I.

Introduction

The air around us is a mixture of gases, mainly nitrogen and oxygen, but containing much

smaller amounts of water vapor, argon, and carbon dioxide, and very small amounts of other

gases. Air also contains suspended dust, spores, and bacteria. Because of the action of wind, the

percent composition of air varies only slightly with altitude and location. Air is the commercial

source for many of the gases it contains. It is separated into its components by fractional

distillation of liquefied air. Before air is liquefied, water vapor and carbon dioxide are removed,

because these substances solidify when cooled and would clog the pipes of the air liquefaction

plant. The dry, CO2-free air is compressed to about 200 atmospheres. This compression causes

the air to become warm, and the heat is removed by passing the compressed air through

radiators. The cooled, compressed air is then allowed to expand rapidly. The rapid expansion

causes the air to become cold, so cold that some of it condenses. By the alternate compressing

and expanding of air, most of it can be liquefied.

Nitrogen is obtained from liquid air by distillation at -196C. The gas obtained by this

process is actually a mixture of nitrogen and about 1.25% noble (or inert) gases, argon, neon,

krypton, and xenon. Its major uses are as an inert blanketing atmosphere in chemical processing

(14%), electronics (15%), and, in liquid form, as a freezing agent (21%). Nitrogen is used to

make agricultural fertilizers, such as ammonia and nitrates. It is also used in the production of

acrylonitrile, CH2=CHCN, which is important in the manufacture of synthetic fibers such as

Orlon, and in the production of cyanamide, HN=C=NH, which is polymerized to Melamine

plastic. Because it is a very poor oxidizing agent, nitrogen is used to pack oxidizable foods, such

as ground coffee, and as an inert atmosphere in the manufacture of electronic components.

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Liquefied nitrogen, because it is very cold, is used extensively to chill materials for preservation,

as in freeze-drying of foods, and in manufacturing processes that require low temperatures, such

as machining of aluminum. Most of the nitrogen produced each year is converted to ammonia,

and one third of that goes to make nitric acid, for use in the fertilizer and explosives industries.

N2 gas is used as an inert atmosphere in the manufacture of semiconductors and glass.

Coffee is the second most consumed beverage in the Philippines next to water. There is

approximately 22 million cups of coffee consumed by Filipinos in a day; with that said, there is a

significant rise in coffee production and consumption. Here in the Philippines, robusta coffee

beans (Coffea canophera) are the most common type used in the manufacturing of instant coffee,

making up around 90% of the total coffee production. As a consequence of this big market,

theres an increase in the coffee waste (including spent coffee grounds) generation. Thus, waste

management and new treatment development or valorization strategies, should be viable both

technically and economically.

Spent Coffee Grounds (SCG) are the residual material obtained during the treatment of

coffee powder with hot water or steam for the instant coffee preparation. Fortunately, there are

many possible ways to reuse this kind of waste. This can be used as compost and fertilizer since

coffee grounds are rich in nitrogen and potassium which is necessary in plant growth. Another

possible way is to use this as a source for the production of biodiesel because it contains oil that

can be converted to biodiesel via trans-esterification methods.

Oxygen is the third most abundant element in the universe and makes up nearly 21% of

the earth's atmosphere. About one-half of the earth's crust is made up of chemical compounds

3
containing oxygen, two thirds of the mass of the human body, nine tenths of the mass of water,

and a fifth of our atmosphere is oxygen gas. Although oxygen has been present since the

beginning of scientific investigation, it wasn't discovered and recognized as a separate element

until 1774 by Joseph Priestley of England. Oxygen is one of the basic chemical elements. In its

most common form, oxygen is a colorless gas found in air. It is one of the life-sustaining

elements on Earth and is needed by all animals. Oxygen is a highly reactive element and is

capable of combining with most other elements. It is required by most living organisms and for

most forms of combustion. It is used in many industrial, commercial, medical, and scientific

applications. It is used in blast furnaces to make steel, and is an important component in the

production of many synthetic chemicals, including ammonia, alcohols, and various plastics.

Ozone (O3) forms a thin, protective layer around the earth that shields the surface from the sun's

ultraviolet radiation. Oxygen is also a component of hundreds of thousands of organic

compounds. When oxygen is cooled below -297 F (-183 C), it becomes a pale blue liquid that

is used as a rocket fuel.

Oxygen can be produced from a number of materials, using several different methods.

The most common natural method is photo-synthesis, in which plants use sunlight convert

carbon dioxide in the air into oxygen. This offsets the respiration process, in which animals

convert oxygen in the air back into carbon dioxide. The most common commercial method for

producing oxygen is the separation of air using either a cryogenic distillation process originally

developed in 1895 which produces oxygen that is 99+% pure, or a vacuum swing adsorption

process that has been used for a limited number of applications that do not require oxygen with

more than 90-93% purity. Oxygen can also be produced as the result of a chemical reaction in

4
which oxygen is freed from a chemical compound and becomes a gas. This method is used to

generate limited quantities of oxygen for life support on submarines, aircraft, and spacecraft.

Large amounts of oxygen can be extracted from liquefied air through a process known as

fractional distillation. Oxygen can also be produced through the electrolysis of water and

collecting the two gases as they bubble off. Hydrogen forms at the negative terminal and oxygen

at the positive terminal. This method produces very pure hydrogen and oxygen. It uses a large

amount of electrical energy, however, and is not economical for large-volume production.

Nitric Acid, HNO3, also called as aqua fortis is a colorless to yellowish liquid; and a

highly corrosive and poisonous chemical that can react with water or steam to produce heat,

toxins, and corrosive & flammable vapors. It is an important industrial chemical for the

manufacturing of fertilizers, dyes, drugs, plastics, and explosives. There are three main stages for

the production of nitric acid - commonly known as The Oswald Process. These stages are: the

Catalytic Combustion, Oxidation of Nitric Oxide (NO), and Absorption. Catalytic Combustion is

a chemical process which uses a catalyst to speed the desired oxidation reactions of a fuel and to

reduce the formation of undesired products. It occurs when ammonia gas is successively

oxidized to nitric oxide and nitrogen dioxide by air or oxygen in the presence of a platinum

gauze catalyst. The next stage is the oxidation of nitric oxide. In this stage, nitric oxide is reacted

to oxygen in air to form nitrogen dioxide. As a result of this process, part of the nitric oxide is

oxidized to nitrogen dioxide and dinitrogen tetroxide (N2O4). Lastly, absorption occurs when

nitrogen dioxide is subsequently absorbed in water to form nitric acid and nitric oxide.

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 Aside from the Oswald process, there are other possible processes for the production of

nitric acid like reacting nitrogen dioxide with water. Another process is thru the bubbling of

nitrogen dioxide through hydrogen peroxide (H2O2) which is cheaper and can also help to

improve acid yield. Among the many important reactions of nitric acid are: neutralization with

ammonia to form ammonium nitrate, used widely in fertilizers and explosives; nitration of

glycerol and toluene, forming the explosives nitroglycerin and trinitrotoluene, respectively;

preparation of nitrocellulose; and oxidation of metals to the corresponding oxides or nitrates.

The process for the production of nitric acid using spent coffee grounds as combustion

fuel is one way to eliminate waste from instant coffee industry. This process can be considered

environment friendly since nitric oxide is recycled and carbon monoxide and carbon dioxide

cannot be considered as waste since it is deposited in the sea bed. The supply of raw materials

will not be a problem since the nitrogen in air is abundant, and theres a growing number of

coffee waste not only in the Philippines but also worldwide.

This plant design technically describes the needed information in the production of nitric

acid using the nitrogen from air with spent coffee grounds used as the fuel in combustion. This

plant design will thoroughly illustrate the processes, equipment, and cost data. The proposed

design is possible to be one of the fundamentals for the industrial development here in the

Philippines.

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 II. Product Profile

A. Main Product

Nitric Acid

Nitric acid is a colorless to slightly yellow liquid, and is a strong oxidizing

organic acid. Commercial nitric acid concentrations are available at a 59-70 % m/m

range. Combustion of nitric acid occurs on contact with a variety of organic substances

such as acetones, acetic anhydrides, alcohols, amines, dichloromethane, and aromatic

compounds. Nitric acid also reacts violently with bases, metallic powders, reducing

agents, carbides and other combustible organic substances.

A.1. Product Information

A.1.1 Technical Specification

Product Identification

Common synonyms Aqua Fortis, Azotic acid, Hydrogen nitrate

Molecular formula HNO3

Chemical Structure ONOOH

A.1.2 Sales Specification

Sales specification

Properties Guarantee Characteristics

Nitric Acid Content 59.0 to 60.0% m/m

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 Balance H2O

Nitrous Acid Content <50ppm m/m

Combined ammonia content <5ppm m/m

Chloride as Cl <1ppm m/m

Flouride as F <0.3 ppm m/m

Sulphate as H2SO4 <2ppm m/m

Calcination residue <50ppm m/m

Grade Industrial

A.2. Product Composition

Chemical Properties

Parameter Typical

Nitric Acid, % 56-64

Water Balance

Chlorides, ppm <50

Iron, ppm <10

Sulfates, ppm <10

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A.3. Product Properties

A.3.1 Physical Properties

Physical Properties

Parameter Specification

Appearance Clear to colorless to slight brown liquid

Physical state Liquid

Odor Acrid, suffocating odor

Odor Threshold Unknown

Specific Gravity 1.4200

Ph 1

Melting Point/ Freezing Point -42C (-44F)

Boiling Point Range 122C (252F)

Vapor Pressure 10mmHg (25C)

Vapor Density 2.5 (air =1 )

Solubility Completely soluble in water

Partition coefficient/n-octane/water -2.3 at 25C

A.3.2 Chemical Properties

Chemical Name Nitric Acid

Chemical Formula HNO3

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 A.3.3 Stability and Reactivity

Stability and Reactivity

Stability Stable

Conditions to avoid Uncontrolled addition of water, contact

with combustible materials.

Incompatibility Moisture, bases, organic material, metals,

hydrogen sulfide, carbides, alcohols,

organic solvents, carbides, cyanides,

sulfides.

Hazardous decomposition products Oxides of nitrogen

A.4. Uses of Nitric Acid

Nitric acid is used in a wide range of industries. The most common of which are the

production of nitrogen fertilizers & jet propellant, explosives, and in chemical and

pharmaceutical industries. In line with this, nitric acids corrosive properties are explored in

several ways, including pickling stainless steel which is commonly used by artists for etching

metals. Furthermore certain strong cleaning products use about 30% nitric acid.

One important use for nitric acid is the

manufacture of various organic nitro

Production of Explosives
compounds, especially explosives, such as

trinitrotoluene (TNT), nitrocellulose and

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 nitroglycerin.

Nitroglycerin is the nitric acid triester of

glycerol and is more correctly called glycerol

trinitrate. It is mixed with an absorbent material

to form dynamite and is also used as a

component of smokeless powder (Chemical

Land 21 , 2014).

Fertilizers replace the chemical components

that are taken from the soil by growing plants.

The presence of nitrates in the soil is of great

importance, since it is from these compounds

Fertilizers
that plants obtain the nitrogen necessary for

their growth. Most nitrogen fertilizers were

synthesized through oxidation of ammonia.

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 Nitric acid is used as an oxidizer

in liquid-fueled rockets with HF

inhibitor. It can be red fuming

nitric acid, white fuming nitric

acid, mixtures with sulfuric acid.

Certain propellant combinations

Rocket Propellant
are hypergolic; that is, they ignite

spontaneously upon contact of the

fuel and oxidizer (National

Aerounotics and Space

Administration, 2014).

The chemical industry mostly

uses nitric acid to produce

ammonia and pharmaceutical

Chemical and Pharmaceutical Industry industry uses this ammonia in the

manufacture of certain products

such as sulfa drugs, vitamins and

cosmetics

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A.5. Packaging, Handling, Storage and Transportation

For Storage tanks:

Storing nitric acid in carbon steel is not

recommended.

Store nitric acid in tightly closed containers, in

a well-ventilated area away from light, organic

Handling and Storage substances, caustic materials, and combustible

materials it should be stored below 0 C to

avoid decomposition.

Avoid vapor inhalation, skin and eye contact.

Reacts explosively with metallic powders,

carbides, cyanides, sulfides, alkalis, and

turpentine.

Strong oxidant and reacts violently with

combustible and reducing materials (e.g.,

turpentine, charcoal, alcohol).

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 Road and Rail Transport

Steel tank wagons or isotanks

Marine Transport

Steel tank barges or isotanks

Air Transport

Glass or earthenware not over 2.5

Product Packaging
L (0.66 gallon) capacity;

Plastic not over 2.5 L (0.66 gallon)

capacity further individually over

packed in tightly closed metal

packaging; or glass ampoule not

over 0.5 L (0.1 gallon) capacity.

Isotanks

Transported under a hazard

Transportation
classification 8.

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III. Raw Materials Profile

A. Air

The common name given to the atmospheric gases used in breathing and photosynthesis

is air. The air around us is a mixture of gases; by volume, dry air contains 78.09% nitrogen,

20.95% oxygen, 0.93% argon, 0.039% carbon dioxide, and small amounts of other gases. Air

also contains suspended dust, spores, and bacteria. Because of the action of wind, the percent

composition of air varies only slightly with altitude and location. Air also contains a variable

amount of water vapor, on average around 1% at sea level, and 0.4% over the entire atmosphere.

Although air content and atmospheric pressure vary at different layers, air suitable for the

survival of terrestrial plants and terrestrial animals currently is only known to be found in Earth's

troposphere and artificial atmospheres. In our study, air will be used for the combustion of NO2

and NO to produce nitric acid.

A.1. Raw Material Information

A.1.3 Raw Material Composition

Compounds Composition by weight

Oxygen 20.95 21.00 %

Nitrogen 78.08 79.00 %

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 A.1.4 Raw Material Profile

A.1.4.1 Physical Properties

Molecular weight 18.02 g/mole

Physical state Gas

Color Colorless

Odor Odorless

Boiling point -194.3C (-317.7F)

Freezing point -216.2C (-357.2F)

Vapor density Highest known value: 1.1 (Air = 1)

(oxygen).

A.1.4.2 Chemical Properties

Chemical Name Air

Substance/mixture Mixture

Chemical Stability Stable

A.2. Raw Material Use

Use

The nitrogen in air will be used as the main raw material in the production of nitric

acid.

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A.3. Transport, Handling and Storage

Store in a dry, cool, well-ventilated

place. Use equipment rated for cylinder

pressure. Keep container tightly closed

and sealed until ready for use. Cylinders

Storage should be stored upright, with valve

protection cap in place. Cylinder

temperatures should not exceed 52 C

(125 F).

Protect from sunlight. Put proper

personal protective equipment when

handling. Do not puncture or incinerate

Handling container. Protect cylinders from

physical damage; do not drag, roll, slide,

or drop.

Use a suitable hand truck for cylinder

Transport movement.

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B. Deionized Water

A water molecule consists of one atom of oxygen bound to two atoms of hydrogen. Water is

called the "universal solvent" because it dissolves more substances than any other liquid. This

means that wherever water goes, either through the ground or through our bodies, it takes along

valuable chemicals, minerals, and nutrients. Water appears in nature in all three common states

of matter (solid, liquid, and gas) and may take many different forms on Earth: water vapor and

clouds in the sky, seawater in the oceans, icebergs in the polar oceans, glaciers and rivers in the

mountains, and the liquid in aquifers in the ground.

B.1 Raw Material Information

B.1.1 Raw Material Information

Classification of water to be used Deionized

B.1.2 Raw Material Profile

B.1.2.1 Physical Properties

Molecular weight 18.02 g/mole

Physical state Liquid

Color Colorless, clear

Boiling point 100C (212F)

Freezing point 0C (32F)

Specific gravity 1 (Water=1)

Vapor pressure 2.3kPa at 20C

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 B.1.2.2 Chemical Properties

Chemical Name Water

Chemical Formula H2O

Synonym Dihydrogen oxide

Chemical Stability Stable

Ph 7

B.2 Raw Material Use

Use

Water will be used as a reactant with dinitrogen tetroxide to produce nitric acid and

nitric oxide.

B.3 Storage, Handling and Transport

Keep in tanks tightly closed place in a

dry, cool and well ventilated place.

Storage Water will be stored in storage tanks.

Suitable for any general chemical

storage area.

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 Handle in accordance with good

industrial hygiene and safety practice.

Protect from freezing. Water is

considered a non-regulated product,

Handling
but may react vigorously with some

specific materials. Avoid contact with

all materials until investigation shows

substance is compatible.

C. Commercial Grade Oxygen

Oxygen was discovered in 1774 by Joseph Priestley in England. It is a chemical element

with symbol O and atomic number 8. It is a member of the chalcogen group on the periodic table

and is a highly reactive nonmetallic element and oxidizing agent that readily forms compounds

(notably oxides) with most elements except noble gases. In its common form, (O2) is a colorless,

odorless and tasteless diatomic gas. Liquid and solid oxygen are pale blue and are strongly

paramagnetic. Large amounts of oxygen can be extracted from liquefied air through a process

known as fractional distillation. Oxygen is the third most abundant element in the universe and

makes up nearly 21% of the earth's atmosphere. Oxygen accounts for nearly half of the mass of

the earth's crust, two thirds of the mass of the human body and nine tenths of the mass of water.

It is required by most living organisms and for most forms of combustion. Oxygen dissolves

more readily in cold water than warm water. As a result of this, our planets cool, polar oceans

are denser with life than the warmer, tropical oceans

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C.1 Raw Material Information

C.1.1 Raw Material Composition

Compounds Composition by weight

Oxygen 100%

C.1.2 Raw Material Profile

C.1.2.1 Physical Properties

Molecular weight 32.0 g/mole

Physical state Gas

Color Colorless

Boiling point -183.0C (-297.3F, 1atm)

Freezing point -361.9 F (-218.8 C)

Specific gravity 1.105 g/ml @21.1C (air=1)

Vapor pressure Not applicable

Vapor density (at 1 atm) 0.083 lb /ft3 (1.326 g/ml) @ 70F (21.1C)

C.1.2.2 Chemical Properties

Chemical Name Oxygen

Chemical Formula O2

Synonyms Dioxygen

Chemical Stability Stable

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C.2 Raw Material Use

Use

Oxygen will be used for the oxidation of Nitric oxide and Nitric dioxide.

C.3 Storage, Handling and Transport

Use equipment rated for cylinder pressure. Store in

tightly-closed container. Cylinder tanks should be

stored upright with valve protection cap. Place in a

Storage cool, well-ventilated area. Separate from acid,

alkalis, reducing agents and any combustibles.

Cylinder temperatures should not exceed 52 C

(125 F).

Avoid contact with combustible materials. Protect

cylinders from physical damage. Do not drag, roll,

slide, or drop. Do not puncture or incinerate

containers. Never allow any unprotected part of the

Handling
body to touch uninsulated pipes or vessels of

cryogenic liquids. Prevent entrapment of liquid in

closed systems or piping without pressure relief

apparatus.

Use a suitable hand truck for container movement or

Transport
transportation.

22
D. Combustion Fuel: Spent Coffee Grounds

Spent coffee grounds are the by-products of brewed coffee production. The spent

Robusta coffee waste from the production of instant coffee contains large amounts of organic

compounds and is a resource for various valuable compounds that rationalize its valorization.

Thereby, coffee residue has been investigated as a good combustion fuel.

D.1 Raw Material Information

D.1.1 Raw Material Composition

Elemental Composition

Elements Composition by Weight

Carbon 53.60 55.43 %

Hydrogen 7.77 8.87 %

Oxygen 32.53 36.46 %

Nitrogen 2.17 3.17 %

Chemical Composition

Compounds Composition by Weight

Dicholoromethane 19.67 25.41 %

Ethanol 3.42 5.36 %

Water 0.89 1.30 %

NaOH (1%) 25.10 26.06 %

Polysaccharides 22.00 24.13 %

Lignin 19.84 26.51 %

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 D.1.2 Technical Specifications

Physical and Chemical Properties of Spent Coffee Grounds

Physical state Solid

Size Fine grind

Colour Dark brown to black

Texture Granular

Odour Phenolic, buttery, caramel-like

Calorific Value 4629 MJ/Kg

Density 0.35g/mL

pH 4.9-5.2

Melting point 235C

D.2 Raw Material Use

Use

The nitric acid from the extraction of spent Robusta coffee grounds from instant coffee

manufacture will be used as the combustion fuel in the production of commercial-

grade nitric acid.

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D.3 Storage, Handling and Transport

Coffee grounds must be placed in a dry and dark plastic

Storage container at room temperature.

Store in a cool, dry and well ventilated place.

The raw material is available in dark plastic sacks and

properly sealed.
Handling
Avoid spilling.

Avoid the coffee grounds from getting wet.

The pile of plastic sacks that contains the coffee grounds

Transport should be transported in a suitable truck or container with

low moisture.

25