Petroleum Refining

Crude Evaluation and product characterization

Contents

About Crude oil Common Refinery Units

Crude Distillation Secondary Refinery Processes Residue processing

Opportunity crudes and its compatibility Crude Evaluation and characterization

About Crude oil

Composition by weight Element Percent range Carbon 83-87% Hydrogen10 - 14% Nitrogen0.1 - 2% Oxygen0.05 - 1.5% Sulfur0.05 - 6.0% Metals < 0.1% Four different types of hydrocarbon molecules appear in crude oil. The relative percentage of each varies from oil to oil, determining the properties of each oil Composition by weight Hydrocarbon Paraffins 30%; Naphthenes49%: Aromatics15% Asphaltene 6%

Common process units found in a refinery

Atmospheric distillation unit distills crude oil into fractions. Vacuum distillation unit further distills residual bottoms after atmospheric distillation. Naphtha hydrotreater unit uses hydrogen to desulfurize naphtha from atmospheric distillation. Must hydro treat the naphtha before sending to a Catalytic Reformer unit. Catalytic reformer unit is used to convert the naphtha-boiling range molecules into higher octane reformate (reformer product). The reformate has higher content of aromatics and cyclic hydrocarbons). An important byproduct of a reformer is hydrogen released during the catalyst reaction. The hydrogen is used either in the hydrotreaters or the hydrocracker. Distillate hydrotreater unit desulfurizes distillates (such as diesel) after atmospheric distillation. Fluid catalytic cracker (FCC) unit upgrades heavier fractions into lighter, more valuable products. Hydrocracker unit uses hydrogen to upgrade heavier fractions into lighter, more valuable products

Common process units found in a refinery

Visbreaking unit upgrades heavy residual oils by thermally cracking them into lighter, more valuable reduced viscosity products. Merox unit treats LPG, kerosene or jet fuel by oxidizing mercaptans to organic disulfides. Alternative processes for removing mercaptans are known, e.g. doctor sweetening process and caustic washing. Coking units (delayed coking, fluid coker, and flexicoker) process very heavy residual oils into gasoline and diesel fuel, leaving petroleum coke as a residual product. Alkylation unit produces high-octane component for gasoline blending. Dimerization unit converts olefins into higher-octane gasoline blending components. For example, butenes can be dimerized into isooctene which may subsequently be hydrogenated to form isooctane. There are also other uses for dimerization. Isomerization unit converts linear molecules to higher-octane branched molecules for blending into gasoline or feed to alkylation units. Steam reforming unit produces hydrogen for the hydrotreaters or hydrocracker.

Common process units found in a refinery

Liquified gas storage vessels store propane and similar gaseous fuels at pressure sufficient to maintain them in liquid form. These are usually spherical vessels or "bullets" (i.e., horizontal vessels with rounded ends). Amine gas treater, Claus unit, and tail gas treatment convert hydrogen sulfide from hydrodesulfurization into elemental sulfur. Utility units such as cooling towers circulate cooling water, boiler plants generates steam, and instrument air systems include pneumatically operated control valves and an electrical substation. Wastewater collection and treating systems consist of API separators, dissolved air flotation (DAF) units and further treatment units such as an activated sludge biotreater to make water suitable for reuse or for disposal. Solvent refining units use solvent such as cresol or furfural to remove unwanted, mainly aromatics from lubricating oil stock or diesel stock. Solvent dewaxing units remove the heavy waxy constituents petrolatum from vacuum distillation products

Addressing the concerns to process Opportune crudes

Blending of Lighter Crudes, Condensate etc for transportation Modifying existing configuration and pipeline of refinery for receipt and processing Opportune crudes

Opportune Crudes could be of High TAN, high pour, Heavy crude of high density

Opportune Crudes and Compatibility

Structure of Crude Oil
A R A S = = = = Asphaltenes (Solute) Resins (Dispersant) Aromatics (Solvent) Saturates(Nonsolvent)

Cause of Instability-Asphaltenes Polyaromatic in nature with alkyl substitution usually contain heteroatoms such as oxygen, nitrogen, sulfur and metal atoms Dispersed in the oil with the resins and this asphaltene-resin dispersion is dissolved into petroleum oils with aromatics (solvent) but opposed by saturates (non-solvents).

Opportune Crudes and Compatibility

Methods For Determination
Conventional Process

P- test Spot test- Insolubility & Solubility Approach Colloidal Instability Index (CII) Stability Number (Turbiscan) Microscope Tests, etc . Limitations in the study of Blend Compatibility of Asphaltenic/waxy Crude Crude oil is a blend containing both saturates and Asphaltene Compatibility of saturate and asphaltenic crudes depends on their content and type Structure property correlation not explored much and is of complex nature

High TAN Crudes

Corrosion due to Naphthenic acids Less than 2000C not a problem since NAs are heavier compounds Greater than 4200C not a problem because NAs breaks down lighter acids. Problem for streams in the range 2000C 4200C (Kero, HSD, and VGO etc)

Difficulties while processing HAC

Desalting (high calcium crude oils) Naphthenic acids can form stable emulsions, foaming problems, formation of calcium naphthenates are particularly bad factors

Rapid corrosion with higher fluid Velocity & dual phase flow

Rapid corrosion due to more physical contact between fluid & metal, Transfer line Furnace, Overhead, Column, Side-cut piping etc Points of vaporization or condensation Vacuum towers and tower internals

Crude Distillation Unit

Problem in Product Streams Diesel and ATF cuts (Higher TAN)

RCO, LVGO, HVGO and VR circuits, Furnace tubes and transfer lines, Accumulation of NAs are more in boiling ranges 2000C to 4200C

Secondary Processing Units (FCC feed etc)

Methods of Processing HAC Crudes

S.N APPROACH REMARKS

1.
2. 3.

Blending/dilution with low TAN crude oils

Caustic treatment Changing the hardware/plant metallurgies Processing High TAN crudes without any hardware change Processing high TAN crudes with the use of corrosion inhibitors & continuous monitoring Crude TAN Removal

Diminishing the value of low TAN crude oils

Effluent and emulsion problem Higher capital cost Small size Refineries like in China, Dismantle the plants after making profits Not commercialized at larger scale

4.

5.

6.

New Approach

Processing Opportune Crude Oils

What Determines Average Crude Prices and Hence Differentials
Specific gravity API a positive factor Sulfur (% by weight) a negative factor Acidity (TAN) a negative factor High Pour :Distillate yields :Cost of Refining :Corrosion & Fouling :Transportation/pumping

Advantages of Processing Opportune Crudes

Ability to process low cost crudes - Crude constitutes more than 80% of input costs of a refinery e.g., For a 15 MMT capacity refinery, processes 1/3 of opportune crudes costing 1$ less would make over 100 crores additional profit which is substantial. Enlarging crude basket reduced dependency of specific crudes i.e., ability to process wide variety of crudes

Each API per $ of Brent is worth +$0.00969. Each % of sulfur is worth -$1.979 Each unit of TAN is worth -$1.435

Crude oil evaluation and product characterization

Detailed Crude Evaluations

Crude Characterizations Density/SG/API SUL KV PP CCR Nitrogen Asphaltene Salt Metals BS&W etc.

Product Characterizations LPG NAPHTHA (IBP-140)

60-70;70-90;110-140 etc.

KERO (140-240 &140-290) HSD (240-360 & 290-360) VGO (360-565) LR (360+) SR (530+ & 565+)

TBP Distillation following ASTM D2892 and D5236

Objectives of Detailed Crude Evaluation

Given the crudes, identifying the suitable crudes for blends through scientific studies. Characterize the individual crudes in terms of :

Assay Corrosivity Fouling and emulsifying species

Assess the compatibility of blends Simulate the deslater performance Impact of Corrosion in atmospheric and vacuum units Assess fouling tendencies of the identified crude blends Suitability of products to meet Euro (III)/(IV) norms. Evaluate economic impact of processing opportune crude blends

THE CHEMISTRY OF CRUDE OIL

Crude oils are organic in nature and are made up of carbon and hydrogen (hydrocarbons) with lesser amounts of sulphur, nitrogen, oxygen and traces of different metals such as cobalt, nickel, potassium, calcium, sodium, silicon, copper vanadium etc Elemental composition of crude oil can be summarized thus: Element/Component Percentage Weight Carbon 85.0 Hydrogen 12.0 Sulphur 0.8 Nitrogen 0.6 Oxygen 0.6 Trace metals (e.g. Fe, Al, Ni, Ca etc) 0.2 Sediments 0.8 The hydrocarbon contents of crude oils are complex but are principally: 1. Paraffins (Alkanes) 2. Napthenes (Cycloparaffins) 3. Aromatics The predominance of one group gives the petroleum certain properties valuable in formulating a general idea of the usefulness of the crude in producing various refinery products.

Crude Characteristics

Density , API, Specific Gravity Flow properties Viscosity, Pour Point Sulfur Residue CCR, Ramsbottom Total Acid Number Mercaptans Basic Nitrogen Asphaltene content Distillation Profile SIMDIST, D86, D1160

Properties of Fuels and their significance

Density

Essential for quantity calculations, setting purifier, indicates specific energy and ignition quality. Density is the absolute relationship between mass and volume at a stated temperature and the SI unit is kg/m3. The standard reference temperature used in international trade for density calculation of petroleum and its products is 15C. Knowledge of density is required for quantity calculations. Its value also needs to be known in order to select the optimum size of gravity disc for the centrifuge. In addition the density gives an indication of other fuel characteristics, including specific energy and ignition quality. Specific gravity of a substance is the ratio of the mass of a given volume to the mass of an equal volume of water at the same temperature. As it is a ratio there are no units. API gravity (degrees) = (141.5 / Relative density @ 60 / 60 F) 131.5

Viscosity

Dynamic viscosity is a property of the internal resistance of a fluid that opposes the motion of adjacent layers. The unit of measure of this resistance in SI units is a Pascal.s. Frequently the unit of a Poise is used, where 1 Pascal.s = 10 Poise. It should be noted that dynamic viscosity is also referred to as absolute viscosity. Fuel viscosity is usually expressed as kinematic viscosity, which is measured in Stokes. Kinematic viscosity is the quotient of the dynamic or absolute viscosity divided by the density, with both expressed at the same temperature. The storage and handling temperature is determined by the viscosity if the pour point of the fuel is low. Typical maximum fuel viscosity for transfer is 800 - 1000 cSt . The temperature for atomisation of the fuel also depends on viscosity. For distillate fuels the reference temperature used is 40C. However for residual fuels 50C is still commonly used, even though the international marine fuel specification has a reference temperature of 100C.

Flash point

The flash point of a fuel is the temperature at which vapour given off will ignite when an external flame is applied under standardised conditions. A flash point is defined to minimise fire risk during normal storage and handling. Important for volatility of fuels Used to evaluate potential hazards on storage and transportation

Pour Point

The pour point is the lowest temperature at which a marine fuel can be handled without excessive amounts of wax crystals forming out of solution If a fuel is below the pour point wax will begin to separate out, which will block filters. Also the wax will build up on tank bottoms and on heating coils. When heat is reapplied difficulties may be experienced in getting the wax to re-dissolve because of its insulating nature

Residue &Ash Content

Residue content of a fuel signifies the tendency to form deposits in the exhaust and the quantum of tail pipe emissions of CO2, SO2, NOx and unburnt HC The ash value is related to the inorganic material in the fuel. The actual value depends upon three factors, firstly the inorganic material naturally present in the crude oil, secondly the refinery processes employed, and thirdly, upon possible subsequent contamination due to sand, dirt and rust scale. The ash level signifies the deposit formation tendency of the fuel.

Sulphur

Sulphur is a naturally occurring element in crude oil that is concentrated in the residual component of the crude oil distillation process. Hence the amount of sulphur in the fuel oil depends mainly on the source of the crude oil and to a lesser extent on the refining process In a diesel engine the sulphur in the fuel having first burnt to SO2, then combines with excess oxygen to form SO3. In the presence of water vapour the SO3 is converted to sulphuric acid, which forms on the cylinder walls if the temperature is below the dew point for condensation of the acid. This dew point is a function of the sulphur content of the fuel and the pressure in the cylinder. World wide refineries have implemented various technologies to reduce fuel sulphur Euro 2 to Euro 5

Total Acid Number

Acidity inherent in crude oils Due to Naphthenic acids and some inorganic acidity Naphthenic acids pose corrosive hazards while processing Quantification of NA still to be explored Literature reports that NA effect is minimized when crude oil sulfur is high

SARA analysis

Saturate-Aromatics-Resins-Asphaltene Components which decide the distillate yield of crude oil Characterization of residue for SARA can aid its application as bitumen, fuel oil, coker feed

Oxidation Stability

Indicates fuel stability on storage Significant for automotive fuels viz., MS, HSD Severely processed fuels show poor oxidation stability due to presence of olefins

Typical Detailed evaluation format

Cut Range
CR LPG Naphtha Kerosene 140 290 C Diesel 290 360 C HVG O LR SR

Whole Crude

LPG

60 70C

70 90C

110 140

140 240C

240 360C

450 565C

360 +C

565+ C

Test
Fractional Distillation Volume Yield Density @15C Specific Gravity @60/60F

Method
D2892 D5236 D4052 D4052 X X X X X X X X X X X X X X X X X X X X X

API Gravity
Aniline Point Aniline Gravity Product Appearance Arsenic Ash

D4052
D611 Calc Visual ICPMS D482

X
X X X X X X

X
X X

X X X X X X

Asphaltenes
Carbon Content Hydrogen Content Carbon Residue - Micro Characterization Factor,calc

IP143
D5291 D5291 D4530 UOP 375

X
X X X X X X X X X X X X X X X X X X X X

X
X

X
X

Cloud Point
Colour - Saybolt DHA - Aromatics

D2500-02
D156-00 D6730-01

X X X X X X X X X X X X X X X X X X X X X

DHA - Naphthenes
DHA - Olefins DHA - Paraffins

D6730-01
D6730-01 D6730-01

DHA - Unknowns
Distillation Distillation - vacuum

D6730-01
D86-01 D1160

X X

X X

X X

FIA - Aromatic
FIA - Olefins FIA - Saturates

D1319-99
D1319-99 D1319-99

X X X X X X X

X X X

X X X

X X X

Hydrogen Sulphide
Kinematic Viscosity @40C Kinematic Viscosity @50C

UOP163
D445-01 D445-01

X X

X X

X X

X X

X X X X X X

Kinematic Viscosity @100C

Kinematic Viscosity @135C LPG Composition (Extended) Mercury Content Metal - Aluminium Metal - Calcium Metal - Chromium Metal - Copper Metal - Iron Metal - Lead Metal - Magnesium

D445-01
D445-01 GPA2286 UOP938-00 ICP ICP ICP ICP ICP ICP ICP

X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X