Cationic Cellulose Betainate Forwastewater Treatment

Cationic Cellulose Betainate forWastewater Treatment

Katja Sievänen*1, Jari Kavakka1, Paula Hirsilä1, Pirjo Vainio2, Kaisa Karisalmi2, Juha Fiskari1, Ilkka Kilpeläinen*1

1 Laboratory of Organic Chemistry, Department of Chemistry, University of Helsinki,

P.O. Box 55, 00014 Helsinki, Finland.

2Kemira Oyj, Luoteisrinne 2, P.O. Box 44, FIN-02271 Espoo, Finland

* Corresponding author. (Tel. +358505181148; email: )

Domsjö Betainate I

Fig.S1. a)1H NMR (500 MHz, D2O) spectrumand b) IR spectrum

of Domsjö betainate I. *Residual THF

Domsjö Betainate II

Fig.S2. a)1H NMR (500 MHz, D2O) spectrum and b) IR spectrum

of Domsjö betainate II. *Residual EtOH

Domsjö Betainate III

Fig.S3. a)1H NMR (500 MHz, D2O) spectrum and b) IR spectrum

of Domsjö betainate III.

Domsjö BetainateIV

Fig.S4. a)1H NMR (500 MHz, D2O) spectrum and b) IR spectrum

of Domsjö betainate IV.

Domsjö Betainate V

Fig.S5. a)1H NMR (500 MHz, D2O) spectrum and b) IR spectrum

of Domsjö betainate V.

Borregaard Betainate I

Fig.S6. a)1H NMR (500 MHz, D2O) spectrum and b) IR spectrum

of Borregaard betainate I. *Residual THF

Borregaard Betainate II

Fig.S7. a)1H NMR (500 MHz, D2O) spectrum and b) IR spectrum

of Borregaard betainate II. *Residual DMA

Borregaard Betainate III

Fig.S8. a)1H NMR (500 MHz, D2O) spectrum and b) IR spectrum

of Borregaard betainate III.

Borregaard Betainate IV

Fig.S9. a)1H NMR (500 MHz, D2O) spectrum and b) IR spectrum

of Borregaard betainate IV.

Borregaard Betainate V

Fig.S10. a)1H NMR (500 MHz, D2O) spectrum and b) IR spectrum

of Borregaard betainate V.

Fig. S11. Example of 1H NMR spectrum of Borregaard betainate, where the residual solvent peak was removed with digital filtering (5 Hz) and an exponential function (lb=2 Hz) was applied prior to FT.

Fig.S12. TGA thermograms of unmodified Domsjö dissolving pulp (—) and Domsjö Betainate III (—).

Fig. S13. TGA thermograms of unmodified Borregaard dissolving pulp (—) and Borregaard Betainate III (—).

Fig.S14. DSC thermograms of Domsjö Betainate III(---) and Borregaard Betainate III (—).

Table S1. Nitrogen contents from elemental analysis,the DS results and yields.

Sample / N% / DS Meas / DS Real / Yield (g)a / Product (yield, g)b / Yield (%)
Domsjö Betainate I / 3.57 / 0.63 / 0.42 / 9.7 / 7.2 / 71
Domsjö Betainate II / 3.48 / 0.61 / 0.59 / 8.3 / 6.3 / 56
Domsjö Betainate III / 3.01 / 0.49 / 0.47 / 9.2 / 6.9 / 66
Domsjö Betainate IV / 5.33 / 1.27 / 1.20 / 10.0 / 8.1 / 54
Domsjö Betainate V / 6.01 / 1.66 / 1.60 / 12.4 / 10.3 / 59
Borregaard Betainate I / 3.23 / 0.55 / 0.47 / 11.9 / 8.9 / 85
Borregaard Betainate II / 5.10 / 1.19 / 1.05 / 13.2 / 10.5 / 75
Borregaard Betainate III / 5.35 / 1.28 / 1.13 / 18.1 / 14.6 / 100c
Borregaard Betainate IV / 5.40 / 1.31 / 1.07 / 17.3 / 13.8 / 97c
Borregaard Betainate V / 5.82 / 1.54 / 1.28 / 21.5 / 17.5 / >100c

aMeasured yield; bYield of the product, where free betaine has been subtracted using formula below: m(product);cDue to the hydroscopic nature of the products, it was impossible to completely remove water from the high MW products.

The yield (%) was calculated based on following formula:

, where

and

Table S2. GPC results of all the products in DMSO media. Due to the solvent (DMSO) used, the products were not fully soluble, which emphasises the low molecular weight polymers.

Reference / Pullulan 112 kDa / Pullulan 404 kDa
Sample / MW (kDa) / PDI / MW (kDa) / PDI
Domsjö Betainate I / 103.1 / 6.04 / 99.4 / 5.88
Domsjö Betainate II* / 50.6 / 1.44 / 53.8 / 1.51
Domsjö Betainate III* / 29.4 / 3.62 / 33.5 / 5.22
Domsjö Betainate IV / 110.9 / 2.04 / 119.7 / 2.19
Domsjö Betainate V / 99.1 / 2.54 / 107.2 / 2.82
Borregaard Betainate I* / 80.6 / 1.78 / 82.4 / 1.68
Borregaard Betainate II / 267.3 / 4.47 / 338.1 / 1.17
Borregaard Betainate III / poor solubility#
Borregaard Betainate IV / poor solubility#
Borregaard Betainate V / poor solubility#

*Cellulose degradation due to moisture in the reaction system.

#The samples were not completely soluble in DMSO due to the high DP and high cationic charge.

Table S3. FBRM results of the reference and products. Maximum floc sizes in the beginning of test, after 60 and 120 sec, and floc size proportions to maximum size after 60 and 120 seconds with dosing 12 milligrams of dry flocculant per gram of dry pulp (mg/g).

Flocculant / Maximum floc size (µm) / 60 sec flocksize BRM (12 mg/g) / 120 sec flocksize FBRM (12 mg/g) / Percentage of max floc size at 60 sec (%) / Percentage of max floc size at 120 sec (%)
Domsjö Betainate I / 12.3 / 11.6 / 11.6 / 94 / 94
Domsjö Betainate II / 11.6 / 10.8 / 11.1 / 93 / 96
Domsjö Betainate III / 11.4 / 11.2 / 11.5 / 98 / 101
Domsjö Betainate IV / 12.4 / 11.6 / 11.5 / 94 / 93
Domsjö Betainate V / 14.1 / 11.7 / 12.0 / 83 / 85
Borregaard Betainate I / 18.5 / 16.9 / 17.1 / 91 / 92
Borregaard Betainate II / 22.6 / 17.2 / 17.2 / 76 / 76
Borregaard Betainate III / 33.1 / 19.1 / 19.1 / 58 / 58
Borregaard Betainate IV / 31.0 / 21.5 / 21.6 / 69 / 70
Borregaard Betainate V / 26.9 / 21.5 / 20.7 / 80 / 77
Fennopol K3400R* / 34.6 / 19.8 / 20.3 / 57 / 59

*Different batch of mechanical pulp