Whey Demineralization: Various Process Options According to Plant
Whey Demineralization: Various Process Options According to Plant
Whey Demineralization: Various Process Options According to Plant
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<strong>Whey</strong><br />
<strong>Demineralization</strong><br />
1<br />
Industrial Biotech / APPLEXION
<strong>Whey</strong> <strong>Demineralization</strong><br />
<strong>Various</strong> <strong>Process</strong> <strong>Options</strong> according <strong>to</strong> <strong>Plant</strong> Capacity<br />
9 th DAIRY INGREDIENTS SYMPOSIUM<br />
Presented by Francis GULA<br />
San Francisco, CA February 26 th -28 th , 2007<br />
2<br />
© Novasep
<strong>Whey</strong> <strong>Demineralization</strong> <strong>Process</strong>es<br />
WHEY<br />
NF NF<br />
ED ED<br />
DK DK<br />
NF<br />
ED<br />
DK<br />
NF<br />
ED<br />
DI<br />
NF<br />
DI<br />
NF<br />
DI<br />
DI<br />
DI<br />
<strong>Demineralization</strong> rate<br />
~ 30%<br />
<strong>Demineralization</strong> rate<br />
~ 60%<br />
<strong>Demineralization</strong> rate<br />
~ 95%<br />
NF: Nanofiltration ED: Electrodialysis<br />
DK: Decalcification DI: Deionization (IX)<br />
3<br />
Industrial Biotech / APPLEXION
Typical Sweet <strong>Whey</strong> Mineral Composition<br />
Total Solids: 6.65%<br />
Lac<strong>to</strong>se: 4.95% w/w<br />
Proteins: 0.8% w/w<br />
NPN: 0.2% w/w<br />
Fat: 0.02% w/w<br />
Ash: 0.59% w/w<br />
Lactate: 0.01% w/w<br />
Phosphate<br />
Sulfate<br />
Sodium<br />
Potassium<br />
Mineral Composition<br />
Na: 410 mg/l Cl: 2102 mg/l<br />
K: 1784 mg/l HPO 4 : 1056 mg/l<br />
Mg: 108 mg/l SO 4 : 103 mg/l<br />
Ca: 415 mg/l<br />
* HPO4 is expressed as divalent ion<br />
Chloride<br />
Monovalent<br />
Divalent<br />
≈ 2<br />
Magnesium<br />
Calcium<br />
Comments:<br />
<strong>Whey</strong> is a complex mixture of ionic and non ionic species. The mineral content is pretty high<br />
therefore several processes have <strong>to</strong> be used <strong>to</strong> decrease it cost effectively.<br />
4<br />
Industrial Biotech / APPLEXION
<strong>Process</strong> <strong>Options</strong> versus Capacity<br />
Investments<br />
DK + NF + DI<br />
NF + DI<br />
DI<br />
Operating Cost<br />
20 gpm 100 gpm 200 gpm<br />
The right technology vs capacity<br />
Comments:<br />
The scope of this brief presentation is <strong>to</strong> look at how the available technologies can be combined<br />
further <strong>to</strong> the daily capacity.<br />
5<br />
Industrial Biotech / APPLEXION
<strong>Whey</strong> processing: : Ion Exchange<br />
Deashing steps:<br />
Sweet <strong>Whey</strong><br />
Decationized<br />
Demineralized<br />
Cation Anion<br />
Ca 2+ , Mg 2+ 2-<br />
HPO 3<br />
Na + , K + Cl -<br />
Proteins<br />
SAC<br />
H +<br />
Cation<br />
H +<br />
Anion<br />
2-<br />
HPO 3<br />
Cl -<br />
Proteins<br />
WBA<br />
OH-<br />
Cation Anion<br />
H +<br />
Proteins<br />
OH -<br />
Lac<strong>to</strong>se<br />
Lac<strong>to</strong>se<br />
Lac<strong>to</strong>se<br />
Key features:<br />
• Benefits:<br />
• High deashing rate<br />
• Bacteria stability (low pH ex SAC)<br />
• Proven technology<br />
• Simple process<br />
• APPLEXION selected resins<br />
• Drawbacks:<br />
• High chemical consumption<br />
• Protein loss (~5%)<br />
• Generates waste<br />
6<br />
Industrial Biotech / APPLEXION
<strong>Whey</strong> processing: Ion Exchange only<br />
IX only: Example of mass balance for a 1000 m 3 /d plant<br />
Water : 6,7 BVT – 1,568 m 3 /d<br />
(414000 gpd)<br />
HCL 100% : 7,605 Kg/d<br />
NaOH 100% : 7,605 Kg/d<br />
(17000 lb/d)<br />
Sweet <strong>Whey</strong><br />
Demineralized <strong>Whey</strong><br />
1000 m 3 /d (~ 183 gpm)<br />
6.6% DS 68 mt/d<br />
(150,000 lb/d)<br />
8.6% ash/DS<br />
SAC<br />
H +<br />
WBA<br />
OH-<br />
SAC<br />
H +<br />
WBA<br />
OH-<br />
SAC<br />
H +<br />
WBA<br />
OH-<br />
1130 m 3 /d (~ 207 gpm)<br />
5.3 % DS 60 mt/d<br />
(132000 lb/d)<br />
Less 1% ash/DS<br />
Effluent:1,474 m 3 /d<br />
(389,000 gpd)<br />
Ash: 5,800 kg/d (12,800 lb/d)<br />
Chemicals: 33,500 lb/d<br />
7<br />
Industrial Biotech / APPLEXION
<strong>Whey</strong> processing: Nanofiltration<br />
FT<br />
RETENTATE Divalent species + Lac<strong>to</strong>se + NPN<br />
PT<br />
NF<br />
PERMEATE Water + monovalent species<br />
FEED<br />
Key features:<br />
• Benefits:<br />
• Pre-concentration of whey<br />
up <strong>to</strong> 18 – 20% DS<br />
• Pre-demineralization of whey<br />
up <strong>to</strong> 30 – 35%<br />
• Proven technology, low effluents<br />
• Drawbacks:<br />
• Divalents remain in retentate<br />
• Limited demineralization rate<br />
• Still scaling risk<br />
8<br />
Industrial Biotech / APPLEXION
<strong>Whey</strong> processing: NF & IX Combination<br />
Effluent: 660 m 3 /d<br />
Ashes: 3600 Kg/d<br />
Chemicals: 10400 Kg/d<br />
Smaller<br />
plant<br />
Sweet <strong>Whey</strong><br />
1000 m 3 /d (~ 183 gpm)<br />
6.6% DS 68 mt/d<br />
(150000 lb/d)<br />
8.6% ashes/DS<br />
NF<br />
20 – 25 Bars VCF 3<br />
Permeate<br />
660 m3/d<br />
121 gpm<br />
Retentate<br />
340 m 3 /d<br />
18% DS<br />
6% ashes<br />
SAC<br />
H +<br />
WBA<br />
OH-<br />
SAC<br />
H +<br />
WBA<br />
OH-<br />
Demineralized<br />
<strong>Whey</strong><br />
420 m 3 /d (~ 77 gpm)<br />
14% DS 59 mt/d<br />
(130,000 lb/d)<br />
Less 1% ashes/DS<br />
Effluents<br />
132 m 3 /d<br />
Ashes: 2200 Kg/d<br />
(4850 lb/d)<br />
RO<br />
30 bars VCF 5<br />
528 m 3 /d Osmosed water<br />
Water: 151 m 3 /d<br />
HCl: 5200 Kg/d<br />
NaOH: 5200 Kg/d<br />
Comments:<br />
The NF unit in front of the IX columns results in a smaller demineralization plant, the amount of<br />
chemicals needed for regeneration have been reduced by 1/3.<br />
9<br />
Industrial Biotech / APPLEXION
Divalent Ions Removal with IX<br />
Regenerant<br />
Monovalents<br />
Cl -<br />
Regenerant<br />
Monovalents<br />
K + or Na +, Cl -<br />
FEED WHEY<br />
Ca 2+ ,Mg 2+<br />
Na + , K +<br />
Cl - ,PO<br />
3-<br />
4<br />
Organic acids<br />
Colorants<br />
ANION<br />
RESIN<br />
“ MR TYPE”<br />
Regeneration effluent<br />
FEED<br />
Ca 2+ ,Mg 2+<br />
Na + , K +<br />
Cl -<br />
STRONG<br />
ACID RESIN<br />
“ GEL TYPE”<br />
SOFTENED FEED<br />
K +<br />
Na +<br />
Comments:<br />
The next step consists in removing the divalent species in a chemical free process, using<br />
the monovalent ions from the feed whey. The front anionic resins operating in chloride form<br />
fixes most of the species which could prevent calcium <strong>to</strong> be exchanged thereby the<br />
following cationic unit can achieve a high divalent removal yield. Such a design allow <strong>to</strong><br />
remove more than 95% of the troublesome divalent species (no more scaling risks).<br />
10<br />
Industrial Biotech / APPLEXION
<strong>Whey</strong> processing: DK + NF + IX Combination<br />
Total Effluent:<br />
905 m 3 /d<br />
Ash:12.3 t/day<br />
COD 8.2 t/d<br />
Pre-concentrated<br />
~ 50% demin<br />
Sweet <strong>Whey</strong><br />
1000 m 3 /d (~ 183 gpm)<br />
6.6% DS 68 mt/d<br />
(150000 lb/d)<br />
8.6% ash/DS<br />
SBA<br />
Cl -<br />
SAC<br />
Na +<br />
SBA<br />
Cl -<br />
SAC<br />
Na +<br />
“Soft <strong>Whey</strong>”<br />
1041 m 3 /d<br />
6.4 % DS<br />
6% ash<br />
NF<br />
20 – 25 Bars VCF 3<br />
Permeate<br />
752 m 3 /d<br />
138 gpm<br />
Retentate<br />
289 m 3 /d<br />
20% DS<br />
4.8% ash<br />
Retentate<br />
Regenerant<br />
75 m 3 /d<br />
Ash: ~50 g/l<br />
Comments:<br />
(4850 lb/d)<br />
The NF performance is enhanced through<br />
divalent ions removal (up <strong>to</strong> 50% predemineralization<br />
and higher DS feed for IX<br />
system). The IX step brings it up <strong>to</strong> 90%<br />
with a smaller unit, using less resins, less<br />
water and less chemicals. An RO unit<br />
allows <strong>to</strong> recover process water<br />
RO<br />
30 bars VCF 5<br />
Demineralized<br />
<strong>Whey</strong><br />
358 m 3 /d (~ 66 gpm)<br />
16% DS 59 mt/d<br />
(130000 lb/d)<br />
Less 1% ash/DS<br />
RO WATER<br />
677 m 3 /d<br />
For DIAF,<br />
Regeneration<br />
Cleaning<br />
SAC<br />
H +<br />
WBA<br />
OH-<br />
HCl 3.7 t/d<br />
NaOH 3.1 t/d<br />
11<br />
Industrial Biotech / APPLEXION
<strong>Whey</strong> processing: Cost Comparison<br />
1000 m 3 /d Capacity EFFLUENT<br />
CHEMICALS<br />
USAGE<br />
Comments<br />
ION EXCHANGE<br />
1,474 m 3 /d<br />
Ash: 5800 kg/d<br />
15,210 kg/d<br />
•Low investments<br />
•High chemicals<br />
•High wastes<br />
NF (& RO)<br />
+<br />
ION EXCHANGE<br />
732 m3/d<br />
Ash: 5800 kg/d<br />
10,400 kg/d<br />
•Less chemicals<br />
•Concentrated and<br />
partly demineralized<br />
whey<br />
DECALCIFICATION<br />
+<br />
NF (& RO)<br />
+<br />
905 m3/d<br />
Ash: 5800 kg/d<br />
6,800 kg/d<br />
•Low chemicals needs<br />
• No M ++<br />
ION EXCHANGE<br />
TO WASTE<br />
12<br />
Industrial Biotech / APPLEXION
<strong>Whey</strong> processing: Cost Comparison<br />
European case s<strong>to</strong>ry<br />
IX only<br />
Water Effluents HCl NaOH Cationic Anionic<br />
( 1.5 €/m 3 ) (2.10 €/m 3 ) (0,15 €/kg) (0.25 €/kg) resin Resin<br />
2,355 €/d 3,098€/d 1,140 €/d 1,900 €/d 120 €/d 700 €/d<br />
TOTAL<br />
9315 €/d<br />
IX + NF + RO<br />
39.2 €/t TS 51.4 €/t TS 19 €/t TS 31.7 €/t TS 1.95 €/t TS<br />
11.7 €/t TS<br />
155 €/t TS<br />
Water<br />
( 1.5 €/m 3 )<br />
Effluents<br />
(2.10 €/m 3 )<br />
HCl<br />
(0,15 €/kg)<br />
NaOH<br />
(0,25 €/kg)<br />
Cationic<br />
resin<br />
Anionic<br />
Resin<br />
Membranes<br />
Power<br />
TOTAL<br />
225 €/d 1,665 €/d 780 €/d 1,300 €/d 79 €/d 475 €/d 546 €/d 562 €/d 5635 €/d<br />
3.8 €/t TS 28 €/t TS 13.2 €/t TS 22 €/t TS 1.33 €/t TS 8 €/t TS<br />
9.2€/t TS<br />
9.5€/t TS<br />
95 €/t TS<br />
DK+ NF + RO + IX<br />
Water<br />
( 1.5 €/m 3 )<br />
Effluents<br />
(2.10 €/m 3 )<br />
NaCl<br />
(0,2 €/kg)<br />
HCL<br />
(0,15 €/kg)<br />
NaOH<br />
(0.25 €/kg)<br />
Cationic<br />
resin<br />
Anionic<br />
Resin<br />
Membranes<br />
power<br />
TOTAL<br />
331 €/d 1900 €/d 205 €/d 555 €/d 775 €/d 87 €/d 665 €/d 425 €/d 535 €/d 4945 €/d<br />
5.7 €/t TS 32 €/t TS 3.5 €/t TS 9.5 €/t TS 13 €/t TS 1.5 €/t TS<br />
11.5 €/t TS<br />
7.3 €/t TS<br />
9.2 €/t TS<br />
85 €/t TS<br />
13<br />
Industrial Biotech / APPLEXION
Conclusions<br />
ION EXCHANGE RESINS ONLY<br />
• Well suited for small daily capacity<br />
NF and ION EXCHANGE<br />
• Drastic reduction in chemicals and wastes<br />
• Well suited for medium size plant<br />
• Divalent species still limit efficiency<br />
DK + NF + ION EXCHANGE<br />
• Well adapted for large capacity where chemical cost would<br />
be prohibitive.<br />
• High quality lac<strong>to</strong>se crystals<br />
• Related <strong>to</strong> monovalent/divalent ions availability<br />
14<br />
Industrial Biotech / APPLEXION
REFERENCES<br />
1. CONTINUOUS CHROMATOGRAPHIC PROCESSES IN THE WHEY INDUSTRY, Francis<br />
GULA APPLEXION IDF Bruges, Belgium 10 & 11 September 2003<br />
2. PURIFICATION OF FOOD STREAMS BY COMBINING ION EXCHANGE AND<br />
MEMBRANES TECHNOLOGIES: APPLICATION OF DECALCIFICATION IN THE WHEY<br />
INDUSTRY, Marc-André THEOLEYRE, Francis GULA ICEF9-2004 Montpellier, France<br />
3. CONTINUOUS CHROMATOGRAPHY FOR WHEY PROCESSING, M.A. THEOLEYRE, J.<br />
KINNA, S. BAUDOUIN, APPLEXION , IWC September 2001<br />
4. A <strong>Whey</strong> <strong>to</strong> the Future – Towards Zero Discharge, University of Western Sydney, Dairy<br />
Australia, Food Science Australia<br />
15<br />
Industrial Biotech / APPLEXION
Thank you for your attention!<br />
Presenter: Francis GULA<br />
francis.gula@novasep.com<br />
16<br />
© Novasep
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