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, close-

boiling 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.

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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 VacuumOperation

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

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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 2006-

07. 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

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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

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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 13-

15 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-GMP-

dependent 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 1.32 tones

Chromic acid 9.02 tones

Nicotinic acid 1.00 tones

CO2 produced 1.43 tones

NOx (calculated as

NO2)

0.37 tones

Water 0.73 tones

Chromic oxide 6.8 tones

Thus almost 9 tones of side product are produced for 1 tones of desire product

Reaction:

2C10H14N2 + 22CrO3 2C6H5NO2 + 8CO2 + 2NO2 + 9H2O + 11Cr2O3

Nicotine Chronic Acid Nicotinic Acid Chronic(III) oxide

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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] ---------- C6H5NO2 + 2CO2 + 3H2O

2-methyl-5-ethylpyridine 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] NO2

3NO2 + H2O 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 + (No)x + H2O

β -Picoloine Sulphate Nicotinic Acid Sulphate

3. C6O6H9SN + 2NH3 Precipitation C6O2H5N + (NH4)2SO4

Nicotinic Acid Sulphate Niacin Ammonium Sulphate

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Separation of Binary Mixture By Using Pervaporation

2.1.7 Finally, Niacin may be synthesized from pyridine:-

Bubbling CO2 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 twenty-

five 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.

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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

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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.

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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.

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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

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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

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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)

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Chapter 3

CONVERSION OF NICOTINE TO NICOTINIC ACID

3.1 NICOTINE - SOURCES AND HEALTH ASPECTS:-

3.1.1 Sources

Animal products: Fruits and

vegetables:

Seeds: Fungi:

liver, heart

and kidney

chicken

beef

fish: tuna,

salmon

milk

eggs

leaf

vegetables

broccoli

tomatoes

carrots

tobacco

leaves

sweet

potatoes

asparagus

avocados

nuts

whole grain

products

legumes

saltbush

seeds

mushrooms

brewer's yeast

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

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function. Smoking results in an elevated incidence of chronic inflammation as a

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 + 9[O] --HNO3--- C6H5NO2 + C2H2O4.H2O + CH3NH2 + CO2

Nicotine Nascent Oxygen 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

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acid and it is extracted and analysis of product is done. Generally beedi tobacco contains

2 to 8 % nicotine. Dry tobacco leaves contain about 5% nicotine combined with citric or

malic acid.

3.2 PHYSICAL PROPERTIES (11)

Sr.

NoName Formula Mol.wt

Form &

colourSp.gravity M.P.0C B.P.0C Solubility in 100 parts

H2O Alcohol Ether

1. Nicotine C10 H14N2 162

Oily

Colourless

Liquid

1.009 < 80 246 Soluble ---- ----

2.Nicotinic acid

(Niacin)C6H5 NO2 123

Colourless

powder1.473 236 Subl

Soluble

hot

Soluble

hot

Very slight

soluble

3. Methyl amine CH3 NH2 31Colourless

gas

0.699 X

10-11-92.5 -6.7

Very

soluble

Very

soluble------

4. Oxalic acidHO2C

CO2H3O126

Colourless

monoclinic1.653 101.5 Subl Soluble Soluble 1.3

5.Carbon

dioxideCO2 44

Colourless

gas1.53 -56.6

Subl.

–78.5

179.7

CC

90.1

CC

Soluble acid

alkali

(aq.NaoH

or KOH)

6. Nitric acid HNO3 63Colourless

Liquid1.502 ---- ----- ------ ----- ---

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.

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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

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 water-

bath, 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

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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

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

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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 ni cotinic ac id + vitam in. Niacin is referred to as Vitamin B3 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.

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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 high-

density 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.

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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 slow-

release 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 life-

threatening 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

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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 Value

Molecular weight 123.11

Melting point 2360 C

Sublimation range >1500 C

Density of Crystals 1.473 gm/cm3

True dissociation constants in water at 250C

Ka 1.5X10-5

Kb 1.04X10-12

pH of saturated aqueous solution 2.7

Solubility of Niacin in Water

At 00 C 8.6 gm/lit.

At 380 C 24.7 gm/lit.

At 1000C 97.6 gm/lit.

Solubility of Niacin in Ethanol,96 %

At 00 C 5.7 gm/lit.

At 780 C 76.0 gm/lit.

Solubility of Niacin in Methanol

At 00 C 63.0 gm/lit.

At 620C 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

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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

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.

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Separation of Binary Mixture By Using Pervaporation

4.7 FUNCTIONS OF VITAMIN B3 NIACIN:-

1. Niacin is important for proper blood circulation and the healthy functioning of the

nervous system.

2. It maintains the normal functions of the gastro-intestinal tract and is essential for the

proper metabolism of proteins and carbohydrates.

3. It helps to maintain a healthy skin.

4. Niacin dilates the blood vessels and increases the flow of blood to the peripheral

capillary system.

5. 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.

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4.9 BIOLOGICAL SYNTHESIS

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.

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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.

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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:

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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.

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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)

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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 B3 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

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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 non-

technical 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.

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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.

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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, long-

term 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 AGE-

RELATED 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)

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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

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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)

FoodServing

SizeCals

Amount

(mg)

DV

(%)

Nutrient

Density

World's

Healthiest

Foods

Rating

Crimini mushrooms, raw 5 oz-wt 31.2 5.39 26.9 15.6 Excellent

Tuna, yellowfin,

baked/broiled4 oz-wt 157.6 13.54 67.7 7.7 Excellent

Tamari (Soy Sauce) 1 tbs 10.8 0.72 3.6 6.0 Good

Chicken breast, roasted 4 oz-wt 223.4 14.41 72.0 5.8 very good

Calf's liver, braised 4 oz-wt 187.1 9.61 48.0 4.6 very good

Halibut, baked/broiled 4 oz-wt 158.8 8.08 40.4 4.6 very good

Asparagus, boiled 1 cup 43.2 1.95 9.8 4.1 very good

Salmon, chinook,

baked/broiled4 oz-wt 261.9 11.34 56.7 3.9 very good

Venison 4 oz-wt 179.2 7.61 38.0 3.8 very good

Romaine lettuce 2 cup 15.7 0.56 2.8 3.2 Good

Lamb loin, roasted 4 oz-wt 229.1 7.75 38.8 3.0 Good

Turkey breast, roasted 4 oz-wt 214.3 7.22 36.1 3.0 Good

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

Shrimp, steamed/boiled 4 oz-wt 112.3 2.94 14.7 2.4 Good

Summer squash, cooked,

slices1 cup 36.0 0.92 4.6 2.3 Good

Green peas, boiled 1 cup 134.4 3.23 16.1 2.2 Good

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Cod, baked/broiled 4 oz-wt 119.1 2.82 14.1 2.1 Good

Collard greens, boiled 1 cup 49.4 1.09 5.5 2.0 Good

Carrots, raw 1 cup 52.5 1.13 5.6 1.9 Good

Broccoli, steamed 1 cup 43.7 0.94 4.7 1.9 Good

Eggplant, cooked, cubes 1 cup 27.7 0.59 3.0 1.9 Good

Peanuts, raw0.25

cup207.0 4.40 22.0 1.9 Good

Spinach, boiled 1 cup 41.4 0.88 4.4 1.9 Good

Fennel, raw, sliced 1 cup 27.0 0.56 2.8 1.9 Good

Turnip greens, cooked 1 cup 28.8 0.59 3.0 1.8 Good

Spelt grains, cooked 4 oz-wt 144.0 2.91 14.6 1.8 Good

Beef tenderloin, lean,

broiled4 oz-wt 240.4 4.44 22.2 1.7 Good

Raspberries 1 cup 60.3 1.10 5.5 1.6 Good

Winter squash, baked,

cubes1 cup 80.0 1.44 7.2 1.6 Good

Swiss chard, boiled 1 cup 35.0 0.63 3.1 1.6 Good

Cauliflower, boiled 1 cup 28.5 0.51 2.5 1.6 Good

Kale, boiled 1 cup 36.4 0.65 3.3 1.6 Good

Green beans, boiled 1 cup 43.8 0.77 3.9 1.6 Good

Mustard seeds 2 tsp 35.0 0.60 3.0 1.5 Good

Cantaloupe, cubes 1 cup 56.0 0.92 4.6 1.5 Good

World's Healthiest

Foods Rating

Rule

excellent DV>=75% OR Density>=7.6 AND DV>=10%

very good DV>=50% OR Density>=3.4 AND DV>=5%

good DV>=25% OR Density>=1.5 AND DV>=2.5%

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Chapter 6

MATERIAL BALANCE

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

6.1.1 Mixing tank:-

5lit of H2O Wet slurry (6 Kg.)

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

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6.1.2 Filtration:-

Wet Tobacco

Wet slurry [i.e.4Kg wet tobacco]

(6 Kg)

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 1040 ml

Filtrate

Waste

360 ml

Overall material balance

Filtrate = Nicotine Solution + Waste

1400 = 1040 + Waste

Waste = 360 ml

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Filtration

Steam Distillation

Separation of Binary Mixture By Using Pervaporation

6.1.4 Separation:-

Nicotine layer

Nicotine solution

(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 Product

Nicotine 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

Separator

Reactor110-115 0 C

30 min

Separation of Binary Mixture By Using Pervaporation

Top Nicotinic acid

(45 gm) layer (36 gm)

Reaction

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 Dry Product

80 % Solid 95 % Solid

20 % Moisture 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

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Accumulator

TrayDryer

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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 Wet Slurry (6 Kg.)

5 lit H2O

1Kg of (T = 580C)

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

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Mixer at 60 0 C

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 Product

of filtrate

(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.

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Steam (110 0C)

Distillation

Separation of Binary Mixture By Using Pervaporation

6.2.3 Oxidation Reactor:

Feed (30 0 C) 45 gm

33mlof Nicotine 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

Reactor

1100C

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 = D 2

Reactor 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 = D 2 X 6 D

4

V = 1.5 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

Thickness is t = PD + C

2 f J

The steel plate IS : 2041- 1962

= 101.325 X 10 3 X 0.2 + 1 X 103

2 X 3.5X106X 0.80

t = 4.62 mm 5mm

The Volume of metal used for constructing the vessel

v = t [ DL + D 2 ]

2

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

v= 40.8 X 10-3 m3

Stoichiometric proportion of Nicotine & HNO3 for oxidation reaction (18)

56

P = 1atm

=101.325 X103 N/m2

D= 0.2 m

F = For Steel plate

allowable stress

= 3.5 X 106N/m2

J = 80%

Separation of Binary Mixture By Using Pervaporation

According to the oxidation reaction

C10H14N2 + 9[O] --HNO3--- C6H5NO2 + C2H2O4.H2O + CH3NH2 + CO2

Nicotine Nascent Oxygen Nicotinic acid Oxalic Acid Ethylamine

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 = 162kg = 0.1605m3

V Density 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

m 189 Kg

57

Separation of Binary Mixture By Using Pervaporation

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 HNO3 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

.

Item Uni

t

Cost /

Unit

Total

Cost(Rs.)

1 Pulverizer 1 200000 200000

2 Mixing Tank 1 3200000 320000

3 Filter press 1 480000 480000

4 Storage Tank 4 4000 16000

5 Steam Distillation

Setup

1 500000 500000

6 Condensor 1 100000 100000

7 Reactor 1 25000 25000

8 Dryer 1 150000 150000

Total ( E ) 1791000

8.2 FIXED CAPITAL INVESTMENT:-

8.2.1 Direct Cost:-

Sr.No

.

Item %

E

Cost

(Rs.)

1 Purchase Equipment Cost E 1791000

2 Equipment Installation 30 537300

3 Instrumentation & Control 15 268650

4 Piping Cost 15 268650

5 Electrical Fitting Cost 5 89550

6 Building Construction & Other

Services

40 716400

7 Yard Investment 3 53730

59

Separation of Binary Mixture By Using Pervaporation

8 Land 30 537300

Total Direct Plant Cost (D) 4262580

60

Separation of Binary Mixture By Using Pervaporation

8.2.2 Indirect Cost:-

Sr.No

.

Item %

E

Cost

(Rs.)

1 Engineering & Supervision

Cost

17 304470

2 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

.

Raw Material Quantity/

Batch

Cost/ Kg Cost

(Rs.)

1 Waste Tobacco 500 Kg. Rs. 30 / Kg 15000

2 NaoH 5 Kg. Rs.180 / Kg 900

3 50 % HNO3 16.5 lit. Rs. 225 /

lit.

3713

Raw Material

Cost

19613

61

Separation of Binary Mixture By Using Pervaporation

For one day three batches

Therefore raw material cost per day = 19613 X 3

= 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

62

Separation of Binary Mixture By Using Pervaporation

= Rs. 1089000

63

Separation of Binary Mixture By Using Pervaporation

8.4 OPERATING LABOUR COST:-

Post Number Salary /

month

Total

salary

General Manager 1 Rs. 15000 Rs. 15000

Engineer 2 Rs. 10000 Rs.20000

Skilled Worker 4 Rs. 5000 Rs.20000

Unskilled Worker 4 Rs. 3000 Rs.12000

Clerk 1 Rs. 3000 Rs.3000

Administrative

staff

2 Rs.3500 Rs.7000

Total Labour

Cost

Rs.77000

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.

64

Separation of Binary Mixture By Using Pervaporation

D.P.C. = 1765170 + 1089000 + 78925 + 78925 + 26986

= Rs. 2967974 / month

65

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

66

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)

67

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

68

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: -

69

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)

70

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.

71

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

72

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.

73

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)

74

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.

75

Separation of Binary Mixture By Using Pervaporation

INDEX

1 INTRODUCTION TO TOBACCO 1

1.1 History of tobacco: 1

1.2 Utilization of Tobacco: 1

1.3 Tobacco post harvest practices: 2

1.4 Nicotine content of tobacco: 2

1.5 Tobacco waste sources: 2

1.6 Availability of tobacco waste: 2

1.7 Chemical constituents of tobacco: 3

1.8 Nicotine alkaloids of tobacco: 3

1.9 Role of tobacco products in the economy: 3

1.10 Recommendations: 4

1.11 Properties of Tobacco Content:- 5

1.12 DIESEASES FROM TOBACCO 7

1.12 .1 Cancers of the urinary tract 7

1.12.2 Occupational exposure to cigarette smoke 7

1.12.3 Passive smoking 8

1.12.4 Nicotine induced nephropathies 8

1.12.5 Associated influence of nicotine on the nervous system 9

1.12.6 Should nicotine be removed from combustion tobacco products? 9

2 LITERATURE SURVEY 10

2.1 Different methods for niacin 10

2.1.1 Liquid phase oxidation of Nicotine using Chromic acid: - 10

2.1.2 Liquid phase oxidation of MEP (2-methyl-5-ethylpyridine) with nitric acid or

air: - 11

2.1.3 Liquid-Phase oxidation of 3-Picoline with Oxygen: - 11

2.1.4 Gas phase oxidation of Picoline to Nicotinic acid: - 12

2.1.5 Gas- Phase oxidation of Picoline to Cyanopyridine:- 12

2.1.6 Commercial method followed by “Amsal Chemical Pvt. Ltd. Ankaleshwar:- 12

2.2 Review Article 13

2.2.1 Effect of tobacco smoking on renal function:- 13

76

Separation of Binary Mixture By Using Pervaporation

2.2.2 Past work: 13

2.2.3 Indian J Med Res 124, September 2006, pp 261-268 14

2.3 Non-Addictive Tobacco Products:- 14

2.3.2. Brief Description of the Related Art 15

2.4 Objectives Of The Invention 17

2.5 Summary Of The Invention 18

3 CONVERSION OF NICOTINE TO NICOTINIC ACID 22

3.1 Nicotine - sources and health aspects:- 22

3.1.1 Food sources 22

3.1.2 Reaction: 23

3.2 Physical Properties: 24

3.3 Process Description:- 24

3.2.1 Nicotine consumption 25

3.2.2 Nicotine addiction and metabolism 26

4.NIACIN 27

4.1 History 27

4.2 Dietary needs 27

4.3 Properties: 27

4.3 Pharmacological uses:- 28

4.4 Toxicity 28

4.5 Biosynthesis 29

4.6 Physical Properties of Nicotinic Acid (12):- 30

4.7 Functions of Vitamin B3 Niacin:- 32

4.8 Chemical Structure 32

4.9 Biological Synthesis 33

4.10 Sources 33

4.11 Source Categories: 34

4.12 Deficiency Disease: 34

4.13 Identification Tests for Niacin:- 34

4.14 Precautions: 34

4.14 Niacin Analogues:- 35

77

Separation of Binary Mixture By Using Pervaporation

4.15 Vitamin B3 Uses 36

5.IMPORTANTS OF NIACIN 38

5.1 Requirements: 38

5.2 Function of vitamin B3 40

5.3 Metabolism of Fats 40

5.4 Support of genetic processes 40

5.5 Deficiency Symptoms 41

5.6 Toxicity Symptoms 41

5.7 Factors that Affect Function 41

5.8 Niacin Protects against Alzheimer's disease and Age-related Cognitive Decline 41

5.9 Form in Dietary Supplements 42

5.10 Introduction to Nutrient Rating System Chart 42

6.MATERIAL BALANCE 45

6.1 Basic: 1 Kg of tobacco powder per batch 45

6.1.1 Mixing tank:- 45

6.1.2 Filtration:- 46

6.1.3 Steam Distillation:- 46

6.1.4 Separation:- 47

6.1.5 Oxidation Reaction:- 47

6.1.6 Drying:- 48

6.2 Energy Balance 49

6.2.1 Mixing Tank: 49

6.2.2 Steam Distillation: 50

6.2.3 Oxidation Reactor : 51

7.REACTOR DESIGN 52

8.COST ESTIMATION 56

8.1 Cost of Equipment:- 56

8.2 Fixed Capital Investment:- 56

8.2.1 Direct Cost:- 56

8.2.2 Indirect Cost:- 57

8.3 Total Production Cost:- 57

78

Separation of Binary Mixture By Using Pervaporation

8.3.1 Direct Production Cost:- 57

8.3.2 Utilities:- 58

8.4 Operating Labour Cost:- 59

9.PLANT LAYOUT 62

10.CONCLUSION 65

FUTURE PROSPECTS 67

REFERENCES 68

79

Separation of Binary Mixture By Using Pervaporation

LIST OF TABLE

SR.

NO.

DESCRIPTION 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

43, 44

80