Flexible Pilot Plant Technology for

Evaluation of Unconventional
Feedstocks and Processes

Kenneth Bryden Abstract

Manager, FCC The fluid catalytic cracking process has been in commercial practice for 70+ years. Feedstocks and
Evaluations Research
process designs have evolved greatly over this period. Today is a time of exciting change in the FCC
world. New feedstocks such as bio-oils (vegetable and pyrolysis), and straight run shale oils are being in-
Gordon Weatherbee
vestigated by refiners. New FCC designs such as High Severity Fluid Catalytic Cracking (HS-FCC) and
Principal Engineer
Deep Catalytic Cracking (DCC) have been developed. On-purpose olefins manufacturing processes, such
E. Thomas Habib, Jr. as ExxonMobil PCCSM and KBR Superflex™, and use of FCC type processes for very light feeds (includ-
Director Customer ing gases and light alcohols) are being proposed. These options represent significant change, and there-
Research Partnerships fore significant risk. One way to minimize the risk associated with these opportunities is to conduct
and DCR Licensing realistic pilot plant testing prior to commercial implementation. One pilot unit that has gained wide accept-
Manager ance in mimicking commercial FCC operation is Grace's DCR™ pilot plant. Including the two DCR pilot
plants operated by W. R. Grace & Co., a total of 26 licensed DCR pilot units have been constructed
Grace Catalysts throughout the world. This paper includes comparisons of DCR pilot plant results to commercial FCC
Technologies units for petroleum derived gas oil and resid feeds, and also describes application of the DCR pilot plant
Columbia, MD, USA
to a variety of alternative feedstocks and process designs. Testing experiences with vegetable oil, pine-
derived pyrolysis oil, and straight run shale oil are described, highlighting the utility of the DCR unit in
evaluating these feedstocks and understanding their effects on yields and operation. Furthermore, appli-
cations of the DCR in studying new high temperature cracking processes designed for high light olefins
yields and processing very light feeds in a circulating fluidized bed are described.

Introduction
Fluid catalytic cracking is one of the most flexible processes in a refinery. It can readily adjust to changes
in feed quality through modifications to catalyst and operating conditions. The FCC unit is one of the few
units in a refinery that can handle a variety of feedstocks, including highly impure feedstocks. FCC feed-
stocks have changed over the 70+ years of commercial application, evolving from light gas oils feeds (31°
API) in the 1940’s, to a variety of streams in the present day which may contain resid, syncrude, as-
phaltenes, and hydrotreated feedstocks1. The flexibility of the FCC unit is of great interest to refiners in
utilizing unconventional feedstocks. A variety of unconventional feedstocks are under consideration for

Grace Catalysts Technologies Catalagram® 3

 MAT/ACE
Nature of Operation Unsteady State
Catalyst Contact Time 12 to 150 secs
Temperature Range 930 to 1100°F
Hydrocarbon Partial Pressure ~12 psia
Catalyst Inventory 5 to 10 grams
Advantage Easy to set up
TABLE I: Comparison of Test Units to Commercial Conditions
motor fuels production. Government mandates on renewable fuel
standards have resulted in interest in co-processing vegetable oils
and pyrolysis oils in refineries2. New technologies are being devel-
oped to convert waste plastics to synthetic crude oil3. The introduc-
tion of new drilling and extraction technologies such as horizontal
drilling and hydraulic fracturing has resulted in large quantities of
shale oil becoming available4.
The flexibility of the fluidized catalytic cracking process, where a
circulating fluidized bed provides excellent heat and mass transfer,
and where a reaction step can be coupled with a catalyst regener-
ation step, have resulted in adoption of FCC-type processes for
applications outside of the conventional molecular weight reduction
of the heavy fraction of crude oil to produce motor fuels. New de-
signs for high temperature cracking to produce light olefins from
heavy feedstocks have been developed, such as High Severity
Fluid Catalytic Cracking (HS-FCC)5, and Deep Catalytic Cracking6.
SM7
FCC-type processes such as ExxonMobil PCC and KBR Super-
flex™8 are designed to crack naphtha range feedstocks preferen-
tially to light olefins. Circulating fluidized bed processes have
been proposed for converting biomass to motor fuels9 and biomass
10,11
to benzene, toluene and xylene . FCC-type processes have
also been developed for propane dehydrogenation12,13 and for con-
verting methanol to olefins14,15. Clearly, circulating fluidized beds
are a versatile technology and are not limited to converting gas oil
to motor fuels.
New feedstocks and process designs represent significant change,
and therefore significant risk. Understanding the potential yields
and performance is vital in assessing the economic viability of
feedstock and process changes. One way to minimize the risk as-
sociated with these opportunities is to conduct realistic pilot plant
testing prior to commercial implementation. As Leo Baekeland, an
entrepreneur and pioneer in the plastics industry, famously spoke
to the importance of lab and pilot plant testing when he stated in
his 1916 Perkin Medal acceptance speech- “The principle: ‘Com-
mit your blunders on a small scale and make your profits on a
large scale,’ should guide everybody who enters into a new chemi-
cal enterprise.”16 Conducting testing before commercial implemen-
tation reduces risk for a refiner or petrochemical manufacturer.
4 Issue No. 113 / 2013
Circulating Riser Commercial
Steady State Steady State
2 to 5 secs 2 to 8 secs
930 to <1100°F 980 to 1030°F
20-45 psia 20-50 psia
2 to 3 kg 100 tons
Mimics commercial
operation
Examples of questions that can be answered via testing include:
What will be the effect of a potential feedstock change on yields
and product quality?
What will be the effect of a new feedstock on operating conditions?
What are the optimum process conditions to maximize desired
yields?
Description of DCRTM Pilot Plant
Performance testing of FCC catalysts can be done by either bench
scale testing or pilot plant scale testing. Examples of bench scale
testing equipment include fixed bed microactivity testing (MAT)17
and fixed fluidized bed testing, one example of which is the ACE™
catalyst evaluation instrument marketed by Kayser Technology18.
Several pilot plant designs are in operation throughout the world
and include both once-through and circulating designs. The most
common is the Grace-developed DCRTM pilot plant. Table I pro-
vides a comparison of the conditions in these test units to commer-
cial operation.
MAT and ACE testing have the advantages that they are easy to
set up and require small amounts of material. However, these
units cannot provide the detailed product analysis or feedback on
extended operation that pilot scale units can. Larger scale test
equipment such as a pilot unit can provide sufficient liquid product
for distillation and detailed analysis (such as API gravity and aniline
point on LCO produced, viscosity of bottoms, octane engine testing
of gasoline, etc.) and can provide information on continuous opera-
tion. Additionally, compared to bench scale units, the DCR pilot
plant has the advantage that it mimics all the processes present in
commercial operation and it can operate at the same hydrocarbon
partial pressure as a commercial unit. The continuous catalyst re-
generation in the DCR allows for the measurement of regenerator
SOx and NOx emissions and testing of environmental additives,
experiments which cannot be done in a batch unit.
The continuous nature of the DCR and the fact that it represents
the commercial FCC process is particularly important when evalu-
ating new process designs based on FCC. A 2007 study by Inde-
pendent Project Analysis19 that examined the success of 850
 Control Control
Meter Valve Valve Meter

Condenser
Heat Exchanger

Stabilizer Column
Feed Feed

Riser Reactor
Storage Storage

Regenerator

Stripper
Tank #1 Tank #2

Feed Feed
Tank Tank

Scale Scale

Feed Preheater Liquid Product Receivers

Dispersant Steam Stripping Steam

Feed Pump

FIGURE 1: Schematic Diagram of Grace DCR T M Pilot Plant

capital projects involving new technology found that “An integrated
pilot run for an extended period of time can dramatically improve
the early operability of new technology processes.” They found
that revolutionary new technology projects that had a pilot facility to
provide basic operability data averaged 79 percent of design ca-
pacity seven to twelve months after startup, while comparable
processes for which pilot facilities were not built only achieved 30
percent of design capacity seven to twelve months after startup.
They concluded “With a pilot facility, operating conditions can be
fully explored and optimal operating ranges established.”
Figure 1 is a schematic drawing of the DCR. The range of typical
operating conditions of the DCR is shown in Table II. The system
consists of three main units - a riser, a stripper, and a regenerator.
Both the regenerator and the stripper are equipped with slide
valves for control of catalyst circulation rate. The DCR riser is typi-
cally operated in adiabatic mode, where changing feed preheat or
regenerator temperature will result in a change in catalyst circula-
tion to maintain reactor outlet temperature, the same process con-
trol strategy used in many commercial FCC units. The catalyst
circulation and thus, the catalyst to oil ratio, is varied by changing
the feed preheat temperature. During operation of the DCR, a me-
tering pump precisely controls the feed rate as feed is pumped
from the load cell through a preheater. Nitrogen and steam, in-
jected through a separate preheater/vaporizer, are used as a feed
dispersant. Catalyst and product pass from the riser to the stripper
overhead disengager. Products exit the disengager through a re-
frigerated stabilizer column to a control valve, which maintains unit
pressure at the desired level. A section of the stripper-regenerator
spent catalyst transfer line consists of a shell and tube heat ex-
changer. The rate of heat transfer across this exchanger provides
a precise and reliable method to calculate the catalyst circulation
rate. The stabilizer column, also called the debutanizer column, is

Operating Condition Min/Max Range Typical for FCC-type operations

System Pressure max. 45 psig (4atm)* 25 psig (2.7 atm)
Catalyst Charge 1.5 – 3.5 liters 2.0 liters
Catalyst Circulation Rate 2500 – 15,000 grams/hr 4,000 – 9,000 grams/hr
Feed Rate 300 – 1500 grams/hr 1000 grams/hr
Feed Pre-heat Temperature 150 – 750°F 300 – 700°F
Riser Temperature 500°F -1300°F* 970 – 1000°F
Regenerator Temperature max. 1375°F* 1300°F
Stripper Temperature max. 1300°F* 950°F
Stabilizer Column Temperature minimum -30°F 0°F
* note: higher maximum pressures and temperatures can be achieved by constructing the unit with specialized alloys

TABLE II: DCR T M Pilot Plant Operating Ranges

Grace Catalysts Technologies Catalagram® 5

operated to separate C4 minus from the liquid product, which is
condensed and collected. The collected liquid is analyzed by GC to
determine its composition. Product can also be collected for sub-
sequent physical analysis. (Under typical FCC operating condi-
tions, approximately one liter of liquid product is generated per
hour.) The gaseous products are metered and batch collected for
subsequent analysis by GC. The carbon on regenerated catalyst
can be maintained at various levels by controlling the regenerator
operating conditions. The continuous nature of the DCR and the
circulation of catalyst between riser and regenerator make it well-
suited to study the effect of process conditions and additives on
fuel sulfur20, and air pollutant emissions such as SOx21 and NOx22.
For pollution control studies, the regenerator temperature can be
varied to match those found in a commercial FCCU. Excess air
and combustion products exit the regenerator through a pressure
control valve and are then metered and continuously analyzed for
O2, CO2, and CO and optionally for SO2 and NO. A more detailed
description of the unit is available in Reference 23.
The DCR's ability to match commercial yields is due in large part to
the adiabatic reactor operating system which controls the reactor
temperature and catalyst circulation rate in much the same manner
as most commercial FCCU's. In this mode, the reactor is setup
with insulation and heaters to prevent any heat from being added
to or lost from the sides of the reactor. The reactor temperature is
then controlled by the amount of hot catalyst added to the reactor
from the regenerator. This operating mode can successfully match
a commercial operation, not only in yields and conversion, but also
in key process variables like catalyst to oil ratio when operating at
the same reactor exit, feed, and regenerator (catalyst) tempera-
tures. While the DCR is significantly smaller than a commercial
unit, it closely matches the operation of commercial units. A study
by Independent Project Analysis on “Best Practices in Process De-
velopment” determined that “Research has shown that the scale
factor of the pilot to the commercial unit is less important than the
19
fact that the pilot truly represents the commercial facility” . Several
Due to its simplicity of operation and ability to match commercial
yields, the DCR has become the leading commercially available
technology for small scale FCC pilot units. There are currently 26
DCR technology licenses worldwide.
Pilot Plant Work with
Unconventional Feedstocks
The DCR has been used to process a variety of petroleum based
feedstocks from hydrotreated VGO to resid feedstocks. The DCR
has been shown to routinely process most feedstocks containing
up to 5 wt.% Conradson carbon and limited success has been pos-
sible with feeds containing up to 9.7 wt.% Conradson carbon25.
In addition to conventional feedstocks, the DCR has been able to
process straight run crude oil, naphthas, gases, and feeds from
non-petroleum sources. Naphthas and gases require a modified
feed system but otherwise generally process similar to standard
feeds. Non-petroleum based feedstocks vary widely in their char-
acteristics and, while some are easily processed in the DCR, oth-
ers are extremely difficult to run, if they can be run at all. Three
illustrative examples of processing unconventional feedstocks are
given below.
Straight Run Shale Oil
The introduction of novel drilling technologies has resulted in large
amounts of oil from shale becoming available in North America.
While fluid catalytic cracking is typically done to reduce the molec-
ular weight of the heavy fractions of crude oil (such as vacuum gas
oil and atmospheric tower bottoms), in some cases refiners are
DCR FCCU
Riser Temperature, °F 959 959

studies have been done in the DCR by using commercial equilib- C/O 6.6 5.9
rium catalysts, feeds, and operating conditions to compare yields Conversion, wt.% 67.2 66.2
obtained from the DCR with commercial yields. Typically, the DCR
yields match very closely the commercial yields at similar condi- Yields, wt.%
tions. Sample data showing the close match between DCR data Fuel Gas 2.2 2.3
and commercial data are shown in Table III for a gas oil feed and LPG 9.2 8.7
Table IV for a resid containing feed. In both cases the coke yield 31.4 31.1
Light Gasoline (C5 – 302°F)
from the DCR is ~10-15% lower than the coke yield in the commer-
RON 93.3 93.1
cial unit. This is because the DCR has excellent stripping due to
MON 79.4 78.3
the small diameter of the stripper and the increased residence time
Heavy Gasoline (302-365°F) 7.2 6.4
relative to a commercial unit (note that while the DCR reactor oper-
Naphtha (365-500°F) 13.1 12.7
ates in adiabatic mode, the overall unit is not necessarily heat bal-
LCO (500-644°F) 11.3 13.3
anced since the regenerator temperature can be controlled
independent of coke yield). When coke from unstripped hydrocar- HCO (644°F+) 21.4 20.4

bons in the commercial unit is accounted for, the coke match of the Coke 3.9 4.5
DCR to commercial becomes even better.
TABLE III: Comparison of DCR to Commercial FCC
Unit Run at Same Operating Conditions Using a Gas
Oil Feed (from Reference 24)

6 Issue No. 113 / 2013

 DCR Run 1 DCR Run 2 Refiner A
Rx Exit Temp, °F 1000 1000 1000
Regen Catalyst Temp, °F 1366 1366 1366
Feed Temp, °F 486 486 486.4
Rx Exit Pressure, psig 40.0 40.1 28.9
Rx Exit HC Pressure, psia 35.3 35.5 19.1
Riser Bot HC Pressure, psia 14.2 14.2 24.3

Cat/Oil Ratio 7.7 7.7 6.5

Conversion, wt.% 76.9 77.5 77.5
Kinetic Conversion 3.34 3.44 3.44

H2 Yield, wt.% 0.17 0.17 0.15

C1 + C2's, wt.% 4.1 4.1 3.9
Total C3, wt.% 6.8 6.8 6.1
C3=, wt.% 5.5 5.5 4.7
Total C4, wt.% 11.2 11.5 10.2

Gasoline, wt.% 50.0 50.1 51.6

RON (DCR - Est from GCON® software) (92.5) (92.6) 91.1
MON (DCR - Est from GCON® software) (80.0) (80.1) 81.6

LCO, wt.% 14.3 13.9 14.9

Bottoms, wt.% 8.8 8.7 7.6
Coke, wt.% 4.7 4.8 5.4

TABLE IV: Comparison of DCR to Commercial FCC Unit Run at Same Operating Conditions Using a
Resid-Containing Feed

charging whole shale oil as a fraction of their FCC feed. Also,

whole crude oil has been charged to FCC units when gas oil feed
is not available due to maintenance on other units in the refinery26,
and to produce a low-sulfur synthetic crude27.

As a model case to understand the cracking of whole crude oil in

the FCC and the effect of process conditions on yields, a straight
run shale oil was processed in the DCR at three riser outlet tem-
peratures: 970°F, 935°F, and 900°F. The whole crude oil was a light
sweet Bakken crude, with an API of 42°. The properties of the
crude were similar to those given in a publically published assay28.
Table V presents a comparison of the properties of the whole crude
used by Grace and the publically available assay data. Additionally,
the straight run Bakken sample was distilled into a 430°F minus
gasoline cut and a 430°F-650°F LCO cut and the properties of
these cuts were measured. Gasoline from the straight Bakken was
highly paraffinic and had low octane numbers (a G-Con® RON soft-
ware of 61 and MON of 58). The LCO fraction had an aniline point
of 156°F and an API gravity of 37.6°, resulting in a diesel index of
59. The catalyst used in the experiments was a high matrix FCC
catalyst, deactivated metals-free using a CPS type protocol. The
properties of the deactivated catalyst are given in Table VI.

Grace Catalysts Technologies Catalagram® 7

 Bakken sample Published Bakken assay
used in Grace work data from Reference 28
API Gravity Degrees 41.9 >41
Sulfur wt.% 0.19 <0.2
Distillation Yield wt.% vol.%
Light Ends C1-C4 1 3
Naphtha C5-330°F 32 30
Kerosene 330-450°F 14 15
Diesel 450-680°F 25 25
Vacuum Gas Oil 680-1000°F 23 22
Vacuum Residue 1000+°F 5 5
Total 100 100
Conradson Carbon Residue wt.% 0.78
G-CON® RON software 60.6
Gasoline Fraction Properties
G-CON® MON software 57.6

LCO Fraction (430°F - 650°F)

Aniline point (˚F) 155.9
properties

API Gravity 37.6

Diesel Index 58.6

TABLE V: Properties of Straight Run Shale Oil Feed Used by Grace Compared to Publically Published Assay Data

C/O Ratio Dry Gas, wt.% Coke, wt.%

10.0 1.50
2.2
8.0 1.25
2.0
1.00
6.0 1.8

0.75 1.6
4.0
1.4
0.50
C5+ Gasoline, wt.% LCO (430-650˚F), wt.% Bottoms (650˚F+), wt.%
70.0
5.0
20.0
67.5
17.5 4.0
65.5
15.0
3.0
62.5 12.5

60.0 10.0 2.0

75.0 80.0 85.0 75.0 80.0 85.0 75.0 80.0 85.0
Conversion, wt.%

Reactor Temperature 900˚F 935˚F 970˚F

FIGURE 2: Effect of DCR Riser Outlet Temperature on Yields of Straight Run Shale Oil

8 Issue No. 113 / 2013

 G-Con® Software RON EST G-Con® Software MON EST
78.0 70.0

77.0 69.0

76.0
68.0
75.0
67.0
74.0
66.0
G-Con® Software O, wt.% G-Con ® Software I, wt.%
17.0
26.0
16.0 25.5

15.0 25.0

14.0 24.5

13.0 24.0

75.0 77.5 80.0 82.5 85.0 75.0 77.5 80.0 82.5 85.0
Conversion, wt.%

Reactor Temperature 900˚F 935˚F 970˚F

FIGURE 3: Effect of DCR Riser Outlet Temperature on Gasoline Properties of Cracked Straight Run Shale Oil

Diesel quality is of great interest to refiners. Syncrude produced in

Total Surface Area, m2/g 196
the DCR runs was distilled to recover the 430°F to 650°F LCO frac-
Zeolite Surface Area, m2/g 110
tion. Aniline point and API gravity of the LCO were then measured
Matrix Surface Area, m2/g 86
to allow calculation of the diesel index, a measure of LCO quality.
Unit Cell Size, Å 24.30
[Diesel Index = (aniline point x API Gravity) / 100] Figure 4 pres-
Rare earth, wt.% 2.1
ents data for LCO yield and LCO quality as a function of conver-
Alumina, wt.% 52.1 sion. As seen in the data, increasing conversion lowers LCO

TABLE VI: Deactivated Catalyst Properties for Whole
Shale Oil Study
For the three different reactor outlet temperatures, plots of catalyst
to oil ratio, dry gas, gasoline, LCO, bottoms and coke yields versus
conversion are shown in Figure 2. As expected, lowering reactor
temperature increases the amount of LCO produced. As seen in
the graphs, cracking straight run shale oil produces little coke and
bottoms. At the same conversion level, lowering reactor tempera-
ture results in slightly more gasoline yield (due to increased C/O),
which is consistent with prior Grace work29. Plots of gasoline
olefins, iso-paraffins and RON and MON estimated via G-Con®
software are shown in Figure 3. Cracking straight run Bakken
shale oil produces a low-quality gasoline with research octane less
than 80 and motor octane less than 70. At constant conversion, in-
creasing reactor temperature results in more gasoline olefins and
higher research octane number.
quality as a result of increased cracking of the LCO range paraffins
to lighter hydrocarbons. Similar to prior Grace work30, LCO quality
follows LCO yield and did not appear to be influenced by reactor
temperature at constant conversion. Diesel index values of the
LCO produced by cracking whole shale oil were significantly higher
than values obtained with typical VGO feeds.
As seen in the results from this study, widely varying ratios of prod-
ucts and product quality can be obtained by changing process con-
ditions. Information from pilot studies such as this one helps
refiners to determine the optimum processing setup to maximize
yields of desired products. The ability of the DCR to produce suffi-
cient liquid product for properties testing assisted greatly in the
measurement of LCO quality.

Grace Catalysts Technologies Catalagram® 9

 Soybean Oil Mid Continent VGO operation. As a control case, a standard mid-continent VGO was

°API 21.6 24.7 run. The catalyst was a low metals refinery equilibrium catalyst. A
riser outlet temperature of 970°F was used. Properties of the feed-
Sulfur, wt.% 0.00 0.35
stocks are presented in Table VII. Note that the simulated distilla-
Oxygen, wt.% 10.5 0.0
tion of the soybean oil is based on the carbon content and
D2887 Distillation, °F
molecular weight of the material and this can sometimes skew the
IBP 702 527
estimated boiling points. Biofeed sources typically have a true
5% 1059 651
boiling point that is much lower than that reported by simulated dis-
10% 1069 691 tillation equipment due to molecular weight interference. Proper-
30% 1090 773 ties of the equilibrium catalyst used in the testing are presented in
50% 1102 848 Table VIII. Figure 5 presents yield curves at constant coke. Figure
70% 1111 928 6 presents gasoline properties at constant coke. Table IX presents
90% 1183 1045 yields of soybean oil and VGO at the same operating conditions.
95% 1232 1108 On a constant coke basis, the soybean oil produced more LCO,
FBP 1301 1259 less gasoline, less C3’s, and less C4’s than the VGO. The gasoline
produced by cracking soybean oil was highly aromatic, consistent
TABLE VII: Feedstock Properties for Study with the results of References 33-35. Gas Chromatography-Atomic
Comparing Vegetable Oil to a Mid-Continent VGO
Emission Detector (GC-AED) was performed in oxygen mode on
the liquid product in order to detect oxygen species, and only trace
amounts of oxygenates were found. While running soybean oil,
Vegetable Oil
CO and CO2 were detected in the product gas, amounting to a total
Government mandates on renewable biofuels have resulted in in-
of ~15% of the oxygen in the soybean oil. By difference, ~85% of
terest in using vegetable oils and Fisher-Tropsch waxes obtained
the oxygen in the soybean oil reacted to water. The DCR riser op-
from biomass. Vegetable oils could be co-fed with VGO to an FCC
erates in adiabatic mode. In typical endothermic gas oil cracking,
unit31, or fed in their entirety32-34. While refiners would be highly un-
the riser bottom is ~70°F hotter than the riser top36. Interestingly
likely to ever process a 100% vegetable oil in a FCC unit, a 100%
for the soybean oil cracking, the riser temperature profile was al-
soybean oil feed was chosen as a test case for pilot DCR work to
most flat, with only a 10°F temperature difference between the riser
understand the impact this type of feed would have on yields and
bottom and top. Figure 7 presents adiabatic riser temperature pro-

LCO (430-650˚F), wt.% Diesel Index

22.0
45.0

20.0
40.0
18.0

35.0
16.0

14.0 30.0

12.0
25.0

10.0
75.0 77.5 80.0 82.5 85.0 75.0 77.5 80.0 82.5 85.0
Conversion, wt.%

Reactor Temperature 900˚F 935˚F 970˚F

FIGURE 4: Effect of Conversion Level on LCO Yield and Quality for Straight Run Shale Oil

10 Issue No. 113 / 2013

files for soybean oil and VGO at the same operating conditions
Total Surface Area, m2/g 171
(250°F preheat, 1300°F catalyst temperature, 970°F Riser Outlet 2
Zeolite Surface Area, m /g 134
Temperature.) Based on the temperature drop across the riser, the
Matrix Surface Area, m2/g 37
heat of cracking of soybean oil is only about 15% of the heat of
Unit Cell Size, Å 24.35
cracking of standard vacuum gas oil, consistent with the exother-
Rare earth, wt.% 3.2
mic formation of carbon monoxide, carbon dioxide and water from
Alumina, wt.% 44.2
oxygen present in the soybean oil. This heat behavior results in
the soybean oil running at a significantly lower catalyst to oil ratio Nickel, ppm 30

than VGO under the same conditions. The discovery of this very Vanadium, ppm 80
interesting effect of running 100% soybean oil (which has implica-
TABLE VIII: Equilibrium Catalyst Properties for
tions for riser operation) shows the utility of the DCR in testing un- Soybean Oil and Pyrolysis Oil Testing
conventional feedstocks and understanding their processing
implications.

Pine-based Pyrolysis Oil

Due to government renewable fuel credits and mandates, there is
considerable refiner interest in using bio-based feedstocks. Co-
processing bio-based pyrolysis oils with conventional vacuum gas
oil (VGO) has been proposed as one method of incorporating bio-
based feedstock into motor fuels37.

C/O Ratio Total C3, wt.% Total C4, wt.%

7.0 14.0
12.0

10.5 12.0
6.0

9.0 10.0

5.0
7.5 8.0

6.0 4.0 6.0

Gasoline, wt.% LCO, wt.% Bottoms, wt.%
25.0 5.0
52.5
22.5
50.0 4.5
20.0
47.5
17.5 4.0
45.0
15.0
3.5
4.8 5.6 6.4 4.8 5.6 6.4 4.8 5.6 6.4
Coke, wt.%

Soybean Oil VGO

FIGURE 5: Yields at Constant Coke for 100% Soybean Oil and a Mid-Continent VGO with a 970°F Riser Outlet
Temperature

Grace Catalysts Technologies Catalagram® 11

 VGO Feedstock Soybean Oil
Riser Outlet Temperature, ˚F 970 970
Feed Temperature, ˚F 1300 1300
Feed Temperature, ˚F 250 248
Pressure, psig 25.2 25.1
C/O Ratio 9.3 6.7
H2 Yield, wt.% 0.02 0.04
C1 + C2's, wt.% 2.1 1.9
Total C3’s, wt.% 6.7 4.3
C3, wt.% 1.1 0.6
C3=, wt.% 5.6 3.8
Total C4’s, wt.% 12.4 6.2
Total C4=, wt.% 6.8 4.3
C4=, wt.% 1.6 1.1
LPG Olefinicity 0.65 0.76
Gasoline (C5-430°F), wt.% 53.1 44.5
G-Con® software P, wt.% 3.6 3.5
G-Con® software I, wt.% 29.8 22.0
G-Con® software A, wt.% 33.9 39.0
G-Con® software N, wt.% 11.9 13.2
G-Con® software O, wt.% 20.8 22.4
G-Con® software RON EST 90.2 90.9
G-Con® software MON EST 79.5 79.0
LCO (430-700°F), wt.% 15.4 22.0
Bottoms (700°F+), wt.% 4.9 3.9
Coke, wt.% 5.2 4.6
Fuel Gas CO, wt.% 0.0 1.2
Fuel Gas CO2, wt.% 0.0 0.9
Fuel Gas H2O, wt.% (by difference) 0.0 10.3

TABLE IX: Yields at Same Operating Conditions for Base Case VGO and 100% Soybean Oil

Water content, wt.% 23.0

Carbon (as-is), wt.% 39.5
Hydrogen (as-is), wt.% 7.5
Oxygen (as-is), wt.% (by difference) 53.0
Carbon (dry basis), wt.% 55.5
Hydrogen (dry basis), wt.% 6.5
Oxygen (dry-basis), wt.% (by difference) 38.0

TABLE X: Properties of Pine-Derived Pyrolysis Oil used in VGO Co-Processing Experiments

12 Issue No. 113 / 2013

 G-Con® Software RON EST G-Con® Software MON EST G-Con® Software P, wt.%
91.0 80.00

79.75 3.7
90.8

79.50
90.6
3.6
79.25
90.4
79.00 3.5
90.2
G-Con® Software I, wt.% G-Con® Software A, wt.% G-Con® Software O, wt.%
40.0
22.8
30.0
38.0 21.6
27.5
20.4
25.0 36.0
19.2
22.5
34.0
18.0
20.0
4.8 5.6 6.4 4.8 5.6 6.4 4.8 5.6 6.4
Coke, wt.%

Soybean Oil VGO

FIGURE 6: Gasoline Properties Versus Coke for Soybean Oil and Mid-Continent VGO with a 970°F Riser Outlet
Temperature

Many groups have published work on co-processing pyrolysis oil

and VGO where the testing was done in a batch fashion in ACE or
MAT units38-44. Continuous pilot operations can identify processing
issues that are not readily apparent in batch testing. Due their high
content of reactive oxygen containing compounds, pyrolysis oils
Increasing Riser Height

are not as stable as conventional petroleum feedstocks and have a

tendency to polymerize and form tars at elevated temperatures
(140°F-212°F)45,46. We are aware of two published reports of circu-
lating pilot plant work with blends of pyrolysis oil and petroleum
based feedstocks47,48. Lappas, et. al.47 describe pilot scale work in
the CPERI FCC circulating pilot plant. They attempted to co-
process the heavy fraction of thermally hydrotreated biomass flash
960 970 980 990 1000 1010 1020 1030 1040 1050 1060
pyrolysis liquid (HBFPL) with VGO. This material had a 4.9 wt.%
Temperature, ˚F
oxygen content. They found that it was necessary to dilute the
Soybean Oil VGO
HBFPL oil in light cycle oil to prevent plugging of the nozzle in their
pilot plant. Their final feed to the FCC pilot unit was 2.25 wt.%
HBFPL / 12.75 wt.% LCO / 85 wt.% VGO. FIGURE 7: Adiabatic Riser Temperature Profiles for
100% Soybean Oil and a Mid-Continent VGO Run at
Same Catalyst Temperature and Same Feed Preheat
with Target Riser Outlet Temperature of 970°F

Grace Catalysts Technologies Catalagram® 13

 3 wt.% Pine-Based Pyrolysis Oil –
100% VGO
97 wt.% VGO
Rx Exit Temperature, ˚F 970 970
Catalyst Temperature, ˚F 1300 1300
Pressure, psig 25 25
Conversion, wt.% (100-LCO-bottoms) 81.6 81.7
Kinetic Conversion 4.42 4.46
C/O Ratio 9.9 9.6
H2 Yield, wt.% 0.05 0.04
C1 + C2's, wt.% 3.15 2.97
Total C3’s, wt.% 8.51 8.05
C3, wt.% 2.57 2.55
C3=, wt.% 5.94 5.51
Total C4’s, wt.% 14.1 13.8
Total C4=, wt.% 5.9 5.5
Gasoline (C5-430°F), wt.% 49.1 47.5
G-Con® software P, wt.% 3.2 3.2
G-Con® software I, wt.% 24.3 24.5
G-Con® software A, wt.% 49.2 50.5
G-Con® software N, wt.% 9.3 9.3
G-Con® software O, wt.% 14.0 12.6
G-Con® software RON EST 92.5 92.1
G-Con® software MON EST 81.6 81.5
LCO (430-700°F), wt.% 14.1 14.2
Bottoms (700°F+), wt.% 4.4 4.2
Coke, wt.% 6.4 7.1
Fuel Gas CO, wt.% 0.0 0.48
Fuel Gas CO2, wt.% 0.0 0.11
Fuel Gas H2O, wt.% (by difference) 0.0 1.42

TABLE XI: Yields at Same Operating Conditions for Base Case Mid-Continent VGO and Blend of 3 wt.% Pine-Based
Pyrolysis Oil and 97 wt.% VGO

Grace work in the DCR has also found that continuous processing
of pyrolysis oils can be difficult due to the high tendency of pyroly-
sis oil to form coke and plug the feed nozzle. Modifications to the
DCR feed delivery system were made that enabled co-processing
of pyrolysis oil with VGO in a continuous fashion. As a model
case, a blend of 3 wt.% pine-based pyrolysis oil was co-processed
with 97 wt.% mid-continent VGO using a low-metals commercial
equilibrium catalyst. The VGO properties are provided in Table VII
and the equilibrium catalyst properties are presented in Table VIII.
The properties of the pyrolysis oil feedstock are given in Table X.
The pyrolysis oil was not hydrotreated and contained 23 wt.%
water. The composition of the pyrolysis oil was 39.5 wt.% carbon,
7.5 wt.% hydrogen and 53 wt.% oxygen. 100% mid-continent VGO
was cracked as a control case. Riser outlet temperature was
970°F for both feeds. Yields at identical operating conditions are
presented in Table XI. Co-feeding pyrolysis oil resulted in more
coke, less gasoline, and production of CO and CO2 in the product
gas. These results are consistent with the observations of other
researchers who processed high oxygen content pyrolysis oils47-49.
At the same feed preheat and catalyst temperature, the blend of
pyrolysis oil and VGO required ~0.3 less cat to oil to maintain a
970°F riser outlet temperature with the DCR operated in adiabatic
mode. We speculate that the exothermic reactions of the oxygen
in the pyrolysis oil reduce the heat requirements for co-processing
pyrolysis oil with VGO. Gas Chromatography-Atomic Emission De-
tector (GC-AED) was performed in oxygen mode on the liquid
product in order to detect oxygen species and only trace amounts
of oxygenates were found. While running pyrolysis oil, CO and CO2
were detected in the product gas, amounting to a total of ~22 per-
cent of the oxygen in the pyrolysis oil. By difference, ~78% of the
oxygen in the pyrolysis oil reacted to water. As seen by these re-
sults with pyrolysis oil, non-petroleum based feedstock compo-
nents can result in significant yield shifts, even at small addition
quantities. The DCR pilot plant has proven to be an invaluable tool
in understanding these yield shifts.

14 Issue No. 113 / 2013

 VGO Feedstock Resid Feedstock
°API Gravity 23.9 20.6
K Factor 11.81 11.76
Refractive Index 1.5064 1.5222
Sulfur, wt.% 0.73 0.42
Basic Nitrogen, wt.% 0.04 0.07
Total Nitrogen, wt.% 0.10 0.18
Conradson Carbon, wt.% 0.33 5.10
ndm analysis
Arom Ring Carbons Ca, wt.% 19.6 25.4
Naphthenic Ring CarbonCn, wt.% 20.6 15.4
Paraffinic Carbons Cp, wt.% 59.8 59.2
Ni, ppm 0.5 6.6
V, ppm 0.2 16.5
Simulated Distillation, °F
IBP 464 455
10% 637 653
30% 730 793
50% 806 894
70% 883 1017
90% 977 1265
End Point 1152 1324

TABLE XII: Properties of Feedstocks for Study of Feedstock Effect on High Temperature Cracking for Light Olefins

Pilot Plant Work on Unconventional steam cracking. New designs for high temperature cracking to pro-
Processes duce light olefins from heavy feed stocks have been developed,
such as High Severity Fluid Catalytic Cracking (HS-FCC)5, and
As mentioned in the introduction, the circulating fluidized bed tech-
Deep Catalytic Cracking6. These processes typically operate at
nology of FCC is being applied to a wide range of processes in-
higher temperatures and more severe conditions than typical FCC
tended for a variety of conversions, including: heavy oil to olefins,
operations. Pilot equipment such as the DCR can be used to eval-
naphtha streams to olefins, paraffins to propylene, light alcohols to
uate the effect of different operating conditions on process yields.
olefins, and biomass to olefins and aromatics. Pilot plant work is
Using data from the DCRTM pilot plant, Grace published an exten-
essential in reducing the risk of scaling up a new process. An ex-
sive study on the effect of ZSM-5 additive concentration (0 to 8
ample of application of DCR technology to process development is
wt.%) and reaction temperature (970°F to 1050°F) on olefins
work done by Nippon Oil and King Fahd University in developing
5 yields50. Grace has also published DCR pilot plant results on the
their High Severity FCC process . In their published work, they de-
effect of hydrocarbon partial pressure on propylene production51.
scribe how they converted the DCR from a riser pilot plant to a
Presented below are three additional examples of work done in
downer pilot plant. In comparing their pilot plant to their demon-
Grace’s pilot plants using the DCR to gain insight into high temper-
stration plant, they wrote: “the pilot plant and demonstration plant
ature cracking for light olefins.
performed similarly. It also confirmed that scaling up the process
was successful.”5
To examine the effect of feedstock on light olefins production at
high temperature, cracking was done on a light VGO feed and a
To show the versatility of FCC-type technology, three illustrative
resid feed using a blend of base catalyst and a ZSM-5 containing
examples of evaluating unconventional processes in the DCR pilot
additive at a riser outlet temperature of 1050°F. Feedstock proper-
plant are given below.
ties are given in Table XII.

Interpolated yields at constant cat to oil ratio are presented in Table

High Temperature Cracking for
Light Olefins
The high rate of growth in propylene demand has resulted in inter-
est in producing propylene from processes other than traditional
XIII. Under these conditions high yields of propylene and butylene
were produced by both feeds. However, as expected, the heavier
feedstock did generate higher coke and lower light olefin yields at
the same catalyst to oil ratio.

Grace Catalysts Technologies Catalagram® 15

 VGO Feedstock Resid Feedstock
Conversion, wt.% 74.7 70.6
Kinetic Conversion 2.89 2.32
H2 Yield, wt.% 0.07 0.08
C1 + C2's, wt.% 7.2 6.6
Total C3’s, wt.% 16.7 14.8
C3=, wt.% 14.6 13.1
Total C4’s, wt.% 13.8 12.2
Total C4=, wt.% 11.2 10.3
Gasoline (C5-430°F), wt.% 34.3 30.5
G-Con® software ,P wt.% 3.2 3.2
G-Con® software I, wt.% 10.1 11.2
G-Con® software A, wt.% 51.5 51.7
G-Con® software N, wt.% 7.0 7.3
G-Con® software O, wt.% 28.1 26.7
G-Con® software RON EST 98.3 97.4
G-Con® software MON EST 83.7 83.8
LCO (430-700°F), wt.% 16.5 17.3
Bottoms (700°F+), wt.% 8.8 12.2
Coke, wt.% 2.0 5.6

TABLE XIII: Interpolated Yields at C/O = 11 for Two Feedstocks at a Riser Outlet Temperature of 1050°F

Determining the effect of added steam on yields is another exam-
ple of the insight that can be gained via pilot plant experimentation.
A mixture of equilibrium catalyst and lab deactivated ZSM-5 was
used to crack the vacuum gas oil described in Table XII at a riser
outlet temperature of 1050°F. Normally, the steam used for feed
atomization is about 3 wt.% of fresh feed. In this study, atomiza-
tion steam was varied between 3 wt.% and 18 wt.% of fresh feed to
understand the effect of increasing steam level on yield structure.
Higher steam rates are expected to reduce hydrocarbon partial
pressure, and reduce the residence time, favoring olefins maxi-
mization. Increasing the steam rate reduces the residence time,
resulting in lower conversion at the same cat to oil ratio. Table XIV
presents interpolated yields at constant conversion for three steam
levels. At constant conversion, increasing the steam level resulted
in the expected higher propylene and butylenes yields.
To examine the effect of going to very high temperatures, cracking
was done at riser outlet temperatures of 1050°F and 1100°F on the

3 wt.% Added Steam 10 wt.% Added Steam 18 wt.% Added Steam

Cat/Oil Ratio 8.6 11.5 15.6

H2 Yield, wt.% 0.08 0.08 0.08
C1 + C2's, wt.% 8.4 8.0 8.2
C2=, wt.% 4.1 4.1 4.5
Total C3’s, wt.% 15.1 15.4 16.9
C3, wt.% 1.9 2.0 1.7
C3=, wt.% 13.2 13.4 15.2
Total C4’s, wt.% 11.3 11.7 12.1
Total C4=, wt.% 9.6 9.7 10.1
Gasoline (C5-430°F), wt.% 30.4 29.9 27.6
LCO (430-700°F), wt.% 18.8 18.7 18.4
Bottoms (700°F+), wt.% 14.2 14.3 14.6
Coke, wt.% 1.4 1.7 2.0

TABLE XIV: Interpolated Yields at 67 wt.% Conversion at Three Different Steam Levels on VGO Feed at a Riser
Outlet temperature = 1050°F

16 Issue No. 113 / 2013

vacuum gas oil described in Table XII using a blend of base cata-
lyst and a large proportion of ZSM-5 based additive. Table XV
presents interpolated yields at constant cat to oil for the two riser
outlet temperatures. Increasing riser outlet temperature from

C2 + C3 Olefins Yield
1050°F to 1100°F resulted in higher conversion and higher light
olefins yields. However, the increase in reactor temperature also
resulted in greater thermal cracking as seen in the higher dry gas
yields at 1100°F.

The preceding three examples show how a flexible pilot plant can
be used to quickly conduct studies to provide insight into the ef-
fects of operating variables like feedstock, steam level and temper- 700 750 800 850 900 950 1000

ature for processes designed for high temperature production of Riser Outlet Temperature, ˚F
olefins.

FIGURE 8: Olefins Yield as a Function of Riser Outlet

Temperature for Reacting a 50 wt.% Methanol/50
wt.% Water Blend Over SAPO-34 Based Catalyst
Processing Naphtha Feeds
Demand for ethylene, propylene and other chemical feedstocks
was reacted over a SAPO-34 based catalyst in the DCR at a series
has resulted in refiners examining naphtha cracking, and in the de-
of increasing riser temperatures. Figure 8 presents ethylene and
velopment of FCC-type processes such as ExxonMobil PCCSM7
propylene yield as a function of riser temperature. Consistent with
and KBR Superflex™8 to crack naphtha range feedstocks prefer-
other published work54, olefins yield increased with temperature
entially to light olefins. In evaluating new processes, it is important
over this operating range. The exothermic nature of the methanol
to understand the effects of critical variables like feedstock,
to olefins reaction was clearly apparent in the temperature profile
process conditions and catalyst. Instituto Colombiano de Petróleo
of the adiabatic riser. In typical endothermic gas oil cracking, the
(a DCR licensee), published a study where they used their DCR
riser bottom is hotter than the riser top. In the case of methanol to
pilot plant to evaluate the potential yields of four different naphtha
olefins, the riser bottom was ~30°F cooler than the riser top, even
feedstocks52. These feedstocks ranged in API from 53° to 60° and
with the addition of 50% water in the feed as a heat sink. This ex-
included straight run naphthas and naphthas from FCC operations.
ample shows that the DCR can be used to examine unconven-
Table XVI provides a summary of some of their findings. The re-
tional processes beyond the traditional feeds and process
searchers at Instituto Colombiano de Petróleo (ICP) found that
conditions associated with fluid catalytic cracking.
feedstock had an important effect on product yields. Compared to
straight run naphtha, FCC naphtha produced less propane, less
butane and iso-butane and more toluene and xylenes. While the
researchers at ICP used the DCR pilot plant to focus on the effect Conclusions
of the naphtha feedstock type at typical FCC process conditions, a
The DCR pilot unit is an excellent tool for simulating commercial
DCR pilot plant could be readily used to evaluate the effect of tem-
FCC units. When run at the same operating conditions with the
peratures and severities greater than typical FCC conditions on
same feedstock and catalyst, the DCR produces yields nearly
converting naphtha to olefins.
identical to commercial FCC units. The DCR can also be used to
test unconventional feedstocks to determine their suitability as
feeds for commercial FCC units. The ability of the DCR to produce
Alcohols to Olefins sufficient quantity of liquid product for properties testing greatly en-
hances the measurement of LCO quality. The adiabatic reactor
Ethanol and methanol have both been proposed as petrochemical
operating system can provide insight into the temperature control
feedstocks. Ethanol can be produced via fermentation and then
behavior of non-petroleum feedstocks. The flexibility of the DCR
reacted via dehydrogenation to produce ethylene. Methanol can
allows for evaluation of process conditions and modes of operation
be produced from coal or from natural gas. Catalytic processes
outside of typical FCC conditions. Feedstocks and process de-
such as methanol to olefins can then be used to convert the
signs will continue to change and evolve and pilot plant testing is a
methanol into valuable products like ethylene and propylene. Sev-
key step in evaluating these changes. Pilot plant testing reduces
eral reactor designs for MTO have been proposed, including fixed
risk and uncertainty by identifying the optimum feedstocks and
bed reactors, fluidized bed reactors and riser reactors15,53. While
process conditions on the lab scale so that fuel and petrochemical
methanol is much lighter than conventional FCC feeds, modifica-
manufacturers can “make their profits on a large scale.”
tions to the DCR feed system enabled the processing of methanol.
As a model case, a blend of 50 wt.% methanol and 50 wt.% water

Grace Catalysts Technologies Catalagram® 17

 Riser Outlet Temperature = 1050°F Riser Outlet Temperature = 1100°F
Conversion, wt.% 69.0 75.3
Kinetic Conversion 2.25 3.06
H2 Yield, wt.% 0.09 0.14
C1 + C2's, wt.% 8.8 13.2
CH4 Yield, wt.% 1.8 3.4
C2, wt.% 1.5 2.7
C2=, wt.% 5.5 7.1
Total C3’s, wt.% 16.0 18.5
C3=, wt.% 12.8 15.0
Total C4’s, wt.% 12.3 11.9
Total C4=’s, wt.% 9.5 9.7
Gasoline (C5-430°F), wt.% 30.4 29.9
G-Con® software P, wt.% 3.0 1.8
G-Con® software I, wt.% 9.2 7.1
G-Con® software A, wt.% 62.0 74.6
G-Con® software N, wt.% 6.2 3.8
G-Con® software O, wt.% 19.7 12.7
G-Con® software RON EST 99.4 101.8
G-Con® software MON EST 85.9 88.4
LCO (430-700°F), wt.% 18.3 15.3
Bottoms (700°F+), wt.% 12.7 9.4
Coke, wt.% 1.4 1.5

TABLE XV: Interpolated Yields at C/O = 13 for VGO Feedstock at Two Riser Outlet Temperatures

Acknowledgements 5. M.H. Al-Tayyar, A.B. Fox, C.F. Dean, Y. Fujiyama, T. Okuhara,

A.M. Aitani, M.R. Saeed, “Development of a Novel Refinery
The hard work and dedication of the technicians and operators as-
Process: From Laboratory Experiments to Commercial Applica-
sociated with Grace’s DCR pilot plants is gratefully acknowledged.
tions,” Saudi Aramco Journal of Technology, Spring 2008, pp. 2-9.

6. D. Dharia, W. Letzsch, L. Chapin, “Advanced Catalytic Crack-

References ing Technologies for Production of Light Olefins from Low Cost Re-
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18 Issue No. 113 / 2013

 Naphthenic Straight- Paraffinic Straight- Light Naphtha from Total Naphtha from
Feedstock Run Naphtha Run Naphtha Model IV FCC Unit UOP II FCC Unit
Feedstock API° 53.2 50.1 60.0 58.6
Feedstock PIANO
Paraffins, wt.% 42.2 56.7 42.0 28.4
Iso-paraffins, wt.% 31.7 34.2 35.0 22.7
Olefins, wt.% 7.5 1.3 20.8 33.7
Aromatics, wt.% 15.7 13.2 26.1 29.7
Naphthenes, wt.% 34.6 28.8 11.1 8.2
Product Yields
H2 0.1 0.1 0.2 0.1
Total Dry Gas 4.2 3.7 4.5 4.4
Total LPG 29.5 28.9 22.4 22.4
C2 0.8 0.7 0.9 0.8
C2= 2.0 1.9 2.0 2.2
C3 6.4 5.6 3.5 2.6
C3= 6.6 7.8 7.5 8.4
nC4 2.9 2.7 1.5 1.5
iC4 10.3 8.4 5.7 4.8
Naphtha (C5-430°F) 60.9 63.1 64.3 65.0
Benzene 1.5 1.7 1.6 1.9
Toluene 6.5 5.9 6.8 8.9
Xylenes 9.8 6.5 9.2 11.0
LCO (430-650°F) 1.8 1.5 3.5 4.1
Slurry (>650°F) 0.7 0.6 1.4 1.2
Coke 2.8 2.1 3.7 2.8

TABLE XVI: Effect of Naphtha Feedstock Properties on Product Yields from DCR Pilot Plant (C/O = 15, 1000°F
Reaction Temperature, with 4% ZSM-5 Additive). Adapted from Reference 52.

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