China Petroleum Processing and Petrochemical Technology

Catalyst Research

2014, Vol. 16, No. 4, pp 7-11

December 31, 2014

Research and Development of Novel Heavy Oil Catalytic

Cracking Catalyst RCC-1
Zhang Jiexiao1; Zhou Yan2; Xu Yun1; Tian Huiping1
(1. SINOPEC Research Institute of Petroleum Processing, Beijing 100083;
2. SINOPEC Catalyst Company Qilu Division, Zibo, Shandong 255336)
Abstract: A novel heavy oil catalytic cracking catalyst RCC-1 was developed by using the ultra-stable zeolite, which was
hydrothermally treated and modified through cleaning its pores to serve as the active component. The chemical composition and physicochemical properties of RCC-1 catalyst were studied by XRF, BET, pore volume analysis, attrition index
analysis, and particle size distribution determination methods, and its catalytic cracking performance was also evaluated by
a microreactor for light oil cracking and the ACE device. The test results showed that the new type of heavy oil catalytic
cracking catalyst RCC-1 had good physicochemical properties and heavy oil cracking ability, strong anti-metallic contamination capability, good product distribution, good coke selectivity and gasoline selectivity, and excellent reduction of gasoline olefin content characteristics.
Key words: heavy oil, catalytic cracking catalyst, activity, stability

1Introduction
With an increasing supply of heavier feedstock for the
catalytic cracking unit, the FCC catalyst is required to
possess a higher activity and more unobstructed porous
channels in order to increase the heavy oil conversion and
metal contamination resistance[1-3]. Therefore, the Y zeolite as the main active component of FCC catalyst should
have such properties as intact crystal structure, proper
distribution of acidic active sites, good active sites accessibility, as well as high thermal and hydrothermal stability[4-8]. This study aims to firstly clean the zeolite channels
followed by modification of rare earth ions to increase
the effective rare earth content in the ultrastable Y zeolite
in an attempt to prepare a novel hydrothermally ultrastable Y zeolite that can integrate high rare earth content
with high stability and high cracking activity of the zeolite.
A light oil cracking microreactor and an ACE-Model R+
type fixed fluidized bed unit have been adopted to study
the performance of FCC catalyst with its active component
composed of the hydrothermally ultrastable Y zeolite.
2Experimental
2.1Preparation of catalyst samples
The DASY series of hydrothermally ultrastable zeolites

were the commercial products manufactured by the Qilu

Division of Sinopec Catalyst Company. At first the hydrothermally ultrastable zeolite DASY0.0 was treated with a
mixed acid solution at a proper concentration to modify
the zeolite structure through cleaning its pores, and then
the zeolite after filtration was subjected to ion exchange
with rare earths followed by filtration and drying to yield
a sample labeled as MDY0-1. If the hydrothermally ultrastable zeolite DASY0.0 was directly modified through
ion exchange with rare earths, followed by filtration and
drying, the product obtained thereby was labeled as DY.
The above-mentioned zeolite samples serving as the active component after being separately mixed with the
binder, pseudo-boehmite and alumina gel, and the support
kaolinite at the same proportion were subjected to spray
drying to form micro-spherical catalyst in accordance
with the conventional procedure for manufacture of FCC
catalyst. The catalyst samples obtained thereby were
calcined at 350 for 2 h, and washed with acidic water.
The washed samples were dried for analytical purpose.
Among these samples the catalyst made of the zeolite DY
Received date: 2014-05-12; Accepted date: 2014-10-16.
Corresponding Author: Professor Tian Huiping, Telephone:
+86-10-82368650; E-mail: tianhp.ripp@sinopec.com.

China Petroleum Processing and Petrochemical Technology

serving as the active component that was not modified by

means of pores cleaning was denoted as the base catalyst,
whereas the catalyst made of the zeolite MDY0-1 serving
as the active component that was modified through pores
cleaning was denoted as RCC-1.
2.2Methods for physical and chemical analysis of
catalysts
The chemical composition of catalyst samples was determined by X-ray fluorescence analysis using a Rigaku
3271E type X-ray fluorescence spectrometer. The specific surface area of catalyst was measured by the static
low-temperature nitrogen adsorption volumetry using
a Micromeritics ASAP2400 static nitrogen adsorption
analyzer. The pore volume of catalyst was determined by
the trickling water method. The attrition index of catalyst
during fluidization was determined by the attrition tester.
2.3Methods for assessing the performance of catalytic cracking catalyst
(1) Microreactor for light oil cracking
Evaluation of microreactor activity for light oil cracking
(micro-activity index): The standard method RIPP 92-90[9]
was adopted to evaluate the microreactor activity for light
oil cracking. The experimental setup consisting of a WFS1D automatic microreactor activity tester, which was
manufactured by RIPP, operated on a Dagang straight-run
light diesel fraction with a boiling range of 239351 .
The microreactor was a fixed-bed reactor with a catalyst
loading of 5 g. The catalytic cracking reaction was conducted at a reaction temperature of 460 , a catalyst/oil
ratio of 3.2, and a WHSV of 16 h-1 along with a stripping
nitrogen flow rate of 30 mL/min and a stripping duration
of 10 min.
(2) Fixed fluidized-bed microreactor
The experimental setup, which was an US KTI Corporations ACE-Model R+ fixed fluidized-bed with a catalyst
loading of 9 g, operated on a VGO derived from the pipeline transported mixed crude at a reaction temperature of
500 and a catalyst/oil ratio of 3.008.04.
3Results and Discussion
3.1Physicochemical properties of RCC-1 catalyst
The novel heavy oil cracking catalyst RCC-1 developed

2014,16(4):7-11

on the basis of hydrothermally ultrastable zeolite serving

as the active component, which was modified through
cleaning of channel pores, was prepared in the pilot plant.
The chemical composition and physico-chemical properties of catalyst samples were analyzed, with the data presented in Table 1.
Table 1The physicochemical properties of RCC-1 catalysts
Item

RCC-1

Industrial index

w(Al2O3), %

51.8

45.0

w(Na2O), %

0.11

<0.35

w(Fe2O3), %

0.33

0.60

11.5

13.0

Pore volume, cm /g

0.39

0.32

Specific surface area, m2/g

258

210

Attrition index, %/h

1.3

2.5

Apparent bulk density, g/cm3

0.76

0.6-0.8

83

74

72.9

65.0-85.0

Loss on ignition, %
3

Micro-activity index (800 , 4 h), %

APS, mm

It can be seen from Table 1 that the chemical composition

of the prepared RCC-1 catalyst including the contents of
Al2O3, Na2O and Fe2O3 met the requirements for commercial catalyst, while the physicochemical properties of the
catalyst including the surface area, pore volume, attrition
index during fluidization, apparent bulk density, and average particle size (APS) all complied with the demand of
commercial catalyst in addition to a higher micro-activity
index. The test results listed in Table 1 have revealed that
the chemical composition and physicochemical indicators
of RCC-1 catalyst all met the specification requirements,
because this catalyst featured high strength, medium bulk
density, large specific surface area, large pore volume,
and high catalytic activity.
3.2Performance of novel heavy oil catalytic cracking
catalyst RCC-1
Based on the concepts aimed at the development of a
novel heavy oil catalytic cracking catalyst, the catalyst
RCC-1 was prepared using the hydrothermally ultrastable zeolite modified through cleaning of channel pores.
This novel catalyst was investigated to compare its performance with a base catalyst that was to be tested in

Zhang Jiexiao, et al. Research and Development of Novel Heavy Oil Catalytic Cracking Catalyst RCC-1

commercial scale at a certain refinery, with the physical

properties of the catalyst RCC-1 presented in Table 2.
The properties of feedstock used in catalyst performance
tests are presented in Table 3. The catalyst samples were
subjected to ageing at 800 for 12 h with 100% steam
before performance tests. The RCC-1 catalyst along with
the base catalyst were tested in the ACE microreactor
unit at a reaction temperature of 500 to compare their
heavy oil cracking ability, their product distribution characteristics and coke selectivity.
Table 2The properties of fresh RCC-1 catalyst
Items

RCC-1 catalyst

AI, %

Base

Base

VBET, mL/g

Base

+21%

VBET, mL/g

Base

+13%

Items

Density (20 ), g/cm3

0.921 7

CCR, %

nH/nC

1.703 3

Elemental
composition, %

Hydrocarbon group
analysis, %

56.5

65.0

71.4

77.5

Bottoms yield on base catalyst, %

22.1

15.2

10.6

6.8

Bottoms yield on RCC-1, %

20.3

13.9

8.7

5.7

catalyst-to-oil ratio
Catalyst/oil ratio

Data

Conversion rate on base catalyst, %

56.5

64.2

71.9

1.95

Conversion rate on RCC-1, %

65.4

72.1

76.4

87.36

Saturated hydrocarbons

59.8

12.4

Aromatics

26.0

0.39

Resins

14.1

0.46

Asphaltenes

0.1

Metal content, g/g

oil conversion

Table 5The conversion depending upon the changes in

Table 3The properties of feedstock

Data

Table 4Bottoms yields depending upon the changes in feed

Conversion, %

Base catalyst

Items

catalyst the yield of unconverted bottoms over the catalyst RCC-1 was reduced. However, it can be seen from
Table 5 that at the same catalyst/oil ratio adopted thereby
the feedstock conversion achieved by the catalyst RCC-1
was greater than the base catalyst. The test results had revealed that compared to the base catalyst the novel heavy
oil cracking catalyst RCC-1 showed a higher heavy oil
cracking ability.

Distillation,
IBP

Ca

3.8

5%

356

Cu

0.2

10%

383

Fe

8.4

30%

422

Na

0.7

50%

447

Ni

6.5

70%

481

0.4

90%

570

3.2.1Study on heavy oil cracking ability of novel

catalyst RCC-1
The bottoms yield depending upon the changes in feedstock conversion is presented in Table 4, and the feedstock conversion depending upon the changes in catalystto-oil ratio is presented in Table 5. It can be seen from
the data listed in Table 4 that in comparison with the base

3.2.2Product distribution characteristics over the

RCC-1 catalyst
The product distribution characteristics obtained over the
RCC-1 catalyst and the base catalyst were studied under
the same reaction conditions. Table 6 shows the total liquid yield depending upon the changes in feed oil conversion, while Table 7 denotes the light oil yield depending
upon the changes in feed oil conversion. It can be seen
from data listed in Tables 6 and 7 that at the same feed
oil conversion the total liquid yield achieved by the novel
catalyst RCC-1 was always higher than that achieved by
the base catalyst, and the light oils yield achieved by the
novel catalyst RCC-1 was also higher that that achieved by
the base catalyst. The test results had revealed that in comparison with the base catalyst the yields of valuable FCC
products, especially the yield of light oils were higher as
compared to those products obtained over the base catalyst.
Table 6Total liquid products yields depending upon the
changes in feed oil conversion
Conversion rate, %

56.5

65.0

71.4

77.5

Liquid yield on Base catalyst, %

70.4

76.3

80.3

81.7

Liquid yield on RCC-1, %

72.7

77.4

80.5

81.9

China Petroleum Processing and Petrochemical Technology

2014,16(4):7-11

Table 7Light oil yields depending upon the changes in

Table 10Gasoline olefins content depending upon the

feed oil conversion

changes in feed oil conversion

56.5

65.0

71.4 77.5

Conversion, %

56.5

65.0

71.4

77.5

Light oil yield over the base catalyst, %

60.4

64.5

66.2 67.8

Olefin content in gasoline obtained

on base catalyst, %

35.6

28.1

21.5

19.4

Light oil yield over RCC-1 catalyst, %

62.6

67.4

68.7 67.4

Olefin content in gasoline obtained

on RCC-1, %

34.2

24.6

19.8

17.7

Conversion, %

The distribution of LPG and gasoline in the FCC products was further investigated. Table 8 shows the LPG

3.2.3Coke selectivity of RCC-1 catalyst

obtained over the base catalyst. Furthermore, it can be

The coke selectivity was studied and compared between

the novel heavy oil FCC catalyst RCC-1 and the base catalyst under the same reaction conditions. Table 11 shows
the coke yield depending upon the changes in the feed oil
conversion, while Table 12 indicates the coke yield depending upon the changes in the bottoms yield. It can be
seen from data presented in Tables 11 and 12 that either at
the same feed oil conversion rate or at the same bottoms
yield the coke yield obtained over the novel heavy oil
FCC catalyst RCC-1 was obviously lower than the case
with the base catalyst. The test results had confirmed that
the novel catalyst RCC-1 possessed a better coke selectivity as compared to the base catalyst.

learned from the gasoline olefins content which depend-

Table 11Coke yield depending upon the changes in feed

ed upon the changes in feed oil conversion presented in

oil conversion

yields depending upon the changes in feed oil conversion, and Table 9 denotes the gasoline yield depending
upon the changes in feed oil conversion, while Table
10 shows the gasoline olefins content depending upon
the changes in feed oil conversion. It can be seen from
the data presented in Tables 8, 9, and 10 that within
the range of feed oil conversion rate changes the LPG
yield obtained over the novel heavy oil cracking catalyst
RCC-1 was less than that obtained over the base catalyst. The gasoline yield obtained over the novel heavy
oil cracking catalyst RCC-1 was much higher than that

Table 10 that at the same feed oil conversion the novel

Conversion, %

56.5

65.0

71.4

77.5

heavy oil catalyst RCC-1 harvested a much lower olefin

Coke yield on base catalyst, %

6.6

7.2

8.5

9.6

content in gasoline as compared to the base catalyst. All

Coke yield on RCC-1, %

5.6

6.3

7.5

9.4

these results have revealed that compared with the base

catalyst the novel heavy oil catalyst RCC-1 had better

Table 12Coke yield depending upon the changes in

bottoms yield

gasoline selectivity coupled with lower olefin content in

Bottoms yield, %

gasoline.
Table 8LPG yields depending upon the changes in feed oil
conversion
Conversion, %

56.5

65.0

71.4

77.5

LPG yield on base catalyst, %

9.8

11.7

14.6

15.7

LPG yield on RCC-1, %

10.3

10.5

12.4

14.9

Table 9Gasoline yields depending upon the changes in

feed oil conversion
Conversion, %

56.5

65.0

71.4

77.5

Gasoline yield on base catalyst, %

38.6

44.5

48.0

50.3

Gasoline yield on RCC-1, %

39.7

47.3

50.6

51.1

10

8.0

10.1

15.2

21.8

Coke yield on base catalyst, %

9.0

8.4

7.5

6.6

Coke yield on RCC-1, %

9.2

7.6

6.7

5.9

3.3Study on resistance of novel heavy oil FCC catalyst RCC-1 against metal contamination
The resistance of novel heavy oil FCC catalyst RCC-1
against metal contamination was investigated. The said
novel heavy oil FCC catalyst RCC-1 after having been
artificially contaminated with vanadium (containing 1 500
wppm of V) was subjected to ageing with 100 % steam at
800 prior to the assessment of its catalytic performance
in the light oil cracking microreactor and the ACE-Model
R+ type fixed fluidized bed unit, while a reference cata-

Zhang Jiexiao, et al. Research and Development of Novel Heavy Oil Catalytic Cracking Catalyst RCC-1

lyst L having good resistance against metal contamination

was studied for comparison under the same treating conditions, with the test results presented in Table 13.
Table 13Evaluation of micro-reactor and ACE of catalyst
contaminated by vanadium (w(V)=1 500 mg/g)
Item
Aging condition

Reference catalyst L

RCC-1

800 , 4 h

800 , 4 h

Intermediate base
heavy oil

Intermediate
base heavy oil

Temperature,

500.0

500.0

m(Catalyst)/m(oil)

4.02

4.02

Feed oil

lowing specific features as compared to the reference catalyst:

1) The novel heavy oil FCC catalyst RCC-1 featured high
mechanical strength, large pore volume and high activity.
2) The novel heavy oil FCC catalyst RCC-1 showed
stronger bottoms cracking ability, better products distribution, better coke selectivity, better gasoline selectivity, and
more significant ability to reduce olefin content in gasoline.
3) The novel heavy oil FCC catalyst RCC-1 possessed
excellent resistance against metal contamination.

References
[1] Yu Shanqing, Tian Huiping, Long Jun. Advances in low

Product distribution, %

and zero rare earth FCC catalysts abroad[J]. Petroleum Pro-

Dry gas

1.80

2.1

LPG

15.14

16.78

[2]Liu Xiaoqing, Duan Hongchang, Zhao Yihua, et al. Com-

Coke

7.53

8.41

mercial application of LDO-70 efficient conversion catalysts

Gasoline

48.01

52.44

for heavy oil[J]. Petroleum Processing and Petrochemicals,

LCO

15.91

12.31

Bottoms

11.62

7.96

Conversion, %

72.47

79.73

Light oil yield, %

63.92

64.75

Total liquid yield, %

79.06

81.53

[4]Grobet P J, Jacobs P A, Beyer H K. Study of the silicon tet-

Coke selectivity, %

10.39

10.54

rachloride dealumination of NaY by a combination of NMR

67

76

Micro-activity, %

The data listed in Table 13 had confirmed that under the

same metal contamination degree and ageing conditions
in comparison with the reference catalyst L operating
at the same catalyst/oil ratio the novel heavy oil FCC
catalyst RCC-1 showed a feed oil conversion increase of
7.26%, a gasoline yield increase of 4.43%, a light oil yield
increase of 0.83%, a total liquid yield increase of 2.47%,
an unconverted bottoms yield reduction of 3.66% and a
micro-activity index increase of 9%, indicating to a better
bottoms cracking ability and better product distribution of
the novel catalyst RCC-1. The overall outcome of analysis has revealed that the novel heavy oil cracking catalyst
RCC-1 possessed a better resistance against heavy metal
contamination.
4Conclusions
Based on the evaluation of physicochemical properties
and reaction performance of catalyst samples, the novel
heavy oil FCC catalyst RCC-1 developed thereby had the fol-

cessing and Petrochemicals, 2013, 44(8): 1-7 (in Chinese)

2013, 44(9): 15-18 (in Chinese)

[3]Duan Hongchang, Tan Zhengguo, Zhang Haitao, et al. Commercial application of heavy oil catalytic cracking LOG-90
catalyst for high octane gasoline[J]. Petroleum Processing
and Petrochemicals, 2013, 44(9): 11-14 (in Chinese)

and IR methods[J]. Zeolites, 1986, 6(1): 47-50

[5]Tang Jinlan, Xu Youhao, Wang Xieqing, et al. Study on the
naphthenic ring opening reacions of tetrahydronaphthalene
over zeolite catalysts[J]. Petroleum Processing and Petrochemicals, 2012, 43(1): 20-25
[6]Skeels G W, Breck D W. Zeolite chemistry: V. Substitution
of silicon for aluminum in zeolite via reaction with aqueous
fluorosilicate[C]//Proc. 6th International Zeolite Conf. (Butterworth), 1984: 87-96
[7]Martens J A, Grobet P J, Jacobs P A. The Chemistry of
the Dealumination of Faujasite Zeolites with Silicon
Tetrachloride[J]. Studies in Surface Science and Catalysis,
1991, 63: 355-379
[8]Wang Mingjin, Xu Mingde, Zhu Yuxia. Development
and application of CDOS series catalysts for bottoms
cracking[J]. China Petroleum Processing and Petrochemical Technology, 2013, 15(4): 9-13
[9]Yang Cuiding Gu Kanying, Wu Wenhui. Methods for
Analysis of Petrochemical Products (Test Methods Proposed by RIPP)[M]. Beijing: The Science Publishing
House, 1990

11