RDIT19_12 Cacia Caustic soda contamination Preliminary report_24/04/2012 1. Samples reference Description 12/01141 Cacia Laboratory sample 2P2 18.04.2012 12/01142 Sample 2P1 18.04.2012 12/01150 Sample 2S1 18.04.2012 12/01151 Sample 6P1 18.04.2012 12/01152 Sample 4S1 18.04.2012 12/01153 Sample 6S1 18.04.2012 12/01154 Sample 4P1 18.04.2012 12/01170 Sample 3P3 18.03.2012 12/01171 Sample Loya 14.04.2012 12/01172 Sample Loya after loading 15.04.2012 12/01175 Sample Inspectorate Portugal, rpt 14731, Vessel Loya, taken from top 18.04.2012 12/01176 MT Loya, TK #2Port, bottom sample #03 w/ autoseal 24.2012 12/01177 Sample 1 12/01178 Sample 6 12/01179 Sample 11 12/01180 Sample 16 12/01187 MT Loya, APD Química TK 2B 24.04.2012 12/01188 APD TK 19 24.04.2012
12/01189 APD TK 20 24.04.2012 12/01190 APD TK 23 24.04.2012 12/01191 APD TK 24 24.04.2012 12/01192 APD TK 25 24.04.2012 12/01193 APD TK 4B 24.04.2012 Origin: gps - Cacia mill Date of reception: 19.04.2012/23.04.20112 2. Conclusions The samples were treated with HCL for ph adjustment. Most of the samples have an evident yellow precipitate mixed with the NaCl crystals, which was chemically identified by FTIR analysis as salts from fatty acids. The infra-red spectroscopy was nor conclusive with some samples, eventually due to a lower contamination. The following table resumes the characterization of the different samples. Chemical Sample Yellow precipitate identification of Reference formed with HCl the yellow (RAIZ) addition precipitate (FTIR) 12/01141 yes fatty acids 12/01142 yes fatty acids 12/01150 yes fatty acids 12/01151 yes not conclusive 12/01152 yes not conclusive 12/01153 yes not conclusive 12/01154 yes fatty acids
Chemical Sample Yellow precipitate identification of Reference formed with HCl the yellow (RAIZ) addition precipitate (FTIR) 12/01170 no - 12/01171 no - 12/01172 no - 12/01175 yes fatty acids 12/01176 yes not conclusive 12/01177 no - 12/01178 yes fatty acids 12/01179 yes fatty acids 12/01180 yes not conclusive 12/01187 yes not conclusive 12/01188 no - 12/01189 yes not conclusive 12/01190 yes not conclusive 12/01191 yes fatty acids 12/01192 yes fatty acids 12/01193 yes fatty acids The caustic soda forms soaps with the fatty acids, which are soluble in the presence of excess of soda. This can explain the high content of organic compounds found in the samples. This should prevent the utilization of the caustic soda represented by mentioned analyzed samples in the industrial process, as any chemical or physical change will lead to the separation and deposition of the fatty compounds.
3. Results The samples were treated with HCL for ph adjustment. Large amounts of precipitate were formed after ph adjustment. The precipitate was filtered, dried and analyzed by infrared spectroscopy. Samples 2P2, 2P1, 4P1, 6P1, 2S1, 4S1, 6S1, 6, 11, 16, S. inspectorate Portugal 18.04.212 and MT Loya 24.2012 have an evident yellow precipitate mixed with the NaCl crystals. The same occurred with the later samples APD TK 20, 23, 24, 25, 2B and 4B 24.04.2012. These yellow particles were considered the contaminants chosen for analysis. On samples 3P3, Loya 14.04.2012 and Loya after loading 15.04.2012 yellow particles were not observed (these samples were the reference). The same occurred with sample 1. On later sample APD TK19 24.04.2012 no evident yellow particles were also found. Carboxylic salts and aliphatic chains (C>6) were identified, confirming a significant presence of organic compounds (salts from fatty acids) in samples 2P2, 2P1, 4P1, 2S1, 6, 11 and s. inspectorate Portugal 24.2012 (Figures 1, 2, 6, 8, 11, 13). Samples APD TK 24, 25 and 4B also show clear evidence of the presence of fatty acids (salts) on the respective infrared spectra (Figures 15, 16, 17). On samples 6P1, 4S1, 6S1, 16 and MT-Loya 24.2012 FTIR spectra are not clear (Figures 3, 4, 5, 9, 16). Images - 41 are pictures of precipitates from samples 6S1 and APDT TK 2B, 20 and 23, where we can see the presence of yellow particles.
2P2 2P1 alifatics C>6 Figure 1 FTIR spectrum of the precipitates formed after HCL treatment of the caustic soda samples 2P2 and 2P1 2S1 alifatics C>6 Figure 2 FTIR spectrum of the precipitate formed after HCL treatment of the caustic soda sample 2S1
6P1 Figure 3 FTIR spectrum of the precipitate formed after HCL treatment of the caustic soda sample 6P1 4S1 Figure 4 FTIR spectrum of the precipitate formed after HCL treatment of the caustic soda sample 4S1
6S1 Figure 5 FTIR spectrum of the precipitate formed after HCL treatment of the caustic soda sample 6S1 Image 1 Picture of the precipitate formed after HCL treatment of the caustic soda sample 6S1
4P1 alifatics C>6 Figure 6 FTIR spectrum of the precipitate formed after HCL treatment of the caustic soda sample 4P1 3P3 LOYA 14.04.2012 LOYA AFTER LOADING 15.04.2012 Figure 7 FTIR spectrum of the precipitates formed after HCL treatment of the caustic soda control samples
INSPECTORATE PORTUGAL alifatics C>6 Figure 8 FTIR spectrum of the precipitate formed after HCL treatment of the caustic soda sample Inspectorate Portugal MT LOYA 24.2012 Figure 9 FTIR spectrum of the precipitate formed after HCL treatment of the caustic soda sample MT Loya 24.2012
SAMPLE 1 Figure 10 FTIR spectrum of the precipitate formed after HCL treatment of the caustic soda sample 1 SAMPLE 6 Figure 11 FTIR spectrum of the precipitate formed after HCL treatment of the caustic soda sample 6
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SAMPLE 16 (??) Figure 14 FTIR spectrum of the precipitate formed after HCL treatment of the caustic soda sample 16 Image 2 Picture of the precipitate formed after HCL treatment of the caustic soda sample MT Loya, APD Química TK 2B
Image 3 Picture of the precipitate formed after HCL treatment of the caustic soda sample APD TK 20 Image 4 Picture of the precipitate formed after HCL treatment of the caustic soda sample APD TK 23
APD TK 24 alifatics C>6 Figure 15 FTIR spectrum of the precipitate formed after HCL treatment of the caustic soda sample APD TK 24 APD TK 25 alifatics C>6 Figure 16 FTIR spectrum of the precipitate formed after HCL treatment of the caustic soda sample APD TK 25
APD TK 4B alifatics C>6 Figure 17 FTIR spectrum of the precipitate formed after HCL treatment of the caustic soda sample APD TK 4B