BUTYLENE DERIVATIVES

Presented By : ANANYA SINGH

(20222009) ,
SHIVANSH SINGH(20220049)
 INTRODUCTION
Naptha Cracking
Naphtha cracking is a key process in the petrochemical industry that converts naphtha, a
liquid hydrocarbon mixture, into valuable chemical products like ethylene, propylene,
butylene, and other light hydrocarbons.

These products serve as important building blocks for plastics, synthetic rubber, and vari
ous chemicals.

Naptha + Steam ​→ smaller hydrocarbons + H2​

 BUTYLENE DERIVATIVES
Butylene, also known as butene (C4H8), is a series of alkene derivatives and the word butylene
(butene) may refer to any of the individual compounds, or to a mixture of them.

They are colorless gases that are present in crude oil as a minor component. Butylene is,
therefore, obtained by cracking of long-chain (higher molecular weight) hydrocarbon derivatives
that are produced during crude oil refining.
BUTYLENE PROPERTIES

REF: https://en.wikipedia.org/wiki/1-Butene
 1.OXIDATION
The mixture of n-butylenes (1-butylene and 2-
butylene isomers) can be oxidized to different
products depending on the reaction conditions and
the catalyst. The two commercially important
oxidation products are acetic acid and maleic
anhydride.

ACETIC ACID :The production of acetic acid from n-butylene mixture is a

vapor-phase catalytic process. The oxidation reaction occurs at
approximately 270°C (520°F) over a titanium vanadate catalyst. A 70%
acetic acid yield has been reported.
 The oxidation of butylene (1-butene) into acetic acid is an industrial
process that generally follows a two-step approach, involving the
production of acetic acid via intermediate steps like butylene
oxidation to butyaldehyde , followed by further oxidation.

uses:It is an important esterifying agent for the manufacture of cellulose acetate and a
versatile reagent.

ENGINEERING PROBLEMS:

Selectivity and Yield Issues: Achieving high selectivity towards acetic acid while
minimizing by-products is challenging.

.
 Maleic anhydride
A solid compound that melts at 53°C (127°F) is soluble in water, alcohol, and
acetone, but insoluble in hydrocarbon solvents. The production of maleic
anhydride from n-butylenes is a catalyzed reaction occurring at approximately
400°C–440°C (750°F–825°F) and 30–60 psi. A special catalyst, constituted of an
oxide mixture of molybdenum, vanadium, and phosphorous, is used.

uses: maleic anhydride, are employed primarily in plastics for the construction,
marine, and transportation industries

ENGINEERING PROBLEMS
Corrosion: The presence of maleic anhydride, along with other by-products and
oxidizing agents, can lead to severe corrosion issues in process equipment
2. HYDRATION
sec-Butanol (2-butanol, sec-butyl alcohol), is a liquid with a
strong characteristic odor. Its normal boiling point is 99.5°C
(211°F).

sec-Butanol is produced by a reaction of sulfuric acid with

a mixture of n-butylenes followed by hydrolysis. Both 1-
butylene and cis-2-butylene and trans-2-butylene yield the
same carbocation intermediate, which further reacts with
the sulfuric acid (H2SO4) or solutions, to produce a sulfate
mixture.

uses : 2-Butanol is also used as a solvent, a paint remover,

and an intermediate in organic synthesis.
ENGINEERING PROBLEMS:

Reaction Selectivity: The hydration of n-butylene can lead to various side reactions,
including the formation of ethers and other alcohols.

Scaling and Reactor Design: Choosing the right type of reactor and scaling the process
up while maintaining efficiency and selectivity can be complex.
3.
OLIGOMERIZATION
Oligomerization is a chemical process where small
molecules react and combine to form oligomers, which are
molecules made up of a few repeating units (typically
between 2 and 10).

It requires the use of catalysts to control the reaction,

typically acidic catalysts like zeolites, transition metal
complexes, or homogeneous catalysts.

The reaction is exothermic, and requires a multi-tubular

carbon steel reactor. The exothermic heat is absorbed by
water circulating around the reactor shell.
oligomerization of butylene results in the formation of higher olefins, with the most
common products being:

Dimers: Two butylene molecules combine to form octenes (C8 olefins).

Example: 2,4,4-trimethylpentene is a common dimer.

Trimers: Three butylene molecules oligomerize to form dodecenes (C12 olefins).

Example: A trimer of butylene could result in 1-dodecene.

Tetramers: Four butylene molecules combine to produce hexadecenes (C16 olefins).

USES : production of plasticizers, lubricants, surfactants, and synthetic lubricants

ENGINEERING PROBLEMS:

Selectivity and Control of Oligomer Chain Length: Achieving control over the degree
of oligomerization is challenging. The process can yield a mixture of dimer, trimer,
tetramer, and higher oligomers, but specific applications require precise control over
chain length distribution.

Heat Management: The oligomerization reaction is exothermic, generating significant

heat that can create hotspots in the reactor, particularly in fixed-bed systems.
Effective heat dissipation and temperature control are essential to prevent thermal
degradation of the product and maintain selectivity.
 ISOBUTYLENE
Chemical formula C4H8

Molar Mass 56.106g/mol

Appearance Colorless gas

Density 0.5879 g/cm3, liquid

Melting Point -140.3 °C

Boiling Point -6.9 °C

Solubility In Water Insoluble

 INTRODUCTION
Isobutylene is a reactive C4 olefin.
Almost all isobutylene was obtained as a byproduct with other C4
hydrocarbons from different cracking processes ( ex: Fluid Catalytic Cracking,
Steam Cracking ).
n-Butane is converted to isobutylene through isomerization to isobutane
followed by dehydrogenation. this serves the dual purpose of utilizing excess
n-butane, required to be removed from gasoline due to vapor pressure
regulations, and produce isobutylene.
Isobutylene is mainly used for production-
Methyl-tert butyl ether (CH3)3COCH3)
Alkylates for the gasoline pool
Isoprene and Di-isobutylene
 OXIDATION
The direct oxidation of isobutylene produces methacrolein and methacrylic acid.the catalyzed
oxidation reaction of isobutylene to methacrylic acid involves two main steps, each utilizing specific
conditions and catalysts due to the differing oxidation behaviors of isobutylene and methacrolein.
Step 1: Isobutylene is oxidized to methacrolein (CH₂=C(CH₃)CHO) using a molybdenum oxide-based
catalyst at a temperature range of 350–400°C (650–750°F) and a slightly above-atmospheric
pressure of around 15–25 psi.

Step 2:Methacrolein is then further oxidized to methacrylic acid at a lower temperature range of
250–350°C (480–650°F), with a catalyst composed of a molybdenum-supported compound and
specific promoters.
 OXIDATION
Methacrylic acid [CH2=C(CH3)COOH] is a carboxylic acid that exists as a colorless, viscous
liquid is with an acrid unpleasant odor.It is soluble in warm water and miscible with most
organic solvents.

Uses
Methacrylic acid is produced industrially on a large scale as a precursor to it is the ester
derivatives such as the methyl methacrylate monomer leading to poly(methyl
methacrylate). The methacrylates have polymers with trade names such as Lucite and
Plexiglas. Methacrylic acid and methacrylates are also produced by the hydrocyanation of
acetone.
 EPOXIDATION
Isobutylene oxide is produced in direct catalytic liquid-phase oxidation using stoichiometric
amounts of thallium acetate catalyst in aqueous acetic acid solution. An isobutylene oxide yield of
on the order of 82% w/w is possible. While in direct non-catalytic liquid-phase oxidation gave low
yield (28.7%) with side products such as acetone, t-butyl alcohol (TBA), and isobutylene glycol.

Isobutylene glycol also be produced by a direct catalyzed liquid-phase oxidation of isobutylene

with oxygen in presence of water. TlCl3/CuCl2 catalyst is employed.

Uses
Lubricants: PIB is used in 2-stroke engine oils, gear oils, hydraulic fluids, and metalworking
fluids.
Adhesives: PIB is used in pressure sensitive (PSA) and hot melt adhesives (HMA).
 ADDITION OF ALCOHOL
Currently the major use of isobutylene is to produce Methyl tert-butyl ether, it is a
colorless liquid with a distinctive anesthetic-like odor. Vapors are heavier than air and
narcotic. This ether has a boiling point 55°C (131°F) with a flash point of −8°C (18°F), it is
less dense than water and miscible in water.
Reaction between isobutylene, methyl alcohol, and ethyl alcohol is an addition reaction
catalyzed by a heterogeneous sulfonated polystyrene resin. When methanol is used a 98%
yield of methyl-t-butyl ether is obtained and Ethyl-t-butyl ether (ETBE) is also produced
 ADDITION OF ALCOHOL
PROCESS FLOW methanol recycle
methanol+c4

water methanol
distillation

recycle of water

99% MTBE to storage

 ADDITION OF ALCOHOL
USES OF MTBE:
1. Gasoline Additive: MTBE is most widely used as an oxygenate in gasoline,
where it helps gasoline burn more completely,reduces harmful emissions,
particularly carbon monoxide and ground-level ozone, and helps engines run
more efficiently.
2. Octane Booster: Due to its high octane rating, MTBE improves gasoline
quality and prevents engine "knocking" or "pinging," allowing for better engine
performance.
3. Solvent in Industrial Applications: used as a solvent in industrial processes,
particularly in the pharmaceutical and chemical sectors, where its properties
can be useful in extractions and chemical reactions.
4.MTBE is water soluble and hazardous for health .
 HYDRATION
The acid-catalyzed hydration of isobutylene produces t-butyl alcohol. The reaction occurs in
the liquid phase in the presence of 50%–65% sulfuric acid at mild temperatures (10°C–30°C;
50°F–86°F).

Uses of tert butyl alcohol:

As a chemical intermediate because a tertiary butyl carbocation forms easily.
As a solvent in pharmaceutical formulations, a paint remover, and a high-octane gasoline additive.
The alcohol is a major byproduct from the synthesis of propylene oxide using tertiary butyl
hydroperoxide.
Surplus t-butyl alcohol could be used to synthesize highly pure isobutylene by a dehydration step:
 CARBONYLATION
The addition of carbon monoxide to isobutylene under high pressures and in the presence of an acid
produces a carbon monoxide-olefin complex, an acyl carbocation. Hydrolysis of the complex at lower
pressures yields trimethyl acetic acid (also known as neopentane acid, (CH3)3CCOOH). isobutene is
hydrocarboxylated by means of the Koch reaction:

The reaction, a special case of hydrocarboxylation, uses a strong acid catalyst like hydrogen fluoride and
can substitute tert-butyl or isobutyl alcohol for isobutene. Catalysis relies on strong acids (e.g., sulfuric
acid or phosphoric acid with boron trifluoride) rather than metal catalysts.
uses of trimethyl acetic acid
An intermediate and an esterifying agent used when a stable neo structure is needed.
adsorbtion at three different sites.
THANK YOU