PROCESSING OR REFINING OF PETROLEUM

REFINING

A low-cost operation compared to chemical processing

Refining/affining is the process of purification of a substance.

REFINING
The term is usually used for a natural resource that is almost usable in form, but which is more useful in its pure form. Involves TWO BRANCHES: SEPARATION and CONVERSION Processes

FRACTIONAL DISTILLATION OF CRUDE OIL

Top Fractions have lower boiling points than the fractions at the bottom.
The heavy bottom fractions are often cracked into lighter, more useful products. All of the fractions are processed further in other refining units.

OTHER PROCESSES

Alkylation
Hydrogenation

Isomerization

Polymerization

Reforming

Dehydrogenation

ENERGY BALANCES

Energy

expense for refining has been the most important manipulatable cost. of energy has been the object of the study.

Conservation

The great needs of growing petroleum industry led to careful study of :

Fluid Flow

Heat transfer

Properties of Petroleum Fractions

Use of instruments and control systems. Direct Digital Control (DDC) computer designed to optimized variables.

SEPARATION PROCESS
Major units are called Stills. A crude Still consists of:

1. Heat Exchangers

2. Furnace

3. Fractionating tower

4. Steam strippers

5. Condensers

6.Coolers

7.Other Auxilliaries (pipes,tanks, etc..)

UNIT OPERATIONS USED IN SEPARATION PROCESS:

1.

Fluid Flow- an operation that must not permit unexpected failure because of fire and explosion might ensue.

2. Heat transfer- Transfer coefficients change daily as fouling occurs. Cooling towers become less effective with time.

3. Distillation Undesirable light volatiles remove by steam stripping Tower contacting material consists of bubble caps and packings designed to reduce Pressure drop while increasing vapor-liquid contact Extractive Distillation- when a solvent of low volatility is added to depress the volatility of one of the components.

DISTILLATION TOWER WITH BUBBLE CAPS

4. Absorption-used to separate high-boilers from gases. 5. Adsorption- used for recovering heavy metals from gases. (e.g. Activated Charcoal) 6. Filtration- used to remove wax precipitated from wax containing distillates 7. Crystallization- Before Filtration, waxes must be crystallized to suitably sized crystals by cooling and stirring. 8. Extraction- removal of a component by selectively dissolving it in a liquid.

CONVERSION PROCESSES
Cracking/ Pyrolysis Polymerization Alkylation

Hydrogenation

Hydrocracking

Isomerization

Reforming/ Aromatization

Esterification & Hydration

CRACKING OR PYROLYSIS

The breaking down of large hydrocarbon molecules into smaller molecules by heat or catalytic action. Zeolite catalysts are common.

Example: cracking of butane CH3-CH2-CH2-CH3

1st possibility : breaking is done on the CH3-CH2 bond. CH3* / *CH2-CH2-CH3; we will obtain an alkane and an alkene : CH4 + CH2=CH-CH3 2nd possibility : breaking is done on the CH2-CH2 bond. CH3-CH2* / *CH2-CH3; we will obtain an alkane and an alkene from different types: CH3-CH3 + CH2=CH2 3rd possibility: breaking of a C-H bond we will obtain an alkene and hydrogen gas: CH2=CH-CH2-CH3 + H2 this is very useful since the catalyst can be recycled.

CRACKING OR PYROLYSIS
Hydrocarbons break into two or more fragments and one of them is always an olefin. Cracking reactions are endothermic and energy involved is high. Orthoflow catalytic cracking converter is a typical unit carrying out reaction, catalyst stripping, regeneration and catalyst circulation in a single converter.

ORTHOFLOW CATALYTIC CRACKING CONVERTER

Hydrocracking strong processing in the presence of hydrogen. Light and heavy oils are altered to distillable light products of good quality, desulfured, demetallized and stabilized.

Hydrotreating is a mild processing in the presence of hydrogen, improves color, reduces metallic contamination, improves storage stability.

REFORMING
Forming new molecules of size similar to the original ones. Fractions are subjected to high temperature catalytic treatment in the presence of hydrogen. Consists of isomerization and cracking.

CATALYTIC REFORMING Involves conversion of hydrocarbons into aromatic compounds. Aromatic compounds have high octane rating Catalysts: platinum on alumina or silica-alumina

COKING
Lighter

oils can be produced from very heavy ones by solely thermal cracking process. The feed is usually a vacuum residue and considerable coke is formed.

OXIDATION
Oxidation-conversion

gives more trouble than useful products, forming gums and resins that interfere with the employment of gasolines. However, some serviceable products are obtained from petroleum by oxidation. E.g. formaldehyde from the oxidation of methanol and natural gas; Blown Asphalt production.

POLYMERIZATION
The linking of similar molecules; joining together of light olefins. Converts by-product hydrocarbon gases produces in cracking into liquid hydrocarbons suitable for use as high-octane motor and aviation fuels and for petrochemicals.

Isobutylene

Diisobutylene

Tetrapropylene (mixed isomers)

ALKYLATION
The union of an olefin with an aromatic or paraffinic hydrocarbon Unsaturated +isosaturated saturated branched chain Process are exothermic and similar to polymerization; they differ in that part of charging stock need to be unsaturated Alkylate products contains no olefins and has higher octane rating. Accomplished on a commercial scale with 2 catalysts: hydrogen fluoride and sulfuric acid.

HF ALKYLATION PROCESS
Acid hydrocarbon ratio is 2:1. Temp. range: 15-35C The catalyst protonates the alkenes (propene, butene) to produce reactive carbocations, which alkylate isobutane

isobutane

propene

ISOMERIZATION

Alteration of the arrangement of the atoms in a molecule without changing the number of atoms.

n-butane

iso-butane

CHEMICAL TREATMENT

To remove or alter the impurities in petroleum products to produce marketable material.

1. 2.

3.
4. 5. 6.

One or more of the ff. purposes are achieved: Improvement of color Improvement of odor Removal of sulfur compounds Removal of gums, resins and asphaltic materials. Improvement of stability to light and air. Improvement of susceptibility to additives.

RESEARCH
The petroleum industry has been characterized by continuous improvement. Development in 2 phases: 1st phase: unit operations, distillation, heat transfer, fluid flow and the like. 2nd phase: study of chemical changes. To maintain competitive position, petroleum compounds must be chemically altered to obtain products of great usefulness or value.

PETROCHEMICALS

HISTORY
The 1st organic chemical made on a large scale from a petroleum base was isopropyl alcohol, first produced by standard Oil New Jersey in 1920. Over 3000 individual petrochemicals enter into commerce. The business changes very rapidly as new process simplified old ones, so many historically processes have become economically or technologically obsolete.

PETROCHEMICALS FROM METHANE

PETROCHEMICALS FROM METHANE

PETROCHEMICALS FROM ETHYLENE

PETROCHEMICALS
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