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Contents Introduction 7 CHAPTER 1: OVERVIEW 9 1.1. AMINOPOLYSACCHARIDE 9 1.1.1 Physical properties and structure of aminopolysaccharide 9 1.1.2 Sources of aminopolysaccharide 11 1.1.3 Chemical modification of Aminopolysaccharide. 12 1.1.4 Application of Aminopolysaccharide 14 1.1.5. Chemical modification of Aminopolysaccharide. 14 1.2 Pigments or Dyes 16 1.2.1 Structure of pigments 16 1.2.2 Effect of textile dyes on environment 16 1.2.3 Some methods to remove dyes 17 1.3 Electroplate wastewater treatment 18 1.3.1 Biological method 18 1.3.2 Chemical method. 19 1.3.3 Different physical methods 19 CHAPTER2: EXPERIMENTS 20 2.1 Materials and Apparatus 20 2.2. Extraction of chitin from shrimp crusts 21 2.3. Evaluation of Aminopolysaccharide quality 26 2.3.1. The degree of deacetylation of Aminopolysaccharide 26 2.3.2 Modification of Aminopolysaccharide by ammonium persulfate 27 2.4 Evaluation the absorption ability of APSAMS for dye in wastewater of electric Samsung company 28 2.5 Method for characterization of the components and structure of APSAMS and dye solution 30 CHAPTER3: RESULTS AND DISCUSSION 32 3.1 The result of conversion of chitin from shrimp crust into aminopolysaccharide 32 3.1.1. Infrared Spectroscopy 32 3.2. Ability absorption of Aminopolysaccharide to dyes Error Bookmark not defined. 3.2.1 Effect of pH Error Bookmark not defined. 3.2.2 Effect of time Error Bookmark not defined. 3.2.3 Effect of dye concentration Error Bookmark not defined. 3.2.4 Effect of concentration of Diramen Yellow Error Bookmark not defined. REFERENCES: 35
C MINISTRY OF EDUCATION AND TRAINING L AS HANOI UNIVERSITY OF MINING AND GEOLOGY S : A D V A N C E D P R O G KIEU NGOC THANH R A M B A T C STUDY ON CHEMICAL MODIFICATION OF NATURAL H AMINOPOLYSACCHARIDE USE AS ABSORBENT TO REMOVE TEXTILE DYES THESIS HANOI, JUNE 2017 MINISTRY OF EDUCATION AND TRAINING HANOI UNIVERSITY OF MINING AND GEOLOGY KIEU NGOC THANH THESIS STUDY ON CHEMICAL MODIFICATION OF NATURAL AMINOPOLYSACCHARIDE USE AS ABSORBENT TO REMOVE TEXTILE DYES SUPERVISOR REVIEWER DR Nguyen Thi Linh HANOI, JUNE 2017 Contents TABLE CONTENTS Table 2.1: Effect of ammonium persulfate on crosslinking Table 2.2: Effect of time reaction on crosslinking Table 2.3: Effect of temperature on crosslinking Table 2.4: Effect of APS-AMS dose on absorption Table 2.5: Effect of dye concentration on absorption Table 2.6: Effect of agitation time on absorption Table 2.7: Effect of initial pH on absorption Table 3.1: Efficiency of samples in changing concentration Table 3.2: Efficiency of sample in changing reaction time Table 3.3: Efficiency of samples in changing temperature Table 3.4: The best condition in chemical modification of aminopolysaccharide FIGURE CONTENTS Figure 1.1: Commercial Aminopolysaccharide Figure 1.2: Shell Biorefinery Figure 1.3: Examples of pigment in the electroplate industry Figure 2.1: Shell shrimp after demineralization process Figure 2.2: Experiment progressing Figure 2.3: Shell shrimp after deacetyl process Figure 2.4: Aminopolysaccharide dissolved in Acetic acid Figure 2.5: Procedure of synthesis of aminopolysaccharide from shrimp crusts Figure 3.1: IR of Aminopolysaccharide Figure 3.2: Infrared spectroscopy of samples in changing concentration Figure 3.3: Infrared Spectroscopy of samples in changing time reaction Figure 3.4: Infrared Spectroscopy of samples in changing temperature Figure 3.5: UV-VIS of sample in different pH Figure 3.6: Investigation of pH Figure 3.7: UV VIS of sample with different time reaction Figure 3.8: Investigation of time reaction Figure 3.9: UV-VIS of samples in different concentration Figure 3.10: Investigation of dye’s concentration Figure 3.11: UV-VIS of samples in different concentration Figure 3.12: Investigation of APS’s concentration Introduction Every year, some million to million tonnes of waste crab, shrimp and lobster shells are produced The shell waste produced by the seafood industry is a growing problem, with significant environmental and health hazards Shrimp processing effluents are very high in biological oxygen demand, chemical oxygen demand, total suspended solids, fat-oil-grease, pathogenic and other microflora, organic matters and nutrients Shrimp processing effluents are, therefore, highly likely to produce adverse effects on the receiving coastal and marine environments Shrimps and lobsters are among the most popular crustaceans For instance, specks of flesh left in the shells serve as an ideal growth media for pathogenic bacteria This leads to the need to burn the shells, an environmentally costly activity given their low burning capacity Chitin is the major component in the shell of the shrimps, and crabs, cartilage of the squid, and outer cover of insects It is also extracted from a number of other living organisms in the lower plant and animal kingdoms, serving in many functions where reinforcement and strength are required Aminopolysacharide is a natural polysaccharide comprising of copolymers of glucosamine and N-acetylglucosamine, and can be obtained by the partial deacetylation of chitin In its crystalline form, aminopolysaccharide is normally insoluble in aqueous solutions above pH7; however, in dilute acids (pH6.0), the protonated free amino groups on glucosamine facilitate solubility of the molecule Aminopolysaccharide has been widely used in vastly diverse fields, ranging from waste management to food processing, medicine and biotechnology Especially, Aminopolysaccharide used absorbent to remove textile dyes CHAPTER 1: OVERVIEW 1.1 AMINOPOLYSACCHARIDE 1.1.1 Physical properties and structure of aminopolysaccharide Chitin found in the exoskeleton of crustaceans, the cuticles of insects, and the cells walls of fungi, is the most abundant aminopolysaccharide in nature This low-cost material is a linear homopolymer composed of b(1-4)-linked Nacetyl glucosamine It is structurally similar to cellulose, but it is an aminopolymer and has acetamide groups at the C-2 positions in place of the hydroxyl groups The presence of these groups is highly advantageous, providing distinctive adsorption functions and conducting modification reactions The raw polymer is only commercially extracted from marine crustaceans primarily because a large amount of waste is available as a byproduct of food processing Chitin is extracted from crustaceans (shrimps, crabs, squids) by acid treatment to dissolve the calcium carbonate followed by alkaline extraction to dissolve the proteins and by a decolorization step to obtain a colourless product More important than chitin is its derivative, aminopolysaccharide Aminopolysaccharide is prepared by deacetylating chitin Chitin Aminopolysaccharide 10 Figure 1.1: Commercial Aminopolysaccharide Physical natural of Aminopolysaccharide Aminopolysaccharide is also crystalline and shows polymorphism depending on its physical state Depending on the origin of the polymer and its treatment during extraction from raw resources, the residual crystallinity may vary considerably Generally, commercial chit- osans are semi-crystalline polymers, Crystallinity plays an important role in adsorption efficiency.it demonstrated that decrystallized aminopolysaccharide is much more effective in the adsorption of anionic dyes Crystallinity controls polymer hydratation, which in turn deter- mines the accessibility to internal sites This para- meter strongly influences the kinetics of hydratation and adsorption Chemical structure of Aminopolysaccharide Commercial aminopolysaccharide also varies greatly in its MW and distribu- tion, and therefore its solution behavior The MW of aminopolysaccharide is a key variable in adsorption properties because it influences the polymer’s solubility and viscosity in solution The degree of N-acetylation (DA) or DD The DD parameter is essential, though the hydroxyl groups on the polymer may be involved in 22 Figure 2.1: Shell shrimp after demineralization process c, Deproteination A total samples from demineralization were added with NaOH 8% then left for 12 hours at room temperature with pH ranged from 11-13 After that, the solution was filtered and the samples were washed with distilled water until neutral pH was achieved (pH=7) Water from the samples was removed and the sample is totally white 23 Figure2.2: Experiment progressing If the sample isn’t white we would use H 2O2 1% to get the completely white The sample was washed with distilled water until neutral pH was achieved After that dried at 600 C and we have dried white Chitin 24 F igure2.3: Shell shrimp after deacetyl process d, Deacetylation 10g Chitin add with NaOH 40% and heated at 80 0C After 6.5h, the samples were washed with distilled water until neutral pH was achieved (pH=7) The sample is known as aminopolysaccharide This step was executed again and again until the desired product and higher value DD were achieved But in reality, we can’t the same as experiment because of the high extra expenditure 5g APS was added with 300ml Acetic Acid 2% and stirring in 30 minutes at room temperature If the sample dissolved in acetic acid, it would be properly APS The residue was grinded to dust and the sample was stored in closed container prior to use And the picture after test showed below: 25 Figure2.4: Aminopolysaccharide dissolved in Acetic acid The above steps were described as figure 2.5 Shrimp shell Demineralization 26 HCl 10% in12h at room temp Deproteination NaOH 8% in 12h at room temp Chitin NaOH 50% in 2.5h at 1000C Chitosan Figure2.5: Procedure of synthesis of aminopolysaccharide from shrimp crusts 2.3 Evaluation of Aminopolysaccharide quality 2.3.1 The degree of deacetylation of Aminopolysaccharide Aminopolysaccharide is typically obtained by partial deacetylation of chitin Molar fraction of Nacetylglucosamine units in the chain, defined as: Where nGLcN is average number of D-glusamine units NGlcNac is average number of N-acetylglucosamine units In some works, degree of acetylation is used DD= 100 – DA 27 5mg Aminopolysaccharide added with 100mg potassium bromine (KBr) Substances were mixed in agate mortar and pressed to tablet form The sample was dried for 24hr at 500C in order to remove moisture The spectra of aminopolysaccharide were obtained within a frequency range of 400 – 4000 cm-1 From the infrared spectrum, absorbance A refers to functional group of hydroxyl (OH), and acetyl (CH3C=O) with wave length range about 2450 and 1650 cm-1 DA% = (A1650/A3450)*115 2.3.2 Modification of Aminopolysaccharide by ammonium persulfate • Aminopolysaccharide and ammonium persulfate 2g Aminopolysaccharide added the solution which contained 150ml distilled water, after that add ammonium persulfate 2% drop by drop into the solution Investigate experiments in main articles: concentration, temperature, time Investigation on concentration of ammonium persulfate Table 2.1: Effect of ammonium persulfate on crosslinking No Concentration (mg/l) 100 Time (h) Temperature (0C) 60 50 60 35 60 25 60 Investigation on time reaction Table 2.2: Effect of time reaction on crosslinking 28 No Concentration (mg/l) 25 Time (h) Temperature (0C) 60 25 60 25 60 25 60 Investigation on temperature Table 2.3: Effect of temperature on crosslinking No Concentration Time (h) 25 Temperature (0C) 60 25 70 25 80 25 90 2.4 Evaluation the absorption ability of APS-AMS for dye in wastewater of electric Samsung company 0.2 gram Drimaren Yellow dissolved in liter distilled water The mixture as known as textile dyes Investigation of the absorption ability of modifiable aminopolysaccharide (APS-MPS) Table 2.4: Effect of APS-AMS dose on absorption No APS-AMS dose (g) 0.05 Concentration of Diramen Yellow (mg/l) 20 Time (min) 30 pH 29 0.1 0.2 0.3 20 20 20 30 30 30 7 Investigation of absorption ability of Diramen Yello Table 2.5: Effect of dye concentration on absorption No APS-AMS dose (g) Concentration of Diramen Yellow (mg/l) Time pH 0.1 0.1 0.1 0.1 0.1 10 20 30 40 50 30 30 30 30 30 7 7 Investigation of absorption ability on agitation time Table 2.6: Effect of agitation time on absorption No APS-AMS dose (g) Time (min) 10 pH 0.1 Concentration of Diramen Yellow (mg/l) 20 0.1 0.1 0.1 0.1 20 20 20 20 20 30 40 50 7 7 Investigation of absorption ability on pH Table 2.7: Effect of initial pH on absorption No APS-AMS dose (g) 0.1 0.1 Concentration of Diramen Yellow (mg/l) 20 20 Time pH 30 30 30 0.1 0.1 0.1 20 20 20 30 30 30 11 2.5 Method for characterization of the components and structure of APSAMS and dye solution *Infrared spectroscopy (IR spectroscopy) Infrared spectroscopy (IR spectroscopy) is the spectroscopy that deals with the infrared region of the electromagnetic spectrum, that is light with a longer wavelength and lower frequency than visible light It covers a range of techniques, mostly based on absorption spectroscopy As with all spectroscopic techniques, it can be used to identify and study chemicals For a given sample which may be solid, liquid, or gaseous, the method or technique of infrared spectroscopy uses an instrument called an infrared spectrometer (or spectrophotometer) to produce an infrared spectrum A basic IR spectrum is essentially a graph of infrared light absorbance (or transmittance) on the vertical axis vs frequency or wavelength on the horizontal axis Typical units of frequency used in IR spectra are reciprocal centimeters (sometimes called wave numbers), with the symbol cm−1 Units of IR wavelength are commonly given in micrometers (formerly called "microns"), symbol μm, which are related to wave numbers in a reciprocal way A common laboratory instrument that uses this technique is a Fourier transform infrared (FTIR) spectrometer Two-dimensional IR is also possible as discussed below The infrared portion of the electromagnetic spectrum is usually divided into three regions; the near-, mid- and far- infrared, named for their relation to the visible spectrum The higher-energy near-IR, approximately 14000–4000 cm−1 (0.8–2.5 μm wavelength) can excite overtone or harmonic vibrations The midinfrared, approximately 4000–400 cm−1 (2.5–25 μm) may be used to study the fundamental vibrations and associated rotational-vibrational structure The farinfrared, approximately 400–10 cm−1 (25–1000 μm), lying adjacent to the 31 microwave region, has low energy and may be used for rotational spectroscopy The names and classifications of these subregions are conventions, and are only loosely based on the relative molecular or electromagnetic properties Infrared spectroscopy exploits the fact that molecules absorb specific frequencies that are characteristic of their structure These absorptions are resonant frequencies, i.e the frequency of the absorbed radiation matches the transition energy of the bond or group that vibrates The energies are determined by the shape of the molecular potential energy surfaces, the masses of the atoms, and the associated vibronic coupling *UV-VIS spectroscopy UV-VIS refers to absorption spectroscopy or reflectance spectroscopy in the ultraviolet-visible spectral region This means it uses light in the visible and adjacent ranges The absorption or reflectance in the visible range directly affects the perceived color of the chemicals involved In the region of electromagnetic atoms and molecules undergo electronic transitions Absorption spectroscopy is complementary to fluorescence spectroscopy, in that fluorescence deals with transitions from the excited state to the ground state, while absorption measures transitions from the ground state to the excited state 32 CHAPTER3: RESULTS AND DISCUSSION 3.1 The result of conversion of chitin from shrimp crust into aminopolysaccharide Aminopolysaccharide produced from chitin by deacetyl reaction In theory, we can create Aminopolysaccharide with different molecular weight and DD by adjusted data of experiments In some research adsorption ability of Aminopolysaccharide doesn’t depend on the DD With DD = 65% - 70% Aminopolysaccharide easily absorb heavy metal and textile dyes from waste water 3.1.1 Infrared Spectroscopy Figure 3.1: FT-IR spectroscopy of Aminopolysaccharide As shown in the figure 3.1, FT- IR spectrum of Aminopolysaccharide showed strong band at 1030, 1081 and 1381 cm -1 characteristic of saccharide structure ( due to O-H bending, C-H stretching, C-N stretching) The strong band at 3475 33 cm-1 could be assigned to the extension vibration of -NH of amino polysaccharide The absorption band at 1643 cm-1 characteristic of unconverted acetyl group of chitin Depend on the absorption bands of amin group and acetyl group of aminopolysaccharide from FT-IR spectrum, we can determine Degree of Deacetylation (DD) of aminopolysaccharide product After calculation, we get the DD of aminopolysaccharide = 68% • The IR of samples with different concentration Figure 3.2: FT-IR spectroscopy of samples in changing concentration Table 3.1: Efficiency of samples in changing concentration No Time (h) Concentration (mg/l) 100 Temperature (0C) 60 Crosslinking Efficiency (%) 86 50 60 90 35 60 58 25 60 83 Determining the degree of deacetyl to figure out what is the most efficient in crosslinking ability And the equation is: Crosslinking efficiency = 100% After calculation, we get the sample with the ratio of APS and AMS is 1:4 is the best solution with the highest crosslinking efficiency • The IR of samples with different time reaction 34 REFERENCES: [6, 7] Al-Qodah, Z (2000), “Adsorption of dyes using shale oil ash”, Water Researchvol 34 (17), 4295 [8] A.J Varma, S.V 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material is a linear homopolymer composed of b( 1-4 )-linked Nacetyl glucosamine It is structurally similar to cellulose, but it is an aminopolymer and has acetamide groups at the C-2... used to remediate organic contaminants, such as oil-based wastewater, dyes, tannins, humic acids, phenols, bisphenoi-A, p-benzoquinone, organo-phosphorus insecticides, among others Aminopolysaccharide... spectrometer Two-dimensional IR is also possible as discussed below The infrared portion of the electromagnetic spectrum is usually divided into three regions; the near-, mid- and far- infrared,