UNIVERSITY OF BENIN

P.M.B. 1154

BENIN CITY, NIGERIA

DEPARTMENT OF CHEMICAL ENGINEERING

CHE581 – CHEMICAL PROCESS INDUSTRIES

A GROUP PRESENTATION

On

“THE INDUSTRIAL PRODUCTION OF PESTICIDES

(A CASE STUDY ON BORIC ACID INSECTICIDE)”

By

GROUP 2

Course Instructor: Dr. (Mrs) E. T. Akhihiero

10TH NOVEMBER, 2016

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 GROUP MEMBERS

NAMES MAT. NO.

 Maxwell A. AGAGBO ENG1202648

 Daye Ugochukwu AGALI ENG1202649

 Stanley Erere AGBAHOWE ENG1202650

 Jeffrey Ede AIGBOVBIOSA ENG1202651

 Godstand AIMIUWU ENG1202652

 Omowaleola O. AKERELE ENG1202653

 Ehijiator AMAGBEWAN ENG1202657

 Adekunle James AROWOPEONILU ENG1202659

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 TABLE OF CONTENTS

Sections Page

Title Page

Group Members

Table of Contents

1. Abstract

2. Introduction

3. Classification of Pesticides

4. Uses of Pesticides

5. Benefits of Pesticides

6. Boric Acid

6.1. Occurrence of Boric Acid

6.2. Laboratory Preparation of Boric Acid

6.3. Some Properties of Boric Acid

6.4. Insecticidal Use of Boric Acid

7. The Industrial Manufacture of Boric Acid Insecticide

7.1. Raw Materials Required

7.2. By-Products of the Process

7.3. Equation of the Reaction

7.4. Process Description

7.5. Images of the Process Equipment Used

8. Conclusion

References

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1. Abstract

The study was based on the production processes involved in the industrial manufacture
of pesticides, using Boric acid insecticide as a case study. The general term pesticides, was
seen to include a wide variety of substances which are used for the general protection and
preservation of farm produce (food and cash crops) and other goods liable to the attack from
different kinds of pests (plants or animals). Each class of pesticide has specific actions and
target pests. Boric acid, the case study of this work, was seen to be relatively cheap and easy
to produce with majorly physical steps and just one chemical step involved.

2. Introduction

Pesticides are substances meant for attracting, seducing, and then destroying any pest.
They are a class of biocide. The most common use of pesticides is as plant protection
products (also known as crop protection products), which in general protect plants from
damaging influences such as weeds, fungi, or insects. This use of pesticides is so common
that the term pesticide is often treated as synonymous with plant protection product, although
it is in fact a broader term, as pesticides are also used for non-agricultural purposes. Hence,
the term pesticide includes all of the following: herbicide, insecticide, insect growth
regulator, nematicide, termiticide, molluscicide, piscicide, avicide, rodenticide, predacide,
bactericide, insect repellent, animal repellent, antimicrobial, fungicide, disinfectant
(antimicrobial), and sanitizer.

In general, a pesticide is a chemical or biological agent (such as a virus, bacterium,

antimicrobial, or disinfectant) that deters, incapacitates, kills, or otherwise discourages pests.
Target pests can include insects, plant pathogens, weeds, molluscs, birds, mammals, fish,
nematodes (roundworms), and microbes that destroy property, cause nuisance, or spread
disease, or are disease vectors. The Food and Agriculture Organization (FAO) has defined
pesticide as

“any substance or mixture of substances intended for preventing, destroying, or controlling

any pest, including vectors of human or animal disease, unwanted species of plants or
animals, causing harm during or otherwise interfering with the production, processing,
storage, transport, or marketing of food, agricultural commodities, wood and wood products

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 or animal feedstuffs, or substances that may be administered to animals for the control of
insects, arachnids, or other pests in or on their bodies. The term includes substances
intended for use as a plant growth regulator, defoliant, desiccant, or agent for thinning fruit
or preventing the premature fall of fruit. Also used as substances applied to crops either
before or after harvest to protect the commodity from deterioration during storage and
transport”.

Although pesticides have benefits, some also have drawbacks, such as potential toxicity
to humans and other species. According to the Stockholm Convention on Persistent Organic
Pollutants, 9 of the 12 most dangerous and persistent organic chemicals are organochlorine
pesticides.

3. Classification of Pesticides

Pesticides can be classified by target organism (e.g herbicides, insecticides, fungicides,

rodenticides, and pediculicides), chemical structure (e.g., organic, inorganic, synthetic, or
biological (biopesticide), although the distinction can sometimes be blur), and physical state
(e.g. gaseous (fumigant)). Biopesticides include microbial pesticides and biochemical
pesticides. Plant-derived pesticides, or "botanicals", have been developing quickly. These
include the pyrethroids, rotenoids, nicotinoids, and a fourth group that includes strychnine
and scilliroside.

Table 1. Classes of Pesticides and their targets

Class of pesticide Action

Algicides Control algae in lakes, canals, swimming pools, water tanks, and
other sites.
Antifouling agents Kill or repel organisms that attach to underwater surfaces, such as
boat bottoms.
Antimicrobials Kill microorganisms (such as bacteria and viruses).
Attractants Attract pests (for example, to lure an insect or rodent to a trap).
(However, food is not considered a pesticide when used as an
attractant).
Biopesticides are certain types of pesticides derived from such

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 Biopesticides natural materials as animals, plants, bacteria, and certain
minerals.
Kill microorganisms.
Biocides Kill or inactivate disease-producing microorganisms on inanimate
Disinfectants and objects.
sanitizers Kill fungi (including blights, mildews, moulds, and rusts).
Fungicides Produce gas or vapour intended to destroy pests in buildings or
Fumigants soil.
Kill weeds and other plants that grow where they are not wanted.
Herbicides Kill insects and other arthropods.
Insecticides Kill mites that feed on plants and animals.
Miticides Microorganisms that kill, inhibit, or out compete pests, including
Microbial pesticides insects or other microorganisms.
Kill snails and slugs.
Molluscicides Kill nematodes (microscopic, worm-like organisms that feed on
Nematicides plant roots).
Kill eggs of insects and mites.
Ovicides Biochemicals used to disrupt the mating behaviour of insects.
Pheromones Repel pests, including insects (such as mosquitoes) and birds.
Repellents Control mice and other rodents.
Rodenticides

Pesticides can be also be classified based upon their biological mechanism function or
application method. Most pesticides work by poisoning pests. A systemic pesticide moves
inside a plant following absorption by the plant. With insecticides and most fungicides, this
movement is usually upward (through the xylem) and outward. Increased efficiency may be a
result. Systemic insecticides, which poison pollen and nectar in the flowers, may kill bees and
other needed pollinators.

4. Uses of Pesticides

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 Pesticides are used to control organisms that are considered to be harmful. For example,
they are used to kill mosquitoes that can transmit potentially deadly diseases like West Nile
virus, yellow fever, and malaria. They can also kill bees, wasps or ants that can cause allergic
reactions. Insecticides can protect animals from illnesses that can be caused by parasites such
as fleas. Pesticides can prevent sickness in humans that could be caused by mouldy food or
diseased produce. Herbicides can be used to clear roadside weeds, trees and brush. They can
also kill invasive weeds that may cause environmental damage. Herbicides are commonly
applied in ponds and lakes to control algae and plants such as water grasses that can interfere
with activities like swimming and fishing and cause the water to look or smell unpleasant.
Uncontrolled pests such as termites and mould can damage structures such as houses.
Pesticides are used in grocery stores and food storage facilities to manage rodents and insects
that infest food such as grain. Each use of a pesticide carries some associated risk. Proper
pesticide use decreases these associated risks to a level deemed acceptable by pesticide
regulatory agencies such as the United States Environmental Protection Agency (EPA) and
the Pest Management Regulatory Agency (PMRA) of Canada.

5. Benefits of Pesticides

The following are some of the benefits of using pesticides:

(1) Controlling pests and plant disease vectors
 Improved crop/livestock yields
 Improved crop/livestock quality
 Invasive species controlled

(2) Controlling human/livestock disease vectors and nuisance organisms

 Human lives saved and suffering reduced

 Animal lives saved and suffering reduced
 Diseases contained geographically

(3) Controlling organisms that harm other human activities and structures

 Drivers view unobstructed

 Tree/brush/leaf hazards prevented

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  Wooden structures protected

In this study, we shall be investigating the process involved in the industrial production
of a particularly very common insecticide, in the form of Boric acid.

6. Boric Acid

Boric acid, also called Hydrogen borate, Boracic acid, Orthoboric acid and acidum
boricum, is a weak, monobasic Lewis acid of boron often used as an antiseptic, insecticide,
flame retardant, neutron absorber, or precursor to other chemical compounds. It has the
chemical formula H3BO3 (sometimes written B(OH)3), and exists in the form of colourless
crystals or a white powder that dissolves in water.

Fig. 1. Boric acid structural formulae and its 3-Dimensional representation

6.1. Occurrence of Boric Acid

Boric acid, or sassolite, is found natively in its free state in some volcanic districts, for
example, in the Italian region of Tuscany, the Lipari Islands and the US state of Nevada. In
these volcanic settings it issues, mixed with steam, from fissures in the ground. It is also
found as a constituent of many naturally occurring minerals – borax, boracite, ulexite
(boronatrocalcite) and colemanite. Boric acid and its salts are found in seawater. It is also
found in plants, including almost all fruits.

Boric acid was first prepared by Wilhelm Homberg (1652–1715) from borax, by the
action of mineral acids, and was given the name sal sedativum Hombergi (i.e sedative salt of
Homberg). However borates, including boric acid, have been used since the time of the
Greeks for cleaning, preserving food, and other activities.

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6.2. Laboratory Preparation of Boric Acid

Boric acid may be prepared by reacting borax (sodium tetraborate decahydrate) with a
mineral acid, such as hydrochloric acid:

Na2B4O7·10H2O + 2HCl → 4B(OH)3 [or H3BO3] + 2NaCl + 5H2O

It is also formed as a by product of hydrolysis of boron trihalides and diborane:

B2H6 + 6H2O → 2B(OH)3 + 6H2

BX3 + 3H2O → B(OH)3 + 3HX (X = Cl, Br, I)

6.3. Some Properties of Boric Acid

 Boric acid is soluble in boiling water. When heated above 170 °C, it dehydrates,
forming metaboric acid (HBO2):

H3BO3 → HBO2 + H2O

 Metaboric acid is a white, cubic crystalline solid and is only slightly soluble in water.
Metaboric acid melts at about 236 °C, and when heated above about 300 °C further
dehydrates, forming tetraboric acid or pyroboric acid (H2B4O7):

4HBO2 → H2B4O7 + H2O

 The term boric acid may sometimes refer to any of these compounds. Further heating
leads to boron trioxide.

H2B4O7 → 2B2O3 + H2O

 Boric acid makes an important contribution to the absorption of low frequency sound
in seawater.
 With polyols such as glycerol and mannitol the acidity of the solution is increased.
With mannitol for example the pK decreases to 5.15. This is due to the formation of a
chelate, [((OH)4C6H8O2)2B]−, and this feature is used in analytical chemistry.
 Boric acid dissolves in anhydrous sulphuric acid.

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 B(OH)3 + 6H2SO4 → 3H3O+ + 2HSO4− + B(HSO4)4−

 Boric acid reacts with alcohols to form borate esters, B(OR)3 where R is alkyl or aryl.
A dehydrating agent, such as concentrated sulphuric acid is typically added:

B(OH)3 + 3ROH → B(OR)3 + 3H2O

6.4. Insecticidal Use of Boric Acid

Boric acid was first registered in the United States as an insecticide in 1948 for control
of cockroaches, termites, fire ants, fleas, silverfish, and many other insects. The product is
generally considered to be safe to use in household kitchens to control cockroaches and ants.
It acts as a stomach poison affecting the insects' metabolism, and the dry powder is abrasive
to the insects' exoskeletons. In combination with its use as an insecticide, boric acid also
prevents and destroys existing wet and dry rot in timbers. It can be used in combination with
an ethylene glycol carrier to treat external wood against fungal and insect attack. It is possible
to buy borate-impregnated rods for insertion into wood via drill holes where dampness and
moisture is known to collect and sit. It is available in a gel form and injectable paste form for
treating rot affected wood without the need to replace the timber. Concentrates of borate-
based treatments can be used to prevent slime, mycelium, and algae growth, even in marine
environments. Boric acid is added to salt in the curing of cattle hides, calfskins, and
sheepskins. This helps to control bacteria development, and helps to control insects.

7. The Industrial Manufacture of Boric Acid Insecticide

For manufacturing boric acid, colemanite ore is charged into an acidifier and dilute
sulphuric acid solution is added slowly until the solution becomes strongly acidic.

The materials and processes involved are outlined below.

7.1. Raw Materials Required

The basic raw materials required for this process are:

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  Colemanite ore (CaB3O4(OH)3.H2O), which is an important borate mineral found in
evaporite deposits of alkaline lacustrine environments. Colemanite is a secondary
mineral that forms by the alteration of borax and ulexite.
 Dilute sulphuric acid (H2SO4) solution.
 Water

7.2. By-Products of the Process

The by-products of the process are:

 Solid waste (Gypsum and other inert solids)

 Water vapour.

7.3. Equation of Reaction

The reaction involved in the production process proceeds thus:

CaB3O4(OH)3.H2O + H2SO4 + H2O 3H3BO3 + CaSO4

7.4. Process Description

As shown in the Fig. 2 above, the colemanite ore in its raw form, is first crushed into
granules and then charged (stream 1) into the reactor, alongside an inlet stream of dilute
sulphuric acid (SA) solution (stream 2). The reaction is carried out in a 4-stage cascade
reaction system. The chemical reaction as shown in the equation above, takes place in all
four stages of the reaction system. Here, the total retention time is about 3 to 3.5 hours, so as
to eliminate the supersaturation of the produced gypsum (CaSO4) and to avoid its
precipitation during boric acid crystallization. Inert solids, consisting of side minerals in the
colemanite ore, (mostly clay and feldspate minerals) remain unreacted in the reaction.

Following from the reaction step, the produced boric acid, together with precipitated
gypsum and inert solids proceeds to the first stage filtration. In order to recover boric acid
from the wet gypsum cake (stream 5), it is mixed with stream 9 and then subjected to a
second stage filtration. The cake obtained in the second stage filtration is washed and the
filtrate is recycled to the reaction step, as it will surely contain some amounts of unreacted
reactants. The production liquor (stream 4), which contains boric acid, approximately 18%,

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is next sent to a 3-stage crystallization unit (in adiabatic vacuum crystallizers) to be
crystallized, where the final temperature is about 35°C. The crystal composition, exiting the
crystallizers as stream 7, is then sent to a hydrocyclone, where it is enriched up to 40%
before it is filtered and washed with an incoming stream of water. Consequently, the moisture
content is reduced approximately to 7% in a centrifuge. The stream 10 with 7% moisture
content is next sent to be dried in a fluidized bed dryer until the crystals get bone dry. Any
fine crystals that escapes

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from the fluidized bed dryer with air are recovered with a cyclone and gas washer,
respectively. The solution taken from the gas washer is mixed with stream 13 and recycled to
the reaction unit as mother liquor which contains approximately 10% boric acid. This
production process has been designed to run on a continuous steady state basis.

The dried boric acid crystals, exiting the dryer as stream 16, can then be packaged for
sale or stored properly in sealed container. Boric acid does not decompose or break down, it
has a very long shelf life as far as it is kept in a tightly closed container and stored in a cool,
dry location that is well ventilated. The boric acid can also be further processed or used as a
raw material for other chemical-based production processes.

Before the boric acid crystals can be used as insecticide, it has to be dissolved in water
to a definite concentration, depending on the specific requirement. Hence, boric acid
insecticide can be sold either in its powdered form or in varying dilute aqueous solutions.

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Fig. 2 Process Schematics (Block) flow diagram for the industrial manufacture of boric
acid from colemanite ore

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7.5. Images of the Process Equipment Used

(a) (b)

(c) (d)

(e) (f)

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 (g)

Fig. 3. (a) Industrial Filter (b) Industrial Reactors (c) Industrial Dryer (d) Industrial
Centrifuge (e) Industrial Crystallizers (f)Crystalline Boric acid powder (g) Packaged
Boric acid insecticide powder

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8. Conclusion
The pesticide manufacturing industry remains a very important chemical process
industry worldwide. As a result of the ever-increasing need to protect various farm products,
to preserve food crops and other perishables liable to pest attack, it becomes expedient to
make use of pesticides, which has been seen to include a very wide range of types. This study
based on the production processes involved in the industrial manufacture of a very common
insecticide – Boric acid. From the process schematics, it could be seen that the steps involved
are mainly physical processes, which were preceded by a chemical process. On the industrial
scale, the process remains a relatively very cheap option for pesticide production.

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 REFERENCES

1. Perelygin, Yu. P.; Chistyakov, D. Yu. (2006). "Boric acid" (PDF). Russian Journal of

Applied Chemistry. Pleiades Publishing. 79 (12): 2041–2042.

doi:10.1134/S1070427206120305.

2. Office of Prevention, Pesticides and Toxic Substances (1993). "R.E.D. Facts: Boric

Acid" (PDF). United States Environmental Protection Agency. Archived from the

original (PDF) on 6 April 2008. Retrieved 2008-04-21.

3. Office of Prevention, Pesticides and Toxic Substances (2006). "Report of the Food

Quality Protection Act (FQPA) Tolerance Reassessment Eligibility Decision (TRED)

for Boric Acid/Sodium Borate Salts" (PDF). United States Environmental Protection

Agency. Retrieved 2008-04-21.

4. https://en.wikipedia.org/wiki/Boric_acid.

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