&EPA
United States
Environmental Protection
Agent.y
Industrial Environmental Research EPA 600 7 78 159
Labord:< • , August 1978
Research Triangle Park NC 2771 1
Catalyst Evaluation
for Denitrogenation
of Petroleum
Residua and
Coal Liquids
Interagency
Energy/Environment
R&D Program Report
-------
RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development, U.S. Environmental
Protection Agency, have been grouped into nine series. These nine broad cate-
gories were established to facilitate further development and application of en-
vironmental technology. Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interface in related fields.
The nine series are:
1. Environmental Health Effects Research
2. Environmental Protection Technology
3 Ecological Research
4. Environmental Monitoring
5. Socioeconomic Environmental Studies
6. Scientific and Technical Assessment Reports (STAR)
7. Interagency Energy-Environment Research and Development
8. "Special" Reports
9. Miscellaneous Reports
This report has been assigned to the INTERAGENCY ENERGY-ENVIRONMENT
RESEARCH AND DEVELOPMENT series. Reports in this series result from the
effort funded under the 17-agency Federal Energy/Environment Research and
Development Program. These studies relate to EPA's mission to protect the public
health and welfare from adverse effects of pollutants associated with energy sys-
tems. The goal of the Program is to assure the rapid development of domestic
energy supplies in an environmentally-compatible manner by providing the nec-
essary environmental data and control technology. Investigations include analy-
ses of the transport of energy-related pollutants and their health and ecological
effects; assessments of, and development of, control technologies for energy
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mental issues.
REVIEW NOTICE
This report has been reviewed by the participating Federal Agencies, and approved
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This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161.
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EPA-600/7-78-159
August 1978
Catalyst Evaluation for Denitrogenation
of Petroleum Residua and Coal Liquids
by
Cecelia C. Kang and Jeffrey Gendler
Hydrocarbon Research, Inc.
P.O. Box 6047
Lawrenceville, New Jersey 08648
Contract No. 68-02-0293
Program Element No. EHE623A
EPA Project Officer: Thomas W. Petrie
Industrial Environmental Research Laboratory
Office of Energy, Minerals, and Industry
Research Triangle Park, NC 27711
Prepared for
U.S. ENVIRONMENTAL PROTECTION AGENCY
Office of Research and Development
Washington, DC 20460
-------
ABSTRACT
This report describes the results of a study of catalysts for denitro-
genation of petroleum residua and coal liquids. The objectives were to
evaluate some existing commercial catalysts for denitrogenation activity in
petroleum residua and coal liquids and then to develop an improved catalyst
for denitrogenation of heavy coal liquids. Under task two, commercial
catalysts failed to reduce nitrogen content of a petroleum vacuum resid from
0.67 percent to the target of 0.3 percent. The observed catalyst deactivation
rate is similar to that of catalysts with similar pore structures which are
being used for hydrodesulfurization of petroleum resid. Under another task,
attempts to denitrogenate heavy, coal-derived liquids with commercial Co-Mo
catalysts pointed to the need for improved catalysts. In the task to improve
catalysts, Ni-Mo was identified as a better active metal pair than Co-Mo or
Ni-W for denitrogenation of coal liquids. Commercial preparation techinques
and lower cerbon deposition also increased denitrogenation activity. On the
basis of catalyst weight, a bimodal pore distribution with some macropores
showed better denitrogenation activity than that with micropores only. The
optimum pore distribution was sought, despite lack of technology to enlarge
macropores. Unusual catalyst preparation techniques were tried but only one
catalyst was prepared and evaluated for the effects of more and larger macro-
pores. It has a low surface area and its denitrogenation acitivity relative
to the base catalyst did not decrease. If this were a general result for
catalysts with more and larger macropores, less metals would be needed to
cover the support and a lower cost catalyst could be developed.
Hydrocarbon Research, Inc., a subsidiary of Dynalectron Corporation, did
this work as Phase V of Contract 68-02-0293 with the U.S. Environmental
Protection Agency. The period of performance of the entire contract was
December 1972 through February 1978 and included the study of demetallization
of heavy residual oils. Phase V work was done from September 1975 through
February 1978.
ii
-------
CONTENTS
Page
No
ABSTRACT ii
TABLE OF CONTENTS iii ,1v
ACKNOWLEDGEMENT v
CONVERSION FACTORS vi
SUMMARY 1
CONCLUSION 4
INTRODUCTION 5
PROCEDURES, RESULTS AND DISCUSSION 7
Task 1 - Denitrogenation of Petroleum Vacuum Resid 9
Task 2 - Denitrogenation of Coal Liquids from H-Coal Process 14
Subtask 2A - Denitrogenation of Gas Oil from
H-Coal Process 14
Subtask 2B - Denitrogenation of Fuel Oil from
H-Coal Process 14
Task 3 - Development of Denitrogenation Catalyst for Heavy
Coal Liquid from Solvent Refining Coal Process 16
Preparation of Feedstock 16
Subtask 3A - Evaluation of American Cyanamid Developmental
Catalysts 16
Effect of Active Metals 19
Effect of Method of Catalyst Preparation 19
Confirmation of Effect of Active Metals 22
Effect of Operating Temperature upon Catalyst 22
Effect of Operating Pressure upon Catalysts 22
Effect of Feed upon Ni -Mo Catalysts 26
Subtask 3B - Evaluation of the Significance of Bimodal
Pore Size Distribution of Ni-Mo Catalyst 26
Subtask 3C - Optimization of the Bimodal Pore Size Dis-
tribution of Ni-Mo Catalysts 26
Description of Catalysts 26
Armak Catalyst Preparati ons 30
Evaluation of Armak Catalysts 30
Effect of Space Vel oci ty- 33
APPENDIX A - Summary of Run Data 37
APPENDIX B - Summary of Operating Conditions, Product Distribution,
Hydrogen Consumption, 975°F+ Conversion and Heteroatom
Removal 44
iii
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FIGURES
Number Page
1 Fixed Bed Denitrogenation Unit - Unit 115 8
2 Pore Size Distribution of Commercial Catalysts 12
3 Denitrogenation of Gach Saran Vacuum Resid 13
4 Solvent Refined Coal Process, Wilsonville Pilot Plant 17
5 Comparison of Denitrogenation Activity Among
Three Developmental Catalysts and HDS 2-A 21
6 Pore Size Distribution of Nickel-Molybdate Catalysts 27
7 Pore Size Distribution of Nickel-Molybdate Catalysts 31
8 Denitrogenation of SRC Blend 34
TABLES
Number Page
•
1 Feedstock Inspections - Gach Saran Vacuum Resid 10
2 Characteristics of Commercial Catalysts 11
3 Inspections of Feedstocks from H-Coal Process 15
4 Analysis of SRC Materials and SRC Feedstock Blend 18
5 Characteristics of American Cyanamid Developmental
Catalysts 20
6 Evaluation of Method of Preparation 23
7 Temperature Effect Upon. Hydrodenitrogenation
SRC Liquids 24
8 Effect of Pressure on Hydrodenitrogenation of SRC
Liquids 25
9 Effect of Macropores in Catalyst Upon Denitrogenation
of Heavy Coal Liquids 28
10 Characteristics of Ni-Mo Catalysts 29
11 Comparison of Armak Catalysts and American Cyanamid
Catalyst HRI 3905 32
12 Enrssion Spectrographic Analysis of Used Catalyst
from Run 115 - 1293 36
-------
ACKNOWLEDGEMENTS
The authors would like to acknowledge the assistance of their
colleague, Peter Maruhm'c, during the experimental phase of
this project.
We also wish to thank Dr. Thomas Petrie for his valuable
assistance during the preparation of this report.
-------
CONVERSION FACTORS FOR U. S. ENGINEERING UNITS TO SI UNITS
Given U. S. Unit
inch
mm
cm
o , .
A (angstrom)
bbl (barrel)
gal (gallon)
cu.ft. (ft3)
cc (cm3)
Ib. (pound)
gm (gram)
psi (Ib/in2)
cp (centi poise)
Multiply By
0.0254
1 x 10"3
1 x 10'2
1 x 10-0
0.1590
0.00379
0.02832
1 x 10-6
0.00454
1 x ID'3
6.895
1 x 10-3
Obtain SI Unit
m (meter)
m
m
m
q 'j
m (meter )
m3
m3
m3
kg (kilogram)
kg
kpa (kilo Pasc<
Pa-S (Pascal -S(
Temperature Conversion:
°K (Kelvin) = & ( Fahrenheit) +459.£|-4- 1.8
°C (Celsius) = & (Fahrenheit)- 32] -J- 1.8
VI
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SECTION 1
SUMMARY
This report covers work done under Phase V of Contract No. 68-02-0293
funded by the Environmental Protection Agency. The objectives of this
final phase were to evaluate a number of commercial catalysts for
denitrogenation of petroleum residua and coal liquids, and to develop an
improved catalyst for denitrogenation of heavy coal liquids. Three main
tasks comprise the work done in this phase.
Under Task 1, two commercial catalysts were evaluated for the de-
nitrogenation of a petroleum vacuum resid. Under mild operating
conditions: 780 F*, 2000 psig and 0.85 liquid hourly space velocity
(LHSV), both catalysts failed to reduce the nitrogen content of the
feed from 0.67 to 0.3%, which is the target set by EPA for this project.
American Cyanamid Ni-Mo trilobe catalyst HDS 9A possesses only micro-
pores. It showed higher level of denitrogenation, but a much faster
rate of deactivation than the American Cyanamid Co-Mo catalyst HDS 2A
possessing both macropores and micropores. This type of catalyst
deactivation exists among catalysts with these pore structures upon
hydrodesulfurizing of petroleum resid.
Task 2 evaluated two commercial catalysts to remove nitrogen from
a gas oil product and a fuel oil product from the H-Coal® Process. Under
mild operating conditions, a commercial Co-Mo catalyst, Harshaw HT-400,
reduced effectively the nitrogen content of the coal-derived gas oil from
0.45 to 0.1% which is. sufficiently low for utilization as turbine fuel.
The H-Coal fuel oil product contained 0.8% nitrogen and 35% resid. The
catalyst used was American Cyanamid HDS 2A, which has been used for
hydroprocessing of petroleum resid and also for coal liquids. Severe
operating conditions were set at 810 F, 2800 psig, and 0.5 LHSV, attempt-
ing to meet the target of 0.3% nitrogen. The nitroger content was re-
duced from 0.84 to 0.28% initially, but at the end of 3-day operation,
the nitre gen content of the liquid product rose to 0.39%. The data con-
firmed the need for improved catalysts for denitrogenation of heavy coal-
derived boiler fuel.
*EPA policy is to use SI units. Non-metric units are used in the text of
this report to increase its utility to the U. S. engineering community.
Conversion factors to SI units are given on page vi.
- 1 -
-------
Task 3, consisting of three subtasks, was undertaken to develop a de-
nitrogenation catalyst better than the base Co-Mo catalyst, American
Cyanamid HDS 2A, for use on heavy coal liquids produced from the Solvent
Refining Coal Process. A 60/40 blend of recycle solvent/SRC product was
prepared to yield a feedstock pumpable at 150°F. Nearly 35 percent by
weight of this blend consists of residua with boiling points above 975°F.
The total liquid contains about 88 percent carbon, 7 percent hydrogen, 1
percent nitrogen, 0.6 percent sulfur and 3 percent oxygen.
Subtask 3A evaluated the denitrogenation capability of three pairs
of active metals: Co-Mo, Ni-Mo, and Ni-W. Ni-Mo had higher denitrogenation
activity than either Co-Mo or Ni-W. The following factors affecting
catalyst activity were studied: method of catalyst preparation, operating
temperature upon Co-Mo, Ni-Mo and Ni-W catalysts, operating pressure upon
Co-Mo, Ni-Mo and Ni-W catalysts, and feedstock upon Ni-Mo catalyst. Four
catalysts prepared by using the commercial technique exhibited higher
activity than those prepared by an impregnation method. Operating para-
meters giving lower carbon deposition on the catalysts resulted in higher
denitrogenation activity. These are: operating temperature lowered from
850 to 810 F, operating pressure raised from 2000 to 2800 psig, and feed-
stock containing no 975°F+ resid.
Subtask 3B evaluated the significance of bimodal pore size distri-
bution in the Ni-Mo catalyst. A catalyst with bimodal pore size distri-
bution and high pore volume exhibited the same activity during the 3-day
test as the corresponding catalyst with a single-modal pore size distri-
bution. Since the weight of catalyst charged to the reactor was 30%
higher for the single-modal than the bimodal catalysts, the data indicated
that incorporating macropores into the catalyst extrudates improves de-
nitrogenation activity per unit of catalyst weight.
The objective of Subtask 3C was to improve the catalyst activity
through optimization of the bimodal pore size distribution of the catalyst.
Armak was subcontracted to prepare four Ni-Mo catalysts with larger macro-
pores and/or larger micropores while maintaining the same total pore volume
as the base catalyst. The technology is available for enlarging the micro-
pores. Armak undertook extrusion research to develop a technique for in-
creasing and enlarging the macropores, but they had limited success.
Data for the Armak catalysts were directly compared to data from the
base catalyst. A catalyst with lower macropore and micropore volume than
in the base catalyst showed a pronounced decrease in denitrogenation activity
on a catalyst weight basis. Lower macropore volume alone also caused a
decrease. The effect of larger micropores was masked by smaller micropore
volume or inferior preparation technique compared to the base catalyst.
The data derived from the evaluation of the only Armak catalyst with
larger and more macropores than the base catalyst did not show any signifi-
cant increase in denitrogenation activity. However, the Mo-containing
- 2 -
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extrudates were calcined at high temperature to reduce total pore volume
to that of the base catalyst. This unusual method of preparation might
have an adverse effect on the catalyst and prevents a conclusion from being
reached about the effect of increasing and enlarging the macropores. How-
ever, this catalyst did have a low surface area which presumably needs less
metals for covering the catalyst support. If denitrogenation activity is
not decreased, a low cost catalyst could result from seeking more and
larger macropores.
The effect of space velocity was investigated for the catalyst with
larger and more macropores by conducting two 15-days runs at 0.5 and 1.0
LHSV. At 0.7 bbl/lb catalyst age, a run at 0.5 LHSV showed a steep de-
activation whereas a run at 1.0 LHSV did not. At 0.8 bbl/lb catalyst age,
the former showed lower denitrogenation activity than the latter. It is
likely that operating at lower space velocity gave deeper 975 F+ resid
conversion initially. This resulted in higher carbon deposition on the
catalyst, which led to steeper catalyst deactivation.
- 3 -
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SECTION 2
CONCLUSIONS
Experimental results allow certain conclusions to be made as
follows:
• The denitrogenation activity of a catalyst decreased markedly with
increasing specific gravity or increasing boiling range of the
feedstock. Denitrogenation of petroleum resid was as difficult as
that of coal-derived resid. Carbon deposition on catalyst from
H-Coal or SRC gas oil boiling range feedstock was only about half
of the amount from feedstock containing about 35% of 975 F+
material. For denitrogenation of coal derived gas oil, commercial
Co-Mo catalyst was capable of reducing the nitrogen content to as
low as 0.1%, which is the level suitable for use as turbine fuel.
• Regarding active metals, Ni-Mo has higher denitrogenation activity
than either Co-Mo or Ni-W. The Ni-Mo catalyst possesses the unique
feature of being more active at 810° than at 850°F.
• Regarding pore size distribution, a Ni-Mo catalyst with bimodal pore
size distribution and higher pore volume exhibited the same activity
as the corresponding catalyst with single-modal pore size distribut-
ion and lower pore volume. In general, Ni-Mo catlayst with much
lower surface area did not lose denitrogenation activity. The
lowering of surface area resulted from larger and more macropores
or larger micropores.
0 Evaluation of one Ni-Mo catalyst with significantly more and larger
macropores did not lead to any conclusion about the expected benefi-
cal effect. The unusual method used in preparing this catalyst
could have had an adverse effect upon its denitrogenation activity.
• Regarding catalyst deactivation, most of the activity loss in 3-day
tests was due to carbon deposition on catalysts. Operating para-
meters resulting in high carbon deposition frequently produced low
denitrogenation activity. These parameters included low hydrogen
pressure, high temperature to certain levels and feedstock with
high boiling temperatures.
• Regarding effect of space velocity, 15-day runs at two space
velocities with the catalyst having more and larger macropores dis-
closed that deeper resid conversion achieved at low space velocity
resulted in high carbon deposition on the catalyst, which caused
steeper deactivation than operating at high space veloctiy. At a
catalyst age greater than 0.8 bbl/lb, low space velocity operation
gave a significantly lower level of denitrogenation than did the
high space velocity operation.
- 4 -
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SECTION 3
INTRODUCTION
The New Source Performance Standards set by the U.S. Environmental
Protection Agency for stationary sources specify a maximum nitrogen oxide
fuels, fixation of atmospheric nitrogen during the combustion process is
the primary source of this emission. If organic nitrogen is present,
roughly one-third of the organic nitrogen content of the fuel can react to
form nitrogen oxides (NOX), the degree of conversion depending on firing
methods. At the conversion of one-third of the nitrogen content of fuel
oil to NOX, this contributes 500 ppm of NOx per percent of nitrogen in fuel
oil, over and above that from the fixation mechanism. Some petroleum
resids contain close to 1% nitrogen. Most of the coal liquids contain
more than 1% nitrogen. Hence processing of high nitrogen-containing
petroleum resid and coal liquids may be required to enable them to
be used as boiler fuel for stationary power plants. The target set
by EPA for this program is a maximum of 0.3% nitrogen in fuel oil.
A program was undertaken to evaluate commercial catalysts for de-
nitrogenation of petroleum resid and coal liquids, and to develop an im-
proved catalyst for denitrogenation of heavy coal liquids.
Under Task 1, two commercial catalysts, American Cyanamid HDS 2A and
HDS 9A, were evaluated for denitrogenation of a Gach Saran vacuum resid.
Task 2 investigated the denitrogenation of a gas oil product and a
fuel oil product containing 30% resid from the H-Coal Process. A commercial
Co-Mo catalyst with only micropores, Harshaw HT-400, was used for the gas
oil feed, and a commercial Co-Mo catalyst with both micropores and macropores,
American Cyanamid HDS 2A, was used for the fuel oil feed. The gas oil feed
was processed at mild operating conditions, mild and severe, to determine the
rate of catalyst deactivation.
The task 3 was devoted to developing an improved catalyst for denitroge-
nation of heavy coal liquids. A blend of 40% SRC product and 60% SRC solvent
was used as the feedstock. Task 3 consisted of three subtasks.
Subtask 3A compared the denitrogenation activity of 3 metal pairs: Co-
Mo, Ni-Mo, and Ni-W. The current commercial hydrotreating and hydrocracking
catalysts contain cobalt-molybdenum, nickel-molybdenum, or nickel-tungsten
as the active metal pairs. It is known that in general the hydrotreating
(desulfurization with minimum ring saturation) capabilities of these three
pairs of active metals are: Co-Mo > Ni-Mo>Ni-W, whereas their hydrocracki ng
- 5 -
-------
capabilities are in the opposite order: Ni-W>Ni-Mo>Co-Mo.
In view of the stable nature of the nitrogen compounds present in the
coal liquids, catalyst possessing somewhat higher hydrocracking capability
than current commercial hydrotreating and hydrocracking catalysts might be
desirable. Therefore, the denitrogenation capability was compared among
the catalysts containing these three metal pairs on a >f -alumina support
at the same pore volume level with similar pore size distribution.
The objective of Subtask 3B was to establish the significance of the
bimodal pore size distribution of Ni-Mo catalyst.
The objective of Subtask 3C was to improve the catalyst activity
through pore size optimization. It has been established in H-Coal
operations that the pore size distribution of the Co-Mo catalyst plays an
important role in catalyst activity and the rate of deactivation. The
presence of sufficient macropores is essential for good performances in
terms of coal conversion, resid conversion and desulfurization. The con-
version of 975°F+ resid to lower boiling materials seems to be the rate
limiting step. The 500 F+ fuel oil fraction produced from the H-Coal
processing of Illinois No. 6 coal contains about 70% 975 F+ resid which
has a nitrogen content of 1.4% (Illinois No. 6 coal contains 1.6% nitrogen
MAP basis). It is very likely that the nitrogen containing compounds in
coal derived resid are just as large as the sulfur and oxygen containing
compounds. Hence, the effect of increasing macropores of catalyst upon
denitrogenation of coal liquids was investigated.
- 6 -
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SECTION 4
PROCEDURES, RESULTS AND DISCUSSION
Experiments were carried out in Unit 115. Unit 115 contains two
parallel, continuous, fixed bed reactor systems in a single lead bath.
Figure 1 is a schematic diagram of one reactor only. Each reactor was
fabricated from 1" o.d. by %" i-d. stainless steel tubing. The volume of
catalyst charged to the reactor was 150 cc (compacted). The catalyst bed
measured 13" long. A 3-point thermocouple was placed in the reactor to
monitor the temperature at the inlet, center, and outlet of the catalyst
bed. Heat was supplied to the reactor by means of an electrically heated
lead bath designed to maintain isothermal operation which was frequently
achieved. However, temperature increases up to 20°F were observed when
good performance was achieved.
The catalysts for Runs 115-1255 through 115-1288 were presulfided
using a procedure furnished by American Cyanamid. Presulfiding was con-
ducted at operating temperature for 1 hour using 10% H£S in an H2 gas
mixture.supplying more than twice the amount needed to convert the
metals to sulfides. A rather time-consuming Armak procedure was followed
for later runs numbered 115-1289 through 115-1294. The catalysts were
presulfided for 1 hour at 400°F, then another hour at 600°F using the
10% H2S in H2 gas mixture. Duplicate runs using these two.presulfiding
procedures did not show any noticeable difference in catalyst activity.
The experiments were carried out at 780-850°F, 2000-2800 psig, 0.5-1.0
LHSV (volume of feed/hour/volume of catalyst), and excess hydrogen of 4000
SCF/Bbl. A 3-day operation was used for catalyst screening. Longer runs
were conducted to assess the deactivation rate of a catalyst when needed.
A summary of data from all runs is given in Appendix A.
The feed was pumped to reactor pressure with a metering pump, mixed
with hydrogen, and fed to the reactor. The mixed vapor and liquid product
from the reactor were cooled and passed to a high pressure receiver. The
liquid was let down in pressure and passed to a low pressure receiver.
The liquid was let down in pressure and passed to a low pressure receiver.
Vent gas was let down in pressure and mixed with flash gas from the low
pressure product receiver. The combined gas stream was sampled, metered
and vented. The liquid product was collected and weighed periodically.
Daily inspection of the liquid product included gravity by hydrometer and
nitrogen by Kjeldahl determination. Besides the daily inspection, at the
end of 3-day operation, the gas product was analyzed by mass spectrometry,
and the liquid product was fractionated. Elemental analyses of C, H, N,
- 7 -
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HYDROGEN
i
oo
AUX. CHARGE
POT
THERMOCOUPLES
CHARGE
POT
PUMP REACTOR
WATER
T -I
•Oh-1
LEAD
BATH
H/P PRODUCT
RECEIVER
REFER: AF-2552. AF-2681
O
-CXH
TO
FLARE
L/P PRODUCT
RECEIVER
HYDROCARBON RESEARCH INC.
TRENTON, N. J.
None DATE-4^28-78
DR.
CKD.-
MO.
2891
oaw •LUIPHINT co. ronM NO. n«a-i
Fiqure 1. Fixo.l .*.jJ : onUrononatlon Unit - Unit 115
-------
S, 0 and ash were carried out on the total liquid product, IBP-975 F
fraction. The 975°F+ fraction was extracted by benzene or toluene in a
Soxhlet extractor for its soluble and insoluble contents. For the 15-day
operations, these detailed analyses were conducted on samples taken every
three days. Appendix B gives a summary for all runs of operating
conditions, product distribution, hydrogen consumption, 975°F+ conversion
and heteroatom removal.
A standard shutdown procedure was used upon completion of a run. The
temperature was lowered to 650°F, and the catalyst was washed with
anthracene oil for 1 hour. A representative sample of the spent catalyst
was obtained by riffling. Absorbed material was extracted with benzene
or toluene in a soxhlet extractor. The carbon content of the catalyst
was determined, and occasionally its nitrogen and sulfur contents were
determined. The commercial catalysts and developmental catalysts
evaluated in this program were extrudates, 1/16" nominal diameter. Develop-
mental catalysts were prepared by American Cyanamid and Armak.
TASK 1 - DENITROGENATION OF PETROLEUM VACUUM RESID
Gach Saran vacuum resid containing 0.67% nitrogen was used as the
feedstock. Inspections of the feedstock are given in Table 1. Since
American Cyanamid Co-Mo catalyst HDS 2A has been used for hydroprocessing
of resid and coal in this laboratory, it was used as the base catalyst.
HDS 9A ni-Mo catalyst, offered by the manufacturer as a good denitrogenation
catalyst, was chosen for evaluation.
The characteristics of these two catalysts are described in Table 2;
pore size distribution is presented in Figure 2. HDS 2A has a bimodal
pore size distribution with macropores in the ranges of 1000 to 7000 A
HDS 9A has essentially no macropores, and has larger micropores than HDS 2A.
The catalysts were evaluated at conditions favorable for hydrodesulfuri-
zation of petroleum resid: 780°F, 2000 psig, 0.75 to 0.40 VHSV. Daily de-
nitrogenation data versus catalyst age are plotted in Figure 3 for a fourteen-
day period. Run 115-1255 failed to yield a product containing no more than
0.3% nitrogen, which is the target set by EPA for this program. The target
of 0.3 W % nitrogen content was met in run 115-1256, but only at an early
catalyst age of 0.1 LB/Bbl, which is unsuitable for equilibrium operations.
Deactivation lines like in Figure 3 exist in operations involving hydro-
desulfurization of petroleum resid using catalysts possessing similar pore
structures.
- 9 -
-------
TABLE 1. FEEDSTOCK INSPECTIONS - GACH SARAN VACUUM RESID
HRI No. 3574
Fraction Total IBP-975 975+
Volume, % 100 4.3 95.7
Gravity, °API 6.2 16.2 6.0
Sulfur, W % 3.78 2.61 3.84
Carbon, W % 85.15 85.28 85.18
Hydrogen, W % 10.32 11.98 10.65
Nitrogen, W % 0.67 0.27 0.74
Ramsbottom Carbon
Residue, W % 19.25 20.31
V, ppm 281
Ni, ppm 102
- 10 -
-------
TABLE 2. CHARACTERISTICS OF COMMERCIAL CATALYSTS
Manufacturer
HRI No.
American Cyananrid
HDS 2A HDS 9A
3556
3687
Harshaw
HT 400
3779
Composition, W %
CoO
NiO
Si02
A1203
15.1
3.2
18.4
-
0.1
Balance
3.3
0.7
Balance
14.4
3.0
Balance
Physical Properties
Compacted Bulk Density, g/cc 0.58
Pore Volume, cc/gm 0.67
Surface area, m^/gin 270
Surface area nr/cc 403
Side Crushing Strength, Ib/mm -
0.82
0.42
150
357
0.76
0.47
241
513
2.6
- 11 -
-------
AMINCO FORM
Cil.No. 6-7135 A
EQUIVALENT PORE DIAMETER (MICRONS)
176/PSI
(CONTACT ANGLE = 130°)
Figure 2. Pore Size Distribution of Commercial Catalysts
-------
LEGEND
O
A
RUN NO.
115-1255
115-1255
115-1256
115-1256
CATALYST
HDS
HDS
HDS
HDS
2A
2A
9A
9A
Co
Co
Ni
Ni
B318
Mo-Al203
PRESSURE
PSIG
2000
ii
,2000
n
TEMP
°F LHSV
780
n
780'
0
0
0
.75
0.5
.75
.40
CATALYST SPACE
BBL/D/LB
0.10
0.05
0.10
0.05
VELOCITY
CO
I
4
3
2-
I I
I I
I I
I I I I
L
0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1 1.2 1.3
CATALYST AGE Bbl/Lb
Figure 3. Denitrogenation of Gach Saran Vacuum Resid
*Feed Nitrogen Content = 0.67 W %
-------
TASK 2 - DENITROGENATION OF COAL LIQUIDS FROM H-COAL PROCESS
Four exploratory runs were conducted to evaluate the denitrogenation
of a gas oil product and a fuel oil product from the H-Coal process using
commercial catalysts.
Subtask 2A - Denitrogenation of Gas Oil from H-Coal Operation
From H-Coal Process Development Unit Run 130-73-13B (coal feed: Illinois
No. 6 out of the Burning Star Mine), two drums of atmospheric still bottoms
were taken and flash distilled at 500 to 550 F to yield the gas oil feed.
Feedstock inspections are given in Table 3. Harshaw HT-400 Co-Mo catalyst
was used for Runs 115-1257 and - 1259. Catalyst characteristics are de-
scribed in Table 2; pore size distribution is shown in Figure 2. The
operating conditions of Run 115-1257 and - 1259 were set at favorable
hydrodesulfurization conditions: 780 F, 2000-2800 psig, excess hydrogen
around 4000 SCF/Bbl, and 2 to 4 VHSV. Run 115-1257 at 2000 psig and 2 VHSV
and Run 115-1259 at 2800 and 3 - 4 VHSV yielded about the same extent of
denitrogenation. Nitrogen reduction was from 0.45% to an average of 0.09%
in the liquid product. At the end of seven days and catalyst age of 1.7
Bbl/lb, there was no noticeable catalyst deactivation. The objective of
reducing the nitrogen content of the H-Coal gas oil product to 0.10% for
use as a turbine fuel was readily achieved. The carbon content of the
spent catalyst from Run 115-1257 operated at 2000 psig was 10.7%, and that
from Run 115-1259 at 2800 psig was 8.6%. The lower carbon deposition on
the catalyst made it possible to operate at higher space velocity and re-
sulted in the same magnitude of denitrogenation.
Subtask 2B - Denitrogenation of Fuel Oil from H-Coal Operation
From H-Coal Process Development Unit Run 130-73-13B (Coal feed:
Illinois No. 6 out of the Burning Star Mine), the naphtha fraction of the
settler overflows was topped off in a continuous unit. L-438 w?s the last
portion of the still bottom, and L-440 a blend of the earlier portions.
L-438 was heavier and contained a higher percentage of ash than L-440.
The feedstock inspections are given in Table 3. Two 3-day runs were con-
ducted using American Cyanamid HDS 2A catalyst. Run 115-1260 was carried
out under normal desulfurization conditions for petroleum resid: 780 F,
2000 psig, 0.5 VHSV. Severe catalyst deactivation was at a moderate rate.
The data indicate that when using a commercial catalyst such as HDS 2A, de-
nitrogenation of heavy coal liquids to 0.3% nitrogen level will require
a catalyst replacement rate about ten times as high as that required for
the hydrodesulfurization of petroleum resid. Carbon deposition on spent
catalyst from these 2 runs is similar, 20.6% and 19.4% respectively, but
much higher than those observed with the H-Coal gas oil feedstock under
comparable operating conditions. (8.6 to 10.7% carbon on spent catalyst).
The data indicate that initial catalyst deactivation resulted mainly from
carbon deposition; heavy feed caused higher carbon deposition than light
feed. Denitrogenation of heavy coal liquids needs an improved catalyst
possessing higher activity than the hydrodesulfurization catalyst available
commercially.
- 14 -
-------
TABLE 3. INSPECTIONS OF FEEDSTOCKS FROM H-COAL PROCESS
*
HRI No.
Gravity, °API
Distillation, °F
IBP
10 V %
30
50
70
90
Elemental Composition, W %
Carbon
Hydrogen
Ni trogen
Sulfur
Oxygen
Ash
Gas Oil
L 428
9.5
494
523
561
606
671
>760
88.90
9.28
0.45
0.06
0
98.69
Fuel Oil
L 438 L 440
-12.6 -3.2
412 362
516 427
600 682
750 905
81.05 86.50
6.49 7.69
0.84 0.81
0.59 0.37
2.28 3.19
5.42 1.72
96.67 100.28
Fractions IBP-945°F IBP-955°F
V % - 68 75
Nitrogen, W % - 0.55 0.47
Sulfur, W % - 0.17 0.13
Oxygen, W X - 1-09 2.09
945°F+* 955°F+**
V % - 32 25
Nitrogen, W X - 1-42 1.58
Sulfur, W % - 1-46 0.90
Oxygen, W % 3.99 3.70
Pour P-oint, °F - 130 55
Viscosity, cp
@ 200°F - 38 49
(3 300°F - 24 7.5
:*41.6 W X
**32.1 W %
- 15 -
-------
TASK 3 - DEVELOPMENT OF DENITROGENATION CATALYST FOR HEAVY COAL
LIQUIDS FROM THE SOLVENT REFINED COAL PROCESS
The objective of this task is to develop an improved denitrogenation
catalyst for heavy coal liquid. American Cyanamid Co-Mo catalyst HDS 2A
is used as the base catalyst. A blend of 40% SRC product and 60% SRC
solvent was used as the feedstock. Task 3 consists of three subtasks.
Subtask 1 compared the denitroqenation activity of three metal pairs: Co-Mo,
Ni-Mo and Ni-W and two methods of catalyst preparation. Subtask 2 evaluated
the effect of the catalyst pore sizes. . Subtask 3 evaluated macropores and/or
larger micropores than those of the base catalyst.
Preparation of Feedstock
Two drums each of SRC product and solvent were acquired from the
Wilsonville Pilot Plant. These two samples were produced from Illinois No.
6 coal from the Monterey Mine. The coal was processed at 835 F, 2400 psig,
coal at 38.5 W % concentration in feed slurry, and 25 Ib/hr/cu. ft. coal
feed rate. Conversion was at 94.7% of MAF feed coal and hydrogen con-
sumption was 3.8 W % of MAF feed coal. A schematic diagram of the Wilson-
ville Pilot Plant is shown in Figure 4. The product sample was taken
from the K-125 product solidifier and the solvent sample from the V-131
recycle solvent storage tank.
Two 450 Ib. batches of the SRC blends were prepared. These blends
contained 40 W % SRC solids and 60 W % solvent. Inspections of the SRC
materials and the feedstock blend are presented in Table 4.
Subtask 3A - Evaluation of American Cyanamid Developmental Catalysts
The objective of this subtask is to compare the denitrogenation
performance of Co-Mo, Ni-Mo and Ni-W. Since the method of preparation
affects catalyst activity, the same method and support were used in these
preparations. The difference given by an impregnation technique and a
commercial method of preparation was investigated. The temperature effect
and pressure effect upon the Co-Mo and Ni-Mo catalysts were evaluated.
The effect of the boiling range of feedstock upon the Ni-Mo catalyst was
investigated.
The experimental data lead to the following conclusions:
(1) The commercial method of preparation is superior to the im-
pregnation technique.
(2) Ni-Mo catalyst has higher denitrogenation activity than the
Co-Mo or Ni-W catalyst.
(3) Ni-Mo catalyst has the unique feature that it possess higher
denitrogenation activity at 810°F than at 850 F. Since low
temperature operation leads to low gas-make, this should re-
sult in less hydrogen consumption at the same level of de-
nitrogenation.
- 16 -
-------
MAKE - UP
HYDROGEN
RECYCLE
SLURRY
PREPARATION
MINERAL
RESIDUE
Finure 4. Solvent Refine Coal Process
ililsoiu/ille Pilot Plant
-------
TABLE 4. ANALYSIS OF SRC MATERIALS AND SRC FEEDSTOCK BLEND
HRI No.
Gravity, °API
Distillation, V % at °F
IBP
10
30
50
70
90
End Point
Fractions
W %
Elemental Analysis, W %
Carbon,
Hydrogen
Sulfur
Ni trogen
Oxygen
Ti, ppm
Ash (ASTM Method)
Total
Viscosity, cs at 200°F
Pour Point, F
Benzene-Insoluble, W %
Benzene-Soluble, W %
Toluene-Insoluble, W %
Toluene-Soluble, W %
Ti in Toluene-Insoluble, ppm
Ti in Toluene-Soluble, ppm
SRC
Solvent
3861
+1.8
378
463
539
605
658
840
935
88.35
7.65
0.67
0.69
-
_
-
97.63
_
_
_
_
_
_
_
_
SRC
Product
3860
-13.4
700
945
-
_
-
_
-
86.39
5.91
0.74
1.82
4.29
_
0.16
99.31
_
_
_
_
_
_
_
_
Total
100%
87.76
6.80
0.60
1.07
3.30
115*
0.09
99.62
85
70
8.5*
26.1*
10.4*
24.2*
-
_
SRC
Feedstock
Blend
L 446
-6.8
403
516
605
730
1000
_
-
IBP-975°F
65.4
88.09
7.46
0.77
0.32
2.32
-
-
98.96
_
-
-
-
-
j
-. t
_
975°F+
34.6
87.56
5.61
1.84
1.11
3.50
-
0.03
99.65
_
-
24.5
75.5
30.0
70.0
1000
50
Calculated values
- 18 -
-------
Effect of Active Metals —
American Cyanamid prepared three developmental catalysts for the
purpose of evaluating the effect upon denitrogenation of the active metals
pairs Co-Mo and Ni-W. The same method and support were used in these
preparations. For the sake of expediency, the incorporation of metals
was carried out by impregnating the extrudates of Y-alumina support with
a solution of the respective metals salts. Commercial catalysts, such as
HDS 2A, are prepared differently.
The characteristics of the three developmental catalysts and HDS 2A
are summarized in Table 5 in first four columns. These four catalysts have
bimodal pore size distributions. The three developmental catalysts have
essentially the same pore size distribution. The significant differences
between the developmental catalysts and HDS 2A are that the developmental
catalysts have higher m^cropore volume than HDS 2A by 0.2 cc/g and their
micropores peak at 100 A whereas HDS 2A peaks at 50 A.
Using the same SRC feedstock, HDS 2A catalyst and the three develop-
ment catalysts were evaluated under the same process conditions, 850 F,
2800 psig, and 0.5 V/Hr/V space velocity. The decline in catalyst
denitrogenation activity is shown in Figure 5. Over a catalyst age of
three days or about 0.2 Bbl/D/Lb, all four catalysts show definite
deactivation. The commercial Co-Mo catalyst HDS 2A is the most stable one.
The Co-Mo development catalyst has slightly higher initial activity and the
highest deactivation rate. These differences in performance are attributed
to the differences in the method of preparation and not to the differences
in the pore size distribution. The effect of active metal shown by the
three developmental catalysts indicates that Ni-Mo is better for denitroge-
nation than the Co-Mo and Ni-W. These preliminary indications were later
followed up by the evaluation of a Ni-Mo catalyst prepared by the same method
used for the commercial catalyst HDS 2A. (discussed on page 22).
The carbon contents of the spent catalysts were very high, 27 to 39%.
In hydroprocessing of petroleum residuum and coal, carbon deposition on
this type of catalyst is 10 to 20%.
Effect of Method of Catalyst Preparation --
Five additional Co-Mo catalysts and Ni-Mo catalysts were furnished by
American Cyanamid. These catalysts were prepared in the laboratory using
the same method as that for HDS 2A. These catalysts were evaluated to
ascertain whether the method of preparation can be an important variable
affecting catalyst activity and whether Ni-Mo is indeed better for de-
nitrogenation than Co-Mo. The characteristics of these five developmental
catalysts are described in the five right hand columns of Table 5. The
two additional Co-Mo catalysts, HRI 3866 and HRI 3867, have similar total
pore volume and similar pore size distribution as the first Co-Mo develop-
mental catalyst HRI 3849, but slightly more micropores than catalyst HDS
2A. The Ni-Mo catalysts vary more in their pore size distribution.
- 19 -
-------
TABLE 5. CHARACTERISTICS OF AMERICAN CYANAMID DEVELOPMENTAL CATALYSTS
Catalyst
HRI No. 3556 3849 3850 3851 3866 3867 3904 3905 3911
American Cyanamid ,No. HDS 2A SN 4412B SN 4412A SN 4412C SN 4424 SN 4425 SN 4474 SN 4475 SN 4510
Active Metals Co-Mo Co-Mo Ni-Mo Ni-W Co-Mo Co-Mo Ni-Mo Ni-Mo Ni-Mo
Composition, %
CoO
NiO - - 3.2 3.2 - - 3.5 3.5 3.2
17.2 15.3
W03"
S102 0.1 - - - 0.06 0.05 - - 1.2
0.015 0.05
^504 ... _ 0.2 0.2 0.3 0.3 0.2
o p2Q5
i
Physical Properties
Diameter, mm 1.68 1.65 1.65 1.65 1.68 1.68 1.63 1.63 1.52
Length, mm 5 9.9 10.9 8.6 5.1 5.3 5.1 5.1 4.3
Pore Volume, cc/g 0.67 0.82 0.83 0.89 0.83 0.85 0.69 0.72 0.50
Surface Area, mfyg 270 195 204 237 339 280 335 267 305
CBD, g/cc 0.58 0.54 0.54 0.51 0.53 0.54 0.61 0.60 0.75
1.5 4.9
Pore Size Distribution
by Hg Porosimeter
PV cc/g <20oRdia 0.43 0.54 0.55 0.60 0.53 0.53 0.43 0.44 0.494
200 -1500A 0.10 0.12 0.11 0.12 0.10 0.12 0.09 0.08 0
>1500A 0.14 0.16 0.17 0.17 0.19 0.20 0.17 0.20 0.02
Total 0.67 0.82 0.83 0.89 0.83 0.85 0.69 0.72 0.496
3556
HDS 2 A
Co-Mo
3.2
-
15.1
_
0.1
-
_
-
1.68
5
0.67
270
0.58
, Ib/mm
n
0.43
0.10
0.14
0.67
3849
SN 44126
Co-Mo
3.2
-
15.5
-
-
-
-
3.5
1.65
9.9
0.82
195
0.54
2.4
0.54
0.12
0.16
0.82
3850
SN 4412A
Ni-Mo
^
3.2
15.5
-
-
-
-
3.5
1.65
10.9
0.83
204
0.54
1.9
0.55
0.11
0.17
0.83
3851
SN 4412C
Ni-W
—
3.2
-
15.5
-
-
-
-
1.65
8.6
0.89
237
0.51
2.5
0.60
0.12
0.17
0.89
3866
SN 4424
Co-Mo
3.2
-
14.4
-
0.06
0.01
0.2
-
1.68
5.1
0.83
339
0.53
3.1
0.53
0.10
0.19
0.83
3867
SN 4425
Co-Mo
3.2
-
14.1
_
0.05
0.01
0.2
-
1.68
5.3
0.85
280
0.54
3.8
0.53
0.12
0.20
0.85
3904
SN 4474
Ni-Mo
.
3.5
15.9
-
-
0.017
0.3
-
1.63
5.1
0.69
335
0.61
2.8
0.43
0.09
0.17
0.69
-------
UJ
8
100-
90-
80-
70-
60-j
50-J
30-
20-
Q_
LEGEND
CATALYST RUN NUMBER
HDS 2A a RUN 1262
HRI 3851 • RUN 1265
HRI 3850 • RUN 1264
HRI 3849 A RUN 1263
ACTIVE METALS \
(Co-Mo)
(Ni-W )
(Ni-Mo)
(Co-Mo)
I [ I I 1
0 10 20 30 40 50
HOURS ON STREAM
I T
60 70
80
90 100
Figure 5. Comparison of Denitrogenation Activity
Among Three Developmental Catalysts and HDS 2-A
- 21 -
-------
Table 6 summarizes the pertinent catalyst characteristics and de-
nitrogenation data of the developmental catalysts and the base catalyst.
The commercial method of preparation was better than the impregnation
method as shown by the higher denitrogenation activity of the two develop-
mental Co-Mo catalysts compared with that of HRI 3849. The commercial
method of preparation is also better than the impregnation technique for
the nickel-molybdenum catalysts. The Ni-Mo catalyst HRI 3905 is the most
active denitrogenation catalyst among the seven developmental catalyst
prepared by American Cyanamid. Three additional Ni-Mo catalysts
were prepared by a technique held as closely as possible to the commercial
method. Catalyst HRI 3911 (not shown in the table) with micropores only
was prepared for use in Subtask 3B, described later.
Confirmation of Effect of Active Metals—
The two Ni-Mo catalysts numbered HRI 3904 and 3905 had pore distributions
similar to the base catalyst HDS 2A. Evaluation of these Ni-Mo catalysts
showed they were better than HDS 2A by virtue of their slightly higher
denitrogenation activity and a temperature rise of about 15°F at the inlet
of the catalyst bed. Hence the superiority of Ni-Mo is apparent in the data
for the two different methods of catalyst preparation.
Effect of Operating Temperature upon Catalysts—
The temperature effects upon the performances of the developmental
catalysts and the base catalyst were evaluated. Runs were carried out at
lower temperature, 810° and 780°, instead of 850°F. Table 7 presents the
denitrogenation data and the carbon content of the spent, catalysts. A 10
to 15% decrease in the absolute carbon content of the spent Co-Mo or Ni-Mo
catalysts resulted from a decrease of the operating temperature.
The Ni-Mo catalysts showed significance improvements in denitrogenation
at 810°F. The best Ni-Mo catalyst, HRI 3905, was reevaluated at 810°F to
show the reproducibi1ity of the test data. A run at 780°F on Ni-Mo catalyst
HRI 3850 gave lower denitrogenation activity at the end of the 3-day operation
than were obtained at 810°F and 850°F. The carbon content of the spent
catalyst was not further lowered through the reduction of operating temperature
from 810° to 780°F.
To achieve a certain denitrogenation level, this unique feature of
Ni-Mo catalyst enables one to operate at significantly lower temperature
than that for the Co-Mo catalyst. This would yield less gas, and thus re-
sults in less hydrogen consumption.
Effect of Operating Pressure Upon Catalysts—
The pressure effect upon the Co-Mo, Ni-Mo, and Ni-W catalysts was
evaluated Runs 115-1275, - 1276, - 1277, - 1278 were conducted at 810°F, 2000
psig, and 0.5 VHSV. The denitrogenation data as shown in Table 8 were rather
scattered. The Ni-Mo catalyst definitely showed lower denitrogenation
activity at lower pressure accompanied by higher carbon deposition on the
catalyst. In the case of Co-Mo and Ni-W catalysts, the pressure effect was
less significant.
- 22 -
-------
TABLE 6. EVALUATION OF METHOD OF PREPARATION
I
CO
I
Catalyst
HRI No.
American Cyanamid No.
Active Metals
Preparation
Pore Volume, cc/g
Total
<200 X
200-1500 A
> 1500 A
% Denitrogenation at
Run No. 115 -
Period IB
2B
3B
3849
SN 4412B
Impreg-
nation
0.82
0.54
0.12
0.16
1263
77.5
50.2
39.0
3556
HDS 2A
Tn-Mn
0.67
0.43
0.10
0.14
1262
68.5
66.8
62.7
3866
SN 4424
0.83
0.53
0.10
0.19
850°
1283
74.9
65.2
34.7
3867
SN 4425
0.85
0.53
0.12
0.20
F, 2800
1284
72.1
78.7
69.7
3850
SN 4412A
Impreg-
nation
0.83
0.55
0.11
0.17
psiq, 0.5 VHSV
1264
76.8
68.6
59.7
3904
SN 4474
MI _Mn
0.69
0.43
0.09
0.17
1281
74.3
56.4
69.6
3905
SN 4475
0.72
0.44
0.08
0.20
1282
61.9
59.1
69.1
*NOTE: Catalysts prefixed by an "SN" before the number are developmental catalysts,
even though some were prepared using commercial methods.
-------
TABLE 7. TEMPERATURE EFFECT UPON HYDROGENITROGENATION OF SRC LIQUIDS
ro
•p*
Catalyst
HRI No.
American Cyanamid No.
Active Metals
Preparation Method
% Denitrogenation at
Run No. 115 -
Period
IB
2B
3B
Spent Catalyst, % C
% Denitrogenation at
Run No. 115 -
Period IB
2B
3B
Spent Catalyst, % C
% Denitrogenation at
Run No. 115 -
Period
IB
2B
3B
NjvlUU
HDS 2 A
1262
B1T5"
66.8
62.7
30.1
1266
64.9
46.6
50.5
25.3
«JUUU
SN 4424
uercial Method-
1283
TO
65.2
34.7
35.7
1270
76.1
70.9
63.0
22.7
•jw i
SN 4425
850°F,
1284
72T
78.7
69.7
31.0
810°F,
1271
63.0
63.6
65.5
24.2
780°F,
OUvJU
SN 441 2A
nation
2800 psig, 0.
1264
7678
68.6
59.7
31.9
2800 psiq, 0.
1267
76.7
75.9
65.9
21.5
2800 psig, 0.
CM 4471;
_M-|_Mn
_ _ _ _ _ Pnmmo v*f* i ^ 1
5 VHSV
1282
6179
59.1
69.1
28.5
5 VHSV
1280
80.4
82.5
72.1
23.3
5 VHSV
Method—
1285
79.6
74.4
70.2
24.3
1269
Spent Catalyst, % C
78.3
75.0
40.3
23.1
-------
TABLE 8. EFFECT OF PRESSURE ON HYDRODENITROGENATION OF SRC LIQUIDS
Catalyst
HRI No.
American Cyanamid No.
Active Metals
% Denitrogenation at
Run No. 115 -
Period IB
2B
3B
Spent Catalyst, % C
% Denitrogenation, at
Run No. 115 -
Period IB
2B
3B
3556
HDS 2 A
Co-Mo
1266
64.9
46.6
50.5
25.3
1275
37.9
59.9
43.9
3849
SN 4412B
Co-Mo
2800 psig, 810°F,
1273*
44.0
70.3
49.1
24.2
2000 psig, 810°F,
1277
65.2
68.3
54.8
3850
SN 4412A
Ni-Mo
0.5 VHSV
1267
76.8
68.6
59.7
21.5
0.5 VHSV
1276
36.2
53.9
61.9
3851
SN 4412C
Ni-W
1274*
45.1
50.2
35.0
15.8
1278
50.7
40.9
41.1
Spent Catalyst, % C
26.2
23.6
30.4
21.1
* After presulfiding, the catalyst was held accidentally under hydrogen
atmosphere for 9 hours at 810°F prior to the start of feed. This might reduce
the catalyst and result in low denitrogenation activity.
- 25 -
-------
Effect of Feed Upon Ni-Mo Catalysts —
From the experiments conducted under Task 2, using H-Coal gas oil product
and H-Coal fuel oil product, it was observed that heavy feed caused higher
carbon deposition resulting in faster catalyst deactivation than with
lighter feed. Run 115 - 1268 was carried out using the SRC solvent with
boiling range comparable to that of H-Coal gas oil and Ni-Mo catalyst HRI
3850. No catalyst deactivation was observed during the 3-day operation.
There was low carbon deposition on the catalyst, viz., 10.7% vs 23.1% from
Run 115-1269 using the SRC blend feedstock under same operating conditions.
Subtask 3B - Evaluation of the Significance of Bimodal Pore Size
Distribution of Ni-Mo Catalyst
After Ni-Mo was found to be more effective in denitrogenation than
Co-Mo, American Cyanamid was requested to prepare a Ni-Mo catalyst having
micropores only. The other variables, such as method of preparation,
support, and metal contents were to be the same as that of catalyst HRI
3905. The characteristic of this catalyst, HRI 3911 was included in Table
5. Pore size distribution of HRI 3905 and HRI 3911 is shown in Figure 6.
HRI 3911 has only 0.5 cc/g total pore volume versus 0.7 cc/g for HRI 3905.
i.e., HRI 3911 has higher density. With a charge of 150 cc catalyst
volume, 118g of HRI 3911 are charged to the reactor vs. 90g of HRI 3905.
As shown in Table 9, HRI 3911 (Run 115-1286) has only an average of
4% higher denitrogenation activity for the 3-day operation than that shown
by HRI 3905 in Runsll5-1280 and 1285. This is true even though Run 115-1286
using HRI 3911 had a mugh higher weight of catalyst than Runs 115-1280 and
- 1285 using HRI 3905. The data indicate that the presence of macropores
in HRI 3905 increases the denitrogenation activity of the catalyst signifi-
cantly on a catalyst weight basis. The presence of macropores in HRI 3905
probably allows the denitrogenation reactions to be less diffusion limited.
The result supports the expectation that by enlarging the macropores and/or
the micropores of a catalyst, its denitrogenation activity will be improved.
Subtask 3C - Optimization of the Bimodal Pore Size Distribution of
Ni-Mo Catalyst
Description of Catalysts —
For the last part of the program, development was sought of an improved
denitrogenation catalyst. Armak was subcontracted to prepare four Ni-Mo
catalysts with larger macropores and/or larger micropores. They were to
maintain the same total pore volume (0.7 cc/g)and the same pore volume
distribution between the macropores and micropores (about 1/3 in macropores
and 2/3 in micropores).
The technology is available for enlarging the .micropores from the 50 A
range to 100'A range, but not for enlarging the macropores. Armak under-
took extrusion research to develop a technique for increasing and enlarging
the macropores with limited success. The characteristics of the four Armak
catalysts and American Cyanamid catalyst HRI 3905 are described in Table 10.
The pore size distribution of these four catalysts and American Cyanamid
- 26 -
-------
AMINCO FORM
C«I.NO. 6-7135 A
EQUIVALENT PORE DIAMETER (MICRONS)
17S/PSI
(CONTACT ANGLE = 130°)
ro
i
Figure 6. Pore Size Distribution of Nickel-Molybdate Catalysts
-------
TABLE 9. EFFECT OF MACROPORES IN CATALYST UPON
DENITROGENATION OF HEAVY COAL LIQUIDS
Run No. 115 - 1280 1285 1286
Catalyst Ni -Mo
HRI No. 0 ' 3905 3911
Pores>1500A 0.20 0.02
Volume Charged, cc 150
Weight Charged, g 90.4 89.5 118.4
Temperature, °F 810
Pressure, psig 2800
Space Velocity, V/Hr/V 0.5
Denitrogenation, %
Period IB 80.4 79.6 81.5
2B 82.5 74.4 79.0
3B 72.1 70.2 78.8
Average 78.3 74.7 79.8
Spent Catalyst, % C 23.3 24.3 22.1
- 28 -
-------
TABLE 10. CHARACTERISTICS OF Ni-Mo CATALYSTS
HRI No.
Manufacturer
No.
Composition
NiO, %
MoOa, %
Si02, %
ro
10
S04,
3905
Am. Cy.
SN 4475
3.5
17.2
0.015
0.3
3922
PA 24268
3.2
14.0
0.74
0.04
0.91
3928 3959
Armak
PA 24266
3.2
14.1
0.48
0.03
0.40
PA 25137
3.3
15.3
0.37
0.06
0.12
3966
PA 24738
4.2
19.5
0.4
0.03
<0.2
Physical Properties
Diameter, mm
Length, mm
Pore Volume, cc/g
Surface Area, m2/g
Surface Area, m^/cc
Compacted Bulk Density, g/cc
Reactor Density, g/cc
Side Crush Strength, Ib/mm
Pore Size Distribution
by Hg Porosimeter
PV cc/g< 2008 dij
200-2000;
> 2000A
Total
1.63
5.1
0.72
267
158
0.60
0.60
1.5
0.45
0.10
0.17
0.72
1.84
0.48
206
167
0.79
0.81
1.5
0.38
0.02
0.08
0.48
1.65
0.61
243
165
0.66
0.68
2.8
0.35
0.09
0.17
0.61
1.71
0.64
139
95
0.68
°66I
0.37
0.10
0.17
0.64
0.71
116
68
0.59
« 1
0.21
0.17
0.33
0.71
-------
Ni-Mo catalyst HRI 3905 is presented in Figure 7.
Armak catalyst HRI 3928 has a pore size distribution roughly like that
of American Cyanamid catalyst HRI 3905. It has higher density and its pore
volume is lower by 0.11 cc/g with 1/3 of the pore volume loss occurring in
the 500-3000 jj range and 2/3 in the 30 to 100 ft range. Armak catalyst HRI
3959 has a bimodal pore sizecdistribution with the micropores shifted from
around the 50A range to 100A and its pore volume is 0.08 cc/g lower than
HRI 3905. Armak catalyst HRI 3922 has the highest density and lowest pore
volume (0.48 cc/g) among the five catalysts. It lacks medium size pores
and its micropores are similar to those of HRI 3905. Armak catalyst HRI
3966 is the onlv catalyst possessing significantly more and larger macro-
pores. Its micropores are around 110 K occupy less than half of the
pore volume as do the micropores in HRI 3905.
Armak Catalyst Preparations —
A brief description of catalyst preparation techniques was furnished
by Armak. Catalyst HRI 3922 was prepared by impregnating the extrudates
of the alumina support. The other three catalysts were prepared differently.
Mo was incorporated by mixing the wet solids. After extrusion, Ni was
impregnated onto the extrudates. The Mo-containing extrudates of catalyst
HRI 3966 had high total pore volume. In order to meet our specifications
of increasing the size and quantity of macropores but keeping the same
total pore volume as that of American Cyanamid catalyst HRI 3905, Armak
calcined the extrudates at high temperature to reduce the quantity of
micropores prior to Ni impregnation. This resulted in a weaker catalyst
and might have adverse effect upon catalyst activity.
Evaluation of Armak Catalysts —
The four Armak catalysts were evaluated in 3-day runs, at 810°F, 2800
psig and 0.5 VHSV. Catalyst HRI 3966 was evaluated at two space velocities,
0.5 and 1.0 V/Hr/V, and the operations were continued for 15 days. Table
11 summarizes the pertinent data for the 3-day operations on the four Armak
catalysts and American Cyanamid catalyst HRI 3905. Triplicate runs were
conducted on HRI 3928 and HRI 3905 under the same operating conditions to
show the precision of denitrogenation data.
Catalyst HRI 3928 with lower macropore volume and micropore volume
than HRI 3905 had slightly lower denitrogenation activity on the catalyst
volume basis. The difference was more pronounced on the catalyst weight
basis. High density catalyst HRI 3922 has much lower macropore volume
than HRI 3905, 0.10 vs. 0.27 cc/g for>200 X dia. as shown in Table 11.
Their initial denitrogenation activities during the 3-day operation are
about the same on catalyst volume basis; however, the weight of HRI 3922
charged to the reactor is 35% higher than that of HRI 3905. Since both the
catalyst age and catalyst cost are on weight basis, HRI 3905 is the
superior catalyst among these three.
- 30 -
-------
AMINCO FORM
C»t.No. S-7135A
EQUIVALENT PORE DIAMETER (MICRONS)
175/PSI
(CONTACT ANGLE - I30°J
pop poop
pop p p p p p
— bb b b b b b
O •Oto >i &• ut * o
HRI 3905
HRI 3922
HRI 3928
HRI 3959
HRI 3966
American Cyanamid SN 4475
Armak PA 24263
Armak PA 24266
Armak PA 25137
Armak PA 24733
HRI 3922
K) *-* k UI
-------
TABLE 11. COMPARISON OF ARMAK CATALYSTS AND AMERICAN CYANAMID CATALYST HRI 3905
Run No. 115.
Catalyst
HRI No.
Manufacturer
No.
Volume Charged, cc
i
w Weight Charged, g
ro
1 Temperature, °F
Pressure, psig
Space Velocity, V/Hr/V
Denitrogenation, W %
IB
2A
2B
3A
3B
Average
1288
101.7
67.9
81.2
74.6
73.7
69.7
73.4
1290
—PA ?4?fifi-
mo.
101.8
70.4
65.8
62.8
66.3
1291
102.0
Of\-~
61.2
68.9
74.7
63.4
78.9
69.4
1287
3922
Pa 24268
122
65.4
75.1
79.4
73.6
73.4
1292
•jqcq
PA 25137
101.5
oin
?800-.
83.7
80.1
84.0
73.6
73.4
78.8
1293
__1Qf
— PA
88.1
83.5
81.8
75.5
76.6
79.4
1294
:c
24738-
75
43.3
1.0
54.5
52.0
48.9
53.8
52.3
1280
American
90.4
80.4
82.5
72.1
78.3
1285
Cyananvid-
CM AAJti
icn
89.5
Oc
79.6
74.4
70.2
74.7
1289
88.9
85.9
77.9
72.9
78.9
-------
HRI 3959 and HRI 3928 are similar in every respect, including the
catalyst preparation technique,except that the micropores of HRI 3959 are
around 100 A vs. 50 A for HRI 3928. HRI 3959 has moderately higher de-
nitrogenation activity than HRI 3928. It is concluded that increasing the
micropore sizes of a catalyst increases its denitrogenation activity
moderately. However HRI 3959 does not show better denitrogenation activity
than HRI 3905, which has micropores as small as those of HRI 3928. This
can be attributed to two possibilities: HRI 3905 has 0.08 cc/q more pore
volume in micropores than HRI 3959; or the method of preparing HRI 3905 is
better than the method for HRI 3959.
The Ni-Mo catalyst HRI 3966 is very high in macrcpore volume and has
0.13 £C/g pore volume of pores> 1000 A It also has large micropores
(100 A range). Its denitrogenation activity is about the same as that of
HRI 3959. The data seem to indicate that increasing macropores at the
expense of the micropores does not increase the demtrogenation activity
of the catalyst. However, as stated above, HRI 3966 was calcined at high
temperature. This deviation from the regular method of preparation may
have an adverse effect on the catalyst activity.
HRI 3966 has the lowest surface area. As shown in Table 10, the
surface area of HRI 3966 is only 68 m2/cc versus 95 to 167 mz/cc for the
other four catalysts. Theoretically, less surface area needs less metals
for covering the catalyst support. HRI 3966 probably can be made into a
version containing substantially less Ni and Mo. If the denitrogenation
activity is not decreased, a low cost catalyst may result.
Effect of Space Velocity—
The Ni-Mo catalyst HRI 3966 was evaluated at 2 space velocities, 0.5
and 1.0 V/Hr/V, over a 15-day period. For Run 115-1294, to achieve 1.0
V/Hr/V, the catalyst was diluted with an equal volume of carborundum. The
catalyst deactivation data are plotted in Figure 8. The effect of space
velocity is rather unexpected. As shown in Figure 8, at 0.7 bbl/lb catalyst
age, Run 115-1293 at 0.5 VSHV shows a steep deactivation, whereas Run 115-
1294 at 1.0 LHSV does not. A line through these later data for 0.5 LHSV
would cross the line for the data at 1.0 VHSV at a catalyst age of 0.8
bbl/lb.
- 33 -
-------
LEGEND RUN NO.
115-1293
115-1294
CATALYST PRESSURE. PSIG
HRI 3966 2800
HRI 3966 2800
TEMP. °F
810
810
LHSV CATALYST SPACE VELOCITY. BBL/LB
0.5
1.0
0.058
0.116
I
CO
7-
6_
5_
4.
3_
2-
i I
0.5 1.0
CATALYST AGE (Bbl/lb)
1.5
Figure 8. Denitrogenation of SRC Blend
-------
Semi-quantitative emission spectrographic analysis of the used catalyst
from Run 115-1293 is presented in Table 12. The major metal contaminants
were boron, titanium and iron. Quantitative analyses of the contaminants
on the used catalyst from Run 115-1293 and - 1294 are tabulated below:
Spent Catalyst
Run No. 115-1293 115-1294
(.5 VHSV) (1.0 VHSV)
Carbon, W % 26.6 17.7
Hydrogen, W % 1.15 0.90
Sulfur, W % 6.01 6.28
Nitrogen, W % 0.58 0.46
Ti, W % 0.31 0.31
These two used catalysts had about the same amount of hydrogen, sulfur and
nitrogen. Titanium deposition on the catalyst amounted to only about 18.3%
of the titanium present in the SRC feedstock. Carbon content of the spent
catalyst from Run 115-1293 was significantly higher than that from Run
115-1294, 26.6% versus 17.7%. Run 115-1293 had significantly higher 975°F+
conversion than Run 115-1294 over the first 6-day operation, an average of
65% versus 49% conversion. It is likely that operating at lower space
velocity gives deeper resid conversion. This results in higher carbon
deposition on-the catalyst which leads to steeper catalyst deactivation.
- 35 -
-------
TABLE 12. EMISSION SPECTROGRAPHIC ANALYSIS
OF USED CATALYST FROM RUN 115 - 1293
Element
Aluminum
Molybdenum
Nickel
Boron
Silicon
Titanium
Iron
Manganese
Magnesium
Lead
Chromi urn
Vanadium
Bismuth
Copper
Silver
Cobalt
Percent
1-10
0.9
0.5
0.5
0.4
0.007
0.04
0.005
0.015
0.05
0.005
0.07
0.01
0.001
- 36 -
-------
APPENDIX A
SUMMARY OF RUN DATA
- 37 -
-------
DENITROGENATION OF PETROLEUM VACUUM RESID
CO
00
Run No.
Period
Unit 115
1255-IB
2
3
4
5
6
7
8
9
10
11
12
13
14
1256-18
2
3
4
5
6
7
8
9
10
11
12
13
14
Catalyst
HRI No. Mfr's No.
3556
3687
American
Cyanamld
HDS 2A
Co-Mo on
A1203,
1/16" extra
-dates
American
Cyanamld
HDS 9A
Ni-Mo on
A1203
Trllobe
Feed
Gach
Saran
Vacuum
Res Id
6.2 OAPI
0.67 % N
3.78 % S
Gach
Saran
Vacuum
Resid
Temp
°F
774
774
779
776
776
776
777
778
782
780
781
780
776
779
782
780
785
785
780
778
780
779
782
780
780
780
776
780
1985
1985
1950
1950
1960
1980
1985
1995
1990
2000
2000
1995
1990
2005
2C10
1995
1995
2010
2015
2000
2020
2015
2000
2000
1990
2000
2000
1995
Space Velocity
V/Hr/Vc
0.86
0.84
0.86
0.87
0.84
0.84
0.88
0.82
0.82
0.54
0.47
0.48
0.48
0.46
0.86
0.75
0.82
0.93
0.90
0.81
0.86
0.84
0.82
0.51
0.44
0.43
0.51
0.42
B/D/Lb
0.103
0.101
0.103
0.104
0.101
0.101
0.106
0.099
0.099
0.065
0.056
0.058
0.058
0.055
0.073
0.064
0.070
0.079
0.077
0.069
0.073
0.071
0.069
0.043
0.038
0.037
0.043
0.035
Excess \\2
SCF/Bbl
6108
5642
6149
7102
5403
5133
4658
5533
5056
3666
6730
3867
3751
4467
4174
5108
4388
3717
4200
4332
4382
4426
4332
4402
4421
4529
4734
4692
Cat. Age
Bbl/Lb
0.138
0.239
0.342
0.446
0.547
0.648
0.745
0.844
0.943
1.008
1.064
1.122
1.180
Liquid Product
1.235
0.093
0.157
0.227
0.306
0.383
0.457
0.535
0.606
0.675
0.718
0.756
0.795
0.833
0.873
°API
13.5
13.3
14.2
13.3
12.5
14.4
11.0
10.4
9.7
13.9
14.3
17.6
13.9
12.6
18.5
18.8
18.2
16'. 7
15.6
17.2
12.8
12.3
11.6
14.9
14.3
15.5
14.4
13.2
% N
0.462
0.456
0.501
0.607
0.542
0.508
0.510
0.563
0.604
0.466
0.515
0.553
0.488
0.513
0.244
0.361
0.442
0.415
0.449
0.387
0.412
0.601
0.597
0.557
0.621
0.583
0.544
0.531
% S
1.94
1.84
1.81
1.88
1.90
2.00
2.44
2.20
2.10
1.88
1.68
1.86
2.04
1.92
0.85
0.78
0.80
1.21
1.53
1.91
2.24
2.47
2.58
2.39
2.42
2.69
2.85
2.87
-------
DENITROGENATION OF COAL LIQUIDS FROM SOLVENT REFINED COAL PROCESS
Liquid Product
CO
10
Run No.-
Perlod
Unit 115
1257- IB
2A
1259- IB
2
3
4
5
6
7A
1260- IB
2
3
1261 -IB
2
3
HRI Mfr's
No. Iden. No.
3779 Harshaw
HT-400
Co-Mo on
A1203
3779 Harshaw
HT-400
Co-Mo on
A1203
3556 American
Cyanamid
HDS 2A
Co-Mo on
A1203
3556 See Above
Temp.
Feed
H-Coal
Gas Oil
Pdt L428
9.5 OAPI
0.45 % N
0.06 % S
H-Coal
Gas Oil
Pdt L428
H-Coal
Fuel Oil
Pdt L438
-12.6 °API
0.841 % N
0.59 % S
41.6 W %
945°F+
H-Coal
Fuel Oil
Pdt L440
3.2 OAPI
0.810 X N
0.37 X S
32.1 W %
955°F+
OF
781
780
780
780
779
810
809
810
780
777
777
779
808
805
806
Pressure
Psig
2015
2010
2710
2800
2805
2800
2810
2785
2775
2010
2000
2010
2810
2820
2790
Space Velocity
V/Hr/V
2.12
2.00
3.01
2.80
2.79
4.00
4.00
4.00
2.60
0.53
0.51
0.43
0.50
0.50
0.50
B/D/Lb
0.183
0.172
0.268
0.249
0.248
0.355
0.355
0.355
0.231
0.065
0.062
0.053
0.061
0.061
0.061
Excess Hp
Bbl/Lb
3950
3920
3630
3910
4610
3890
4200
4340
4250
4350
4563
4990
5320
5070
4862
Cat. Age
Bbl/Lb
0.149
0.220
0.166
0.415
0.662
1.009
1.363
1.718
1.834
0.046
0.107
0.168
0.047
0.111
0.172
H? Consumption
SCF/Bbl
1165
1065
_
-
925
-
-
945
-
1707
-
918
1914
_
1634
W %
W % Output Basis °API
1.75
1.60
_
-
1.42
-
-
1.41
-
2.17
-
1.17
2.61
_
2.22
99.8
99.7
„
-
100.0
-
-
98.6
-
93.3
_
96.7
93.0
_
93.8
17.0
16.4
17.6
17.3
17.3
17.0
17.4
17.2
16.5
7.3
1.1
-3.2
13.3
9.2
975°F+
% N W %
0.097
0.088
0.105
0.098
0.108
0.098
0.088
0.078
0.086
0.344 14.7
0.482
0.539 31.2
0.267 12.3
0.331
0.372 16.9
Spent
Catalyst, % C
10.7
8.6
20.6
19.4
-------
DENITROGENATION OF COAL LIQUIDS FROM SOLVENT REFINED COAL PROCESS
Feed L446 - Blend of 40 W X SRC Product and 60 M % SRC SRC Solvent,
-6.8 °API, }.07«. N, Q.f>7% S, 34.7 W 7. 975°F+, 8.5 W X 975°F+ Benzene - Insoluble
Run No.-
Period
Unit 115
1262- IB
2
3
1263- IB
2
3
i 1264- IB
4* 2
o 3
1 1265- IB
2
3
1266- IB
2
3
1267- IB
2
3
Catalyst
HRI Manufacture
Liquid Product
Temp.
No. Identification °F
3556 American
Cyanamid
HDS 2A
3849 American
SN4412B
Co-Mo, 1/16"
3850 American
Cyanamod
SN4412A
3851 American
Cyanamid
Ni-W, 1/16"
3556 American
Cyanamid
Ni-W, 1/16"
3850 American
Cyanamid
Ni-W, 1/16"
1268- IB/ 1/ 3850 American
2
3
Cyanamid
Ni-W, 1/16"
845
849
847
850
850
854
850
849
850
850
852
847
819
813
810
807
811
815
776
780
781
Pressure
Psig
2825
2800
2785
2835
2790
2795
2825
2805
2785
2790
2810
2810
2800
2800
2780
2810
2830
2805
2810
2800
2780
Space
V/Hr/V
0.51
0.64
0.57
0.51
0.53
0.71
0.51
0.44
0.50
0.49
0.42
0.53
0.54
0.53
0.51
0.28
0.50
0.53
0.53
0.53
0.43
Velocity
B/D/Lb
0.061
0.068
0.068
0.065
0.067
0.089
0.065
0.057
0.064
0.065
0.056
0.070
0.067
0.066
0.063
0.062
0.064
0.068
0.069
0.069
0.056
Excess H2
Bbl/Lb
5890
5500
6030
7600
4830
3150
6170
6840
5490
6010
5760
5440
3340
2830
4560
4940
5460
5250
5610
4180
5380
Cat. Age
Bbl/Lb
0.082
0.150
0.218
0.067
0.132
0.256
0.082
0.144
0.210
0.077
0.138
0.210
0.073
0.139
0.203
0.062
0.126
0.193
0.073
0.143
0.191
HZ Consumption
SCF/Bbl
2420
810
2730
2270
2230
2890
3220
W %
W % Output Basis °API
3.35
1.12
3.79
3.22
2.95
3.82
4.7
91.5
95.4
90.3
90.8
94.1
94.0
97.4
12.8
12.0
10.5
10.5
3.3
2.7
12.7
11.3
11.6
8.8
9.1
8.7
11.0
9.4
8.6
14.1
15.6
13.5
18.8
19.9
23.7
975°F+ W %
% N Total Insoluble
0.337
0.355
0.399 16.8 0.38
0.241
0.533
0.653 24.1 5.09
0.248
0.336
0.431 17.2 0.62
0.418
0.444
0.615 11.9 0.66
0.375
0.571
0.529 20.3 0.37
0.249
0.258
0.365 12.3 0.14
0.182
0.169
0.90
Spent
Catalyst
55 C
30.1
39.1
31.9
27.1
25.3
21.5
10.7
* Feed HRI 3861 SRC Solvent, 1.8<> API, 0.69% N, 0.67% S
-------
DENITROGENATION OF COAL LIQUIDS FROM SOLVENT REFINED COAL PROCESS
Run No.-
Period
Unit 115
1269- IB
2
3
1270- IB
2
3
1271-1B
2
3
1272- IB
2B
3B
4B
5B
6B
78
1273-1B
2
3
1 274-1 B
2
3
1275-18
2
3
1 276-1 B
2
3
1277- IB
2
3
HRI
No.
3850
3866
3867
3850
3849
3851
3556
3850
3849
Manufacture
Identification
American
Cyanamid
SN4412A
Ni-Co 1/16"
Extrudate
SN4424
1/16" Size
SN4425
1/16" Size
American
Cyanamid
SN4412A
Ni-Co 1/16"
Extrudate
American
Cyanami d
SN4412B
Co-Mo, 1/16"
Extrudate
American
Cyanami d
SN4412C
Ni-W, 1/16"
Extrudate
American
Cyanamid
HOS-1442A
American
Cyanamid
SN4412A
N1 -Co, 1/16"
Extrudate
American
Cyanamid
SN4412B
Co-Mo, 1/16"
Extrudate
Temp.
°F
777
777
780
813
811
813
810
813
810
803
802
806
813
811
811
805
812
810
803
812
810
802
809
808
810
809
809
-
809
810
811
Pressure
Psig
2805
2800
2790
2810
2800
2785
2800
2795
2770
2825
2780
2810
2815
2815
2790
2800
2805
2795
2815
2765
2790
2800
2000
2000
1990
1965
1975
1945
1995
2015
1995
Space
V/Hr/V
0.45
0.56
0.56
0.53
0.51
0.51
0.47
0.51
0.49
0.39
0.33
0.51
0.51
0.49
0.45
0.26
0.53
0.53
0.52
0.49
0.55
0.52
0.57
0.53
0.50
0.57
0.53
0.54
0.51
0.49
0.50
Velocity
B/D/Tb
0.058
0.023
0.073
0.067
0.064
0.064
0.075
0.064
0.061
0.052
0.044
0.067
0.066
0.064
0.059
0.034
0.068
0.068
0.067
0.067
0.075
0.071
0.070
0.065
0.061
0.076
0.070
0.062
0.065
0.062
0.064
Excess H?
Bbl/Lb
6600
3710
4180
2880
4000
3680
5050
7620
4400
6630
6680
3550
4980
3830
6990
10640
5840
8770
7150
4170
3620
3870
4600
4300
5260
5010
4670
4610
5120
7280
4860
Cat. Age
Bbl/Lb
0.052
0.120
0.191
0.064
0.128
0.193
0.069
0.140
0.204
0.066
0.117
0.183
0.248
0.311
0.374
0.422
0.075
0.144
0.211
0.038
0.111
0.182
0.078
0.145
0.207
0.080
0.151
0.205
0.068
0.132
0.196
H2 Consumption W %
SCF/Bbl W~f Output Basis °API
12.8
10.7
1900 2.51 96.4 5.8
10.5
12.8
2637 3.4J 94.3 1 i .6
14.0
10.6
2663 3.53 94.7 10.7
14.1
12.0
2350 3.20 93.3 9.6
9.0
8.0
2360 3.27 91.6 7.6
9.1
7.2
11.2
2640 3.60 92.0 10.2
10.2
9.8
2340 3.16 96.6 7.7
4.0
7.6
1770 2.42 91.3 7.0
2.5
8.1
2070 3.02 91.2 9.0
9.3
9.8
2220 2.95 90.6 8.4
% N
0.232
0.268
0.638
0.256
0.311
0.396
0.396
0.390
0.369
0.265
0.416
0.368
0.372
0.550
0.619
0.663
0.599
0.318
0.544
0.587
0.533
0.695
0.665
0.429
.600
0.683
0.494
0.408
0.372
0.390
0.484
- opcui.
975°F+ W % Catalyst
Total Insoluble ^ f.
21.4 .41 23.1
13.5 1.35 22.8
14.0 1.41 24.2
14.0 .10 29.2
17.9 .31 28.2
14.7 .15 24.2
18.0 .21 15.8
16.9 .48 26.2
15.9 .37 30.4
16.8 .25 23.6
-------
DEJilTROGEHATlON OF COAL LIQUIDS FROM SOLVENT REFINED COAL PROCESS
Liquid Product
ro
Run No.-
Perlod
Unit 115
1 278-1 B
2
3
1279-1B
2
3
1280-18
2
3
1281-18
2
3
1282-18
2
3
1283-18
2
3
1284-18
2
3
1285-18
2
3
1286-18
2
3
1287-18
2
3
1288-18
2
3
1289- IB
2
3
1290- IB
2
3
1291-18
HRI
No.
3851
3904
3905
3904
3905
3866
3867
3905
3911
3922
3928
3905
3298
3928
Manufacture Temp.
Identification °F
American
Cyananvid
SN4412B
Co-Mo, 1/16"
Extrudate
American
Cyanamid
ACCO-SN4474
American
Cyanami d
ACCO-SN4475
See Above
See Above
American
Cyanami d
SN4424
American
Cyanamid
SN4425
American
Cyanamid
ACCO-SN4475
American
Cyanamid
SN4510
Armak
PA24268
Armak
PA24266
See Above
See Above
See Above
808
810
809
805*
809
808
815*
821
828
846
839
851
847
851
855
843
846
842
849
851
852
827
825
823
820
819
818
826
822
810
805
811
809
816
812
811
816
816
815
810
809
809
Pressure
Psig
1985
2025
1980
2790
2810
2775
2795
2800
2785
2795
2805
2800
2650
2795
2785
2815
2795
2790
2810
2790
2790
2800
2805
2790
2800
2785
2815
2805
2795
2800
2800
2790
2780
2805
2775
2790
2820
2780
2800
2785
2775
2810
Space Velocity Excess Hg
V/Hr/V B/D/Lb Bbl/Lb
0.48
0.49
0.51
0.51
0.53
0.55
0.55
0.53
0.52
0.47
0.51
0.51
0.53
0.50
0.51
0.54
0.55
0.53
0.50
0.51
0.51
0.54
0.53
0.51
0.50
0.50
0.47
0.42
0.47
0.50
0.50
0.55
0.50
0.51
0.52
0.54
0.49
0.49
0.49
0.54
0.53
0.051
0.066
0.067
0.071
0.058
0.060
0.063
0.062
0.060
0.059
0.055
0.059
0.059
0.059
0.056
0.057
0.069
0.069
0.068
0.053
0.065
0.065
0.062
0.060
0.058
0.043
0.043
0.041
0.035
0.040
0.042
0.050
0.056
0.051
0.058
0.116
0.181
0.050
0.050
0.049
0.055
5740
0.052
5630
6360
4710
5980
5170
5630
5450
4770
3630
5910
5480
4480
5110
5000
4560
4770
4750
5510
4680
7990
5740
4120
3970
3660
4940
5280
5280
6030
4680
5490
3690
4540
6060
5530
4220
5320
5910
5440
6000
3200
0.107
4980
Cat. Age
Bbl/Lb
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
.069
.137
.209
.064
.123
.186
.063
.123
.182
.059
.118
.178
.059
.116
.173
.069
.138
.207
.063
.125
.192
.064
.124
.181
.045
.089
.131
.044
.086
.129
.052
.106
.158
.058
.116
.181
.049
.099
.150
H? Consumption
SCF/Bbl W ?
1760
2500
2840
3040
2880
2380
3080
2670
2990
3010
2900
3190
2531
2.44
3.56
3.84
4.07
3.97
3.26
4.28
3.43
3.89
3.96
3.82
4.22
3.34
0.054
0.159
3110
4.11
89.5
91.8
92.4
90.1
88.8
88.0
87.4
92.3
91.4
87.9
89.7
91.1
91.1
92.7
"API
7.7
7.7
6.7
N
0.527
0.632
0.630
975°F+ W
Total
17.6
— Spent
Catalyst
Insoluble t r
.31
3.8
11.7
8.5
14.2
14.4
12.4
15.1
14.2
12.8
8.2
12.1
11.6
13.7
10.7
4.8
12.8
13.2
13.0
16.9
15.5
14.6
15.7
14.8
13.4
7.0
14.6
12.4
14.9
14.5
11.4
16.6
13.9
12.6
10.3
8.2
8.7
7.5
13.2
13.0
0.615
0.330
0.492
0.228
0.207
0.274
0.275
0.467
0.320
0.408
0.438
0.331
0.269
0.372
0.711
0.299
0.241
0.306
0.218
0.274
0.319
0.198
0.225
0.227
0.560
0.266
0.282
0.343
0.272
0.324
0.151
0.236
0.294
0.317
0.366
0.398
0.415
0.271
0.266
16.1
11.5
10.5
12.1
18.3
9.5
10.9
10.0
11.2
13.5
14.1
17.2
13.0
.56
.10
.08
.09
2.93
.10
.04
.02
.30
.42
.14
.20
.19
21.1
25.1
23.3
27.4
28.5
35.7
31.0
24.3
22.1
19.1
19.8
18.8
23.2
15.0
-------
DENITROGEKATIa'! OF COAL LIQUIDS FROM SOLVENT REFIMLU COAL PROCESS
CO
Run No.-
Perlod
Unit 115
1292-1B
2
1293- IB
2
3
4
5
6
7
8
9
10
11
12
13
14
15
1294- IB
2
3
4
5
6
7
8
9
10
11
12
13
14
15
HRI Manufacture Temp.
No. Identification °F
3959 Armak 804
PA25137 806
805
3966 Armak 811
PA24738 808
Ketjen Ni-Mo 816
816
812
813
813
813
813
811
816
811
809
811
810
3966 See Above 811
803
812
809
804
808
807
808
808
806
808
806
806
808
803
Pressure
Psig
2800
2800
2800
2795
2785
2805
2805
2795
2790
2760
2800
2790
2800
2815
2800
2795
2800
2800
2785
2795
2805
2800
2780
2730
2780
2805
2735
2785
2775
2800
2780
2820
2790
Space Velocity
V/Hr/V BTn/lb
0.54
0.53
0.51
0.49
0.49
0.50
0.52
0.50
0.51
0.49
0.50
0.51
0.50
0.52
0.56
0.54
0.53
0.53
0.51
0.50
0.49
0.50
0.51
0.49
0.54
0.53
0.50
0.55
0.54
0.54
0.53
0.43
0.50
0.054
0.54
0.052
0.057
0.057
0.059
0.061
0.059
0.060
0.057
0.058
0.059
0.059
0.061
0.065
0.062
0.061
0.062
0.122
0.118
0.117
0.120
0.122
0.115
0.128
0.126
0.118
0.131
0.132
0 128
0.125
0.101
0.118
Excess H2
Bbl/Lb
4850
6280
4770
6450
5240
4730
4730
4570
5820
5140
4320
7200
5340
4790
4330
6080
5200
4075
4520
4G90
5800
5280
3570
5250
7720
5550
5720
5740
5040
5930
4590
6240
4660
Cat. Age
Bbl/Lb
0.057
0.105
0.158
0.057
0.114
0.170
0.232
0.291
0.351
0.410
0.467
0.527
0.586
0.646
0.711
0.774
0.832
0.893
0.117
0.235
0.353
0.472
0.593
0.710
0.836
0.960
1.076
.209
.338
.461
.586
.701
.818
H? Consumption M %
SCF/Bbl W ? Output Basis
3140 4.15 91.4
3230 4.27 92.1
2830 3.74 90.0
2340 3.09 90.4
1610 2.13 93.2
2310 3.05 92.6
.1990 2.63 92.9
1840 2.43 93.7
°API
16.8
14.2
12.8
16.1
14.2
13.4
11.9
11.5
11.6
10.9
10.1
9.9
10.3
10.1
6.6
2.7
2.2
3.0
7.9
7.4
7.6
6.9
5.5
6.5
5.5
5.4
5.5
5.3
4.8
5.3
3.9
4.4
5.1
% N
0.174
0.171
0.284
0.197
0.262
0.250
0.249
0.361
0.370
0.385
0.377
0.408
0.388
0.394
0.561
0.831
0.764
0.766
0.487
0.547
0.494
0.595
0.636
0.642
0.702
0.696
0.680
0.707
0.749
0.656
0.751
0.702
0.649
975°F+ W %
total Insoluble
10.5 .22
12.5 .13
12.0 .42
19.6 1.89
23.3
17.5 .20
18.2 .55
19.4 .74
:>pent
Catalys
17.5
26.6
26.6
26.6
26.6
1
17.7
17.7
17.7
-------
APPENDIX B
SUMMARY OF OPERATING CONDITIONS, PRODUCT DISTRIBUTION, HYDROGEN
CONSUMPTION, 975°F+ CONVERSION, AND HETEROATOM REMOVAL
- 44 -
-------
The product distribution was normalized to give complete material
balance closure by prorating the weights of liquid product and the
gas product e"qual to the weight of feed plus hydrogen consumed.
H2S, NH3 and ^0 were calculated from the sulfur, nitrogen and
oxygen balances of the feed and the liquid product. Hydrogen
consumption was the sum of the increase between the hydrogen
contents of the liquid and gas products and that of the feed and
the hydrogen required for formation of f^S, NH3 and H20.
-- 45 -
-------
SUMMARY OF OPERATING CONDITIONS AND PERFORMANCES
Run Number
Period
Hours on Stream
Feed (HRI No.)
Catalyst (HRI No.)
Catalyst Age. Bbl/Lb
OPERATING CONDITIONS
Pressure, psig, outlet
Reactor Temperature
Space Velocity, Vf/Hr/Vcat
Space Velocity, Bbl/D/Lb
Hydrogen Rate, SCF/Bbl (Outlet)
YIELDS. H % ON OUTPUT BASIS
CO+C02
H2S+NH3+H20 (Calculated)
115-1285 115-1286 115-1287 115-1288 115-1289 115-1290 115-1291 115-1292 115-1293 115-1294
3B 3B 3B 3B 3B 3B 3B 3B 3B 3B
59-71 59-71 60-72 60-72 60-72 60-72 1,9-71 59-71 60-72 60-72
IBP-975°F
975°F+ (Benzene Soluble)
975°F+ (Benzene Insoluble)
975°F+ (Toluene Soluble)
975°F+ (Toluene Insoluble)
Ash
Total
Hydrogen Consumption, SCF/Bbl
975°F+ Conversion, %
Benzene Insoluble Conversion, %
Toluene Insoluble Conversion, W %
HETEROATOM REMOVAL
Hi trogen
Sulfur
Oxygen
SPENT CATALYST ANALYSIS
Carbon, %
Hydrogen, %
Sulfur, %
Nitrogen, %
Titanium
L-446
3905
0.181
2790
811
0.51
0.058
3430
0.04
6.58
3.09
1.42
82.23
10.02
0.04
0.01
103.43
2670
71.01
99.8
70.2
99
89.6
24.30
1.44
.
.519
L-446
3911
0.131
2815
811
0.47
0.041
3980
0.13
6.35
3.93
2.04
82.29
9.12
0.02
0.01
103.89
2990
73.65
99.9
78.8
99
83.1
22.07
1.43
.
.485
L-446
3922
0.129
2800
810
0.50
0.042
5500
0.86
6.10
3.24
5.81
78.09
9.59
0.26
0.01
103.96
3010
71.62
91.8
73.6
100
79.3
19.13
1.30
_
5.81
L-446
3928
0.158
2785
809
0.50
0.051
6060
0.62
6.02
3.69
3.76
77.61
11.73
0.38
0.01
103.82
2900
65.09
91.5
69.7
100
77.9
19.78
1.32
_
5.37
L-446
3905
0.181
2790
811
0.54
0.063
4970
0.29
6.58
4.03
2.17
78.29
12.72
0.13
0.01
104.22
3190
62.97
96.2
72.5
99.3
89.0
18.78
1.33
6.06
0.12
L-446
3928
0.150
2800
806
0.49
0.049
4810
0.06
6.54
3.86
1.78
75.42
15.49
0.18
0.01
103.34
2531
54.85
95.9
62.8
98.5
SO. 6
23.20
1.31
5.42
0.50
L-446
3928
0.159
2810
809
0.51
0.052
4750
0.14
6.43
3.08
1.75
80.64
11.87
0.18
0.02
104.11
3110
65.27
96.5
69.2
97.8
89.6
14.99
1.18
0.44
6.11
L-446
3959
0.158
2800
809
0.51
0.052
4470
0.08
6.65
4.12
1.90
81.79
9.35
0.24
0.01
104.15
3140
72.35
93.0
73.8
98.0
91.8
17.53
1.14
0.44
6.08
0.305
L-446
3966
0.143
2800
813
0.50
0.050
4460
0.12
6.59
3.13
2.30
80.61
11.31
0.20
0.01
104.27
3230
66.82
95.3
76.6
95
90.2
26.6
1.15
6.01
0.58
L-446
3966
0.353
2800
810
0.98
0.117
5480
0.30
5.99
2.71
1.40
76.41
16.02
0.19
0.03
103.05
2310
53.29
94.7
53.8
95
88.3
17.7
0.90
6.28
0.46
0.307
-------
SUMMARY OF OPERATING CONDITIONS AND PERFORMANCES
Run Number
Period
Hours on Stream
Feed (HRI No.)
Catalyst (HRI No.)
Catalyst Age, Bbl/Lb
OPERATING CONDITIONS
Pressure, pslg, outlet
Reactor Temperature
Space Velocity, Vf/Hr/Vcat
Space Velocity. Bbl/D/Lb
Hydrogen Rate, SCF/Bbl (Outlet)
YIELDS. M X ON OUTPUT BASIS
i CO+COz
^ H2S+NH3+H20 (Calculated)
•vj Ci-C.i
i
IBP-975°F
975°F+ (Benzene Soluble)
975°F+ (Benzene Insoluble)
Ash
Total
Hydrogen Consumption, SCF/Bbl
975°F+ Conversion, W X
Benzene Insoluble Conversion, %
HETEROATOH REMOVAL. %
Nitrogen
Sulfur
Oxygen
SPENT CATALYST ANALYSIS. W %
Carbon
Hydrogen
Sulfur
N1trogen
115-1273 115-1274 115-1275 115-1276 115-1277 115-1278 115-1279 115-1280 115-1231 115-1282 115-1283 115-1284
IR 3B 3B 3B 3B 3B 3B 3B 38 3B 3B 3B
60-72 60-72 60-72 60-72 60-72 60-72 60-72 60-72 60-72 60-72 ' 60-72 60-72
L-446 L-446 L-446 L-446 L-446 L-446 L-446 L-446 L-446 L-446 L-446 L-446
3849 3851 3556 3850 3849 3851 3904 3905 3904 3905 3866 3867
0.0211 0.1B2 0.207 0.205 0.196 0.209 0.186 0.182 0.178 0.173 0.207 0.192
2815
804
0.52
0.067
7150
0.31
6.43
3.54
1.24
78.52
13.39
0.14
0.03
103.60
2640
61.00
99
4.91
q? 2
yf. . t-
93.0
24.17
1.24
2800
800
0.52
0.071
3870
0.25
6.25
2.95
1.05
75.96
16.47
0.20
0.03
1C3.16
2340
51.95
99
35.0
99
92.6
15.79
1.02
1990
810
0.50
0.061
5250
0.15
6.50
3.27
1.15
75.90
15.00
0.44
0.01
102.42
1770
55.51
98.2
43.9
-
26.15
1.10
1950
810
0.54
0.062
4600
0.40
6.66
3.64
1.16
76.66
14.16
0.34
0.01
103.02
2070
58.23
98.7
61.9
-
30.37
0.97
2000
811
0.50
0.064
4850
0.04
6.73
4.08
1.53
75.34
14.98
0.23
0.02
102.95
2220
56.16
99.1
54.8
-
23.65
1.28
1980
809
0.51
0.071
4700
0.19
6.55
4.30
1.85
73.77
15.47
0.28
0.02
102.44
1760
54.59
98.9'
41.1
-
21.11
1.36
2775
808
0.55
0.063
5340
0.43
5.98
3.33
1.99
77.03
14.27
0.51
0.02
103.56
2500
57.40
98.3
54.1
95.8
81.9
25.13
1.52
2785
808
0.52
0.059
3360
0.17
6.30
3.35
1.61
81.77
10.53
0.09
0.01
1-3.84
2840
69.38
99.7
74.5
98.7
83.7
23.28
1.39
2800
851
0.51
0.059
4090
0.10
6.43
5.36
2.07
80.64
9.39
0.07
0.01
104.07
3040
72.74
99.4
70.1
799
86.5
27.45
1.65
2785
85!
0.51
0.057
4120
0.27
6.46
5.92
2.47
78.09
10.67
0.08
0.01
103.97
2880
69.02
99.2
69.1
799
86.7
28.53
1.56
2790
848
0.53
0.068
5040
0.19
6.43
'6.35
2.31
71.87
13.52
2.58
0.01
103.26
2330
53.61
73.5
33.6
91.2
95.0
35.73
1.81
2790
848
0.51
0.065
5240
0.35
6.70
6.57
3.20
79.14
8.22
0.09
0.01
104.28
3080
76.06
99.2
72.1
799
90.8
31.03
-1.65
0.80
0.61
-------
SUMMARY OF OPERATING CONDITIONS AND PERFORMANCES
00
Run Number
Period
Hours on Stream
Feed (HRI No.)
Catalyst (HRI No.)
Catalyst Age, Bbl/Lb
OPERATING CONDITIONS
Pressure, psig, outlet
Reactor Temperature
Space Velocity, Vf/Hr/Vcat
Space Velocity, Bbl/D/Lb
Hydrogen Rate, SCF/Bbl (Outlet)
YIELDS. H % ON OUTPUT BASIS
CO+C02
H2S+NH3+H20 (Calculated)
IBP-975°F
975°F+ (Benzene Soluble)
975°F+ (Benzene Insoluble)
Ash
Total
Hydrogen Consumption, SCF/Bbl
975°F+ Conversion, W %
Benzene Insoluble Conversion, %
HETEROATOH REMOVAL. %
Nitrogen
Sulfur
Oxygen
SPENT CATALYST ANALYSIS. H %
Carbon
Hydrogen
Sulfur
Nitrogen
115-1260 115-1261 115-1262 115-1263 115-1264 115-1265 115-1266 115-1267 115-1268 115-1269 115-1270 115-1271 115-1272
3B 3B 30 3B 3B 3B 3B 3B 3B 3B 3B 3B 3B
60-72 60-72 60-72 60-72 60-72 60-72 60-72 60-72 60-72 60-72 60-72 60-72 60-72
L-438
3556
0.168
2010'
774
0.43
0.53
4990
—
2.71
1.48
0.30
66.29
30.06*
0.02
101.17
918
21.3
-
35.9
23.9
33.3
L-440
3556
0.172
2790
806
0.50
0.061
4855
_
3.51
2.22
2.17
77.15
15.69*
1.48
102.22
1634
42.1
-
54.1
792
69.3
L-446
3556
0.218
2785
850
0.57
0.68
6025
3.38
1.32
5.34
1.81
76.12
15.02
0.35
0.01
103.35
2420
55.71
95.2
62.7
68.3
89.8
30.14
1.24
L-446
3849
0.256
2795
850
0.71
0.089
3150
0.83
1.05
2.73
1.06
76.06
14.52
4.86
0.02
101.12
810
44.17
27.5
39.0
74.7
16.8
39.14
1.64
L-446
3850
0.210
2785
847
0.50
0.064
5491
1.63
1.28
6.38
4.21
74.74
14.97
0.56
0.01
103.79
2730
55.26
92.5
59.7
65.0
32.0
31.93
1.32
L-446
3851
0.210
2810
850
0.53
0.070
5435
2.73
1.24
5.88
2.54
80.01
10.21
0.60
0.01
103.22
2270
68.85
92.2
42.5
94.3
64.4
27.12
1.15
L-446
3556
0.203
2785
810
0.51
0.063
4564
0.21
4.12
3.10
1.44
72.57
18.14
0.35
0.02
102.95
2230
46.73
96.6
50.6
83.7
-
25.29
1.20
L-446
3850
0.193
2805
810
0.53
0.068
5254
0.40
3.77
3.07
2.58
82.43
11.43
0.13
0.02
103.82
2890
66.68
98.4
65.9
93.3
-
21.47
0.91
L-446
3850
0.191
2780
781
0.43
0.056
5382
0.18
3.93
3.22
0.00
97.37
0.00
0.00
0.00
104.70
3220
0
0
92.7
92.1
-
10.68
0.85
L-446
3850
0.191
2790
780
0.56
0.073
4184
0.07
4.41
1.63
0.00
75.75
20.22
0.40
0.04
102.51
1900
40.57
95.41
48.6
86.3
90.3
23.07
1.27
L-446
3866
0.193
2785
813
0.51
0.64
3682
0.07
4.06
3.36
1.34
81.81
11.50
1.27
0108
103.49
2637
63.20
96
63.0
795
64.7
22.73
1.30
L-446
3867
0.204
2770
810
0.49
0.061
4405
0.39
4.03
2.27
2.05
81.44
11.92
1.34
0.09
103.53
2663
61.79
94
65.5
795
63.1
24.18
1.37
L-446
3850
0.183
2810
806
0.51
0.067
3550
0.14
5.07
3.22
1.49
80.20
12.97
0.09
0.01
103.20
2350
62.38
99.7
72.9
95
-
28.22
1.31
0.464 0.649 0.524 0.517
0.264 0.547
*The value represents total 975 F+
-------
TECHNICAL REPORT DATA
(Pteate read Inunctions on the reverse before completing)
. REPORT NO.
EPA-600/7-78-159
2.
3. RECIPIENT'S ACCESSION-NO.
AND SUBTITLE
Catalygt
Petroleum Residua and Coal Liquids
Denitrogenation
5. REPORT DATE
August 1978
6. PERFORMING ORGANIZATION CODE
'. AUTHOR(S)
Cecelia C. Kang and Jeffrey Gendler
8. PERFORMING ORGANIZATION REPORT NO.
>. PERFORMING ORGANIZATION NAME AND ADDRESS
hydrocarbon Research, Inc.
P.O. Box 6047
Lawrenceville, New Jersey 08648
10. PROGRAM ELEMENT NO.
EHE623A
11. CONTRACT/GRANT NO.
68-02-0293
12. SPONSORING AGENCY NAME AND ADDRESS
EPA, Office of Research and Development
Industrial Environmental Research Laboratory
Research Triangle Park, NC 27711
13. TYPE OF REPORT AND PERIOD COVERED
Phase V; 9/75-2/78
14. SPONSORING AGENCY CODE
EPA/600/13
is. SUPPLEMENTARY NOTESJERL-RTP project officer is Thomas W. Petrie, Mail Drop 61, 919/
541-2708.
16. ABSTRACT
The report covers the final phase of a study of catalysts for demetallization
heavy residual oils and for denitrogenation. Objectives were to evaluate some com-
mercial catalysts for denitrogenation activity in petroleum residua and coal liquids,
uid then to develop an improved catalyst for denitrogenation of heavy coal liquids.
LJnder one task, two commercial catalysts failed to reduce nitrogen content of a
petroleum vacuum resid from 0.67% to the 0.3% target. The observed catalyst deac-
:ivation rate is similar to that of catalysts with similar pore structures which are
Deing used for hydrodesulfurization of petroleum resid. Under another task, attempts
:o denitrogenate heavy coal-derived liquids with commercial Co-Mo catalysts pointed
:o the need for improved catalysts. In the task to improve catalysts, Ni-Mo was iden-
ified as a better active metal pair than Co-Mo or Ni-W for denitrogenation of coal
iquids. Commercial preparation techniques and lower carbon deposition also increa-
sed denitrogenation activity. On the basis of catalyst weight, a bimodal pore distribu-
:ion with some macropores showed better denitrogenation activity than that with micro-
Dores only. Efforts to find the optimum pore distribution were hampered by lack of
technology to enlarge macropores. One experimental catalyst was tried. Denitrogen-
ation activity did not decrease despite a low surface area.
7.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.IDENTIFIERS/OPEN ENDED TERMS
c. COSATI Field/Group
Pollution
Residual Oils
Coal
Liquefaction
Nitrogen
Catalysts
Evaluation
Metals
Pollution Control
Stationary Sources
Coal Liquefaction
Denitrogenation
De metallization
13B
08G
21D
07D
07B
14B
11F
18. DISTRIBUTION STATEMENT
Unlimited
19. SECURITY CLASS (This Report)
Unclassified
21. NO. OF PAGES
55
20. SECURITY CLASS /This page I
Unclassified
22. PRICE
EPA Form 2220-1 (»-73)
- 49 -
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