Petrochemicals Technology

References
1. Oleochemical manufacture and applications F.D. Gunstone & Richard John Hamilton Sheffield Academic Press 2001

2.
3. 4. 5. 6.

www.americanpalmoil.com/publication
The Changing World of Oleochemicals Wolfgang Rupilius* and Salmiah Ahmad** www.lurgi.com www.surfatech.com Oleochemicals producer

Nik Norma Nik Mahmood USIM Bandar Baru Nilai, Nilai,N.Sembilan

www.elmhurst.edu/~chm/vchembook

Introduction. Petrochemistry is the study of chemical products derived from petroleum and natural gas. Some chemical compounds made from petroleum are also obtained from other component of fossil fuels such as coal, or renewable sources such as corn or sugar cane. petrochemicals are grouped into two classes: i) olefins including ethylene and propylene, and (ii) aromatics including benzene, toluene and xylene isomers. Petroleum and natural gas are components of fossil fuel. petrochemicals are products, manufactured by chemical modifications of various chemical feedstocks.

Petrochemical Technology Raw material Technology: chemical & physical improved over time 1st stage Hydrocarbons - starting material
Technology:

Basic petrochemicals 2nd stage

chemical = catalyst; solvent; physical = refining capacities

End products / derivatives application

Fossil fuel Composed of various types of major constituents: volatiles (hydrocarbons; natural gas), liquid (oil/petroleum) and non-volatile material (coal). are non-renewable resources because they take millions of years to form. Starting material are decomposed dead huge trees, ferns and other large leafy plants, algae, land animal and fishes buried under layers and layers of mud, rock, sand and ocean floor of reseded seas. Natural processes eg. anaerobic decomposition , exposure of the decomposed starting material for long long duration (million of years) to heat and high pressure ( from pilling of rock) During the millions of years that passed, slow decomposition of the dead plants and animals into organic materials took place and formed fossil fuels. Stages progress: dead trees peat loss of H2O pressured from pilling of sand, clay, minerals (sedimentary, a type of rock ) coal, oil, natural gas. Peat is precursor of coal.

 Different types of fossil fuels were formed depending on what combination of animal and plant debris was present, how long the material was buried, and what conditions of temperature and pressure existed when they were decomposing. coal, oil and natural gas constitute 86.5% of world energy consumption Formation Oil (petroleum) and hydrocarbon Different views i- Dead aquatic animal buried under ocean or river sediments. Long after the great prehistoric age seas and rivers vanished, heat, pressure and bacteria combined to compress and "cook" the organic material under layers of silt into a thick liquid called oil. In deeper, hot regions underground, the cooking process continued until natural gas was formed. This oil and natural gas began working its way upward through the earth's crust and accumulated/trapped in dense regions of the rock (= caprocks) that prevent them from seeping to the surface

ii- some scientist believed that the source of oil are tiny diatoms which are pin-size head sea creatures possessing ability to convert sunlight directly into stored energy. Upon death they fell to the sea floor , got buried under sediment and other rock . The event created great pressure and heat hence squeezed the diatoms forcing the stored energy to turn carbon to oil. As the earth changed and moved and folded, pockets where oil and natural gas can be found were formed. i- petroleum is a mixture of alkanes, cycloalkanes and aromatic hydrocarbons, formed by the slow decomposition of buried marine life notably planktons and algae. ii- crude oil is the petroleum pumped directly from the ground; a mixture, constituted of hydrocarbons of 1C50C iii- not useful must fractionate by distillation into useful fractions

Coal is a hard, black colored rock-like substance. originated the dead decomposed remains of trees, ferns and other plants buried under layers and layers of mud, rock, sand and ocean floor of reseded seas. Exposure of the decomposed starting material for long long duration (million of years) to heat and high pressure ( from pilling of rock) caused loss of H2O. In areas of dried swamps of sea water the sulfur originally contain in sea water was left behind in the coal. made up of C,H,O, N and varying amounts of S. There are three main types : anthracite, bituminous and lignite. Anthracite coal is the hardest and has more carbon, which gives it a higher energy content. Lignite is the softest and is low in carbon but high in hydrogen and oxygen content. Bituminous is in between.

Formation of Coal

www.zenitec.com
-Two processes for the production of synthetic fatty alcohols are based on the work of Prof. Dr. Ziegler using organic aluminum compounds : i) the ALFOL process, developed by Conoco, and (ii) Ethyl Corporation's EPAL process. Fatty alcohols synthesized by these processes are structurally identical to natural fatty alcohols and are thus ideal substitutes for natural products. Conoco started the first ALFOL plant in the United States in 1962. This plant is now operated by Condea Vista. In 1964 Condea Chemie built a similar plant in Brunsbttel, Federal Republic of Germany. Additional ALFOL alcohol plants were built in Ufa/ Russia in 1981 and in Jilin/ China in 1998. In ALFOL Process, a hydrocarbon is used as solvent. The process involves five steps : hydrogenation, ethylation, growth reaction, oxidation and hydrolysis. Figure on next slide: ALFOL-Alcohol- Process - Ethyl Corporation (today BP/Amoco) developed its own process (EPAL process) and started operations in 1964.

From petrochemical ( conventional detergent) Ziegler-Alcohol-Processes Fatty alcohols. In the Ziegler process, ethylene is oligomerized using triethylaluminium followed by air oxidation. This process affords even-numbered alcohols: Al(C2H5)3 + 18 C2H4 Al(C14H29)3 Al(C14H29)3 + 1.5 O2 + 1.5 H2O 3 HOC14H29 + 0.5 Al2O3 Alternatively ethylene can be oligomerized to give mixtures of alkenes, which are subjected to hydroformylation, this process affording odd-numbered aldehyde, which is subsequently hydrogenated. For example, from 1-decene, hydroformylation gives the C11 alcohol: C8H17CH=CH2 + H2 + CO C8H17CH2CH2CHO C8H17CH2CH2CHO + H2 C8H17CH2CH2CH2OH In the Shell higher olefin process, the chain-length distribution in the initial mixture of alkene oligomers is adjusted so as to more closely match market demand. Shell does this by means of an intermediate metathesis reaction. The resultant mixture is fractionated and hydroformylated/hydrogenated in a subsequent step.

ALFOL-Alcohol- Process

1. Hydrogenation 2 Al(CH2CH3)3 + Al + 1.5 H2 3 Al(CH2CH5)2 H (a) 2. Ethylation 3 Al(CH2CH5)2H + 3 CH2CH2 3 Al(CH2CH5)3 (b) 3. Growth Reaktion (CH2CH2)x +1H 3 Al(CH2CH5)3 + (x+y+z)CH2CH2 Al (CH2CH2)y+1H (CH2CH2)z+1H 4. Oxidation R1 OR1 AlR2 + 1.5 O2 Al OR2 R3 OR3 (d) 5. Hydrolysis OR1AlOR2 AlO(OH) + R1OH + R2OH + R3OH OR3 (e)

Reaction Steps of the ALFOL-Process

...(Google book) production of fatty alcohol

Synthetic alcohol Fatty alcohols : anthropogenic and natural occurrence in (Google book)

Figure 7: Flow Diagramm of the EPAL-Process

Sulfonation/sulfation of alkylbenzene www.chemiton.com/pdf/ surfatech.com

Oxo process (production of synthetic alcohol from olefin). The product has 1 C more than the starting olefin. Branching can occur during the process so product alcohol unlike the alcohol from the other 2 process ( Zieglar & natural: even #C and straight chain)

Petrochemicals (elmhurst.edu/~chm/vchembook)
Defination/characteristics Petrochemicals are chemicals made from raw materials petroleum (crude oil) and natural gas, oil and gas source of raw material Feedstock are : ethane, propane and butane from natural gas and naphtha from crude oil. Are molecules of hydrocarbons. Comprise of primary petrochemicals: olefins group (ethylene, propylene, butadiene), aromatics group ( benzene, toluene, xylene) and methanol ; Natural gas is source of feedstock for methanol ; ethylene, propylene; butadiene AND crude oil is the raw material for naphtha from which butadiene; benzene, toluene, xylene are produced The primary petrochemicals are used to manufacture petrochemical intermediates by chemical conversion. The petrochemical intermediates are then processed further to form more complicated derivative products

olefins group are ethylene, propylene, butadiene are unsaturated molecules of carbon (C) and hydrogen (H) are short chains of two, three or four carbons in length

Aromatics group a six carbon ring structure

Intermediates and Derivatives: Petrochemical intermediates are generally produced by chemical conversion of primary petrochemicals to form more complicated derivative products (see graphic on the left). Petrochemical derivative products can be made in a variety of ways: directly from primary petrochemicals; through intermediate products which still contain only carbon and hydrogen; and, through intermediates which incorporate chlorine, nitrogen or oxygen in the finished derivative. In some cases, they are finished products; in others, more steps are needed to arrive at the desired composition.