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Separation of Binary Mixture By Using Pervaporation Chapter 1

INTRODUCTION TO PERVAPORATION 1.1 BACKGROUND: Compared with traditional separation processes, such as distillation, extraction and filtration, membrane technology is a relatively new method that has been developed in the past few decades, but it has been widely adopted in many industries. The membrane processes have the following distinguishing characteristics [Mulder 1991]: 1) Continuity and simplicity of the processes, 2) Adjustability of the separation properties, 3) Feasibility of incorporation into hybrid processes, 4) Low energy consumption and moderate operating conditions. Developments in membrane formation techniques and materials science accelerate the research and applications of membrane technology. Now commercial membrane applications have successfully displaced some conventional processes, and membrane technology has become an indispensable component in many industrial fields and our daily life.

Figure 1.1 Schematic membrane separation processes Figure 1.1 shows a schematic membrane process [Mulder 1991; Baker 2004]. Separation membranes are located between the feed side and the permeate side. In most membrane processes, such as gas separation, reverse osmosis and ultra filtration, both the feed and the permeate sides are in the same phases, gas or liquid, while in

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Separation of Binary Mixture By Using Pervaporation pervaporation, the liquid feed is separated into vaporous permeates with the aid of vacuum or a purge gas in the downstream side. Pervaporation has become a very important technique to separate azeotropes, closeboiling mixtures, and recover volatile organic chemicals from liquid mixtures, and now it has emerged as a good choice for separating heat sensitive products. The phenomenon of pervaporation was first discovered in 1917 by Kober [1995], but no extensive research was carried out until in the 1950s by Binning et al. [1961]. In pervaporation processes with functional polymer membranes, the non-porous dense membranes are essential. By choosing proper membranes, pervaporation has great advantages as an alternative separation method in the following separation tasks: 1) Dehydration of organic solvents, 2) Removal of organics from water, 3) Separation of organic liquids. Non-porous dense membranes can also be applied in other separation processes such as gas separation. Furthermore, both gas separation and pervaporation can be interpreted with the solution diffusion mechanism for mass transport in membranes. Membrane-based pervaporation or vapor permeation is a promising alternative to distillation since it is an energy-saving one-step separation process. If the proper membrane material is selected, pervaporation can separate azeotropic

mixtures and close boiling

mixtures that traditional

distillation has difficulties in processing [3]. 1.2 MEMBRANE BASED PERVAPORATION SEPARATION: Pervaporation, in its simplest form, is an energy efficient combination of membrane permeation and evaporation. Liquid mixtures can be separated by partial vaporization through a non-porus permselective membrane. This technique, which was originally called “Liquid permeation” has subsequently been termed “pervaporation” in order to emphasized the fact that permeate undergoes a phase change, from liquid to vapor, during the transport through the barrier. 2

Separation of Binary Mixture By Using Pervaporation It's considered an attractive alternative to other separation methods for a variety of processes. For example, with the low temperatures and pressures involved in pervaporation, it often has cost and performance advantages for the separation of constant-boiling azeotropes. Pervaporation is also used for the dehydration of organic solvents and the removal of organics from aqueous streams. Additionally, pervaporation has emerged as a good choice for separation heat sensitive products. Pervaporation involves the separation of two or more components across a membrane by differing rates of diffusion through a thin polymer and an evaporative phase change comparable to a simple flash step. A concentrate and vapor pressure gradient is used to allow one component to preferentially permeate across the membrane. A vacuum applied to the permeate side is coupled with the immediate condensation of the permeated vapors. Pervaporation is typically suited to separating a minor component of a liquid mixture, thus high selectivity through the membrane is essential.

Figure

1.2 Overview of Pervaporation process

In addition, a pervaporation unit can be integrated into a bioreactor to improve bioconversion rate and reduce downstream processing costs, if membranes can selectively remove volatile inhibitory substances from fermentation broths [7]. Compared to the relatively easy separation of non-aggressive chemicals from water in industry, very few commercial systems have been developed to separate aggressive organics-water systems [8-11]. The most significant opportunity to use pervaporation is in splitting an azeotrope or a close boiling-temperature mixture, where distillation is less efficient due to the huge amount of energy consumption. Theoretically, if a liquid feed contacts a nonporous membrane with vacuum downstream, the vaporization rate of each component in the liquid is limited by the membrane permeability. In other words, the concentration

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Separation of Binary Mixture By Using Pervaporation distribution of each component in the liquid and vapor is not only controlled by the thermodynamic equilibrium [12], but also is governed by the membrane permeability. In this case, the membrane is sometimes referred to as a “mass separating agent”. Nevertheless,

the

membrane-mediated

evaporation

is

generally

regarded

as

pervaporation. In order to maximize the driving force, i.e. an activity difference between a feed liquid and permeate vapor, heating the feed liquid at the boiling temperature on one side of the membrane and pulling a vacuum or cooling the permeate vapor to condense on the other side are generally applied in the pervaporation process [3].

Figure 1.2.1: Membrane-based pervaporation separation processes Vacuum Operation Pervaporation can used for breaking azeotropes, dehydration of solvents and other volatile organics, organic/organic separations such as ethanol or methanol removal, and wastewater purification. Characteristics of the pervaporation process include: 1. Low energy consumption 2. No entrainer required, no contamination 3. Permeate must be volatile at operating conditions 4. Functions independent of vapor/liquid equilibrium 1.2.1 1.3 MEMBRANE MATERIAL: Tobacco plants require fertile well-drained moist soil and warm temperatures. Most types of tobacco are grown in full sun to counteract these problems; tobacco farmers grow strains of tobacco that resist disease and insects. By rotating crops (planting tobacco one year and different crop in the same field next year i.e. change of crop successively) farmers keep the population of tobacco pests in check by depraving them of tobacco plants on alternate years.

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Separation of Binary Mixture By Using Pervaporation The right stage for harvesting tobacco crop is when the leaves are mature. In tobacco, generally lower leaves mature first and then the upper leaves in regular ascending order. In India a number of tobaccos such as cigar tobacco, chewing tobacco, natu tobacco, hookah tobacco and beedi tobacco are sun cured. 1.4 NICOTINE CONTENT OF TOBACCO: Nicotine content is an important factor, which determines the quality of tobacco from the point of view of the marketability of tobacco products since nicotine is believed to be addictive in nature. Nicotine content is highest in beedi tobacco (6.5 % to 8.25 %). 1.5 TOBACCO WASTE SOURCES: Tobacco waste or dust is generated at various stages of post harvest processing of tobacco and also while manufacturing various tobacco products like cigarette and beedi. The types of wastes generated during pre & post harvest practice of tobacco include suckers, stems, mid ribs, leaf waste and dust. Most cigarette factories are recycling the waste to produce reconstituted tobacco sheet and blending for the production of cheap tobacco products. 1.6 AVAILABILITY OF TOBACCO WASTE: Patel and Ramakrishna surveyed the tobacco wastes suitable for nicotine extraction available in the country during 1985. According to their data an average of as million kg of tobacco waste is available annually. According to Patel and Ramakrishna in general 11% of total production of tobacco results in waste. The quality of tobacco waste available if organized efforts are made to collect the waste from all economical sources will be on an average 16% of the tobacco production as published. The tobacco waste is also exported mainly to USA to some extend. The tobacco dust consumed at present based on the sample data would be 25,000 tones per year for production of 600 tones per year of nicotine content in tobacco waste. 1.7 CHEMICAL CONSTITUENTS OF TOBACCO: Due to health and social concerns, tobacco has been the most thoroughly researched natural products in history. Millions of dollars have been expended in the study of tobacco constituents composition over 2700 compounds have been identified in 5

Separation of Binary Mixture By Using Pervaporation various tobacco variety and it is estimated that in excess of 6000 may be in tobacco smoke. 1.8 NICOTINE ALKALOIDS OF TOBACCO: The species most often use for the production of tobacco because of its high level of nicotine is N. tabacum, which is cultivated for the preparation of cigarettes, cigars and pipe tobacco. Nicotine (C10H14 N2 ) is readily extracted from tobacco roots and stalks that remain after the leaves have been picked for tobacco production and from waste tobacco. It is optically pure when obtained from the tobacco plant, (pure liquid Nicotine content varied between 2.8% to 6.5% for Beedi tobacco waste and 1.2% to 2.7% for other tobacco wastes). 1.9 ROLE OF TOBACCO PRODUCTS IN THE ECONOMY: Tobacco and tobacco products contributes over Rs.600 million to the export earnings and over Rs. 30,000 million to excise revenue of the country. Tobacco sector employees even 7.5 million people in farming curing, marketing, grading, redrying, packing, manufacturing, exports and retail trade. India’s export of tobacco products increase from 12,337 tones in 1981 to 18,957 tones in 1998-99 and 21,837 tones in 200607. The short fall in revenue is made good by increasing rates of excise duty on manufactured tobacco products and bringing all tobacco products under tariff structure. The current excise revenue from tobacco products in India is esteemed at Rs. 75,000 million a year. It is because of these reasons and the difficulty in finding suitable alternate crop to tobacco the governments are hesitance to impose total ban on tobacco use in spite of known health risk from the use of tobacco and the related expenditure. According to a study the cost of treating each cancer patient is Rs. 3.5 lakhs. The study has given a boost of the campaign against tobacco, since the health cost of tobacco are much more than the gains from its cultivation. Tobacco made for million preventable deaths annually. In India alone 7 lakh people die due to tobacco related diseases every year. There is a continued effort to control the usage of tobacco globally. In the absence of suitable alternative for tobacco crop farmers are not likely to discontinue cultivation of tobacco in spite of health risks associated with it in such a situation alternative use for tobacco could help to control the 6

Separation of Binary Mixture By Using Pervaporation supply side of tobacco for the manufacture of smoking and chewing products. Even if the present usages of tobacco for smoking or in other forms are to continue alternate routes of tobacco usage will help in controlling the supply side for such use. The products developed so far include tobacco leaf proteins, tobacco seed oil, photochemical, pharmaceutical products based on nicotine such as nicotinic acid, etc. Increasing the cost of tobacco products has done demand side control of tobacco usage to some extend. In country like India excise duty and sales tax compound of tobacco products in some are as high as 60%. However, the alternate use of tobacco will help the farmer as well as in controlling the tobacco use in the present form i.e. due to the carcinogenic effects of tobacco can be reduced by converting nicotine to nicotinic acid (Niacin) as per as the protection form treatment of tobacco. 1.10 RECOMMENDATIONS: According to the global health report estimates 65% of all men use some from of tobacco (35% smoking, 22% chewing tobacco, 8% use both). The use of smokeless tobacco is similar among women and men. At least 1/3 of women use form of tobacco. There are 23 major tobacco growing districts in the county. Natu tobacco is grown in Sap districts, Hookah tobacco is grown in Bihar, WB, Gujarat and UP, chewing tobacco is grown in TN, WB, UP and Orissa. India is the third largest consumer of tobacco next to China (Ranks No.1) and USA. Tobacco is rich source of protein, edible oil and various useful chemicals like aromatic compounds, solanesol, nicotine, organic acid etc. The excise revenue from tobacco products in India estimated at Rs.75,000 million a year. The current export earnings from tobacco and tobacco products are about Rs.1750 million. According to Food Administration Organisation about 7 lakh people in India die due to tobacco related diseases per year. According to ICMR average cost of treating tobacco related cancers in India is Rs. 3.5 lakh per case. The need for development of alternate use for tobacco arises because of compulsion generated mainly out of health risks of using tobacco for introducing tobacco control laws. Tobacco is major revenue generating commodity of many countries. Tobacco is addictive and if the use of tobacco has to be stopped it is necessary to help 7

Separation of Binary Mixture By Using Pervaporation tobacco users to get rid of the habit nicotine replacement therapy needs. Nicotine produced from tobacco for the manufacture of smoking cassation products and nicotinic acid. Product technologies to be commercialized include nicotine extraction by Ion exchange method, technology for other nicotine salt and nicotinic acid. Efforts should be made to be commercialized the laboratory technology for protein extraction, tobacco seed oil extraction. Color extraction and tobacco flavor and coenzyme and also nicotinic acid. As a long term plan country should have its own products base for tobacco control, nicotine and its derivatives are not used at present for the treatment of brain related disorders research in such medical fields should be encouraged. 1.11 PROPERTIES OF TOBACCO CONTENT:A. Nicotine 1.

It is a hazardous poison if taken in pure form.

2.

It is responsible for the temporary stimulation following smoking.

3.

It is the addictive property of tobacco.

4.

It raises blood pressure.

5.

It increases rate of heart beats.

6.

It stimulates the flow of saliva.

7.

It causes vasoconstriction (narrowing of the blood vessels) and lowered skin temperature.

8.

After its use it effects wear off and depresses the system.

9.

Boiling point is 2470C, it is the best known and most widely distributed of the tobacco alkaloids, it occurs naturally, when oxidized with dichromate ,H2SO4 (or HNO3) and it forms niacin. (10)

B. Tar 1.

It is a yellowish brown sticky mass of condensed particulate matter from

tobacco smoke. 2.

It contains carcinogenic hydrocarbons which have tumor promoting

activity and damages the lungs. 3.

It is also related to black lung diseases.

C. Carbon Monoxide

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Separation of Binary Mixture By Using Pervaporation 1. It is one of the gaseous elements found in tobacco smoke. 2. It combines with the hemoglobin on the red blood cells and thereby reduces the oxygen-carrying capacity of the blood. Factors governing the nicotine content of tobacco are:1. The species, variety and strain. 2. The environment in which the plant is grown, primarily the condition of the climate and soil. 3. Cultural, curing and handling methods employed. The nicotine content of commercial tobacco types varies considerably, while the ash content is high and ranges from 15 to 25% of the leaf on a water free basis. Nicotine is used in agriculture as an insecticide and in chemistry as a source of nicotinic acid, which is obtained by the oxidation of nicotine. Tobacco smokers absorb small amounts of nicotine and inhales smoke and then they feel certain physiological effects as a nerve stimulant, especially upon the autonomic nervous system promoting the flow of adrenalin and other internal secretions. It is also believed that it can inhibit the activity of a receptor in the brain that regulates the release the brain memory and movement control. This can offer beneficial medical side effects and the united status it has been used with some success in the treatment of people suffering from Parkinson’s and Alzheimer’s deceases and children with Tourette’s syndrome. In large doses, nicotine paralyses the autonomic nervous system by preventing the transmission of nerve impulses across the space between cells. Still large doses of nicotine may causes convulsions and death. The effects of nicotine upon the nervous system vary among individuals. In some people nicotine hastens the formation of gastric ulcers. Nicotine is now considered to be an addictive drug. Tobacco is grown with assistance of man with the leaf as the most valuable part of the plant. Almost all countries are capable of growing tobacco but the United States, China, India and Brazil are the leading countries to grow tobacco. In any case it is the nicotine content in the leaves, which attracted man to the tobacco plant. Tobacco is primarily used for cigarette, cigar, chewing tobaccos and snuff. Other products from

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Separation of Binary Mixture By Using Pervaporation tobacco include beedi and hookah and are typically Indian products with 90% of production coming from India. 1.12 DIESEASES FROM TOBACCO 1.12 .1 Cancers of the urinary tract Cigarette smoke and its metabolites cause cancers of the bladder and kidney resulting in the death of over 40 % of men in some countries of Eastern and Central Europe, and 17 % of women in USA. Tobacco and cigarette use especially on a Western diet (high total fat; fried or boiled meats; low in fiber, vegetables and fruits) pose a high risk for renal cancer growth. Cigarette smoking is associated with elevated plasma carcinoembryonic antigen (CEA) levels among patients suffering from non-neoplastic diseases including chronic renal failure. Further studies have demonstrated that the prominent nicotine-related alkaloid ß-nicotyrine present after smoking potentially inhibits human CYP2A630. As CYP2A630 is involved in the metabolic activation of numerous carcinogens reduction in this enzyme could potentially promote the development of renal carcinoma. 1.12.2 Occupational exposure to cigarette smoke A recent report indicates the passing of a new federal bill in Germany to reduce exposure to environmental tobacco smoke in the workplace .Exposure to tobacco smoke at work increases the risk of urinary detection of nicotine and cotinine two-fold. Of concern, however, is the exposure of non-smokers to smoking family members at home. Serum cotinine concentration by occupation has been detailed .Mean serum cotinine levels ranged from 0.09 (farming, forestry and fishing jobs) to 0.22 ng/ml (operators, fabricators and laborer jobs). It is interesting to note that waiters had the highest cotinine output suggesting a high stress job. Such working conditions would presumably favour repeated smoking and further reinforce addictive behaviors. 1.12.3 Passive smoking Exposure to passive smoke is clearly a health risk. This includes an enhanced exposure to carbon monoxide of a non smoking visitor in a recreational environment and in the workplace. There is some indication of an elevated breast cancer risk associated

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Separation of Binary Mixture By Using Pervaporation with passive smoking exposure of 5 hr or more per day at work . Occupational exposure to tobacco smoke is damaging to children .In their questionnaire study on pupils aged 1315 yr, smoking was found to occur at home (30.2%), at a friend’s place (29.3%), in public places (12.1%), at social events (10.4%), and at workplaces (1.5%). Group therapy, individual counseling, use of self-help materials, and nicotine replacement therapy have been described. Strong evidence suggested that interventions directed at individual smokers helped them to quit following advice from a health professional, individual and group counseling, and pharmacological treatment. 1.12.4 Nicotine induced nephropathies Nephropathies are accelerated by nicotine with an increased incidence of microalbuminuria progressing to proteinuria, followed by type-1 diabetes mellitus induced renal failure. The risk for end stage renal disease (ESRD) was independent of age, ethnicity, income, blood pressure, diabetes mellitus, prior history of myocardial infarction, or serum cholesterol. Smoking vastly accelerates mortality in diabetic patients. The increased risk for macro vascular complications coronary heart disease (CHD), stroke, and peripheral vascular disease, is most pronounced in type 2 diabetic patients. The development of type 2 diabetes is another possible consequence of cigarette smoking besides the better known increased risk for cardiovascular disease. Smoking is harmful to albumin excretion because it increases the risk of microalbuminuria; shortens the interval between onset of diabetes and the start of albuminoidal or proteinuria; accelerates the rate of progression from microalbuminuria to persistent proteinuria; and pathologically promotes the progression of diabetic nephropathy to ESRD. 1.12.5 Associated influence of nicotine on the nervous system Renal injury induced by cigarette smoke condensate is reversed by renal denervation. Cigarette smoke-induced renal damage is due, at least in part, to activation of the sympathetic nervous system. In a study on rats exposed to long-term passive smoking for a short period of about 24 hr after birth, the diameter of glomerulus’s in smokers was slightly smaller than in non-smokers (96.42 ± 7.15 μm , 99.92 ± 5.56 μm respectively).Associated elevations in nicotine-induced sympathetic nervous activity, would justify the increase in heart rate and arterial pressure mediated by systemic

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Separation of Binary Mixture By Using Pervaporation vasoconstriction in healthy non smokers, probably through alteration of a cyclic-GMPdependent vasoactive mechanism. Additionally, alterations of normal sympathetic nervous activity may contribute to volume expansion (VE) in the nephron causing a significantly blunted diuresis and natriuresis. 1.12.6 Nicotine should be removed from combustion tobacco products Behavioural manipulations to reduce exposure to inhalation of cigarette smoke are important and include a switch to denicotinised cigarettes. The authors demonstrated that switching to smoking denicotinised cigarettes for two weeks decreased the rewarding effects of the usual-brand test cigarettes. In order to re-enforce this smoking cessation, positive changes in behaviour through motivational counselling have been suggested. During treatment of nicotine addiction, one study found that there is a dose-response relationship between the number and duration of sessions and the quit rate. It was demonstrated that smokers must select a target quit day and stop smoking completely on that day as even a few cigarettes per day in the first fortnight resulted in relapse. The use of nicotine replacement products or bupropion improved success rates. Alternatively nicotine-free combustion cigarettes may help, although exposure to other combustibles would not be prevented. (22)

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Separation of Binary Mixture By Using Pervaporation Chapter 2

LITERATURE SURVEY 2.1 DIFFERENT METHODS FOR NIACIN 2.1.1 Liquid phase oxidation of Nicotine using Chromic acid: The classic method of preparing nicotinic acid was by oxidizing nicotine with potassium dichromate. This was discovered over a hundred years ago. This also serves as an excellent example when considering green technology. Chromic acid (CrO3) is carcinogenic and environmentally threatening. It is on the other hand is extensively used in the tanning industry and has higher present value on the market than its precursor. Assuming an ideal chemical reaction (100% yields) the reaction gives the following figures: Nicotine Chromic acid Nicotinic acid CO2 produced NOx (calculated as

1.32 tones 9.02 tones 1.00 tones 1.43 tones 0.37 tones

NO2) Water Chromic oxide

0.73 tones 6.8 tones

Thus almost 9 tones of side product are produced for 1 tones of desire product Reaction: 2C10H14N2 + 22CrO3 Nicotine

Chronic Acid

2C6H5NO2 + 8CO2 + 2NO2 + 9H2O + 11Cr2O3 Nicotinic Acid

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Chronic(III) oxide

Separation of Binary Mixture By Using Pervaporation 2.1.2 Liquid phase oxidation of MEP (2-methyl-5-ethylpyridine) with nitric acid or air: To avoid the problem of Picoline sourcing non-pyridine producers have used methyl ethyl pyridine as an alternative for niacin. The liquid phase oxidation with nitric acid is surprisingly selective and has been used since 1965 by Lonza to produce up to 15000 tones/year niacin. The reaction can be approximately represented as follow. i)Oxidation of MEP to Nicotinic acid (Niacin):C8H12N

+

9[O]

----------

2-methyl-5-ethylpyridine

C6H5NO2 + 2CO2 + 3H2O Nicotinic acid

ii) Oxidation of MEP with Nitric acid:C8H12N

+

6HNO3 ------ - C6H5NO2 + 2CO2 + 6H2O + 6NO

2-methyl-5-ethylpyridine

Nicotinic acid

iii) Regeneration of Nitric Acid:NO + [0] 3NO2 + H2O

NO2 2HNO3 + NO

Methyl ethyl pyridine (MEP) is itself produced by the liquid-phase condensation of paraldehyde and ammonia. Again this complex reaction proceeds surprisingly selectively (>70%) and is the main reason why this material offers itself as an alternative to the simpler molecule picoline.Continuous development and improvement of this process over the years have led to high-quality product and to LonZa’s ability to maintain their position as the world leader in niacin manufacture. But however many improvements and developments have been made to this process, it intrinsically holds some disadvantages, when considered from the ‘green’ stand point. 2.1.3 Liquid-Phase oxidation of 3-Picoline with Oxygen: Picoline can be selectively oxidized with air in the liquid phase to niacin. A catalyst combination such as cobalt and manganese acetate or bromide is usually used in

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Separation of Binary Mixture By Using Pervaporation an acetic acid medium and the air-oxidation takes place under elevated temperatures and pressures. 2.1.4 Gas phase oxidation of Picoline to Nicotinic acid: Employing the cyanopyridine route for the production of nicotinic acid involves the fixation of a nitrogen atom in the ammoxidation step, followed by its removal in the ultimate hydrolysis. This is a contradiction to the principles of a green process and in the last ten years, efforts have been made to oxidize Picoline in the gas phase directly to nicotinic acid. It is this process that in terms of green chemistry represents the state of the art today. 2.1.5 Gas- Phase oxidation of Picoline to Cyanopyridine:The gas phase ammoxidation to cyanopyridine followed by a hydrolysis either to nicotinamide or nicotinic acid are commercial processes and for the production of nicotinamide, represents the most logical and direct route via 3-picoline. 2.1.6 Commercial method followed by “Amsal Chemical Pvt. Ltd. Ankaleshwar:98% H2SO4 is taken in stainless steel batch reactor, in which 90% β-picoline was charged slowly to maintain the temp of the reactor 40-500C. Due to exothermic reaction, the vessel is cooled externally by cold water in jacket and reactor is stirred continuously for time span of 30-40hrs. When charging of β-picoline is completed the mass in vessel is heated up to 800C, β-picoline sulphate is formed. The reaction mass is charged in the second reactor which is glass line reactor for oxidation with 60% HNO3. The temp of the vessel is maintained at 180-1900C. Nicotinic acid sulphate forms along with NO and water, then precipitations was carried out with NH3 to get niacin. Reaction: 1. C6H7N + H2SO4

Sulphonation

C6H11SO4

B-Picoline

β - Picoline Sulphate

2. C6H11SO4 + 2HNO3

Oxidation

C6O6H9SN

β -Picoloine Sulphate 3. C6O6H9SN

+ 2NH3

+ (No)x

+ H2O

Nicotinic Acid Sulphate Precipitation

Nicotinic Acid Sulphate

C6O2H5N Niacin

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+

(NH4)2SO4 Ammonium Sulphate

Separation of Binary Mixture By Using Pervaporation 2.1.7 Finally, Niacin may be synthesized from pyridine:Bubbling CO 2 into a solution of pyridine and LiAlH4 in dioxane gives an 80-90% yield of nicotinic acid. (3) 2.2 REVIEW ARTICLE (20) 2.2.1 Effect of tobacco smoking on renal function:Nicotine is one of many substances that may be acquired through active and passive smoking of tobacco. In man, nicotine is commonly consumed via smoking cigarettes, cigars or pipes. The addictive liability and pharmacological effects of smoking are primarily mediated by the major tobacco alkaloid nicotine. High stress jobs favour repeated smoking and further reinforce addictive behaviors. There are elevated serum cadmium and lead levels in smokers resulting in glomerular dysfunction. Nephropathies are accelerated by nicotine with an increased incidence of microalbuminuria progressing to proteinuria, followed by type-1 diabetes mellitus induced renal failure. Cigarette smoke-induced renal damage is due, at least in part, to activation of the sympathetic nervous system resulting in an elevation in blood pressure. Ethanol, nicotine, or concurrent intake significantly increases lipid peroxidation in liver, and decreased superoxide dismutase activity and increased catalase activity in the kidney. This review describes the effects of nicotine, smoking, smoke extracts and other tobacco constituents on renal and cardiovascular functions, and associated effects on the nervous system. Both active and passive smoking is toxic to renal function. 2.2.2 Past work: Past work was carried out By Prof. B.V.Babu et. al. They conclude that pure tributyl phosphate (TBP) and the combination of TBP and diluents gave a higher distribution coefficient as compared to pure solvent the polar diluents may be more effective with phosphorus – bonded oxygen bearing extractants distribution coefficients for extraction of nicotinic acid using TBP was higher than pure solvents.

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Separation of Binary Mixture By Using Pervaporation 2.2.3 Indian J Med Res 124, September 2006, pp 261-268 There are numerous harmful substances found in tobacco and tobacco smoke. Nicotine is one of these substances that may be acquired through active and passive smoking. Associated with nicotine exposure is the incidence of occupational influences, passive smoking, nephrotoxicity, induced nephropathy and possible treatments. This review aims to describe the influence of nicotine, smoking, smoke extracts and tobacco contaminants on renal function, with associated effects on cardiovascular function and various signal transduction pathways, by incorporating current references and expounding on previous reviews. A discussion and recommendation for denicotinising cigarettes and tobacco products are also presented. 2.3 NON-ADDICTIVE TOBACCO PRODUCTS (24) Cut tobacco used for processing cigarettes or other smoking articles is reacted with an agent such as an oxidant or subject to an extraction/removal process for a suitable period of time, dependent upon the nicotine content, the oxidant employed and the reaction temperature or extraction condition, or distillation, such that the nicotine embedded in the leaf is then converted into nicotinic acid or niacin. Sufficient conversion or extraction or distilled is allowed to occur so that either no nicotine or only a minimal amount of free nicotine remains in the smoking article. Upon intake into the lungs and hence the blood stream of the smoker or other tobacco user, will result in a blood plasma content of nicotine ranging from 0 to less than about 5 nanograms per milliliter of blood plasma. This effectively insures that the addictive process in smoking or other tobacco intake cannot be initiated or maintained. Nicotinic acid or niacin is not an addictive component of the tobacco. The niacin thus formed is located in the interstices or on the surface of the tobacco and when inhaled, actually serves as a beneficial nutrient, such as a vitamin. Flavorants can be added for taste and other non-addictive stimulants can be used to produce a heightened sense of awareness or well being. 2.3.1. Field of the Invention This invention relates in general to certain new and useful improvements in processing of tobacco to eliminate or convert nicotine in the tobacco into nicotinic acid as

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Separation of Binary Mixture By Using Pervaporation a harmless or beneficial product such that the nicotine level which can be achieved by use of the tobacco product results in a blood plasma level consonant with non-addiction. 2.3.2. Brief Description of the Related Art The effect of nicotine in tobacco on the central nervous system primarily is located in the locus ceruleus, which produces increased mental activity, as well as in the mesolimbic center, which stimulates the desire for more nicotine, giving rise to nicotine addiction. The basic cause of addiction lies in the inhalation of small amounts of nicotine and the circulation in the blood of amounts of nicotine in the order of twenty to twentyfive nanograms per milliliter. Conventional cigarettes contain a varying range of nicotine content which may vary, for example, from about 0.2% to about 5%. It is also well known that the smoking of tobacco products generates other deleterious components, such as tars, and upon combustion, carbon monoxide. It is also well established, (New Scientist, 1938, Aug. 13, 1994 v. 143, page 10) that about one to three milligrams of nicotine will be absorbed in the lungs during each smoking interval. Information exists on the proof of the addictive properties of nicotine in the aforementioned New Scientist article. There is a wealth of literature relevant to the elimination of deleterious substances, such as the nicotine and tar from tobacco products. U.S. Pat. No. 5,240,014 teaches of the catalytic conversion of carbon monoxide. U.S. Pat. No. 5,158,099 teaches of a wetted impact barrier for reduction of tar and nicotine. U.S. Pat. No. 4,700,723 teaches of a filter consisting of a fibrous ion exchange resin which removes ionic and carcinogenic constituents, as well as nicotine and tar from the tobacco smoke. U.S. Pat. No. 4,250,901 describes a chemical denaturant, such as water, to eliminate or trap nicotine, tar and carbon monoxide. However, each of these approaches are highly impractical. As an example, nicotine reacted with peroxide results in n-methylpyrolle pyridine and nicotinic acid and in which the n-methylpyrolle pyridine is far less than a healthful addition to a tobacco product. The prior art also teaches of the extraction of nicotine from a raw tobacco product by steaming procedures. For example, in German Patent No. 25,403 by Dr. Johannes Sartig using super heated steam. In like matter, and in related techniques, U.S. Pat. Nos. 18

Separation of Binary Mixture By Using Pervaporation 2,525,784 and 525,785 teach of the use aluminum sulfate and ammonia-ethylene dichloride to separate nicotine from raw tobacco product. In addition to the foregoing, various nicotine blood plasma antagonists have also been suggested for use in eliminating nicotine addiction. However, these antagonists, such as mecamylamine, have only proved partially successful, if at all. One practical solution, however, to the nicotine addiction problem is suggested in this application namely a chemical conversion of the nicotine in tobacco to obviate its effect on the acetylcholine brain receptor. The alternative use of antagonists however only lends itself to expensive long term basic research and with vanishingly small chances of success. There is other patent literature available which has tangential relationship to the use of modified tobacco products or agents related to the use of tobacco products. U.S. Pat. No. 5,122,366 teaches of the incorporation of silver nitrate in mouthwash to reduce nicotine taste from the mouth after smoking and ingestion of nicotine into the lungs. However, this is obviously no impediment to an addictive process. U.S. Pat. No. 4,620,554 uses a composition for enhancing the taste of cigarettes and which includes a filter containing ascorbic acid, powdered vegetable oil and fats, comfrey leaves, wheat protein, beef stock plant and a flavorant, such as a Japanese mint and vanilla. The effect of the composite is to produce a mellow taste and less irritation. Nicotine and the tar are absorbed by the oils and the fats and the ascorbic acid and its isomers decrease the nicotine, tar and carbon monoxide which is drawn into the lungs of the user. Potassium nitrate is also incorporated in the filter and improves combustion and catalyzes nicotine to nicotinic reaction. U.S. Pat. No. 3,943,940 teaches of the contacting of potassium permanganate to oxidize nicotine just before smoking. However, this technique is quite awkward and expensive and not amenable to widespread public acceptance. More importantly, the results have been found to be quite variable and have no relationship to the amount of nicotine ingested by the individual. Not with standing the foregoing, none of the proposed approaches for modifying tobacco have recognized any relationship between the amount of nicotine present and the amount absorbed in the blood stream of the user compared to the addictive effects

19

Separation of Binary Mixture By Using Pervaporation thereof. Nevertheless, the importance of nicotine in the addictive process is indicated in the Wall Street Journal of Oct. 18, 1995, where it was acknowledged that diammonium phosphate (DAP) increases nicotine delivery in reduced nicotine and tar cigarettes. 2.4 OBJECTS 1) It is, therefore, one of the primary objects of the present invention to provide a tobacco product adapted for human use and which eliminates an addictive response to the user. 2) It is another object of the present invention to provide an improved tobacco product of the type stated which utilizes an oxidized tobacco in which nicotine has been converted to nicotinic acid or extraction to a level such that when used, the blood plasma nicotine level resulting in the user is about 0 to about 5 nanograms per milliliter. 3) It is a further object of the present invention to provide an improved tobacco product of the type stated in which a tobacco product is converted chemically or by physical means to obviate any effects on the acetylcholine brain receptors in an individual smoking or otherwise ingesting such tobacco product. 4) It is an additional object of the present invention to provide an improved tobacco product of the type stated which can be produced at a relatively low cost and which is highly effective in eliminating any addictive response. 5) It is another salient object of the present invention to provide a method for altering a tobacco product in order to reduce the nicotine content therein to a level where the resulting nicotine blood plasma level of the user has a range of about 0 to 5 nanograms per milliliter of blood. With the above and other objects in view, the invention resides in the novel features of the modified tobacco product and the process for the same as hereinafter described and pointed out in the claims.

20

Separation of Binary Mixture By Using Pervaporation 2.5 SUMMARY OF THE INVENTION In accordance with the present invention, it has been found that by converting the nicotine of a tobacco product into a harmless and actually beneficial substance, such as nicotinic acid, addiction to the tobacco product can be avoided. Conversion allows for a tobacco product relatively free of nicotine and when taken into the lungs does not result in or sustain addiction. The addictive nature of the nicotine is eliminated when the resultant amount of the nicotine in the blood plasma of a user has a level of about 0 to about 5.0 nanograms of nicotine per milliliter of blood. Nicotine intake in women was measured by the presence of cotinine, which is an oxidative metabolite of nicotine, and was detected in 84% of the female smokers and found in the cervical mucous. See J. Cancer Epidemiol, Biomarkers Prev. 1992 (1)(2) 125-9. In numerous other citations in the literature, there is described a movement of nicotine into the blood plasma and then into vital organs. Indeed, the impact of nicotine on heart and pulmonary system and the resultant formulation of neoplastic conditions in the body are well known and acknowledged in the art. The important aspect of the present invention is the actual finding that nicotine addiction can be reduced and completely eliminated by use of smoking devices such as cigarettes in which the nicotine content is sufficiently small so that when introduced into the blood stream of a user, it will not cause a nicotine level exceeding 0 to about 5 nanograms

per milliliter of blood plasma. This can be easily accomplished by

conventional oxidation techniques or steamed installation/extraction techniques known in the prior art for removal of nicotine. It can also be more readily accomplished by the oxidation of the nicotine. The key to the use of an economical treatment of a tobacco leaf or processed tobacco are those chemical agents capable of converting nicotine into a neutral or beneficial compound which does not require removal from the tobacco or any surrounding matrix. Moreover, use of preferred chemical or oxidizing agents render the content of tar in the tobacco less noxious or otherwise, more solubilized if extraction of the tars is required.

21

Separation of Binary Mixture By Using Pervaporation In accordance with the present invention, there is provided an improved tobacco product adapted for human use and which eliminates an addictive response in the user. The improved tobacco product has been oxidized under conditions in which the nicotine contained in the product has been converted to nicotinic acid to a level such that the resulting nicotine concentration in the blood plasma of the user has a level of 0 to about 5 nanograms of nicotine per milliliter of blood. As indicated previously, it has been found in accordance with the present invention that when the nicotine level is reduced to about 5 nanograms per milliliter or less, there is no addictive response in the user. This is an important factor in that it has now been realized that one can actually continue to use a tobacco product without at least suffering the addictive effects which otherwise arise based on prolonged use of tobacco products. In a more preferred embodiment of the invention, the nicotine in the tobacco product is converted to nicotinic acid by means of an oxidizing agent, such as nitric acid. Otherwise, the oxidizing agent for converting the nicotine to nicotinic acid can be selected from the class consisting of catalyzed sulfuric acid, alkaline potassium permanganate, hydrogen peroxide, ozone and combinations thereof, as well as other known oxidizing agents for this purpose. While the literature has discussed the use of oxidizing agents for oxidizing the nicotine contained in the tobacco to nicotinic acid, no one has recognized that reducing the nicotine concentration to a level of approximately 5 nanograms of nicotine per milliliter of blood or less will eliminate the harmful addictive effects of the nicotine. In accordance with the present invention, it is also possible to incorporate a flavoring agent in the resultant oxidized product. Further, it is also possible to incorporate in the tobacco a stimulatory agent which is non-addictive. For example, caffeine is a highly effective stimulatory agent and while it has habit forming effects, it has been generally recognized that those effects are not harmful. The present invention also provides an improved process for enabling the use of tobacco products for human intake without any addictive response arising out of the use thereof. Again, this process comprises the converting of the nicotine contained in the tobacco product to nicotinic acid such that there is no nicotine or only a relatively small

22

Separation of Binary Mixture By Using Pervaporation amount of nicotine remaining in the tobacco product. The process further allows the use of the converted tobacco product so that the resultant nicotine concentration in the blood stream of the user, when the tobacco product is used, is zero or less than about 5 nanograms of nicotine per milliliter of blood. As indicated, this eliminates an addictive response to the use of the tobacco product. The complexity of nicotine addiction likely will result in a bifurcated approach in which the use of nicotine converted tobacco will be emphasized for pre-addictive individuals, such as the pre-addictive teenager, as opposed to the experienced smoker, already well addicted and experiencing nicotine blood level steady state concentrations from about twenty to twenty-five nanograms per milliliter or higher. It may be that the long term strongly addicted smoker may not only require the physiological impact of this invention but that additional or concurrent auxiliary treatment may be required due to ingrained motivational factors. This invention possesses many other advantages and has other purposes which will be made more clearly apparent from a consideration of the forms in which it may be embodied. Some of these forms will be described in detail in the following detailed description which is set forth merely for purposes of illustrating the general principles of the invention. However, it is to be understood that this detailed description is not to be taken in a limiting sense. There is also a large amount of patent literature relating to the above reactions, although all of the literature to date does not reflect the very essence of this present invention which is the reduction of substantially all of the nicotine and conversion to nicotinic acid which thereby results in an nicotine concentration in the blood stream of the tobacco user in an amount of about 5 nanograms per milliliter of blood or less. This level has been found to eliminate tobacco product addiction in the user. In accordance with the present invention, it has been found that the user of a tobacco product can still continue to use the tobacco product for the other sensory effects which are provided without being addicted. Thus, the conversion of the nicotine in accordance with the present invention not only eliminates the addiction, but also reduces some of the harmful effects of the tars. In this way, a party may continue to use tobacco 23

Separation of Binary Mixture By Using Pervaporation products without the attendant fear of becoming addicted. This is particularly effective for those parties who wish to experiment or use tobacco and who have not yet become seriously addicted to the tobacco product. Even upon smoking or other use of the product, some niacin particulates may be ingested or inhaled. This is not detrimental and indeed may be beneficial to the user. Upon inhalation of tobacco smoke or other use of the tobacco treated according to the present invention, blood levels of nicotine will not rise above 5 nanograms per milliliter of blood and will preferably approach 0 nanograms per milliliter of blood plasma. (24)

24

Separation of Binary Mixture By Using Pervaporation Chapter 3

CONVERSION OF NICOTINE TO NICOTINIC ACID 3.1 NICOTINE - SOURCES AND HEALTH ASPECTS:3.1.1 Sources

Animal products:

Fruits and

liver, heart

vegetables: • leaf

•

and kidney

Seeds:

vegetables

•

nuts

•

mushrooms

•

whole grain

•

brewer's yeast

•

chicken

•

broccoli

•

beef

•

tomatoes

•

legumes

•

fish: tuna,

•

carrots

•

saltbush

salmon

•

tobacco

•

milk

•

eggs

Fungi:

products

seeds

leaves •

sweet potatoes

•

asparagus

•

avocados

The tobacco plant contains over 2,200 compounds of which nitrogenous compounds.Comprise more than 30 percent. Torikai et al demonstrated that in burley tobacco leaves; there is a significantly higher content of pyridinic nitrogen than in bright or oriental tobacco leaves. The profiles of 29 known toxic compounds in tobacco smoke have been mentioned. Nicotine C10H14N2; Mol.wt = 162.23 is one important alkaloid contained in tobacco leaves. Nicotine, however, is not the principle adverse constituent in combustion cigarette products. The primary commercial source of nicotine is by extraction from the dried leaves of the tobacco plant (Nicotinia tabacum). Smoking may affect people of any age, nicotine traveling rapidly in the blood stream and carbon monoxide binding to haemoglobin in red blood cells. In addition, the carcinogen benzo pyrene binds to cells in the airways and major organs of smokers, and depresses immune function. Smoking results in an elevated incidence of chronic inflammation as a 25

Separation of Binary Mixture By Using Pervaporation consequence of oxidative stress. Cigarette smoking increases the risk of developing numerous cancers including the lip, mouth, pharynx, oesophagus, pancreas, larynx, lungs, uterine cervix, urinary bladder and kidneys. Cigarette smokers are 2-4 times more likely to develop coronary heart disease than non-smokers. Contact with second hand or passive smoke exposes people to approximately 50 carcinogens resulting in an elevated risk of lung cancer and coronary heart disease, and an increased incidence of asthma, bronchitis and pneumonia in children. 450 gms. (One pound) of smoke curved burley tobacco is treated with 9.50 lit (2.5 gallons) of an oxidizing agent having 50% of HNO3 for about 30 min at a temp of about 1100C to 1150C. The burley tobacco was introduced into a glass container and the HNO3 was poured directly onto the tobacco and the tobacco was allowed to remain in the oxidizing bath in this container for the 30 min period at 1100C temp. After 30 min. the treated tobacco was rinsed with tap water and dried in a tray dryer and with filter paper. (24)

Nicotine may be recognized by the addition of a drop of 30 % formaldehyde, the mixture being allowed to stand for one hour and the solid residue then moistened by a drop of concentrated H2SO4 , when an intense rose red colour is produced. It was found that the HNO3 contacts with tobacco (Nicotine) for sufficient time (30min) convert all of the nicotine to nicotinic acid.(24) 3.1.2 Main Reaction: C10H14N2 Nicotine

+ 9[O] --HNO3--- C6H5NO2 Nascent Oxygen

+ C2H2O4.H2O + CH3NH2 + CO2

Nicotinic acid

Oxalic Acid

Methylamine

With the help of this treatment to tobacco the addictive nature of man towards tobacco becomes non-addictive. Also it provide an improved tobacco product of the type which utilizes an oxidized tobacco in which nicotine has been converted to nicotinic acid or extraction to a level such that when used the blood plasma nicotine level resulting about 0 to 5 nanograms / ml. With the above objective in view, the different unit operations and process are carried out to covert maximum amount of nicotine to nicotinic acid and it is extracted and analysis of product is done. Generally beedi tobacco contains

26

Separation of Binary Mixture By Using Pervaporation 2 to 8 % nicotine. Dry tobacco leaves contain about 5% nicotine combined with citric or malic acid. 3.2 PHYSICAL PROPERTIES (11) Sr .

Name

Formula Mol.wt

No

Form & colour

Sp.gravity M.P.0C B.P.0C

Solubility in 100 parts H2O Alcohol

Ether

Oily 1.

2.

Nicotine Nicotinic acid

C10 H14N2

162 Colourless

C6H5 NO2

123

3. Methyl amine CH3 NH2

31

(Niacin)

4. Oxalic acid

HO2C CO2H3O

126

Liquid Colourless

1.009

< 80

246 Soluble

1.473

236

Subl

-92.5

-6.7

101.5

Subl Soluble Soluble

powder Colourless 0.699 X gas Colourless monoclinic

10-11 1.653

----

----

Soluble Soluble Very slight hot Very

hot Very

soluble soluble

soluble -----1.3 Soluble acid

5.

Carbon

CO2

dioxide

44

Colourless gas

1.53

-56.6

Subl. 179.7

90.1

alkali

–78.5

CC

(aq.NaoH or

CC

KOH) 6.

Nitric acid

HNO3

63

Colourless Liquid

1.502

----

-----

------

-----

---

3.3 PROCESS DESCRIPTION:The waste tobacco from tobacco processing industries and tobacco farms was collected and dried in sun light to crush for 40 mesh size. Crushing is done in Pulverizer. The crushed tobacco was feed in to mixing tank. In mixing tank it is mixed with water at 60 0 C to get tobacco extract. This tobacco extract was filtered, the filtrate was used for further processing and the wet tobacco after drying can be used as non addictive tobacco product. The filtrate from filter press was send to mixing tank. In mixing tank little amount of NaOH is added to maintain pH in the range 8.0 to 9.5. This mixture from storage tank was send to Steam Distillation. In Steam distillation initially the steam is fed with feed

27

Separation of Binary Mixture By Using Pervaporation mixture and then it is feed to the jacket. From the top of steam distillation the vapours are send to condenser & waste can be withdrawn from bottom, which can be used as fertilizer for farming purpose. The condensed Nicotine solution was stored in separator at room temperature.After half an hour the oily top Nicotine layer was send to Oxidation reactor & other constituents are withdrawn from bottom of separating tank. In oxidation reactor the main oxidation reaction occurs at 1100C and after 30 min. time span. 50 % HNO3 was used as oxidant. The nascent oxygen according to reaction reacts with Nicotine and it forms Nicotinic acid, methylamine, oxalic acid and carbon dioxide. These products are stored in accumulator at room temperature. After half an hour there was formation of two layers. The top layer is of nicotinic acid and the bottom layer is of oxalic acid. The wet nicotinic acid was dried in a tray dryer with hot air and finally we get nicotinic acid powder. The confirmation of Nicotinic Acid was done as, 100 mg of dried powder was mixed with 10 mg of citric acid, 3 drops of acetic anhydride and heat on a waterbath, the mixture attains red-violet color. (5) 3.2.1 Nicotine consumption In man, nicotine is commonly consumed via smoking cigarettes, cigars or pipes. Nicotine may also enter the body via low tar Eclipse cigarettes, snuff, tobacco chewing, and pharmaceutical nicotine products like nicotine patches. Smokeless tobacco contains 28 carcinogenic agents and increases the risk of developing cancer in the mouth, as well as leading to nicotine addiction and dependence. The cigarette has been described as an efficient nicotine carriage device delivering an optimum dose of nicotine to the dependent brain. Ventilated cigarette filters dilute smoke with air and reduce standard yields of tar, nicotine and carbon monoxide. There is, however, no convincing evidence that changes in cigarette design have significantly reduced diseases caused by cigarettes. Nicotine replacement therapy can occur through products like the Niquitin CQ transdermal patch; the Nicorette Microtab; the Nicorette inhalator; and the Nicotinell lozenge. These alternatives are safer than exposure to combusted tobacco which has numerous other constituents that are harmful to the body. Indeed, the risk of nicotine replacement therapy is very low. Other therapies promoting an increased smoking cessation rate with little

28

Separation of Binary Mixture By Using Pervaporation effect on withdrawal symptoms, for example, nortriptyline (started at 25 mg 14 days before quit day, titrated to 75 mg/day as tolerated) combined with transdermal nicotine (21 mg/day) may represent an option for smokers in whom standard therapy has failed 3.2.2 Nicotine addiction and metabolism Nicotine has a dangerous effect on the body by modulating behaviour and dependence resulting in addiction and subsequent repeated exposure to toxins found in tobacco and tobacco smoke. Social aspects, peer pressure, stress, alcohol consumption, etc., are all behavioural factors that contribute towards addiction. The addictive liability and pharmacological effects of smoking are primarily mediated by the major tobacco alkaloid nicotine. Nicotine is metabolized to S- (-)-nicotine D1'–5'-iminium ion by the genetically variable hepatic enzyme cytochrome P-450 2A6 (CYP2A6) and then to the pharmacologically less active derivative, S-cotinine (cotinine), by aldehyde oxidase. "A hundred pounds of the dry tobacco-leaf yield about seven pounds of nicotine. One drop applied to the tongue of a cat brought on convulsions, and in two minutes occasioned, death. The Hottentots are said to kill snakes by putting a drop of it on their tongues. Under its influence, the reptiles die as instantaneously as if killed by an electric shock," says John Lizars, M.D., The Use and Abuse of Tobacco (Edinburgh: 1856, 1857, 1859, reprinted, Philadelphia: P. Blakiston, Son & Co, 1883), p 57.

29

Separation of Binary Mixture By Using Pervaporation Chapter 4

NIACIN 4.1 HISTORY Niacin was first described by Weidel in 1873 in his studies of nicotine. The original preparation remains useful: the oxidation of nicotine using nitric acid. Niacin was extracted from livers by Conrad Elvehjem who later identified the active ingredient, then referred to as the "pellagra-preventing factor" and the "anti-blacktongue factor." When the biological significance of nicotinic acid was realized, it was thought appropriate to choose a name to dissociate it from nicotine, in order to avoid the perception that vitamins or niacin-rich food contains nicotine. The resulting name 'niacin' was derived from nicotinic acid + vitamin. Niacin is referred to as Vitamin B 3 because it was the third of the B vitamins to be discovered. It has historically been referred to as "vitamin PP." 4.2 DIETARY NEEDS Severe deficiency of niacin in the diet causes the disease pellagra, where as mild deficiency slows the metabolism, causing decreased tolerance to cold. Dietary niacin deficiency tends to occur only in areas where people eat corn (maize), the only grain low in niacin, as a staple food, and that do not use lime during meal/flour production. Alkali lime releases the tryptophan from the corn in a process called nixtamalization so that it can be absorbed in the intestine, and converted to niacin. The recommended daily allowance of niacin is 2-12 mg/day for children, 14 mg/day for women, 16 mg/day for men and 18 mg/day for pregnant or breast-feeding women. 4.3 PROPERTIES: 1. Anti pellagra vitamin. 2. Colorless or white crystalline powder. 3. Soluble in water and boiling alcohol. 4. Insoluble in most lipid solvent. 5. No hygroscopic and stable in air. 6. It is resistant to heat, oxidation and alkalis. 30

Separation of Binary Mixture By Using Pervaporation 7. It is in fact, one of the most stable vitamins. 4.3 PHARMACOLOGICAL USES:Niacin, when taken in large doses, blocks the breakdown of fats in adipose tissue, thus altering blood lipid levels. Niacin is used in the treatment of hyperlipidemia because it reduces very-low-density lipoprotein (VLDL), a precursor of low-density lipoprotein (LDL) or "bad" cholesterol. Because niacin blocks breakdown of fats, it causes a decrease in free fatty acids in the blood and, as a consequence, decreased secretion of VLDL and cholesterol by the liver. By lowering VLDL levels, niacin also increases the level of highdensity lipoprotein (HDL) or "good" cholesterol in blood, and therefore it is sometimes prescribed for patients with low HDL, who are also at high risk of a heart attack. Niacin is sometimes consumed in large quantities by people who wish to fool drug screening tests, particularly for lipid soluble drugs such as marijuana. It is believed to "promote metabolism" of the drug and cause it to be "flushed out." Scientific studies have shown it does not affect drug screenings, but can pose a risk of overdose, causing arrhythmias, metabolic acidosis, hyperglycemia, and other serious problems. 4.4 TOXICITY People taking pharmacological doses of niacin (1.5 - 6 g per day) often experience a syndrome of side-effects that can include one or more of the following: 

Dermatological complaints.



Facial flushing and itching.



Dry skin.



Skin rashes including acanthosis nigricans .



Gastrointestinal complaints.



Dyspepsia (indigestion).



Liver toxicity.



Fulminant hepatic failure.



Hyperglycemia.



Cardiac arrhythmias.



Birth defects.

31

Separation of Binary Mixture By Using Pervaporation Facial flushing is the most commonly-reported side-effect. It lasts for about 15 to 30 minutes, and is sometimes accompanied by a prickly or itching sensation, particularly in areas covered by clothing. This effect is mediated by prostaglandin and can be blocked by taking 300 mg of aspirin half an hour before taking niacin, or by taking one tablet of ibuprofen per day. Taking the niacin with meals also helps reduce this side-effect. After 1 to 2 weeks of a stable dose, most patients no longer flush. Slow or "sustained"-release forms of niacin have been developed to lessen these side-effects .One study showed the incidence of flushing was significantly lower with a sustained release formulation though doses above 2 g per day have been associated with liver damage, particularly with slowrelease formulations. High-dose niacin may also elevate blood sugar, thereby worsening diabetes mellitus. Hyperuricemia is another side-effect of taking high-dose niacin, and may exacerbate gout. Niacin at doses used in lowering cholesterol has been associated with birth defects in laboratory animals, with possible consequences for infant development in pregnant women. Niacin at extremely high doses can have lifethreatening acute toxic reactions. Extremely high doses of niacin can also cause niacin maculopathy, a thickening of the macula and retina which leads to blurred vision and blindness. 4.5 BIOSYNTHESIS

Biosynthesis:

Tryptophan

→

Kynurenine

→

Niacin

The liver can synthesize niacin from the essential amino acid tryptophan, requiring 60 mg of tryptophan to make one mg of niacin. The 5-membered aromatic heterocycle of tryptophan is cleaved and rearranged with the alpha amino group of tryptophan into the 6-membered aromatic heterocycle of niacin. Vitamin B3 is made up of niacin (nicotinic acid) and its amide, niacinamide, and can be found in many foods, including yeast, meat, fish, milk, eggs, green vegetables, and cereal grains. Dietary tryptophan is also converted to niacin in the body. Vitamin B 3 is

32

Separation of Binary Mixture By Using Pervaporation often found in combination with other B vitamins including thiamine, riboflavin, pantothenic acid, pyridoxine, cyanocobalamin, and folic acid. 4.6 PHYSICAL PROPERTIES OF NICOTINIC ACID (11) Property Molecular weight Melting point Sublimation range Density of Crystals True dissociation constants in water at 250C Ka Kb pH of saturated aqueous solution Solubility of Niacin in Water At 00 C At 380 C At 1000C Solubility of Niacin in Ethanol,96 % At 00 C At 780 C Solubility of Niacin in Methanol At 00 C At 620C

Value 123.11 2360 C >1500 C 1.473 gm/cm3 1.5X10-5 1.04X10-12 2.7 8.6 gm/lit. 24.7 gm/lit. 97.6 gm/lit. 5.7 gm/lit. 76.0 gm/lit. 63.0 gm/lit. 345.0 gm/lit.

Basically, the coenzymes of niacin help break down and utilize proteins, fats, and carbohydrates. Vitamin B3 also stimulates circulation, reduces cholesterol levels in the blood of some people, and is important to healthy activity of the nervous system and normal brain function. Niacin supports the health of skin, tongue, and digestive tract tissues. Also, this important vitamin is needed for the synthesis of the sex hormones, such as estrogen, progesterone, and testosterone, as well as other corticosteroids. Niacin, taken orally as nicotinic acid, can produce redness, warmth, and itching over areas of the skin; this "niacin flush" usually occurs when doses of 50 mg. or more are taken and is a result of the release of histamine by the cells, which causes vasodilation. This reaction is harmless; it may even be helpful by enhancing blood flow to the "Flushed" areas, and it lasts only 10-20 minutes. When these larger doses of niacin are taken regularly, this reaction no longer occurs because stores of histamine are reduced. Many people feel benefit from this "flush," but if it is not enjoyable, supplements that contain vitamin B3 in the form of niacinamide or nicotinamide can be

33

Separation of Binary Mixture By Using Pervaporation used, as they will not produce this reaction. (Note: When vitamin B3 is used to lower cholesterol levels, the nicotinic acid form must be used; the niacinamide form does not work for this purpose.) Niacin is used to support a variety of metabolic functions and to treat a number of conditions. Many niacin deficiency symptoms can be treated by adjusting the diet and by supplementing B3 tablets along with other B complex vitamins. Many uses of niacin are based primarily on positive clinical experience and are not as well supported by medical research, although more studies are being done. Niacin helps increase energy through improving food utilization and has been used beneficially for treating fatigue, irritability, and digestive disorders, such as diarrhea, constipation, and indigestion. It may also stimulate extra hydrochloric acid production. Niacin, mainly as nicotinic acid, helps in the regulation of blood sugar (as part of glucose tolerance factor) in people with hypoglycemia problems and gives all of us a greater ability to handle stress. It is helpful in treating anxiety and possibly depression. B3 has been used for various skin reactions and acne, as well as for problems of the teeth and gums. Niacin has many other common uses. It is sometimes helpful in the treatment of migraine-type headaches or arthritis, probably in both cases through stimulation of blood flow in the capillaries. This vitamin has also been used to stimulate the sex drive and enhance sexual experience, to help detoxify the body, and to protect it from certain toxins and pollutants. For most of these problems and the cardiovascular-related ones mentioned below, the preference is to take the "flushing" form of niacin, or nicotinic acid, not niacinamide.

34

Separation of Binary Mixture By Using Pervaporation 4.7 FUNCTIONS OF VITAMIN B3 NIACIN:Niacin is important for proper blood circulation and the healthy functioning of the nervous system. It maintains the normal functions of the gastro-intestinal tract and is essential for the proper metabolism of proteins and carbohydrates. It helps to maintain a healthy skin. Niacin dilates the blood vessels and increases the flow of blood to the peripheral capillary system. This vitamin is also essential for synthesis of the sex hormones, namely, oestrogen, progesterone, and testosterone, as well as cortisone, thyroxin, and insulin. 4.8 CHEMICAL STRUCTURE (25) Nicotinic Acid is water soluble. This is quite important because it may be lost when we cook our food by boiling it in water! It is also important because it cannot be stored in the body and must therefore be present in our diet to replace that which is lost in urine. It is more important for us to understand why a deficiency of this chemical causes pellagra.

Nicotinamide

can

be used instead of nicotinic acid. As we can see from these two structural formulae they are almost the same.

4.9 BIOLOGICAL SYNTHESIS

35

Separation of Binary Mixture By Using Pervaporation Humans do not have the ability to synthesise sufficient nicotinic acid, this means that it is an essential component of a balanced diet. Some mammals are able to synthesise this chemical so it is not an essential component of their diets. For example, dogs can synthesise nicotinic acid from the amino-acid tryptophan. This might be an essential amino-acid, but for dogs, nicotinic acid is definitely NOT a vitamin. Bacteria in our large intestines, the colon, may convert tryptophan into nicotinic acid; this means that we could survive if sufficient bacterial activity took place. Our intestinal bacteria would require 60 mg of tryptophan to synthesise 1 mg of nicotinic acid so don't count on them. 4.10 SOURCES Nicotinic Acid is found in milk, yeast, eggs, etc. Here is a table of average values for the Nicotinic Acid content of a variety of foods. Food Content mg/100gg/10gm Meat Extract 60.0 Marmite 58.5 Roast Beef 5.0 Sardines in Oil 5.0 Kippers 4.2 Whole meal Bread 3.5 Beer 0.7 Boiled Cabbage 0.15 Milk 0.08 Pellagra is associated with a low standard of living. It is particularly prevalent; in areas where maize forms the staple diet. Maize has a very low content of nicotinic acid; furthermore, the proteins in maize are deficient in tryptophan.

36

Separation of Binary Mixture By Using Pervaporation 4.11 SOURCE CATEGORIES: 

Richest Sources: Yeast, Rice polishing, & Tobacco.



Good sources: Meat, Liver & Poultry.



Fair sources: Milk, Eggs, Tomatoes, Leafy green vegetables.



Poor sources: Most Fruits & Vegetables.

4.12 DEFICIENCY DISEASE: The main deficiency disease caused by lack of nicotinic acid is “pellagra”. This disease affects epithelia & nervous system. It is accused by the accumulation of the intermediate products of respiration; this is because nicotinic acid is required for the synthesis of co-enzymes used by dehydrogenises. Nervousness, headaches, fatigue, mental depression, skin, disorders, muscular weakness, & indigestion are the symptoms of deficiency of niacin. 4.13 IDENTIFICATION TESTS FOR NIACIN (2) 1. Mix about 100 mg with 1 ml of dil NaOH solution & boil, no ammonia is evolved (distinction from nicotinamide). 2. Mix about 100 mg with 10mg of citric acid & 3 drops of acetic anhydride & heat on a water bath, a red – violet colour is produced. Synonyms: - Acid Nicotinique (French), Acidum Nicotinicum, Akotin, Anti-pellagra Vitamin, Apelagrin, Nico, etc. 4.14 PRECAUTIONS: 

The use of large doses of niacin for long periods causes release of histamine. This in turn can cause severe flushing, severe itching of the skin and gastro intestinal disturbances.



If taken in does of 3gm per day, niacin has been reported to cause elevation of uric acid in the blood and glucose.

37

Separation of Binary Mixture By Using Pervaporation 4.14 NIACIN ANALOGUES:Tobacco products are considered to be predisposing factors in several forms of cancer. Accordingly there are 43 carcinogenic substances in tobacco smoke, and nicotine makes the use of tobacco products addictive. Smokeless tobacco (plug or leaf chewable tobacco or snuff) is considered to be a predisposing factor in oral cancers (US Surgeon General, 1986). Cadmium and nickel also have been implicated in the carcinogenicity of tobacco products. Since removal of tar by filters and the use of smokeless tobacco do not eliminate the risk of cancer associated with tobacco, the question remains "What are the components of tobacco most responsible for the increased risks of cancer?" One obvious possibility from our perspective is nicotine, itself, for its potential to interfere with monooxygenase-catalyzed reactions in about five ways. 1.

Nicotine is a known substrate of this monooxygenase, so this non-nutritive

compound can interfere directly with oxidations of regulatory substrates catalyzed by this enzyme. 2.

Nicotine is also a close structural analogue of nicotinamide and has the

potential for depleting NADPH by competitively inhibiting the absorption and incorporation of the vitamin. 3.

Theoretically, nicotine can also interfere with the production and redox

recycling of NADPH from NADP+, NAD+, and NADH. 4.

In addition to the possibility of causing metabolic losses of NADPH,

nicotine may compete directly with NADPH for the monooxygenase and other critical regulatory enzymic activities Consistent with this inhibitory potential is the observation that porcine liver monooxygenase catalyzes the oxidation of nicotine at a saturated maximum rate that is only 60 to 67% of that reported for good substrates for this monooxygenase. 5.

Finally, any depletion of NADPH by nicotine described, can result in an

additional irreversible inactivation of the monooxygenase by normal body temperatures. The monooxygenase is highly vulnerable to thermal inactivation under two very interesting circumstances:

38

Separation of Binary Mixture By Using Pervaporation 1) When deprived of NADP+ and especially NADPH, or 2) When deprived of oxygen in the presence of NADPH. The latter condition may exist in the center of rapidly growing tumors. An interesting general feature about the regulation of biological systems is that minor inhibition at any one step in a regulatory cascade (10% here, 10% there) can be amplified by multiple affected sites along the entire pathway to produce dramatic inhibition at the end point. The potential for cascade-amplified inhibition of the monooxygenase with nicotine clearly exists. If nicotine proves to be a predisposing factor through this proposed mechanism, nicotine patches will solve a tobacco consumer's risk for cancer only if used to completely end the addiction. 4.15 VITAMIN B3 USES Nicotinic acid, niacinamide, and inositol hexaniacinate (the three forms of Vitamin B3) have all proved very successful in various clinical applications. However, the forms of nicotinic acid and niacinamide consumed in access may prove to be toxic.Conversely, inositol hexaniacinate has been supplemented in excess in scientific studies and proved tolerable. Inositol hexaniacinate has been shown to lower elevated LDL (bad cholesterol) and triglyceride (fat) levels in the blood, while concurrently raising the HDL (good cholesterol) levels. Inositol hexaniacinate has also been used for the prevention and treatment of peripheral vascular disease, especially intermittent claudication (or the atherosclerosis of the blood vessels in the legs that can cause pain with walking).Vitamin B3 may also be helpful in preventing the development of atherosclerosis, and may aid in the reduction of complications arising from those who suffer from specific heart conditions. As well, vitamin B3 may prove to be as effective as prescription medications for treatment of atherosclerosis and problems associated with the heart. Niacin, specifically the form of niacinamide, has also been shown to provide relief with complications resulting from diabetes. In a recent clinical study consisting of 343 individuals without diabetes and 125 with the disease, roughly 3000 milligrams per day were administered. Hemoglobin A1C (a particular measure of blood sugar over a period of time) actually decreased in the diabetic group over a 60-week follow-up period. 39

Separation of Binary Mixture By Using Pervaporation Further research is needed on niacinamide, but intial studies indicate its potentiality in the treatment of arthritis. In addition, Vitamin B3 may reduce inflammation, increase joint mobility, and may also aid in cartilage repair. Eye health is another area of interest regarding the dietary supplementation of niacin. In a recent study that included participants from the U.S. and Australia, participants whose diets were supplemented with the highest amount of protein, Vitamin A, B1, B2, and B3 (niacin) were considerably less likely to develop cataracts. Studies have also shown riboflavin and niacin alone, to be effective in the prevention of cataract formation. Ongoing applications of this B-vitamin compound include; vitamin replacement in burn victims, topical solutions for acne, and as an anti-cancer agent. Taking niacin with food may reduce stomach upset and the risk of stomach ulcer. Doses are usually started low and gradually increased to minimize the common side effect of skin flushing. Taking aspirin or non-steroidal anti-inflammatory drugs (NSAIDs) at the same time during the first one to two weeks may reduce this flushing. Use of an antihistamine 15 minutes prior to a niacin dose may also be helpful. The flushing response may decrease on its own after one to two weeks of therapy. Extended release niacin products may cause less flushing than immediate release (crystalline) formulations, but may have a higher risk of stomach upset or liver irritation. In general, not all niacin products are equivalent. Patients switching from one product to another may have an increase or decrease in side effects. Other Members of the Vitamin B Complex Thiamine (B1), Riboflavin (B2), Pyridoxine (B6), Pantothenic Acid, Biotin, Cyanocobalamin (B12). (23)

40

Separation of Binary Mixture By Using Pervaporation Chapter 5

IMPORTANTS OF NIACIN Niacin deficiency symptoms can be seen in diets with niacin intake below 7.5 mg. per day, but often this is not the only deficiency; vitamin B1, vitamin B2, and other B vitamins, as well as protein and iron may be low. To treat pellagra and niacin deficiency disorders, vitamin B3 supplements should be taken along with good protein intake to obtain adequate levels of the amino acid tryptophan. As described earlier, about 50 % of daily niacin comes from the conversion in our liver of tryptophan to niacin with the help of pyridoxine (vitamin B6). 5.1 REQUIREMENTS: Many food charts list only sources that actually contain niacin and do not take into account tryptophan conversion into niacin. Approximately 60 mg. of tryptophan can generate 1 mg. of niacin. But tryptophan is available for conversion only when there are more than sufficient quantities in the diet to synthesize the necessary proteins as tryptophan are used in our body with the other essential amino acids to produce protein. Niacin needs are based on caloric intake. We need about 6.6 mg. per 1,000 calories, and no less than 13 mg. per day. Women need at least 13 mg. and men at least 18 mg. per day and for children ranges from 9-16 mg. Niacin needs are increased during pregnancy, lactation, and growth periods, as well as after physical exercise. Athletes require more B 3 than less active people. Stress, illness, and tissue injury also increase the body's need for niacin. People who eat much sugar or refined processed foods require more niacin as well. Realistically, 25-50 mg. per day is adequate intake of niacin if minimum protein requirements are met. On the average, many supplements provide at least 50-100 mg. per day of niacin or niacinamide, which is a good insurance level. For treatment of the variety of conditions described previously, higher amounts of niacin may be needed to really be helpful, and levels up to 2-3 grams per day are not uncommon as a therapeutic

41

Separation of Binary Mixture By Using Pervaporation dose. The other B vitamins should also be supplied so as to not create an imbalanced metabolic condition. Excellent sources of vitamin B3 (niacin) include crimini mushrooms and tuna. Very good sources include salmon, chicken breast, asparagus, halibut, and venison. Vitamin B3, also commonly called niacin, is a member of the B-complex vitamin family whose discovery was related to work by the U.S. Public Health Service in the early 1900's. At that time, a disease called pellagra, characterized by cracked, scaly, discolored skin, digestive problems, and overall bodily weakness was increasingly prevalent in the southern region of the country. The Public Health Service established a connection between the prevalence of the disease and cornmeal-based diets, and addition of protein to these diets was found to cure many cases of pellagra. Several years later, vitamin B3 was formally identified as the missing nutrient in the cornmeal-based diets that had led to the symptoms of pellagra. We now know that corn as a whole food contains significant amounts of vitamin B3, but that vitamin B3 cannot readily be absorbed from corn unless corn products (like cornmeal) are prepared in a way that releases this vitamin for absorption. For example, the use of lime (as in limestone, the mineral, not lime juice in the fruit) can help release vitamin B3 from corn and make it available for absorption. Native American food practices that involve the addition of ash from cooking fires ("pot ash" or "potash") to corn-based recipes are one type of cooking technique that helps make vitamin B3 available for absorption. The term "niacin" used interchangeably with vitamin B3 is actually a nontechnical term that refers to several different chemical forms of the vitamin. These forms include nicotinic acid and nicotinamide. (Nicotinamide is also sometimes called niacinamide.) The names "niacin," "nicotinic acid," and "nicotinamide" are all derived from research studies on tobacco in the early 1930's. At that time, the first laboratory isolation of vitamin B3 occurred following work on the chemical nicotine that had been obtained from tobacco leaves.

42

Separation of Binary Mixture By Using Pervaporation 5.2 FUNCTION OF VITAMIN B3 Like its fellow B-complex vitamins, niacin is important in energy production. Two unique forms of vitamin B3 (called nicotinamide adenine dinucleotide, or NAD, and nicotinamide adenine dinucleotide phosphate, or NADP) are essential for conversion of the body's proteins, fats, and carbohydrates into usable energy. Niacin is also used to synthesize starch that can be stored in the body's muscles and liver for eventual use as an energy source. 5.3 METABOLISM OF FATS Vitamin B3 plays a critical role in the chemical processing of fats in the body. The fatty acid building blocks for fat-containing structures in the body (like cell membranes) typically require the presence of vitamin B3 for their synthesis, as do many fat-based hormones (called steroid hormones). Interestingly, although niacin is required for production of cholesterol by the liver, the vitamin has repeatedly been used to successfully lower total blood cholesterol in individuals with elevated cholesterol levels. This cholesterol-lowering effect of vitamin B3 only occurs at high doses that must be obtained through nutrient supplementation, and most likely involves a chemical feature of vitamin B3 that is not directly related to fat or fat processing. 5.4 SUPPORT OF GENETIC PROCESSES Components of the primary genetic material in our cells, called deoxyribose nucleic acid (DNA) require vitamin B3 for their production, and deficiency of vitamin B3 (like deficiency of other B-complex vitamins) has been directly linked to genetic (DNA) damage. The relationship between vitamin B3 and DNA damage appears to be particularly important in relationship to cancer and its prevention.

43

Separation of Binary Mixture By Using Pervaporation 5.5 DEFICIENCY SYMPTOMS Because of its unique relationship with energy production, vitamin B3 deficiency is often associated with general weakness, muscular weakness, and lack of appetite. Skin infections and digestive problems can also be associated with niacin deficiency. 5.6 TOXICITY SYMPTOMS Use of high-dose, supplemental niacin to lower serum cholesterol levels has given nutritional researchers a unique opportunity to examine possible toxicity symptoms associated with this vitamin. In the amounts provided by food, no symptoms of toxicity have been reported in the scientific literature. In 1998, the Institute of Medicine at the National Academy of Sciences set a tolerable upper limit (UL) for niacin of 35 milligrams. This UL applies to men and women 19 years or older, and is limited to niacin that is obtained from supplements and/or fortified foods. 5.7 FACTORS THAT AFFECT FUNCTION Intestinal problems, including chronic diarrhea, inflammatory bowel disease, and irritable bowel disease can all trigger vitamin B3 deficiency. Because part of the body's B3 supply comes from conversion of the amino acid tryptophan, deficiency of tryptophan can also increase risk of vitamin B3 deficiency. (Tryptophan deficiency is likely to occur in individuals with poor overall protein intake.) Physical trauma, all types of stress, longterm fever, and excessive consumption of alcohol have also been associated with increased risk of niacin deficiency. 5.8 NIACIN PROTECTS AGAINST ALZHEIMER'S DISEASE AND AGERELATED COGNITIVE DECLINE Niacin (vitamin B3) is already known to lower cholesterol. Now, research published in the August 2004 issue of the Journal of Neurology, Neurosurgery and Psychiatry indicates regular consumption of niacin-rich foods also provides protection against Alzheimer's disease and age-related cognitive decline. Researchers from the Chicago Health and Aging Project interviewed 3,718 Chicago residents aged 65 or older about their diet, then tested their cognitive abilities over the following six years. Those getting the most niacin from foods (22 mg per day) 44

Separation of Binary Mixture By Using Pervaporation were 70% less likely to have developed Alzheimer's disease than those consuming the least (about 13 mg daily), and their rate of age-related cognitive decline was significantly less. In addition to eating the niacin-rich foods, another way to boost our body's niacin levels is to eat more foods rich in the amino acid tryptophan. Our body can convert tryptophan to niacin, with a little help from other B vitamins, iron and vitamin C. Foods high in tryptophan include shrimp, crimini mushrooms, yellow fin, tuna, halibut, chicken breast, scallops, salmon, turkey and tofu. As we can see, several foods rich in tryptophan provide two ways to increase niacin levels as they are also rich in the B vitamin. (August 23, 2004) 5.9 FORMS IN DIETARY SUPPLEMENTS The term "niacin," often used interchangeably with the term "vitamin B3," is a non-chemical term that can actually refer to several different forms of the vitamin. Most often, "niacin" is used to refer to "nicotinic acid," the form of vitamin B3 with documented cholesterol-lowering potential. This form of the vitamin also carries with it the greatest risk of side effects. Supplements focused on cholesterol reduction and alteration of fat metabolism typically include vitamin B3 in the form of nicotinic acid. The nicotinamide form of vitamin B3 is also widely available in supplement form. This chemical form of vitamin B3 carries a much lower risk of side effects and is commonly used in supplement formulas designed to support health in conditions not involving cholesterol excess or altered fat metabolism. Particularly in formulas for pregnancy or in children's formulas, the nicotinamide version is often preferred. Many formulas include both forms of vitamin B3, with small amounts of nicotinic acid and larger amounts of nicotinamide. 5.10 INTRODUCTION TO NUTRIENT RATING SYSTEM CHART In order to better help we identify foods that feature a high concentration of nutrients for the calories they contain, we created a Food Rating System. This system allows us to highlight the foods that are especially rich in particular nutrients. The following chart shows the World's Healthiest Foods that are either an excellent, very good, or good source of vitamin B3 (niacin). Next to each food name, we shall find the serving size we used to calculate the food's nutrient composition, the calories contained in

45

Separation of Binary Mixture By Using Pervaporation the serving, the amount of vitamin B3 (niacin) contained in one serving size of the food, the percent Daily Value (DV%) that this amount represents, the nutrient density that we calculated for this food and nutrient, and the rating we established in our rating system. For most of our nutrient ratings, we adopted the government standards for food labeling that are found in the U.S. Food and Drug Administration's "Reference Values for Nutrition Labeling."(25) World's Healthiest Foods ranked as quality sources of:vitamin B3 (niacin) World's Nutrien Serving Amount DV Healthiest Food Cals t Size (mg) (%) Foods Density Rating 26. Crimini mushrooms, raw 5 oz-wt 31.2 5.39 15.6 Excellent 9 Tuna, yellowfin, 157. 67. 4 oz-wt 13.54 7.7 Excellent baked/broiled 6 7 Tamari (Soy Sauce) 1 tbs 10.8 0.72 3.6 6.0 Good 223. 72. Chicken breast, roasted 4 oz-wt 14.41 5.8 very good 4 0 187. 48. Calf's liver, braised 4 oz-wt 9.61 4.6 very good 1 0 158. 40. Halibut, baked/broiled 4 oz-wt 8.08 4.6 very good 8 4 Asparagus, boiled 1 cup 43.2 1.95 9.8 4.1 very good Salmon, chinook, 261. 56. 4 oz-wt 11.34 3.9 very good baked/broiled 9 7 179. 38. Venison 4 oz-wt 7.61 3.8 very good 2 0 Romaine lettuce 2 cup 15.7 0.56 2.8 3.2 Good 229. 38. Lamb loin, roasted 4 oz-wt 7.75 3.0 Good 1 8 214. 36. Turkey breast, roasted 4 oz-wt 7.22 3.0 Good 3 1 Tomato, ripe 1 cup 37.8 1.13 5.6 2.7 Good Mustard greens, boiled 1 cup 21.0 0.61 3.0 2.6 Good 112. 14. Shrimp, steamed/boiled 4 oz-wt 2.94 2.4 Good 3 7

46

Separation of Binary Mixture By Using Pervaporation Summer squash, cooked, slices

1 cup

Green peas, boiled

1 cup

Cod, baked/broiled

4 oz-wt

Collard greens, boiled Carrots, raw Broccoli, steamed Eggplant, cooked, cubes Peanuts, raw Spinach, boiled Fennel, raw, sliced Turnip greens, cooked Spelt grains, cooked Beef tenderloin, lean, broiled Raspberries Winter squash, baked, cubes Swiss chard, boiled Cauliflower, boiled Kale, boiled Green beans, boiled Mustard seeds Cantaloupe, cubes World's Healthiest Foods Rating excellent very good good

1 cup 1 cup 1 cup 1 cup 0.25 cup 1 cup 1 cup 1 cup 4 oz-wt 4 oz-wt

36.0 134. 4 119. 1 49.4 52.5 43.7 27.7 207. 0 41.4 27.0 28.8 144. 0 240.

1 cup

4 60.3

1 cup 1 cup 1 cup 1 cup 1 cup 2 tsp 1 cup

0.92 3.23 2.82 1.09 1.13 0.94 0.59 4.40 0.88 0.56 0.59 2.91 4.44

4.6 16. 1 14. 1 5.5 5.6 4.7 3.0 22. 0 4.4 2.8 3.0 14. 6 22.

2.3

Good

2.2

Good

2.1

Good

2.0 1.9 1.9 1.9

Good Good Good Good

1.9

Good

1.9 1.9 1.8

Good Good Good

1.8

Good

1.7

Good

1.6

Good

1.10

2 5.5

80.0

1.44

7.2

1.6

Good

35.0 28.5 36.4 43.8 35.0 56.0

0.63 3.1 0.51 2.5 0.65 3.3 0.77 3.9 0.60 3.0 0.92 4.6 Rule

1.6 1.6 1.6 1.6 1.5 1.5

Good Good Good Good Good Good

DV>=75% OR Density>=7.6 AND DV>=10% DV>=50% OR Density>=3.4 AND DV>=5% DV>=25% OR Density>=1.5 AND DV>=2.5%

47

Separation of Binary Mixture By Using Pervaporation Chapter 6

MATERIAL BALANCE

6.1 BASIS: 1 KG OF TOBACCO PER BATCH (18)

6.1.1 Mixing tank:-

Mixer

5lit of H2O 1 Kg of Raw tobacco

Overall material balance over mixer Water added + Raw tobacco = Wet slurry 5 lit of water + 1Kg of tobacco = Wet slurry ∴ Wet slurry = 6 Kg As tobacco contains 5% nicotine Material balance of nicotine Let “X” be the quantity of nicotine in wet slurry Nicotine in tobacco = Nicotine in wet slurry 0.05 X 1000 = X ∴ X ∴

= 50 gm

Nicotine in wet slurry = 50 gm

48

Wet slurry (6 Kg.)

Separation of Binary Mixture By Using Pervaporation 6.1.2 Filtration:Wet Tobacco Wet slurry

Filtration

(6 Kg)

[i.e.4Kg wet tobacco] Filtrate (1400 ml)

Overall material balance Wet Slurry in = Wet Tobacco + Filtrate + Loss 6000 = 4000 + 1400 + Loss Loss = 600 ml The wet tobacco after filtration can be dried and send to the cigarette manufacturing unit to get non addictive cigarette. 6.1.3 Steam Distillation:-

Nicotine Solution 1400 ml of Filtrate

Steam Distillation

1040 ml Waste 360 ml

Overall material balance Filtrate = Nicotine Solution + Waste 1400 = 1040 + Waste Waste = 360 ml

49

Separation of Binary Mixture By Using Pervaporation 6.1.4 Separation:Nicotine layer Nicotine solution

Separator

(1040 ml) Other constituents Overall material balance over separator Nicotine solution = Nicotine layer + other constituents After measurement we get 1007 ml of other constituents from bottom of separator 1040 = Nicotine layer + 1007 Nicotine layer = 33 ml.

6.1.5 Oxidation Reaction:33ml of HNO3 Reaction 33ml of Nicotine

Reactor 110-115 0 C 30 min

Product Niacin, Methylamine; Oxalic acid & CO2

Overall material balance: 33 ml of HNO3 + 33 ml of Nicotine = Reaction Product ∴ Reaction Product = 45 gm. The product from oxidation reaction in the form of precipitate was kept in the accumulator for near about half hour. In the accumulator there was formation of two layers due to density difference, the lower layer of Oxalic acid and upper layer of Nicotinic acid, which was send to dryer.

50

Separation of Binary Mixture By Using Pervaporation

Top Nicotinic acid (45 gm)

Accumulator

Reaction

layer (36 gm)

Product Bottom Oxalic acid layer (9 gm) Overall material balance Reaction product =

Top Nicotinic acid layer + Bottom Oxalic acid layer

45 = Top Nicotinic acid layer + 9 ∴ Top Nicotinic acid layer = 36 gm

6.1.6

Drying:-

Moisture removed Top Niacin layer 80 % Solid

Tray Dryer

20 % Moisture

Dry Product 95 % Solid

5 % Moisture

Let X and Y are the gm of water removed and product Niacin obtained. Overall material balance Top Nicotinic acid layer = Dried product + Moisture removed 36 =

X+Y

Solid balance 0.8 X 36 = 0.95 Y

51

Separation of Binary Mixture By Using Pervaporation Y = 30 gm Nicotinic acid = 30 gm X = 6 gm Moisture removed = 6 gm

6.2 ENERGY BALANCE

(18)

6.2.1 Mixing Tank: T = 250C 5 lit H2O

Wet Slurry (6 Kg.) Mixer at 60 0 C

(T = 580C)

1Kg of Tobacco (T = 300C)

Amount of heat required to raise the temperature of tobacco mixture in mixing tank from room temp. (i.e. 300C) to 600C Q = m Cp ∆ T Q = 6 X Cp X (60-30) Approximate Specific heat capacity (Cp) values can be calculated for solids and liquids by using a modified form of Kopp’s law, which is given by Werner (1941). (19) Molecular formula of Nicotine is C1OH14 N2 Element

Mol. Mass

Heat capacity

C

120

120 X 7.5

= 900.0

H

14

14 X 9.6

= 134.4

N

28

28 X 26.0

= 728.0

162

1762.4

52

Separation of Binary Mixture By Using Pervaporation 1762.4 ∴ Specific heat = ------------ - = 10.88 J / g oc [ KJ / Kg 0C ] Capacity

162

(Of Nicotine extract) ∴ Q = 6 X 10.88 X 30 = 1958.4 KJ 6.2.2 Steam Distillation: Steam in Feed 1400 ml of filtrate

Steam (110 0C) Distillation

(280C) Condensate Amount of heat required in steam distillation section. Q = m Cp ∆ T = 1.4 X 10.88 X (110-28) Q = 1249.024 KJ/hr Amount of steam required is Q = mCp ∆ T 1249.024 = m X 1 X (110-28) ∴ m = 15.232 kg/hr ∴ Amount of steam required was = 15.232 Kg/hr.

53

Product

Separation of Binary Mixture By Using Pervaporation

6.2.3 Oxidation Reactor:

Feed (30 0 C) 33mlof Nicotine

45 gm

Reactor 1100C

Product

33mlofHNO3 Amount of heat required in reactor is Q = mCp ∆ T Q = 0.066X10.88 X (110-30) Q = 57.4464 KJ /hr

54

Separation of Binary Mixture By Using Pervaporation Chapter 7

REACTOR DESIGN For 33 lit. of total reaction mixture. V = 33 lit. 1m3 = 1000 lit. = 33 lit. For design purpose 10 % extra, ∴ V = 33 X 10-3 + 10 % Excess ∴ V = 36.3 X 10-3 m3 Diameter of reactor can be found out from volume of reactor; as we know.(16) Volume = Area X Length --------------- (1) Let, Diameter of reactor = D Length of the reactor = L Volume of the reactor =V ∴ Area of

=

Reactor

π D2 4

For plate thickness up to 50 mm (16) L

= 6

D ∴ Length of reactor = L = 6 D Substituting area & length in equation (1) ∴ Volume = π D 2 X 6 D 4 ∴ V = 1.5π D3

55

Separation of Binary Mixture By Using Pervaporation

36.3X10-3 = 4.712 D 3 ∴ D 3 = 7.7X 10-3 ∴ D = 0.19 m Di = 20 cm ≈ 200mm

Since

L = 6 D

∴ L = 6 D = 6 X 20 = 120 cm L = 1.2 m P = 1atm Thickness is t = PD

=101.325 X103 N/m2

+C

D= 0.2 m

2fJ

F = For Steel plate allowable stress

The steel plate IS : 2041- 1962 3

= 101.325 X 10 X 0.2 + 1 X 10

3

2 X 3.5X106X 0.80 t = 4.62 mm ≈ 5mm

The Volume of metal used for constructing the vessel v = t [π DL + π D 2 ] 2 -3

v = 5X 10 [0.754 +0.063] v= 40.8 X 10-3 m3

56

= 3.5 X 106N/m2 J = 80%

Separation of Binary Mixture By Using Pervaporation Stoichiometric proportion of Nicotine & HNO3 for oxidation reaction (18) According to the oxidation reaction C10H14N2 Nicotine

+ 9[O] --HNO3--- C6H5NO2 Nascent Oxygen

+ C2H2O4.H2O + CH3NH2 + CO2

Nicotinic acid

Oxalic Acid

1 mole of Nicotine ≡ 3 mole of HNO3 1X162 kg of Nicotine ≡ 3 X 63 kg HNO3 162 kg of Nicotine ≡ 189 kg HNO3 Specific gravity of Nicotine = 1.009 1.009 =

Density of Nicotine Density of H2O

1.009 = Nicotine 1 gm/cm3 ∴ Density of Nicotine = 1.009 gm/cm3 = 1009 kg/m3

But Density =

M

i.e V = M

V

Density

= 162kg 1009 kg/m3

∴ Volume of Nicotine = 0.1605 m3 = 160.5 lit. Volume of Nicotine = 160 lit. Again specific gravity of HNO3 = 1.502 Density of HNO3 ∴ 1.502 =

-----------------Density of H2O

∴ Density of HNO3 = 1.502 gm/cm3 = 1502 kg / m3

57

= 0.1605m3

Ethylamine

Separation of Binary Mixture By Using Pervaporation

m

189

Kg

Volume of HNO3 = -------- = --------- = --------- = 0.1258 m3 1502

Kg/m3

∴ Volume of HNO3 = 0.1258 m3 = 125.8 lit Volume HNO3 = 125 lit. So for carrying oxidation reaction, take 1.6 ml of Nicotine & 1.25 ml HNO 3 to get the desired product i.e. Nicotinic acid (Niacin). (18)

58

Separation of Binary Mixture By Using Pervaporation Chapter 8

COST ESTIMATION 8.1 COST OF EQUIPMENT:Sr.No . 1 2 3 4 5

Item

Uni

Cost /

Total

t 1 1 1 4 1

Unit 200000 3200000 480000 4000 500000

Cost(Rs.) 200000 320000 480000 16000 500000

1 1 1

100000 25000 150000

100000 25000 150000 1791000

Pulverizer Mixing Tank Filter press Storage Tank Steam Distillation Setup Condensor Reactor Dryer Total ( E )

6 7 8

8.2 FIXED CAPITAL INVESTMENT:8.2.1 Direct Cost:Sr.No . 1 2 3 4 5 6 7 8

Item Purchase Equipment Cost Equipment Installation Instrumentation & Control Piping Cost Electrical Fitting Cost Building Construction & Other Services Yard Investment Land Total Direct Plant Cost (D)

59

%

Cost

E E 30 15 15 5 40

(Rs.) 1791000 537300 268650 268650 89550 716400

3 30

53730 537300 4262580

Separation of Binary Mixture By Using Pervaporation 8.2.2 Indirect Cost:-

Sr.No

Item

%

.

Cost

E

(Rs.)

1

Engineering & Supervision

17

304470

2

Cost Construction Expenses

32

573120

Total Indirect Cost ( I )

877590

Total direct & indirect cost (I + D) = Rs. 5140170 Contractor Fees 5 % (I+D) = Rs.257000 Fixed Capital Investment (FCI) = Rs.5397170 Working Capital (WC) 20 % (I+D) = Rs.1028034 Total Capital Investment = FCI + WC

= 5397170 + 1028034 = Rs. 6425204 8.3 TOTAL PRODUCTION COST:8.3.1 Direct Production Cost:1) Raw Material Cost:Sr.No . 1 2 3

Raw Material

Quantity/Batc

Waste Tobacco NaoH 50 % HNO3

h 500 Kg. 5 Kg. 16.5 lit.

Cost/ Kg

Cost

Rs. 30 / Kg Rs.180 / Kg Rs. 225 /

(Rs.) 15000 900 3713

lit. Raw Material

19613

Cost

For one day three batches Therefore raw material cost per day = 19613 X 3

60

Separation of Binary Mixture By Using Pervaporation = Rs. 58839 Raw material cost per month

= 58839 X 30 = Rs. 1765170

8.3.2 Utilities:-

a) Water:Water requirement per batch = 25000 lit. Cost of Water = Rs. 1 / lit. Cost of Water per batch = Rs.2500 b) Steam:Requirement of Steam per batch = 900 Kg. Cost of Steam = Rs. 5.33 / Kg. Cost of Steam per batch = Rs. 4800 Cost of steam per day = 3 X 4800 = Rs. 14400 c) Electricity:Requirement of Electricity per batch = 800 Kwh Cost of Electricity = Rs. 6 /Kwh Cost of Electricity per batch = 800 X 6 = Rs. 4800 Cost of Electricity per Day = 3 X 4800 = Rs. 14400 B) Total cost of Utilities = 7500 + 14400 + 14400 = Rs. 36300 /day Total cost of Utilities per month = 30 X 36300 = Rs. 1089000

61

Separation of Binary Mixture By Using Pervaporation 8.4 OPERATING LABOUR COST:Post

Number

Salary /

Total

1 2 4 4 1 2

month Rs. 15000 Rs. 10000 Rs. 5000 Rs. 3000 Rs. 3000 Rs.3500

salary Rs. 15000 Rs.20000 Rs.20000 Rs.12000 Rs.3000 Rs.7000

General Manager Engineer Skilled Worker Unskilled Worker Clerk Administrative staff

Total Labour

Rs.77000

Cost

Bonus = 0.3 X Total labour cost = 0.3 X 77000 = Rs.23100 Operating labour cost per month = 77000 + 1925 O.L.C. = Rs. 78925 /month Lab Charges = 10 % OLC = 0.1 X78925 = Rs.7893 /month Maintenance & repair = 0.5 % FCI = 0.005 X 5397170 = Rs. 26986 / month A) Direct production cost = Raw material cost + Cost of Utilities + Operating Cost + Lab Charges + Main. & repair. D.P.C. = 1765170 + 1089000 + 78925 + 78925 + 26986 = Rs. 2967974 / month

62

Separation of Binary Mixture By Using Pervaporation B) Depreciation & Taxes = 2 % FCI = 0.02 X 5397170 = Rs. 107943 C) Insurance = 1 % FCI = 0.01 X 5397170 = Rs. 53972 D) Distribution & Marketing = 20 % OLC = 0.2 X 78925 = Rs.15785 E) Other Cost (R & D ) = 1 % FCI = 0.01 X 5397170 = Rs. 53972 Total production cost per month = A + B + C + D + E = 2967974 +107943 + 53972 + 15785 + 53972 = Rs.3199646 Now, 15 Kg Niacin, 15 Kg of Oxalic acid and 450 Kg of nonaddictive tobacco were obtained from one batch process. Therefore for one month, Niacin produced = 15 X 3 = 45 Kg / day = 45 X 30 = 1350 Kg / month Similarly Oxalic acid = 1350 Kg / month And Nonaddictive tobacco = 450 X 3 X 30 = 40500 Kg / month

63

Separation of Binary Mixture By Using Pervaporation Sale:- (14) Selling price of Niacin = Rs. 2100 / Kg Selling price of Oxalic acid = Rs. 280 /Kg Selling price of Tobacco = Rs. 15 / Kg

Monthly Sale:Niacin = 1350 X 2100 = Rs. 2835000 Oxalic acid = 1350 X 280 = Rs. 378000 Tobacco = 40500 X 15 = Rs. 607500 Total monthly sale = 2835000 + 378000 +607500 = Rs. 3820500 Gross profit = Total monthly sale - Total monthly production cost = 3820500 – 3199646 = Rs. 620854 Income tax = 40 % Gross profit = 0.4 X 620854 = Rs. 248342 Net profit = Gross profit – Income tax = 620854 – 248342 = Rs. 372512 /month = 372512 X 12 = Rs. 4470144 /year Rate of return on investment =

Net profit per year Fixed Capital Investment = 4470144 5397170 = 0.83

Rate of return = 0.83 This evaluation is based on laboratory readings & previous literature on Niacin, so before going for large scale production a test on pilot plant is necessary. (14)

64

Separation of Binary Mixture By Using Pervaporation

Chapter 9

PLANT LAYOUT After the process flow diagram was completed and before detailed piping design and layout can begin, the layout of process unit must be planned and equipment within these process unit must be planned. This layout can play an important role in determining constructing and manufacturing cost; and thus must be planned carefully. Good plant layout keeps safety, appearance, convenience, overall cost, erecting cost, operating and maintenance cost to the minimum. Safety and optimum utilization of available area should be given prime importance in plant layout. The key to economical construction and efficient operation is a carefully planned functional agreement of equipment, piping and building. An accessible and aesthetically pleasing plot plan can make major contribution to safety, employee satisfaction and sound community relation. The handling of the material is kept to minimum by provision of gravity transportation wherever possible. Provision should be also made for necessary service area; the administration or office building, canteen, workshops, laboratories, etc. The main process plant should be isolated from administration building, canteen, workshops, laboratories, etc, the storage tanks area, security room should be also isolated from main plant. The canteen should also be neat to office building, laboratories; workshops etc. process plant should be located on one side of a tank farm while shipping, transport, and loading/unloading facilities on another side. Intermediate tanks should be located close to the process unit. Administration and service facilities should be located near the process plant entrance. Warehouses, salvage yard should be close together. Cooling towers should be located where water drift from the tower will not cause excessive corrosion of process equipment. They should be oriented cross way to the wind direction in order to minimize recycling of air from the discharge of one tower to an adjacent tower. All hazardous tank of larger size should be located at least 65m away from the building, process plant, fired heaters. Pumping arrangement of liquid from the tank should be decentralized. In process plant there should be sufficient space between the process

65

Separation of Binary Mixture By Using Pervaporation equipment. It avoids congestion after piping, valves, instrumentation is done on equipment. Storage Layout:Raw material storage tank should be located such that the transportation to the process area is done easily loaded and unloaded. Equipment Layout:Equipment should be installed in the process direction, maintaining reasonable space between them. To consume space economically they should be arranged so that the final product and initial reactants are near to storage tanks. The equipment should be installed in the process direction in such a manner that handling of the material is kept to minimum by provision of gravity transportation wherever it is possible; without disturbing the main process. Safety: Fire station should be located nearer to process area. In every unit hose pipes, fire extinguisher should be placed. Plant Expansion: Some space should be allocated for future expansion of the plant. Utilities: Placing them nearer to the process area should effectively do distribution of steam, power, water etc. Administrative building: This should be located at the entrance of the main gate of the factory and there must be provision made for communicating with every plant. Laboratory and Quality Control: These should be located near the process plant. Due to which the evaluation results and hence correction can be easily done within no time. Commodities: 66

Separation of Binary Mixture By Using Pervaporation Parking and canteen should be located near to the unit but not too close to the unit. They should be separated from actual plant by the road. Security Office: The security office and time office (checkers gate) should be located near to the entrance of the factory. In short the plant should fill the following points: 

More efficient use of land space.



Lower cost of construction per square feet floor space.



The upper stores building (e.g. administrative building etc) should be free

from street noise, dust, odor, etc). 

Use of gravity flow of materials, which is cheaper method of

transportation. 

More compact layout because of vertical arrangement of production area.

Market Area: Nicotinic acid is used by wider range of pharmaceutical industries. Major part of nicotinic acid is exported and there were large transportation facilities in Ankalashawar . Previously Amsal Chemical and their group is the only major manufacturer of nicotinic acid. This provides opportunity to capture nearby market easily.

Raw Material Supply: Raw material required for production of Nicotinic Acid i.e. Waste Tobacco was collected from tobacco farming nearby area and also from tobacco processing industries. (13)

67

Separation of Binary Mixture By Using Pervaporation Chapter 10

CONCLUSION Nicotinic acid is an antipellagra factor is a group of vitamin B3 . Majority sources of it are Yeast, Rice polishing, Meatextract & Tobacco. By oxidation of tobacco with the help of HNO3, nicotine is converted to nicotinic acid (Niacin). With this treatment to tobacco the addictive nature of man towards tobacco becomes non-addictive & also provide an improved tobacco product, so that blood plasma nicotine level resulting about 0 to 5 nanograms /ml. The main aim is to go for experimental work in lab-scale for conversion of Nicotine to Nicotinic acid from Tobacco.It is a two step process,firstly Extraction of nicotine from tobacco and secondly conversion of nicotine to nicotinic acid. The reactor was to be designed for this oxidation process and the analysis of product & by- products was to be carried out. The objective of the process is to get non addictive tobacco product, the poisonous Nicotine is converted to Vitamin B3, and to reduce the Carcinogenic effect of tobacco on human health i.e. to get alternate use of tobacco for Nicotine Sulphate (as pesticide), Niacin (Vitamin B3) pharmaceutical product, etc. This invention relates in general to certain new and useful improvement in processing of tobacco to eliminate or convert nicotine in the tobacco in to nicotinic acid as a harmless or beneficial product such that the nicotine level which can be achieved by use of the tobacco product result in a blood plasma level consonant with non-addiction. The primary objects of the present invention is to provide a tobacco product adapted for human use and which eliminates an addictive response to the user there of the another object of the present invention to provide an improved tobacco product of the type which utilized an oxidized tobacco in which nicotine has been converted to nicotinic acid or extraction to a level resulting in the user is about 0 to about 5 nanograms per milliliter. The another object of the present invention to provide an improved tobacco product of the type stated in which a tobacco product is converted chemically or by physical means to obviate any effects on the acetykholine brain receptors in an individual smoking or otherwise ingesting such tobacco product.

68

Separation of Binary Mixture By Using Pervaporation In accordance with the present invention it has been found that by converting the nicotine of a tobacco product in to a harmless and actually beneficial substance, such as nicotinic acid, addiction to the tobacco product can be avoided. Thus the conversion of the nicotine in accordance with the present invention not only elements the addiction but also reduces some of the harmful effects of the identified as being generally recognized as safe or approved. Nicotinic acid is also known as Niacin, Nicotineamide and anti pellagra factor is a group of vitamin B3. Its compound was known before its vitamin activity observed. It is widely used in the food, pharmaceutical & biochemical industries. An odorless, white, crystalline substance, readily soluble in water. It is resistant to heat, oxidation, and alkalis. It is, in fact, one of the most stable vitamins. Cooking causes little actual destruction of niacin, but a considerable amount may be lost in the cooking water and drippings from cooked meat if these are discarded. In a mixed diet, 15 to 25 percent of niacin of the cooked food stuff may be lost in this way. It is excreted in the urine, mostly as its salts, and to a smaller extent, as free niacin. The main deficiency disease caused by lack of nicotinic acid is “pellagra”. This disease affects epithelia & nervous system. It is accused by the accumulation of the intermediate products of respiration, this is because nicotinic acid is required for the synthesis of co-enzymes used by dehydrogenises. Nervousness, headaches, fatigue, mental depression, skin, disorders, muscular weakness, & indigestion are the symptoms of deficiency of niacin. Exposure to nicotine and combustible products from cigarette smoking is toxic to renal function. In particular, nicotine has an adverse effect on behavior as it results in people becoming addicted. Patients are predisposed to urinary tract cancers. Further kidney damage can result from accumulation of heavy metals from tobacco. Associated with altered renal function is a direct effect on nervous innervations, blood pressure and blood vessels. Antismoking campaigns should be focused on achieving more success. For instance, banning smoking in public venues and at workplaces will decrease the deleterious effects of long-term exposure to nicotine. From 2nd Oct. 2008 it was banned to smoke at public places and also at work places by the Government. Nicotine could also be removed from combustion tobacco products. Alternatively nicotine-replacement therapies may be used. One should avoid smoking by inhalation either actively or passively

69

Separation of Binary Mixture By Using Pervaporation

FUTURE PROSPECTS

1. With the help of this treatment to the tobacco the addictive nature of tobacco due to Nicotine becomes non-addictive. 2. The harmful nicotine can be converted to Niacin. 3. The carcinogenic effect of tobacco due to nicotine can be reduced. 4. We can convert the harmful nicotine to the niacin which was pharmaceutical product. 5. For the waste coming from the tobacco industries & also from tobacco farming, this was the important technique to get the valuable product. 6. The treated tobacco can also be used as a fertilizer for the farming purpose. 7. The main aim is to get alternative use of tobacco for Farmers due to the ban of tobacco for beedi, hooka, chewing etc. by the Government. 8. To treat one cancer patient approximately Rs. 3.5 lacks required and near about 7.5 lacks people die due to cancer from tobacco, this can be avoided. 9. Due to commercialization of this process, the addictive tobacco becomes nonaddictive and the pharmaceutical product Niacin can be produced. 10. By this method we can convert waste tobacco to the valuable pharmaceutical product 11. By optimizing the process the yield of Niacin from tobacco can be increased.

70

Separation of Binary Mixture By Using Pervaporation

REFERENCES 1.

Agarwal O.P. “Chemistry of Organic Natural Product”(2004) Volume I, Himalaya Publishing House, (p.280,281).

2. Dr.Deb A. C. “Fundamentals of Biochemistry”(1990) A.Sen New Central

Book Agency, Calcutta,(p.191,192). 3. Kirk- Othmer “Encyclopedia of Chemical Technology”III rd ed.(1984)

Volume 24 A Wiley- Interscience Publication John Wiley & Sons (p.80-87). 4. Gurdeep Chatural “Organic Chemistry of Natural Products”(2004) Volume I

Himalaya Publishing House(p.571,573). 5. “The Pharmaceutical Codex” XI

th

ed.(1979) The Pharmaceutical Press

London (p.593,594). 6. Harold Varley “Practical Clinical Biochemistry”

IVth

ed.(1969), CBS

Publisher & Distributors, Daryaganj New Delhi (p.622). 7. Richard J.Lewis Sr, Van Nostraud Reinhold “Hazardous Chemicals Desk

Reference” IInd ed. (2002),McGraw Hill Publication New York (p.844). 8. David L. Nelson & Michael M. Cox “Lehningers Principles of Biochemistry”

IVth ed (2005) W.H. Freeman & company New York (p.514, 515). 9. Finar I .L. “Organic Chemistry”(1994) Vth ed. Longman Singapore

Publishers Ltd. Singapore (p.717) 10. Douglas M. Considine “Chemical and Process Technology Encyclopedia”

(2004) Mc Graw Hill Book Company (page 71, 946). 11. Robert H. Perry, Don W. Green, “Perry,s Chemical Engineering Hand Book”

VIIth ed.(1997) Mc Graw Hill Publications,New York (p 2-41,42,43). 12. Larry Ricci & The Staff of Chemical Engineering “Seperation Techniques in

Liquid-Liquid System”.(2001) McGraw Hill Publications Co, New York (p.552) 71

Separation of Binary Mixture By Using Pervaporation 13. Khana O.P. “Industrial Engineering & Management” (1999), Dhanpat Rai

Publications (P.) Ltd.(p.4.1-4.35). 14. Peter Timmerhaus, West “Plant Design & Economics for Chemical

Engineers” Vth ed. (2004) Mc Graw Hill Publication, New York (p.323) 15. Warren L. McCabe, J.C. Smith, Peter Harriott, “Unit Operations of Chemical Engineering V th ed. (1993) McGraw Hill Book Co. Singapore (p.614, 615). 16. Dr. S.D. Dawande “ Process Design of Equipments” I

st

ed. (1999), Central

Techno Publications,Nagpur-12 (p.19,20). 17. Robert E. Treybal “Mass– Transfer Operations”III

rd

ed. (1981) McGraw-Hill

Book Co. Singapore (p.717, 718,719). 18. Bhatt B.I. & Vora S.M. “Stoichiometry” III rd ed. (1998) Tata Mc Graw Hill

Publishing Company Ltd. (p.66, 67,187). 19. Richardson and Colusion. “Chemical Engineering Volume IV th ed.

“Chemical Engineering Design” (2008), Elsevier India Private Ltd. (p.322,323). 20. http://icmr.nic.in/ijmr/2006/september/0905.pdf cited on 1/11/2006. 21. http://www.Properties of Tobacco.htm cited on 30/5/2008. 22. http://en.wikipedia.org/wiki/Nicotinicacid, cited on 25/10/2008. 23. http://www.Vitamin B3 Niacin Healthy Body,Healthy Mind, Holistic

Healing,Home Remedi, cited on 18/4/2008 24. http://Non-addictive tobacco products – Patents 5713376.htm cited on

22/9/2007. 25. http://www.purchon.com/biology/nicotinic acid cited on 3/3/2007. 26. http://www.Nicotine & its Derivatives from Tobacco Waste.htm, cited on

30/5/2008.

72

Separation of Binary Mixture By Using Pervaporation

INDEX Introduction to pervaporation

1

1.2 MEMBRANE BASED PERVAPORATION SEPARATION:.................................2 ..........................................................................................................................................3 ..........................................................................................................................................4 1.3 membrane material:...................................................................................................4 1.4 Nicotine content of tobacco:......................................................................................5 1.5 Tobacco waste sources:..............................................................................................5 1.6 Availability of tobacco waste:...................................................................................5 1.7 Chemical constituents of tobacco:.............................................................................5 1.8 Nicotine alkaloids of tobacco:...................................................................................6 1.9 Role of tobacco products in the economy: ................................................................6 1.10 Recommendations:...................................................................................................7 1.11 Properties of Tobacco Content:-..............................................................................8 1.12 DIESEASES FROM TOBACCO..........................................................................10 1.12 .1 Cancers of the urinary tract............................................................................10 1.12.2 Occupational exposure to cigarette smoke.....................................................10 1.12.3 Passive smoking..............................................................................................10 1.12.4 Nicotine induced nephropathies......................................................................11 1.12.5 Associated influence of nicotine on the nervous system................................11 1.12.6 Nicotine should be removed from combustion tobacco products..................12 Literature survey 13 2.1 Different methods for niacin....................................................................................13 2.1.1 Liquid phase oxidation of Nicotine using Chromic acid: - ..............................13 2.1.2 Liquid phase oxidation of MEP (2-methyl-5-ethylpyridine) with nitric acid or air: - ...........................................................................................................................14 2.1.3 Liquid-Phase oxidation of 3-Picoline with Oxygen: - .....................................14 2.1.4 Gas phase oxidation of Picoline to Nicotinic acid: - ........................................15 2.1.5 Gas- Phase oxidation of Picoline to Cyanopyridine:- ......................................15 2.1.6 Commercial method followed by “Amsal Chemical Pvt. Ltd. Ankaleshwar:-.15 2.2 Review Article (20)..................................................................................................16 2.2.1 Effect of tobacco smoking on renal function:-.................................................16 2.2.2 Past work:..........................................................................................................16 2.2.3 Indian J Med Res 124, September 2006, pp 261-268.......................................17 2.3 NON-ADDICTIVE TOBACCO PRODUCTS (24)..............................................17 2.3.2. Brief Description of the Related Art ...............................................................18 2.4 OBJECTS ................................................................................................................20 2.5 SUMMARY OF THE INVENTION ......................................................................21 CONVERSION OF NICOTINE TO NICOTINIC ACID 25 3.1 Nicotine - sources and health aspects:-....................................................................25 3.1.1 Sources..............................................................................................................25 3.1.2 Main Reaction:..................................................................................................26 3.2 Physical Properties (11)...........................................................................................27 3.3 Process Description:- ..............................................................................................27 73

Separation of Binary Mixture By Using Pervaporation 3.2.1 Nicotine consumption.......................................................................................28 3.2.2 Nicotine addiction and metabolism..................................................................29 NIACIN 30 4.1 History......................................................................................................................30 4.2 Dietary needs...........................................................................................................30 4.3 Properties: ..............................................................................................................30 4.3 Pharmacological uses:-............................................................................................31 4.4 Toxicity....................................................................................................................31 4.5 Biosynthesis.............................................................................................................32 4.6 Physical Properties of Nicotinic Acid (11)..............................................................33 4.7 Functions of Vitamin B3 Niacin:-............................................................................35 4.8 Chemical Structure (25)...........................................................................................35 4.9 Biological Synthesis ................................................................................................35 4.10 Sources...................................................................................................................36 4.11 Source Categories:.................................................................................................37 4.12 Deficiency Disease:...............................................................................................37 4.13 Identification Tests for NIACIN (2)......................................................................37 4.14 Precautions:............................................................................................................37 4.14 Niacin Analogues:-................................................................................................38 4.15 Vitamin B3 Uses....................................................................................................39 IMPORTANTS OF NIACIN 41 5.1 Requirements: ........................................................................................................41 5.2 Function of vitamin B3............................................................................................43 5.3 Metabolism of Fats ................................................................................................43 5.4 Support of genetic processes....................................................................................43 5.5 Deficiency Symptoms..............................................................................................44 5.6 Toxicity Symptoms..................................................................................................44 5.7 Factors that Affect Function....................................................................................44 5.8 Niacin Protects against Alzheimer's disease and Age-related Cognitive Decline...44 5.9 FORMS in Dietary Supplements.............................................................................45 5.10 Introduction to Nutrient Rating System Chart.......................................................45 MATERIAL BALANCE 48 6.1 Basis: 1 Kg of tobacco per BATCH (18).................................................................48 6.1.1 Mixing tank:-....................................................................................................48 6.1.2 Filtration:-.........................................................................................................49 6.1.3 Steam Distillation:-...........................................................................................49 ...................................................................................................................................49 6.1.4 Separation:-.......................................................................................................50 6.1.5 Oxidation Reaction:-.......................................................................................50 6.1.6Drying:- .............................................................................................................51 6.2 Energy Balance (18) ........................................................52 6.2.1 Mixing Tank: ...................................................................................................52 6.2.2 Steam Distillation:............................................................................................53 6.2.3 Oxidation Reactor:............................................................................................54 Reactor Design 55 74

Separation of Binary Mixture By Using Pervaporation Cost Estimation

59

8.1 Cost of Equipment:-.................................................................................................59 8.2 Fixed Capital Investment:-.......................................................................................59 8.2.1 Direct Cost:-......................................................................................................59 8.2.2 Indirect Cost:-...................................................................................................60 8.3 Total Production Cost:-............................................................................................60 8.3.1 Direct Production Cost:-...................................................................................60 8.3.2 Utilities:-...........................................................................................................61 8.4 Operating Labour Cost:-..........................................................................................62 PLANT LAYOUT 65 CONCLUSION

68

Future Prospects.............................................................................................................70 REFERENCES 71 Index

73

75

Separation of Binary Mixture By Using Pervaporation

LIST OF TABLE SR.

DESCRIPTION

NO.

PAGE NO.

1

Liquid phase o`xidation reaction yields

10

2

Sources

22

3

Physical properties

24

4

Physical properties of Niacin

30

5

Food Sources

33

6

Worlds healthiest foods ranked as quality sources of Niacin

76

43, 44