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_._ _-----qI-iifs -__.- --
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Thesis Title Preparation of Cellulose Acetate Membrane for
Reverse Osmosis
Thesis Credits 6
Candidate Mr. Kowit Kala
Supervisor Associate Prof. Dr.Surin Laosooksathit
Degree of Study Master of Science
Department Environmental Technology
Academic Year 1996
Abstract
This project is to study the preparation of cellulose
acetate for reverse osmosis. Acetone and magnesiun perchlorate have
been used as solvent and swelling agent, respectively. Proportion
of magnesium perchlorate to polymer solution have been varied as
0.0, 0.5, 1.0, 1.5, 2.0, 2.5 and 3.0 percent by weight, while other
components were kept constant. Proportion of cellulose acetate to
polymer solution in 13.2, 15.0 and 18.0 percent by weignt have also
been investigated. Separation of phenol solution were carried out in
the wide pH range, starting from pH 6, 7, 8, 9, 10, 11 and 12,
respectively.
It was found that the polymer solution contains 1.0 percent
by weight of magnesium perchlorate gave the maximum flux at 56.10
liter per squaremetre-hour. Flux is increase with decreasing
proportion of cellulose acetate in the polymer solution.
At pH6 and7, percent reject ion of the phenol solution
have the negative values. This is due to the membrane has slightly
nagative charge and can act as a proton acceptor. Thereface, phenol
- 3 -
is preferentially adsorbed on the membrane surface. At PH 11 and 12,
the structure of cellulose acetate would be destroyed by hydrolysis
giving cellulose and acetic acid. This causes the fluctuation of the
flux. At pH 9 and 10, sepatation of phenol solution are as hight as
88.03 and 66.68 percent, respectively, and the flux is smooth
throuyhout the experiment.
structure is asymmetry. Thickness of the
in the ranges 90-120 micrometres. Th
approximately 5-10 micrometres and the
in the ranges of 95-100 micrometres.
Investigation of the structure of membrane was carried out
by Scanning Electron Microscopes. The results show that the
approximately
in layery are
thickness are
membranes are
ickness of sk
support layer
Keywords : Membrane/Cellulose Acetate/Reverse Osmosis/
Polymer solution/Flux/Percent rejection/p8
1.6
2.3
Mfil
a
9
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1
1
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5
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8
9
10
10
10
10
10
11
11
13
13
16
22
24
24
24
25
25
25
25
25
25
26
26
26
26
26
29
29
30
31
31
31
31
35
36
37
39
-al-
39
39
40
40
40
40
41
41
41
44
45
47
47
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1.1
1.2
1.3
2.1
2.2
2.3
2.4
2.5
2.6
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4
4
7
14
16
17
18
19
20
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72
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75
76
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2
2
3
11
12
12
13
15
16
17
19
23
33
33
34
34
35
37
38
4.4
4.5
4.6
4.7
4.8
4.9
4.10
4.11
4.12
4.13
4.14
4.15
4.16
4.17
4.18
4.19
4.20
4.21
9-l
46
46
47
48
49
51
51
52
52
53
54
55
56
57
57
58
59
59
81
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D
dx
K
k
L
R
AP
AY
- 2 -
I I I 1 I I
b Electron Microscopy Q Optical Microscopy 4 Visible to Naked EylI I / I I
tonic Ranga Molecular Range MacrlMolecuiara”Q.3 Micro Particle Range Macro Particle Range
!‘p lo” IO“ I !O I 01
J - J ! ! / I illiN ! j i!!#l I ! !!!Im I i !au 1 I !!!I“#“WI I O IO’ IO’ I O ’ IO’ 1.0’
II
ol.Wt.rongc 100 200 1 0 0 0 1 0 0 0 0 2 0 0 0 0 l00000 3 0 0 0 0 0
I , tIllood Ctlls, , Sandt Human ~tlalt ,I
- 3 -
43.0-44.8 lnaaaS%il?lu kla&EiU (Acetone)
(Dichloromethane)
37-42 ed4wu IwiaaTsLlM
24-32 2-LNYlkNl tOl?lXGla!I ad-lwu
(2-Methoxymethanol)
15-20 :7 2-L91Yl&lfl LUYl7MBa%\
0.5 11.7
0.75 16.7
1.0 21.1
1.5 28.7
2.0 35.6
2.5 40.3
3.0 44.8
- 5 -
- 6 -
dl%~UYl~~
Loln7odBa (Methanol) ww~ade~ (Alcohol 1
LBRIUFIB (Ethanol) ueanetie~
Ja4flwwiuaa (Isopropanal) uilanelei
nmaai?h (Acetic Acid) n%61 (Acid)
vle&?a&ti6 (Formaldehyde) sbaa;Jb?! (Aldehyde)
W%SWM z4wu (Ketone)
ba’ia~bna~ (Ethyl Ether) zbna%” (Ether)
iris (Urea) aa’!ol~ (Amide)
dLda?ia (Glycerol) 4w~KSn%~keaneSe~ (polyhydric Alcohol)
Jwla dObaa
ZSTn%abuu (Hydroquinone) ‘hI8n%duaa (Dihydric Phenol)
breu%w (Aniline) ~ai’ld (Amine)
L~J%+~z:$L~~w (Methyl Acetate) balbwesd (Ester)
- 8 -
-9-
- 11 -
- 12 -
,&! 2.2 nlsbk Gel Concentrat ion Cl71
- 13 -
0.0 15
0.4 30
3.3 600
- 15 -
r
1 7 . 5 0. 2o2xlo1o 5 6 . 6
19 0.205~10~~ 4 0 . 4
20 0.206~10~~ 3 0 . 0
21 o.195xlo1o 2 3 . 3
ZEAS52QS’seolee ee
W
- 16 -
60 600
60 500
40 400
1 %Jsrls 13.9 72 98.0
3 II 12.2 50 98.0
5 II 10.2 54 98.8
10 ,I 8 .5 50 96.3
20 4n1~wh 5.8 50 75.1
30 ,t 5.3 36 71.5
Ycmp6xAufe (‘Cl
80 1253 70.3
82 1129 75.4
a4 1080 80.0
86 1032 05.6
89.5 976 92.0
92 941 96.2
94.5 665 97.5
- 21 -
C6, 191
- 22 -
(2.5)
"AR = (l-C,) X 100 (2.6)-
x = A_, c = cw
AI L
‘47fWJn7%~ (2.8) J, J’dx =Dj dc
0 c, (C-C,)
(2.9)
- 24 -
J, = D In (C,-C,)-
AX w,-C,)
& J, = K, In (Cw-C,)
(2.10)
(2.11)
- 27 -
- 28 -
1.
2.
3.
4.
5.
6.
7.
6.
9.
10.
11.
12.
13.
14.
15.
16.
- 30 -
1.
2. i!ld‘IBw (Acetone)
3. Uln~~%flu~~8~saa~~~ (Magnesium Perchlorate)
4. em&& (Distilled Water)
5. Sti~~au4~a~Knrsfl (Sodium Cocadylate)
6. oJeh~7a~Kti~ (Formaldehyde)
7. n$h7aiKd (Glutyraldehyde)
6. bK~YYwaa (Ethanol)
9. n%nKsfw%eaaa?n (Hydrochloric Acid)
10. MULTI, (Phenol)
11. 4-ezh~uau~Ku%~ (4-Aminoantipyrine)
12. Swun~b%surSn~7K~aiS~~~~~~~~ (III)
13.
14.
15.
16.
(Potassium Hexacyanoferrate (111))
uauKiln?dldrhdarJw (Anhydraus Sodium Sulfate)
‘d~%aaa~aueu‘h~&l (Aqueous Ammonia)
aae5wJab (Chloroform)
S$rzauaaaKd (Sodium Chloride)
Fluka,
- 31 -
$au~~~nouSwa~lM~ntnTu,% iN:euiu
nmpder%rwa ea%lifw iI uun~b$suL~a~RaaLs~
FK-1 22.2 66.8 11.0
FK-2 22.2 66.8 11.0 0.5
FK-3 22.2 66.8 11.0 1.0
FK-4 22.2 66.8 11.0 1.5
FK-5 22.2 66.8 11.0 2.0
FK-6 22.2 66.8 11.0 2.5
FK-7 22.2 66.8 11.0 3.0
SG-1 22.2 66.8 11.0
SG-2 22.2 66.8 11.0 0.5
SG-3 22.2 66.8 11.0 1.0
SG-4 22.2 66.8 11.0 1.5
SG-5 22.2 66.8 11.0 2.0
SG-6 22.2 66.8 11.0 2.5
SG-7 22.2 66.8 11.0 3.0
;K-3(CA 12) 12.0 66.8 11.0 1.0
;K-3(CA 14) 14.0 66.8 11.0 1.0
;K-3(CA 18) 18.0 66.8 11.0 1.0
WllflL~~ FK L Idlda~4a~~~~LRR~U~19InUiBn Fluka1
&&l=sarafp 37000 w+dhbla~ 40
SG rSldrSlsrlla~4a~e-~~~~~~~~~~~~~~~ Sigma
ih&xasaa 40'I
- 33 -
- 34 -
.
.
- 33 -
qi
- 34 -
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- 38 -
a
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
Feed
Pump
By pass valve
Pulsation damper
Test cell
Inlet pressure
Regulator pressure
Outlet pressure
Brine tank
Permeate outlet
. .
- 39 -
(2 .6 )
- 40 -
I
s:I
i i
- 44 -
- 45 -
I I I I I I I I II I I I I I I I I
- 47 -
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12
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7 -
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10 20 30 40 50 60 70 60 90 100 110 120 130 140 100 160 170 1110
L?al(ul;;)
- 48 -
10 , I
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10 20 30 40 $0 60 70 80 90 100 110 120 iS0 140 130 160 170 100
- 49 -
- 50 -
- 51 -
100
90 -
80 -
70 -
60 -
50 -
0 ’-10
pH 6 LLB:: pH 7
90
0 1 2 3
b?ill ta*,nJ4,
-f3- pll 0 + pll 9 -+ pl1 IO
4
- 52 -
I
0 1 2 J 4
100 [
PO -
I30 -
70 -60 -50 -
40 -so -
10 -10 -
-43 t I I I I I
6 7 b Q 10 11PH
- 54 -
II
- 57 -
'=$ 4.18 ihhBs7a (X 500)
- 58 -
- 59 -
- 61 -
1.
2. Joseph, G.J., Marco, E.A., Ke
1989, “Assessing Hollow Fiber
Removal, ” Journal of American
No. 11, pp. 68-75.
Morrison, T-R. and Boyd, N.R., 1981, Organic Chemistry, 3rd ed.,
New Delhi, Prentice Hall, p. 788.
ith E.C., Edward W.C. and Joel M.,
Ult ra f i l t ra t ion for Particalate
Water Work Association, Vol. 81,
3.
4.
5.
6.
7.
a.
9.
Bipin, S.P., 1988, Reverse Osmosis Technology, New York, Marcel
Dekker, pp. 142-145, 220-221.
Herman, F.M., Norbert, M.B., Charles, G.O. and Georg, M., 1985,
Encyclopedia of Polymer Science and Engineering, Volume 3,
2nd ed., New York, John Wiley & Sons, pp. 158-162.
Puleo, A. C., Paul, D.R. and Kelley, S.S., 1989, “The Effect of
Degree of Acetylation on Gas Sorption and Transport Behavior in
Cellulose Acetate,” Journal of Membrane Science, Vol. 47,
pp. 301-332.
Sourirajan, S. , 1970, Reverse Osmosis, New York, Academic Press,
pp. 54-86.
Kunst, U. and Vajnath, Z., 1981, Synthetic Membrane, Volume 1:
Desalination, New York, American Chemical Society, pp. 235-245.
Boddeker, K.W., Finken, H. and Wenzlaff, A., 1981, Synthetic
Membrane, Volume 1: Desalination, New York, American Chemical
Society, pp. 191-197.
Thiel, W.S. and Lloyd, R.D., 1990, “Frictional and Osmotic
Effects in the Pressure-Driven Membrane Separation of Dilute
Solution, ” Journal of Membrane Science, Vol. 50, pp. 131-139.
- 63 -
10. d1sfta %dl%, 2529, nl%u~wb~au~~dlw~un%-~a~nl~~~~~~~~~~n~~~lnstia~%aGdraw, ~ns1~wu~~~~~i~dan%4u~1~a~~w1~~~~ d1p1121-
%fan7wsaii ~nl~uana%ldra~w%-7a~~n~is~~~, 97 41.
11. Schwarz, H.H. and Hicke, G.H., 1989, “Influence of Casting
Solution on Structure and Performance of Cellulose Acetate
Membrane, ” Journal of Membrane Science, Vol. 46, pp. 325-334.
12. Katoh, M. and Suzuki, S., 1981, Synthetic Membrane, Volume 1:
Desalination, New York, American Chemical Society, pp. 247-252.
13. Herbert, H.P. and Edward, S.K., 1976, “Reverse Osmosis
Separation of Pola Organic Compounds in Aqueose Solution,”
Environmental Science &Technology, Vol. 10, No. 4, pp. 364-369.
14. Mehdizadeh, H. and Dickson, J.M., 1993, “Modeling of Reverse
Osmosis in the Presnce of Strong Solute-Membrane Affinity,”
Journal AIChE, Vol. 39, No. 3, pp. 434-445.
15. Lonsdale, H.K., Merten, U. and Tagami, M., 1967, “Phenol
Transport in Cellulose Acetate Membrane,” Journal of Applide
Polymer Science, Vol. 11, pp. 1807-1820.
1 6 . olssia Y?az~~Ywas~G naz ?aa%ti wsaZa%iqoa, 2 5 3 5 , n2Wk~suaani3
nn~a~ba~asw~wb~euj~~*~~~~~~~~~~, ~nai~~~~~~~~i~d?nas~~i~~~~~~~
d787?$7%4anawbaii ~n7~~rnR~~Ta~u4a7a~~n~i~~~~, wtii 10-21.
17. Kesting, R.E., 1971, Synthetic Polymeric Membrane, New York,
McGraw-Hill, pp. 116-157.
18. Prabhakar, S. and Merra, M.B., 1986, “Studies on The Structural
Kinetic and Thermodynamic Parameter of Cellulose Acetate
Membrane, ” Journal of Membrane Science, Vol. 29, pp. 143-153.
- 64 -
19. dld& %&& llaa tiyns +l%a bd4%& 2526, n7%alenTd%~uuaa~7w7aeen
uln~lurwi7?Taen%-uau~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~ %w&w&
~~~~7~danaaudi~w%~~~w ditii?d7%4an3aubd, dnGubna%u%aF!-
ww4m~n~wmuY, 67 9-7 _9
20. Josept, I.G., 1981, Scanning Electra Microscope and X-Ray
Micronalysis, New York, Plenum Press, pp. 495-539.
21. Arif, A.H., 1970, Principles and Techniques of Electron
Microscopy Biology Application, Volume 6, Nek- York,
Van Nostrand Reinhold, pp. 290-296.
22. Arif, A-H., 1977, Principles and Technipues of Electron
Microscopy Biology Application, Volume 7, New York,
Van Nostrand Reinhold, pp. 79-92.
23. Kimmerle, K. and Strathmann, H., 1990, “Analysis of the
Structure-Determining Process of Phase Inversion Membrane,”
Desalination, Vol. 79, pp. 283-302.
24. Kesting, R-E., 1985, Synthetic Polymer Membrane, 2nd ed.,
25
26
New York, John Wiley & Sons, pp. 189-190.
Strathmann, H., 1985, Synthetic Membrane, Volume 2: Material
Science of Synthetic Membrane, New York, American Chemical
Society, pp. 165-194.
Wood, H. and Sourirajan, S., 1991, “The Effect of Additive,
Solvent Type, and Polymer Concentration on Macromolecule
Dimension, ” Journal of Applied Polymer Science, Vol. 43,
pp.213-217.
27. Montgomery, J-M., 1985, Water Treatment Priciplcs and Design,
New York, John Wiley & Sons, pp. 229.
- 65 -
20. Dickson, J.M., Matsuura, T. and Sourirajan, S., 1979,
“Transport Characteristics in the Reverse Osmosis System
p-Chlorophenol-Water-Cellulose Acetate Membrane,” Industrial &
Engineering Chemistry Process Design and Development, Vol. 18,
No. 4, pp. 641-647.
29. Sourirajan, S., 1981, Synthetic Membrane, Volume 1:
Desalination, New York, American Chemical Society, pp. 11-62.
30. Perry, R-H., 1984, Perry’s Chemical Engineering Handbook,
New York, McGraw-Hill, pp. 17-25.
31. Williams, M., Deshmukh, R. and Bhattacharyya, D., 1990,
“Separation of Hazadous Organic by Reverse Osmosis Membrane,”
Environmental Progress, Vol. 9, No. 2, pp. 318-125.
32. Jeffery, G-H., Bassett, J., Mendham, J. and Denney, R-C., 1989 ,
Vogel’& Textbook of Quantitative Chemical Analysis, 5th ed.,
London, Longman, pp. 707-708.
10
20
30
40
50
60
FK-1 FK-2 FK-3 FK-4 FK-5 FK-6 FK-7
1.53
1.53
1.53
1.53 53.89 64.09 56.44 54.06 48.46 46.24
55.08 66.30 60.18 57.12 51.00 46.92
55.08 65.28 59.16 56.10 51.00 46.92
55.08 64.26 57.12 54.06 49.98 46.92
54.06 64.26 56.10 53.04 47.94 46.92
52.02 63.24 54.06 53.04 47.94 45.90
52.02 61.20 52.02 51.00 44.8t! 43.86
J~n~!~a%~awl%lJl~w%-~a~~~)
kaav(ui?i)
FK-3(CA 12) FK-3tC.A 14) FK-3(CA 18)
10 130.56 109.14 70.51
20 130.56 108.12 70.51
30 129.54 106.08 69.63
40 128.52 105.06 69.63
50 128.52 102.00 68.59
60 127.50 102.00 68.81
&l 129.19 105.40 69.58
10
20
30
40
50
60
L&l
FK-1 FK-2 FK-3 FK-4 FK-5 FK-6 FK-7
48.96
42.84
41.82
38.76
36.72
33.66
73.44
62.22
56.10
52.02
49.98
42.84
40.46 56.10
4.51 7.94
56.10
53.04
49.98
44.88
42.84
40.80
47.94
4.22
47.94
44.88
41.82
36.72
33.66
33.66
38.76 34.6E
34.68 31.62
32.62 28.56
28.56 25.5C
26.52 23.4f
26.52 21.4:
39.78 31.35 27.67
5.72 4.66 4.13
10 29.41 43.86 60.18 46.92 47.94 35.70
20 28.09 40.80 56.10 44.88 40.80 33.66
30 26.74 37.74 55.08 42.84 37.74 31.62
40 25.15 36.72 54.06 38.76 35.72 29.58
50 24.56 34.68 52.02 33.66 31.61 27.54
60 23.42 32.64 49.98 32.64 30.66 27.54
26.23 37.74 54.74 39.95 37.40 30.94
7.01
SG- 1 SG- 2 SG-3 SG-4 SG-5 SG-6 SG-7
4.80 5.65 3.86 6.14 5.26
- 73 -
"K-3(CA 12) ;K-3(CA 14) ?K-3(CA 18)
10 131.59 73.44 55.08
20 121.39 70.38 49.98
30 114.25 67.32 48.96
40 113.22 65.28 47.94
50 100.98 64.26 47.94
60 90.78 63.24 42.84
112.03
3.51
67.32
2.89
48.79
4.56
aai(u7ii) ~~n~c~w%denl%lJbuw%-~a~~~)
10 8.65
20 8.56
30 8.48
40 8.31
50 8.25
60 8.19
70 7.91
80 7.81
so 7.70
100 7.68
110 7.61
120 7.53
130 7.23
140 7.30
150 7.33
160 7.32
170 7.42
180 7.35
LP& 7.82
J~n~c~A7daal%lJlu~%-~a~~~)
Laa7(uiiY)
PH 6 PH 7 PH 8 PH 9 pH 10 pH 11 pH 12
10 5.78 6.28 7.14 8.37 4.87 5.68 4.82
20 5.69 6.21 6.89 8.45 4.77 5.50 5.01
30 5.61 6.24 6.85 8.39 4.76 5.55 5.20
40 5.65 6.12 6.80 8.49 4.61 5.77 5.34
50 5.73 6.20 6.68 8.42 4.91 5.74 5.47
60 5.67 6.16 6.98 8.59 4.58 5.81 5.55
70 5.75 6.23 6.99 8.65 4.32 5.72 6.18
80 5.71 6.22 6.93 8.71 4.85 6.05 6.61
90 5.50 6.25 6.72 8.80 4.89 5.91 7.28
100 5.27 6.14 7.22 8.85 5.05 5.66 7.88
110 5.35 6.15 7.20 8.90 4.96 5.77 8.56
120 5.43 6.12 7.00 8.94 4.95 5.88 9.37
130 5.32 6.11 6.98 8.86 4.99 5.88 9.96
140 5.22 6.08 6.92 8.89 4.99 5.82 10.58
150 5.25 6.05 7.09 8.83 4.84 5.86 11.21
160 5.21 6.20 6.90 8.78 4.94 29.92 19.25
170 4.98 6.14 7.03 8.72 5.02 36.62 25.03
180 5.03 6.19 7.08 8.94 5.00 47.88 44.48
hIfIiWIl%UBfI -17.81 -28.12 15.18 88.03 66.68 / yEi.62 / 67.00
- 78 -
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
- I30 -
- 81 -