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ULSD
HYDROTREATING1
Design considerations
The ULSD hydrotreater designer
must account for these factors during
the front-end design process:
Feed characteristics and variability.
Other product-quality requirements, especially cetane index.
Catalyst selection.
Optimization of reactor process
variables.
Equipment design requirements.
Reliability.
Future off-road diesel sulfur standards.
Minimizing product contamination.
Handling of off-specification
diesel product.
Les Harwell
Sam Thakkar
Stan Polcar
R.E. Palmer
Mustang Engineers & Constructors LP
Houston
Pankaj H. Desai
Akzo Nobel Catalysts LLC
Houston
Process flow
Fig. 1 shows a simplified process
flow diagram for a diesel hydrotreater.
Stripper bottoms heats fresh feed
from the surge drum, which then mixes with recycle hydrogen. Reactor effluent further heats the combined feed,
which is then heated in the charge
heater.
Reactor inter-bed quench may be required depending on the volume of
Based on a presentation to the 2003 NPRA Annual Meeting, Mar. 23-25, 2003, San Antonio.
Reprinted with revisions to format, from the July 28, & August 4, 2003 editions of OIL & GAS JOURNAL
Copyright 2003 by PennWell Corporation
PROCESSING
cracked stocksFCC light cycle oil and
light coker gas oilin the feed. Fig. 1
shows recycle gas used as quench.
Reactor effluent heats the combined feed and flows to a hot, highpressure separator (HHPS). Vapor from
the HHPS heats the recycle gas and
stripper charge before cooling in the
product condenser and entering the
cold, high-pressure separator (CHPS).
Wash water, injected upstream of the
products condenser, helps remove ammonium hydrosulfide. HHPS liquid
combines with heated CHPS liquid and
flows to the product stripper.
Vapor from the CHPS contacts with
amine in a scrubber for H2S removal
and flows to the recycle compressor
ULSD HYDROTREATER
Fig. 1
Makeup H2
LCO
Feed heater
Makeup H2
compression
Reactor
Recycle
compressor
Amine
treating
Quench
Feed
ULSD product
Gas to fuel
Sour water
Sour naphtha
Cold
high-pressure
separator
Hot
high-pressure
separator
Steam
Stripper
Wash water
Sour water
PROCESSING
Reactor design
A superficial mass velocity set at
2,000-5,000 lb/hr/sq ft determines
the initial reactor diameter. A value of
3,500 allows for a reasonable turndown rate and some upside allowance.
Mass flow includes all hydrocarbons
and hydrogen at the reactor inlet.
The refiner should consider a twotrain design if the required reactor diameter is larger than could be shop
fabricated and shipped to the plant
siteusually 12-14 ft for overland
shipment. For diesel hydrotreaters, this
is normally 30,000-40,000 b/sd for
each reactor train.
Refiners with adequate water access
and dock facilities can consider larger
P RESSURE PROFILE
Fig. 2
Makeup H2
1,200
LCO
1,198 1,100
Feed heater
1,102
1,252
Makeup H2
compression
957 1,054
P = 233
1,152
1,290
Reactor
1,190
Recycle
compressor
Amine
treating
Quench
1,025
1,274
1,120
1,174
1,060
1,123
1,022
963
Feed
1,154
ULSD product
1,002 1,100
1,254
1,186
1,096
998
1,086
1,073
1,065
988
975
968
Gas to fuel
1,176 1,276
1,000
Sour water
Sour naphtha
Pressure, psi
Normal
Relieving
978
965 1,062
Hot
high-pressure
separator
Cold
high-pressure
separator
Steam
Stripper
Wash water
Sour water
Pressure drops for the feed distributor and redistributors, quench internals, and collector are added to the bed
values to provide the overall fouled-reactor pressure drop. For ULSD, the feed
distributor and redistributor design is
crucial for obtaining the target product
sulfur level.
Several designs provide internal reactor quench to limit the temperature
rise. The normal method is to use hydrogen-rich recycle gas. Quench gas also causes liquid vaporization in the reactor, which provides an extra heat sink
for heat removal.
Another less-common approach is to
recycle CHPS liquid to the reactor. The
quench limits the reactor bed temperature rise to 40-50 F.
Reactor metallurgy is typically 114chrome, 12-molybdenum with 18-in. 347
stainless overlay or cladding. The metallurgy choice often depends on the vessel thickness, which affects the cost.
Cladding is usually more economical
for vessels with a wall thickness up to
about 4 in. An overlay is normally used
with thicker walls.
PROCESSING
weight. This is a potential problem for a
Table 2 shows that the assumed
centrifugal recycle compressor because pressure profile is consistent with 900the lower molecular weight requires
psi flanges in the reactor loops alloy
more head and potentially more stages. piping. The relieving pressure profile
This is not as serious for a reciprosets the design pressure for equipment
cating machine; however, higher hydro- in the reactor loop.
gen purity increases the discharge temEarly in the design process, the deperature, which is limited to 275 F. per signer develops a sized equipment list
API-618.
that allows for plot plan studies. The
Makeup gas normally feeds to the
designer checks preliminary reactorrecycle compressor
discharge unless it P RESSURE ALLOWANCES
Table 1
needs an additionEquipment
item
Pressure
drop,
psi
al stage of makeup
Combined feed exchangers, both sides
40
compression. This
Feed heater
50
has the advantage
Reactor, fouled
75
HHPS
vapor-recycle
hydrogen,
both
sides
20
of maintaining
HHPS vapor-CHPS liquid
10
some hydrogen
Effluent air condenser
10
Amine
system,
knock
out
drums
5
flow through the
Piping
25
reactor loop in
Total reactor loop
235
case of a recycle
compressor emergency outage.
loop pipe sketches and rechecks allowances for piping pressure drops before specifying the recycle compressor.
Reactor-loop hydraulics
The designer checks reactor-loop
A hydraulic profile for the reactor
hydraulics a final time after receiving
loop provides the recycle compressor
equipment vendor information and afhead requirements and establishes the
design pressure of piping and equipment. ter completing piping isometrics for
Reactor inlet pressure is set based on the reactor loop.
Compression
We established design pressures in
conditions that the catalyst supplier esInlet flow and head requirements
the reactor loop assuming the CHPS retablishes, and the pressure limits of
determine the recycle compressor delief valve set pressure is 10% higher than
sign. Adequate suction flow is required standard piping flanges.
the normal operating pressure. The reTwo case studies are presented in
for a centrifugal compressor, and the
head should be low enough to limit the Part 2 for reactor inlet pressures of 800 finer can set this margin at 5% with a
pilot-operated relief valve, which will
and 1,100 psig.
number of stages so that only a single
Table 1 shows a typical allowance for lower the reactor loops design pressures.
body machine is needed; this is usually
A 10% margin in a grassroots facility
reactor-loop equipment and piping
a maximum of 10 stages.
allows for future capacity increases
In the past, most diesel hydrotreaters pressure drop for the 1,100-psig case.
Fig. 2 shows a point-to-point pres- while staying within equipment design
had an inadequate volume of recycle
sure profile for normal operations and pressure limits. API Recommended
gas for a centrifugal compressor. New,
Practice 521, Appendix G recommends
larger ULSD hydrotreaters that circulate for the relieving case in which the
a design pressure of 105% of the setCHPS is 10% greater than the operat3,000-5,000 cu ft of gas/bbl of feed
tling-out pressure, which would make
are candidates for centrifugal compres- ing pressure.
the design pressure about 115% of the
Table 2 shows maximum pressures
sors.
normal operating pressure.
A reciprocating compressor used for at relieving conditions and typical deWhile the designer is establishing
recycle normally also provides makeup sign temperatures for critical piping
equipment design conditions, insuffiservices in the reactor section comservice in a multiple-throw machine.
pared to a maximum allowable pressure cient information exists to calculate the
For reciprocating compressors greater
for 900-psi, type-321 stainless flanges. settling-out pressure accurately. When
than 500 hp, two 60% capacity machines are typically used. For smaller
compressors, two 100% units are used.
PIPING CONDITIONS
Table 2
Makeup compressor discharge feeds
to the recycle compressor suction or
Pipe section
Design pressure,
Design temperature,
Maximum allowable
psi
F.
pressure, psi
discharge.
Exchanger to heater
1,252
700
1,260
Makeup gas flowing to the suction
Heater to reactor
1,200
775
1,242
increases recycle gas purity and volReactor to exchanger
1,123
825
1,233
ume, and decreases the molecular
Determine the quantity of circulating water to ensure that 25% of the
total water injected in the liquid phase
is upstream of the condenser.
Limit the mixed-phase velocities
in the piping and tubes to 20 fps for
carbon steel and 30 fps for alloys. The
minimum velocity should be 10 fps.
Provide symmetrical piping into
and out of the condenser.
Ensure that the wash water source
is a stripper dedicated to hydrotreating
spent wash water if stripped sour water
is used.
Ensure that wash water is injected
into the main effluent line upstream of
the condenser, or independently into
each air cooler nozzle through a distribution device like a spray nozzle or restriction orifice. Injecting into piping
provides more time for mixing and vaporizing the water and is less expensive. Injection into individual air condenser nozzles ensures good distribution in each air cooler bay.
Typical alloys, if required, are Incoloy 800 or 825, and duplex stainless
steel 2205.
Product stripper
The product stripper removes H2S
and light hydrocarbons from the ULSD
product. Light material removal must
be high enough to meet a flash-point
specification of 140 F. This ensures removal of nearly all H2S.
The stripper requires about 30 trays.
Overhead products include sour gas, unstabilized naphtha, and sour water.The
design also includes equipment for intermittently water washing the condenser.
Steam or vapors from a fired reboiler
serve as the stripping medium. Due to
temperature constraints of about 700
F. maximum, the stripper operating
pressure is limited to 40-50 psig for a
fixed reboiler.
Unless the refinery has a low-pressure gas recovery system, a small compressor and spare are needed to handle
the offgas.
A steam stripper can operate at pressures greater than 100 psig, which allows routing into an existing refinery
sour fuel gas system.
Diesel product from a steam stripper
must have all water removed. Vacuum
drying or coalescing followed by salt
drying can accomplish the water removal. If this type of system already exists, the steam-stripping option has a
lower capital cost vs. a fired reboiler. A
steam-stripped tower is also a little
smaller than a reboiled tower.
If the product drying system is not
in place, the refiner should consider the
fired reboiler option. It will also create
less sour water to process.
Product stripper material is killed carbon steel with 410 stainless steel trays
The authors
Leslie J. Harwell is a senior
consulting process engineer at
Mustang Engineers & Constructors LP, Houston. He is
primarily involved in ultra-low
sulfur projects and midstream
Feed filtration
gas processing. Harwell has also
Although distillate stocks are relatively clean, feed filtration is important worked for Fish Engineering
and Litwin Engineering & Construction Inc.
to mitigate exchanger and reactor plug- Corp.
He holds a BS (1967) in chemical engineering
ging. A cartridge filter with 25-m re- from the University of Texas, Austin. Harwell is a
tention is typical for this application.
registered professional engineer in Texas and a
Cracked feeds should feed the hymember of the Gas Processors Suppliers Associadrotreater hot from the upstream facili- tion.
ties or from gas blanketed storage.
Shrikant (Sam) Thakkar is a
senior specialist for ChevronReferences
Texaco Corp., Bellaire,Tex. He
1. Palmer, R.E., Ripperger, G.L.,
previously worked for Mustang
Migliavacca, J.M., Revamp your hyEngineers & Contractors LP
drotreater to manufacture ultra low sul(when this article was written).
fur diesel fuel, presented to the 2001
He holds a BS (1981) in
chemical engineering from
NPRA Annual Meeting, Mar. 18-20,
Bombay University.
New Orleans, paper AM-01-22.
2. Leliveld, B., Mayo, S., Miyauchi,Y.,
and Plantenga, F., Elegant solutions for Stan Polcar is a principal
engineer for Mustang
ultra low sulfur diesel, presented to the process
Engineers & Constructors LP.
2001 NPRA Annual Meeting, Mar. 18He has also worked for Litwin
20, New Orleans, paper AM-01-09.
Engineering & Construction
3. Brevoord, E., Gudde, N., Hoekstre, Inc. and The Pritchard Corp.
Polcar holds a BSc (1968) in
G., Mayo, S., and Plantenga, F., ULSD
chemical engineering from Case
real life: Commercial performance of
Stars and Nebula technology, present- Western Reserve University, Cleveland. He is a reged to the 2002 NPRA Annual Meeting, istered chemical engineer in Texas.
Mar. 17-19, 2002, San Antonio, paper
R.E. Palmer is the manager of
AM-02-38.
downstream process engineering
4. Landue, M.V., Catalysis Today, Vol.
for Mustang Engineers & Con36 (1997), pp. 393-429.
structors LP. He is responsible
for process design and market5. Piehl, R.L., Refiners tame effluing support for all refining,
ent air-cooler corrosion, OGJ, Aug. 18,
petrochemical, and chemical
1975, pp. 119-20.
projects. He has led numerous
6.Torrisi, S., Proven best practices for
studies,
technology
evaluations, and projects relatULSD production, presented to the
ing to clean fuels production. Palmer previously
2002 NPRA Annual Meeting, Mar. 17-19, spent 23 years with Litwin Engineers & Con2002, San Antonio, paper AM-02-35.
structors Inc. and 5 years with Conoco Inc. He
7. Schmidt, M., Premium perform- has a BS in chemical engineering from the Uniance hydrotreating with Axens HR 400 versity of Missouri, Rolla.
series hydrotreating catalysts, presented to the 2002 NPRA Annual Meeting, Pankaj H. Desai is the new
business development manager
Mar. 17-19, 2002, San Antonio, paper
for Akzo Nobel Catalysts LLC,
AM-02-57.
Houston. He joined Akzo Nobel
8. Larkins, R.P., White, R.R., and Jef- in 1980 and has held various
fery, D.W., Two Phase Concurrent Flow positions in hydroprocessing
in Packed Beds, AICHE Journal, June
and FCC catalyst research and
development. Desai holds a
1961, pp. 231-39.
BTech degree (1974) in chemical engineering
9. Knudsen, K.G, Cooper, B.H., and
Topsoe, H., Catalyst and Process Tech- from Indian Institute of Technology, Kanpur, and a
PhD in chemical engineering from the University
nologies for Ultra Low Sulfur Diesel,
of Houston.
Applied Catalysis A: General, Vol. 189
(1999), pp. 205-15.
PROCESSING
ULSD HYDROTREATING
Conclusion
Fig. 1
Makeup H2
LCO
Feed heater
Makeup H2
compression
Straight-run
diesel
Reactor
Recycle
compressor
Quench
Amine
treating
Feed
ULSD product
Gas to fuel
Cold highpressure
separator
Sour water
Sour naphtha
Steam
Wash water
Sour water
7
F.
Base
13 F.
increases 14-15% for the two
cycle cost.
Chemical hydrogen
extremes in reactor inlet pres Operating cost is the
consumption, cu ft/bbl
Base
Base x 1.075
Base x 1.14
Cycle length, months
20-22
29-31
38-40
sure. This increase, however, can
major component in unit
Product sulfur, ppm (wt)
10
10
10
Product nitrogen, ppm (wt)
<10
<10
<10
have a significant impact on the
life-cycle cost.
Yields, wt %
projects life-cycle cost, especial At different pressures
Start of run Feed
100.00
100.00
100.00
C4 and lighter 0.07
0.07
0.07
ly if the refinery is hydrogen
(700-1,100 psig) and
Naphtha
3.32
3.27
3.24
limited.
feed and process condiDistillate
96.04
96.15
96.22
End of run
Feed
100.00
100.00
100.00
For ULSD applications, the
tions, the increase in
C4 and lighter 0.17
0.17
0.16
Naphtha
3.54
3.46
3.41
quantity of cracked stocks in the
chemical hydrogen conDistillate
95.78
95.97
96.11
feed strongly influences chemisumption is a modest
cal hydrogen consumption. Hy15%. For ULSD designs,
drogen solution loss (nonchemhydrogen consumption is ULSD REACTION CONDITIONS, CONSTANT CYCLE LENGTH Table 3
ical consumption) increases
mainly a function of feed
Reactor inlet pressure, psig 700
900
1,100
with pressure.
characteristics, particularly
Reactor LHSV, hr1
Base
Base x 1.20
Base x 1.35
Tables 2 and 3 LHSVs were
aromatics content, and
Start of run WABT, F.
Base
Base + 5 F.
Base + 7 F.
1.0-1.75 hr1, which is rather
unit operating pressure.
Chemical hydrogen
consumption, cu ft/bbl
Base
Base x 1.08
Base x 1.15
Makeup hydrogen
modest with a feed that contains
Cycle length, months
23-25
23-25
23-25
Product
sulfur,
ppm
(wt)
10
10
10
purity has a major impact
a substantial LCO fraction. This
Product nitrogen, ppm (wt)
<10
<10
<10
on the recycle gas comis due to a somewhat low feedYields, wt %
Start of run Feed
100.00
100.00
100.00
pressor. For a makeup hynitrogen content, a processing
C4 and lighter 0.07
0.07
0.07
drogen purity of 85 mole
objective of lower product sulNaphtha
3.30
3.29
3.28
Distillate
96.05
96.12
96.18
%, the centrifugal recycle
fur only and not cetane imEnd of run
Feed
100.00
100.00
100.00
C4 and lighter 0.17
0.16
0.17
compressor requires two
provement, and the application
Naphtha
3.53
3.46
3.42
or three stages. For highof new generation, high-activity
Distillate
95.8
96.0
96.1
purity hydrogen makeup,
catalysts.
eight or nine stages are required. It is
If the feed contains more nitrogen,
Tables 2 and 3 show various reactor
impractical to design for this range of
which is common with coker light gas
parameters and product yields and
purities.
oil, the volume of catalyst required to
qualities using Akzo Nobel Catalysts
Recycle gas purification via recon- LLCs Stars KF-848 high-activity, nickel- meet the target sulfur specification intact with liquid from a cold low-presmoly catalyst for different reactor inlet creases significantly. Also, changing feed
sure separator (CLPS) is not justified
sulfur quantities and sulfur species
pressures and hydrogen partial presbased on energy savings. For an existmight move the design to a more consures at the reactor outlet. The catalyst
ing unit, however, higher-purity recycle is dense loaded into the reactor.
servative LHSV.
gas can extend cycle length or help
We further analyzed reactor yields
Table 2 shows the different cycle
meet the treating specification.
lengths at each pressure level to obtain and process conditions for a LHSV of
1.25 hr1 and reactor inlet pressures of
a 10-ppm (wt) sulfur product given a
constant liquid hourly space velocity
800 and 1,100 psi. We also considered
Case studies
(LHSV). Cycle length varies from 20-22 other design options, including:
Table 1 shows the feed characterismonths at a 700-psig reactor pressure
A two-separator system with an
tics used for this study. The feed is a
HHPS and CHPS.
blend of two-thirds straight-run diesel to 33-35 months at 1,100 psig.
The higher hydrogen partial pres A single-separator system with a
and one-third FCC light cycle oil
(LCO); the combined nitrogen content sure corresponding to each reactor inlet CHPS only.
pressure decreases catalyst deactivation
An HHPS-CHPS system that enis 242 ppm (wt).
PROCESSING
the various options. For
riches recycle hydrogen
each case, the LHSV and
using a CLPS and recon- M AKEUP HYDROGEN Table 4
product sulfur content
tacts the liquid with re- COMPOSITION
were constant. We set
actor effluent that feeds
Component
Fraction, vol %
the recycle hydrogen
the products condenser.
Hydrogen
85.00
Nitrogen
1.00
rate to achieve a ratio of
High-purity hyMethane
3.21
total hydrogen to the
drogen makeup for the
Ethane
3.10
Propane
3.80
reactor to chemical hytwo-separator case.
i-Butane
1.27
drogen consumption of
High-purity hyn-Butane
1.10
i-Pentane
0.64
5.5 for the 1,100-psi
drogen makeup for the
n-Pentane
0.32
C6+
0.56
case, and 6.0 for the
single separator case.
Total
100.00
800-psi case.
Table 4 shows the
Based on the calculow-purity makeup hylated reactor outlet hydrogen partial
drogen composition. We assumed that
high-purity makeup gas was 99.9 mole pressure, Akzo Nobel estimated the cycle length, chemical hydrogen con% hydrogen.
The low-purity makeup is typical of sumption, and weighted average bed
a blend of hydrogen from a catalytic re- temperature to calculate the final reactor yields and other process conditions.
former and a high-purity source, such
as membrane purification or purchased
hydrogen.
Case descriptions
Table 5 shows the results of simulaWe used the simulation results to
tions for the 13 cases corresponding to prepare heat and material balances,
SIMULATION RESULTS
Case
Table 5
Reactor inlet
pressure, psig
1,100
1,100
Makeup H2
purity, mole %
85
85
Number of
separators
2
1
Cold high-pressure separator
Temperature, F.
110
110
Pressure, psig
965
993
H2 partial pressure
at reactor outlet,
psia
612
674
Cycle length,
months
33-35
36-38
Chemical H2
consumption,
cu ft/bbl
400-500 400-500
Makeup H2
flow, MMcfd
19.4
18.8
H2 at reactor inlet:
Chemical H2
consumption, ratio
5.5
5.5
Total H2 at reactor
inlet, cu ft/bbl
2,673
2,673
H2 purity at reactor
inlet, mole %
70.2
76.5
Purge, MMcfd
1
1
Enrichment
liquid, b/sd
0
0
Recycle gas
Flow rate, MMcfd 114.5
104.4
H2 purity, mole %
67.0
75.0
Molecular weight
8.8
6.6
Recycle gas compressor
Normal bhp
1,902
1,741
Number of stages
2
3
Stripper
Offgas flow, MMcfd 4.0
3.5
Overhead liquid
flow, b/sd
1,117
1,140
Overhead liquid
cut point, F.
350
350
ULSD product
Flow, b/sd
29,841
29,856
Gravity, API
33.0
33.1
Cetane index
45.5
45.5
Sulfur, ppm (wt)
10
10
Nitrogen, ppm (wt) <10
<10
10
11
1,100
1,100
1,100
1,100
1,100
85
85
85
99.9
110
965
110
965
110
965
110
993
12
13
800
800
800
800
800
800
99.9
85
85
85
85
99.9
99.9
110
965
110
693
110
693
110
693
110
665
110
693
110
665
644
661
687
898
893
448
492
508
408
612
611
34-36
36-38
37-39
48-50
47-49
18-20
22-24
22-24
<20
33-35
33-35
400-500
400-500
400-500
400-500
400-500
400-500
400-500
400-500
400-500
19.8
19.8
19.8
15.3
15.3
17.0
20.9
25.9
17.3
13.8
14.5
5.5
5.5
5.5
5.5
5.5
6.0
6.0
6.0
6.0
6.0
6.0
2,673
2,673
2,668
2,668
2,668
2,622
2,622
2,622
2,622
2,622
2,622
73.5
1
75.2
1
77.9
1
98.5
0
98.1
0
72.2
1
79.9
5
82.7
10
65.2
1
97.9
0
98.0
0
3,126
6,117
11,756
109.0
71.0
7.9
106.6
73.0
7.4
103.0
76.0
6.7
81.3
98.1
2.3
81.6
97.6
2.5
109.5
69.4
7.5
98.0
79.0
6.3
95.0
82.0
5.9
122.1
61.0
9.7
80.4
97.4
2.4
80.5
97.3
2.6
1,769
3
1,502
2
1,725
3
1,368
9
1,382
8
2,503
4
2,311
5
2,238
5
2,760
3
1,405
9
1,787
8
3.62
3.4
3.1
1.3
2.1
2.9
2.7
2.7
3.0
0.9
1.4
1,080
1,046
1,000
942
971
1,131
1,182
1,226
1,101
969
995
350
350
350
350
350
350
350
350
350
350
350
29,821
33.1
45.5
10
<10
29,814
33.1
45.5
10
<10
29,810
33.1
45.5
10
<10
29,919
33.1
45.5
10
<10
29,859
33.1
45.5
10
<10
29,834
32.5
44.7
10
<10
29,829
32.5
44.7
10
<10
29,824
32.5
44.7
10
<10
29,837
32.5
44.7
10
<10
29,885
32.6
44.8
10
<10
29,882
32.6
44.8
10
<10
400-500 400-500
HHPS ADVANTAGES
Table 6
PROCESSING
ULSD 20-YEAR COSTS
Life-cycle cost, million $
400
350
300
250
200
150
100
50
0
Case 1
Case 2
140
Case 1
Case 2
120
Case 13
100
80
60
40
20
0
Utilities
Maintenance