LUBRICANT BASE OIL

HYDROGEN REFINING PROCESSES

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 Band Crush !

• Ngô Thị Hiền

• Phạm Thị Xuân Quỳnh Lương
• Phan Thị Lệ Thanh

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 CONTENT

A INTRODUCTION

B HYDROCRACKING PROCESSES

C HYDROREFINING PROCESSES

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 A. INTRODUCTION
 Hydrogen refining, commonly called lube hydrocracking or
severe hydrotreating was first used in the 1930s.
 Converts the undesirable constituents into the desirable lubricant
base oil components and other higher valued by-products.
 The hydrogen refining processes consist of:
HYDROREFINING - Purification and saturation reactions
HYDROCRACKING – Purification, saturation and cracking
reactions

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 1- Purification Reactions

Pressure 200 to 2000 psi

Temperature 500 to 700°F
Space velocity 1 to 5
H2 consumption 100 SCFB 5
 2- Saturation Reactions

 Involve the purification reactions and saturation reactions

 Convert olefins to paraffins and aromatics to cycloparaffins.

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 2- Saturation Reactions

Pressure 500 to 3000 psi

Temperature 450 to 750°F
Space velocity 0.5 to 3.0
H2 consumption about 100 to 1000 SCFB 7
 3- Cracking Reactions

 The breaking of carbon-to-carbon bonds, scission of condensed

ring structures and molecular rearrangement via isomerization.

Pressure 500 to 4500 psi

Temperature 625 to 850°F
Space velocity 0.5 to 3.0
H2 consumption 500 to 2000 SCFB 8
 B. Hydrocracking Processes

To permit use of low quality crude oils

The lube
hydrocracking For viscosity reduction
processes are
the most
severe As a replacement for solvent extraction
lubricant base
oil hydrogen
refining To increase the yield of base oils
processes obtained by solvent extraction

To improve the quality of lubricant base

oils
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 Process Flow

Figure II.1. Bulk feed hydrocracker flow diagram

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Effect of Hydrocracking on Feedstock Properties

Decreases viscosity Increases viscosity index

Improves color Reduces color stability

Improves inhibitor response Decreases oxidative stability
Reduces sulfur content Reduces nitrogen content
Reduces carbon residue Reduces specific gravity
Reduces aromatic content Increases iso-paraffin content

Increases viscosity index Permits use of non-lube crudes

Table II.1. Effects of Hydrocracking on Properties of Base Oil Feedstocks

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 Feedstocks to Hydrocracking Processes

Unrefined distillates
Deasphalted oils
Hydrocracked deasphalted oils
Solvent refined distillates
Solvent extracted deasphalted oils
Scale and slack waxes
Mixtures of the above

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 Comparison with Solvent Extraction

Advantages of hydrocracking:

Higher VI base oils

Higher valued by-products
Use of poorer quality crudes
Conversion of residual oils to distillate oils
Viscosity adjustment to meet demand
Base oils of better inhibitor response
Elimination of finishing in some cases

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 Comparison with Solvent Extraction

Disadvantages of hydrocracking:
Form sludge and darken on exposure to heat or light
Require stabilization by extraction or hydrorefining
Investment costs are higher at the 95 VI level
Operating costs are higher at the 95 VI level
Solvent dewaxing filter rates are poorer
Catalytic dewaxed bright stocks are hazy
Uninhibited base oil oxidation is poorer
Exhibit additive solubility problems
Aromatic extract oils are not produced
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 Processing Conditions
Operating conditions
Process variable
Range Typical
Pressure, psig 1500-4000+ 2500-3000
Temperature, °F 625-850 725-825
Space velocity, Vo/Vc/hr 0.25-1.25 0.5-1.0
Hydrogen recycle, SCFB 3000-8000 3500-5000
Recycle hydrogen purity, mole % 70-100 90-95
Hydrogen consumed, SCFB 500-3000 700-1200
Lube yield, volume % 30-90 40-80
Catalyst life, years 1-3 1-2

Table II.2. Lube Hydrocracking Process Conditions 15

 Hydrocracking Catalysts

Figure II.2. Some Commercially Available Hydrocracking Catalysts 16

 Process Variables

The process variables for lube hydrocracking processes are listed in Table
II.3 Although operating pressure, hydrogen purity and hydrogen rate have
a significant effect on catalyst life and product yield, other important
variables are feedstock quality, temperature, space velocity and catalyst.

Table II.3 Lube Hydrocracking Process Variables

Feedstock Pressure
Temperature Space velocity
Catalyst Hydrogen purity
Recycle hydrogen rate

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 Process Variables

Effects of Effects of
Feedstock Temperature and
Quality Space Velocity

Process Variables

Bulk Feed Blocked Feed

Hydrocracking Hydrocracking

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 1. Effects of Feedstock Quality

Figure II.4
Effect of feed composition on product character. 19
 2. Effects of Temperature and Space Velocity

The process temperature and space velocity (LHSV) are the primary
process variables which affect base oil VI and yield.

Figure II.5
Effect of process severity on product character.
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 2. Effects of Temperature and Space Velocity

Figure II.6 Figure II.7
Effect of reaction conditions o Effect of reaction conditions on m
n iso-paraffin content. ononaphthene content.
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 2. Effects of Temperature and Space Velocity

Table II.4
Effect of Process Severity on Base Oil Yield and VI
Middle East Feed Low severity High severity
DA oil Dewaxed oil Dewaxed oil
Dewaxed
Dewaxed oil
oil 77.4
77.4 64.4
64.4
Yield,
Yield, volume %
volume %
Base
Base oil
oil properties
properties
API
API gravity
gravity 19.8
19.8 24.9
24.9 28.6
28.6
Viscosity 231 149.9 75.5
Viscosity 231 149.9 75.5
Viscosity index 74 84 103
Viscosity index 74 84 103
Pour point, 130+ -10 -15
130+ -10 -15
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 3. Bulk Feed Hydrocracking

The use of bulk feed lube hydrocracking often leads to a low viscosity base oil
fraction which is low in viscosity index in comparison to the heavy base oil
fraction of the hydrocrackate.

Table II.5 VI Droop in Lube Hydrocracking

Alaskan North Slope Abrian Light

Viscosity Droop Viscosity Droop

500 neutral 100 Base 100 Base

24 neutral 92 8 99 1
100 neutral 75 25+ 88 12

VI droop depends on crude source and is greater for poor quality as compared to
good quality crude oils.
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 4. Blocked Feed Hydrocracking

Figure II.8
Blocked distillate lube hydrocracker flow diagram

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 Stabilization of Hydrocracked Base Oils

Hydrocracked oils tend to darken and form sediment on exposure to light. Methods
used to stabilize these oils consist of clay treating, solvent refining or hydrorefining
of the hydrocracked oil after dewaxing.

Figure II.9
Simplified flow diagram of Chevron's Richmond Lube Oil Plant. 25
Hydrocracking and Solvent Extraction Combinations

Figure II.10
Simplified flow diagram of Sun's Yabucoa Lube Plant.
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 Wax Hydrocracking and Hydroisomerization

have developed processes for

Shell the manufacture of very high
VI base oils by the
hydrocracking and
Several hydroisomerization of slack
base oil Releford waxes and high wax content
refiners and Ball feedstocks.

Chevron
development of a catalytic dewaxing process which
permits manufacture of very high VI base oils from
slack waxes or from high wax content feedstocks
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 Performance Economize
Licensors process

1) available crude source and

Performance of the its cost
Licensors of the 2) the final use and value of
hydrocracked base
the by-products
oils is equivalent to base oil 3) availability of hydrogen
or better than that of hydrocracking and other process units
the solvent refined processes include 4) desired product quality
oils in formulated 5) whether the plant is a
Chevron, IFP, stand-alone lube plant or is
products. integrated into a fuels
Unocal and UOP
refinery
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 HYDROREFINING PROCESSES

Feedstocks

Processing conditions

Hydrorefining catalysts

Process variable

Process flow
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 Feedstocks
Hydrorefining
Hydrorefining processes
processes

Solvent
Hydrocracked extracted Naphthenic
feedstocks feedstocks distillates
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 Processing Conditions
Operating conditions
Process variable
Range Typical
Pressure, psig 200-3000 1500-3000
Temperature, °F 480-850 500-600
Space velocity, Vo/Vc/hr 0.3-5.0 0.5-1.0
Hydrogen recycle, SCFB 550-8000 1000-3000
Hydrogen purity, mole % 90-100 90-95
Hydrogen consumed, SCFB 50-3000 100-1000
Yield, volume % 80-100 95-98
Catalyst life, years 1-3 1-2

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 Hydrorefining Catalysts

Lube Hydrorefining Catalysts

Nickel-molybdenum on alumina

Nickel-tungsten on silica alumina

Nickel-tungsten on alumina (most common)

High nickel (Low sulfur and nitrogen content feedstocks)

Platinum (Low sulfur and nitrogen feedstocks)

Palladium (Low sulfur and nitrogen feedstocks)

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 Process Variables

Hydrocracking Hydrorefining Hydrofinishing

processes processes processes

Pressure/Tempareture/Hydrogen recycle rate increase

• Operating temparature of Hydrorefining may be equivalent to

Hydrocracking
• Operation of the hydrorefining processes at higher temperatures
would result in hydrocracking reactions, the breaking of carbon-
to-carbon bonds and significant viscosity reductions which are
undesirable in the hydrorefining operation.

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 Process Variables

1. Effect of Feedstock Quality

• The yield of base oil depends on the quality of the feedstock and
base oil specifications, catalyst and process severity
• Feedstocks which are high in sulfur, nitrogen and/or aromatic
content provide lower yields and are usually processed in the
two-stage hydrorefining units.
2. Effects of Temperature and Space Velocity
• The process temperature and space velocity (LHSV) are the
primary process variables which affect base oil or wax yield.
• The use of low space velocity and low temperature is usually
preferred over high space velocities and high temperatures.
• Excessively high temperatures increase the amount of
extraneous cracking and coke deposits on the catalyst which lead
to short catalyst life and poor color stability of the finished oil.
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 Process Flow

Figure III.1 Single stage base oil hydrorefining unit.

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 Process Flow

Figure III.2 Two-stage base oil hydrorefining unit.

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 CONCLUSION
• Hydrogen refining is used for the purpose of removing other
undesirable constituents into the desirable lubricant base oil
components to improve VI, quality of lube stocks and other
higher valued by-product.

• The hydrogen refining processes consist of:

Lube hydrocracking
Hydrorefining

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