Molecular sieve abstract
A molecular sieve-containing catalyst for cracking hydrocarbons,
comprising molecular sieve, refractory inorganic oxide, clay and
a metal component, wherein the amount of said molecular sieve is
from 1 to 90% by weight, the refractory inorganic oxide is from
2 to 80% by weight, the clay is from 2 to 80% by weight, and the
metal component is from 0.1 to 30% by weight, calculated as the
oxide of said metal having its maximum valence state, based on the
total amount of the catalyst, wherein said metal component exists
essentially in a reduction state and is one or more metals selected
from the group consisting of metals of Group III A(other than aluminum),
and metals of Group IVA, VA, IB, IIB, VB, VIB and VIIB, and non-noble
metals of Group VIII of the periodic table. The catalyst has higher
cracking activity and higher sulfur reduction activity.
Molecular sieve claims
1. A molecular sieve-containing catalyst for cracking hydrocarbons,
comprising molecular sieve, refractory inorganic oxide, clay and
a metal component, wherein the amount of said molecular sieve is
from 1 to 90% by weight, the refractory inorganic oxide is from
2 to 80% by weight, the clay is from 2 to 80% by weight, and the
metal component is from 0.1 to 30% by weight, calculated as the
oxide of said metal having its maximum valence state, based on the
total amount of the catalyst, wherein said metal component exists
essentially in a reduction state and is one or more metals selected
from the group consisting of metals of Group III A (other than aluminum),
metals of Group IVA, VA, IB, IIB, VB, VIB and VIIB, and non-noble
metals of Group VIII of the periodic table.
2. The catalyst according to claim 1 wherein the amount of said
molecular sieve is from 10 to 60% by weight, the refractory inorganic
oxide is from 10 to 50% by weight, the clay is from 20 to 70% by
weight, and said metal component is from 0.50 to 20% by weight,
calculated as the oxide of said metal having its maximum valence
state.
3. The catalyst according to claim 1 wherein said metal component
has a ratio value of its average valence state to the maximum valence
state of from 0 to 0.95.
4. The catalyst according to claim 3 wherein said metal component
has a ratio value of its average valence state to the maximum valence
state of from 0.1 to 0.7.
5. The catalyst according to claim 1 wherein said metal component
is one or more metals selected from the group consisting of gallium,
germanium, tin, antimony, bismuth, lead, copper, silver, zinc, cadmium,
vanadium, molybdenum, tungsten, manganese, iron, cobalt and/or nickel.
6. The catalyst according to claim 1 wherein said metal component
is one or more metals selected from the group consisting of gallium,
tin, copper, silver, zinc, vanadium, molybdenum, manganese, iron,
and/or cobalt.
7. The catalyst according to claim 1 wherein said molecular sieve
is one or more selected from the group consisting of large pore
size zeolites or intermediate pore size zeolites.
8. The catalyst according to claim 7 wherein said molecular sieve
is one or more selected from the group consisting of Y-zeolite,
phosphorus- and /or rare-earth-containing Y-zeolite, ultra-stable
Y-zeolite, phosphorus- and/or rare-earth-containing ultra-stable
Y-zeolite, beta zeolite, zeolites having MFI structure, and phosphorus-and/or
rare-earth-containing zeolites having MFI structure.
9. The catalyst according to claim 1 wherein said refractory inorganic
oxide is one or more selected from the group consisting of alumina,
silica, amorphous silica-alumina, zirconia, titanium oxide, boron
oxide, and oxides of alkaline earth metals.
10. The catalyst according to claim 9 wherein said refractory
inorganic oxide is one or more selected from the group consisting
of alumina, silica, amorphous silica-alumina, zirconia, titanium
oxide, magnesium oxide, and calcium oxide.
11. The catalyst according to claim 1 wherein said clay is one
or more selected from the group consisting of kaolin, halloysite,
montmorillonite, kieselguhr, halloysite, soapstone, reactorite,
sepiolite, attapulgus, hydrotalcite, and bentonite.
12. The catalyst according to claim 1 wherein the catalyst further
comprises a rare-earth metal component, wherein the amount of said
rare-earth metal component is from 0 to 50% by weight, calculated
as the oxide, based on the total amount of the catalyst.
13. The catalyst according to claim 12 wherein the amount of said
rare-earth metal component is from 0 to 15% by weight.
14. The catalyst according to claim 12 wherein said rare-earth
metal is selected from the group consisting of lanthanum, cerium,
rich-lanthanum norium or rich-cerium norium.
15. The catalyst according to claim 1 wherein the catalyst further
comprises a phosphorus component, wherein the amount of said phosphorus
component is from 0 to 15% by weight calculated as element phosphor,
based on the total amount of the catalyst.
16. The catalyst according to claim 15 wherein the amount of said
phosphorus component is from 0 to 8% by weight calculated as element
phosphor, based on the total amount of the catalyst.
17. The catalyst according to claim 1 wherein said metal component
exists in the molecular sieve, refractory inorganic oxide, clay,
or the combination thereof.
18. The catalyst according to claim 17 wherein said metal component
exists in refractory inorganic oxide and/or clay.
19. A method for preparing the catalyst according to claim 1 wherein
said method comprises contacting the composition containing metal
component compound, molecular sieve, refractory inorganic oxide
and clay with a reducing gas-containing atmosphere at suitable temperature
for enough time so that said metal component has an average valence
state lower than its maximum oxidation state, and said metal component
is one or more metals selected from the group consisting of metals
of Group III A (other than aluminum), metals of Groups IVA, VA,
IB, IIB, VB, VIB and VIIB, and non-noble metals of Group VIII of
the periodic table, wherein the amount of each component is such
that the final catalyst comprises, based on the total amount of
the catalyst, from 1 to 90% by weight of the molecular sieve, from
2 to 80% by weight of the refractory inorganic oxide, from 2 to
80% by weight of the clay, and from 0.1 to 30% by weight of the
metal component, calculated as the oxide of said metal having its
maximum valence state.
20. The method according to claim 19 wherein said reducing gas-containing
atmosphere is an atmosphere of pure reducing gas or an atmosphere
containing reducing gas and inert gases.
21. The method according to claim 20 wherein said pure reducing
gas comprises one or more selected from the group consisting of
hydrogen, carbon monoxide and hydrocarbons having 1-5 carbon atoms.
22. The method according to claim 21 wherein said pure reducing
gas comprises one or more selected from the group consisting of
hydrogen, carbon monoxide, methane, ethane, propane, butane and
its isomers, pentane and its isomers.
23. The method according to claim 20 wherein said atmosphere containing
reducing gas and inert gases comprises a mixture of one or more
gases selected from hydrogen, carbon monoxide and hydrocarbons containing
1-5 carbon atoms and inert gases, or refinery dry gas.
24. The method according to claim 20 wherein said reducing gas-containing
atmosphere has at least 10% by volume of the reducing gas.
25. The method according to claim 19 wherein said contact temperature
is from 100 to 900.degree. C. and said contact time is from 0.1
seconds to 10 hours.
26. The method according to claim 19 wherein said reducing gas-containing
atmosphere is used in an amount no less than 5 ml of the reducing
gas per gram of catalyst per hour.
27. The method according to claim 19 wherein the amount of each
component is such that the final catalyst comprises, based on the
total amount of the catalyst, from 10 to 60% by weight of the molecular
sieve, from 10 to 50% by weight of the refractory inorganic oxide,
from 20 to 60% by weight of the clay, from 0.5 to 20% by weight
of the metal component, calculated as the oxide of the metal having
its maximum valence state.
28. The method according to claim 19 wherein said composition
containing the metal component compound, molecular sieve, refractory
inorganic oxide and clay further contains rare-earth compound and/or
phosphorous compound.
29. A molecular sieve-containing catalyst for cracking hydrocarbons,
wherein said catalyst comprises molecular sieve, refractory inorganic
oxide, clay and a metal component, wherein the amount of the molecular
sieve is from 1 to 90% by weight, the refractory inorganic oxide
is from 2 to 80% by weight, the clay is from 2 to 80% by weight,
said metal component is from 0.1 to 30% by weight, calculated as
the oxide of said metal having its maximum valence state, based
on the total amount of the catalyst; wherein said metal component
is one or more selected from the group consisting of metals of Group
IIIA (other than aluminum), metals of Groups IVA, VA, IB, IIB, VB,
VIB and VIIB, and non-noble metals of Group VIII of the periodic
table; said catalyst is prepared by the method according claim 19.
30. The method according to claim 23 wherein said reducing gas-containing
atmosphere has at least 10% by volume of the reducing gas.
Molecular sieve description
TECHNIQUE FIELD
[0001] The present invention relates to a catalyst for cracking
hydrocarbons and a method for preparing the same, more particularly,
to a molecular sieve-containing catalyst for cracking hydrocarbons
and a method for preparing the same
TECHNIQUE BACKGROUND
[0002] In recent years, requirement for fuel oil standards becomes
increasingly stricter due to the consideration of environmental
protection worldwide. For instance in China, "Controlling Criterion
of Hazardous impurities for Car Gasoline" has been drown up
by National Quality Monitoring Bureau in 1999. According to the
requirement of this Criterion, the sulfur content of gasoline as
a finished product must be less than 800 ppm. In fact, more than
90% of sulfur in finished gasoline comes from FCC gasoline. On the
other hand, the tendency that catalytic cracking feedstock grows
heavier is becoming increasingly acute, and the proportion of middle-east
crude oils refined by refineries in China is increasingly high,
which have higher sulfur content. Therefore, there is a desire to
develop a cracking catalyst with higher cracking activity and higher
sulfur reduction activity.
[0003] U.S. Pat. No. 6036847 and its family patent EP 0798362
A2 disclose a process for fluidized catalytic cracking a hydrocarbon
feedstock, wherein said hydrocarbon feedstock is cracked in a cracking
zone in absence of added hydrogen, and all particles including catalyst
particles are repeatedly circulated between a hydrocarbon cracking
zone and a catalyst regeneration zone, wherein said all particles
contain additional particles having less activity for catalyzing
the cracking of hydrocarbon oils compared to said catalyst particles,
said activity being on a fresh particle basis. The additional particles
consist essentially of titania and inorganic oxide other than titania.
Said inorganic oxide other than titania contains Lewis acid selected
from the group consisting of elements and compounds of nickel, copper,
zinc, silver, cadmium, indium, tin, mercury, thallium, lead, bismuth,
boron, aluminum (other than alumina) and germanium supported on
alumina. The sulfur content of FCC gasoline in cracked products
is decreased by using this type of additive containing titanium
oxide.
[0004] U.S. Pat. No. 5376608 discloses a cracking catalyst composition
having a function of desullfunrzation, which comprises (a) a zeolite/molecular
sieve dispersed in an inorganic oxide matrix; (b) a Lewis acid-containing
alumina component which comprise from 1 to 50% by weight of Lewis
acid selected from the group consisting of elements and compounds
of nickel, copper, zinc, silver, cadmium, indium, tin, mercury,
thallium, lead, bismuth, boron, aluminum (other than alumina) and
germanium supported on alumina.
[0005] WO 99/49001A1 discloses a composition for reducing the sulfur
content of hydrocarbon components, wherein said composition contains
a hydrotalcite material which has been impregnated with a Lewis
acid and optionally a FCC catalyst. Said Lewis acid comprises transition
metal elements, especially zinc, copper, nickel, cobalt, iron or
manganese, and their compounds.
[0006] WO 01/21733A1 discloses a catalytic cracking process for
cracking a hydrocarbon feedstock containing organo-sulfur compounds
in the presence of hot regenerated cracking catalyst. Said catalyst
contains a product sulfur reduction component containing a metal
component in an oxidation state greater than zero. Said metal component
includes compounds or complexes of metal elements selected from
the group consisting of Period 3 Groups VB, VIIB, VIII, IIB and
IVA of the periodic table, such as metal compounds or complexes
of vanadium, zinc, iron, cobalt, manganese and gallium. Said product
sulfur reduction component comprises a molecular sieve of which
the porous structure contains aforementioned metal component, also
comprises aforementioned metal component dispersed anywhere on the
catalyst carrier structure, e. g. a porous oxide carrier.
[0007] WO 01/21732A1 discloses a process for reducing the sulfur
content of a cracked petroleum fraction, comprising catalytically
cracking a petroleum feed fraction at elevated temperature in the
presence of cracking catalyst and a product sulfur reduction additive
to obtain liquid cracking products of reduced sulfur content, wherein
said product sulfur reduction additive comprises a non-molecular
sieve carrier containing vanadium; said non-molecular sieve carrier
may be an organic or inorganic carrier; preferred the carrier is
amorphous or paracrystal inorganic oxides, such as alumina, silica,
clay or their mixture.
[0008] CN 1281887A discloses a process for reducing the sulfur
content of catalytically cracked petroleum fractions, comprising
catalytically cracking a petroleum feed fraction at elevated temperature
in the presence of a pruduct sulfur. reduction catalyst to produce
liquid cracked products of reduced sulfur content. The product surlfur
reduction catalyst contains a porous molecular sieve having a metal
component which is within the interior pore structure. Said porous
molecular sieve may be a large pore size zeolite, i. e. the zeolite
having a pore structure with a ring pore opening of at least 0.7
nm such as, Y-zeolite, rare-earth Y-zeolite (REY), ultra-stable
Y-zeolite (SY), L-zeolite, beta-zeolite, mordenite, ZSM-18 zeolite.
Said molecular sieves may also be a intermediate pore size zeolite,
i. e. the zeolite having a pore structure with a ring pore opening
of larger than 0.56 nm but smaller than 0.7 nm such as Pentasil
zeolite, ZSM-5 zeolite, ZSM-22 ZSM-23 zeolite, ZSM-35 zeolite,
ZSM-50 zeolite, ZSM-57 zeolite, MCM-22 zeolite, MCM-49 zeolite,
MCM-56 zeolite. Said molecular sieves may further be non-zeolite
molecular sieves such as silicates of varying silica-alumina ratios
(e.g. metallosilicates, titanosilicates), metalloaluminates (e.
g. germaniumaluminates), metallophosphates, aluminophosphates, mnetalloaluminophosphates,
metal integrated silicoaluminophosphates (MeAPSO and ELAPSO), silicoaluminophosphates
(SAPO), gallogermanates and combinations of these.
[0009] CN 1261618A discloses a process for reducing the sulfur
content of a catalytically cracked petroleum fraction, comprising
catalytically cracking a petroleum feed fraction containing organo-sulfur
compounds at elevated temperature in the presence of a cracking
catalyst and a product sulfur reduction catalyst to produce liquid
cracked products of reduced sulfur content. Said product sulfur
reduction catalyst contains a porous molecular sieve containing
a first metal component and a second metal component. Said first
metal component is within the interior pore structure of the molecular
sieve and exists in an oxidation state greater than zero. The second
metal component comprises at least a rare-earth element and is within
the interior pore structure of the molecular sieve. Said first metal
component is a metal selected from the group consisting of elements
of Period 4 and Groups IIB, VB, IIIA and VIII of the periodic table,
especially vanadium, zinc, iron, gallium.
[0010] Since aforesaid catalysts are subjected to drying, calcining
and/or hydrothermal treating without reduction process during the
preparation of them, the metal component contained in aforesaid
catalysts exists all in respective maximum oxidation states.
[0011] CN 1382199A discloses an adsorbent composition, consisting
of a bimetal promoter and a granular carrier, said bimetal promoter
exists essentially in a reduction state in an amount enough to remove
sulfur from cracked gasoline under desulfurization conditions. Said
bimetal promoter is any two or more selected from the group consisting
of cobalt, nickel, iron, manganese, copper, zinc, molybdenum, tungsten,
silver, tin, antimony and vanadium. Said carrier consists of zinc
oxide in combination with any suitable inorganic and organic carrier.
Said inorganic carrier includes silica, silica gel, alumina, clay,
aluminum silicate, silica-alumina, titanium oxide, zirconia, zinc
aluminate, zinc titanate, zinc silicate, calcium aluminate, calcium
silicate, magnesium silicate, magnesium aluminate, magnesium titanate,
synthetic zeolites and/or natural zeolites. The composition is used
as an adsorbent for removing sulfur from cracked gasoline and diesel
fuel, not as a cracking catalyst.
[0012] CA2444461 discloses an equilibrium cracking catalyst and
a method for reducing sulfur content of gasoline fraction during
the process of catalytically cracking. Said equilibrium cracking
catalyst comprises at least one Y-type zeolite and Lewis acid addictive,
wherein said lewis acid is a metal selected from the group consisting
of Ni, Cu, Zn, Ag, Cd, In, Sn, Hg, TI, Pb, Bi, B, Al, Mg, Mn, Ga
or the combination thereof, and said metal is in zero valence state
or is an oxide. The Lewis acid addictive is obtained by drying the
alumina impregnated with the Lewis acid at mild temperature(100
to 150.degree. C.), and calcining at 200 to 850.degree. C. to remove
the anionic portions of the Lewis acid salt. Although it is mentioned
in the application that the metal can be in zero valence state,
it is not suggested how to obtain a catalyst containing metals in
zero valence state from the process.
[0013] An object of the present invention is to provide a novel
molecular sieve-containing catalyst for cracking hydrocarbons, having
higher cracking activity and higher sulfur reduction activity.
[0014] The inventor of the present invention has discovered that,
if a metal. component is introduced into a cracking catalyst in
reduction state, not only the sulfur reduction activity of the cracking
catalyst can be increased, but also, unexpectedly, the cracking
activity of the cracking catalyst can be increased significantly.
[0015] The catalyst according to the present invention comprises
molecular sieve, refractory inorganic oxide, clay and a metal component.
The amount of the molecular sieve is from 1 to 90% by weight, the
refractory inorganic oxide is from 2-80% by weight, the clay is
from 2 to 80% by weight, and the metal component is from 0.1 to
30% by weight calculated as the oxide of said metal having its maximum
valence state, based on the total amount of the catalyst. Said metal
component exists essentially in a reduction state and is one or
more metals selected from the group consisting of metals of Group
IIIA(other than aluminium), and metals of Groups IVA, VA, IB, IIB,
VB, VIB, VIIB, and non-noble metals of Group VIII of the periodic
table.
[0016] The process for preparing the catalyst according to the
present invention comprises contacting the composition comprising
metal-containing component compound, molecular sieve, refractory
inorganic oxide and clay with a reducing gas-containing atmosphere
at enough temperature for enough time so that the metal component
has an average valence state less than its maximum oxidation state.
Said metal component is one or more metals selected from the group
consisting of metals of Group IIIA(other than aluminum), and metals
of Groups IVA, VA, IB, IIB, VB, VIB and VIIB, and non-noble metals
of Group VIII of the periodic table. The amount of each component
is such that the final catalyst comprises, based on the total amount
of the catalyst, from 1 to 90% by weight of the molecular sieve,
from 2 to 80% by weight of the refactory inorganic oxide, from 2
to 80% by weight of the clay, and from 0.1 to 30% by weight of the
metal component, calculated as the oxide of said metal having its
maximum valence state.
[0017] Compared with the catalyst of the prior art, the catalyst
according to the present invention has higher sulfur reduction activity,
and further, unexpectedly, higher cracking activity. For example,
by using the catalyst of the present invention, which contains 30
wt % of MOY-zeolite, 34 wt % of alumina, 35 wt % of kaolin, 1 wt
% of cobalt, calculated as Co.sub.2O.sub.3 in which cobalt has
+1.5 of an average valence state (thereby the ratio value of the
average valence state to maximum valence state of cobalt is 0.5),
(after deactivated by steam-aging at 800.degree. C. for 8 hours,
then reduced), the catalytically cracking of the vacuum gas oil
with a distillation range of 329-550.degree. C. and a sulfur content
of 2.0% by weight was carried out under conditions of a reaction
temperature of 500.degree. C., a WHSV of 16 hr a weight ratio of
catalyst to oil of 4.0 as a result, the conversion was 78.6% by
weight, the sulfur content of gasoline product was only 416.7 mg/l.
However, when a cracking catalyst having the same content of zeolite
but no cobalt and a catalyst having all the same contents of each
component but cobalt only in its maximum valence state(+3 valence)
were used to carry out the catalytic cracking reaction of the same
feedstock oil at the same conditions, only 68.9 wt % and 75.1 wt
% of conversions were obtained respectively, and the sulfur contents
of gasoline products were up to 758.3 mg/l and 670.6 mg/l, respectively.
[0018] Specific Embodiment Modes
[0019] The catalyst according to the present invention contains
from 1 to 90% by weight of the said molecular sieve, from 2 to 80%
by weight of the refractory inorganic oxide, from 2 to 80% by weight
of the clay and from 0.1 to 30% by weight of the said metal component
calculated as the oxide of the metal having its maximum valence
state. Preferably, said molecular sieve is from 10 to 60% by weight,
the refractory inorganic oxide is from 10 to 50% by weight and the
clay is from 20 to 70% by weight, and said metal component is from
0.5 to 20% by, weight, calculated as the oxide of said metal having
its maximum valence state.
[0020] Said reduction state refers to an average valence state
of metal at which the state is zero valence or higher than zero
valence but less than the maximum oxidation state. In the preferred
case, said metal has a ratio value of its average valence state
to the maximum valence state from 0 to 0.95 more preferably from
0.1 to 0.7.
[0021] The maximum valence state of said metal herein refers to
that of said metal able to exist stably in metal oxide afterbeing
oxidized completely. For example, the maximum oxidation state of
non-aluminum metals of Group IIIA of the periodic table is generally
+3 valence (e.g. gallium); the maximum oxidation state of Group
IVA metals is generally +4 valence; the maximum oxidation state
of Group VA metals is generally +5 valence; the maximum oxidation
state of Group I B metals is generally +2 valence (e. g. copper)
or +1 valence (e. g. silver); the maximium oxidation state of Group
IIB metals is generally +2 valence; the maximum oxidation state
of Group V B metals is generally +5 valence; the maximum oxidation
state of Group VIB metals is generally +6 valence; the maximum oxidation
state of Group VIIB metals is generally +4 valence (e.g. manganese)
or +7 valence(e.g. rhenium); the oxidation state of Group VIII non-noble
metals is generally +3 valence (e. g. iron or cobalt) or +2 valence
(e.g. nickel).
[0022] Said average valence state of metal is measured as followed:
[0023] Weighing precisely about 0.4 g of a catalyst and placing
it in the sample cell of TPDIR/O analysis instrument, introducing
a mixed gas of hydrogen and nitrogen, in which the amount of the
hydrogen is 5% by volume, into the sample cell at a hydrogen flow
rate of 20 ml/min, heating the sample cell from room temperature
to 1000.degree. C. at a speed of 10.degree. C./min by means of a
temperature programming procedure to reduce the catalyst in the
cell, then measuring TPR characteristic peaks of the metal component
in the catalysts reduced before and after respectively, and calculating
the average valence state of the metal according to formulae:
.beta..sub.M=.beta..sub.M'-2f(A.sub.1-A)/N
[0024] Wherein .beta..sub.M is an average valence state of the
metal component M in the catalyst; .beta..sub.M' is the maximum
valence state of the metal component in the catalyst; A is an area
of TPR characteristic peak of metal M in the catalyst when the metal
component M is in a reduction state; A.sub.1 is an area of TPR characteristic
peak of metal M in the catalyst when the metal component is in a
maximum oxidation state; N is the content of metal component M in
the catalyst (by mole); f is a correction factor and is measured
as follows: weighing precisely about 6.5 mg of CuO, and placing
it in the sample cell of aforementioned TPD/R/O analysis instrument;
measuring the area K.sub.2 of TPR characteristic peak when CuO has
been completely reduced under the same conditions as those mentioned
above; calculating the hydrogen consumption (by mole) K.sub.1 according
to the stoichiometric number of the reduction reaction; f is a ratio
of the hydrogen consumption to TPR characteristic peak area, i.e.
f=K.sub.1/K.sub.2 and expressed by a unit of mole/area of TPR characteristic
peak.
[0025] Since TPR characteristic peak of each metal has a different
position, thus even though the catalyst contains more than two metal
components, TPR characteristic peak of each metal can also be measured.
[0026] Said metal component is one or more metals selected from
the group consisting of metals of Group IIIA(other than aluminum),
and metals of Groups IVA, VA, IB, IIB, VB, VIB and VIIB, and non-noble
metals of Group VIII of the periodic table. Said metals of Group
IIIA include gallium, indium and thallium. Said metals of Group
IVA include germanium, tin and lead. Said metals of Group VA include
antimony and bismuth. Said metals of Group I B include copper and
silver. Said metals of Group IIB include zinc and cadmium. Said
metals of Group VB include vanadium, niobium and tantalum. Said
metals of Group VIB include chromium, molybdenum and tungsten. Said
metals of Group VIIB include manganese, technetium and rhenium.
Said non-noble metals of Group VIII include iron, cobalt and nickel.
Said metal component is preferably one or more selected from the
group consisting of gallium, germanium, tin, antimony, bismuth,
lead, copper, silver, zinc, cadmium, vanadium, molybdenum, tungsten,
manganese, iron, cobalt and nickel; more preferably is one or more
selected from the group consisting of gallium, tin, copper, silver,
zinc, vanadium, molybdenum, manganese, iron and cobalt.
[0027] Said metal component may exist simultaneously in the molecular
sieve, refractory inorganic oxide and clay, or in any two of the
molecular sieve, refractory inorganic oxide and clay, or even in
any one of the molecular sieve, refractory inorganic oxide and clay.
[0028] In a specific embodiment according to the present invention,
said metal component may exist in the refractory inorganic oxide
and/or clay, especially when said metal component is vanadium, nickel
and/or iron.
[0029] Said molecular sieve is one or more selected from the group
consisting of zeolites and non-zeolite molecular sieves, which are
used as an active component of cracking catalyst. These zeolites
and molecular sieves are well known for one skilled in the art.
[0030] Said zeolite is preferably one or more selected from large
pore size zeolites and intermediate pore size zeolites. Said large
pore size zeolites are those having a pore structure with a ring
pore opening of at least 0.7 nm, such as, one or more selected from
the group consisting of faujasite, L-zeolite, beta zeolite, .OMEGA.-zeolite,
mordenite, ZSM-18 zeolite, especially one or more selected from
the group consisting of Y-zeolite, phosphorus- and/or rare-earth-containing
Y-zeolite, ultra-stable Y-zeolite, phosphorus-and/or rare-earth-containing
ultra-stable Y-zeolite, beta zeolite.
[0031] Said intermediate pore size zeolites are those having a
pore structure with a ring pore opening of higher than 0.56 nm but
less than 0.7 nm, such as one or more selected from the group consisting
of zeolites having a MFI structure (e.g. ZSM-5 zeolite), phosphorus-
and/or rare-earth-containing zeolites having a MFI structure (e.g.
a phosphorus- and/or rare-earth-containing ZSM-5 zeolites, phosphorus-containing
zeolites having a MFI structure as disclosed in CN 1194181A), ZSM-22
zeolite, ZSM-23 zeolite, ZSM-35 zeolite, ZSM-50 zeolite, ZSM-57
zeolite, MCM-22 zeolite, MCM-49 zeolite, MCM-56 zeolite.
[0032] Said non-zeolite molecular sieve refers to one or more molecular
sieves in which part or all of aluminum and/or silicon are substituted
by one or more other elements such as phosphor, titanium, gallium
and germanium. Examples of these molecular sieves include one or
more molecular sieves selected from silicates of varying silica-alumina
ratios(e. g. metallosilicate, titanosilicate), metalloaluminates
(e. g. germaniumaluminates), metallophosphates, aluminophosphates,
metalloaluminophosphates, metal integrated silicoaluminophosphates
(MeAPSO and ELAPSO), silicoaluminophosphates (SAPO), and gallogermanates.
Especially it is one or more selected from the group consisting
of SAPO-17 molecular sieve, SAPO-34 molecular sieve and SAPO-37
molecular sieve.
[0033] Preferably, said molecular sieve is one or more selected
from the group consisting of Y-zeolite, phosphorus- and/or rare-earth-containing
Y-zeolite, ultra-stable Y-zeolite, phosphorus- and/or rare-earth-containing
ultra-stable Y-zeolite, beta zeolite, zeolites having a MFI structure,
phosphorus- and/or rare-earth-containing zeolites having a MFI structure.
[0034] Said refractory inorganic oxide is one or more selected
from the group consisting of refractory inorganic oxides which are
used as a matrix material and a binder component in conventional
cracking catalysts, such as one or more selected from the group
consisting of alumina, silica, amorphous silica-alumina, zirconia,
titanium oxide, boron oxide, and/or oxides of alkaline earth metals.
Preferred is one or more selected from the group consisting of alumina,
silica, amorphous silica-alumina, zirconia, titanium oxide, magnesium
oxide, and calcium oxide. The refractory inorganic oxides are well
known for one skilled in the art.
[0035] Said clay is one or more selected from the group consisting
ofclays used as the active component of cracking catalysts, such
as one or more selected from the group consisting of kaolin, halloysite,
montmorillonite, kieselguhr, endellite, soapstone, reactorite, sepiolite,
attapulgus, hydrotalcite and bentonite. More preferred clay is kaolin.
These clays are well known for-one skilled in the art.
[0036] The catalysts according to the present invention may further
contain a rare earth metal component existing in a form of metal
and/or its compounds. Said rare-earth metal component may exist
simultaneously in the molecular sieve, refractory inorganic oxide
and clay, or in any two of the molecular sieve, refractory inorganic
oxide and clay, or even in any one of the molecular sieve, refractory
inorganic oxide and clay. Said rare earth metal is one or more selected
from the group consisting of lanthanide- and actinide-rare earth
metals, preferably one or more selected from the group consisting
of lanthanum, cerium, praseodymium, neodymium, promethium, samarium,
europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium,
ytterbium, lutetium, more preferably is lanthanum, cerium, rich-lanthanum
norium or rich-cerium norium. Based on the total amount of catalyst,
the amount of said rare-earth metal component is from 0 to 50% by
weight, calculated as oxide, preferably from 0 to 15% by weight.
[0037] The catalyst according to the present invention may further
contain phosphorus component existing in a form of phosphorous compounds,
such as oxides of phosphorus and/or phosphates. Said phosphorus
component may exist simultaneously in the molecular sieve, refractory
inorganic oxide and clay, or in any two of the molecular sieve,
refractory inorganic oxide and clay, or even in any one of the molecular
sieve, refractory inorganic oxide and clay. Based on the total amount
of catalyst, the amount of said phosphors component content is from
0 to 15% by weight, calculated as element phosphorus, preferably
from 0 to 8% by weight.
[0038] In Examples of the present invention, if the rare-earth
component and/or phosphorus component are contained in the molecular
sieve which is used in the preparation of the catalyst, the amount
of said molecular sieve is just that of the rare-earth component
and/or phosphorus component-containing molecular sieve. The amount
of phosphorus component and rare-earth component is neither separately
calculated, nor given.
[0039] In the preparation process of the catalyst according to
this invention, said reducing gas-containing atmosphere refers to
an atmosphere of pure reducing gas or an atmosphere containing reducing
gas and inert gases.
[0040] Examples of said pure reducing gas include one or more gases
selected from the group consisting of hydrogen, carbon monoxide
and hydrocarbons containing 1-5 carbon atoms, preferably include
one or more selected from the group consisting of hydrogen, carbon
monoxide, methane, ethane, propane, butane and its various isomers,
pentane and their isomers.
[0041] Said inert gases refer to gases that do not react with said
composition or metal compounds, such as one or more selected from
the group consisting of Group 0 gases of the periodic table, nitrogen,
carbon dioxide.
[0042] Examples of said atmosphere containing the reducing gas
and inert gases include a mixture of one or more gases selected
from the group consisting of hydrogen, carbon monoxide and hydrocarbons
containing from 1 to 5 carbon atoms and one or more inert gases,
or refinery dry gas.
[0043] In said reducing gas-containing atmosphere, the concentration
of the reducing gas is not particularly limited, as long as the
reducing gas is in an amount enough to reduce said metals. Preferably,
in said reducing gas-containing atmosphere, the amount of the reducing
gas is at least 10% by volume, more preferably 50% by volume.
[0044] Said contact temperature and contact time are high or long
enough to decrease the ratio of the average valence state to the
maximum valence state of said metal component to from 0 to 0.95
preferably from 0.1 to 0.7. In general, said contact temperature
may be from 100.degree. C. to 900.degree. C., preferably from 400
to 700.degree. C., said contact time may be from 0.1 second to 10
hours, preferably from 1 second to 5 hours. Said contact may be
one carried out in static state, that is, said composition is contacted
with a reducing gas-containing atmosphere in a closed vessel. Said
contact may also be one carried out in dynamic state. Namely, said
reducing gas-containing atmosphere is passed through the bed of
said composition. Said contact pressure is not limited. The contact
may be carried out under an atmospheric pressure, and also may be
carried out under a pressure higher than or less than atmospheric
pressure. Said reducing gas-containing atmosphere is used in an
amount no less than 5 ml per gram of catalyst per hour, preferably
no less than 10 ml per gram of catalyst per hour, more preferably
100-2000 ml per gram of catalyst per hour.
[0045] The amount of each component preferably is such that the
final catalyst comprises, based on the total amount of catalyst,
from 10 to 60% by weight of the molecular sieve, from 10 to 50%
by weight of the refractory inorganic oxide, from 20 to 60% by weight
of the clay and from 0.5 to 20% by weight of the metal component,
calculated as the oxide of said metal having its maximum valence
state.
[0046] Said composition containing metal component compound, molecular
sieve, refractory inorganic oxide and clay may be an conventional
cracking catalyst containing metal component, or may be a composition
obtained by introducing metal component compound into the cracking
catalyst having no metal component.
[0047] Methods for preparing said conventional cracking catalysts
containing metal component are well known for one skilled in the
art, which are not further described thereafter.
[0048] The method for introducing metal component compound into
a cracking catalyst containing no metal component is also a conventional
one. For example, said composition containing metal component compound,
molecular sieve, refractory inorganic oxide and clay may be prepared
by introducing metal component into the cracking catalyst containing
no metal component using the following methods.
[0049] Method One
[0050] (1) a). Impregnating molecular sieve, refractory inorganic
oxide, precursor of the refractory inorganic oxide and/or clay with
a solution containing metal component compound, then drying or not
drying the resultant slurry; or b). mixing the molecular sieve,
the refractory inorganic oxide, the precursor of refractory inorganic
oxide and/or the clay with a solution containing said metal component
compound, then drying or not drying the resultant slurry; or c).
mixing physically said metal component compound with the molecular
sieve, the refractory inorganic oxide, the precursor of refractory
inorganic oxide and/or clay; or d). mixing the molecular sieve,
the refractory inorganic oxide, the precursor of refractory inorganic
oxide and/or clay with a solution of said metal component compound,
adding a precipitant used for said metal component compound to the
resultant mixture to precipitate said metal component onto the molecular
sieve, the refractory inorganic oxide, the precursor of refractory
inorganic oxide and/or the clay, then drying or not drying the resultant
solid; or e). mixing the molecular sieve, the refractory inorganic
oxide, the precursor of refractory inorganic oxide and/or the clay
with the solution containing said metal component compound to prepare
a colloid with the obtained slurry; or f). or mixing the molecular
sieve, the refractory inorganic oxide, the precursor of refractory
inorganic oxide and/or the clay and deionized water with the metal
component compound insoluble in water to prepare a colloid with
the obtained slurry, then drying or not drying the resultant colloid,
[0051] (2) slurrying said molecular sieve, the refractory inorganic
oxide, the precursor of refractory inorganic oxide and/or the clay,
or said mixture, or colloid, which have been introduced with metal
component compound, with deionized water and the molecular sieve,
the refractory inorganic oxide, the precursor of the refractory
inorganic oxide and/or the clay, which contain no metal component
compound, to prepare a slurry having a solid content of from 10
to 60% by weight, preferably from 20 to 50% by weight, then drying
the obtained slurry, and then calcining or not calcining the dried
solid.
[0052] Method Two
[0053] Slurrying molecular sieve, refractory inorganic oxide and/or
the precursor of refractory inorganic oxide and clay and deionized
water to prepare a slurry having a solid content of from 10 to 60%
by weight, preferably from 20 to 50% by weight, then drying the
obtained slurry, and then calcining or not calcining the resultant
solid, then impregnating the dried solid with a solution containing
said metal component compound, or mixing said solution of metal
component compound with the dried solid, then drying, calcining
or not calcining the resultant solid.
[0054] Method Three
[0055] Slurrying the molecular sieve, the refractory inorganic
oxide and/or the precursor of refractory inorganic oxide, the clay,
deionized water and said metal component compound to prepare a slurry
having a solid content of from 10 to 50% by weight, preferably from
20 to 50% by weight, then drying the resultant slurry, calcining
or not calcining the dried solid.
[0056] If the catalyst contains further a rare-earth metal component
and/or a phosphorus component, the method above-mentioned may be
used alternatively or additionally to introduce the rare-earth metal
component and/or phosphorus component just by using the rare-earth
compound and/or phosphorous compound to replace the compound of
aforementioned metal component. Said rare-earth metal component
and/or phosphorus component may also be contained in the commercial
molecular sieve per se (such as rare-earth- and/or phosphorus-containing
Y-zeolites or ultra-stable Y-zeolites).
[0057] The methods and conditions for drying the mixture after
the metal component compound has been introduced and for drying
the slurry are well known for one skilled in the art. For example,
the drying method may be air-drying, oven-drying, air-blown drying,
spray drying. Method for drying slurry is preferably spray drying.
Drying temperature may be in the range of from room temperature
to 400.degree. C., preferably from 100 to 350.degree. C. The conditions
of the calcination after the slurry is dried and the calcination
after the metal compound is impregnated are well known for one skilled
in the art. Generally, the calcination temperature after the slurry
is dried and the calcination temperature after the metal compound
is impregnated are all in the range of from 400.degree. C. to 700.degree.
C., preferably from 450.degree. C. to 650.degree. C., and the calcination
time are at least for 0.5 hours, preferably from 0.5 to 100 hours,
more preferably from 0.5 to 10 hours.
[0058] Said precursor of refractory inorganic oxide refers to one
or more selected from substances able to form said refractory inorganic
oxide during the preparation of said cracking catalyst. For example,
the precursor of alumina may be selected from the group consisting
of hydrated alumina (e. g. pseudo-boehmite) and/or alumina-sol.
The precursor of silica may be one or more selected from the group
consisting of silica-sol, silica gel and water glass. The precursor
of amorphous silica-alumina may be one or more selected from the
group consisting of silica-alumina sol, mixtures of silica-sol and
alumina sol, silica-alumina gel. The precursor of other refractory
inorganic oxides may be selected from their hydroxides, e.g. hydroxides
of zirconium, titanium, earth alkali metals, and boric acid.
[0059] Said metal component compound may be water-soluble metal
compounds, also may be water-insoluble or non-soluble metal compounds
such as one or more nitrates, chlorides, hydroxides, oxides of metals
selected from the group consisting of metals of Group IIIA(other
than aluminum), metals of Group IV, VA, IB, IIB, VB, VIB and VIIB,
and non-noble metals of Group VIII of the periodic table. Especially
one or more nitrates, chlorides, hydroxides and oxides of metals
selected from the group consisting of gallium, tin, copper, silver,
zinc, vanadium, molybdenum, manganese, iron, cobalt.
[0060] Said rare-earth metal compound may be water-soluble compounds
of the rare-earth metal, also may be water-insoluble and/or non-soluble
compounds of the rare-earth metal, such as one or more selected
from the group consisting of chlorides, nitrates, hydroxides, oxides
of rare-earth metal.
[0061] Said phosphorous compound may be water-soluble compounds
of said phosphorous, also may be water-insoluble and/or non-soluble
compounds thereof, such as one or more selected from the group consisting
of phosphoric acid, phosphorous acid, ammonium phosphates, alkali-metallophosphates,
oxides of phosphorus, aluminum phosphate.
[0062] The catalyst according to the present invention may be used
alone as FCC catalyst, also may be used as a sulfur reduction additive
in combination with various cracking catalysts. The proportion of
the catalyst of the present invention in the catalyst mixture is
dependent on the sulfur content of feedstock oils and the sulfur
content required for gasoline products. Usually, the proportion
of the catalyst according to the present invention comprises at
least 0.1% by weight of the catalyst mixture, preferably at least
1% by weight, more preferably at least 3% by weight, most preferably
at least 10% by weight. Furthermore, as an additive of the cracking
catalyst, the catalyst according to the present invention may be
further used in combination with other additives, such as, combustion
improver, sulfur transforming catalyst, octane improver and the
like, mixed together with various cracking catalyst.
[0063] The catalyst according to the present invention is used
whether as a main catalyst, or an additive, the operation conditions
are conventional reaction conditions for a cracking process of hydrocarbons,
such as, a reaction temperature of from 400.degree. C. to 700.degree.
C., preferably from 450.degree. C. to 600.degree. C., a WHSV of
from 10 hr.sub.-1 to 120 hr.sub.-1 preferably from 10 hr.sub.-1
to 80 hr.sub.-1 a catalyst-oil weight ratio of from 1 to 20 preferably
from 3 to 15. Also, these may be used in a deep catalytic cracking
process or deep catalytic pyrolysis process.
[0064] The catalyst according to the present invention may be used
as a main catalyst for catalytic cracking of hydrocarbon oils containing
no sulfur in order to increase conversion of hydrocarbon oils. The
catalyst according to the present invention may also be used as
a main catalyst or additive for catalytically cracking of sulfur-containing
hydrocarbon oils in order to increase the conversion of hydrocarbon
oils and simultaneously reduce the sulfur of cracked products. These
hydrocarbon oils may be one or more selected from the group consisting
of petroleum oils and various fractions containing sulfur or no
sulfur, such as, atmospheric residues, vacuum residuum, vacuum gas
oils, atmospheric gas oils, straight gas oils, propane-deasphalted
light/heavy oils, and coking gas oils, as well as hydrotreated atmospheric
residues, vacuum residuum, vacuum gas oils, atmospheric gas oils.
[0065] Following examples are provided to illustrate further the
present invention.
[0066] Unless stated otherwise, kaolin used is a product having
a solid content of 76% by weight, available from Suzhou Kaolin Corporation,
Jiangsu Province, China; pseudo-boehmite used is a product having
a solid content of 62% by weight, available from Zibo 501 Factory,
Shangdong Province, China; alumina-sol used is a product having
a Al.sub.2O.sub.3 content of 21% by weight, available from ChiLu
Catalyst Factory, Shangdong Province, China; silica-sol used is
a product having a SiO.sub.2 content of 27% by weight, available
from ChiLu Catalyst Factory, Shangdong Province, China; metal component
compounds used are all in chemical grade.
[0067] Zeolite in fresh cracking catalysts has a very high cracking
activity. In practical industrial production, the catalyst is used
circularly. After the fresh catalyst is used for a period of time,
the catalyst will reach a relatively stable activity level. Thus,
the true activity of the catalyst should be estimated by using a
catalyst deactivated to an activity level corresponding to that
an equilibrium catalyst has. This may be realized by aging hydrothermally
the catalyst to deactivate the zeolite therein. In following examples
of the present invention, there is a step for aging catalyst before
the reduction step. The step added is for ease in evaluating the
activity of catalyst without any meaning to show that the aging
step is required for the process of the preparation of the catalyst
provided in the present invention. In fact, the aging step is not
necessary in industrial production.
EXAMPLE 1
[0068] The example is provided to illustrate the catalyst according
to the present invention and a method for preparing the same.
[0069] Kaolin and pseudo-boehmite were mixed with a 30 wt % aqueous
cobalt nitrate solution, added thereto deionized water and then
mixed homogeneously. A 36.5 vol % hydrochloric acid was slowly added
into the resultant mixture under fast stirring to adjust pH value
of the slurry to 2.0 then added thereto a phosphorus- and rare-earth-containing
HY-zeolite (Commercial trademark MOY, having a unit cell size of
24.59A, a Na.sub.2O content of 1.5% by weight, a phosphorus content
of 1.2% by weight, calculated as element phosphorus, and a rare-earth
oxide content of 8.5% by weight, wherein a lanthanum oxide content
was 4.5% by weight, a ceria content was 1.1% by weight, and other
rare-earth oxides content was 2.9% by weight, produced by Chilu
Catalyst Factory, Shangdong, China), and then mixed homogeneously.
Deionized water was used in such an amount that the slurry was obtained
having a solid content of 25% by weight. Kaolin, pseudo-boehmite,
MOY-zeolite and the aqueous solution of cobalt nitrate were used
in amounts such that the weight ratio between kaolin (on the weight
of dry basis), Al.sub.2O.sub.3 MOY-zeolite (on the weight of dry
basis) and Co.sub.2O.sub.3 was reached to 35.0:34.0:30.0:1.0.
[0070] The obtained slurry was dried by spraying at a temperature
of 150.degree. C., then the resultant solid was calcined at 550.degree.
C. for 1 hour, and then aged at 800.degree. C. with 100% steam for
6 hours. A fixed bed reduction reactor was filled with 200 g of
the obtained catalyst, and hydrogen was passed through the reactor
at a temperature of 400.degree. C. in a flow of 1000 ml/minute to
contact said solid for 0.5 hour, then the reactor was cooled to
room temperature, the reduced solid was discharged to obtain catalyst
C1 according to the present invention. The composition of catalyst
C1 and the type, distribution, average valence state and the ratio
of the average valence state to the maximum valence state of metal
components are shown in Table 1. The catalyst compositions shown
in table 1 are obtained by calculation, and metal component contents
are calculated respectively as the oxide having its maximum oxidation
state of said metal component.
EXAMPLE 2
[0071] This example is provided to illustrate the catalyst according
to the present invention and a method for preparing the same.
[0072] Catalyst C2 according to the present invention was obtained
by using the same method as that in Example 1 for preparing catalyst,
except that the contact temperature of said solid with hydrogen
was 500.degree. C. and the contact time was 3 hours. The composition
of Catalyst C2 and the type, distribution, average valence state
and ratio of the average valence state to the maximum valence state
of metal component are shown in Table 1.
EXAMPLE 3
[0073] This example is provided to illustrate the catalyst according
to the present invention and a method for preparing the same.
[0074] A kaolin containing 2.78% by weight of Co.sub.2O.sub.3 was
obtained by impregnating 3.0 kg(on the weight of dry basis) kaolin
with 3.65 kg of a 10 wt % aqueous cobalt nitrate hexahydrate solution,
then the impregnated kaolin was dried in an oven at 120.degree.
C., then calcined at 600.degree. C. for 1 hour.
[0075] Catalyst C3 according to the present invention was obtained
by using the same method as that in Example 1 for preparing catalyst,
except that the kaolin containing 2.78 wt % of Co.sub.2O.sub.3 was
used to replace said kaolin in Example 1 and no aqueous cobalt nitrate
solution was added. The composition of Catalyst C3 and the type,
distribution, average valence state and ratio of the average valence
state to the maximum valence state of metal component are shown
in Table 1.
EXAMPLE 4
[0076] This example is provided to illustrate the catalyst according
to the present invention and a method for preparing the same.
[0077] A MOY-zeolite containing 3.23% by weight of Co.sub.2O.sub.3
was obtained by impregnating MOY-zeolite with a 10 wt % aqueous
cobalt nitrate hexahydrate solution in a ratio by weight of solution
to MOY-zeolite(on the weight of dry basis) of 1.42:1 then the impregnated
MOY-zeolite being dried in an oven at 120.degree. C., then calcined
at 550.degree. C. for 1 hour.
[0078] Kaolin, pseudo-boehmite and deionized water were mixed homogeneously.
A 36.5 vol % hydrochloric acid was slowly added into the resultant
mixture under fast stirring to adjust pH value of the slurry to
2.0 then added thereto the MOY-zeolite containing 3.23% by weight
of Co.sub.2O.sub.3 and then mixed homogeneously. Deionized water
was used in such an amount that the slurry was obtained having a
solid content of 25% by weight. Kaolin, pseudo-boehmite and MOY-zeolite
containing 3.23% by weight of Co.sub.2O.sub.3 were used in amounts
such that the weight ratio between kaolin (on the weight of dry
basis), Al.sub.2O.sub.3 MOY-zeolite (on the weight of dry basis)
and Co.sub.2O.sub.3 was 35.0:34.0:30.0:1.0.
[0079] The obtained slurry was dried by spraying at a temperature
of 150.degree. C., then calcined at 550.degree. C. for 1 hour, and
then aged at 800.degree. C. with 100% steam for 6 hours. A fixed
bed reduction reactor was filled with 200 g of the obtained catalyst,
and hydrogen was passed through the reactor at a temperature of
400.degree. C. in a flow of 1000 ml/minute to contact said solid
for 0.5 hour, then the reactor was cooled to room temperature, the
reduced solid was discharged to obtain catalyst C4 according to
the present invention. The composition of catalyst C4 and the type,
distribution, average valence state and ratio of the average valence
state to the maximum valence state of metal component are shown
in Table 1.
COMPARATIVE EXAMPLE 1
[0080] The Comparative Example is provided to illustrate a reference
catalyst containing no metal component and a method for preparing
the same.
[0081] The catalyst was prepared by the same method as that in
Example 1 except that no aqueous cobalt nitrate solution was added
and the procedure of contacting the solid with hydrogen was not
carried out in the fixed-bed reactor, and kaolin, pseudo-boehmite
and MOY-zeolite were used in amounts such that the ratio between
kaolin (on the weight of dry basis), pseudo-boehmite (on the weight
of dry basis) and MOY-zeolite (on the weight of dry basis) was 35.0:35.0:30.0.
Reference catalyst CB1 obtained has the same contents of both the
molecular sieve and kaolin and no metal component. The composition
of CB1is shown in Table 1.
COMPARATIVE EXAMPLE 2
[0082] The Comparative Example is provided to illustrate a reference
catalyst containing the metal component in a maximum oxidation state
and a method for preparing the same.
[0083] Reference catalyst CB2 was obtained by using the same method
as that in Example 1 for preparing catalyst, except that the procedure
of contacting solid with hydrogen was not carried out in the fixed-bed
reactor. The composition of CB2 is shown in Table 1.
COMPARATIVE EXAMPLE 3
[0084] The Comparative Example is provided to illustrate a reference
catalyst containing the metal component in a maximum oxidation state
and a method for preparing the same.
[0085] Reference catalyst CB3 was obtained by using the same method
as that in Example 3 for preparing catalyst, except that the procedure
of contacting the solid with hydrogen was not carried out in the
fixed-bed reactor. The composition of CB3 is shown in Table 1.
1 TABLE 1 Example No. Comp. Comp. Comp. 1 2 3 4 Ex. 1 Exp. 2 Exp.
3 Catalyst No. C1 C2 C3 C4 CB1 CB2 CB3 Type of molecular MOY MOY
MOY MOY MOY MOY MOY sieve Molecular sieve 30.0 30.0 30.0 30.0 30.0
30.0 30.0 content, wt % Type of refractory Al.sub.2O.sub.3 Al.sub.2O.sub.3
Al.sub.2O.sub.3 Al.sub.2O.sub.3 Al.sub.2O.sub.3 Al.sub.2O.sub.3
Al.sub.2O.sub.3 inorganic oxide Content of 34.0 34.0 34.0 34.0 35.0
34.0 34.0 refractory inorganic oxide, wt % Type of clay Kaolin Kaolin
Kaolin Kaolin Kaolin Kaolin Kaolin Clay content, wt % 35.0 35.0
35.0 35.0 35.0 35.0 35.0 Type of metal Co Co Co Co -- Co Co component
Content of metal 1.0 1.0 1.0 1.0 -- 1.0 1.0 component, wt % Average
valence +1.5 0 +1.5 +1.5 -- +3 +3 state of metal component Ratio
of an 0.5 0 0.5 0.5 -- 1 1 average valence state to the maximum
valence state of metal component Distribution of Homogeneous Homogeneous
Homogeneous Homogeneous -- Homogeneous Homogeneous metal component
distribution distribution distribution distribution -- distribution
distribution in the in the in the clay in the in the in the clay
catalyst catalyst molecular catalyst sieve
EXAMPLE 5
[0086] The example is provided to illustrate the catalyst according
to the present invention and a method for preparing the same.
[0087] (1) A kaolin containing 3.1% by weight of ZnO was obtained
by impregnating 3.0 kg (on the weight of dry basis) kaolin with
3.19 kg of a 7.0 wt % aqueous zinc nitrate solution, and the impregnated
kaolin being dried in an oven at 120.degree. C. and calcined at
600.degree. C. for 1 hour.
[0088] (2) 500 g NaY (a Na.sub.2O content of 11% by weight, a silica-alumina
ratio of 5.6 produced by Changlin Catalyst Factory) was exchanged
with 10 liters of a 0.15 mol/liter aqueous ammonium chloride solution
at 60.degree. C. for 1 hour, then filtered and the filter cake obtained
was calcined at 550.degree. C. for 2 hours. By repeating the above-mentioned
steps of exchanging and calcining twice, HY-zeolite having 0.3 wt
% of sodium oxide content was obtained.
[0089] (3) Catalyst C5 according to the present invention was obtained
by using the same method as that in Example 1 for preparing catalyst,
except that said ZnO-containing kaolin prepared in step (1) was
used to replace said kaolin in Example 1; no aqueous cobalt nitrate
solution was added; HY-zeolite prepared in (2) was used to replace
MOY; said ZnO-containing kaolin, pseudo-boehmite, HY-zeolite were
used in amounts such that the weight ratio between kaolin (on the
weight of dry basis), Al.sub.2O.sub.3 HY-zeolite (on the weight
of dry basis) and ZnO was 25.0:119.2:55.0:0.8; the reductive atmosphere
was a mixed gas of hydrogen and carbon monoxide, which contained
50% by volume of hydrogen and 50% by volume of carbon monoxide,
the flow of the mixed gas was 2000 ml/minute, the contact temperature
of said solid with the mixed gas was 800.degree. C., the contact
time was 3 hours. The comnposition of Catalyst C5 and the type,
distribution, average valence state and ratio of the average valence
state to the maximum valence state of metal component are shown
in Table 2.
EXAMPLE 6
[0090] This example is provided to illustrate the catalyst according
to the present invention and a method for preparing the same.
[0091] A kaolin containing 3.1 wt % of Fe.sub.2O.sub.3 was obtained
by impregnating 3.0 kg (on the weight of dry basis) kaolin with
2.90 kg of a 10 wt % aqueous ferric nitrate solution, then the impregnated
kaolin was dried in an oven at 120.degree. C., and then calcined
at 600.degree. C. for 2 hour.
[0092] Catalyst C6 according to the present invention was obtained
by using the same method as that in Example 1 for preparing catalyst,
except that aforesaid Fe.sub.2O.sub.3-containing kaolin prepared
in step (1) was used to replace said kaolin in Example 1 no aqueous
cobalt nitrate solution was added; HY-zeolite prepared by (2) in
Example 5 was used to replace MOY; said Fe.sub.2O.sub.3-containing
kaolin, pseudo-boehmite, HY-zeolitic were used in amounts such that
the weight ratio between kaolin (on the weight of dry basis), Al.sub.2O.sub.3
HY-zeolite (on the weight of dry basis) and Fe.sub.2O.sub.3 was
25.0:19.2:55.0:0.8; the reductive atmosphere was a mixed gas of
hydrogen and carbon monoxide, which contained 50% by volume of hydrogen
and 50% by volume of carbon monoxide, the flow of the mixed gas
was 1200 ml/minute, the contact temperature of said solid with the
mixed gas was 800.degree. C., the contact time was 0.5 hours. The
composition of Catalyst C6 and the type, distribution, average valence
state and ratio of the average valence state to the maximum valence
state of metal component are shown in Table 2.
[0093] EXAMPLE 7
[0094] The example is provided to illustrate the catalyst according
to the present invention and a method for preparing of the same.
[0095] A kaolin containing 8.68 wt % of CuO was obtained by impregnating
a mixture of 2.925 kg(the weight of dry basis) kaolin and 0.075
kg TiO.sub.2 with 3.36 kg of a 20.0 wt % aqueous copper nitrate
solution, then the impregnated solid was dried in an oven at 120.degree.
C., then calcined at 600.degree. C. for 2 hour.
[0096] Catalyst C7 according to the present invention was obtained
by using the same method as that in Example 1 for preparing catalyst,
except that the aforementioned CuO-containing kaolinwas used to
replace said kaolin in Example 1; no aqueous cobalt nitrate solution
was added; ultra-stable Y-zeolite (commercial trademark DASY, having
a unit cell size of 24.45 a Na2O content of 1.0 wt %, produced
by Chilu Catalyst Factory) was used to replace MOY; CuO-containing
kaolin, pseudo-boehmite, DASY-zeolite were used in amounts such
that the weight ratio of kaolin (on the weight of dry basis), TiO2
Al.sub.2O.sub.3 DASY-zeolite (on the weight of dry basis) and CuO
was 39.0:1.0:26.2:30:3.8; the reductive atmosphere was a mixed gas
of hydrogen and carbon monoxide, which contained 50% by volume of
hydrogenand 50% by volume of carbon monoxide, the flow of the mixed
gas was 1000 ml/minute, the contact temperature of said solid and
the mixed gas was 400.degree. C., the contact time was 0.5 hours.
The composition of Catalyst C7 and the type, distribution, average
valence state and ratio of the average valence state to the maximum
valence state of metal component are shown in Table 2.
EXAMPLE 8
[0097] The example is provided to illustrate the catalyst according
to the present invention and a method for preparing the same.
[0098] A kaolin containing 2.63 wt % of MnO.sub.2 was obtained
by impregnating 3.0 kg (on the weight of dry basis) kaolin with
3.34 kg of a 5.0 wt % aqueous manganese nitrate solution, then the
impregnated solid was dried in an oven at 120.degree. C., then calcined
at 550.degree. C. for 2 hour.
[0099] Catalyst C8 according to the present invention was obtained
by using the same method as that in Example 1 for preparing catalyst,
except that MnO.sub.2-containing kaolin mentioned above was used
to replace said kaolin in Example 1; no aqueous cobalt nitrate solution
was added; DASY-zeolite and phosphorus- and rare-earth-containing
zeolite having MFI structure (commercial trademark ZRP-1 having
a phosphorus content of 2.0 wt % based on element phosphorus, a
rare-earth oxide content of 1.0 wt %, wherein the lanthanum oxide
content was 0.53 wt %, ceria content was 0.13 wt %, the other rare-earth
oxides content was 0.34 wt %, the Na.sub.2O content was less than
0.1 wt %, and a molar ratio of SiO.sub.2 to Al.sub.2O.sub.3 was
60 produced by Chilu Catalyst Factory) were used to replace MOY;
MnO.sub.2-containing kaolin, pseudo-boehmite, DASY-zeolitic and
ZRP-1 zeolite were used in amounts such that the weight ratio of
kaolin (on the weight of dry basis), Al.sub.2O.sub.3 and DASY-zeolite
(on the weight of dry basis), ZRP-1 zeolite (on the weight of dry
basis) and MnO.sub.2 was to 37.0:27.0:30.0:5.0:1.0; the reductive
atmosphere was a mixed gas of hydrogen and propane, which contained
80 vol % of hydrogen and 20 vol % of propane, the flow of the mixed
gas was 1500 ml/minute, the contact temperature of said solid with
the mixed gas was 500.degree. C. and the contact time was 1 hour.
The composition of Catalyst C8 and the type, distribution, average
valence state and ratio of the average valence state to the maximum
valence state of metal component are shown in Table 2.
2 TABLE 2 Example No. 5 6 7 8 Catalyst No. C5 C6 C7 C8 Type of
molecular HY HY DASY DASY + sieve ZRP Content of molecular 55.0
55.0 30.0 35.0 sieve, wt % Type of refractory Al.sub.2O.sub.3 Al.sub.2O.sub.3
Al.sub.2O.sub.3 + TiO.sub.2 Al.sub.2O.sub.3 inorganic oxide Content
of refractory 19.2 19.2 27.2 27.0 inorganic oxide, wt % Type of
clay kaolin kaolin kaolin kaolin Content of clay, wt % 25.0 25.0
39.0 37.0 Type of metal Zn Fe Cu Mn component Content of metal 0.8
0.8 3.8 1.0 component, wt % Average valence state +1.4 +2.0 +0.6
+1.5 of metal component Ratio value of the average 0.70 0.67 0.3
0.38 valence state to the maximum valence state of metal component
Distribution of metal Homogeneous Homogeneous Dispersed in Homogeneous
component distribution in distribution in the clay and distribution
in the clay the clay refractory the clay inorganic oxide
EXAMPLE 9
[0100] This example is provided to illustrate the catalyst according
to the present invention and a method for preparing the same.
[0101] A mixture of 3.0 kg (on the weight of dry basis) kaolin
and 0.5 kg (on the weight of dry basis) kieselguhr (a solid content
of 85.0 wt %, produced by Huali Kieselguhr Factory Chenzhou, Zhejiang
Province) was impregnated with 3.22 kg of a 5.0 wt % aqueous ammonium
molybdate ((NH.sub.4).sub.6Mo.sub.7O.sub.24. 4H.sub.2O) solution,
then impregnated solid was dried in an oven at 120.degree. C, then
the dried solid was impregnated with 2.41 kg of a 2.0 wt % aqueous
silver nitrate solution, and then the impregnated solid was dried
in an oven at 120.degree. C., and calcined at 600.degree. C. for
2 hours, a mixture of kaolin and kieselguhr containing 3.58 wt %
of MoO.sub.3 and 0.90 wt % of Ag.sub.2O was obtained.
[0102] Catalyst C9 according to the present invention was obtained
by using the same method as that in Example 1 for preparing catalyst,
except that MoO.sub.3- and Ag.sub.2O-containing mixture of kaolin
and kieselguhr mentioned above was used to replace said kaolin in
example 1; no aqueous cobalt nitrate solution was added, the MoO.sub.3-
and Ag.sub.2O-containing mixture of kaolin and kieselguhr, pseudo-boehmite,
MOY-zeolite were used in amounts such that the weight ratio between
the mixture of kaolin and kieselguhr (on the weight of dry basis),
Al.sub.2O.sub.3 MOY-zeolite (on the weight of dry basis), MoO.sub.3
and Ag.sub.2O was 32.0:21.5:45.0:1.2:0.3; the reductive atmosphere
was a mixed gas of nitrogen and hydrogen, which contained 50 vol
% of hydrogen, the flow of the mixed gas was 2500 ml/minute, the
contact temperature of said solid with the mixed gas was 650.degree.
C., the contact time was 1 hour. The composition of Catalyst C9
and the type, distribution, average valence state and ratio of the
average valence state to the maximum valence state of metal component
are shown in Table 3.
EXAMPLE 10
[0103] This example is provided to illustrate the catalyst according
to the present invention and a method for preparing the same.
[0104] A mixture of 3.0 kg (on the weight of dry basis) kaolin
and 0.08 kg magnesium oxide was impregnated under stirring with
2.97 kg of a 2.0 wt % aqueous ammonium metavanadate (NH.sub.4VO.sub.3)
solution, then the resultant slurry was dried in an oven at 120.degree.
C. and the resultant slurry was calcined at 550.degree. C. for 2
hours, the kaolin containing 2.46 wt % of MgO and 1.48 wt % of V.sub.2O.sub.5
was obtained.
[0105] Catalyst C10 according to the present invention was obtained
by using the same method as that in Example 1 for preparing catalyst,
except that the MgO and V.sub.2O.sub.5-containing kaolin mentioned
above was used to replace said kaolin in Example 1; no aqueous cobalt
nitrate solution was added; DASY-zeolite (the same specification
as that in Example 7) was used to replace MOY-zeolite; MgO- and
V.sub.2O.sub.5-containing kaolin, pseudo-boehmite, DASY-zeolite
were used in amounts such that the weight ratio between kaolin (on
the weight of dry basis), magnesium oxide, Al.sub.2O.sub.3 DASY-zeolite
(on the weight of dry basis) and V.sub.2O.sub.5 was 39.0:1.0:24.4:35.0:0.6;
the contact temperature of said solid with hydrogen was 550.degree.
C., the flow of hydrogen was 1000 ml/minute, the contact time was
1 hour. The composition of Catalyst C10 and the type, distribution,
average valence state and ratio of the average valence state to
the maximum valence state of metal component are shown in Table
3.
EXAMPLE 11
[0106] The example is provided to illustrate the catalyst according
to the present invention and a method for preparing the same.
[0107] A mixture of 3.0 kg (on the weight of dry basis) kaolin
and 0.86 kg (on the weight of dry basis) pseudo-boehmite was impregnated
with 2.74 kg of a 40 wt % aqueous gallium chloride solution, then
the impregnated solid was dried in an oven at 120.degree. C., then
calcined at 600.degree. C. for 2 hour to obtain a mixture of kaolin
and alumina, containing 13.1 wt % of Ga.sub.2O.sub.3.
[0108] The Ga.sub.2O.sub.3-containing mixture of kaolin and alumina,
silica-sol and deionized water were mixed homogeneously, DASY zeolite
and ZRP-1 zeolite were added to the resultant mixture, then mixed
homogeneously. Deionized water was used in an amount so as to obtain
a slurry having a solid content of 25% by weight. The Ga.sub.2O.sub.3-containing
mixture of kaolin and alumina, silica-sol, ultra-stable Y-zeolite
and the zeolite having MFI structure were used in amounts such that
the weight ratio between kaolin (on the weight of dry basis), alumina,
silica, DASY-zeolite (on the weight of dry basis), ZRP-1 zeolite
(on the weight of dry basis) and Ga.sub.2O.sub.3 was 35.0:10;13.2;30:5:6.8.
[0109] The obtained slurry was dried by spraying at a temperature
of 150.degree. C., then the resultant solid was calcined at 550.degree.
C. for 2 hours, and then aged with 100% steam at 800.degree. C.
for 8 hours. 200 g of the obtained solid was filled in a fixed bed
reduction reactor, hydrogen was passed through the reactor at a
temperature of 600.degree. C. in a flow of 3000 ml/minute to allow
said solid contact with hydrogen for 2 hours, then the reactor was
cooled to room temperature, the reduced solid was discharged to
obtain Catalyst C11 according to the present invention. The composition
of Catalyst C11 and the type, distribution, average valence state
and ratio of the average valence state to the maximum valence state
of the metal component are shown in Table 3.
EXAMPLE 12
[0110] This example is provided to illustrate the catalyst according
to the present invention and a method for preparing the same.
[0111] A mixture of kaolin and silica, which contained 4.0 wt %
of SnO.sub.2 was obtained by mixing homogeneously 3.15 kg of a
6.0 wt % aqueous stannous chloride (SnCl.sub.2) solution, 0.6 kg
(on the weight of dry basis) of silica-sol and 3.0 kg (on the weight
of dry basis) of kaolin, and drying in an oven the obtained slurry
at 120.degree. C., then calcining the resultant solid at 550.degree.
C. for 3 hours.
[0112] The SnO.sub.2-containing mixture of kaolin and silica, alumina-sol
and deionized water were mixed homogeneously, DASY-zeolite and ZRP-1
zeolite were added to the resultant mixture, and then mixed homogeneously.
Deionized water was used in such an amount that the slurry was obtained
having a solid content of 25% by weight. The SnO.sub.2-containing
mixture of kaolin and silica, alumina-sol, DASY and ZRP-1 zeolite
were used in amounts such that the weight ratio between kaolin (on
the weight of dry basis), alumina, silica, DASY-zeolite (on the
weight of dry basis), ZRP-1 zeolite (on the weight of dry basis)
and SnO.sub.2 was 40.0:20.0:8.0:25:5:2.0. The obtained slurry was
dried by spraying at a temperature of 150.degree. C., then the resultant
solid was calcined at 550.degree. C. for 2 hours, then aged with
100% steam at 800.degree. C. for 8 hours.
[0113] 200 g of the obtained solid was filed in a fixed bed reduction
reactor, hydrogen was passed through the reactor at a temperature
of 650.degree. C. in a flow of 1000 ml/minute to allow said solid
contact with hydrogen for 1 hour, then the reactor was cooled to
room temperature, then the reduced solid was taken down to obtain
Catalyst C12 according to the present invention. The composition
of Catalyst C12 and the type, distribution, average valence state
and ratio of the average valence state to the maximum valence state
of metal component are shown in Table 3.
3 TABLE 3 Example No. 9 10 11 12 Catalyst No. C9 C10 C11 C12 Type
of molecular MOY DASY DASY + DASY + sieve ZRP-1 ZRP-1 Content of
molecular 45.0 35.0 35.0 30.0 sieve, wt % Type of refractory Al.sub.2O.sub.3
Al.sub.2O.sub.3 + MgO Al.sub.2O.sub.3 - SiO.sub.2 Al.sub.2O.sub.3
+ SiO.sub.2 inorganic oxide Content of refractory 21.5 25.4 23.2
28.0 inorganic oxide, wt % Type of clay Kaolin + Kaolin Kaolin Kaolin
kieselguhr Clay content, wt % 32.0 39.0 35.0 40.0 Type of metal
Mo, Ag V Ga Sn component Content of metal Mo 1.2 0.6 6.8 2.0 component,
wt % Ag 0.3 Average valence Mo +3.0 +2.3 +1.5 +2.2 state of metal
Ag 0 component Ratio value of the Mo 0.5 0.46 0.5 0.55 average valence
state Ag 0 to the maximum valence state of metal component Distribution
of metal Homogeneous Homogeneous Dispersed in Dispersed in component
distribution in distribution in clay and clay and the clay clay
and alumina silica magnesium oxide
EXAMPLES FROM 13 to 24
[0114] Following examples are provided to illustrate the catalytic
performances of the catalysts according to the present invention.
[0115] In a small scale of fixed bed reaction apparatus filled
with 4.0 g of catalyst, the catalytically cracking of the sulfur-containing
vacuum gas oil with a distillation range of 329-550.degree. C. as
shown in Table 4 was carried out by using the catalysts from C1-C12
respectively. The reaction conditions and reaction results are shown
in Tables from 5-7 respectively. The sulfur content of cracked products
was measured by gas chromatography-atomic emission spectrometry,
using HP 6890GC-G2350A AED gas chromatography-atomic emission spectroscopy
meter.
[0116] Wherein, catalyst-oil ratio refers to a weight-ratio of
a catalyst to said feedstock oil.
COMPARATIVE EXAMPLES 4 to 6
[0117] Following Comparative Examples are provided to illustrated
catalytic performances of reference catalysts.
[0118] The catalytically cracking of the same feedstock oil was
carried out by the method according to Example 13 except that Reference
Catalyst CB1 CB2 and CB3 were used respectively, the reaction conditions
and reaction results are shown in Table 5.
4 TABLE 4 Atmospheric Vacuum Name of feedstock oil residue gas
oil Density (20.degree. C.), g/cm.sup.3 0.8906 0.9154 Viscosit ,
mm.sup.2/sec 50.degree. C. -- 34.14 100.degree. C. 24.84 6.96 Asphaltenes,
wt % 0.8 0.0 Conradson carbon 4.3 0.18 residue content, wt % S.
wt % 0.13 2.0 Distillation range, .degree. C. IBP 282 329 10% 370
378 50% 553 436 90% -- 501 95% -- 518 FBP -- 550
[0119]
5 TABLE 5 Example No. Comp. Comp. Comp. 13 14 15 16 Exp. 4 Exp.
5 Exp. 6 Catalyst No. C1 C2 C3 C4 CB1 CB2 CB3 Reaction temperature,
.degree. C. 500 500 500 500 500 500 500 WHSV, hour.sup.-1 16 16
16 16 16 16 16 Catalyst-oil ratio 4 4 4 4 4 4 4 Conversion, wt %
78.6 76.8 78 76.4 68.9 75.1 74 Yield of product, wt % Dry gas 2
2.5 1.9 2.4 2.2 1.8 1.9 LPG 15.9 15.0 15.8 14.9 12.6 15.9 14.8 Gasoline
52 50.3 51.8 50.2 45.2 47.9 47.5 Diesel oil 14.3 15.3 15.2 15.0
14.8 13.8 14.2 Heavy oil 7.1 7.9 6.8 8.6 16.3 11.1 11.8 Coke 8.7
9 8.5 8.9 8.9 9.5 9.8 Sulfur content of gasoline, mg/l 416.7 475.6
403.5 482.2 758.3 670.6 681.2
[0120] Results in Table 5 show that, as compared with the catalyst
having the same zeolite content but no metal component and the catalyst
having the same content of each component but said metal component
only in maximum oxidation state, the cracking activities of the
catalysts according to the present invention are increased greatly,
and the sulfur reduction activities are also increased greatly.
6 TABLE 6 Example No. 17 18 19 20 Catalyst No. C5 C6 C7 C8 Reaction
temperature, .degree. C. 480 480 480 480 WHSV, hour.sup.-1 16 16
16 16 Catalyst-oil ratio 5 5 5 5 Conversion, wt % 83.2 82.1 75.1
80.6 Yield of product, wt % Dry gas 2.3 22 2 2.1 LPG 13.2 14.8 10.5
17.4 Gasoline 58.6 56.2 54 51.8 Diesel oil 6.3 8.1 11.9 13.3 Heavy
oil 10.5 9.8 13 6.1 Coke 9.1 8.9 8.6 9.3 Sulfur content 530.5 562
421.3 454.2 of gasoline, mg/l
[0121]
7 TABLE 7 Example No. 21 22 23 24 Catalyst No. C9 C10 C11 C12 Reaction
520 520 520 520 temperature, .degree. C. WHSV, hour.sup.-1 16 16
16 16 Catalyst-oil ratio 3.5 3.5 3.5 3.5 Conversion, wt % 83.2 75.6
74.5 67.9 Yield of product, wt % -- -- -- -- Dry gas 2.5 2.3 1.9
2.2 LPG 14.8 13.5 15 13.6 Gasoline 56.6 50.2 48.2 43.5 Diesel 9.3
11.2 13.2 13.2 Heavy oil 7.5 13.2 12.3 18.9 Coke 9.3 9.6 9.4 8.6
Sulfur content of 415.2 423.6 520.1 489.3 gasoline, mg/l
EXAMPLES 25 to 26
[0122] Following examples are provided to illustrate the catalytic
performances of the catalysts according to the present invention.
[0123] A commercial cracking catalyst (produced by Chilu Catalyst
Factory) with commercial trademark MLC500 was aged at 800.degree.
C. with 100% steam for 8 hours, then mixed with the Catalyst C1
and Catalyst C8 respectively to obtain a mixed catalyst containing
20 wt % of C1 and 80 wt % of MLC500 and a mixed catalyst containing
5 wt % of C8 and 95 wt % of MLC500. In a small scale of the fixed
bed reaction apparatus, the catalytically cracking of the mixed
oil which contained 20 wt % of atmospheric residuum and 80 wt %
of vacuum gas oil as shown in Table 4 was carried out by using the
two mixed catalysts respectively. The reaction conditions and reaction
results are shown in Table 8.
COMPARATIVE EXAMPLE 7
[0124] Following examples are provided to illustrate the case where
commercial catalyst MLC500 was used alone.
[0125] The catalytically cracking of the same feedstock oil was
carried out by the same method as that in Examples 25 and 26 except
that the catalyst used was a MLC500 which had been aged under the
same condition. Reaction results are shown in Table 8.
8 TABLE 8 Example No. 25 26 Comp. Exp. 7 Catalyst 20% C1 + 5% C8
+ 80% 95% MLC500 MLC500 MLC500 Reaction temperature, .degree. C.
500 500 500 WHSV, hour.sup.-1 20 20 20 Catalyst-oil ratio 6.0 6.0
6.0 Conversion, wt % 75.3 72.1 70.3 Yield of product, wt % Dry as
1.8 1.7 1.6 LPG 21.1 18.7 18.9 Gasoline 45.4 44.9 43.5 Diesel oil
17.5 19.9 20.8 Heavy oil 7.2 8.0 8.9 Coke 7.0 6.8 6.3 Sulfur content
of 626.5 725.4 856.3 gasoline, mg/l
[0126] The results in Table 8 show that when the catalyst according
to the present invention is used as a additive for the catalytically
cracking catalyst, the result of substantially reducing sulfur of
gasolines can be obtained similarly. The product distribution is
also improved and conversion is increased significantly.
[0127] The present application claims priority under 35 U.S.C.
.sctn. 119 of Chinese Patent Application No. 03137906.0 filed on
May 30 2003. The disclosure of the foregoing application is expressly
incorporated by reference herein in its entirety. |