INTERNATIONAL JOURNAL OF SCIENTIFIC & TECHNOLOGY RESEARCH VOLUME 5, ISSUE 07, JULY 2016 ISSN 2277-8616

Manufacture Of Pozzolanic Cement From RFCC

Spent Catalyst In Khartoum Refinery
Husam E Mustafa, Gurashi A Gasmelseed

Abstract: Pozzolana is defined as Siliceous and aluminous material which reacts with calcium hydroxide in presence of water at room temperature to
form strong slow-hardening cement. Pozzolana has the advantage of reduction of leachibility of calcium hydroxide liberated during the setting and
hydration of cement. In Khartoum Refinery five to ten tons per week of spent catalyst are produced in fine powder, this quantity is sent to dumping sites
or landfills. In this study pilot experiments were successfully carried out at different ratios to produce cement. The RFCC spent catalyst samples were
subjected to chemical analysis to determine the content of Al 2O3, SiO3,TiO3, CaO and V2O5 …..etc. These were found to be 49.5, 41.1, 0.32, 1.4 and 0.09
percent respectively, other compounds are, Na2O, MgO, P2O5,SO3, K2O, MnO,Fe2O3,Co3O4 and NiO2 with. It is found that the percentages of SiO2,
Al2O3, and Fe2O3 amount up to 91.5% that is above the ASTM standard C618:2003 which stipulated that the minimum of such compound is 70 %.
Physical properties of RFCC spent catalyst were also carried out including, crystallinity and Pozzolanicity index. The cement produced was tested for
compressive strength, consistency and setting time .It is concluded that RFCC spent catalyst in Khartoum Refinery is a Pozzolanic material and up to
30% replacement from Portland cement (blended cement) complies with the Sudanese and European Standards No SSMO 3998:2011and EN-197-
1:1992 respectively. The study shows that the compressive strength of blended Pozzolanic cements decreases with increasing Pozzolana content. From
the foregoing, it is recommended to use RFCC spent catalyst with Portland cement as blended cement to produce mortars for construction and concrete.

IndexTerms: Compressive strength, Pozzolanic Cement, Residual fluidized Catalytic cracking unit, Spent Catalyst.
————————————————————

1 INTRODUCTION The catalyst selection is based on feed property, products

The Residue Fluid Catalytic Cracking unit (RFCC) in
Refineries is used to convert heavy oils and residues of low
valuable price into light transporting oils of higher value.
The catalyst active sites are irreversibly covered by
chemical impurities, causing a Permanent reduction of
catalytic activity and requiring the catalyst to be replaced by
a new one. The disposal of spent catalyst is of major
concern to oil refineries. [1]. Pozzolanas have been defined
as substances which, though not themselves cementitious,
contain substance which combine with lime at ordinary
temperature in aqueous media to form insoluble substance
which possess cementing properties. They include various
natural materials, most of which are of volcanic origin, and
also artificial products such as burnt clays, Spent Oil Shale,
and pulverized fuel ash (fly-ash) [6].
2 LITERATURE REVIEW
RFCC unit is one of the main units in Khartoum refinery for
increasing light oil yields and reducing heavy oil yields, with
a processing capacity of 1.8 million ton per year. The main
feed stock of (RFCC) is atmospheric residue of crude oil,
and the main products are gasoline, diesel, liquid petroleum
gas (LPG), dry gas and heavy oil (slurry).
_______________________________
 Author name is currently pursuing PhD degree program
in chemical engineer in university of kararry, sudan, PH
-249123400373, Email, husamustafa@gmail.com
 Co-Author name is currently PhD holder in University of
science and technology, faculty of chemical
engineer,sudan,PH-249919634134,
Emailgurashigasm@gmail.com
scheme and unit type. The activity, specific surface area,
selectivity, anti - fouling and stability should be focused on
in catalyst selection [7]. The catalyst replacement should be
depended to the operation and loses for balance, fresh
catalyst have been made - up resulting in too high activity of
equilibrium catalyst. It is consists of, the reaction-
regeneration section, fractionation section, absorption-
stabilization section, desulphurization section and waste-
heat boiler section [1]. Pozzolanic materials are natural
substances of siliceous or silico-aluminous composition or a
combination thereof. Although fly ash and silica fume have
Pozzolanic properties. Pozzolanic materials do not harden
in themselves when mixed with water but, when finely
ground and in the presence of water, they react at normal
ambient temperature with dissolved calcium hydroxide
(Ca(OH)2) to form strength-developing calcium silicate and
calcium aluminate compounds[18]. Pozzolanic materials
when used in mortar and concrete works improve durability
which is the ability of concrete to resist weathering action,
chemical attack and abrasion. The higher strength of
concrete with pozzolanas at later ages is as a result of the
pozzolanic reactions increasing the amount of calcium
silicate hydrates while diminishing Ca(OH)2 [25]. It is
obvious that minimization of production of Portland cement
clinker would greatly help to reduce the CO2 emission
produced by the cement industry. One wise solution is to
promote the usage of pozzolanic materials in mortar and
concrete works thereby reducing the world‗s demand for
Portland cement which eventually reduces the emission of
CO2 into the atmosphere. Pozzolanic materials also bring
in other technical advantages such as low heat of hydration
.The heat evolved during the hardening of Portland Cement
concretes is reduced by the substitution of Pozzolana
though not proportionately to the degree of substitution
since the reaction between lime and Pozzolana itself
evolves some heat. As a rough approximation the
percentage reduction in heat evolution at 7 to 28 days may
be taken at about one-half the percentage substitution, but
it varies appreciably for different Pozzolanic cement [17].

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3 MATERIAL AND METHODS TABLE 4.1

In June 2015, Spent RFCC Catalyst sample were collected CHEMICAL ANALYSIS OF RFCC SPENT CATALYST
from RFCC Unit, after discharge the periodically amount of
Spent catalyst. Ordinary Portland cement of class (42.5N) NO Items %
according to the Sudanese Standard (164/2011) and 1 Al2O3 49.514
European Standard (EN 197-1/2000)‖Sakhr Alsudan‖ 2 SiO2 41.113
manufactured by Altakamol Cement CO.LTD, was used for 3 Na2O 0.350
4 MgO 0.198
the preparation of the mortar and paste specimens. The
5 P2O5 1.363
tests for the determination of the compressive strength of 6 SO3 0.141
the pozzolana cement mortar cubes were carried out 7 K2O 0.204
according to methods specified by the British Standard BS 8 CaO 1.427
EN 196-1:1995.At Building And Roads Research Institute – 9 TiO2 0.323
University Of Khartoum .The pozzolana was blended with 10 V2O5 0.091
ordinary Portland cement ( Sakhr Alsudan) using cement 11 MnO 0.035
replacement of 10, 20, 30 , 40,50,60,70,80 and90% by 12 Fe2O3 0.879
mass. River sand was used to prepare mortar cubes for the 13 Co3O4 0.054
compressive strength determination. The sand satisfied the 14 NiO 1.542
requirements of the European Standard EN 196-2:2000. 15 LOI 2.17
Pozzolana cement to sand ratio of 1:3, water to pozzolana
cement ratio of 0.5 for all levels of Portland cement From Table (4.1), it can be seen that the SiO2 for RFCC
replacement were used to prepare the mortar test cubes. Spent Catalyst is 41.1% with 49.5% Al2O3 and 0.87% of
The cubes after curing were tested for compressive Fe2O3, and have some minor oxides such as alkalis,
strength by loading the sides of the cubes uniformly with a sulfate, and calcium oxide. The SiO2 + Al2O3 + Fe2O3 of
compressive strength testing machine until fracture RFCC Spent Catalyst were 91.5%. Based on the data
appeared. The maximum load in KN at which fracture presented in Table (4.1) and with ASTM C618:2003
occurred was recorded and used to calculate the definition, i.e. for a material to be classified as pozzolan, it
compressive strength as should have SiO2 + Al2O3 + Fe2O3 minimum of 70%, while
for loss of ignition (LOI) a maximum of 6%. Therefore from
1000 this study, the RFCC Spent Catalyst used can be classified
Rc = Fc C ………………………………… 1
Ar as Class N Pozzolanic. The LOI for RFCC Spent Catalyst is
about 2.17%.
Where:
Rc = compressive strength, MPa . TABLE 4.2
Fc = maximum load at which fracture occurs, KN. PHYSICAL PROPERTIES OF RFCC SPENT CATALYST
Ar = area of a face of the cube, mm2.
C = Machine Correction Factor. 1 Property Result
2 Density 2770 g/cm3
The Pozzolanicity Index is the Comparison between The 3 Fineness 428 m2/kg
Compressive strength of ordinary Portland Cement with
specific curing period 2,28 days and 20% cement According to the Sudanese standard of Pozzolana (SSMO
replacement with the same curing period. The Vicat method 3998:2011), the fineness should not be less than 300 m2/kg
as specified by British Standard BS EN 196-3:1995.At
Building And Roads Research Institute – University Of 4.2 Determination of Crystallinity:
Khartoum- was used to determine the standard consistency
of both Pozzolana and ordinary Portland cement. In this
method a measured quantity of the cement is gauged with
water until the resistance to penetration of a plunger
reached a specified level. The Vicat method was also used
for the determination of the initial setting time. The
Pozzolana cement paste, using the percentage of water
recorded for the standard consistency, was gauged into the
Vicat mould. The paste, confined in the mould and resting
on the base plate, was placed under the Vicat apparatus
with the needle provided for the initial setting time Fig 4.1 XRD For RFCC Spent Catalyst
determination in place
The mineralogical composition of the spent catalyst was
4 RESULT AND DISCUSSION determined by the use of XRD .Figure( 4.1 )shows the X-
ray diffraction pattern of the material. As seen, the shape of
4.1 Chemical Analysis the pattern and the broad diffuse halo at 2Theta-angle of 24
RFCC spent Catalyst sample were collected from Khartoum degrees clearly shows that the spent catalyst is mainly an
Refinery, and subjected immediately to the following amor-phous material.
analysis.
4.4 Pozzolanicity Index

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60 35.00
47.9 30.00
50 44.2

Strength(N/mm2)
25.00 7 days(N/mm2)
40 Ordinary
20.00
Portland
30 15.00
Cement
20 16.4 10.00
10.7 20% pozzolana 5.00
10 0.00

10
20
30
40
50
60
70
80
90
OPC
0
(N/mm2)
Replacement %
2-days strength(N/mm2)
28-days strength

Fig 4.2 The Pozzolanicity Degree of RFCC Spent catalyst Fig 4.4 7 days Compressive Strength of RFCC blended
cement
The Pozzolanicity degree is comparison between 20%
replacement strength and ordinary Portland cement
60.00
strength , the result in figure (4.2) shown that the
Pozzolanicity degree of RFCC Spent catalyst are 65% at 2 50.00
days curing and 92% at 28 days curing time .which are very

Strength(N/mm2)
close to the strength of ordinary Portland cement in early 40.00
28
curing time. 30.00 days(N/mm2)

4.5 Compressive Strength 20.00

10.00
TABLE 4.3
COMPRESSIVE STRENGTH OF RFCC BLENDED CEMENT 0.00

10
20
30
40
50
60
70
80
90
Replacement % 2 days 7 days 28 days 90 days OPC
Ordinary portland Replacement %
16.46 30.00 47.88 47.95
Cement
10 12.39 27.29 46.28 47.41
20 11.04 25.74 44.25 48.08
30 6.10 18.76 32.17 44.36 Fig 4.5 28 days Compressive Strength of RFCC blended
40 5.42 13.34 23.48 37.93
cement
50 1.56 7.65 11.51 19.44
50.00
60 0.68 2.51 4.97 7.65
Strength(N/mm2)

70 0.68 1.83 1.58 4.54 40.00

90
80 0.00 0.00 0.00 1.35 30.00 days(N/mm2)
90 0.00 0.00 0.00 0.00
Should not be Should not be 20.00
SSMO 3998:2011
- less than less than
Requirements
(16N/mm2) (32.5N/mm2) 10.00
0.00
10
20
30
40
50
60
70
80
90
OPC

20.00
Strength(N/mm2)

15.00 Replacement %
2 days(N/mm2)
10.00

5.00 Fig 4.6 90days Compressive Strength of RFCC blended

cement
0.00
OPC 20 40 60 80
Replacement %

Fig 4.3 2 days Compressive Strength of RFCC blended

cement

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60.00 450
400
50.00 350 Final

Time (Min.)
300
Strength(N/mm2)
Settin
40.00 250 g
200 time(
30.00 150 min.)
100
Initial
20.00 50
Settin
0
g
10.00 O 10 20 30 40 50 Time
P (min.)
0.00 C
OPC 20 40 60 80 Replacement%

Fig 4.8 Initial and Final Setting Time Of RFCC Blended

2 days(N/mm2) Cement
7 days(N/mm2)

Fig 4.7 2,7,28 and 90days Compressive Strength of RFCC 50

blended cement
40

Consistency%
Compressive strength of the specimens prepared at
30
different levels of substitution was measured after 2, 7,
28and 90 days of curing. The results obtained are 20
presented in Table (4.3) and figures from (4.2) to (4.6). As
seen after 2 days of curing, the strength enhancement 10
occurs at replacement level of 10 %. By increasing the
curing time to 7 days, maximum compressive strength 0
belongs to samples with 10 % to 20 % substitution and at O P 10 20 30 40 50
the age of 28 days, 10 % to 30 % replacement show the C
greatest improvement in compressive strength. These
results clearly show that when curing time is short, only a
limited amount of calcium hydroxide is released from
hydration reactions that could be consumed by a small Fig 4.9 Consistency of RFCC Blended Cement
portion of spent catalyst through the Pozzolanic reaction. A
s curing time increases and more calcium hydroxide is It is clear that from Figure (4.9) water demand increased
produced, more spent catalyst would be required with increase in the Pozzolana content. This progressive
accordingly to achieve sufficient Pozzolanic reaction. increase in water demand is due to the smaller particle size
of the Pozzolana which increases the surface area of the
4.6 Consistency and Setting Time whole mix translating into higher water demand .Therefore,
as the Pozzolana content increases, the surface area
TABLE 4.4 becomes greater thereby requiring greater volume of water.
CONSISTENCY AND SETTING TIME RESULTS Experimental results Figure (4.8) also show that initial and
final setting times of Portland cement are significantly
influenced by the presence of spent catalyst. Generally, the
Initial Setting Final Setting more the cement substitution by the spent catalyst, the
Replacement% Consistency% Time time shorter the setting times. Such high water absorption can
H:m H:m significantly reduce both initial and final setting times.
Ordinary
Portland 29.7 2:25 4:27 5 CONCLUSION AND RECOMMENDATION
Cement
10 31.3 1:47 2:19
5.1 Conclusion
20 32.5 1:07 3:39
30 36.3 0:41 2:31 According to the test results, the following conclusions are
40 38.5 0:42 1:29 drawn:
50 39.5 0:13 1:11 - The chemical analysis, XRD and the Pozzolanicity
SSMO Should not Should not be degree test results confirm that RFCC spent catalyst
3998:2011 26-33% be less than more than 6.5 from Khartoum refinery is a Pozzolanic material.
Requirements 75 min hrs - According to the Sudanese standard (SSMO
3998:2011) ,European standard ( EN-197-1:1992) up to
30% replacement of RFCC spent catalyst shall meet
the requirements as (blended Pozzolanic cement).
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INTERNATIONAL JOURNAL OF SCIENTIFIC & TECHNOLOGY RESEARCH VOLUME 5, ISSUE 07, JULY 2016
- Compressive strengths (2, 7, 28 and 90 days) of
blended Pozzolanic cement decrease with increasing
Pozzolana content.
- Compressive strength of blended Pozzolanic cement
gave significant increase after 28 days curing while the
ordinary Portland cement strength was not affected.
- The initial and final setting times of the Pozzolana
cement increased significantly because of the
incorporation of large volumes of Pozzolana.
5.2 Recommendation
- It is recommended to use RFCC spent catalyst from
Khartoum refinery with Portland cement to produce
mortars for building and plaster and to some extent to
be used in foundation concrete.
- Further research work is recommended to be carried
out in order to evaluate the effect of fineness of
Pozzolana on the properties of burnt clays is
recommended to be studied.
ACKNOWLEDGMENT
- The authors wish to thanks the college of graduate
studies and research to their help and support. This
paper is generated from partial fulfillment for the degree
of PhD in chemical engineer, university of kararry to
whom the authors offer this thanks, respect and
appreciation
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