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BIOTECHNOLOGY LETTERS

Volume 15 No.3 (March 1993) pp.317-320


Received 8#, Jamuzry

~IOGAS PURIFICATION PROCESS USING INTENSIVE MICROALGAE


CULTURES

J.L. Conde, L.E. Moro, L. Travieso, E.F'. S-~chez, A. Leiva,


R. Dupeirdn and R- E~,:obedo

Environmental Pollution Department. National Center Tot


ScientiTic Research ,'CNIC). P.O. Box 699':'~. Havana City. Cuba.

Summary

The main contaminants ( C O ~ a n d H ~ S ) in biogas produced by


anaerobic digestion can 15,e remo~'ed b y an intensive mas,~
culture oT m i c r o a l g a e .

I NTRODIJCT ! ON

The use oT biogas 9rom anaerobic digeetion for some -pe,:izi,:


procee-e- requires its. puri;icatior~ ~ . ....
~ - ,,_,, " :,m
" = ': arbon
r ,~i,_-,:i d e
""

(CO_.,)~ hy'drogen sui~ide (H~) an-: ~_,.midit: tc ,~btain pL~.~-i~i~.~,,J


met,%ane .,,~m 4 ) < L,=.. e-.'- al . , t ~84, Baade~- ~ !=SS
At the =.~,n~ time, the use c~ ~ ~r,,~ -~,:e.ie c,_~itu..-e= o~
micrc, alcae t o o b t a i r ; '÷'aiuabl~-~ . . . . ~ .....
+_h ~.. d o v e ! o p-, m,-=.,,~
~=~+ o +- technique,~ ~ in,ci'-~.a._:-=
+__ -- the pr,c,,dL,:.tl,c:n
~ '='~ ~. T r a v i ~:
I ~ ' ~- ~.I . - ._.'"- . ~ . 3 r . o w i .k .~ k•: a ~ I'.~,,_~ . . ~. . 1 ~' ':; i .
. =.=-
hiterat,.,,re --c,arcerly. r-oporto. ~h~-,_
,.: ,. , q.e . . o.- . ~.i,:qa=._ -~or in:on.iv=_
,:,J.ltL~re~ r~__. m : i c r , _ , ~ . ~ g a L = , . Thi~ iM=~.=., c c , n . -, ~ =Z r ,: ~ ._+ _=, . ~__ _ ,a <,,-'.,-,el ~,.5.~, tc
obtain hiqh_ prodL,.cti,,'":__+4_. . .=. .~ ,-,-;~
. i . ' . ~.i z r o a l q.a e ~ . a~,d -~+ ~--,,_:,~: s.~:ne
ti m e , to, "ecover methane ~ ~ree { t-Loi~ CC_,mi"_3.~Tilm~.c~sE ~ i ~_t.SH
19S4, Samson • et a! " 1982
9 ~ , , T'- ~ d ~_ ,- ~ i n i t i ~ n
,!It. c.,T l a b , o r a t o r , .
~,::ale techn(.~Iog.:/ and the basis #or pi!=.t plar, t -,:ale are
su.g,gested in this paper.

~" i.-7"TL~'-- " -

= - . . . . . . ,-h
-.=r g i ass a r - , a . e r _,,..... c- ,:] i g e s .. . . . . . . L~.Ee':.',. ~ ,--,t"
e : : r.~,~,
. . . . i h,=,~
. . . . . . . k. ...= wi =;"....: a t , , ~ { { e c t l - . . e , c _ , i ,_.me ,-,# 2(> ~ i -_e:,i--~ E-,~.:::r:. ir .-.
, L. .. ,

escape LL'be and ~.r~,z, t h e r • t.L;be w~: "~L,~ a. v_~.i . ' e .~.Dr- f-~i.: J.r,q_ '---,=-,~m~T-.;.co,-.
m--..'- e L , . b . e . t r a t e , disri ' " ].~,m_r,/ ~ ., .~. s. .~. .e. *rein moi÷.s.'£es .#:-,-,m E.u,:~a'- ,:nme
wa=_ u.sed, with a Chemical O>;ygen L',emar:d , Z:C_,D, ,-_..+ 4 . 4 ,.90? m.,q. i .
Four 1 i ter~. o4 digest =~H '=-.e~-~,~,__- e ,~e:.r- e '._ s e . ~ e..-~ di 9e-tee
inOCL',IL:m =- t h a L ,:,:,r~:~itL~te 20 :: c , ; e#4e,znl.,e VOIL,,T,e.
0 U F ' i C,,--..= +'P;=_
._ ¢'~i
~ : 4 ~.r - e r.~ h =. . e. x p e. , .r i , ~ e r , ~ ~_-~,_e_,p: , , ~:,i~ '~aE ad .~. .,.,.=. . .k~,-- -,-; 7 , r,.
using lime liqLtC, r'.
For mic.~-G-~'la~,_~.,j.:
. c u l t u.r e , _ = . - , . T r.~ u ; p l.a s t i c p,:.r,d~ ,-,~ 2E cm ienqth,_
.... cm ~iu~h arid 3], cm he£glT.i~ ,,~ere u.~.ed, rSe =;~e,ztive V,:~Iu,T,e
oT each pond was 15 liter~. Two o< ~_h,e=_e p , u n d s w e r e Tilled
with s:/nthezi< media (L-C~ (,:c.mp,c, slt/,:,r, it,. T.~.ble t ~ ,, The ,:,th~,r

317
t w o p o n d s w e r e f i l l e d w i t h s e t t l e d d i l u t e d p i g g e r y w a s t e at a
dilution of 1 to 9 s h o w i n g C O D v a l u e of 2(30 mg/l. One pond
w i t h s y n t h e t i c m e d i a and o n e w i t h p i g g e r y w a s t e w e r e u s e d for
t h e e x p e r i m e n t s , t h e two o t h e r w e r e u s e d as i n t e n s i v e c u l t u r e
process controls.
One l i t e r of C h l o r e l ! a v u l g a r i s sutspension,( obtained from
the A u t o t r o p h i c C u l t u r e s C o l l e r t i o n of t h e B o t a n i c a l Garden
of C i e n f u e g o s , C u b a n A z a d e m y o9 S c i e n c e ) p r e v i o u s l y g r o w n on
L-C synthetic m~dia, w e r e u s e d as i n o c u l u m for e a c h pond,
rep:-esenting 6 % o~ the total v o l u m e and g i v e n an initial
co-centration of 0 , 2 8 3 2 mg/! of t o t a l c h l o r o p h y l l (Ct>.
The biogas p r o d u c e d in t h e a n a e r o b i c d i g e s t e r s w a s bubbled
into the ponds through a BiOLIFT device ( Conde and Leiva,
i?ga).
The r e s u l t i n g p u r i f i e d m e t h a n e w a s c o l l e c t e d in a gasometer
at the e n d of t h e p r o c e s s . Figure I shows a technological
s c h e m e of t h e p r o c e s s .
Standard analysis < APHA, 1985 ) were done for the
determination of chlorophyll a (Ca), Ct and COD. Gas
composition w a s m e a s u r e d in a L l o y d G a s A n a l y z e r G a l l e n k a m p ,
excepting H~S determined by Tutweiler method
<Coppolechia,19~4).
T h e a n a l y s i s w e r e d o n e e v e r y t w o days. The experimental time
w a s 15 d a y s and f o u r r e p l i c a r u n s w e r e d o n e in e a c h case.

RESULTS

F i g u r e s 2 and 3 s h o w s t h e s i g n i f i c a n t d i 4 e r e n c e s b e t w e e n the
C H . and CO b e f o r e and a f t e r t r e a t m e n t by m i c r o a l g a e . T h e r a w
2
biogas w a s c o m p o s e d p r i m a r i l y of 5 5 - 7 1 % of CH4, 4 4 - 4 8 % of
CO~ and l e s s t h a n 1 % of H~S. T h i s p u r i f i e d bioqas~ c o n t a i n e d
88=97 % of CH4, 2 , 5 - I i , .5 ~ % of C O ~".. and l e s s t h a n ,"
.,, 5 %. of
H~S. T h i s s y s t e m b e h a v i o u r ~ o u l d ~e e x p l a i n e d b y c o n s u m p t i o n
o~ t h e C O o as c a r b o n s o u r c e by C h l o r e i l a v u l ~ a r i s c e l l s and
by r e m o v a ~ of H.~S b e c a u s e of its r e l a t i v e l y h i g h solubility
in w a t e r . B e s i d e ~ , m i c r o a l g a e n e e d s o m e q u a n t i t i e s of s u l p h u r
for t h e b i o c o n v e r ' s i o n to e s e n t i a l s u l p h u r e d a m i n o a c i d s . The
efficient removal of H 2 S is a s p e c i a l advantage of this
system.
F r o m an i n i t i a l level of 0 , 9 to 1 % H 2 S a final level of 0 , 3 -
0 , 4 % is r e a d i l y a t t a i n e d .
Figure 4 shows the level of chlorophyll a and total
~hlorophyli when L-C m e d i a w a s u s e d as c u l t u r e media for
~hlorella vuL~aris. It can be s e e n t h a t when biogas was
introduced into the pond, the m i c r o a l g a e r e s p o n s e is an
increase o~ cell p r o d u c t i o n as c o m p a r e d w i t h the controls.
The same behaviour was observed when diluted piggery waste
was used as culture media. Figure 5 shows this. The
productivity of the system with L-C media and biogas was
almost 5 t i m e s h i g h e r t h a n t h a t for t h e s a m e m e d i a without
biogas. When piggery waste was used, the utilization of
biogms b r i n g s a p r o d u c t i v i t y g a i n of about 2-5 ~imes h i g h e r .

318
]
i
I 3 I
1
! ! _ 1 i
![

I 11
."~ig,1,- Technological Scheme of the Process,
(I) Pond; (2) BIOLIPT mud (3) Gasometer.

'~00-
5oI
90- 4~,__..q~.~ ~ : , 404 ,---._.___.__
i
g i
80
~0 i
o
70-
J

I i
I
..l
5O i r
10 I?
0 o
days days
Fig. 2.- ~[ethane percentage before and Fig. 3,- ~02 percentage before and
after microalgae process. after microa!gae process,
• after microalgse process 0 after microalgae process
before microalgae process * before nicroalgae proces

2T
i
i

g
I

t,5-~
c,
£
/2a
/~i~
/

,
"\\

~,,
i
o
=

0+_.~ . ..,

o g days 4
days
Fig. 4.- Chlorophyll b e h ~ _ o u r ?is. 5 .- Chlorophyll behavlour
using synthetic ~edia. using piggery waste,
* Chl total L-C media with biogas m Chl tot, with biogas
• Chl ~ L-C media with biogas X Chl a_ w i . t h biogas
X Chl total control • Chl tot. control
m Chl ~ comtrol 0 Chl a control

319
Table 1

Syntheti~ M e d i a <L-C> composition per liter, adjusted to pH


6 , 8 - 6 , 9 w i t h Ca(OH) ~.

KNO 3 (4 %) ............................. 5 m!

K2HPO4 (4 "/.~. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . I ml

MgSO 4 (3 % ) ............................. ! ml

Ca (NO_. ~ (3 %) ......................... 1 ml

geCi 3 ............................ "'i

Earth liquor . ........................... iC. n~!

REFERENCES

American Public Health Association (1785). S t a n d a r d Idethods


for the examination o; w a t e r s and wastewaters, 16 Eds.
ARNA/AWWA/WCPF, W a s h i n g t o n D.C.
Baacer W. (1988>. A n a e r o b i c D i g e s t i o n o¢ Piggery Wastes.
Technical Report, Institute o~ Technology, FAL,
Braunschweig, Germany.
B o r o w i t z k a M. (!988>. Microa!gae Biotechnology. Borowitzka
and B o r o w i t z k a E0s.. C a m b r i d g e Press.
C o n d o J.L. and L e i v a A. (1992). BIOLiFT. C ~ b a n F'atent RPI
i~ ,~
Coppolecchia H. (1974). Gas C h r o m a t o g r a p h y . CT Press. La
Habana 108-118.
Kiauss W. (1984>. Microalgae CL~itivation for Energy
Production. Practical Achievements and Commercial
feasibility. Bioenergy'84 F rote. S w e d e n , 298.
Lo. K.W. et al (1984). A g r i c u l t u r a l Wastes, ~ 175-178.
S a m s o n R. and Le Duy A. (1982). B i o t e c h , and B i e n g . , 2 4 , 1 9 i ? .
S a n c h e z E.P. etal. (1988). D i s t i l l e r y W a s t e ~ a t e r Treatment.
t e c h n i c a l R e p o r t to Cu~ban S u g a r M i n i s t r y , ICIDCA, MINAZ.
T r a v i e s o L. (1991). B i o r e s o u r c e Technology, 40,2,77-79.

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