JPS649046B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention applies to sulfur-containing hydrocarbon feedstocks.
and in the exhaust gas of the regenerator.
Significantly reduces carbon monoxide and sulfur oxide emissions
A cycle characterized by reducing
The contact cracking method used in the fluid contact cracking method
Relating to a medium composition. Hydrocarbons in the reaction zone
During the cracking of the so-called "coke"
Due to the adhesion of carbonaceous deposits,
The cracking catalyst, which has become inactive, will stop the reaction.
Continuously removed from the zone. This kind of anti-
Spent catalyst from reaction zone can be stripped
carbonaceous deposits, i.e. hydrocarbons, from the catalyst.
passed through the stripping zone.
and then passed through a regeneration zone where the coke is
Combustion in oxygen-containing gas produces carbon monoxide and carbon dioxide.
By making carbon oxide, it is possible to remove the
the catalyst by removing hard carbonaceous deposits.
activity is restored. Thermally regenerated catalyst
is then continuously returned to the reactor and the cycle continues.
Repeated. In catalytic cracking (catalytic cracking)
Conversion of carbon monoxide to carbon dioxide in the green zone
Problems arise from complete combustion and the flue gas in the regeneration zone
The problem is that significant amounts of carbon monoxide remain in the gas.
There is a problem. Release of carbon monoxide to the environment is desirable
Apart from the fact that the regeneration zone flue gas
Carbon monoxide and residual oxygen tend to react and
combustion occurs in the ducts and flues in the plant.
and excessive temperatures can damage such structures.
cause damage to. In addition, high sulfur feedstocks, i.e. organic sulfurized
Petroleum hydrocarbon fractions containing compounds are
When fed to the catalytic cracking device, the catalyst
The coke deposited on top contains sulfur. Coking
This process is achieved through the regeneration of deactivated and deactivated catalysts.
The arc is burned from the catalyst surface. and this combustion
In the process, the sulfur present is in small proportion
is converted to sulfur dioxide with sulfur trioxide of
In this way the regeneration zone flue gas effluent fluid
contained within. Crackkin high sulfur feedstock
sulfur oxide emissions are approximately
It is often in the 1200ppm range. for the release of carbon monoxide, and of certain substances.
Pollution control standards have been set for
But other emissions like sulfur oxides especially sulfur dioxide
Control standards for physical goods are also expected to be established in the near future.
be done. In the end, the review regarding oil cracking equipment
Various combustion products and
Much attention has been paid to reducing particulate emissions.
It is being said. To reduce such emissions
The method chosen depends on the activity and
effective without compromising selectivity
It is necessary. one of the unwanted emissions
The morphology may be affected by other issues, such as increases in certain emissions or
or replace increased operating costs.
Both are necessary. Taking these into account, the reduction in emissions
A highly desirable method for reducing
is in any of the new cracking devices,
Catalytic activity, stability and wear resistance under normal cracking conditions
Carbon monoxide and sulfur oxidation while maintaining wear resistance
A chemical modified to minimize emissions of both
The purpose is to use a racking catalyst. When it comes to carbon monoxide emissions, it is generally
The metal in the cracking catalyst is removed and the cracking catalyst is removed.
Cracking metal-containing raw materials in the presence of media
Although it is thought that there is a problem with
South African Patent No. 7924/72 and subsequent issues.
Corresponding U.S. Pat. No. 3,909,392 (1975) (later
(considered in more detail) within the regeneration zone.
Combustion catalysts or promoters are used with King catalysts.
Discloses that it will be used. This combustion catalyst or
The accelerator is also a metal bar, mesh in the combustion zone.
or screens, and fluidizable metal compounds.
oxides of substances, especially powdered fiber metals, e.g.
Contains iron oxide, manganese dioxide and rare earth oxides.
These are added to the catalyst feedstock or recycled.
It is used only in containers for biological organs. Belgian special
No. 826266 (1975) requires at least 20 atomic numbers.
Metallic carbon monoxide oxidation promoting catalyst and physics
Contains a catalytic cracking catalyst formulated in the U.S.
A method very similar to the method of Patent No. 3909392
Disclosed. This Belgian patent is a useful oxidant
As a stimulant, B, B and no of the periodic table
Metals selected from the Shi tribe, especially platinum, palladium
rhodium, molybdenum, tungsten, copper,
Chromium, Nickel, Manganese, Cobalt, Banerjee
um, iron, cerium, iteribium and urani
It says um. Additionally, U.S. Patent No. 3808121
The number refers to the carbon monoxide oxidation catalyst held in the regeneration zone.
Discloses the regeneration of cracking catalysts in the presence of catalysts
There is. Dutch patent number 7412423 is based on periodic table number 7412423.
Metals from the fifth and sixth periods of the group, rhenium and
and a small number of compounds selected from the group consisting of
At least one metal component should be 100 ppm based on the total catalyst.
Kratskin, which contains less (calculated as metal) amount
the cracking catalyst in the flue gas from the cracking catalyst.
resulting in a particularly significant reduction in carbon monoxide content;
It shows. This patent also states that the sodium form
created by and ion-exchanged with ammonium ions.
and then a molecular sieve type impregnated with rare earth metals.
discloses a cracking catalyst. Furthermore, regarding the release of sulfur oxides, flue gas
Various methods for treating the
is scrubbing, chemical absorption, neutralization and chemical reaction
Alternatively, conversion of sulfur oxides is considered, but
All these methods for removal are extensive and
Requires expensive auxiliary equipment and is therefore difficult to operate and install.
increases both the cost and cost of US Patent No.
The method described in No. 3699037
Regarding the amount of sulfur deposited on the catalyst during the
at least a stoichiometric amount of calcium or mag
We are considering adding a nesim compound. child
The additive substance is one that reacts with sulfur oxides.
and then playback under finely divided conditions.
The compound is identified as a specific substance in the flue gas stream of the zone.
ejected from the picking cycle. like this
Continuous addition of substances clearly increases operating costs
let Similarly, U.S. Patent No. 3030300 (1962)
and No. 3030314 (1962) is a moving bed kratskin
boron, alkali gold,
one or more of the genus and alkaline earth metals
Contact methods involving continuous addition of compounds
King method is disclosed. Addition of these compounds
In addition, boron, alkali metals and alkali
one or more compounds of lithium earth metals and silica
Has an adhesive protective coating of brightener consisting of
Siliceous catalyst particles with a microporous catalytically active core
resistant to impact fracture and surface abrasion.
catalyst particles with increased resistance to U.S. Patent No. 3,835,031 (1974)
Cycle to reduce the release of sulfur oxides in gases
Discloses a fluid contact cracking method using
Ru. This method uses a silica-alumina matrix.
consisting of a molecular sieve in a glass containing Group A metal oxides.
carried out using a catalyst impregnated with one or more
It will be done. U.S. Patent No. 3388077 (1968), No. 3409390
No. (1968) and No. 3849343 (1974) are monoacid
Hazardous exhaust gas fluids containing carbon dioxide and sulfur oxides
discloses a method for converting This method is
The above gaseous fluid is transferred to a catalyst complex on a porous refractory support material.
compounds, catalytically active metal components (e.g. platinum metals) and
and calcium, barium and strontium
contact with an alkaline earth component selected from the group consisting of
consists of doing. However, the method of the present invention is not disclosed anywhere.
Not yet. The present invention provides carbon monoxide in the flue gas of the regeneration zone.
Cycles that reduce the release of sulfur oxides and sulfur oxides
Provides catalyst compositions for fluidized catalytic cracking
It is something to do. In some embodiments
also substantially eliminates carbon monoxide in the regeneration zone.
Provides total combustion and also reaction zone and regeneration zone
is circulated to the stripping zone before being returned to the
solid particles produced during combustion as described above.
heat is absorbed. Such solid particles are
Sieve type cracking catalyst and metallic reactant?
and also amorphous cracking catalyst, charcoal
Substantially inert solids and hydrogen cracking
and a metallic promoter. alternative method
As such, metallic accelerators should be confined within the regeneration zone.
may exist. The metallic promoter and/or metallic reactant is
Molecular sieve type cracking catalyst, amorphous cracking catalyst
Formulated in King catalyst and substantially inert solids
and the cracking process
Can be cycled through the cycle. Such a combination
is a specific process during the cracking process cycle.
performed either before or after the support is introduced.
It can be done. This cracking process
In the regeneration zone, solid particles are
definite metal- and sulfur-containing compounds are formed;
and the sulfur-containing gas exits the stripping zone.
Conditions are adopted such that it is taken out. Using the catalyst composition according to the invention, organic sulfur
A hydrocarbon feedstock containing compounds is present in the reaction zone.
Molecular sieve type cracking contact under fluidized conditions
Renewable fluidization homogeneous or heterogeneous
Even solid particles are cracked and the cracks are
King catalyst is accompanied by sulfur-containing carbonaceous deposits
A cyclical fluidized catalytic converter that is deactivated
The tracking method is improved. This fluidized solid particle
then the gaseous stripping zone effluent
and passed to the regeneration zone. the reproduction
In the zone, it is stripped and deactivated.
The cracking catalyst is an oxygen-containing gas fluid and
The strip is heated by contacting it with a metallic oxidation promoter.
and deactivated cracking catalyst.
Burns trippy sulfur-containing carbonaceous deposits
In particular, it is regenerated with high activity. This results in
Carbon monoxide, carbon dioxide and sulfur oxides are produced
be done. Flow containing regenerated cracking catalyst
solid particles are separated from the effluent flue gas in the regeneration zone.
and recycled to the reaction zone. The improvement in the present invention is that in the flue gas of the regeneration zone
Reduces carbon monoxide and sulfur oxide emissions
This improvement consists of solid particles, (1)
Contains crystalline aluminosilicate distributed throughout
Molecular sieve consisting of a cracking catalyst matrix
(2) Reaction with sulfur oxide
metal- and sulfur-containing compounds in the solid particles.
solid particles consisting of a metallic reactant that produces a substance.
Using stripping gas including steam
using a stripped and deactivated clip.
The racking catalyst is treated with a metallic oxidation promoter (carbon monoxide).
and for the oxidation of sulfur oxides),
Metal- and sulfur-containing compounds in solid particles are
be regenerated at a regeneration temperature range that is
In the regeneration zone within the oxygen-containing regeneration gas fluid, molecular
Flue gas containing oxygen is removed from the regeneration zone.
by providing sufficient oxygen to
achieved. The solid particles are preferably
It also contains metallic accelerators. The metal promoter can be recycled
Exist only within the zone or contact cluster
in solid particles during the picking process cycle.
Can be cycled. Kuratu, a molecular sieve type cracking catalyst
The King catalyst matrix is preferably made of silicon.
Mosquito, alumina, zirconia, titania, magnesia
At least one selected from A, Tria, and Boria.
A combination of two substances, more preferably
is silica-alumina. This cracking touch
The medium matrix preferably has a weight of about 10 to about 65
% by weight, more preferably from about 25 to about 60% by weight.
alumina, and preferably about 35 to about 90% by weight
%, more preferably from about 35 to about 70% by weight.
rica, and preferably from about 0.5 to about 50% by weight,
More preferably about 5 to about 50% crystallinity by weight
Contains aluminosilicate. This molecular sieve type
The cracking catalyst preferably has a concentration of about 10 to about
99.999% by weight, more preferably about 30 to about
99.995% by weight, and most preferably about 90 to
Consists of approximately 99.995% solid particles by weight. Metallic promoters have an atomic number greater than or equal to 20
a first metal, preferably B, B of the periodic table;
selected from the group consisting of and - group, and more preferably
Preferably, the fifth and sixth periods of groups of the periodic table.
From the period, from vanadium, silver and rhenium.
most preferably selected from the group of
5th and 6th period of the group and rhenium
Ideally selected from the group consisting of platinum and para
at least one selected from the group consisting of
First metals, their compounds and mixtures thereof
chosen from a group of things. Metallic reactants are preferred.
Preferably sodium, magnesium, and calcium
strontium, barium, scandium,
titanium, chromium, molybdenum, manga
iron, cobalt, nickel, antimony, copper,
Selected from zinc, cadmium, lead and rare earth metals
more preferably sodium, magnesium
calcium, strontium, barium, sulfur
Candium, titanium, chromium, molybdenum
manganese, cobalt, nickel, copper, zinc,
Cadmium, antimony, lead and rare earth metals?
most preferably sodium, magnetic
sium, calcium, strontium, barium
chromium, manganese, copper, zinc, cadmium
and rare earth metals, and ideally
contains sodium, magnesium, manganese and
at least one second selected from the group consisting of copper;
metals, their compounds and their mixtures?
selected from the group consisting of The metallic reactant is metallic.
a second metal different from the first metal in the promoter;
nothing. Metallic promoters and metallic reactants are
release of carbon monoxide and sulfur oxides in flue gases.
present in average amounts sufficient to reduce
Ru. The metal is ruthenium, rhodium, palladium
osmium, iridium, platinum, silver and resin.
selected from the group consisting of
is about 0.1 ppb of the solid particles, calculated as the metal content.
0.1% by weight, more preferably about 0.1ppb
about 50ppm, and most preferably about 0.1ppm.
The average level is in the range of approximately 10 ppm. banaji
There are metals selected from the group consisting of aluminum and copper.
If the metal content is calculated as solid particles,
Preferably from about 10 ppm to about 10% by weight of
Preferably about 50 ppm 0.1% by weight, and most preferably
Preferably an average in the range of about 50ppm to about 250ppm
level. When iron is present, this iron
is calculated as iron content, preferably of solid particles
about 50 ppm to about 5% by weight, more preferably about
0.1% to about 1% by weight, and most preferably
levels ranging from about 0.3% to about 0.8% by weight.
It is le. Magnesium, zinc, calcium,
Domium, manganese, strontium, barium
from the group consisting of scandium, scandium and cobalt
If the metal of choice is present, this metal is gold.
of solid particles, preferably about
20 ppm to about 7% by weight, more preferably about
0.01% to about 5% by weight, and most preferably
or about 0.01% to about 0.5% by weight.
Average level. Chromium, antimony or lead
When present, this metal is
Calculated, preferably about 10 ppm or more of solid particles
Not about 1% by weight, more preferably not about 0.01% by weight
about 0.1% by weight, and most preferably about 0.01% by weight
% to about 250 ppm.
When sodium is present, this
The solid particles preferably contain approximately
0.6% to about 3% by weight, more preferably
about 0.8% to about 2% by weight, and most preferably
or in the range of about 0.85% to about 1.5% by weight.
level. When titanium is present, this
This is calculated as the titanium content of the solid particles.
Preferably about 10 ppm to about 10% by weight, more preferably
preferably about 0.5% to about 1% by weight, and
Most preferably from about 0.5% to about 0.8% by weight
It's a range of levels. When rare earth metals are present
, this is calculated as the metal content and the solid particles
preferably from about 0.2% to about 10% by weight,
More preferably about 2% to about 6% by weight, and
and most preferably from about 2% to about 4% by weight.
The level ranges from . When nickel exists
, this is calculated as the nickel fraction, and the solid particle
Preferably from about 10 ppm to about 10% by weight of
preferably from about 50 ppm to about 0.5% by weight, and
most preferably from about 50 ppm to about 0.1% by weight.
It's a range of levels. in the solid particles in the catalyst composition according to the invention.
Some of the individual solids are metallic promoters and metals.
the average amount of at least one of the reactants in the solid;
It may be contained in a larger amount. However, that
individual solids such as
and metallic reactants at the average levels stated above.
Sea urchin, low in metallic accelerators and metallic reactants.
and the other in said solid particles containing a smaller amount of one or the other.
shall be mixed with the individual solids. The stripped and deactivated catalyst is a solid
Stable from metallic reactants and sulfur oxides in particles
range in which metal- and sulfur-containing compounds are formed.
Regenerated at ambient regeneration temperature. Regeneration temperature is preferred
is about 565.6℃ (1050〓) to about 787.8℃ (1450〓)
〓), and more preferably about 637.8°C (1180
〓) to about 732.2℃ (1350〓).
The hydrocarbon feedstock consists of metals in solid particles and
The sulfur-containing compound reacts to form the metal in the metallic reactant.
Crats at reaction temperatures in the range that produces metal sulfides.
King. This cracking reaction temperature is
Preferably about 454.4℃ (850〓) or about 648.9℃
(1200〓), more preferably about 465.6℃ (870〓)
to 593.3℃ (1100〓). Stoli
Possible deposits include steam-containing gases and gold.
The metal sulfide in the metal reactant reacts with water and becomes sulfurized.
Inert at strip temperatures that produce hydrogen gas
is stripped from the sexualized catalyst. this strike
The ripping temperature is preferably about 454.4°C (850°C
〓) to about 648.9℃ (1200〓), more preferably
is about 465.6℃ (870〓) to about 593.3℃ (1100〓)
is within the range of supplied to the stripping zone
Stiffness against molecular sieve-type cracking catalysts
The weight ratio of the arms is preferably from about 0.0005 to about
0.025, more preferably about 0.0015 to about 0.0125
is within the range of The flue gas in the regeneration zone is
The desired phenomenon of reduced gas emissions is achieved.
Preferably at least 0.01 volume of oxygen
% by volume, more preferably at least 0.5% by volume
include. In one embodiment of the invention, metallic
At least one of the promoter and the metallic reactant is
It is blended into a small sieve type cracking catalyst.
In such cases, metallic accelerators and metallic
At least one of the reactants is crystalline aluminosilica
Cate or molecular sieve type cracking catalyst
Contains in Trix. Other aspects of the invention
In some cases, the solid particles are further added to the hydrocarbon feedstock.
solids that are substantially inert to cracking of materials and
selected from the group consisting of amorphous cracking catalysts
Contains at least one substance and promotes metallicity
At least one of the agent and the metallic reactant is
It is incorporated into substances such as Still other aspects of the present invention
In some cases, the use of metallic accelerators and metallic reactants
at least one is itself solid in the solid particle
It is. Metallic accelerator or metallic reactant or the like
Both include the cracking reaction zone and the stripping reaction zone.
The catalytic converter consists of a processing zone and a regeneration zone.
either external or internal to the king process cycle.
In either case, it can be incorporated into solid particles. Catalyst
When incorporated during the racking process cycle.
In cases where metallic accelerators and metallic reactants are
at least one gold in solid, liquid or gas form
In metallic promoters and/or metallic reactants
oil- or water-soluble of the metal(s);
As a catalytic or dispersible compound, it can be used as a fluid catalyst catalyst.
Introduced during the racking process cycle,
and can be incorporated into solid particles at that location.
Ru. Such compounds are preferably metal diketo
nate, metal carbonyl, metallocene, 2 or
20 carbon atom metal olefin complex
metal acetylene complex alkyl
Or arylphosphine metal complex
carbon atoms and metal carbon atoms having 1 to 20 carbon atoms.
selected from the group consisting of carbonate salts. This kind of transformation
A more preferred compound is platinum acetylacetate.
It is Tonate. According to the present invention, the compressor used in fluidized catalytic conversion
Improved regeneration of cracking catalysts, cracking
The catalyst is damaged due to the deposition of sulfur-containing coke on its surface.
The sulfur-containing hydrocarbon feed is deactivated by
Improved conversion of feedstock and cracking contact
Carbon monoxide and
A reduction in sulfur oxide emissions is achieved. To the present invention
The solid particles of the composition are molecular sieve type crackers.
These are cracking catalysts.
zones, stripping zones and regeneration zones
through the cracking process cycle consisting of
so that they circulate in a well-distributed physical unity with each other.
It is surrounded. Depending on usage conditions, the flue gas in the regeneration zone may
resulting in a reduction of carbon monoxide and sulfur oxides in the
Ru. The cracking catalyst in the composition of the invention, gold
Metallic promoters and metallic reactants have separate required
Has a function. Crutzking catalyst is Crutzkin
metallic promoters, while metallic promoters
and metallic reagents for cracking reactions.
are virtually inert and under the conditions of use.
For catalytic conversion, there are few, if any,
Does not exhibit any harmful effects. For combustion of carbon monoxide
may suitably serve as a metallic promoter.
All metals and their compounds are
oxidation of carbon monoxide to carbon dioxide in the tank.
Indicates mediating action. Sulfur acids in the flue gas of the regeneration zone
Regarding chemical reduction, solid particles are
absorbs sulfur oxides. Molecular sieve type kuratu
King catalysts themselves often absorb sulfur oxides.
Useful as an adhesive. Metallic accelerators are sulfur oxides
or oxidation of sulfur oxides in metal compounds.
showed a mediating effect, and the metallic reactant was adsorbed.
Reacts with sulfur oxides to form metals and
Forms sulfur-containing compounds, especially metal sulfates.
Such metal- and sulfur-containing compounds can be recycled
If stable under the operating conditions in the zone, this
creates reaction zones and stripes on the surface of solid particles.
It is transported to the Tuping zone, where it is returned to the
separated as sulfur-containing gases, especially hydrogen sulfide.
Ru. Carbon monoxide and sulfur in the flue gas of the regeneration zone
The activity that reduces the release of yellow oxides is
Useful as a metal in promoters or metallic reactants
Within these types of metals obtained may vary depending on the metal.
Ru. Similarly, in metallic promoters or metallic reactants
Many of the specific metals that can serve as
in metallic accelerators or metallic reactants, respectively.
When compared to certain other metals that may be used,
or when used under changing conditions.
does not necessarily produce equivalent results. The solid particles in the composition of the invention are finely divided
and these are suitable forms for fluidization.
such as about 20 microns or more.
Average particle size ranging from below to about 150 microns
has. Suitable cracking catalyst matrix
contains silica and/or alumina.
be. Other refractory metal oxides can be used.
and their use is effective under selected conditions.
limited only by their ability to be played
Ru. Similar clay-enriched alumina mixtures
It can be used for. A preferred catalyst is zeola
Same as crystalline aluminosilicate or crystalline aluminosilicate
It was mixed with the “molecular sieve” known as
Contains a combination of silica and alumina. Appropriate
Cracking catalysts are effective under selected conditions
The catalyst is limited only by its ability to be regenerated into
to substantially increase the cracking activity of
Contains a sufficient amount of crystalline aluminosilicate.
nothing. This crystalline aluminosilicate is usually
at least about 2:1, such as from about 2 to about 12:1,
Preferably from about 4 to about 6:1 silica to aluminum.
It has a molar ratio of n. Large proportions of silica, e.g.
For example, about 35% to about 90% by weight silica and about 10% by weight silica.
Silica-based with approximately 65% alumina by weight
cracking catalysts are preferred. This way
The final catalyst is in a physical form that can be fluidized.
Any suitable catalyst can be used as long as a suitable catalyst is provided.
methods, such as fine grinding, cojelling, etc.
It can be manufactured by. Suitable molecular sieves include hojiasite, chabasite,
X-type and Y-type aluminosilicates
materials, as well as ultra-stabilized macroporous crystalline alumino
Natural and synthetic aluminum, such as silicate materials
Contains both nosilicate substances. For example, silica
Those mixed with alumina are petroleum cracking
of the molecular sieve giving the catalyst and new final catalyst particles
The content preferably ranges from about 0.5 to about 50% by weight.
It is appropriate to set it within the range of about 5% to about 50%.
be. An equivalent amount of molecular sieve cracking catalyst is about 1
may contain small amounts of crystalline material, such as %. crystal
Aluminosilicates are usually in the sodium form
available or manufactured by Next this nato
Lithium components are usually hydrogen ions, ammonium
Hydrogen precursors such as ions, or calcium
strontium, barium, and cerium
lanthanium, neodyminium and natural
Polyvalent metals including rare earth elements and mixtures thereof
By exchanging ions with
In small amounts, generally less than about 0.30% by weight
reduced. Crystalline substances that can be used are for catalyst production,
Under high temperature conditions in hydrocarbon processes and catalyst regeneration
can maintain their pore structure. The crystalline aluminum
Nosilicate is a uniform gas of very small size.
It has a pore structure, and the cross-sectional diameter of those pores is about 6
no more than about 20 angstroms, preferably no more than about 10 angstroms
The size ranges from approximately 15 angstroms. Catalytic cracking of heavy mineral oil fractions
is a high-performance engine used in spark-ignition internal combustion engines.
Desirable fuel production such as carbon-gasoline fuel
of the major refining operations used in the conversion of crude oil to
There is one. The “fluidized” catalytic conversion process
The explanation is that a high molecular weight hydrocarbon liquid or vapor is
In a fluidized bed reactor or extended riser reactor
Either finely divided thermal solid catalyst
the catalyst-hydrocarbon mixture;
products, typically motor gasoline and distillate fuels
Desirable degree to low molecular weight hydrocarbons present in
Flow for a sufficient period of time to cause degree cracking.
Flow maintained at high temperatures in a dispersed or dispersed state
This is a contact cracking method. Suitable hydrocarbons for cracking process
The feed is generally above the boiling range of gasoline, e.g.
For example, about 204.4℃ (400〓) to about 648.9℃ (1200〓)
〓) and usually boils within the range of about 454.4℃
(800〓) to approximately 648.9℃ (1200〓)
cracked by temperature. supplies like this
is widely used in light gas oil, heavy gas oil,
gas oil, reduced pressure gas oil, kerosene
oil, decant oil, residue fraction, reduced crude oil and
and cycles drawn from either of these.
Oil or similar oil, tar sands
Appropriate oil extracted from natural gas, synthetic oil, coal liquefaction, etc.
higher than the gasoline range, such as
fractions of various mineral oils that boil at low temperatures.
include. Such fractions can be used alone or
They can be used in any desired combination. The catalyst composition according to the invention can be used in any conventional
Can also be used in contact cracking method.
However, at least a substantial amount of hydrocarbon conversion is possible.
A highly active system used at relatively high space velocities.
Catalyzed dilute phase transport line or riser
– Fluid contacting carried out in reactor systems
Can be used advantageously in cracking systems
Ru. Cracking occurs essentially in the riser reactor.
Exclusively carried out, the next rich catalyst bed is
It is not used for hunting. riser club
Typical pumping is used for gas oil conversion.
In certain cases, the total
The feed throughput or volume ratio is from about 1 to about 3.
It can change to This conversion level is about 40 to 110
Weight% can vary, and about 60% by weight
or more, e.g. between about 60 and 90% by weight
That is advantageous. Conversion is the process of converting lighter substances or
Approximately 221.1°C (430°C) at atmospheric pressure due to coke formation
〓) is the rate of decrease in weight of boiling hydrocarbons.
Taste. Overall for oil in riser reactor
The weight ratio of the cracking catalyst is determined by the flow ratio of the dispersion.
Approximately 0.0160~0.320g/cm ³ (approximately 1 to 20 pounds/ft ³ )
to have a density in the range of about 2 to about 20
May vary within a range. Preferably against oil
The catalyst ratio ranges from about 3 to about 20, preferably about 3.
is maintained within a range of about 7. riser reactor
Fluidization speed of approximately 3.05 to 30.5 m/sec (approximately 10 to 100 m/s)
ft/sec). The riser reactor
generally has a length to average diameter ratio of about 25.
Ru. For the production of typical naphtha products,
The bottom mixing temperature in the iser reactor is controlled by the oil supply
Approximately 537.8℃ (1000〓) or approx.
It is advantageous to maintain it at 593.3℃ (1100〓),
And in this way the top outlet temperature is about 510.0℃
(950〓). Cracking residue
(resids) and synthetic fuels, substantially
Higher temperatures will be required. spilled oil
To quickly separate spent catalyst from steam
Under these conditions, including the preparation of
The contact time between the oils is kept very short.
Dew. The contact time in the riser reactor is generally approximately
within the range of 1 to about 15 seconds, and preferably
is in the range of about 3 seconds to about 10 seconds. short tangent
Most of the hydrocarbons are at the beginning of the contact time.
occur in increments, and undesired secondary reactions
This is preferable because it can be removed. This means fewer codes.
Higher product yields and selectivity including
This is particularly important if it is to be expressed. The short contact time between catalyst particles and oil vapor is
This can be achieved by various means. For example, catalyst
is the lower or bottom length of the riser
Note at one or more points along
can be entered. Similarly, the oil feed
Inject at all points along the length of the bottom of the reactor
can be done. Also about the new recirculating supply fluid
different injection points may be used. for this purpose
In the bottom of the riser reactor, the oil feed is optimally
Obtain extremely short effective contact times leading to conversion
up to approximately 80% of the total riser length.
may include. When a rich catalyst bed is used,
contact particles and/or oxygen in the zone of the dense bed.
Preparations for direct injection of oil supplies are similar.
can be done. The conversion conditions stated above apply to spark-ignited internal combustion engines.
Intended for the production of gasoline as fuel for gin
However, an overview of this process is
fuel, diesel fuel, heating oil and chemical raw materials
materials, such as olefins and aromatics.
To allow maximum production of heavy hydrocarbon products such as
can be changed appropriately to In this contact process some non-volatile carbon
A substance, or “yoke,” is deposited on the catalyst particles.
Ru. Coke generally contains a small amount of hydrogen, e.g.
A highly concentrated aroma containing approximately 10% hydrogen by weight.
Consists of aromatic hydrocarbons. Hydrocarbon feedstock is organic
When containing sulfur compounds, this coke also
Contains sulfur. When coke forms on the catalyst, the coke
Catalyst activity against racking and gasoline
Selectivity of catalyst for producing rend feedstock disappears
do. The catalyst particles are then subjected to a suitable regeneration process.
By removing most of this coke,
and restore most of their original abilities.
can. Spent catalyst from oil conversion reactor is transferred to regenerator
They are stripped before entering. fluidized bed contact
The stripping container used in the king device is
Officially, it is essentially about 454.4℃ (850〓) or
Maintain the conversion reactor temperature at approximately 648.9°C (1200°C)
and preferably about 465.6℃
(870〓) or more will be maintained. preferred
A good stripping gas is steam;
Nitrogen containing steam or other steam-containing
Active or flue gases may be used as well. Applicable
The stripping gas is vaporized from the used conversion catalyst.
Suitable for virtually complete removal of generated compounds
Generally at least about 0.704Kg/cm ² (10Ib/
in ² ), preferably about 2.46Kg/cm ² (35 lb/in ² )
Introduced at gauge pressure. The method described above does not involve any ordinary cracking
Can be used with media regeneration systems, but at least
Also includes one concentrated bed and at least one dilute phase zone.
Advantageously used with playback systems that include
It is. Stripped used catalyst particles
is passed through a suitable line exiting the stripping container.
can be introduced into the thick bed section of the regeneration vessel. Enter
The mouth can be opened from the bottom or from the side.
but preferably at the top of the fluidization zone of the dense bed.
The closer the better. The inlet is similarly catalytic, but restricted
Substantially spent regeneration gas and
It may be the top of the regenerator that is first contacted. Catalyst regeneration is carried out using molecular oxygen-containing gases such as air.
by burning off coke deposits from the catalyst surface.
It will be achieved. Many regeneration technologies are commercially implemented
These have been used to remove coke to a certain degree.
There is a corresponding significant recovery of catalyst activity.
As coke is progressively removed from the catalyst,
Removal of the remaining coke becomes very difficult and
In fact, an intermediate level of recovered catalytic activity can be achieved over time.
It is accepted as a financial compromise. To burn off the coke deposits from the catalyst, a large amount of
Requires oxygen or air. This is the disclosed invention
oxidation of coke, including but not limited to
is characterized in a simplified manner as the oxidation of carbon.
can be expressed by the following chemical formula:
can be done. (a) C+O ₂ →CO ₂ (b) 2C+O ₂ →2CO (c) 2CO＋O ₂ →2CO ₂ Both reactions (a) and (b) have a catalyst temperature of about 565.6
In the range of ℃ (1050〓) to 787.8℃ (1450〓)
Occurs under typical catalyst regeneration conditions in some cases;
gas when regenerating the catalyst at temperatures in this range.
- Typical of solid state chemistry. Effect of increasing temperature
increases the burning rate of carbon and removes carbon from catalyst particles.
This results in a more complete removal of base or coke.
Ru. As an increase in combustion rate is accompanied by an increase in heat production,
If sufficient free or molecular oxygen is present,
In some cases, a gas phase reaction (c) may occur. This latter
The reaction is initiated and promoted by free radicals and
catalytic action is exerted. Burns off sulfur-containing coke deposits from the catalyst
Similarly, sulfur oxides are produced. And this
Combustion is not limited by the invention disclosed herein.
Although not determined, it is represented by the following chemical formula:
can be done. (d) S (in coke) + O ₂ →SO ₂ (e) S.O. ₂ +1/2O ₂ S.O. ₃ Reactions (d) and (e) are also typical cracking
Occurs under catalyst regeneration conditions. Reaction (d) is fast, but the reaction
(e) is relatively slow. Reaction (e) is a catalyst for reaction (c) above.
Catalytic action is provided by any catalyst that provides action.
may be given. Molecular sieves adsorb sulfur oxides,
Therefore, reaction (e) is the reaction of crackkin in the solid particles of the present invention.
can occur on catalysts. Other components of the solid particles are
Similarly, sulfur oxides can be adsorbed. The trioxide obtained
Sulfur is then added to a suitable metal, especially in a metallic reactant.
Metal sulfur reacts with metal oxides and is stable in solid particles.
Produces acid salts. Solid particles are trapped in the flue gas in the regeneration zone.
The metal in this solid particle when separated from the
Sulfate is recycled to the reaction zone. Do it like this
The sulfur is removed from the flue gaseous sulfur oxides in the regeneration zone.
will be prevented from being emitted as These sulfates are known as cracking reaction zones.
remains on the solid particles as they pass through the
The metal of the metallic reactant is
Converted to sulfide and possibly hydrogen sulfide.
Steam-containing strips in the stripping zone
When stripping with ping gas, sulfur is converted into sulfurized water.
The flow of the stripping zone is
Comes out in the fluid. This metallic reactant is
the next pass through the regeneration zone.
used again for reaction with sulfur oxides.
can be done. Hydrogen sulfide then stritupine
recovered along with the cracking products from the gas zone.
separated into elemental sulfur by conventional means.
can be transformed. The invention disclosed herein is not limited hereto.
However, these reactions are as follows:
I think it can be summarized as follows. Regenerator MxO+SO ₂ +1/2O ₂ →MxO＋SO ₃ →MxSO _Four Reactor MxSO _Four +4H ₂ →MxS＋4H ₂ O → MxO＋H ₂ S＋
3H ₂ O stripper MxS+H ₂ O → MxO＋H ₂ S Here, x is the metallic reaction when combined with oxygen.
The acidity of oxide ions relative to the oxidation state of the metal in the agent
It is the ratio of the state of These reactions are carried out according to the method of the present invention.
Molecular sieve type cracking catalyst, metallic promotion
and metallic reactants. minutes
High degree of cracking activity normally present in small sieve catalysts
Whether metallic promoter or metallic reactant
remain substantially unaffected by the presence of
and therefore the expected feedstock conversion and
Racked product yield carbon monoxide and sulfur
This is achieved with a reduction in yellow oxide emissions. Metallic accelerators are limited to the regeneration zone.
It can be a solid. This metallic accelerator or gold
Genus-reactive agents or both of these can be used as molecular sieves as well.
type of cracking catalyst or other support.
It is a finely divided powder-like form.
can be obtained. metallic accelerator or metallic reactant or
Both of these are hydrocarbon cracking catalysts and
mixed and contact cracking process support.
It can be a powder that is circulated through a cycle. In general
Powdered metallic promoters or metallic reactants such as
or both, the powder can be fluidized by contact
It is advantageous in that it is easy to insert into the processing equipment and easy to handle.
be. The particle size of the powder is determined by the fluidization speed, which causes particle separation.
should be selected so that it does not like that
Powder particles are removed from the floor as containing particles.
It is so fine that there is a problem of excessive emissions along with
It is preferable not to have it. However, gas-borne granules
Recover most of the material and return it to the system for loss
fluidized contact cracking operations to reduce
Along with the production, filters, cyclones, sedimentators, etc.
Usually used. This powder is produced by superseding the sized powder.
Sufficient strength to prevent wear and deterioration
should have. often promotes metallicity of powders
agent or metallic reactant, or the average of both.
The particle size is approximately 0.5 or 1 to 100
microns, preferably less than about 50 microns.
Microsized particles, i.e. smaller than about 1 micron
grain size, e.g. an average grain size of about 0.01 to 0.5 microns
Particles having a child size are advantageously used in the present invention.
forming larger size aggregates used
A trend was observed. Usable powder
As metal promoters and metal reactants, secondary oxide
Iron, ferrous oxide, zinc oxide, manganese dioxide, acid
Cerium chloride etc., dolomite and trimex
(manufactured by Trimex Corporation)
(described in U.S. Pat. No. 3,630,696)
can give. Instead of the above, metallic promoters or metallic reactions
The agent or both are formulated on a suitable carrier.
obtain. This metallic promoter and metallic reactant are
at the same time or at different times, and at the same time.
or incorporated into the support by a different addition method.
obtain. Such carriers are suitable for amorphous cracking contact.
solids that are substantially inert to the catalyst or cracking reaction.
It can be a body, for example a natural ceramic. like this
supported metallic promoters or metal
The reactants or both are then passed through a molecular sieve tie.
mixed with a cracking catalyst. Desirably
, the carrier is porous and the area of pores on the surface is
including at least about 10, preferably at least
Approximately 50m ² It often has a specific surface area of /g. Applicable
As a carrier, silica, alumina, silica-aluminum
Examples include Mina. Metallic promotion instead of above
or metallic reactive agents, or both.
Molecular sieve type cracks in solid particles in light
may be incorporated into the catalyst or a part thereof. This way
If this is the case, use a metallic accelerator or metallic reactant.
Or both of these may be produced by Klutzkin during catalyst production.
into the catalyst matrix or
It can be impregnated onto the racking catalyst structure. like this
In some cases, cracking activity and cracking
The formulation method is such that the selectivity of the catalyst does not have an adverse effect.
Care should be taken in the choice of law. if kratsuki
A type of catalyst with an ion exchange site
If so, this ion exchange can be carried out using metallic reactants or
and/or completed prior to incorporation of metallic accelerators.
It is preferable. In any of the above cases, metallic accelerators
or metallic reactants or both metals.
(singular or plural) is a molecular sieve type kratskin
catalyst, amorphous cracking catalyst or substantially
The detailed method of incorporation into an inert support is
It is not known with relative certainty. the metal
is the combination of the carrier material and other components of the solid particles of the invention.
Can be included in complex combinations. did
Therefore, “metallic accelerator” or “metallic reactant”
and the use of the term “formulation” in the support
The combined form and/or
or present on a carrier material in an elemental state
It is understood that The metallic promoter and/or metallic reactant is
Supported by ion exchange, impregnation, or other means
Can be incorporated into the body, this can be a support or
Its components can be combined with metallic promoters within the scope of the present invention or
is the desired concentration of metallic reactants or both.
the appropriate amount of the metallic promoter needed to provide the desired degree of
or in metallic reactants or both.
Compound(s) of metal(s)
contact with solution(s) of
It is carried out by. The metallic promoter and/or metallic reactant is
During the creation of the support or after the support has been created
It should not be combined with the support at any stage of the process.
I can do it. One of the formulation methods is to ionize the support.
This means replacing the parts. For example, crystalline alumino
Silicates can also be used as metallic promoters or metallic reactants.
or metal(s) in both of these.
Solution(s) of compound(s)
The ion-exchanged product is
composited with a porous cracking catalyst matrix
It is preferable to Similarly metallic accelerators or
Metal (singular) in the metallic reactant or both
solution of compound(s)
(single or plural) of siliceous solids or clays.
On-exchange is also useful. for this purpose
Suitable compounds are metal halides, preferably chlorides.
substances, nitrates, amine halides, oxides, sulfates,
phosphates and other water-soluble organic salts, and
Similarly, metal carboxylic acids having 1 to 5 carbon atoms.
Includes salts and alcoholates. for a specific example
is palladium chloride, chloroplatinic acid, ruthenium chloride.
tamamine chloride, osnium chloride, perureni
Tsuccic acid, dioxobis(ethylene-diamine)
Contains nium (V) chloride, rhodium chloride, etc.
Ru. Metallic promoter or metallic reaction used in the present invention
Other methods of producing the agent or both are suitable.
A suitable carrier is combined with a metallic promoter and/or a metallic reactor.
Water- or
solvent-soluble or -dispersible compounds (singular or
impregnated with (or multiple) This impregnation
in any way that does not destroy the structure of the support.
It can also be carried out at any time. The metallic accelerator
or metallic reactants or both.
Hydrogen cracking, molecular sieve type cracking
Inert to catalyst or amorphous cracking catalyst
It can be impregnated into a carrier. Impregnation is different from cation exchange. Adhesion with impregnation
The amount is large and mainly physically on the support surface.
However, in ion exchange, the chemical action is mainly
, resulting in greater diffusion and therefore less surface adhesion.
do not have. In impregnation, metal is deposited and gold
There is little ion exchange between the genus and the support.
stomach. When impregnating the support, metallic promoters or
is the metal (single) in the metallic reactant or both.
water or water in an organic solvent
or organic solvent-soluble or-dispersible compounds
as required on the support(s)
Filled to contain an amount of metal(s).
can be present in such amounts as to
The support is contacted with these. This composite is
It can be dried to remove the agent, and then
metallic promoter or metallic material deposited on the support
Reactants or both remain. Water-soluble nitrates are preferably used in the impregnation solution.
I can stay. This is because the residue from the pyrolysis of nitrates is
Relatively harmless to the activity of hydrocarbon cracking catalysts
Because there is. Metal halide impregnated
and sulfates can be used as well. But long
During the thermal decomposition of the salt, halogens or sulfides are released.
production and activity of hydrocarbon cracking catalysts.
Because these salts can be harmful,
substantially inert to the
Has no harmful effect on elementary cracking reactions
If there is a metallic promoter or metallic reactant on the support,
is most often used when attaching both.
be done. Metallic accelerator or metallic reactant or the like
both on supports, especially crystalline aluminosilicate.
Other methods of deposition on porous supports such as
is a metallic promoter or metallic reaction on the support.
the metal(s) in the agent or both.
adsorbs fluid-decomposed compound(s) of
and then thermally or chemically separate the compound.
It is something to understand. This support is heated and adsorbed.
can be activated by removing the water
and then this is a metallic promoter or
The metal (singular or
fluid-degradable compound(s)
thereby depositing the compound on the support.
is adsorbed. A typical example of such a compound is
is metal carbonyl, metal alkyl, volatile metal
There are halides, etc. Adsorbed compound (singular or
(or compounds) is then thermally or chemically activated.
active metals promoted on the support.
homogeneous agent or metallic reactant or both.
to be dispersed. Thermal reduction can be used, for example, in regeneration processes.
This can be done in a regeneration vessel in a bath. Both impregnation and adsorption are possible when the support is
the support before being introduced during the
It can be done about the body. However, metallic
in the promoter or metallic reactant or both.
Compound(s) of metal(s)
) introduced during the cracking process cycle
and formulate it on the support in situ.
That is equally advantageous. Such compounds (single
(number or plurality) are oil- or water-soluble or
- Can be introduced in dispersible form and solid
cracking clamp to obtain a wide distribution of particles.
solids at any stage of the process cycle;
It can be introduced in liquid or gaseous state. example
For example, such compound(s) may
mixing with the feedstock or fluidizing gas in the reaction zone.
can also be used with regeneration gas and torch oil.
or mixed with the water in the regeneration zone, or
Mixed with the stripping gas in the ripping zone
or introduced as a separate fluid. the
Compounds suitable for in situ introduction include metal salts, organic
metallic compounds, metal diketonates, carbonyl,
Metallocene, olefin co of 2 to 20 carbons
complex, acetylene complex, acetylene complex,
Lucyl or aryl phosphine complexes
carbonaceous acid and 1 to 20 carbon carboxylates.
nothing. These specific amounts are platinum acetylacetonate.
Tri(acetylacetonate) rhodium
(), triodoridium (), tricarbonyl,
Cyclopentadienylrhenium() tricarbo
nil, ruthenocene, cyclopendadiene sodium
Mu() dicarbonyl dimer, dichloro(ethyl
Palladium() dimer, cyclopenate
dienyl (ethylene) rhodium (), dipheni
acetylene bis(triphenyl)phosphino-
Platinum (0), bromoethylbis(triethylphos)
Huino) Palladium (), Tetrakis (Triff)
enylphosphine) palladium(0), chloroca
rubonylbis-(triphenylphosphine)iri
dium (), palladium acetate, palladium
Munafthenate, and zinc dimethyl, and
There is zinc diethyl. The key aspects of activity and stability are monoacid
to reduce carbon and sulfur oxide emissions
During the cracking process cycle, metallic
introducing at least one of a promoter and a metallic reactant;
and this is used during the production of the cracking catalyst.
rather than combining it with the cracking catalyst.
By blending this into solid particles on the spot.
Therefore, it can be achieved more easily. Crat King
Metallic promoters and metals during the process cycle
at least one of the reactants is introduced, and this
during the production of the cracking catalyst.
In contrast to combining with a medium, it is possible to place this on the spot.
Carbon monoxide in the flue gas of the regeneration zone
significantly reduce the release of sulfur oxides and sulfur oxides.
It was discovered that gold during a cracking cycle
At least one of a metallic promoter and a metallic reactant
Incorporating the lead during the cracking cycle
Such metallic promoters and/or
The ratio and/or amount of metallic reactants may be varied.
In the cracking reaction, such metals
potential of quality promoters and/or metallic reactants.
Greater control over harmful effects
It is equally advantageous in that it is maintained.
Also, during the cracking process cycle the catalyst
be pre-compounded with the cracking catalyst before introduction.
The metallic promoter and/or metallic reactant are
Lost as fine particles through wear and tear of the cracking catalyst.
can be lost. Metallic promotion in cracking cycle
and/or metallic reactant, and
It is possible to blend this into solid particles on the spot.
Desired amount of gold on the outside of the child or its adjacent parts
Withhold metallic accelerators and/or metallic reactants
enable. Still other methods include spray drying or other
Before the physical formation process, a metallic promoter or
is a metallic reactant or both as a support precursor.
substances such as silica gel or silica-alumina
formulating with a gel and drying the precursor;
Including manufacturing a support. of the obtained support
The body can be fired to form the active material.
Ru. Heat during cracking cycle instead of above
Processing may also be performed. In a preferred embodiment of the present invention, metallic reaction
The agent is mainly a physical sieve type cracking catalyst.
and sodium, rare earth metals, etc.
A group consisting of these compounds and mixtures thereof?
selected from. In practicing this embodiment, metal
The metal(s) of the reactant is
In the crystalline aluminosilicate of the catalyst,
The substantial chemical composition of the metal(s)
molecular sieve type by all methods that do not cause
It may also be combined with a cracking catalyst. In the end, this
In this embodiment, the metallic reactant is an ion exchanger.
Depending on the molecular sieve type cracking catalyst,
It cannot be combined with However, molecular sieve type
support except in the case of ion exchange over cracking catalysts.
The above-mentioned technique of introducing a metallic reactant into a carrier is
Generally, it is suitable for use in implementing this embodiment. The great benefits derived from this invention are typically
Due to the low carbon monoxide content in the gaseous fluid effluent from the
related. Smoke from normal regeneration of cracking catalyst
Road gas usually contains about 6 to 10% carbon monoxide.
contains the same amount of carbon dioxide and a small amount of oxygen.
However, the flue gas in this new regeneration method
The carbon monoxide content is less than about 0.2% by volume;
For example, it can be maintained at about 500 to 1000 ppm (capacity).
Ru. Furthermore, this content may be, for example, between 0 and
Even with low values in the range of 500ppmv (v: capacity)
Ru. This low concentration of carbon monoxide in the flue gas fluid
allows direct release of effluent gas into the atmosphere,
Moreover, it can meet the environmental air quality standards.
Ru. If necessary, any remaining carbon monoxide can be removed from the regenerator smoke.
The gas can be properly combusted while being discharged from the chimney.
Ru. These advantages of the invention further extend to others.
The law requires carbon monoxide boilers and joint
Bottle type equipment or subsequent oxidation of carbon monoxide
to partially recover the energy produced by
equipment costs required for other means of
It can be removed and also due to the release of carbon monoxide
meets current air quality standards. The present invention provides further additional benefits. child
Benefits such as post-combustion and heat balance issues
Regarding. Especially when implementing fluidized catalyst regeneration.
frequently encountered and desired to be eliminated.
The big problem is “afterburning”.
This is a phenomenon known as For example,
Hengstebeck's Petroleum Processing, Mc
Graw-Hill Book Co., 1959, page 160 and
and on page 175, and Oil and Gas
Journal, Volume 53 (No. 3), 1955, pages 93-94
This is currently being considered in this page. This term was previously
Carbon monoxide burns as represented by reaction (C).
This refers to the burning of carbon dioxide into carbon dioxide, which is an altitude
It is exothermic. After-burning can damage equipment and
creates permanent deactivation of cracking catalyst particles.
Do not touch as this can lead to very high temperatures.
In the media regeneration process,
came. Many fluidized catalyst regeneration operations experience after-combustion.
And the actual main body of the technology is excluding after-combustion.
Many to control playback technology for
It has developed around means. More recently, many
It is necessary to increase the regeneration temperature for many reasons.
It is being For example, U.S. Patent No. 3,161,583 and
No. 3,206,393, as well as U.S. Pat. No. 3,513,087.
As stated in
The point of initial afterburning can be adjusted by appropriate adjustment of the feed rate.
to control the temperature of the regenerator in
Elaborate arrangements are similarly developed. therefore later
Typical current practices for combustion removal
In some cases, the flue gas from the catalyst regenerator is usually extremely
a small amount of oxygen and an approximately equal amount of real carbon monoxide.
Contains carbon dioxide and carbon dioxide. In the combustion of carbon monoxide to carbon dioxide, the reaction (C) is
Highly exothermic and therefore attractive thermal energy
It is the source. After-burning exceeds approximately 593.3℃ (1100〓)
oxidized
1095Kcal per 0.454Kg (1 pound) of carbon monoxide
(4350BTU). This is typically
of the total amount of heat produced by the combustion of the
Shows about 1/4. Combustion of carbon monoxide is e.g.
As stated in National Patent No. 2753925
After separating the effluent gas from the catalyst, the separation zone
This can be done in a carbon monoxide boiler or in a carbon monoxide boiler.
The heat energy released is generated by high pressure steam.
It is used in various refinery operations such as refinery production. child
Other uses of thermal energy, such as U.S. Patent No.
Nos. 3012962 and 3137133 (turbine driven) and
and U.S. Patent No. 3,363,993 (Preheating Petroleum Feedstock)
It is stated in This type of heat recovery method is
Although it requires sophisticated equipment separated by
to minimize carbon monoxide released into the atmosphere.
and therefore prevent potentially serious contamination risks.
useful for. Additionally, for cracking petroleum hydrocarbons
It has been commonly used for many years in various methods.
The silica-alumina catalyst used in
0.5% by weight or less, the
Not particularly sensitive to residual coke levels.
stomach. However, silica-alumina catalysts
A crystalline aluminosilicate component is added to the
into catalysts known as zeolites or molecular sieves.
Most of them have since been replaced. This molecular sieve contains
Catalyst is more sensitive to residual coke levels
and the catalytic activity and desired product (single
catalyst for the conversion of the feed into
Extremely sensitive regarding selectivity. residual charcoal
Conventional catalyst regeneration to remove the last components of the
Due to the difficulties encountered in the technology, the actual coke
Levels range from about 0.2 to about 0.3% by weight.
Corresponds to the content of residual coke on the medium. High activity and selectivity at low coke levels
Achieved molecular sieve type cracking catalyst
can reduce residual coke levels.
There is a strong incentive to find ways to further reduce
Given. Less than about 0.05% by weight coke leve
Although highly desirable, commercial
This can be achieved by some practical means.
do not have. Larger regeneration vessel, more catalyst residue, more
Considering the large amount of heat loss, etc., this ideal
All are satisfactory in reaching the equilibrium catalyst activity level.
It's not something you can do. A preferred embodiment of using the catalyst composition of the present invention is
U.S. Patent no.
No. 3909392, regarding the regeneration method of U.S. Patent No. 3909392.
Contains related operations. This method provides improved contact
Coatings on the catalyst surface for the purpose of racking process.
Hydrocarbon water in which the catalyst is inactivated by the adhesion of
Used in fluidized catalytic conversion of elementary feedstocks
Including improved catalyst regeneration methods. This method plays
Coke level on catalyst maintained at very low level
on the other hand in the conversion equipment.
simultaneously maintain a favorable thermal balance of and very
Obtain flue gas fluid with low carbon monoxide content
It is something that Heat from combustion of carbon monoxide is regenerated
absorbed by the catalyst and converted into a hydrocarbon conversion zone.
supplying some of the process heat required within the
Ru. In one embodiment of the method of the invention, carbon monoxide
Conversion of elemental carbon dioxide to carbon dioxide, which is relatively rare in the regeneration vessel.
In the second catalyst regeneration zone, preferably about
Temperature between 648.9℃ (1200〓) and 815.6℃ (1500〓)
degree, preferably about 651.7℃ (1205〓) to 787.8℃
(1450〓) was carried out virtually completely. No.
The temperature of the second zone is higher than that of the first regeneration zone.
Approximately 27.8℃ (50〓) or 55.6℃ (100〓) higher
You may. Is it the relatively rich first catalyst regeneration zone?
The partially regenerated catalyst is then regenerated in the second zone.
absorbs virtually all of the heat released by combustion.
the second zone in an amount and at a rate sufficient to
can be flowed adjustably through the tube. most of coke
is burned from the catalyst in the first zone, but
On the other hand, from the partially regenerated catalyst existing in the second zone,
Additional coke burns and essentially
Because no catalyst is recycled to the hydrocarbon conversion level
can be recovered. In the second embodiment of the method of U.S. Pat. No. 3,909,392
oxidation and monomerization of coke or carbon on the catalyst.
Substantially total combustion, including both oxidation of carbon oxides
However, this mainly depends on proper control of regeneration temperature and gas velocity.
Depending on the roll, a single relatively dense phase regeneration zone
occurs within the Similarly, contact cracking has been proposed in U.S. Pat.
Performed in the embodiment including the reproduction method of No. 3909392
combustion of carbon monoxide in the regeneration zone.
Most of the heat released by the cracking catalyst
is absorbed by the solid particles of the present invention containing
part of the heat required within the cracking zone.
give. Advantageously, in such an embodiment
is a dilute phase zone that disperses the heat generated from it.
(assumed that there is one)
Dense phase zones (one
(assumed to be present) significant coke and monoxide
Carbon combustion becomes possible. Occurs within the dense phase zone.
in the dilute phase zone as the combustion fraction increases.
Heat generation is substantially reduced, thus absorbing the generated heat
solid particles quickly within the dilute phase zone to
The need for inversion is reduced or eliminated. In such embodiments, the process comprises monoacid
systems that support virtually complete combustion of carbonized carbon.
It consists of a molecular sieve type cracking catalyst,
and likewise metallic promoters and metals in this method.
including the use of solid particles of the present invention which may contain a reactive agent.
nothing. The low catalyst coke level achieved is approximately 0.2
less than 0.05% by weight, preferably less than about 0.05% by weight
There are few. This method uses less than approximately 0.2% by volume.
For example, about 500 to 100 ppm, and about 0.
Carbon monoxide levels as low as 500ppm
It is possible to obtain flue gas with this method
transports the generated heat directly to the solid particles in the regeneration vessel.
This includes recovering that heat by In such embodiments, the rich zone of the regenerator
The fluidizing gas in the tank is, for example, approximately 0.0610 to 1.22 m/
seconds (0.2 to 4 ft/sec), preferably about 0.152~
Speeds ranging from 0.914 m/sec (0.5 to 3 ft/sec)
may have. Regeneration to help fluidize dense beds
The gas contains free or molecular oxygen and
Oxygen is converted into carbon dioxide and steam by coke (carbon
and hydrogen) required for complete combustion.
A slight excess amount of water is also supplied to the regenerator. Cork's
Amount of oxygen in excess of that required for complete combustion
is the theoretical requirement for complete combustion of the coke.
from about 0.1 to about 25% or more of the stoichiometric amount of oxygen.
can be in the range, but advantageously needs to be greater than about 10%.
There's no need. For example, air is used as the regeneration gas.
When the 10% excess air is removed from the exhaust gas fluid
Approximately 2% by volume of oxygen is provided in the container. All the water in the regenerator
Molecular or free oxygen or monoxide at the point
Carbon concentration remains outside the explosive range for these conditions
It is advantageous to do so and avoid the risk of explosion.
, the concentration of carbon monoxide should preferably be within these conditions.
preferably below the explosive range of The regeneration gas contains nitrogen in addition to free or molecular oxygen.
Inert or diluted gas such as pure water, steam, etc.
gas, recirculated gas from regenerator effluent, etc.
Ru. The oxygen concentration of the regeneration gas at the inlet of the regenerator is
It is often about 2 to 30% by volume.
and preferably about 5 to 25% by volume. oxygen
Air is usually used as the source, so an inert gas
may be mostly nitrogen. This inert gas
dissipates excessive heat from combustion of coke from medium
It can be helpful. The thermal inert gas source is from the regenerator.
effluent, and some of this gas is sent to the regenerator.
can be recirculated and, for example,
air containing sufficient essentially pure oxygen to
The required oxygen is combined with other oxygen-containing gases.
content can be given. In this way, re-
Circulating gas provides further thermal economy in the system.
direct to increase the temperature of the regeneration gas to
Can be used for heat exchange. Solid particles in the dilute phase are typically separated by a large number of stages.
into the separation zone consisting of a cyclone separator in the
solids from this separation zone.
Particles are returned directly to the dense bed zone through the dip leg
and used regeneration and combustion gas
The gas is collected in and contained within the plenum.
In order to appropriately recover the thermal energy
is discharged. Heat recovery process from flue gas
Steam regeneration, stripping of used catalysts
seeds, such as feeds to specific conversion processes.
Indirect heat exchange with seed refinery fluids, and various
Including use in drying or evaporation equipment. Figures 1 and 2 of the accompanying drawings are from U.S. Pat.
Catalyst assembly according to the invention including the regeneration method of No. 3909392
Catalyst regeneration according to method embodiments that can be used for products
1 is a partial cross-sectional elevational view of an embodiment of the apparatus suitable for use in FIG. this
Such embodiments are suitable for many existing petroleum hydrocarbon
cracking process equipment, especially cracking,
Various spatial arrangements of tripping and its regeneration
Advantageous for fluid type catalytic cracking equipment with
can be used. Figure 1 shows the cracking reactor (not shown).
(2) to the regenerator.
An Embodiment of the Invention Using a Bottom Inlet of a Finished Catalyst
It shows the situation. Stritzpi in collaboration with the catalyst
Metallic Reactants and Metallic Accelerators from Engineering Gases
Solid particles containing spent catalyst impregnated with
It exits the reactor and enters the regeneration container 1 from the bottom. the solid particles
The child flows upward through inlet lines 2 and 3;
and into the thick bed through discharge heads 4 and 5.
be discharged. This thick phase bed is regenerated.
held within the lower part 6 of the container and above the phase interface 7
spread to The solid particles in this dense phase bed are
line 8, valve 9 and air ring 11.
fluidized by the flow of combustion air through tube 10.
Ru. Virtually balanced air passing through the regeneration zone
Flow pattern not shown as required
Achieved by using additional air rings
It can be done. Empty coke contained on spent catalyst
Combustion with air is initiated within a bed of dense phase. Yo
For higher temperatures, torch oil, e.g.
By primarily burning the oil fluid within the bed.
You can get it. Torch oil is
on the air ring 12, valve 13 and air ring 11.
Line 14 terminating at the located nozzle
can be added through. The velocity of fluidizing air is
Some of the particles occupy the upper part of the recycling container.
In the phase zone, i.e. the upper part of the phase interface 7, the upper
move continuously. The combustion of coke is a dilute phase process.
solid particles that are carried out continuously and entrained within the chamber
Most of the exhaust combustion gas is from the first stage.
removed into Ikron separators 20 and 21.
Ru. Most of the solid particles are in the size of the first stage.
separated within the clone and immersed legs 22 and 2
3 and discharged downward into the dense phase zone.
It will be done. Gas and remaining solid particles are removed from the internal
through the cyclone lines 24 and 25 of
Second stage cyclone separators 26 and 27
, where virtually all of the remaining solid particles are
separated and through dip legs 28 and 29
It passes downward and into the dense phase bed. Next, exhaust combustion gas
The gas is substantially charged through lines 30 and 31.
enters room 32 and finally passes through line 33
is discharged from the regenerator vessel. This effluent is
Although not shown, refinery steam and
is suitable for heat exchange for the production of process steam
can be done. Solid particles containing regenerated catalyst from the concentrated phase
is a collection head for return to the cracking reactor.
Standpipe with 36 and 37 attached
34 and 35. The supply of combustion air stifles the coke on the catalyst particles.
required for complete combustion to gas and carbon dioxide.
Provides excess oxygen to the required amount, but the coke
Combustion uses the regeneration method of U.S. Patent No. 3909392.
In one embodiment, the process is completed in the dense phase bed.
Maybe not. rising from the dense bed zone
The combustion gases therefore include carbon dioxide and oxygen.
contains substantial amounts of carbon monoxide. Residue on catalyst
Coke and carbon monoxide generate a lot of heat.
and substantially complete combustion within the dilute phase zone.
If carbon monoxide burns within this dilute phase, the high temperature
The phase zone typically spans much of the dilute phase zone.
and especially not shown in the horizontal plane.
By the X, which can be easily seen through the window
It will be present in the vicinity of the indicated position.
Control of the regeneration temperature in the dilute phase zone is
carried upward by the rising combustion gas fluid,
Rain or fountain of solid particles dispersed in the dilute phase zone
extraction tube 40 and solid separator head 41
collection of solid particles extracted upward from the dense bed through
Occurs in part through absorption of heat by coalescence. solid
The body particles are connected to the line 42, the valve 43 and the extraction pipe 4.
A jet that extends a short distance within the lower edge of 0.
Air, steam, or
May be extracted by other inert gas means
Ru. The level of excess temperature at the top of the regenerator is
steam distribution, e.g. lines 45 and 46;
Lights leading to valve 47 and steam pot 49
can be further controlled by a button 48. Mitsuru
The temperature near the air chamber is determined by the line 50, valve 51 and
and reaches the steam ring 53 surrounding the filling chamber 32.
using steam supplied through line 52.
can be similarly controlled. If desired, additional
Additional cooling is provided by internal stage cyclone lines.
Advantageously directed within the area of 24 and 25
using a water spray (not shown).
and can be given by. Such low temperatures
Stable metal and sulfur content in the regeneration zone
This is advantageous for producing compounds. Figure 2 shows the cracking reactor leading to the regenerator.
Stripped spent catalysts and metals from
side of solid particles containing quality promoter and metallic reactant
Regeneration method of U.S. Pat. No. 3,509,392 with an inlet
This shows another embodiment using. metallic
Used impregnated with accelerators and metallic reactants
The solid particles containing the catalyst are located on the side of the regeneration vessel.
Flows downward through inlet line 102 to reach the phase interface.
held within the bottom 106 just below 107
Enter the thick phase floor. Fluidization of solid particles causes combustion
Connect air to line 108, valve 109 and air
passing through the line 110 leading to the ring 111.
caused by Although not shown, if desired
The passing air ring directs the airflow through the regeneration zone.
Can be used to further balance the pattern
can. As mentioned in Figure 1, used
The combustion of coke on the catalyst particles causes a torrent in the zone.
By temporarily burning the oil fluid
open in the dense phase zone where the desired high temperature can be obtained.
will be started. Such torch oil is
112, terminating at valve 113 and nozzle
can be added through line 114. The fluidizing air velocity is at the top 11 of the regenerator vessel.
5, that is, the dilute phase occupying the upper part of the phase interface 107
Continuous solid particles to absorb heat within the zone
can be controlled to carry it upward. monoacid
The combustion of not only carbonized carbon but also coke occurs in the dilute phase zone.
can be continued, and the entrained part of the solid particle is
The accompanying large amount of exhaust combustion gas is
removed into Chron separators 120 and 121
Ru. Most of these solid particles are in the first stage
separated in the cyclone of and immersed leg 122
and 123 and discharged downward through the dense phase zone.
enter the mode. The gas and remaining solid particles are essentially
The second stage cyclone separator 126 and
Internal cyclone lines 124 and 127
and 125 of this second stage.
In the cyclone separator, the remaining solid particles
Substantially all of the child is separated and the submerged leg 12
8 and 129, and the dense phase
Get on the floor. Substantial spent gas is then transferred to the line
It enters the air chamber 132 through 130 and 131.
and finally from the regenerator vessel via line 133.
is discharged. Solid containing regenerated catalyst from concentrated phase
Particles are returned to the catalytic cracking reactor
Collection heads 136 and 137 are installed.
via standpipes 134 and 135.
be taken out. As mentioned in the embodiment of Figure 1, carbon monoxide is
burns in the dilute phase, and burns in many of the dilute phase zones, especially
Give a high temperature zone near the position indicated by
I can do it. Control of regeneration temperature in the dilute phase zone
is mostly driven upward by the rising combustion gas fluids.
through absorption of heat by aggregates of transported solid particles.
It is done. Near air chambers, cyclones and piping
Temperatures near line 150, valve as required.
Steam surrounding the chamber 151 and the plenum chamber 132
is supplied through line 152 to ring 153.
can be reduced using steam. illustrated
However, water spray means can also be used.
Ru. In other particularly preferred embodiments, FIG.
The apparatus shown in FIG. 2, compared to the embodiments described above,
used with considerable changes in operating parameters.
Ru. In these embodiments, gas velocity and
Body particle input is the essence of coke and carbon monoxide
complete combustion takes place in the rich phase, and
The heat is regulated to spread across the entire floor. In all of these embodiments, the safety of the combustion reaction is
The stabilization is particularly facilitated by the use of metallic promoters.
increased and the regenerator is thereby lower
Can be operated at temperature, or carbon monoxide
can burn a larger amount of the element, and
regenerates more cracking catalyst at the same temperature
can do. Such low temperatures will cause the regenerator to
Formation of stable metal- and sulfur-containing compounds in
It is advantageous for If the system meets any of the first two aspects above.
When carried out in accordance with
released by essentially complete combustion of carbon oxides
The heat recovery is due to the absorption of solid particles in both phases.
solid particles return to the dense phase.
Similarly, at an appropriately high temperature in the dense phase zone,
Helps ensure maintenance. returned solid particles
has extra heat and this heat is the final
coke such that incremental combustion is substantially complete;
The dense phase zone is placed at a temperature favorable to the combustion of additional components of the deposit.
helps raise the temperature of the chamber. This system
essentially all combustion is completed within the rich catalyst phase.
If the heat is
absorbed by solid particles and coke
split across that phase so that the final increment burns out.
clothed. Therefore, in all such aspects
The regeneration is returned from the regenerator to the cracking reactor.
The solid particles containing the catalyst are coated with carbon or coating on the catalyst.
It is appropriate to contain about 0.01 to about 0.10% by weight of
and preferably 0.01 to 0.05% by weight, and
and preferably about 0.01 to about 0.03% by weight.
Ru. This solid particle is used in the cracking reactor.
can be removed from the regenerator at a temperature convenient for The significant advantages of these aspects are that they generally
catalysts, especially very short contacts in riser reactors.
Conversion catalysts used in catalytic conversions
with high activity and selective properties that are more similar to
The objective is to provide a regenerated catalyst having the following characteristics. Contains molecular sieves
Catalyst cracking activity and hydrocarbon feed
Their selectivity for conversion into the desired product is
Both remove residual carbon or coke on the catalyst during regeneration.
advantageous direction by progressively removing
are significantly affected. Low coke on regenerated catalyst
The level of catalytically active, crystalline aluminosiloxane
About fluidized cracking catalysts containing cate
Particularly preferred. Therefore higher conversion of feedstock and
and obtain higher yields of the desired conversion products.
can. The metallic promoter in the present invention is monoxide.
Regeneration by controlling carbon oxidation
Helps stabilize control of the device. Sara
In addition, there is a possibility of temperature drop and blowout.
increase gas velocity or reduce carbon monoxide content.
The danger of extinction due to the oxidation of carbon monoxide is
This is substantially reduced as carbon oxidation is promoted.
Metallic promoters also have lower regeneration temperatures.
stable metals outside the regeneration zone and
Facilitates the formation of sulfur-containing compounds. Upper dense phase zone and lower in regeneration zone
These cracking using a dilute phase zone of
In the process, carbon monoxide turns into carbon dioxide.
oxidation is in the majority range, often at least about 60
%, and frequently about 65 to 95% or more.
and is completed within the rich phase of the regenerator. Acidification of carbon monoxide to carbon dioxide in the concentrated phase
maintains combustion of coke deposits from fluid catalyst
Provides heat to help. Additionally, carbon monoxide
oxidized in the dense phase.
If the fluid in the regenerator is
present for combustion in the phase above the catalyst and therefore
Materials used in reactor construction, flue gas flue,
Collector for specific substances in gas, e.g.
have a detrimental effect on phosphorus and reduce catalytic activity.
Controls on the top of the regenerator that may
“Afterburn” caused by the combustion of excessive carbon monoxide that is not
” and high temperatures are substantially reduced, and
can be removed. Regenerated catalyst granules with very low residual coke content
solid particles containing particles are recovered from the concentrated phase, and
New hydrocarbon feed or recycled hydrocarbon feed
For contact with laxions and their mixtures
stand pipes at virtually dense bed temperatures.
and then passed to a cracking reactor. on the catalyst
Carbon monoxide generated from combustion of coke deposits
The advanced oxidation occurs mostly within the dense phase and
In a preferred embodiment, the process occurs essentially completely within the concentrated phase.
Since the regenerated catalyst can
at much higher temperatures as well as higher activity than
It can be recycled to the cracking reactor. Many hydrodynamic cracking devices are mainly used for
This process
combustion of coke to release the required heat in the
Depends on. However, such devices
Advantages of racking catalysts, especially zeolite catalysts
I couldn't make full use of it. This is
A lamp with an extremely short contact time between medium and oil vapor.
can be especially achieved in Iser reactors.
Ru. A tag that gives high conversion coupled with high selectivity.
The operation of the pipe produces heat by combustion within the regenerator.
Risers that reduce coke are used to
Advantage of low catalyst-to-oil ratio in the reactor
Ru. Therefore, external heating sources such as feed preheating furnaces
Often used to increase catalyst temperature, or
or alternatively, if the equipment is
May be manipulated. This kind of undesirable
A similar embodiment is caused by solid particles moving into the riser reactor.
The present invention enables effective recovery of additional heat.
can be eliminated or minimized by
The heat of combustion of coke in normal operation is approximately
It is 6661Kcal/Kg (12000BTU/lb).
The present invention utilizes the heat available from the combustion of coke.
Approximately 9437Kcal/Kg (17000BTU/lb) or
It can be increased beyond that. This high combustion
The heat increases the temperature of the regenerator and causes coke on the regenerated catalyst.
and a certain conversion level.
solid particles while giving improved yields in
tend to slow down the child's circulation. Example 1 5.3% hydrogen and ion-exchanged rare earth
Calcined equilibrium commercially available, including
Molecular sieve cracking catalyst 200g aluminosilicate
crystalline, silica aluminum containing 30% by weight alumina
3.90g of 50% by weight manganese nitrate solution and water
Impregnated with 210ml. Approximately 80% by weight of the catalyst is
Sizes ranged from 20 to 75 microns. Contains
The soaked catalyst particles are recovered and heated to 121.1℃ (250〓)
and then dried at 676.7℃ (1250〓) for 3 hours.
fired. The obtained catalyst contained 0.3% by weight of manganese.
It contained. Example 2 Nitric acid dissolved in 210 ml of water as impregnation solution
Example 1, except that 1.265 g of uranium is used.
The method was repeated. This impregnated catalyst has a temperature of 121.1℃
(250〓) and then 648.9℃ (1200〓)
It was baked for 3 hours. This catalyst contains uranium 0.3
% by weight. Example 3 Anhydrous solution dissolved in 210 ml of water as impregnation solution
Monium metatungstate 0.82g is used
The method of Example 1 was repeated except that: This catalyst is
Dry at 121.1℃ (250〓), then 648.9℃
(1200〓) for 3 hours. The obtained catalyst is
It contained 0.3% by weight of tungsten. Example 4 As an impregnating solution, a second solution dissolved in 200 ml of water
Since 2.35g of cerium ammonium nitrate is used
Otherwise, the method of Example 1 was repeated. This catalyst is an example
Dry and calcined in the same manner as 1, and add 0.3% by weight of cerium
It contained mu. Example 5 Zinc dissolved in 200 ml of water as impregnation solution
Except 2.73g of hexahydrate nitrate is used
The method of Example 1 was repeated. This catalyst is Example 1
as well as dried, calcined, and zinc 0.3% by weight
It contained. Example 6 Nitric acid dissolved in 200 ml of water as impregnation solution
The method of Example 1 is used, except that 4.35 g of ferric iron is used.
repeated. This impregnated catalyst was dried as in Example 1.
It was dried and calcined and contained 0.3% iron. Example 7 Molybdenum in 210 ml of aqueous solution as impregnation solution
Example 1 except that 1.1 g of ammonium acid is used
method was repeated. This impregnated catalyst has a temperature of 121.1℃
(250〓) for 3 hours, then 648.9℃
(1200〓) for 3 hours. The obtained catalyst is
It contained 0.3% by weight of molybdenum. Example 8 Peroxide diluted with 200 ml of water as impregnation solution
1st titanium sulfuric acid dissolved in 25 ml of a 30% aqueous solution of hydrogen.
The method of Example 1 is repeated except that 5.0 g of tan is used.
It was returned. This solution will completely dissolve the titanium salt.
heated until it melts. This catalyst was heated at 121.1℃ (250
〓) and baked at 648.9℃ (1200〓) for 3 hours.
accomplished. The obtained catalyst contained 0.3% by weight of titanium.
I was reading. Example 9 Oxidation dissolved in 200 ml of water as impregnation solution
The method of Example 1 is used, except that 1.2 g of chromium is used.
repeated. This impregnated catalyst is 121.1℃ (250〓)
dried for 3 hours at 648.9℃ (1200〓)
Baked for 3 hours. The resulting catalyst contains 0.6 chromium
It included the amount%. Example 10 Zil dissolved in 200 ml of water as impregnation solution
Example 1 except that 2.12 g of conyl chloride is used
method was repeated. This impregnated catalyst has a temperature of 121.1℃
(250〓) for 3 hours, then 678.9℃
(1200〓) for 3 hours. The obtained catalyst is
It contained 0.3% by weight of zirconium. Example 11 As impregnation solution, 50% manganese nitrate solution 0.2506
The method of Example 1 is used, except that g and 200 ml of water are used.
repeated. This impregnated catalyst is 121.1℃ (250〓)
dried for 3 hours at 648.9℃ (1200〓)
Baked for 3 hours. The catalyst obtained was manganese 0.02
It contained %. Example 12 Manganese nitrate in 210 ml of water as impregnation solution.
Example 1, except that 1.253 g of a 50% aqueous solution was used.
The method was repeated. The resulting catalyst is manganese
It contained 0.1% by weight. Example 13 Two molecular sieves in a silica-alumina matrix
Calcined, coke-free equilibrium containing 4% by weight
50g of commercially available cracking catalyst
is 5.2 g of magnesium nitrate trihydrate in 50 ml of water.
The cracking catalyst is completely wetted with a solution of
It was sufficiently impregnated to the extent that This wetted catalyst
is then dried at 121.1℃ (250〓) and then
It was fired for 3 hours at 537.8℃ (1000℃). This touch
The medium contained 1% by weight of magnesium. Example 14 Half the amount of magnesium nitrate is 0.5
Used to give catalyst impregnated with wt%
The method of Example 13 was repeated, except that Example 15 Molecular sieve in silica-alumina matrix
Contains 3.8% by weight, calcined, coke-free,
Equilibrium, commercially available cracking contact
36.3 Kg (80 lb) of medium was dissolved in 12 lbs of water.
Magnesium nitrate 1.91Kg (4.2 lbs) is 3 x
to the extent that it just fills the pore volume of the catalyst in
Thoroughly impregnated. The wetted catalyst is placed on the catalyst
121.1℃ to provide 0.5% magnesium by weight
(250〓) and then 537.8℃ (1000〓)
It was fired in Example 16 100 mg of chloroplatinic acid is dissolved in 1 part of water.
18ml of the solution was removed from the commercial equipment and then
Molecular sieve baked at 537.8℃ (1000〓) for 5 hours
Equilibrium containing 2.5% by weight and 0.6% by weight of sodium
State of the art, commercially available cracking catalysts
Diluted with enough water to wet 300g.
This wetted catalyst was heated to 121.1℃ (250〓) for 3 hours.
It was dried and fired at 537.8℃ (1000℃) for 3 hours.
Ta. This catalyst contains 6 ppm platinum by weight.
there was. Example 17 95g of commercially available alumina contains vanadate
With 3.22 g of ammonium and 5 g of oxalic acid in 95 ml of water
moistened and then dried at 121.1℃ (250〓) for 3 hours
and fired for 3 hours at 537.8℃ (1000℃).
This vanadium-impregnated alumina was then dissolved in 95 ml of water.
It was wetted with a 9.3g solution of copper catalyst. This wet aluminum
Na was dried at 121.1℃ (250〓) for 3 hours and 537.8
It was baked at ℃ (1000〓) for 3 hours. This alumina
contains 2.5% vanadium and 2.5% copper by weight
It was. Example 18 Magnesium hydroxide, magnesium carbonate and
Magnesium polypropylbenzenesulfonate and
Contains 9.2% by weight of magnesium distributed as
and dissolved in 33.1g of catalytic light cycle oil.
10 g of a solution of 6.9 g of lubricating oil additive was passed through a 2.5-weight molecular sieve.
Commercial containing % and sodium 0.6% by weight
It is removed from the fluid catalytic cracking equipment and then
Calcined at equilibrium, commercially available
Ben with a fluidized bed of 220 g of cracking catalyst.
Cracking in Chiscale's cracking device
It was done. The cycle oil is at 371.1℃ (700〓)
I was cracked for 4 minutes. Catalyst bed at 676.7℃
After purging with nitrogen for 10 minutes at (1250〓), the catalyst
The floor is cooled to 371.1°C (700°) and this cooling
The racking-purging-regeneration cycle
The magnesium, zinc and phosphorus content of the medium
reaching levels of 1100, 703 and 59ppm respectively.
It was repeated until Example 19 The cracking-purging-regeneration cycle is
6.5g of the oil and 1.6% by weight of Zn, 1.3% of P and
Using 10 g of a solution containing 4.6% Mg and Mg,
nesium, zinc and phosphorus content each 2400,
repeated until reaching 1200 and 1097ppm
The method of Example 18 was repeated except that: Example 20 Molecular sieve 3.3 in silica-alumina matrix
Commercial fluid catalytic cracking, including wt%
The equilibrium state of the product taken out from the equipment and fired
Commercially available cracking catalysts are used;
and cracking-purging-regeneration cycle
is the magnesium, zinc and phosphorus content of the catalyst
until reaching 4600, 304 and 1136ppm respectively.
The method of Example 19 is repeated except that
Ta. Example 21 Magnesium carbonate, magnesium hydroxide and
Magnesium polypropylbenzene sulfonate
8.2% by weight of magnesium distributed as
7.3 g of lubrication, including sufficient amounts of xylene and xylene.
Oil additives are removed from commercial catalytic cracking equipment.
It is taken out and fired to form a silica-alumina matrix.
Molecular sieve 2.5% by weight and sodium 0.6 in Tuxus
Equilibrium commercially available clusters containing wt%
Used to moisten 2000g of Tsuking catalyst.
Ta. The wetted catalyst was heated to 204.4℃ (400〓) for 3 hours.
It was dried and baked at 537.8℃ (1000℃) for 20 hours.
Ta. The catalyst contains 3000ppm magnesium.
Ta. Example 22−27 Reduction Zone Flue Gas Carbon Monoxide Emissions
Bench-scale regeneration experimental equipment for
tested the performance of many of the impregnated catalysts in Examples 1-21.
It was used to carbon monoxide, oxygen and water
from 4% by volume of steam and 88% by volume of nitrogen, respectively.
Synthetic flue gas is passed through a metal-impregnated molecular sieve.
Approximately 1000ml of fixed fluidized bed of cracking catalyst
[measured at 15.6℃ (60〓)]
The fluidized bed has a required regeneration of 648.9℃ (1200〓)
Stored in a glass regenerator surrounded by a furnace that provides
It was held. The entrained catalyst is extracted from the outflow gas from the regenerator.
a sieve to separate and return the catalyst to the catalyst bed.
Kron was used. For a given setup with a regenerator
The operating time under constant conditions is the actual flow equation.
In operation of a catalytic cracking device,
Allow sufficient time to obtain the oxidation state of the metal.
This ranged from approximately 40 to 90 minutes. Outflow gas from the regenerator contains oxygen, nitrogen, and monoxide.
Gas chromatograph for carbon and carbon dioxide
Analyzed by F. of converted carbon monoxide
The amount of carbon monoxide in a clean synthesis gas mixture
measured as the difference between the
It was done. Impregnated catalysts synthesized in Examples 1, 4, 5, 6 and 10
Monoacid converted in Examples 22-26 where medium was used
The volume% of carbonized carbon is 65, 72, 55, and 75, respectively.
It was 65 years old. Used in Examples 1, 4, 5, 6 and 10
Conversion in Example 27 using a non-impregnated catalyst
The volume percent of carbon monoxide produced was 31. Example 28-31 To determine the desired selectivity of catalytic cracking
For this reason, it is used in the industry for microfluidized catalyst devices.
Some of the above catalysts were tested according to standard homogeneity tests.
was tested. In Example 28 as a basis, e.g.
The non-impregnated cracking catalyst used in 1 had a relative
Microactivity is 154, Coke factor is 1.0 or
and the molar percentage ratio of hydrogen to methane was 0.64. example
In 29, the impregnated catalyst produced in Example 1 was used.
However, the relative micro-activity was 147, compared to coke.
The factor is 1.1, and the mole % of hydrogen to methane
The ratio showed approximately 1.1-1.2. In example 30, example 4
An impregnated catalyst produced in
Coke activity is 150, Coke factor is 1.1 and
and the molar percentage ratio of hydrogen to methane should be between 0.9 and 1.1.
was recognized. In example 31, generated in example 6
A catalyst with a relative activity of 134 and
The factor is 2.0, and the hydrogen versus methane model is 2.0.
The % ratio was 6.5. Examples 32-38 Instead of the impregnated catalyst, the non-impregnated catalyst used in Example 1
5 microns and finer mixed with medium
Powdered metal oxides with large particle sizes are used.
The method of Examples 22-27 was repeated except that: example
Carbon monoxide converted to carbon dioxide in 32−35
The volume % of the element and the amount of powdered metal oxide are the first
Shown in the table. Without metal oxides, others
Comparative Example 36 under the same conditions is also shown in Table 1.
Ru. Example 37, and others without metal oxides
The similar data of Comparative Example 38 under the same conditions are also the same.
It is shown in Table 1.

[Table] Example 39-40 676.7 consisting of 1500 ppm sulfur dioxide in a mixture containing 4% by volume each of oxygen and steam in nitrogen
℃ (1250〓) synthetic flue gas at 1500ml per minute
Examples 22-27, except that an ultraviolet analyzer was used to continuously measure the sulfur dioxide content in the effluent gas, which was passed through the regenerator at 15.6°C (60°C). method was repeated. Comparative tests were conducted using the unimpregnated catalyst used in Example 16 and the impregnated catalyst produced in Example 16. Example 39 contained unimpregnated catalyst, while Example 40 contained impregnated catalyst. The volume percent sulfur dioxide removed from the regeneration zone flue gas is shown in Table 2 as a function of elapsed time after the start of the experiment. The volume percent sulfur dioxide removed decreased over time as the catalyst surface became saturated. In Example 39, the sulfur level in the form of soluble sulfate on the catalyst was
111 ppm and then 733 ppm, which is 91 ppm of the sulfur removed from the regeneration zone onto the catalyst.
Corresponds to weight percent recovery.

Table Examples 41-42 Example 39 in a comparative test using a molecular sieve type cracking catalyst and a mixture of different amounts of vanadium- and copper-impregnated alumina produced in Example 17.
−40 methods were repeated. In Example 41, 10 g of vanadium- and copper-impregnated alumina are
3.3% by weight, was removed from a commercial fluidized catalytic cracking unit and mixed with a commercially available equilibrium cracking catalyst that had been calcined at 537.8°C (1000°C) for 5 hours. The flow rate of the synthetic flue gas was 854 cm ³ /min (at 60 °C). In Example 42, the vanadium and copper of Example 17
0.5 g of impregnated alumina was mixed with 49.5 g of the same commercially available calcined equilibrium cracking catalyst used in Example 41. The flow rate of this synthetic flue gas is 513cm ³ /min [15.6℃ (60〓)
[measured]. The volume percent sulfur dioxide removed from the flue gas of Examples 41-42 is shown in Table 2. Examples 43-47 The method of Examples 39-40 was repeated using a regeneration temperature of 676.7°C (1250°). Example 43 shows the flow rate of a synthetic flue gas mixture of 1084 ml/min and Examples 18-19
Examples 44-45 were compared with the impregnated catalysts prepared in Examples 18-19 and 989 and 1014, respectively.
Includes the flow rate of the synthetic flue gas mixture in ml/min.
Example 46 is a comparative test using the unimpregnated catalyst used in Examples 20, 41, and 42 and a synthetic flue gas mixture flow rate of 891 ml/min. Example 47 includes the impregnated catalyst prepared in Example 20 and a flow rate of the synthetic flue gas mixture of 992 ml/min. The volume percent sulfur dioxide removed from the flue gases of Examples 43-47 is shown in Table 2. Examples 48-50 Bench scale experimental fluid catalytic cracking tests were conducted on a gas oil feed containing 2.4% by weight sulfur in the form of organosulfur compounds. For the calcined, unimpregnated, equilibrium catalyst used in Example 13 and the impregnated catalysts prepared in Examples 13 and 14, respectively, in comparative cracking tests at the constant cracking severity of Examples 48-50, The amount of sulfur dioxide released from the stripped and deactivated catalyst was measured and calculated as ppm by weight of sulfur on the catalyst. The sulfur that could be removed from the catalyst containing 1% magnesium by weight in Example 49 was 52 ppm, a reduction of 61%. The sulfur that can be removed from the catalyst containing 0.5% magnesium by weight in Example 50 is 73 ppm and 46
% reduction rate. Examples 51-52 In a continuous cracking regenerator of the type described in U.S. Pat. Comparative tests involving cracking gas oil were conducted. Example 51 contains an impregnated catalyst whereas Example 52 contains an impregnated catalyst.
Contains unimpregnated catalyst. The operating conditions and composition of the regenerator flue gas are shown in Table 3. Examples 53-54 Cyclic fluidized cracking in a pilot plant using the unimpregnated catalyst used in Example 15 and the impregnated catalyst prepared in Example 15 on a gas oil feed having a sulfur content of 2.4% by weight. A test was conducted. Examples 53 and 54 contain unimpregnated and impregnated catalysts, respectively. The operating conditions and regeneration zone flue gas composition are shown in Table 3. The impregnated catalyst reduces sulfur dioxide emissions in the regenerator flue gas by 57.5%. Conversion and product yield were essentially the same for each catalyst.

[Table] Playback conditions:
Concentrated bed temperature, °C 648.9 648.9
585.5 587.2 687.8
707.2
(〓) (1200) (1200)
(1086) (1089) (1270)
(1305)

Claims (1)

[Scope of Claims] 1 Consisting of a mixture of the following separate particles (a) and (b), where (a) is at least one selected from the group consisting of silica, alumina, zirconia, titania, magnesia, thoria and boria. (b) a particulate solid cracking catalyst for cracking hydrocarbons comprising a matrix of two types, the matrix comprising a crystalline aluminosilicate, the amount of the cracking catalyst being greater than about 30% by weight of the particulate physical mixture; is at least one first metal in elemental or compound form selected from the group consisting of palladium and platinum, and sodium, magnesium, titanium, manganese, copper, zinc, cadmium,
At least one second metal in the form of an element or compound selected from the group consisting of lead and rare earth metals, and at least one inorganic oxide selected from the group consisting of silica and alumina,
the amount of the first metal is from about 0.1 ppm to about 10 ppm, calculated as metal, of the particulate physical mixture, and the amount of the second metal is from about 50 ppm to about 10%, calculated as metal, of the particulate physical mixture; A catalyst composition for the catalytic cracking of a hydrocarbon feedstock containing a sulfur compound, which is a particulate solid separate from the particulate cracking catalyst. 2. The second metal in elemental or compound form is sodium, magnesium, manganese, copper, zinc,
A catalyst composition according to claim 1 selected from the group consisting of cadmium and rare earth metals. 3. A catalyst composition according to claim 1, wherein the second metal in elemental or compound form is selected from the group consisting of sodium, rare earth metals and magnesium. 4. According to claim 1, the second metal in elemental or compound form comprises sodium, and the amount of sodium is from about 0.6 to about 3% by weight of the particulate physical mixture, calculated as metal. Catalyst compositions as described. 5. The second metal in elemental or compound form is selected from the group consisting of magnesium, zinc, cadmium and manganese, and the amount of this second metal, calculated as metal, is about 0.01 of the particulate physical mixture.
5. The catalyst composition of claim 1, wherein the catalyst composition is about 5% by weight. 6. The catalyst composition according to claim 1, wherein the inorganic oxide is alumina. 7. The catalyst composition of claim 1, wherein the inorganic oxide has a surface area of at least about 10 m ² per gram. 8. The catalyst composition of claim 1, wherein the inorganic oxide has a surface area of at least about 50 m ² per gram. 9 Particulate solids approximately 20 microns or less to approx.
A catalyst composition according to claim 1 having an average particle size in the range of 150 microns. 10. The catalyst composition of claim 1, wherein the matrix is selected from the group consisting of silica, alumina, thoria and boria. 11. The catalyst composition of claim 1, wherein the matrix is a mixture of silica and alumina. 12 Matrix is about 10 to about 65% alumina by weight
and about 35 to about 90 weight percent silica. 13. The composition of claim 1, wherein the cracking catalyst contains from about 0.5 to about 50% by weight of crystalline aluminosilicate. 14. The composition of claim 1, wherein the inorganic oxide constitutes the major portion of the particulate solid other than the cracking catalyst. 15 Consisting of a mixture of separate particles of the following (a), (b) and (c), where (a) is at least two types selected from the group consisting of silica, alumina, zirconia, titania, magnesia, thoria and boria. a first particulate solid comprising a fluidizable particulate solid cracking catalyst for hydrocarbon cracking comprising a matrix comprising a crystalline aluminosilicate, the amount of the cracking catalyst being about more than 30% by weight, (b) the first metal in elemental or compound form of at least one selected from the group consisting of palladium and platinum is at least one selected from the group consisting of silica and alumina; in combination with an inorganic oxide, the amount of the first metal being from about 0.1 ppm to about 0.1 ppm, calculated as metal, of the particulate physical mixture.
a second particulate solid separate from the particulate cracking catalyst, about 10 ppm; (c) at least one selected from the group consisting of sodium, magnesium, titanium, manganese, copper, zinc, cadmium, lead and rare earth metals; A granular solid consisting of a second metal in elemental or compound form and at least one inorganic oxide selected from the group consisting of silica and alumina, the amount of the second metal being calculated as metal. from about 50 ppm to about 10% by weight of the particulate physical mixture, separate from the particulate cracking catalyst, capable of adsorbing sulfur components;
A catalyst composition for the catalytic cracking of a hydrocarbon feedstock containing an organosulfur compound, which is a particulate solid. 16 The second metal in elemental or compound form is sodium, magnesium, manganese, copper, zinc,
A catalyst composition according to claim 15 selected from the group consisting of cadmium and rare earth metals. 17. Catalyst composition according to claim 15, wherein the second metal in elemental or compound form is selected from the group consisting of sodium, rare earth metals and magnesium. 18 First and second separate from cracking catalyst
16. The catalyst composition of claim 15, wherein the particulate solid inorganic oxide is alumina. 19. Catalyst composition according to claim 15, wherein the inorganic oxide of the first particulate solid, separate from the cracking catalyst, constitutes the main part of this first particulate solid. 20. The catalyst composition of claim 15, wherein the inorganic oxide of a second particulate solid separate from the cracking catalyst constitutes a major portion of this second particulate solid.