Application of Fermentation Techniques in the Utilization of Prawn Shell Waste

The present study aimed at the utlisation of microbial organisms for the production of good quality chitin and chitosan. The three strains used for the study were Lactobacillus plantarum, Lactobacililus brevis and Bacillus subtilis. These strains were selected on the basis of their acid producing ability to reduce the pH of the fermenting substrates to prevent spoilage and thus caused demineralisation of the shell. Besides, the proteolytic enzymes in these strains acted on proteinaceous covering of shrimp and thus caused deprotenisation of shrimp shell waste. Thus the two processes involved in chitin production can be affected to certain extent using bacterial fermentation of shrimp shell.Optimization parameters like fermentation period, quantity of inoculum, type of sugar, concentration of sugar etc. for fermentation with three different strains were studied. For these, parameters like pH, Total titrable acidity (TTA), changes in sugar concentration, changes in microbial count, sensory changes etc. were studied.Fermentation study with Lactobacillus plantarum was continued with 20% w/v jaggery broth for 15 days. The inoculum prepared yislded a cell concentration of approximately 108 CFU/ml. In the present study, lactic acid and dilute hydrochloric acid were used for initial pH adjustment because; without adjusting the initial pH, it took more than 5 hours for the lactic acid bacteria to convert glucose to lactic acid and during this delay spoilage occurred due to putrefying enzymes active at neutral or higher pH. During the fermentation study, pH first decreased in correspondence with increase in TTA values. This showed a clear indication of acid production by the strain. This trend continued till their proteolytic activity showed an increasing trend. When the available sugar source started depleting, proteolytic activity also decreased and pH increased. This was clearly reflected in the sensory evaluation results. Lactic acid treated samples showed greater extent of demineralization and deprotenisation at the end of fermentation study than hydrochloric acid treated samples. It can be due to the effect of strong hydrochloric acid on the initial microbial count, which directly affects the fermentation process. At the end of fermentation, about 76.5% of ash was removed in lactic acid treated samples and 71.8% in hydrochloric acid treated samples; 72.8% of proteins in lactic acid treated samples and 70.6% in hydrochloric acid treated samples.The residual protein and ash in the fermented residue were reduced to permissible limit by treatment with 0.8N HCI and 1M NaOH. Characteristics of chitin like chitin content, ash content, protein content, % of N- acetylation etc. were studied. Quality characteristics like viscosity, degree of deacetylation and molecular weight of chitosan prepared were also compared. The chitosan samples prepared from lactic acid treated showed high viscosity than HCI treated samples. But degree of deacetylation is more in HCI treated samples than lactic acid treated ones. Characteristics of protein liquor obtained like its biogenic composition, amino acid composition, total volatile base nitrogen, alpha amino nitrogen etc. also were studied to find out its suitability as animal feed supplement.Optimization of fermentation parameters for Lactobacillus brevis fermentation study was also conducted and parameters were standardized. Then detailed fermentation study was done in 20%wlv jaggery broth for 17 days. Also the effect of two different acid treatments (mild HCI and lactic acid) used for initial pH adjustment on chitin production were also studied. In this study also trend of changes in pH. changes in sugar concentration ,microbial count changes were similar to Lactobacillus plantarum studies. At the end of fermentation, residual protein in the samples were only 32.48% in HCI treated samples and 31.85% in lactic acid treated samples. The residual ash content was about 33.68% in HCI treated ones and 32.52% in lactic acid treated ones. The fermented residue was converted to chitin with good characteristics by treatment with 1.2MNaOH and 1NHCI.Characteristics of chitin samples prepared were studied and extent of Nacetylation was about 84% in HCI treated chitin and 85%in lactic acid treated ones assessed from FTIR spectrum. Chitosan was prepared from these samples by usual chemical method and its extent of solubility, degree of deacetylation, viscosity and molecular weight etc were studied. The values of viscosity and molecular weight of the samples prepared were comparatively less than the chitosan prepared by Lactobacillus plantarum fermentation. Characteristics of protein liquor obtained were analyzed to determine its quality and is suitability as animal feed supplement.Another strain used for the study was Bacillus subtilis and fermentation was carried out in 20%w/v jaggery broth for 15 days. It was found that Bacillus subtilis was more efficient than other Lactobacillus species for deprotenisation and demineralization. This was mainly due to the difference in the proteolytic nature of the strains. About 84% of protein and 72% of ash were removed at the end of fermentation. Considering the statistical significance (P

Surface acidity and catalytic activity of sulphated samaria

We have investigated the changes in surface acidity/basicity and catalytic pro~erties of samarium oxide due to surface modification by SO42- ion. The acidity/basicity of the catalysts is determined by titration method using Hammett indicators. Esterification of acetic acid by n-butanol is chosen as a test reaction. Sm203, owing to its high basicity and low acidity, does not catalyze the reaction. But sulphated Sm20J catalyzes the esterification reaction effectively. Activation temperature does not have much effect on the acidity of sulphated samaria.

Acidity/basicity, electron donor properties and catalytic activity of sulphate modified stannic oxide

The surface electron donor properties of sulphate modified stannic oxide have been determined from the adsorption of electron acceptors of various electron affinities on the oxide surface. The acid base properties of stannic oxide have been determined by titration method using Hammett indicators. Catalytic activities of the oxide for esterification of acetic acid using n-butanol.reduction of cyclohexanone in 2-propanol and oxidation of cyclohexanol with benzophenone have been studied. The data have been correlated with the surface electron donor properties of these oxides. The activity for reduction and oxidation decreases and that for esterification reaction increases on modification with sulphate ion. It has heen found that electron donating capacity decreased when stannic oxide was modified with sulphate ion.

Acidity and catalytic activity of rare earth modified Al/Zr pillared clays

The pillared montmorillonite has been prepared by exchanging Na+ in the interlayer of montmorillonite with Al hydroxy cation followed by calcination. Pillared clays are also prepared after exchanging Na' ions with Ce, La, Sm-ions and then pillarcd with aluminium oxides, The surface characterisation of the prepared catalysts has been done using XRD and surface area measurements. To probe the acidic property of the system, temperature programmed desorption (TPD) of NH, has been done. Toluene alkylation by benzyl chloride has been carried out for the evaluation of catalytic activity. The most active system is found to be mixed Al/Zr pillarcd montrnorillonite.

Acidity / basicity and electron donor properties and catalytic activity of sulphated titania

The surface acidity/ basicity of TiO2 (rutile) and its sulphate modified form have been determined by titration method using Hammett indicators after activation at different temperatures. The electron donating properties of these oxides are also studied from the adsorption of electron acceptors of different electron affinity values. The data have been correlated with the catalytic activity of these oxides towards esterification of acetic acid using n-butanol, reduction of cyclohexanone in isopropanol and oxidation of cyclohexanol in benzophenone. Catalytic activity for esterification and oxidation reaction parallels the acidity while that for reduction reaction parallels the basicity of these oxides.

Acidity and catalytic activity studies on the benzylation of o-xylene using some rare-earth exchanged zeolite-Y

The acidity of the various rare-earth exchanged zeolite-Y catalysts has been examined by titration method using Hammett indicators and is correlated with the catalytic activity of the samples in the benzylation of 0-xylene.

Acidity/basicity, electron donor properties and catalytic activity of sulphate modified ceria

The changes in surface acidity/basicity and catalytic activity of cerium oxide due to surface modification by sulphate ion have been investigated. Electron donor properties of both the modified and unmodified oxides have been studied using electron acceptors of various electron affinity values, viz. 7,7,8,8-tetracyanoquinodimethane, 2,3,5,6-tetrachloro--l, 4-benzoquinone. p-dinitrobenzene and m-dinitrobenzene in order to find out whether the increase in acidity on suphation is due to the generation of new acidic sites or they are formed at the expense of some of the basic sites. The surface acidity/basicity has been determined using a set of Hammett indicators. The data have been correlated with the catalytic activity of the oxides for esterification of acetic acid using l-butanol, reduction of cyclohexanone with 2- propanol and oxidation of cyclohexanol using benzophenone.

Surface acidity and catalytic activity of mixed Fe-Al and Cr-Al pillared montmorillonites

The incorporation of transition metal oxide pillars such as those of iron and chromium along with Al2O3, pillars within the interlayers of a montmorillonite clay is investigated. The surface acidity of these catalysts has been evaluated for the first time employing the equilibrium adsorption of an electron donor, perylene, and the results are compared with those obtained by temperature programmed desorption of ammonia. The principle is based on the ability of a catalyst surface site to accept a single electron from an electron donor like perylene to form charge transfer complexes and the amount of adsorbed species is measured quantitatively by UV-vis spectroscopy. Fina1ly, an attempt has been made to correlate the acidity determined by the two independcnt methods and the catalytic activity of present systems in the benzoylation of toluene with benzoyl chloride. Incorporation of Fe and Cr has changed the properties of AI pitlared montmorillonite. Fe pillared systems have been found to be vcry good catalysts for benzoylation reaction

Surface acidity/basicity and catalytic activity of Zr-Sm mixed oxide systems

The surface acidity and basicity of oxides of Sm and Zr and their mixed oxides have been determined using a set of Hammett indicators. The data have been correlated with the catalytic activity of these oxides towards the liquid phase reduction of cyclo-hexanone in 2-propanol.

Surface acidity/basicity of yttria and its mixed oxides with alumina catalysts

Acid/base strength distribution of Y2O3 and its mixed oxides with alumina catalysts are measured on Hammett acidity function scale and expressed in terms of H0max value. Basicity of Y2O3 increases with increase in activation temperature and for mixed oxides the basicity increases with increase in concentration of Y2O3, in the catalyst.

The surface acidity/basicity and catalytic activity of ternary oxides of La, Ce and AI

The surface acidity and basicity of ternary oxides of La, Ce and AI have been determined using a set of Hammett indicators. The data have been correlated with the catalytic activity of these oxides towards the liquid phase reduction of cycIohexanone in 2-propanol.

Surface acidity/basicity and catalytic activity of ternary oxides of Al, Ce and Dy

The surface acidity and basicity of ternary oxides of AI, Ce and Dy have been determined using a set of Hammett indicators. The data have been correlated with the catalytic activity of these oxides towards the liquid phase reduction of cyclohexanone in 2-propanol. The reaction is favoured by the higher basicity of the ternary oxide.

Surface acidity/basicity and catalytic activity of mixed oxides of Zr, La and Al

The surface acidity/basicity of binary oxides of Zr and La and the ternary oxides of Zr, La and Al are reported. The data have been correlated with their catalytic activity towards liquid phase reduction of cyclohexanone.

Acidity, basicity and catalytic activity of La−Zn mixed oxides

Surface acidity/Basicity of mixed oxides of La and Zn activated at three different temperatures were determined. The data have been correlated with the catalytic activity for liquid phase reduction of cyclohexanone in isopropanol.

Lewis acidity of rare earth exchanged zeolites

The Lewis acidity of yttrium and dysprosium exchanged zeolite Y and ZSM-5 has been determined by titration method using Hammett indicators. The acidity of the Y form increases with increase in concentration of the rare earth cation in the Y zeolite. It is independent of the amount of the rare earth ion for ZSM-5. The data have been correlated with the activity of these zeolites for the esterification of butanol using acetic acid.