JONSSON and W I N G

i s i s of less i The u l t r a f i l t r a t i o n process has been employed on a l a b o r a t o r y s c a l e t o remove

nient and f r a c t i o s o l i d s from d i l u t e paper m c h i n e w h i t e water (ref.4). A membrane
o f suspended s o l i d s o f o v e r 99 % was achieved.
The treatment of paper m i l l w h i t e water by membrane f i l t r a t i o n was i n v e s t i -
p t e d , both on l a b o r a t o r y - and p i l o t - p l a n t scales, i n a c o l l e c t i v e p r o j e c t
o r r i e d o u t by t h e Swedish Foundation f o r Membrane Technology (ref.5). The

tudied on a l a b o r a t o r y scale. I n a second stage, t h e i n v e s t i g a t i o n was extended

'uctioii Reverse osmosis gave a v e r y c l e a n permeate i n t h e l a b o r a t o r y t e s t s . B u t a

neral f i n d i n g o f t h e l a b o r a t o r y t r i a l s was t h a t tube modules a r e t h e o n l y ones
f t a b l e f o r membrane f i l t r a t i o n o f paper m i l l w h i t e water. And, a t t h e time,

ultrafiltration

PAPER MACHINE PERMEATE

W H I T E WATER

ier industry duri

7000 L / U I N 800 L / U I N
. r i a l applications

V
10s: 2.5 G/L TDS: 2 . 0 G/L
i s presented. ResearC' coo: 2070 HWL COD: 1120 HG/L
BOO. 935 U W L 800: 835 NG/L
the Swedish Foundatio XA: 249 U G / L CONCENTRATE Nh: 229 U W L
AL: 2 . 3 WG/L AL: 0 . 7 WG/L
200 L / U I N

TOS: 4 . 7 G / L
i
COO: 4200 U W L
BOD: 1590 H W L
NA: 260 UG/L
l a t i o n i n t h e p u l p an AL: 7 . 7 nG/L
Packaging I n c , USA z

the c l o s e d w h i t e wat
''9 2 U l t r a f i l t r a t i o n o f paper machine irrhjte water. The riiimbranes used were
, b u t changes i n the I from Paterson Candy I n t ( P C I ) . The o p e r a t i n g pressure was 8 bar, t h e tem-
tem. *'rdtdre 50°C and the f l o w v e l o c i t y 4.4 m/s.
186 JUNSSON and WIX-tERSTFDT

The treatment of bleach e f f l u e n t w i t h reverse osmosis has been shown t o 1(.,4 I__--

a permeate stream of high purity ( r e f . 8 ) . Membrane r e j e c t i o n s of b o t h i n o r g a q f c

and organic components were above 90 % f o r t o t a l s o l i d s concentrations in t h e
range 5-30 g / l . --_
A combination of reverse osmosis and f r e e z e concentration has a l s o heen
I
-

i n v e s t i g a t e d ( r e f . 9 ) . I n t h i s case RO was used t o remove 90 % of the water frca

a stream continain: 5 g/1 t o t a l solids. The concentrate was then f u r t h e r c:;c- 1733 L I N I N

c e n t r a t e d by f r e e z e concentration t o about 200 g/l. coo 2200 PPH

The drawback with these processes, i s t h a t they a r e q u i t e expensive.
Continuous multi-stage u l t r a f i l t r a t i o n has, however, been demonstrated t 3 be a
t e c h n i c a l l y and economically feasible colour removal process f o r k r a f t ca:,stic
.
e x t r a c t ion ef f 1 uent
A long-term f i e l d demonstration of u l t r a f i l t r a t i o n f o r colour rermval h i l i
becn conducted a t Champion InternatiGfial Mill Canton, North Carolina, ( r e f . i $ j s
The reported r e s u l t s ( r e f s . 11-12] are encouraging, b u t no commercial i n -
s t a l l a t i o n has followed as of today, as a r e s u l t of t h i s work. P o s i t i v e rescitt,
from u l t r a f i l t r a t i o n of the f i r s t c a u s t i c extraction washer on the s o f % w m d .&P# -
l i n e a t a French mill have a l s o been reported ( r e f . 1 3 ) .
t (EKA) p u t a l a r g e p i l o t plar: 1t r a f i 1 tra t i on pl arr
t a l membrane area was 168 if& 3 brane a t w of the I;
ocessed. T h i s ULTRASEP plarlt w15 he reduction of COC:
n J a p a n was p u t i n t o o p e r i t f o n . o t a l s o l i n s i s lobe
In January 1981 an U l t r a f i l t r a t i o n plant a a s i n s t a l l e d a t the S i i i y o Kffki
iwakrini Mill, Jtpz!! f e r the concentration of the E-stage efflueilt fia w o t h e r Japdnfse irii 111
the k r a f t p u l p production lines (ref.14-16). The annual capacity of t h i s i:.",p sl cnt of E-st:ge etficerr
110 000 t o n s of hleaLhed pulp. The ULTRASEP i n s t a l l a t i o n replaces the C l l 1 f fit w i t h N i L t o tubular
method of t r e a t i n g bleach e f f l u e n t s , using lime p r e c i p i t a t i o n . Polyc.u1Pq02r;Q r1t i s t r e a t e d by UF. 11
membranes a r e used and the t o t a l membrane area i s 672 m2. The UF plant f.; t r a t e i s t a k e n bjck i v
tored and c o n t r o l l e d by a micro computer from the control panel o f t h e b f t ' K A heat value of tire c c
p l a n t . Cleaning, i s done once a day, and i s controlled by t h e micro cOWUt*r* ne replacement CGst. TI
Fig. 4 gives t h e operation figures. I n t h e plant 104 m3/h of bleach e f f i nes was changed a f t e r
i s t r e a t e d , giving 13 m3 /h concentrate which i s returned t o t h e recowrY $Ysc d t o be two years d u e
The permeate may p a r t l y be used as wash l i q u o r i n the brown washer but wdl
discharged. Durfng the f i r s t year of operation the reduction of COO in t h e -_-_I__ -
f e f f l u e n t aff
meate stream was reported t o be 82 %, the colour reduction 94 %, and the re f i rs t f u 1 1- sca 1e menib)

t i o n of suspended s o l i d s 100 %. The f i r s t s e t of membranes had a l f f 2 t f r r r i n t o operation i n Ap,

The operating cost of the UF p l a n t amount t o approximately 2 * % - n t of an e f f l u e n t h i 9
lars per ton of pulp produced (ref.14). u l p h i t e mill. The t o )
factured by P C I , i s e
 About 240 000 tons of bleached s u l p h i t e pulp a r e produced annitally a t t k c
Domsjo m i l l . Previously the wood was stored i n the form of chips i n chip r*lea,
___-_-__
Concentrdtion of _ s p ~
e s o l i d s content of 5
before i t was f u r t h e r processed. During t h i s storage process, t h e wood m s t . t r 4 a
and the pitch content decreased. B u t the long storage time in t h e chip p l l e : 5
n m i l l s . The mayimum
25 %.This i s due ic
now replaced by mechanical treatment of the pulp in a s o - c a l l e d FROTAPULPih.
US only provide a l i i
Through the introduction of the frotapulper the s t o r a g e time i n the C ~ I Ct i l p
a l s have shown t h a t
has been reduced, and a t the same time, the strength o f the pulp pr0durc.l hie,
a f l u x of a b o u t 40 111
increased. The amount o f pitch introduced i n t o t h e system has however 1 n c . c t t . p . :
6.8 kWh/m3 permeate N
as a r e s u l t of the new process, and the progressive closirlg of t h e water s j i t f n l
ermeate h a d a s o l i d s
a t t h e mill has lead t o problems of build-up of unwanted substances, suck as
c o n t r a s t t o modern r~
pitch and resins.
s u l p h i t e mills i s c((
I n order t o reduce the pitch level i t has been found t o be necessary to h l c t f
v i a bl e conc e n t ra t i 0 n
off some of the pitch-rich water. For environmental reasons, t h i s water n,s: :e
ns a r e overloaded. TI)
p u r i f i e d before i t is released. The i n s t a l l a t i o n o f the u l t r a f i l t r a t i o n i l d n t at
1976 DDS i n s t a l l e d ( (

the Domsjo m i l l , as shown in Fig.5 has lead t o an 80-85 % reduction in t h e ~ { t c *

l a t i o n was folloded
l e v e l , as well as a reduction o f 70 % in COD. During u l t r a f i l t r a t i o n the u f t z h
I n Quebec, Cdnada. II
content increases from 0.5 t o 10 %. The permeate i s r e c i r c u l a t e d througll t 4 e
1atioqs. Both cil
bleach plant. The concentrate i s f u t h e r t r e a t e d t o o b t a i n 80 % concentratton dnd
S RO modules with a
i s t h e n taken t o the recovery b o i l e r .
riles with a t o t a l 31
t c d from 6 t o 12 %

__.---

f l C C O V E R Y DOIl E R

EVAPORATION

SCREENING CONCENTRAlE 1 % )
&ONSUMP T I O N

_..- -..

Concentration 011
nts from De Danskrr
 .%NSSON and WIMMERSTEDT 189

J %ncentration of spent sulphite liquor

T ~ Q s o l i d s content of spent sulphite liquor ( S S C ) i s t y p i c a l l y 15-16 I in
n mills. The maximum concentration t h a t can be obtained by reverse osmosis
-25 %. This i s due t o the increasing osmotic pressure of t h e solution. RO
thus only provide a limited supplement t o evaporation f o r these l i q u o r s .
Trials have shown t h a t SSL can be concentrated from 11 t o 22 % t o t a l s o l i d s
aa f l u x o f about 40 l/m2h. (ref. 18). The energy consumption was aproxima-
1~ 6.8 kWh/m3 permeate which i s much lower than f o r m l t i - s t a g e evaporation.
permeate had a s o l i d s content of 0.01 % and a COO content of 1100 nig/l.
In c o n t r a s t t o modern mills the solids content before evaporation i n many
der sulphite mills i s considerably lower. I n t h e s e m i l l s reverse osmosis may
11 viable concentration a l t e r n a t i v e in ciijes i&isrc^ exist!ng evapnration
stems are overloaded. Two such cases a r e Toten and Reed Mil 1 s ( r e f s . 19-22).

Ctnttated from 6 to 12 % t o t a l s o l i d s and a t the Reed p l a n t from 12 t o 18 %.

&clluloseacetat membranes are used i n both p l a n t s . Membrane l i f e t i m e s of more
;Pia9 a year a r e obtained, despite the f a c t t h a t the pH i s on t h e low s i d e of the

KceDtdble pH range. The membrane cleaning frequency is 2-6 times a week f o r

b t h systems.

1O T E N REED

INSTALLATION YEAR 1976 1978

MEMBRANE AREA Id1 332 4413
CUNF ICURA T I ON 4 STAGE 4 STAGE
PROWCT NH4-SSL CA-SSL
pn 2-2.5 3-3.5
ros FEED I % ) 6-10 10- 12
TUS CONCENTRATE I X ) 12 18
POYER CCNSUUPTION 7.5 8.8
I Kh4i/t? PERHEATE)

e Domsja H i 1 1 , SWr ''9. 6. Concentration of spent sulphite l i q u o r . Feautures of the reverse osmo-
y I n t . (PC!), hd5 Plants from De Danske Sukkerfabrikker (DDS) a t Toten and Reed Mills ( r e f . 2 1 ) .
mechanical p u l p i n g proces

l e v e l i n p o l l u t i o n c h a r a c t e r i s t i c s (BOD, COD, c o l o u r and s o l i d s ) was obtained.

However, a serious decrease i n f l u x r a t e due t o f o u l i n g was experienced. F o n l i n p a n t produci qg p u r i fiedl
was thought t o be caused by c o l l o i d a l o r g a n i c s i n t h e feed. t y is 2 500 tons o f hi44
The concentration o f spent l i q u o r from chemical thermomechanical pulp (CTM?) mbrane area i s 336 m2.
by reverse osmosis i s c u r r e n t l y being s t u d i e d i n a c o l l e c t i v e p r o j e c t by the A t Borregaard I n d u s t r -
Swedish Foundation f o r Membrane Technology. The p r o j e c t i s being c a r r i e d out f n c t i o n of v a n i l l i n . Sin(<
co-operation w i t h the Swedish F o r e s t Products Research Laboratory ( S T F I ) . 4 t ed t o produce a cleaneit
STFI t h e p o s s i b i l i t y o f t r e a t i n g t h e RO c o n c e n t r a t e together w i t h black l i q u u r I t r a t i o n reiiioves the I C
i n a k r a f t black l i q u o r recovery system i s being i n v e s t i g a t e d . reduce the capacity off
The reverse osmosis t r i a l s were performed w i t h tube membranes, ZF99, f r o m onal advaqtage o f reduc:
PCI. The r e j e c t i o n o f d i s s o l v e d s o l i d s by these t h i n - f i l m composite membranes
was high. The q u a l i t y o f the permeate was such t h a t i t c o u l d be reused as fresh
water. i t was noted t h a t t h e f l u x was s t r o n g l y i n f l u e n c e d by t h e feed tempera-
ture; the f l u x increase was 2 l/m2h p e r degree C e l c i u s (see Fig. 8). The revei'sc
osmosis experiments demonstrated t h a t a spent l i q u o r w i t h a t o t a l dry solids
content o f 1 % can be concentrated t o 5 % w i t h an average f l u x o f 45 l/m 2 h , a t
an w e r a t i n g temperature of 60°C. This p r o j e c t i s t o be continued and the
d e t a i l s o f the work are s t i l l unpublished.

process, about
o r i g i n a l raw wood ma ent pulping liquor.
major p a r t o f t h e s o l i d s i n spent s u l p h i t e l i q u o r i s lignosulphonate. The con-
p o s i t i o n v a r i e s w i t h t h e type o f wood pulped and d i g e s t i n g process, !xi: !:
general SSL contains approximately 60 X l i g n i n , 30 % reducing sugars arid 10 f: 9 U l t r a f i l t r a t i o n off
inorganic materials. Using u l t r a f i l t r a t i o n i t i s p o s s i b l e t o separate the W- Y. The t o t a l solids 11
i n t o p u r i f i e d f r a c t i o n s o f , i n p a r t i c u l a r sugars and lignosulphonate ( r e f s . Paterson Candy I n t . ,
28-32).
The p u r i f i e d sugars are o f commercial value f o r fermentation purposes.
Aerobic fermentation processes produce p r o t e i n f o r use as animal feed, and ale@-
hol i s produced by anaerobic fermentation. The e n r i c h e d lignosulphonate fr-actiiEl the k r a f t ( s u l p h a t c )
i s conmercially used i n many a p p l i c a t i o n s , such as i n d u s t r i a l detergents, g process, the l i g n i l l
dispersants, p r e c i p i t a t e s , b i n d e r s and'adhesives. ock for chemical pro^^

With simple u l t r a f i l t r a t i o n , it i s o n l y p o s s i b l e t o o b t a i n a lignosulPh~ssir black l i q u o r (KBL) s((

purity o f approximately 80 %.
I n combination w i t h d i a f i l t r a t i o n a COnCentfatC '' Eplaced by another heaR
25 % t o t d l s o l i d s c o n t a i n i n g 95 X l i g n o s u l p h o n a t e i s produced (ref~.19,3!-~')' ? t h e e x t r a processing ii
Ple, i n adhesives.
ri. n
$. Z l t r a f i i t r a t i o n o f spent s u l p h i t e liquor a t Borregaard I n d u s t r i e s ,
3

bway. The t o t a l s o l i d s level i s increased from 8-10 % t o 22 %.The UF p l a n t ,

ff-%n Paterson Candy I n t . , has a t o t a l membrane area of 1 116 3. The operating
i'essure i s 10 bar and t h e power consumption 380 kW (ref.37).

'.2 V l E a f i l t r a t i o n o f k r a f t black l i q u o r
in the k r a f t ( s u l p h a t e ) process, which today i s the dominating chemical
:*Jl?ing process, the l i g n i n occurs as a l k a l i l i g n i n , which can be u t i l i z e d as
t~ .,tack f o r chemical processes. however, in removing a l k a l i l i g n i n frore the
t r d f t black l i q u o r ( Y B L ) some o f the heat value i s l o s t (about 35 X ) , a n d has t o

replaced by another heat source. The cost o f the product thus has t o pay f o r
the extra processing and the l o s s o f eneryy. Alkali lignin can be used, for
''I'DJ~, in adhesives.
 An adhesive (Karatex) from high m l e c u l a r weight lignin h a s been develop($ ). .K. B a n s a l , AIChE Syii
the Finnish Pulp and Paper Research I n s t i t u t e (ref.33,38). The lignin i s
. Eriksson, Meiiibrane
6 (19811, ( i n Swedistt
separated from k r a f t black l i q u o r by u l t r a f l l t r a t i o n . The fractionatiop, c c :cI , Sandstram, Treatinerr
SVL-85 Report No 18 (1
KBL i s c a r r i e d o u t by u l t r a f i l t r a t i o n and d i a f i l t r a t i o n in a s i m i l a r wa
fractionation of SSL ( r e f . 3 9 ) . A material balance f o r the process i s 9:
. Sivik and M. Jacob::
SVL-85 Report No 24 //
.J. Simpson and G.R.
Fig. 10. Ultrafiltration-diafiltration on 15 % TUS ( t o t a l dry s o l i d s ) 11qLcr
.J. Wiley, L.E. Dambn
from pulp washers gives a product with 90 % purity in a l k a l i l i g n i n . Tt,t y i e i d roc. (1978) 63-70.
.A. Fremont a n d M.H.
of t o t a l s o l i d s i s about 25 % and the y i e i d o f l i g n i n about 55 %.Thc ---.--.-'
PL e - .,%
.A. Fremont, D.C. Tatt
from the process, containing 75 % o f the t o t a l s o l i d s and 45 % of the a l k d l ! f f l u e n t s by U l t r a f i l tt
A. Fremont and D.J.
l i g n i n , i s returned t o t h e recovery system f o r evaporation and combustlo-. t r a f i l t r a t i o n , EPA I??
Muratore, M. Pichom
_I."...__
RECOVERY SY ST E: !I. .H. Haagensen, Case S5
nske Sukkerfabrikker
t .TRASEP, Sanyo Kokusnj
tlallstrijm e t a]., MI
ternal report by t h e
K R A F T BLACK LlOUOR Mizuhara, Y. E l u w t n i
per Plant Wasfe M a t e
PFpper and J . ringll
.
Claussen, 4 t h Int:
200 L/i4lN

.agner, I . Chcpn. E .
Clausscn, i861-CB!
C 1au s sen, i4c;nbra n
!dflcy, G.A. Duhpyv
u t i a n Control Fedeb
Kjellberg and P. Cr
t r a t i o n , SSVL-pro j m
Eviksson, P i l o t Pla
11, RPyor t L I J T K ~ I H /r!(

E(. Erikcson, r a i l p i 11
r'ence, Boston (1983)

Fig. 10 Material balance f o r the u l t r a f i l t r a t i o n o f k r a f t black l f r l u f i r i r c z + Eriksson, AIChE SymII

J. Zawielski. S.0. Pi1
The Karatex-process i s patented, and t h e patent r i g h t s are held by 3 Ft
Company, Metsaliiton Teollisuus OY ( r e f . 40). A commercial-size plant h3S
i n s t a l l e d i n Finland, a n d i s a 4-module ( 1 6 8 in2) continuous p l a n t w i t h *31
 MOHRMANN, WJ
SCHtfGERL, A .
ITUT FUR TECHNISCHE CHE:
00 H a n n o v e r

h e s e p a r a t i o n o f t h e COIT
h i n g s o l u t i o n s were car2
e u s i n g d i f f e r e n t Carrie
t h e s e p a r a t i o n of t h e
r o c o a l e s c e n c e , t h e y wen

ong t h e s e p a r a t i o r . tech1
a n d more i m p o r t a n c e i n

selective w i t h i n p a r t .
1 c o n c e n t r a t i o n s , sol

p o s s i b l e t o overcomff
t e c h n i q u e , w!inre a ::

RINCIPLES OF THE L I Q U E

s a q u e o u s o u t e r p h a s e ii
i s s e p a r a t e d by a l i q u
t and a n e x t r a c t a n t fro)
i n which a n e n r i c h m e n t
m e t a l - e x t r a c t a n t compl
a q u e o u s p h a s e a n d t h e mi
6 t h e mernbrane a n d decom