08/22/09 ENVIRONMENTALLY FRIENDLY CATALYTIC STARCH OXIDATION BY HYDROGEN PEROXIDE 8th World Congress of Chemical Engineeri...
<ul><li>Introduction </li></ul><ul><li>Starch modification </li></ul><ul><li>Experimental </li></ul><ul><li>Results </li><...
What is starch and its applications? <ul><li>A polysaccharide carbohydrate in  potato, corn, ... </li></ul><ul><li>Glucose...
<ul><li>Starch oxidation reactions </li></ul><ul><li>- introducing carboxyl and carbonyl groups to starch </li></ul><ul><l...
Reactor setup -1000 ml glass reactor  - pH-stat to control pH (2M NaOH) - H 2 O 2  feed 22 ml/h or initially 0.7 w-% in ba...
<ul><li>Operation policies </li></ul><ul><li>1. Starch and catalyst in batch, H 2 O 2  added </li></ul><ul><li>gradually <...
<ul><li>Offline analysis methods </li></ul><ul><li>Titration of carboxyl groups COOH (and carbonyl groups CO) by modified ...
In our previous study  [1] : Semibatch by feeding  H 2 O 2  constantly to reactor Slightly alkaline environment.:  pH 7-10...
<ul><li>New approaches </li></ul><ul><li>- All H 2 O 2  + catalyst added at   start  of the  reaction </li></ul><ul><ul><l...
<ul><li>Results </li></ul><ul><li>DS COOH  and H 2 O 2  concentrations - H 2 O 2 -batch, at pH 7.5, 8.4 and 10 </li></ul>E...
<ul><ul><li>SEM </li></ul></ul>Native potato starch BET: 10 m 2  /g Native potato starch treated with ultrasound 24 h at 3...
<ul><li>Results </li></ul><ul><li>DS COOH  and H 2 O 2  concentrations -  with or without ultrasound pretreated </li></ul>...
<ul><li>Results </li></ul><ul><li>DS COOH  and H 2 O 2  concentrations – H 2 O 2  -batch, catalyst solution </li></ul><ul>...
<ul><li>Left:  catalyst and H 2 O 2  only, compared with using starch in same </li></ul><ul><li>conditions. Right: Effect ...
<ul><li>Summary of COOH and  H 2 O 2  results: </li></ul>h ENVIRONMENTALLY FRIENDLY CATALYTIC STARCH OXIDATION BY HYDROGEN...
<ul><li>Low molecular products </li></ul><ul><li>GC extraction: 2 ml of aqeous phase from sample, acidified and </li></ul>...
<ul><li>Conclusions </li></ul><ul><li>Starch oxidation is studied using a cheap iron complex FePcS as a catalyst, and hydr...
<ul><li>Thank you for your kind attention! </li></ul><ul><li>Questions...? </li></ul>Department of Industrial Chemistry an...
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Wcce08 Pasi Tolvanen Final

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presentation from the World Congress in Chemical Engineering 08, held in Montreal, Canada 26.08 2009

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Wcce08 Pasi Tolvanen Final

  1. 1. 08/22/09 ENVIRONMENTALLY FRIENDLY CATALYTIC STARCH OXIDATION BY HYDROGEN PEROXIDE 8th World Congress of Chemical Engineering, Montreal, August 23 to 27, 2009 P. Tolvanen , P. Mäki-Arvela, A. B. Sorokin, T. Salmi, D. Yu. Murzin, Åbo Akademi Process Chemistry Centre Turku, Finland Collaboration with Institut de Recherches sur la Catalyse-CNRS, Villeurbanne Cedex, France
  2. 2. <ul><li>Introduction </li></ul><ul><li>Starch modification </li></ul><ul><li>Experimental </li></ul><ul><li>Results </li></ul>ENVIRONMENTALLY FRIENDLY CATALYTIC STARCH OXIDATION BY HYDROGEN PEROXIDE
  3. 3. What is starch and its applications? <ul><li>A polysaccharide carbohydrate in potato, corn, ... </li></ul><ul><li>Glucose units linked together forms </li></ul><ul><li>amylose (planar) and amylopectin (branched) </li></ul><ul><li>Starch modification in industry: </li></ul><ul><li>- Fuel ethanol by fermentation </li></ul><ul><li>- Bioplastics, films, hygiene products </li></ul><ul><li>- pharmaceuticals (vitamins B) </li></ul><ul><li>- organic chemicals (ascorbic acid, aspartame...) </li></ul><ul><li>- in paper and board industry </li></ul><ul><li>as a surface sizing agent </li></ul><ul><li>as a coating binder </li></ul><ul><li>--> produced by partial oxidation </li></ul>(C 6 H 10 O 5 ) n ENVIRONMENTALLY FRIENDLY CATALYTIC STARCH OXIDATION BY HYDROGEN PEROXIDE
  4. 4. <ul><li>Starch oxidation reactions </li></ul><ul><li>- introducing carboxyl and carbonyl groups to starch </li></ul><ul><li>- A degree of substitution (DS) of only 1-20 AGU </li></ul><ul><li>(anhydro glucose unit) per 100 is of </li></ul><ul><li>commercial interest. </li></ul>Carboxyle Carbonyle Traditional oxidation methods use: - heavy metals (Fe, Cu, W) as catalysts - NaOCl, N 2 O 4 as oxidants ---> large amounts of inorganic waste In our work: Green Chemistry - iron tetrasulfonatophthalocyanine (FePcS) as catalyst - hydrogen peroxide as oxidant ENVIRONMENTALLY FRIENDLY CATALYTIC STARCH OXIDATION BY HYDROGEN PEROXIDE
  5. 5. Reactor setup -1000 ml glass reactor - pH-stat to control pH (2M NaOH) - H 2 O 2 feed 22 ml/h or initially 0.7 w-% in batch mode Parameters - pH = 7-10 - T = 52 degrees celsius - conc. of FePcS catalyst 0.014 mmol/L Typically 260g potato starch added to 800ml deionized water ENVIRONMENTALLY FRIENDLY CATALYTIC STARCH OXIDATION BY HYDROGEN PEROXIDE
  6. 6. <ul><li>Operation policies </li></ul><ul><li>1. Starch and catalyst in batch, H 2 O 2 added </li></ul><ul><li>gradually </li></ul><ul><li>2. Starch and H 2 O 2 in batch, catalyst a </li></ul><ul><li>gradually </li></ul><ul><li>3. Starch pretreated with ultrasound, starch </li></ul><ul><li>and H 2 O 2 in batch, catalyst a gradually </li></ul>ENVIRONMENTALLY FRIENDLY CATALYTIC STARCH OXIDATION BY HYDROGEN PEROXIDE
  7. 7. <ul><li>Offline analysis methods </li></ul><ul><li>Titration of carboxyl groups COOH (and carbonyl groups CO) by modified Smith´s method [2] </li></ul><ul><li>Iodometric titration of remaining H 2 O 2 concentration in samples </li></ul><ul><li>Separation of organic low-mol. weight compounds by extraction (ethyl acetate) </li></ul><ul><li>GC-MS for identification of low-mol. weight compounds </li></ul><ul><li>(e.g. oxalic, lactic, malonic acid ) </li></ul><ul><li>Quantitative analysis of low-mol. weight compounds by GC </li></ul><ul><li>SEM, nitrogen adsorption for granular surface structure and surface area. </li></ul>[2] R.J. Smith, Starch: Chemistry and technology, 2 (1967) 620-625 ENVIRONMENTALLY FRIENDLY CATALYTIC STARCH OXIDATION BY HYDROGEN PEROXIDE
  8. 8. In our previous study [1] : Semibatch by feeding H 2 O 2 constantly to reactor Slightly alkaline environment.: pH 7-10 H 2 O 2 constant feed at 22 ml/h (30%) catalyst (FePcS) added initially reaction time 7h --> high pH gave good degree of substitution but not good yield [1] Tolvanen et al. Chem . Eng. J. (2009) ENVIRONMENTALLY FRIENDLY CATALYTIC STARCH OXIDATION BY HYDROGEN PEROXIDE
  9. 9. <ul><li>New approaches </li></ul><ul><li>- All H 2 O 2 + catalyst added at start of the reaction </li></ul><ul><ul><li> broader understanding of H 2 O 2 decomposition </li></ul></ul><ul><ul><li> easier kinetics </li></ul></ul><ul><ul><li> study of catalyst deactivation </li></ul></ul><ul><ul><li>- H 2 O 2 added instantly, catalyst solution fed into to reactor </li></ul></ul><ul><ul><li>- Starch pretreated with ultrasound </li></ul></ul><ul><ul><li> higher surface available for reaction </li></ul></ul>ENVIRONMENTALLY FRIENDLY CATALYTIC STARCH OXIDATION BY HYDROGEN PEROXIDE
  10. 10. <ul><li>Results </li></ul><ul><li>DS COOH and H 2 O 2 concentrations - H 2 O 2 -batch, at pH 7.5, 8.4 and 10 </li></ul>ENVIRONMENTALLY FRIENDLY CATALYTIC STARCH OXIDATION BY HYDROGEN PEROXIDE
  11. 11. <ul><ul><li>SEM </li></ul></ul>Native potato starch BET: 10 m 2 /g Native potato starch treated with ultrasound 24 h at 38 deg. celsius BET: 18m 2 /g Ultrasound treated starch after reaction in pH = 8.4 ENVIRONMENTALLY FRIENDLY CATALYTIC STARCH OXIDATION BY HYDROGEN PEROXIDE
  12. 12. <ul><li>Results </li></ul><ul><li>DS COOH and H 2 O 2 concentrations - with or without ultrasound pretreated </li></ul><ul><li>starch, H 2 O 2 -batch, at pH 8.4 </li></ul>30 % higher yield ENVIRONMENTALLY FRIENDLY CATALYTIC STARCH OXIDATION BY HYDROGEN PEROXIDE
  13. 13. <ul><li>Results </li></ul><ul><li>DS COOH and H 2 O 2 concentrations – H 2 O 2 -batch, catalyst solution </li></ul><ul><li>feed 12 mg cat /h for 10h </li></ul>50 % higher yield ENVIRONMENTALLY FRIENDLY CATALYTIC STARCH OXIDATION BY HYDROGEN PEROXIDE
  14. 14. <ul><li>Left: catalyst and H 2 O 2 only, compared with using starch in same </li></ul><ul><li>conditions. Right: Effect of temperature increase on H 2 O 2 decomposition </li></ul>ENVIRONMENTALLY FRIENDLY CATALYTIC STARCH OXIDATION BY HYDROGEN PEROXIDE
  15. 15. <ul><li>Summary of COOH and H 2 O 2 results: </li></ul>h ENVIRONMENTALLY FRIENDLY CATALYTIC STARCH OXIDATION BY HYDROGEN PEROXIDE
  16. 16. <ul><li>Low molecular products </li></ul><ul><li>GC extraction: 2 ml of aqeous phase from sample, acidified and </li></ul><ul><li>extracted with aid of ethyl acetate, and run with GC. Betulinol used as </li></ul><ul><li>internal standard </li></ul><ul><li>Low molecular : </li></ul><ul><li>hydroxyacetic acid (glycolic acid ) - high formation at pH 10 </li></ul><ul><li>Ethanedioic acid (oxalic acid) - high formation at pH 10 </li></ul><ul><li>Lactic acid – lower pH favors formation </li></ul><ul><li>2,3-dihydroxypropanoic acid – high formation at pH 10 </li></ul><ul><li>+ Formic acid (probably high concentration), can be determined by HPLC </li></ul><ul><li>+ over 30 other unidentified, lower concentration compounds </li></ul>ENVIRONMENTALLY FRIENDLY CATALYTIC STARCH OXIDATION BY HYDROGEN PEROXIDE
  17. 17. <ul><li>Conclusions </li></ul><ul><li>Starch oxidation is studied using a cheap iron complex FePcS as a catalyst, and hydrogen peroxide as an oxidant, resulting in a waste free oxidation method. </li></ul><ul><li>By optimizing rection contions to constantly feeding catalyst during reaction, higher DS values were obtained compared to batch mode. DS still lower than when constantly feeding H 2 O 2 . </li></ul><ul><li>Experiments with both catalyst and H 2 O 2 are of future interest </li></ul><ul><li>Ultrasound pretreated starch reacts faster in beginning, but conversion remains moderate. </li></ul><ul><li>Experiments using ultrasound during reaction is of future interest. </li></ul>ENVIRONMENTALLY FRIENDLY CATALYTIC STARCH OXIDATION BY HYDROGEN PEROXIDE
  18. 18. <ul><li>Thank you for your kind attention! </li></ul><ul><li>Questions...? </li></ul>Department of Industrial Chemistry and reaction Engineering Åbo Akademi Univesity Turku/Åbo Suomi/Finland

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