COURSE OUTLINEIMPORTANT OF CHEMICAL PROCESS

INDUSTRIES IN MALAYSIAUTILITIES REQUIREMENT IN PROCESS

INDUSTRIESINDUSTRIAL POLLUTIONSPECIAL TOPICS

IMPORTANT OF CHEMICALPROCESS INDUSTRIES IN MALAYSIA

PETROLEUMNATURAL GASPALM OILSURFACE COATING INDUSTRIESRUBBER INDUSTRIESCEMENT INDUSTRIES

CHAP 1.1: PETROLEUMOrigin and DistributionPetroleum Drilling OperationPetroleum Refining ProcessesSelected Petrochemicals Processing

1859 – First well was drill in Pennsylvania, USA

1897 – First well was drilled offshore in California, USA

1910 – First well was drilled in Malaysia (Well no. 1 is in Sarawak)

OIL AND GAS INDUSTRY

Petroleum: A form of bitumen composed principally of hydrocarbons which exists in the gaseous or liquid state in its natural reservoirs.

Petroleum = Hydrocarbon Compound + Non-Hydrocarbon Compound

Hydrocarbon = Organic Compounds of Carbon (C) and Hydrogen (H) only

Non-Hydrocarbon = Compound that contain some sulphur, oxygen or nitrogen atoms besides hydrogen and carbon

- Petroleum means oil (oleum) rock (petra).- Petroleum is synonymous with hydrocarbon.

DEFINITION: PETROLEUM

Hydrocarbon can be found as:

(i) Natural gases. e.g. methane, ethane(ii) Liquid. e.g. liquid crude, medium crude and heavy crude(iii) Semi-solid. e.g. asphalts, waxes

Principal forms of petroleum are:

(i) Crude oil(ii) Natural gas(iii) Condensate(iv) Asphalt

HYDROCARBON

(i) Crude oil- A mixture of hydrocarbons that exists in the liquid phase in natural underground reservoirs and remain liquid at the atmospheric pressure after passing through surface separating facilities. - Appearance: dark brown to yellowish brown.- Density: ranges from very dense - denser than water - to very light.- Viscosity: ranges from solid to very thin liquid.

(ii) Natural gas- A mixture of hydrocarbon compounds and small quantities of various non-hydrocarbons (e.g. nitrogen and carbon dioxide) existing in the gaseous phase or in solution with oil in natural underground reservoirs at reservoirs conditions.- Main hydrocarbon component is methane (CH4).- Dry gas contain 90-100% CH4.- Wet gas contain greater proportion of ethane (C2H6), propane C3H8), butane (C4H10), etc.- Carbon dioxide (CO2) and hydrogen sulphide (H2S) and nitrogen may also be present.

HYDROCARBON

- Sweet and sour gases refer to the low and high content of hydrogen sulphide, respectively.- Use in power generation, industrial feedstock like fertilizers and liquefied into LNG for efficient transport.

(iii) Condensate- The hydrocarbons which are in the gaseous state under reservoir conditions but become liquid either in passage up the hole or at surface due to the reduced pressure condition.- Appearance: yellow to colourless.- API gravity > 60 degrees- Some hydrocarbons mixtures are gaseous at subsurface temperature and become liquid when cooled to surface temperature.- The fluid therefore condense and liquefy when produced- There is no fundamental difference between wet gases and condensate.- Condensate are composed mainly of compounds in which molecules contain at least 5 carbon atoms.- Most gas field produce a lot of condensate which are measured in barrels per day and treated like oil.

HYDROCARBON

(iv) Asphalt- Hydrocarbon which is sticky, black and highly viscous liquid or semi-solid- Difficultly salable material, is by product of the refining process- Difficult to dispose and relatively unprofitable- The properties can be changed by heating it and partly oxidizing it by blowing air through it.

HYDROCARBON

What is the process involve in formation of oil and gas?

In general, 2 theories are exists for the origin of oil and gas.

(1)Inorganic theories – reactions of carbon dioxide with water under suitable conditions.

(2)Organic theories – main source of petroleum is organic remains of plants and animals.

Organic theory is the most widely accepted today.

- The organic theory is based on accumulation of hydrocarbon from lying things and the generation of hydrocarbon by heat action on biogenically formed organic matters.

- The inorganic hypothesis assumes oil form from the reduction of primordial carbon or its oxidized form at high temperatures deep in the earth.

ORIGIN OF PETROLEUM

CONSITUENT OF PETROLEUM

Crude petroleum is made up of thousands of different chemical substances including gases, liquids and solids and ranging from methane to asphalt. Most constituents are hydrocarbons but there are significant amounts of compounds containing nitrogen (0-0.5%), sulfur (0-6%) and oxygen (0-3.5%).

Below is list of major constituents of petroleum.

a) n-Parafin Series or Alkanes, CnH2n+2

b) iso-Parafin Series or iso-Alkanes, CnH2n+2

c) Olefin or Alkene Series, CnH2n

d) Naphthene Series or Cycloalkanes, CnH2n

e) Aromatic or Benzoid Series, CnH2n-6

Aliphatic or open chain

hydrocarbons

Ring compounds

CONSITUENT OF PETROLEUM

a) n-Parafin Series or Alkanes, CnH2n+2

- Comprise a larger fraction of most crude than any other- Most straight-run (distilled directly from crude) gasolines a

predominantly n-paraffin- Poor antiknock properties - e.g. n-hexane, n-heptane

b) iso-Parafin Series or iso-Alkanes, CnH2n+2

- Perform better in internal-combustion engines than n-paraffin, more desirable

- Formed by catalytic reforming, alkylation, polymerization or isomerization

- e.g. 2- and 3-methylpentanes, 2,3-dimethylhexane

c) Olefin or Alkene Series, CnH2n

- Generally absent in crudes but produce in refining process (cracking-making smaller molecules from large one)

- Unstable molecules improve the antiknock quality of gasoline (not as effective a iso-paraffin)

CONSITUENT OF PETROLEUM

- On storage, they polymerize and oxidize, undesirable, very tendency to react but useful for forming other compounds, petrochemicals by additional chemical reactions. e.g. ethylene, propylene, butylene

d) Naphthene Series or Cycloalkanes, CnH2n

- Different from naphthalene- Having same chemical formula as olefins - Lower members of this group are good fuels- Higher molecular weight are predominant in gas oil and lubricationg oil- e.g. methylcyclopentane, cyclohexane, dimethylcyclopentanes,

methylcyclohexane

e) Aromatic or Benzoid Series, CnH2n-6

- Only small amounts of this series occur in most common crudes but they are very desirable in gasoline since they have high antiknock value

- Only special crude (Borneo Sumatra) has relatively high amount- Good storage stability and many uses besides fuel- Many aromatic are formed by refining processes- e.g. benzene, toluene, ethylbenzene, xylene

ACTIVITIES IN PETROLEUM INDUSTRY

EXPLORATION

PRODUCTION

APPRAISAL

DEVELOPEMENT

Acquisition of Right

Export or Processing

Sequence of activities in petroleum industry.

ACTIVITIES IN PETROLEUM INDUSTRY

Activities:

• Acquisition of Right: To obtain permission from government or relevant agency before drilling of exploration well.

• Exploration: To search for oil and gas• Appraisal: To determined the commercial significance of the

discovery and to shape the initial development plan for the field.• Development: to formulate the field development plan of the field, to

install the platform to drill and complete the development well.• Production: To bring oil/gas from subsurface to surface and to

separate between gas/oil/water before the oil is stored and gas is processed.

• Transportation: To bring oil from storage to refinery and gas to gas processing plant either by pipeline or floating tanker.

• Refining/gas processing: To manufacture petroleum products from crude oil.

• Marketing: To distribute the petroleum products to customers.

Purpose of refining- The refinery is designed to process several different types of

crude oil to produce useful petroleum product.

Refining crude oil is carried out in 3 main stages.

(1) SeparationTo split the crude oil into groups of hydrocarbon using distillation process.

(2) ConversionCracking or breaking down of large hydrocarbon molecules. Smaller at temperature higher than used in distillation.

(3) TreatmentTo remove impurities

PETROLEUM REFINING

PETROLEUM REFINING - SEPARATION

(1) Separation

- Process to split the crude oil into groups of hydrocarbon- Done according to the size of different molecules, normal

practice is to define the molecular size according to the number of carbon atom present

- Generally, the larger and more complex the molecules, the higher tends to be the boiling point of the compound and consequently the temperature at which it vaporizes.

- When crude oil is heated, the lightest hydrocarbons boil first. As the vapours are cooled, they then condense back to liquid in reverse order; this technique known as distillation (used to separate the hydrocarbons into fractions or groups having similar boiling points).

Fractional distillation of fractionation takes place in a tower known as a fractionators, temperature of ~340ºC at its base and gradually decrease towards the top, ~110ºC

Inside fractionator, the column is divided at intervals by horizontal trays (perforated or valve trays).

PETROLEUM REFINING - SEPARATION

PETROLEUM REFINING - SEPARATION

- Valve trays are more common type since they can accommodate a wider range of loading than perforated trays.

- As the vapour load in the column increases, so does the number of valves which open on each tray.

- Each tray is cooler than the one below it, thus providing a temperature gradient on which separate vapours can condense.

- The crude oil is first heated by a furnace and then passes into the lower part of the column. Since most of the fractions in the oil are already boiling, they vaporize and rise up the column through the valve trays. As each fraction condense and change back into liquid.

As the fraction condenses on their separate trays, they are drawn off.

This distillation process is continuous, with hot crude oil flowing near the base of the column and separate fraction flowing at each level.

The first distillation is carried out at essentially atmospheric pressure and separates crude oil into gasses, light distillates, middle distillates and residue.

The very lightest fraction is termed refinery gas which remain as a vapour and is used as a fuel in the refinery.

PETROLEUM REFINING - SEPARATION

PETROLEUM REFINING - SEPARATION

- Depending upon the crude oil being processed, a single atmospheric distillation process will not necessarily separate out the required range of product efficiently, and often a series of distillation columns is used.

- e.g. the naphtha may be further split into a light and heavy naphtha stream, the heavy stream typically goes on for treatment and reforming whereas the light stream may be further distillated to provide petrochemical feedstock stream.

PETROLEUM REFINING - CONVERSION

(2) Conversion

- Conversion technique is used to enable the yield of products to be re-shaped to match market demand.

- Main conversion process is cracking, the breaking down of large hydrocarbon molecules of heavy fractions into smaller more valuable molecules at temperature higher than those used in distillation.

Types of cracking process(1) Catalyst cracking• Produce components for blending into high-

octane motor gasoline, diesel components and C3 - C4, gasses used largely as raw material for petrochemical industry.

• Gasoline and kerosene can be produced from the heavier fractions if the cracking process is carried out in the presence of catalyst and hydrogen at high pressure. This hydrocracking process is supplement to other cracking process.

PETROLEUM REFINING - CONVERSION

PETROLEUM REFINING - CONVERSION

(2) Thermal crackingUsing heat and pressure alone, original method of

obtaining greater amounts of motor gasoline. e.g. visbreaking used to improve the quality of heavy fuel oils and to make diesel oil components, production of coke for industrial carbon electrodes.(3) Steam cracking

• Process in which LPG or light distillates are broken down in the presence of steam at high temperature and low pressure.

(4) Reforming• Light distillate (usually naphtha) containing

hydrocarbon molecules smaller than those found in cracking feedstock are reformed by heat and pressure into more useful molecules of the same size and boiling range.

• A catalyst improve catalytic process (platinum) and the process known as platformer (platinum catalytic reformer).

• Its product include components for motor gasoline and jet fuel and aromatic (cyclic) hydorcarbons for petro-chemical feedstock.

• Also produce large quantities of hydrogen which in an integrated refinery, is used in treating processes and for hydrocraking.

PETROLEUM REFINING - CONVERSION

PETROLEUM REFINING - CONVERSION

(5) Other conversion process • Linking or changing the arrangement of molecules to

obtain additional quantities of high-octane motor gasoline • Alkylation: combines the lightest fractions by using

sulphuric acid as a catalyst. • The heaviest residue (after vacuum distillation) is

converted by blowing air through it at high temperature, to give a variety of grades of bitumen for industrial uses.

PETROLEUM REFINING - TREATMENT

(3) Treatment

- The products of the conversion have to be treated to remove impurities.

- Impurities reduce the efficiency of conversion process, make product corrosive or unpleasant fro customer to handle.

- Major impurity: SULPHUR• Sweet crude oil, small amount of sulphur• Sour crude oil, large amount of sulphur

The most common are a group of organic sulphur called mercaptants.

Hydrogen sulphide gas is also found dissolved in crude oil and is produces by the thermal decomposition of some mercaptants.

Remove sulphur by passing the untreated product with a stream of hydrogen through a bed of catalyst. Sulphur converted to hydrogen sulphide which the aid of chemicals, is extracted and converted into liquid or solid sulphur for sale to chemical industry.

Other impurities: nitrogen, oxygen and various metallic compounds, all which have to be removed at a certain extent.

PETROLEUM REFINING - TREATMENT

PRODUCT OF REFINING

Crude oil distillation is the first stage of a series of complex petroleum processing process. The distillation consists of light, intermediate, heavy distillates and residue. Below are the list of the distillate (product obtain from the condensation of vapour in a distillation column).

(i) Light Distillate Aviation gasoline, motor gasoline (automobile), naphtha, petroleum solvents, jet fuel and kerosene.

(ii) Intermediate DistillateGas oil, light and heavy domestic furnace oils, diesel fuel and distillate used for cracking to produce more gasoline. Used mainly for transportation fuels in heavy trucks, railroads, small commercial boats.

PRODUCT OF REFINING

(iii) Heavy DistillateThese are converted into lubricating oils, heavy oils for a variety offuel uses, waxes and cracking stock. Lubricating oils of high quality can readily be made from paraffin-base oils but most oils are mixed or naphtene base and solvent.

(iv) ResidueThe residue including asphalt, residue fuel oil, coke and petrolatum. Asphalt used as road-paving material, for water proofing structures and roofing material. Petroleum coke commercially used in making electrodes, manufacture of calcium carbide, paint and ceramics.