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Grace Catalysts Technologies Catalagram® 3

Kenneth BrydenManager, FCCEvaluations Research

Gordon WeatherbeePrincipal Engineer

E. Thomas Habib, Jr.Director CustomerResearch Partnershipsand DCR LicensingManager

Grace CatalystsTechnologiesColumbia, MD, USA

AbstractThe fluid catalytic cracking process has been in commercial practice for 70+ years. Feedstocks and

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-

vestigated by refiners. New FCC designs such as High Severity Fluid Catalytic Cracking (HS-FCC) and

Deep Catalytic Cracking (DCC) have been developed. On-purpose olefins manufacturing processes, such

as ExxonMobil PCCSM and KBR Superflex™, and use of FCC type processes for very light feeds (includ-

ing gases and light alcohols) are being proposed. These options represent significant change, and there-

fore significant risk. One way to minimize the risk associated with these opportunities is to conduct

realistic pilot plant testing prior to commercial implementation. One pilot unit that has gained wide accept-

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

throughout the world. This paper includes comparisons of DCR pilot plant results to commercial FCC

units for petroleum derived gas oil and resid feeds, and also describes application of the DCR pilot plant

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.

IntroductionFluid 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

Flexible Pilot Plant Technology forEvaluation of UnconventionalFeedstocks and Processes

4 Issue No. 113 / 2013

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.

FCC-type processes such as ExxonMobil PCCSM7 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

to benzene, toluene and xylene10,11. 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.

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 PlantPerformance 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

TABLE I: Comparison of Test Units to Commercial Conditions

MAT/ACE Circulating Riser Commercial

Nature of Operation Unsteady State Steady State Steady State

Catalyst Contact Time 12 to 150 secs 2 to 5 secs 2 to 8 secs

Temperature Range 930 to 1100°F 930 to <1100°F 980 to 1030°F

Hydrocarbon Partial Pressure ~12 psia 20-45 psia 20-50 psia

Catalyst Inventory 5 to 10 grams 2 to 3 kg 100 tons

Advantage Easy to set up Mimics commercialoperation


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

ControlValveMeter

Feed Pump

Feed Preheater

Dispersant Steam Stripping Steam

Liquid Product Receivers

FeedStorageTank #1

FeedStorageTank #2

FeedTank

FeedTank

Scale Scale

Reg

ener

ato

r

Ris

erR

eact

or

Hea

tE

xch

ang

er

Str

ipp

er

Co

nd

ense

r

Sta

bili

zer

Co

lum

n

MeterControlValve

FIGURE 1: Schematic Diagram of Grace DCRTM Pilot Plant

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: DCRTM Pilot Plant Operating Ranges

6 Issue No. 113 / 2013

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

fact that the pilot truly represents the commercial facility”19. Several

studies have been done in the DCR by using commercial equilib-

rium catalysts, feeds, and operating conditions to compare yields

obtained from the DCR with commercial yields. Typically, the DCR

yields match very closely the commercial yields at similar condi-

tions. Sample data showing the close match between DCR data

and commercial data are shown in Table III for a gas oil feed and

Table IV for a resid containing feed. In both cases the coke yield

from the DCR is ~10-15% lower than the coke yield in the commer-

cial unit. This is because the DCR has excellent stripping due to

the small diameter of the stripper and the increased residence time

relative to a commercial unit (note that while the DCR reactor oper-

ates in adiabatic mode, the overall unit is not necessarily heat bal-

anced since the regenerator temperature can be controlled

independent of coke yield). When coke from unstripped hydrocar-

bons in the commercial unit is accounted for, the coke match of the

DCR to commercial becomes even better.

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 withUnconventional FeedstocksThe 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 OilThe 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

C/O 6.6 5.9

Conversion, wt.% 67.2 66.2

Yields, wt.%

Fuel Gas 2.2 2.3

LPG 9.2 8.7

Light Gasoline (C5 – 302°F) 31.4 31.1

RON 93.3 93.1

MON 79.4 78.3

Heavy Gasoline (302-365°F) 7.2 6.4

Naphtha (365-500°F) 13.1 12.7

LCO (500-644°F) 11.3 13.3

HCO (644°F+) 21.4 20.4

Coke 3.9 4.5

TABLE III: Comparison of DCR to Commercial FCCUnit Run at Same Operating Conditions Using a GasOil Feed (from Reference 24)


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 aResid-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.

8 Issue No. 113 / 2013

Bakken sampleused in Grace work

Published Bakken assaydata 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

Gasoline Fraction PropertiesG-CON® RON software 60.6

G-CON® MON software 57.6

LCO Fraction (430°F - 650°F)properties Aniline point (˚F) 155.9

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

C5+ Gasoline, wt.% LCO (430-650˚F), wt.%

Dry Gas, wt.% Coke, wt.%

Bottoms (650˚F+), wt.%

Conversion, wt.%

75.0 80.0 85.0 75.0 80.0 85.0 75.0 80.0 85.0

10.0

8.0

6.0

70.0

62.5

4.0

65.5

67.5

60.0

1.50

1.25

1.00

0.75

0.50

20.0

17.5

15.0

12.5

10.0

2.2

2.0

1.8

1.6

1.4

5.0

4.0

3.0

2.0

900˚F 935˚F 970˚FReactor Temperature

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


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.

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

the DCR runs was distilled to recover the 430°F to 650°F LCO frac-

tion. Aniline point and API gravity of the LCO were then measured

to allow calculation of the diesel index, a measure of LCO quality.

[Diesel Index = (aniline point x API Gravity) / 100] Figure 4 pres-

ents data for LCO yield and LCO quality as a function of conver-

sion. As seen in the data, increasing conversion lowers LCO

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.

Total Surface Area, m2/g 196

Zeolite Surface Area, m2/g 110

Matrix Surface Area, m2/g 86

Unit Cell Size, Å 24.30

Rare earth, wt.% 2.1

Alumina, wt.% 52.1

78.0

77.0

76.0

75.0

74.0

17.0

16.0

15.0

14.0

13.0

70.0

69.0

68.0

67.0

66.0

26.0

25.5

25.0

24.5

24.0

75.0 77.5 80.0 82.5 85.0 75.0 77.5 80.0 82.5 85.0

G-Con® Software RON EST

G-Con® Software O, wt.% G-Con® Software I, wt.%

G-Con® Software MON EST

Conversion, wt.%


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

TABLE VI: Deactivated Catalyst Properties for WholeShale Oil Study

10 Issue No. 113 / 2013

Vegetable OilGovernment mandates on renewable biofuels have resulted in in-

terest in using vegetable oils and Fisher-Tropsch waxes obtained

from biomass. Vegetable oils could be co-fed with VGO to an FCC

unit31, or fed in their entirety32-34. While refiners would be highly un-

likely to ever process a 100% vegetable oil in a FCC unit, a 100%

soybean oil feed was chosen as a test case for pilot DCR work to

understand the impact this type of feed would have on yields and

operation. As a control case, a standard mid-continent VGO was

run. The catalyst was a low metals refinery equilibrium catalyst. A

riser outlet temperature of 970°F was used. Properties of the feed-

stocks are presented in Table VII. Note that the simulated distilla-

tion of the soybean oil is based on the carbon content and

molecular weight of the material and this can sometimes skew the

estimated boiling points. Biofeed sources typically have a true

boiling point that is much lower than that reported by simulated dis-

tillation equipment due to molecular weight interference. Proper-

ties of the equilibrium catalyst used in the testing are presented in

Table VIII. Figure 5 presents yield curves at constant coke. Figure

6 presents gasoline properties at constant coke. Table IX presents

yields of soybean oil and VGO at the same operating conditions.

On a constant coke basis, the soybean oil produced more LCO,

less gasoline, less C3’s, and less C4’s than the VGO. The gasoline

produced by cracking soybean oil was highly aromatic, consistent

with the results of References 33-35. Gas Chromatography-Atomic

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,

CO and CO2 were detected in the product gas, amounting to a total

of ~15% of the oxygen in the soybean oil. By difference, ~85% of

the oxygen in the soybean oil reacted to water. The DCR riser op-

erates in adiabatic mode. In typical endothermic gas oil cracking,

the riser bottom is ~70°F hotter than the riser top36. Interestingly

for the soybean oil cracking, the riser temperature profile was al-

most flat, with only a 10°F temperature difference between the riser

bottom and top. Figure 7 presents adiabatic riser temperature pro-

Soybean Oil Mid Continent VGO

°API 21.6 24.7

Sulfur, wt.% 0.00 0.35

Oxygen, wt.% 10.5 0.0

D2887 Distillation, °F

IBP 702 527

5% 1059 651

10% 1069 691

30% 1090 773

50% 1102 848

70% 1111 928

90% 1183 1045

95% 1232 1108

FBP 1301 1259

TABLE VII: Feedstock Properties for StudyComparing Vegetable Oil to a Mid-Continent VGO

22.0

20.0

18.0

16.0

12.0

14.0

10.0

30.0

25.0

35.0

40.0

45.0

75.0 77.5 80.0 82.5 85.0 75.0 77.5 80.0 82.5 85.0

LCO (430-650˚F), wt.% Diesel Index

Conversion, wt.%


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


Total Surface Area, m2/g 171

Zeolite Surface Area, m2/g 134

Matrix Surface Area, m2/g 37

Unit Cell Size, Å 24.35

Rare earth, wt.% 3.2

Alumina, wt.% 44.2

Nickel, ppm 30

Vanadium, ppm 80

TABLE VIII: Equilibrium Catalyst Properties forSoybean Oil and Pyrolysis Oil Testing

Coke, wt.%

Soybean Oil VGO

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

Gasoline, wt.% LCO, wt.% Bottoms, wt.%

12.0

10.5

9.0

7.5

6.0

52.5

50.0

47.5

45.0

7.0

6.0

5.0

4.0

22.5

20.0

17.5

15.0

25.0

14.0

12.0

10.0

8.0

6.0

5.0

4.5

4.0

3.54.8 5.6 6.4 4.8 5.6 6.4 4.8 5.6 6.4

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

files for soybean oil and VGO at the same operating conditions

(250°F preheat, 1300°F catalyst temperature, 970°F Riser Outlet

Temperature.) Based on the temperature drop across the riser, the

heat of cracking of soybean oil is only about 15% of the heat of

cracking of standard vacuum gas oil, consistent with the exother-

mic formation of carbon monoxide, carbon dioxide and water from

oxygen present in the soybean oil. This heat behavior results in

the soybean oil running at a significantly lower catalyst to oil ratio

than VGO under the same conditions. The discovery of this very

interesting effect of running 100% soybean oil (which has implica-

tions for riser operation) shows the utility of the DCR in testing un-

conventional feedstocks and understanding their processing

implications.

Pine-based Pyrolysis OilDue 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.

12 Issue No. 113 / 2013

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


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

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

pyrolysis liquid (HBFPL) with VGO. This material had a 4.9 wt.%

oxygen content. They found that it was necessary to dilute the

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.

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

G-Con® Software I, wt.% G-Con® Software A, wt.% G-Con® Software O, wt.%

4.8 5.6 6.4 4.8 5.6 6.4 4.8 5.6 6.4

90.8

90.6

90.4

90.2

30.0

27.5

25.0

22.5

20.0

91.0

79.75

79.50

79.25

79.00

80.00

38.0

36.0

34.0

40.0

21.6

20.4

19.2

18.0

22.8

3.6

3.5

3.7

18.0

Coke, wt.%

Soybean Oil VGO

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

Temperature, ˚F

960 970 980 990 1000 1010 1020 1030 1040 1050 1060

Soybean Oil VGO

Incr

easi

ng

Ris

erH

eig

ht

FIGURE 7: Adiabatic Riser Temperature Profiles for100% Soybean Oil and a Mid-Continent VGO Run atSame Catalyst Temperature and Same Feed Preheatwith Target Riser Outlet Temperature of 970°F

14 Issue No. 113 / 2013

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

100% VGO 3 wt.% Pine-Based Pyrolysis Oil –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








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-BasedPyrolysis Oil and 97 wt.% VGO

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.


Pilot Plant Work on UnconventionalProcessesAs mentioned in the introduction, the circulating fluidized bed tech-

nology of FCC is being applied to a wide range of processes in-

tended for a variety of conversions, including: heavy oil to olefins,

naphtha streams to olefins, paraffins to propylene, light alcohols to

olefins, and biomass to olefins and aromatics. Pilot plant work is

essential in reducing the risk of scaling up a new process. An ex-

ample of application of DCR technology to process development is

work done by Nippon Oil and King Fahd University in developing

their High Severity FCC process5. In their published work, they de-

scribe how they converted the DCR from a riser pilot plant to a

downer pilot plant. In comparing their pilot plant to their demon-

stration plant, they wrote: “the pilot plant and demonstration plant

performed similarly. It also confirmed that scaling up the process

was successful.”5

To show the versatility of FCC-type technology, three illustrative

examples of evaluating unconventional processes in the DCR pilot

plant are given below.

High Temperature Cracking forLight OlefinsThe high rate of growth in propylene demand has resulted in inter-

est in producing propylene from processes other than traditional

steam cracking. New designs for high temperature cracking to pro-

duce light olefins from heavy feed stocks have been developed,

such as High Severity Fluid Catalytic Cracking (HS-FCC)5, and

Deep Catalytic Cracking6. These processes typically operate at

higher temperatures and more severe conditions than typical FCC

operations. Pilot equipment such as the DCR can be used to eval-

uate the effect of different operating conditions on process yields.

Using data from the DCRTM pilot plant, Grace published an exten-

sive study on the effect of ZSM-5 additive concentration (0 to 8

wt.%) and reaction temperature (970°F to 1050°F) on olefins

yields50. Grace has also published DCR pilot plant results on the

effect of hydrocarbon partial pressure on propylene production51.

Presented below are three additional examples of work done in

Grace’s pilot plants using the DCR to gain insight into high temper-

ature cracking for light olefins.

To examine the effect of feedstock on light olefins production at

high temperature, cracking was done on a light VGO feed and a

resid feed using a blend of base catalyst and a ZSM-5 containing

additive at a riser outlet temperature of 1050°F. Feedstock proper-

ties are given in Table XII.

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

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.

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 analysisArom 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

16 Issue No. 113 / 2013

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

VGO Feedstock Resid Feedstock



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







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

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 RiserOutlet temperature = 1050°F


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

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-

ature for processes designed for high temperature production of

olefins.

Processing Naphtha FeedsDemand for ethylene, propylene and other chemical feedstocks

has resulted in refiners examining naphtha cracking, and in the de-

velopment of FCC-type processes such as ExxonMobil PCCSM7

and KBR Superflex™8 to crack naphtha range feedstocks prefer-

entially to light olefins. In evaluating new processes, it is important

to understand the effects of critical variables like feedstock,

process conditions and catalyst. Instituto Colombiano de Petróleo

(a DCR licensee), published a study where they used their DCR

pilot plant to evaluate the potential yields of four different naphtha

feedstocks52. These feedstocks ranged in API from 53° to 60° and

included straight run naphthas and naphthas from FCC operations.

Table XVI provides a summary of some of their findings. The re-

searchers at Instituto Colombiano de Petróleo (ICP) found that

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

of the naphtha feedstock type at typical FCC process conditions, a

DCR pilot plant could be readily used to evaluate the effect of tem-

peratures and severities greater than typical FCC conditions on

converting naphtha to olefins.

Alcohols to OlefinsEthanol and methanol have both been proposed as petrochemical

feedstocks. Ethanol can be produced via fermentation and then

reacted via dehydrogenation to produce ethylene. Methanol can

be produced from coal or from natural gas. Catalytic processes

such as methanol to olefins can then be used to convert the

methanol into valuable products like ethylene and propylene. Sev-

eral reactor designs for MTO have been proposed, including fixed

bed reactors, fluidized bed reactors and riser reactors15,53. While

methanol is much lighter than conventional FCC feeds, modifica-

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

was reacted over a SAPO-34 based catalyst in the DCR at a series

of increasing riser temperatures. Figure 8 presents ethylene and

propylene yield as a function of riser temperature. Consistent with

other published work54, olefins yield increased with temperature

over this operating range. The exothermic nature of the methanol

to olefins reaction was clearly apparent in the temperature profile

of the adiabatic riser. In typical endothermic gas oil cracking, the

riser bottom is hotter than the riser top. In the case of methanol to

olefins, the riser bottom was ~30°F cooler than the riser top, even

with the addition of 50% water in the feed as a heat sink. This ex-

ample shows that the DCR can be used to examine unconven-

tional processes beyond the traditional feeds and process

conditions associated with fluid catalytic cracking.

ConclusionsThe DCR pilot unit is an excellent tool for simulating commercial

FCC units. When run at the same operating conditions with the

same feedstock and catalyst, the DCR produces yields nearly

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

sufficient quantity of liquid product for properties testing greatly en-

hances the measurement of LCO quality. The adiabatic reactor

operating system can provide insight into the temperature control

behavior of non-petroleum feedstocks. The flexibility of the DCR

allows for evaluation of process conditions and modes of operation

outside of typical FCC conditions. Feedstocks and process de-

signs will continue to change and evolve and pilot plant testing is a

key step in evaluating these changes. Pilot plant testing reduces

risk and uncertainty by identifying the optimum feedstocks and

process conditions on the lab scale so that fuel and petrochemical

manufacturers can “make their profits on a large scale.”

Riser Outlet Temperature, ˚F

700 750 800 850 900 950 1000

C2

+C

3O

lefi

ns

Yie

ld

FIGURE 8: Olefins Yield as a Function of Riser OutletTemperature for Reacting a 50 wt.% Methanol/50wt.% Water Blend Over SAPO-34 Based Catalyst

18 Issue No. 113 / 2013

AcknowledgementsThe hard work and dedication of the technicians and operators as-

sociated with Grace’s DCR pilot plants is gratefully acknowledged.

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Riser Outlet Temperature = 1050°F Riser Outlet Temperature = 1100°F



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

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Gasoline (C5-430°F), wt.% 30.4 29.9








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


FeedstockNaphthenic Straight-

Run NaphthaParaffinic Straight-

Run NaphthaLight Naphtha fromModel IV FCC Unit

Total Naphtha fromUOP II FCC Unit

Feedstock API° 53.2 50.1 60.0 58.6

Feedstock PIANO

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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°FReaction Temperature, with 4% ZSM-5 Additive). Adapted from Reference 52.

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