d in t a b le

Ba se d on the va r ia nc e a na lys i s o f mul t ip le -popu la t ions fo r the me a n a t 95% c onf ide nc e le ve l , te le me nta l c om pos i t ion s o f c a rbon , hyd roge n , n i t roge n a nd su lfu r be tw e e n d i f f e re n t p roc e s s ga se s wenot s ign i f ic a n t ly d i f f e re n t . T he c a rbon c on te n t s ta ye d a t a n a ve ra ge le ve l o f 72%. Al though td i f f e re nc e be twe e n the c a rbon c on te n t o f the o i l s w i th CO2 a nd H2 a s p roc e s s ga se s wa s 6 . 6%, i t wins ign i f ic a n t be c a us e o f the l a rge va r ia tions o f the me a sure m e nts . W he n CO wa s a dde d a s the p roc eg a s , t h e h y d r o g e n c o n t e n t w a s 9 . 6 % , w h i c h w a s h i g h e r t h a n w h e n o t h e r p r o c e s s g a s e s w e r e u s e d ( a b o8 . 8%) . T h is 0 . 8%w t d i f f e re nc e is ve ry impor ta n t to the e ne rgy c on te n t o f o i l p roduc ts . N i t roge n wh i g h i n a ll m e a s u r e m e n t s , r a n g e d f r o m 4 . 1 % t o 4 . 6 % . I t w a s s l i g h tl y l o w e r w h e n C O w a s a d d e d , a


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s t a y e d at a b o u t t he s a m e l e v e l o f 4 . 4 % w h e n o t h e r p r o c e s s g a s e s w e r e a d d e d . S u l f u r c o n t e n t a ls o s ta y ea t a b o u t t he s a m e l e v e l ( 0 . 2 % ) w i t h d if f e r e n t p r o c e s s g a s e s . W h e n h y d r o g e n w a s u s e d a s t h e p r o c e s s gt h e su l f u r c o n t e n t a p p e a r e d w a s l o w e r . D u e t o t h e l a r g e s ta n d a r d d e v i a t i o n , h o w e v e r , t h i s v a l u e d id ns i g n i f i c a n t l y d i f f e r f r o m t h e o t h e r s b a s e d o n v a r i a n c e a n a l y s i s a t 9 5 % c o n f i d e n c e l e v e l f o r t h e m e a n .

Ta b l e 2 . C h a r a c t e r i s t i c s o f t h e T C C o i l s a n d o t h e r b i o m a s s - d e r i v e d o i ls .T C C P r o c e s sPropert i es

C o m p o s i t i o n , % w tC a r b o nH y d r o g e nN i t r o g e nS u l f u rO x y g e nA s h

W a t e r , %L o w h e a t in g v a l u e , MJ/kg

F e e d s t o c k ( 1 )

(1) Dry matter basis.

4 5 . 6 7 + 1 . 1 26 .45 + 0 .213 .45 + 0 .380.3 8 _+ 0. 06

3 1 . 3 3 (6 )12 .72 + 1 .27

i i

T C C o il (2)7 1 . 1 + 4 . 5

9.0+_0.54 . 1 + 0 . 4

0.2_+0.0312.2_+4.8 (6 )

3.4_+3.113.5_+2.2 (7 )32 .5+2 .3 (8 )

Pyrolys i so il ( 3 )5 0 - 6 7

7 - 88 - 1 0< 0 . 0 1

1 5 - 2 50 . 4 - 1 01 0 - 1 4

2 1 . 1 - 2 4 . 7

Liquef iedo il ( 4 )7 6 . 7

8 .93 .5n/a (5)9 .9n /an /an /a

(2) Averaged from 78 different oil samples with CO as the process gas.(3) Sum ma rized from different pyrolysis and liquefaction processes (Rick and Vix, 1991).(4) Extracted from kelp liquefaction product obtained at 350 C and 27.3-35.5 MPa, CO initialpressure was 5 MPa (Elliott et al., 1988).(5) n/a = not available.(6) By difference, O - 100 - C - H - N - S - ash.(7) Based on 4 measurements. Each measurement was conducted on the mixed samp le of several oilproducts from different runs.(8) Calculated using equation 3.

T a b l e 3 . E f f e c t s o f a l t e r n a t i v e p r o c e s s g a s e s o n e l e m e n t a l c o n t e n t o f t h e T C C o ilp r o d u c t s . T h e o p e r a t i n g c o n d i t i o n s w e r e 3 0 5 C , R T = 1 2 0 m i n , T S = 2 0 % , p i, i =0 . 6 9 M P a , f e e d s t o c k p H = 6 .1 . T h e c o r r e s p o n d i n g o p e r a t i n g p r e s s u r e w a s 1 0 .5M P a . T h e e r r o r te r m s a r e s t a n d a r d d e v i a ti o n s . T h e o x y g e n c o n t e n t o f t h e o i lp r o d u c t s w i t h C O 2 a s t h e p r o c e s s g a s ( t r e a t m e n t A ) w a s s i g n i f i c a n t l y d i f f e r e n tf r o m t h e r e s t ( t r e a t m e n t B ) a t 9 5 % c o n f i d e n c e l e v e l f o r t h e m e a n s .

P r o c e s s G a sCO N2 CO2 H2 Air

Y i e l d s , % w t 5 7 . 1 + 8 . 3 6 4 . 9 _ _ _ 6 . 4 6 0 . 8 + 8 . 0 7 7 . 7 + 0 . 7 7 0.2 _+ 5. 0E l e m e n t c o n t e n t ,%

C a r b o nH y d r o g e nN i t r o g e nS u l f u rO x y g e n

6 9 . 6 9 + 3 . 6 19.58_+0.344 . 0 6 + 0 . 1 30 . 2 3 + 0 . 0 5

7 . 6 7 + 1 . 3 1 B

7 5 . 5 0 + 2 . 5 58 . 9 7 + 0 . 3 84.58_+0.050 . 2 2 + 0 . 0 1

9 . 4 1 + 0 . 1 1 B

6 7 . 2 0 + 0 . 5 78 . 9 0 + 0 . 7 14 . 2 4 + 0 . 2 20 . 2 1 + 0 . 0 2

1 5 . 2 2 + 0 . 5 5 A

7 3 . 8 4 + 0 . 1 18 . 8 8 + 0 . 4 24 . 5 0 + 0 . 5 30 . 1 2 + 0 . 0 8

6 . 7 0 + 0 . 7 7 B

7 1 . 3 6 + 2 . 1 18.81_+0.334 . 4 4 + 0 . 0 10.20_+0.01

1 0 . 2 8 + 2 . 6 1 B


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Unl ike o the r e l emen t s , t he oxy gen con ten t o f the o i l p roduc t s v a r i ed s ign i f i can t ly based on ths t a ti s t ica l ana lys i s . I t happ ened when CO2 was used as the p rocess gas and the oxygen con ten t wa15 .2%, the h ighes t among the f ive p rocess gases . A poss ib l e exp lana t ion i s t ha t t he oxygen e l imina t iof rom b iomass was h indered by the h igh CO2 par t i a l p r essu re p r esen t and no r eac t ion mechan i sms cou lbe expec ted be tween the h igh ly ox ida t ive CO2 and the oxygen -con ta in ing g roups in the b iomass . On tho ther hand , t he oxygen con ten t was lowered when the r educ t ive CO and H2 were added (7 .7% and 6 .7%respec t ive ly ) . High oxygen con ten t l eads to a low hea t ing va lue o f an o i l p roduc t . There fo re , t hadd i t ion o f a r educ ing gas i s des i r ab le fo r ob ta in ing an o i l p roduc t wi th a h igh hea t ing va lue .

Viscosity and Oil StorageViscos i ty i s one o f the mo s t imp or t an t c r i te r i a f o r d if f e r en t i a ting o i l g r ades . A lowe r v i scos i

ind ica tes a h igher l i gh t -o il con ten t i n l i quefac t ion o i l samples . F igure 3 p r esen t s the v i scos i ty o f r aTCC o i ls measured a t 65C as a func t ion o f the TCC opera t ing t empera tu r e . The r esu l ts i nd ica ted ththe v i scos ity o f t he raw T CC o i l samples d r am at i ca l ly dec reased f rom 15 .5 Pa . s t o 0 .843 Pa . s a s the TCopera t ing t empera tu r e inc r eased f rom 285 C to 315C. The v i scos i ty the r ea f t e r l eve led o f f a t 0 .5 Pa. s t he opera t ing t empe ra tu r e fu rthe r inc r eas ed to 350C. Th i s was poss ib ly because decom pos i t ion o rgan ic po lym er s occur r ed be low 315C du r ing the 120 min r e ten t ion time . Com par i son show ed thr aw TC C o i ls had a much h igher v i scos i ty than tha t o f t yp ica l c rude pe t ro l eum o i l, wh ich i s 0 .02 Pa . s 65C (Beckman , 1981) .

0 . . . . . . . .

1 2 -4 , , , , a

>

1 6 -

_

_

".O-_I t ' I

r a e ~

UI ~ ' I 7

280 300 320 340 360TCC opera t ing t empera tu r e ( C)

F igure 3 . E f f ec t o f opera t ing t empera tu r es on o i l v i scos i ty . The o i l samples wereob ta ined wi th CO as the p rocess gas and under the opera t ing cond i t ions o f P in i- 0 .69M P a , T S - 20%, RT= 120 min , and f eeds tock pH - 6 .1 . The co r r espond ing opera t ingpressu res were 7 -18 MPa . Vi scos i t i e s were mea sured a t 65C.

In th i s s tudy , t he v i scos i ty change was s tud ied as an ind ica to r o f TC C o i l s t ab il i ty under ambien t env i ronme nt ( abou t 22C) . The o i l samples were ob ta ined under opera t ing t empera tu r e


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3 1 5 C wi t h 0 .6 9 M P a CO as t h e p ro cess g a s . S ix me asu rem en t s w e re co n d u c t ed t o t ak e an av e ragThe v iscosi ty of raw o i l p roducts increased from 9 Pa .s to about 13 Pa .s in the f i rs t 15 d of s to rage , and id n o t su b s t an t i a l l y ch an g e o v e r t h e re s t o f t h e 6 0 d s t o rag e t i me wh i ch ag reed wi th t h e o b se rv a t i o n s oAd jay e e t al . (1 9 9 2 ) . Th i s ch an g e i n v i sco s i t y sh o u ld b e co n s id e red d u r i n g t h e TC C o i l u p g rad in g anuti l izat ion.

Th e o i l v i sco s i t ie s w i th d i f fe ren t p ro cess g a se s d i f fe red co n s i d e rab ly . F ig u re 4 sh o ws t h e e f feo f a lt e rn a ti v e p ro cess g a se s o n TC C o i l v i sco s i ty . Each co lu m n rep re sen t s t h e av e rag e o f th ree to f ivd i f fe ren t me asu rem en t s an d t h e e r ro r b a rs a re s t an d a rd d ev i a t io n s . Based o n t h e s t a ti s t ic a l an a ly si s v a r i an ce fo r mu l t i p l e p o p u l a t i o n mean s , t h e d i f fe ren ces b e t ween t h e v i sco s i t i e s wi t h t h e f i v e p ro cesg ase s we re s i g n i f ican t a t 9 5 % co n f id en c e l ev e l . Un d e r t h e g i v en o p e ra t i n g co n d i t io n s , t h e l o wev i sco s i t y o ccu r red w h en C O was ap p l i ed a s t h e p ro cess g a s . Th e T CC o i l wi t h CO2 h ad t h e n ex t lo wev i sco s i t y o f 1 4 .4 Pa . s , an d , u n ex p ec t ed ly , t h e o i l v i sco s i t y wi th h y d ro g en a s t h e p ro cess g a s was t hh ighest (50 Pa .s) .

r . / 3

CO 2

v - , , Ira ~

v . , , ~>

5 0 -

4 0

30

20

10

0 CO N 2 H 2 Ai r

6 0 -

T C C P r o c e s s G a sFigure 4 -V i sco s i t y o f oi l p ro d u c t s w i t h d i f fe ren t p ro cess g a se s . Th e v i sco s i t i e s we remea su red a t 6 5 C . Th e TC C o p e ra t i n g co n d i t i o n s we re 3 0 5C , Pin i = 0 .6 9 M Pa , RT = 1 2 0min , TS = 2 0 %, an d feed s to ck p H = 6 .1. Th e co r re sp o n d in g TCC o p e ra t i n g p re ssu re was1 0 .2 M Pa . Th e e r ro r b a rs a re s t an d a rd d ev i at i o n s . Based o n t h e s t a ti s t ic a l an a l y s is o fv a r i an ce fo r mu l t i p l e p o p u l a t i o n mean s , t h e d i f fe ren ces b e tween t h e f i v e p ro cess g a se swere a l l s ta t i s t ica l ly s ign i f ican t a t 95% confidence leve l .

Con c l u s i o n sTh e TCC p ro cess was su ccess fu l l y ap p l i ed t o t h e t r ea tmen t o f swin e man u re s l u r ry red u ce t

was t e s t ren g t h an d to p ro d u ce l i q u id o i l wi t h o u t an y ex tra ca t a ly s t ad d i ti o n . Th e TC C o i l p ro d u c t s hs i mi l a r p ro p e r t i es a s t h o se o f l i q u e fac t i o n o i ls f ro m o f o t h e r b i o mass . S in ce t h e TCC p ro cess o f swi


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manure or igina ted as an a l te rna t ive process for waste t rea tment , the ut i l iza t ion of the TCC oi ls as fue l to f f se t ene rgy consum pt ion i s promis ing . How eve r , u t i li z a t ion of the TCC oi ls a s fue l w il l r equifur ther t rea tment to reduc e the high ni t rogen and sulfur content in the raw oi l products . I t is a lsnecessa ry to upgrade the r aw TCC oi l to enhance i ts u t il i z at ion va lue. A cont inuou s - f low TC C procei s de s i r ab le for produc in g co mpo s i t ion-cons i s ten t o i l s from a sca led-up process . Fur the r ana lyse s, e .qua l i t a t ive and quant i t a t ive chemica l compos i t ion , a re needed in orde r to fu l ly explore o the r poss ibut i l iza t ion of the TCC oi ls .

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0

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Q


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