JPS5946994B2 - Method for converting vanadium-containing hydrocarbon oil to light products - Google Patents

Abstract

A process is disclosed for catalytic cracking a hydrocarbon oil feed having a significant vanadium content to produce lighter products. The catalyst, from the cracking step, coated with coke and vanadium in an oxidation state less than +5, is regenerated in the presence of an oxygen-containing gas at a temperature high enough to burn off a portion of the coke under conditions keeping the vanadium in an oxidation state less than +5.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for converting heavy hydrocarbon oils into light fractions, particularly for converting heavy hydrocarbon oils containing high concentrations of coke@1 precursor materials and heavy metals into gasoline and other The present invention relates to a method for converting hydrocarbon fuel oil into hydrocarbon fuel oil.

The introduction of catalytic cracking into the petroleum industry in the 1930's established a major advance over previous technology with the aim of improving the yield of gasoline and its quality.

Initially fixed bed, moving bed and fluidized uncatalyzed cracking FCC processes used vacuum gas (UGO) from crude oil feedstock sources considered sweet and light.

The term sweet refers to low sulfur content, while the term light refers to approximately 1
Refers to crude oil that boils below 0.000-1025°F.

The catalysts originally used in homogeneous dense fluidized beds were amorphous silicon materials from naturally occurring materials that were either synthetically produced or activated by acid leaching.

During the 1950's tremendous advances were made in FCC technology in the areas of metallurgy, processing equipment, regeneration, and new, more active and more stable amorphous catalysts.

However, the increasing demand for quantities of gasoline to satisfy new high-horsepower, high-compression engines driven by the automobile industry and the need for improved octane ratings put extreme pressure on the oil industry to increase FCC capacity and harsh operations. I hung it.

A major breakthrough in FCC catalysis was the introduction of molecular sieves or zeolites in the early 1960s.

These materials were incorporated into the amorphous matrix and/or matrix of amorphous/kaolin material that comprised the then FCC catalyst.

These new zeolite catalysts containing crystalline aluminosilicate zeolites in silica, alumina, silica-alumina, kaolin, china clay, etc./kaolin mal-IJ lux are suitable for the decomposition of hydrocarbons in the initial amorphous or amorphous form. / was at least 1000 times more active than the kaolin-containing silica-alumina catalyst.

This zeolite cracking catalyst revolutionized the fluidized catalytic cracking process.

Techniques have been developed to handle these high activities such as riser cracking, short contact times, new regeneration methods, development of improved zeolite catalysts, etc.

The development of new catalysts has led to the development of various zeolites, such as synthetic Improvements have been made in the development of matrices with increased thermal) stability and abrasion resistance to support the zeolites.

The development of these zeolite catalysts provides the petroleum industry with the ability to significantly increase the throughput of feedstock with increased conversion and selectivity using the same equipment without expansion and without the need for new equipment construction. gave.

After the introduction of zeolite-containing catalysts, the petroleum industry began to suffer from a lack of availability of crude oil in terms of quantity and quality as the demand for gasoline increased with increasing octane numbers.

The world's crude oil supply sphere changed laterally in the late 1960s and early 1970s.

From a glut of light and sweet crude oils, the supply situation has changed to a tight supply with ever-increasing amounts of heavy crude oils with high sulfur content.

These heavy crude oils also presented petroleum refiners with the problem of processing these heavy high sulfur crude oils containing extremely high levels of metals and Conradson carbon along with significantly increased asphalt content.

Fractional distillation of the total crude oil to provide the catalytic cracking feed also results in metal and Conradson carbon values associated with the overhead distillate.
Better control was needed to ensure not contaminating the CC feedstock.

Zeolite-containing F of heavy metals and Conradson carbon
The effects on CC catalysts have been described in the literature for their unfavorable effects on gasoline production, reducing catalyst activity and selectivity, and their equally deleterious effects on catalyst life.

As noted, these heavy crude oils also contain large amounts of heavy fractions, typically boiling below about 1025°F and typically bringing total metal levels below 1 p1) I[l, preferably below 0.1 ppm. and also contain fewer or less high quality FCC feedstocks that are processed to contain a Conradson Carbon Value of substantially less than 1.0.

Due to the increasing supply of heavy crude oil, which means low yields of gasoline, and the increasing demand for liquid transportation fuels, the petroleum industry has begun researching processing methods to utilize these heavy oils to produce gasoline.

Many of these processing methods are described in the literature.

These include Gulf's Gulffining and Union Oil's unifying processes for processing residual oils, UOP's Orlabon process for producing hot gasoline and coke, Hydrocarbon Research's H-Oil process, Exxon's Flexicoke process, and H-Oil process for producing hot gasoline and coke. Da f na Cracking and Philip's Baby Oil Cracking (HOC
) law is included.

These methods utilize pyrolysis or hydrotreating to treat high metal contaminants with FCC or hydrocracking operations (high vanadium-iron-copper-sodium) and high Conradson carbon values of 5-15. ing.

Some deficiencies in these types of processing are noted.

Coking has a much lower octane number than cracked gasoline, resulting in unstable pyrolysis gasoline due to the formation of rubber from diolefins and requiring further hydrocracking or reforming to produce a higher octane product.

The properties of gas oils are degraded by thermal reactions that produce products containing high levels of refractory polynuclear aromatics and Conradson carbon that are highly unsuitable for catalytic cracking.

Hydroprocessing also requires expensive high pressure hydrogen, multi-reaction systems made of special alloys, expensive operating equipment, and separate expensive equipment for hydrogen production.

To further understand the reasons for the evolution along the described processing mechanism, the known effects of contaminant metals (Kkkeru vanadium-iron-copper monosodium) and Conradson carbon on the operating parameters of zeolite-containing cracking catalysts and FCC equipment are discussed. must understand the established influence of

Metal content and Conradson carbon are two limitations that greatly affect the operation of FCC units and also impose unfavorable limitations on atmospheric resid conversion in terms of maximum conversion, selectivity and lifetime. .

These relatively low levels of contaminants are extremely damaging to FCC equipment.

As metal and Conradson carbon levels further increase, the operational capacity and efficiency of FCC equipment is adversely affected and becomes uneconomical.

This is true even if there is enough hydrogen in the feedstock to produce an ideal gasoline consisting only of toluene and pentene isomers (assuming a catalyst with such ideal selectivity is devised). There are negative effects.

The effect of increased Conradson carbon is that the portion of the feed that is converted to coke deposited on the catalyst increases.

A typical V using a zeolite-containing catalyst in an FCC unit
The amount of coke deposited on the catalyst in GO operations is on average 4-5% by weight of the feedstock.

This coke formation involves four different coking mechanisms.

i.e., contaminated coke from back reactions caused by deposited metals, catalytic coke from acid site cracking, hydrocarbons resulting from pore structure sorption and/or insufficient stripping, and hydrocarbons in the conversion zone. Conradson carbon produced by pyrolytic distillation.

In addition to the four present in VGO, two other sources of coke present in the atmospheric distillation residue are assumed.

These are (1) sorbed and absorbed high boiling hydrocarbons that do not evaporate and are not removed by normal efficient stripping and (2) high molecular weight nitrogen-containing hydrocarbons that are absorbed into the acid sites of the catalyst. .

Both of these two new types of coke formation phenomena greatly increase the complexity of residue processing.

Therefore, in the treatment of high-boiling fractions such as atmospheric distillation residual oil, residue fraction, prefixed crude oil, etc., coke formation based on feedstock oil is
The sum of the four species present in the GO process (Conradson carbon values are generally much higher than in VGO) plus coke from unstripped high-boiling hydrocarbons and coke associated with high-boiling nitrogen-containing molecules adsorbed onto the catalyst. It is.

Coke production on clean catalysts during the processing of atmospheric distillation residues is estimated to be approximately 4% of the feedstock plus the Conradson carbon value of the heavy feedstock.

The coked catalyst is brought back to equilibrium activity by burning the deactivated coke in the presence of air in the regeneration zone, and the regenerated catalyst is recycled to the reaction zone.

The heat generated during regeneration is removed by the catalyst and transferred to the reaction zone for evaporation of the feedstock to provide heat for the endothermic cracking reaction.

The temperature in the regenerator is limited due to metallurgical limitations and the hydrothermal stability of the catalyst.

The hydrothermal stability of zeolite-containing catalysts is measured by the temperature and vapor partial pressure at which the zeolite begins to rapidly lose its crystalline structure, resulting in a less active amorphous material.

The presence of vapor is very critical for the absorption of sorbed carbonaceous materials with sufficient hydrogen content (hydrogen to carbon atomic weight ratio is generally less than about 0.5). Generated by combustion.

This carbonaceous material is primarily a high boiling sorbent hydrocarbon having a high boiling point, such as 1500-1700 DEG F., with a moderate hydrogen content and high boiling nitrogen-containing hydrocarbons and associated porphyrins and asphaltenes.

High molecular weight nitrogen compounds usually boil above 1025'F and are either basic or acidic in nature.

The basic nitrogen compound neutralizes the acid sites, while further acidic moieties are attracted to the metal portion of the catalyst.

Porphyrins and asphaltenes are also commonly 102
Boils above 5°F and contains elements other than carbon and hydrogen.

As used herein, the term "heavy hydrocarbon" includes all carbon- and hydrogen-containing compounds that do not boil below 1025°F, regardless of whether other elements are present in the compound. do.

Heavy metals in feedstocks are generally present as porphyrins and/or asphaltenes.

However, some of these metals, particularly iron and copper, exist as free metals or inorganic compounds resulting from corrosion of processing equipment or contaminants from other refining methods.

As the Conradson carbon value of the feed increases, coke production increases and the load of this increase causes the regeneration temperature to rise.

The equipment is therefore limited in the amount of feedstock it can process due to the Conradson carbon content.

Early ■ GO equipment had a playback device of 1050-1250°F.
It was operated with.

New developments in the treatment of atmospheric distillation residues, namely pending U.S. Patent Application No. 94.091, No. 94,092, No. 94,
No. 216, No. 94,217 and No. 94,227
``Reduced Crude Conversion Process (RCC) Process for Anland Oil'' described in No. 1, No. 1, No. 1, filed November 14, 1979, the regenerator temperature is operated in the range of 1350-1400'F.

However, these high regenerator temperatures limit the Conradson Carbon value of the feedstock to about 8, which represents about 12-13 weight percent coke based on feed weight catalyst ratio.

This level is regulated unless a significant amount of water is introduced to further control the temperature, which addition is also practiced in the Ashland RCC process.

The metal-containing fraction of atmospheric distillation residue is nickel-vanadium.
Contains iron-copper in the form of porphyrins and asphaltenes.

These metal-containing hydrocarbons are either deposited on the catalyst during processing and decomposed in the riser to deposit metals, or
It is carried by the coked catalyst as porphyrins or asphaltenes and is converted to metal oxides during regeneration.

The negative effect of these metals, as the literature teaches, is to cause non-selective or decompositional cranking and hydrogenation, producing increased amounts of coke and light gases such as hydrogen, methane, and ethane.

These mechanisms adversely affect selectivity, resulting in poor gasoline and light cycle oil yields and quality.

The increase in the production of light gases, on the one hand, worsens the yield and selectivity and also increases the demands on the capacity of the gas compressor.

In addition to its negative impact on yield, increased coke production also negatively impacts catalyst activity-selectivity, significantly increasing regenerator air requirements and compressor capacity, and regulating regenerator temperature. disable and/or make dangerous.

These problems of the prior art have been significantly reduced with the development of Anland Oil's atmospheric residue conversion (RCC) process described above and in related applications incorporated herein.

This new process can process atmospheric distillation residues or crude oils containing high metal and Conradson carbon values that were previously not possible for direct processing.

It has long been recognized that atmospheric distillation residues with high nickel levels present significant problems with respect to catalyst failure at high metal contents on the catalyst, e.g. 5.000-10.00 Qppm, and at high regenerator temperatures. known from.

It is now recognized that when atmospheric distillation residues with high vanadium levels are processed over zeolite-containing catalysts, rapid disqualification of the zeolite can occur, especially in the case of high vanadium levels on the catalyst.

This disqualification in itself proves the loss of the zeolite structure.

This loss was observed at vanadium levels of 1.0001) III[l by weight or less.

This loss of zeolite structure becomes more rapid and severe with higher vanadium levels, and is approximately 5.
At the vanadium level of OOOI)I)m, especially 10
．． Complete destruction of the zeolite structure will occur at levels close to 0OOpFl.

Before this invention, 10.000 pl) m for this phenomenon.
It was considered impossible to operate economically at higher vanadium levels.

Conventionally, catalyst failure due to vanadium at vanadium levels below 10.00 Qppm has been slowed by lowering the regenerator temperature and increasing the rate of fresh catalyst addition.

However, lowering the regenerator temperature has the disadvantage of increasing the amount of coke produced and requiring a high catalyst-to-oil ratio, which negatively affects yield.

Also, increasing the catalyst addition rate increases costs and makes operation uneconomical.

Vanadium has been found to be particularly detrimental to catalyst life.

The vanadium deposited on the catalyst is in an oxidation state below +5 under reducing conditions in the riser.

At the high temperatures and oxidizing conditions encountered in the regenerator, the vanadium on the catalyst is converted to vanadium oxide, particularly vanadium pentoxide.

This vanadium pentoxide has a melting point lower than the temperatures encountered in the regeneration zone and therefore can become a free-flowing liquid that flows across the catalyst surface and plugs the pores.

This vanadia also enters the zeolite structure, neutralizing its acid sites and, more importantly, irreversibly destroying its crystalline aluminosilicate structure,
There may be some formation of amorphous material with low activity.

Additionally, the molten vanadia, especially at high vanadia levels, can coat the catalyst microspheres and cause the particles to adhere to each other, adversely affecting their fluidization, especially for low surface area catalyst materials.

The inventors have discovered that vanadium has a lower melting point than oxides of vanadium at low oxidation numbers when forming vanadium pentoxide (V2O5).

By the way, the melting point of vanadium pentoxide (V2O5) is 69.
At 0°C, the melting point of vanadium dioxide (VO2) is 1967
℃, the melting point of vanadium trioxide (V203) is 1970℃
, the melting point of vanadium oxide (■0) is higher than that of vanadium trioxide.

Fused vanadium tautomide overcomes three potential problems with the recirculating Lygo cracking/regeneration process for hydrocarbon conversion or the sorbent catalysis/regeneration process for removing carbon and metals from hydrocarbons contaminated with carbon and metals. had.

First, vanadium migrates to the outer surface of the catalyst and plugs the pores in the catalyst by sintering the catalyst matrix, forming a glass-like smooth material that converts to active sites inside the catalyst matrix. This is to prevent contact with hydrocarbons.

Second, vanadium migrates into the zeolite portion of the catalyst, which is usually protected by a porous material, disrupting the zeolite structure and converting it to mullite or other catalytically inactive products. be.

The third problem, perhaps the most serious with respect to mobile vanadium, is the ability of vanadium to flow to the outer surface of the sorbent or catalyst.

This causes the individual particles to become non-cohesive, causing agglomeration and consequent loss of fluid, and forming large clumps that block the conical leg of the cyclone and cause loss of catalyst.

Applicants have discovered that the three problems mentioned above can be avoided by preventing the vanadium from forming vanadium pentoxide, which has a low melting point.

As mentioned above, the findings of the present invention are that the oxidation state of vanadium +
This is based on the fact that the melting point in the case of 5 is extremely lower than that in the case of +4 or higher.

Therefore, in the present invention, any numerical value may be used as long as it is +4 or less, and the form of vanadium oxide is VO2V2O.
, V2O3, or other oxides with an oxidation state of +4 or lower, but are not limited to these compounds.

Further, any of these compounds may be used and there is no particular preference for any compound.

In other words, the object of the present invention can be achieved if the oxidation state of vanadium is +4 or less.

Applicants have discovered that maintaining vanadium in a low oxidation state produces significant effects.

This knowledge is one of the features of the present invention, and once the effectiveness of this low oxidation state is recognized, many means or methods can be considered and provided relatively easily.

The claims of the invention are intended to cover all such means and methods.

According to the invention, a feedstock of vanadium-containing hydrocarbon oil is contacted with a cracking catalyst under conversion conditions to form light products and coke, whereby vanadium in an oxidation state less than +5 is transferred to the catalyst along with the coke. A method for converting a vanadium-containing hydrocarbon oil feedstock to a light product is provided, comprising the step of depositing a vanadium-containing hydrocarbon oil feedstock.

The light products are cracked from the depleted catalyst, which is contacted with an oxygen-containing gas under conditions in which the coke is combusted to form CO and CO2, and the vanadium is maintained in an oxidation state below +5. It is played by

The depleted catalyst is the catalyst that has accumulated coke and metals after contact with the feed oil in the riser and separation from the reaction products.

This has not been stripped.

Further, the definitions of matters related to catalysts used in this specification are as follows.

Equilibrium catalyst refers to the catalyst obtained from the regenerator after regeneration and sent to the bottom of the riser for contact with the feed.

Refers to the catalyst in its instant state as it is sent to the bottom of the riser.

Its activity is a function of the quality of the feed oil, the amount of fresh catalyst added and the amount of regenerated catalyst recovered.

Reference catalyst and standard catalyst are used interchangeably.

That is, they are used to measure the catalytic performance of new or existing catalysts.

Operating catalyst and production catalyst have the same meaning.

In particular, operating catalysts are catalysts that are actually used, and production catalysts are catalysts that are used on a commercial scale.

This invention provides vanadium as high as 10.000 pI)m by maintaining it in an oxidized state with a high melting point.
or an additional 20,000p11+11 or 50.
Enables catalyst recirculation to vanadium levels as high as 0.000[]pm.

In this way, various negative effects such as catalyst agglomeration and pore blockage caused by melted vanadium particles are avoided.

This catalyst can withstand significantly higher vanadium loadings than previously experienced, thereby reducing the amount of catalyst composition required.

The invention can be carried out by controlling the regeneration of the vanadium-containing depleted catalyst using several methods alone or in combination.

The purpose of these methods is to maintain the vanadium in a low oxidation state by not exposing it to oxidizing conditions or exposing it to oxidizing conditions for a very short time without oxidizing significant amounts of vanadium to the +5 state. be.

The concentration of vanadium in the catalyst particles increases as the catalyst is recycled, and the vanadium in the catalyst introduced into the reactor becomes coated with the coke formed in the reactor.

In one method of practicing the invention, regenerator conditions are selected to ensure that the coke concentration is maintained at least at a minimum level above the catalyst.

This coke acts either to ensure a reducing environment for the vanadium or to provide a barrier to the movement of oxidizing gases to the underlying vanadium.

The coke concentration on the catalyst is small, at least about 0.05%.
and the preferred coke concentration is at least about 0
．． It is 15%.

One method of carrying out this invention - a method that can be used in conjunction with the previous method of retaining at least about 0.05% coke on the catalyst, or used to achieve lower coke concentrations, in which regeneration is less than +5 It is carried out in an environment that is non-oxidizing to vanadium in the oxidation state.

This can be achieved by adding a reducing gas to the regenerator, such as CO or ammonia, or by regenerating under oxygen-deficient conditions.

Regeneration under oxygen-deficient conditions increases the ratio of CO to CO□,
And in this method of providing a non-oxidizing atmosphere, the CO/CO2 ratio is at least about 0.25, preferably at least about 0.3, and most preferably at least about 0.4.

This CO/CO2 ratio can be controlled by controlling the degree of oxygen starvation within the regenerator.

The CO/CO2 ratio can be increased by adding chlorine to the oxidizing atmosphere within the regenerator.

Preferably, the chlorine concentration is about 100 to 400 pHl.

This method of increasing the CO/CO2 ratio was introduced on March 23, 1981.
US Pat.

This patent application involves adding salt (e-magnesium) to the depleted catalyst in a regenerator to convert it to magnesium chloride and chlorine components.

Magnesium oxide reduces sulfur oxide emissions and the chlorine component increases the CO/CO2 ratio.

It is disclosed that thereby reducing the heat emission of the regenerator.

The use of a reducing atmosphere in the regenerator is particularly useful in burning coke in zones where coke levels approach or fall below about 0.05%;
And it is preferred to have a CO/CO□ ratio of at least about 0.25 in zones where the coke loading is about 0.05% by weight or less.

Vanadium is particularly effective when kept in a reduced state under conditions where the catalyst particles are in constant contact or relatively often in contact with each other.

Therefore, when carrying out this process, it is specifically intended to maintain a reducing atmosphere in a zone within the regenerator in which the catalyst particles are in a relatively dense bed, such as a dense fluidized or settled bed. be done.

Reducing gases such as CO, methane or ammonia are
For example, it can be added to a zone having a dense catalyst bed, such as a bed having a density of about 25 pounds per cubic foot to about 50 pounds per cubic foot.

Another method of carrying out the invention uses a riser regenerator as one stage of a multi-stage regenerator to expose the catalyst to an oxidizing atmosphere, such as for less than about 2 seconds, preferably for about 1 hour.
Contact for a short period of time, such as less than a second.

The riser stage of the regenerator is advantageous in reducing the carbon concentration to levels below about 0.15%, or below about 0.05%, where the vanadium (no longer protected by the carbon coating) is in the oxidation state +5. The oxidizing atmosphere cannot exist long enough to form molten vanadium.

Furthermore, in riser regenerators, the low density of catalyst particles minimizes the adhesion of particles that would have liquid vanadia on their surface.

In this preferred method using a riser regenerator,
After the catalyst particles exit the riser, they are contacted with a reducing atmosphere, such as an atmosphere containing CO or other reducing gases.

The catalyst particles are then recycled, for example, to accumulate in a settling bed, before contacting additional fresh feedstock oil.

The catalyst particles to be accumulated are preferably contacted with a reducing atmosphere immediately after leaving the riser and before being accumulated into a dense bed of regenerated catalyst particles, and in this preferred method of carrying out the process of the invention. The catalyst particles are maintained in a reducing atmosphere within such a dense bed, and in the most preferred method the reducing atmosphere is also applied to the catalyst particles until the time they contact the fresh feedstock. It is given.

A preferred riser regenerator is disclosed in U.S. Pat.
, 066,533 and 4,070,159.

This device has the advantage of achieving virtually instantaneous separation of the regenerated catalyst, now containing some vanadia, from the oxidizing atmosphere to which the oxygen present will be accessible.

In this preferred method of reducing the coke concentration to a level of about 0.15% or less, particularly 0.05% or less, the catalyst is added to the reducing atmosphere, preferably immediately after its separation from the oxidizing atmosphere, and most preferably Contact is preferably made in the collection zone of the regenerated catalyst.

This invention can be used to treat any hydrocarbon feedstock containing significant concentrations of vanadium and
C method and RCC method are intended.

However, this invention is particularly useful in treating atmospheric distillation residues having high metal values and high Conradson carbon values, and will therefore be described in detail regarding the use of this invention in treating RCC feedstock oils. .

Carbo-metal feed
lic feed), or carbon-metal feedstock oil, comprises or consists of oil that boils at a temperature of about 650°F or higher.

Such oil, or the at least 650° F.+ oil portion thereof, has a heavy metal content of at least 4 ppI by weight as nickel equivalents, preferably greater than about 5μ, and most preferably at least about 5.51) carbon residue of at least about 1% by weight, more preferably at least about 2% by weight.

In accordance with the present invention, a carbon-metal feedstock oil in the form of a feedable liquid is contacted with a thermal conversion catalyst at a catalyst to feedstock weight ratio of about 3 to about 18, preferably about 6 or more.

The feedstock oil, in the form of said mixture, undergoes a conversion step that includes a step in which the mixture of feedstock oil and catalyst undergoes cracking while flowing through a gradual flow type reactor.

Feedstock oil, catalyst and other materials can be introduced at one or more points.

The reactor is at least partially vertical or tilted in such a way that the feed material, resulting product, and catalyst flow relative to each other as a dilute phase or stream for a predetermined riser residence time ranging from about 0.5 seconds to about 10 seconds. It contains an elongated reaction chamber that is held in contact with the reactor.

The reaction provides a conversion of about 50% or more per throughput and includes coke on the catalyst in an amount ranging from about 0.3% to about 3%, preferably at least about 0.5% by weight. Under sufficiently severe conditions to cause deposition, approximately 10
psia to about 900° F. measured at the exit of the reaction chamber at a total pressure of about 50 psia (pounds per square inch absolute)
Perform at a temperature of ~1.400°F.

The total coke production rate ranges from about 4% to about 14% by weight based on the weight of the fresh feedstock.

At the end of a given residence time, the catalyst is separated from the product and stopped to remove high boiling components and other entrained or sorbed hydrocarbons, and then reduce the carbon content on the regenerated catalyst to about 0.25% or less. enough time to lower the
Regenerate with oxygen-containing combustion sustaining gas under temperature and ambient conditions.

Depending on how the method of the invention is implemented, one or more of the following additional advantages may be realized.

Optionally, and preferably, the process of this invention can be operated without added hydrogen in the reaction chamber.

Optionally, and preferably, the process can be operated without prior hydrorefining treatment of the feedstock and/or without other methods of removing metal asphaltenes from the feedstock, and it The metallic oil as a whole is about 499,111 or more by weight as nickel equivalents or about 5 ppII or more, and about 5.51)I)1
11 or more, contains heavy metals, and has a pyrolytic carbon residue of about 1% by weight or more, or about 1.4% by weight or more, or about 2% by weight or more.

Furthermore, as mentioned above, the feedstock oil for the converter is all 1
can be decomposed in the same conversion chamber.

This cracking reaction is carried out over conventionally used (recycled except for such substitutions required to compensate for normal losses and deactivation) catalysts and under the above conditions carbon-metal feedstocks. Can break down oil.

Heavy hydrocarbon oils that are not cracked into gasoline in the first pass can be recycled with or without hydrorefining treatment for further cracking in contact with like feedstock oils.

In this cracking, the hydrocarbon oil is first subjected to cracking conditions similar to those described above, but in a substantially single pass, i.e. Operation with a recirculation amount of less than % by volume) is preferred.

According to one preferred embodiment or aspect of the invention, at the end of said predetermined residence time, the catalyst is injected in the direction defined by the elongated reaction chamber or in the direction of its extension;
Meanwhile, the momentum causes a sudden change in direction of the product, causing a rapid, virtually instantaneous ballistic separation of the product from the catalyst.

The catalyst thus separated is then subjected to an IJ sputtering process.
It is regenerated and recycled to the reactor.

According to another preferred embodiment or aspect of the invention, the converter feedstock oil has not undergone hydrorefining treatment and is at least about 5.51) liters of nickel equivalent.
65, which is characterized in part by containing heavy metals of
Contains material at 0°F+.

The feedstock oil of this converter is not only combined with the cracking catalyst described above, but also with additional gaseous materials, including water vapor, so that the resulting suspension of catalyst and feedstock oil is Also included are gaseous materials having a ratio of the partial pressure of the gaseous material to the partial pressure of the feedstock oil in the range of about 0.25 to about 4.0.

The residence time of the vapor when practicing this embodiment or aspect ranges from about 0.5 seconds to about 3 seconds.

The preferred embodiments or aspects of this and the embodiments or aspects of the preceding paragraphs can be used in combination with each other or separately.

According to yet another preferred embodiment or aspect of the invention, the carbon-metal feedstock is not only catalyzed but also catalyzed with one or more additional substances, including in particular liquid water. about 0.04 to about 0
．． 25, preferably in a weight ratio ranging from about 0.04 to about 0.2, more preferably from about 0.05 to about 0.15.

Such additional substances, including liquid water, may be added to the feedstock oil either before, during or after mixing the feedstock oil with said catalyst, and either before or after vaporization of the feedstock oil, preferably before vaporization. Can be mixed with.

Feedstock oil, catalyst and water (eg, in the form of liquid water or water vapor produced by vaporization of liquid water in contact with the feedstock oil) are introduced into a gradual flow type reactor.

A progressive flow type reactor may or may not be a reactor that achieves the ballistic separation described above at one or more points across the reactor.

While the mixture of feedstock oil, catalyst, and water vapor produced by vaporization of liquid water flows through the reactor, the feedstock oil is subjected to the conversion step described above, including the cracking step.

The feedstock oil material, catalyst, steam, and resulting product are allowed to flow together in said elongated reaction chamber as a dilute phase or stream for said predetermined riser residence time ranging from about 0.5 seconds to about 10 seconds. The tangential solution between is preserved.

This invention maximizes the production of highly valuable liquid products and enables a wide range of carbon-metal production while allowing vacuum distillation and other costly processes such as hydrorefining processes to be avoided if desired. A process for the continuous catalytic conversion of oil to low molecular weight products is provided.

The term "oil" refers not only to those consisting primarily of hydrocarbon compositions that are liquid at room temperature (i.e., 63°F), but also to asphalt or tar at ambient temperatures, but at temperatures ranging up to about 800°F. It includes those consisting primarily of hydrocarbon compositions that liquefy when heated to.

The invention is applicable to carbon-metallic oils, whether of petroleum origin or not.

For example, the required boiling range of these oils, the pyrolytic carbon residue 6
This invention applies to heavy residual oils from crude oil, heavy bituminous residues, crude oils known as "heavy crude" with properties similar to those of atmospheric distillation residues, and sierre oil. , tar sands extracted oils, products from coal liquefaction and solvated coal, atmospheric and vacuum distillation residues, extracts and residues from solvent deasphalting processes (raffinate)
, aromatic extracts from lubricating oil refining processes, tar residues,
It can be applied to the treatment of a wide variety of materials such as heavy cycle oil, slop oil, other refinery effluents and mixtures thereof.

Such mixtures can be prepared by mixing available hydrocarbon fractions including, for example, oils, tars, pitch, and the like.

Powdered coal may also be suspended in carbon-metal oil.

Those skilled in the art know how to demetallize carbon-metal oils, and demetalized oils can be converted using this invention, but carbon-metal oils that have not undergone any prior demetallization treatment are used as feedstock. It is an advantage of this invention that it can be done.

Similarly, it is an advantage of the present invention that carbon-metal oils that have not been subjected to hydrorefining treatment can also be successfully converted.

However, the preferred application of this process is to atmospheric distillation residues, that is, fractions of crude oil boiling at 650"F and above, either alone or mixed with virgin gas oil. .

Although it does not preclude the use of materials that have been subjected to pre-vacuum distillation, it is an advantage of this invention that materials that have not undergone pre-vacuum distillation can also be adequately treated, thus replacing conventional FCC processes that require vacuum distillation equipment. Investment and operating costs are saved when compared to.

In accordance with the present invention, a carbon-metal oil feedstock is provided, of which at least about 70%, preferably at least about 85%, and more preferably about 100% (by volume) is above 650°F and above. Boil at a temperature of

Here, all boiling temperatures are based on standard atmospheric pressure conditions.

In carbon-metallic oils that are partially or wholly composed of substances boiling at temperatures below and above 650°C,
Such materials are referred to in this invention as 650'''F+ materials, and may form part of, or be separated from, oils containing formed metals that boil above and below 650°F. The 650°F+ material is referred to as the 650°F fraction.

However, the term "boiling at 65 or above" and "65
The term 0'F+j is not meant to characterize all substances that have the ability to boil by these terms.

The carbon-metal oil contemplated by this invention can contain materials that do not boil under any conditions.

For example, some asphalts and asphaltones are thermally decomposed without apparent boiling during distillation.

Thus, for example, the feedstock oil may contain at least about 70% by volume.
It should be understood that when a substance is said to consist of a substance that boils at a temperature above about 650”F, it is possible that 70% of the problem contains some substance that does not boil or vaporize at any temperature. It is.

These non-boiling materials, when present, often or generally have a temperature of about 1.000°F, 1025
It will be concentrated in the portion of the feedstock that does not boil below temperatures of 0.degree. F. or higher.

Thus, at least about 10%, preferably at least about 15%, more preferably at least about 20% (by volume) of the 650°F fraction is about 1.000°F or 102
When it is said that it will not boil below 5°F, approximately 1
．． All or any portion of a substance that does not boil below 000°F or 1025°P may or may not vaporize at its indicated temperature and above.

the intended feedstock oil, or at least 650% thereof;
Preferably, the °F+ material has at least about 2 or more pyrolytic carbon residues.

For example, Conradson carbon content ranges from about 2 to about 12, and most often takes values of at least 4.

A particularly common range is about 4 to about 8.

The feedstock oil has an average composition characterized by a hydrogen to carbon atomic ratio ranging from about 1.2 to about 1.9, preferably from about 1.3 to about 1.8. preferable.

The carbon-metal feedstock used in accordance with this invention, or at least 650° F.+ material therein, can contain a nickel equivalent of at least about 4 ppIn, where the In is vanadium (at least about 0.1 pI).

Carbon-metal oils in the above range can be prepared from mixtures of two or more, some of which contain the above amounts of nickel equivalents and vanadium, and some of which do not.

The above values for nickel equivalent and nickel are given over time for a substantial period of operation of the converter, e.g. 1 month.
It should also be noted that weighted average values are represented.

It should also be noted that heavy metals have shown a slightly reduced tendency to become catalyst poisons after repeated oxidation and reduction of catalysts under certain circumstances, and the literature
Describes the criteria for determining "effective metal" values.

For example, “Deposited Metals Poison FCC Catalyst”
Oil and Gas Journal (Oil and Gas Journal)
urnal), May 15, 1972, No. 112-1
Please refer to page 22).

The contents of this report are cited and referred to in this invention.

When deemed necessary or desirable, the nickel equivalent and vanadium content of the carbon-metal oils treated according to this invention can be expressed in terms of "effective metal" values.

Despite the gradual decrease in catalyst poison activity noted by Sinhalo et al., regeneration of the catalyst under normal FCC regeneration conditions reduced the dehydrogenation demethanization of heavy metals accumulated on the catalyst and the condensation activity of aromatics. It can't and usually won't hurt you too much.

0.2% to about 5% by weight of "sulfur" in the form of elemental sulfur and/or its compounds (reported as elemental sulfur based on the weight of the feedstock) is found in the FCC feedstock. , also that sulfur and modified forms of sulfur can be found in the gasoline products so obtained;
And it is known that ships tend to reduce their susceptibility to octane enhancement when added.

It is often necessary to reduce sulfur in the product gasoline when processing high sulfur containing crude oils.

Depending on the extent to which sulfur is present in the coke, the regenerator can
It is said to be a potential source of air pollution because it is combusted to produce O2 and SO3.

However, in the process of the present invention, sulfur in the feedstock oil can on the other hand suppress the activity of heavy metals by retaining metals such as Ni, V, Cu and Fe in the form of sulfides in the reactor. Found out.

These sulfides are considerably less active than the metal itself in promoting dehydrogenation and coking reactions.

Accordingly, it is acceptable for this invention to be practiced in carbon-metallic oils with at least about 0.3 weight percent sulfur in 650°F+ minutes, and even at least about 0.8 weight percent sulfur.
Even 5% by weight is acceptable.

Carbon-metal oils useful in this invention can, and usually do, contain significant amounts of nitrogen-containing compounds.

A substantial portion of the nitrogen in the nitrogen-containing compound can be basic nitrogen.

For example, the carbon-metal oil has a total nitrogen content of at least about 0.
05% by weight.

Since the decomposition activity of the decomposition catalyst is carried out by the acid sites on the surface of the catalyst or its pores, basic nitrogen-containing compounds temporarily neutralize these sites and exert a toxic effect on the catalyst.

However, the catalyst is not permanently damaged since this nitrogen can be scavenged from the catalyst during regeneration, so that the acidity of the active sites is restored.

The carbon-metal oil may also contain a significant amount, such as at least about 0.
It may contain 5% by weight pentane insolubles, more typically 2% or more, and even about 4% or more.

These insoluble substances may include, for example, asphaltone and other substances.

Alkali metals and alkaline earth metals generally do not tend to vaporize in large quantities under the distillation conditions used when crude oil is distilled to produce vacuum gas oils commonly used as FCC feedstock oils.

Rather, these metals remain to a large extent in the bottom residue (non-vaporised high boiling fraction) which can be used, for example, for the production of asphalt or other by-products.

However, atmospheric distillation residues and other carbon-metallic oils are often bottoms products and therefore significant amounts of Nato IJ
It will contain alkali metals and alkaline earth metals such as aluminum.

These metals are deposited on the catalyst during decomposition.

These metals may be used under the normal processing conditions of the FCC depending on the catalyst composition and the high regeneration temperatures to which the catalyst is exposed. subject to significant interactions and reactions.

Of course, necessary precautions will be taken to limit the amount of alkali and alkaline earth metals in the feedstock oil if the catalyst properties and regeneration conditions so require, but those metals are present in the crude oil and in its natural state. It may enter the feedstock oil not only as associated brine, but also as a component of the water or steam fed to the cracker.

Thus, when the catalyst is particularly sensitive to alkali and alkaline earth metals, it may be important to carefully desalinate the crude oil used to produce the carbon-metal feedstock.

In such circumstances, the content of such metals (hereinafter collectively referred to as "I-IJ") in the feedstock oil may be maintained at about 1 pIllll or less based on the weight of the feedstock. can.

On the other hand, the feedstock sodium level is relative to the catalyst sodium level to maintain a catalyst sodium level that is substantially the same as, or less than, the sodium level of the displacement catalyst that is charged to the cracker. Can be adjusted.

In accordance with a particularly preferred embodiment of this invention, the carbon-metal oil feedstock boils at a temperature of about 6500"F or greater with at least about 70% by volume of material boiling at a temperature of about 650"F or greater, but about 1025" It is composed of at least about 10% material that does not boil at temperatures below .degree.F.

The average composition of this 650°F+ material is: (a) the ratio of atomic hydrogen to atomic carbon is in the range of about 1.3 to about 1.8; and (b) it has a low Conradson carbon value. Both are 2.

(C) the nickel quotient as defined above is at least about 41;
]pm, of which at least about 2p- is nickel (
(as metal, by weight), at least about 0,1111
) m is vanadium, and (d) the following, (1
) at least about 0.3% by weight sulfur; (11) at least about 0.05% by weight nitrogen; and (11) at least about 0.05% by weight nitrogen.
It can be characterized in that it contains 5% by weight of at least one component of pentane insolubles.

Very generally, preferred feedstock oils are those listed in (1) above.
, (11) and (including all of the songs), it is understood that other components found in oils of petroleum and non-petroleum origin may be present in varying amounts so long as such components do not interfere with operation of the method of this invention. .

Although we do not exclude the possibility of using feedstocks that have traditionally been subjected to some cracking, the present invention provides high conversion and very high It has certain advantages of being able to successfully produce liquid hydrocarbon fuels in high yields.

Thus, for example, and preferably at least about 8
5%, more preferably at least about 90%, and most preferably substantially all of the carbon-metal feedstock oil introduced to the process of this invention is an oil that has not previously been contacted with a cracking catalyst under cracking conditions. It is.

Furthermore, the method of the invention is substantially single-pass or single-pass.
Suitable for passing type operation.

Thus, the amount of recirculation, if any, is preferably about 15% or less, more preferably about 10% or less, based on the volume of fresh feed oil.

Typically, the weight ratio of catalyst to fresh feedstock oil (feedstock oil that has not previously been exposed to cracking catalyst under cracking conditions) used in this process ranges from about 3 to about 18.

Preferred and more preferred ratios are from about 4 to about 12, more preferably from about 5 to about 10, and even more preferably from about 6 to about 10, with a ratio of about 10 currently being the most optimal ratio. It is believed that

Within the limits of product quality requirements, controlling the catalyst to oil ratio to a relatively low level within the above range tends to reduce the coke yield of this process based on fresh feedstock oil.

In conventional FCC processing of VGC, the ratio between the barrels per day of plant throughput and the total tonnage of catalyst that undergoes circulation throughout all phases of the process can vary widely.

For purposes of this disclosure, the plant throughput per day is approximately 4
It is defined as the number of barrels of new feedstock oil boiling above about 650°F that the plant processes per average day of operation for liquid products boiling below 30°F.

For example, one commercially successful type of FCC-
In VGO operation, about 8 tons to about 12 tons of catalyst are under circulation in this manner for a plant throughput of 1.000 barrels/day.

In another commercially successful method, this ratio is in the range of about 2-3.

The invention provides from about 2 tons to about 30 tons, more typically from about 2 tons to about 30 tons per 1.000 barrels of daily plant throughput.
Although it can be carried out in the catalyst residual range of about 12 tons, it is preferred to carry out the process with a very small ratio of catalyst weight to daily plant throughput.

More specifically, the amount of residual catalyst, relative to the plant throughput, which is undergoing recycling or is retained for processing in other phases of the process, such as stripping, regeneration and similar processing. It is preferred to carry out the process of this invention with sufficient residual amount of catalyst to contact the feedstock oil for the desired residence time at the above catalyst-to-oil ratio while minimizing .

Thus, more particularly, the process of the invention may be practiced with catalyst residuals of from about 2 tons to about 5 tons, more preferably about 2 tons or less, per 1.000 barrels of daily plant throughput. preferable.

In the practice of this invention, catalyst can be added continuously or periodically, eg, to compensate for normal loss of catalyst from the system.

Additionally, catalyst addition can be performed in conjunction with catalyst withdrawal to maintain or increase the average activity level of the catalyst in the device.

For example, the rate at which fresh catalyst is added to the device is from about 0.1 pounds to about 3 pounds, more preferably from about 0.15 pounds to about 2 pounds, and most preferably from about 0.2 pounds per barrel of feed oil. It can range from 1 pound to about 1.5 pounds.

On the other hand, when an equilibrium catalyst from FCC operation should be used,
Displacement rates as high as about 5 pounds per barrel can be carried out.

If the catalyst used in the device is below average in its resistance to deactivation and/or the conditions prevailing in the device are such that conditions make deactivation more rapid. may use addition rates greater than those listed above, while lower addition rates may be used in the opposite environment.

For illustration purposes, 5.0001 parts by weight for equilibrium catalyst
) If the unit were to be operated at a metal or metals loading of pIIIN i +V, for example, the catalyst would be introduced and used at a displacement rate of about 2.7 pounds for each barrel (42 gallons) of feedstock treated. You can do it.

However, the metal loading on the catalyst is 10,000
Operation at higher levels, such as pI]I[l of Ni+V, can also substantially reduce the displacement rate to, for example, up to about 1.3 pounds of catalyst per barrel of feedstock oil. Seems possible.

Thus, the level of metal or metals on the catalyst and the rate of displacement of the catalyst are generally acceptable for carrying out the process;
and can be increased and decreased, respectively, to any value consistent with the desired catalyst activity.

Without wishing to be bound to any theory, a number of features of this process, described in detail below, such as residence time and optional mixing of the steam and feedstock, indicate that the cracking conditions are compatible with the carbon-metal feedstock conditions and Pre-exposure to regeneration conditions tends to limit the extent to which metals are brought to a reduced state on the catalyst from the sulfide or sulfides, sulfate or sulfates or oxides or oxides of heavy metals deposited on the catalyst particles. It is recognized that

Thus, this method appears to provide significant control over the poisoning effects of heavy metals on the catalyst even when heavy metal accumulation is quite substantial.

The process can therefore be carried out with catalysts having high accumulations of heavy metals in the form of elemental metals or metals, oxides or oxides, sulfides or sulfides or other compounds.

Thus, it is contemplated to operate the process with catalysts having heavy metals in the accumulation range as nickel equivalents of about 3,000 ppm or more on average.

The concentration of deposited metal on the catalyst as nickel equivalents is approximately 50
．． It can range up to 000 pIlm or more.

More specifically, the accumulation is approximately 3.000 pI
)m to about 30,000 ppI[l, preferably in the range of about 3,000 to 20,000 ppIn, more particularly about 3.0001) p11 to about 12,000 pI'
m.

Within these ranges mentioned above, approximately 4.000p1)Ill
or more, about 5. oooppm or more,
Alternatively, operation at metal loading levels of about 7,000 pI)m or higher may tend to reduce the required catalyst displacement rate.

However, the above ranges are based on parts per million of nickel equivalent by weight measured on a regenerated equilibrium catalyst, and in this definition metals are expressed as metals.

However, if catalysts of suitable activity allowing very fast displacement rates of the catalyst are available at very low cost, carbon-metal oils can be used as catalysts with heavy metals below 3,000 nickel equivalents. can be converted to lower boiling liquid products.

For example, from another equipment, such as an FCC equipment, used in the cracking of one feedstock oil, such as a vacuum gas oil,
Equilibrium catalysts with a pyrolysis carbon residue of less than 1 pl)m and a heavy metal content of less than 4 ppm as nickel equivalent could be used.

Even so, the equilibrium concentration of heavy metals in the recycled residual catalyst can be controlled by adjusting the catalyst addition rate discussed above (maintaining or changing as desired or required). (including).

Thus, for example, the addition of catalyst can be maintained at a rate that controls the amount of heavy metal accumulation on the catalyst to one of the set ranges.

It is generally preferred to use catalysts that have relatively high levels of cracking activity and provide high levels of conversion and production at low residence times.

The conversion capacity of a catalyst can be expressed by the conversion obtained during the actual operation of the process and/or by the conversion obtained in standard catalyst activity tests.

For example, at least about 50%, more preferably at least about 60% during long-term operation under prevailing process conditions.
It is preferred to use a catalyst that is sufficiently active to maintain % conversion levels.

In this relationship, conversion is expressed as a volume percentage of liquid based on fresh feedstock oil.

Also, for example, a preferred catalyst can be defined as one which, in its fresh or equilibrium state, exhibits a specified activity expressed as a percentage with respect to MAT (Micro-Activity Test) conversion.

For purposes of this invention, the above percentages mean that the catalyst under evaluation test was prepared using an appropriate standard feedstock at 900°F.
6WH8V (weight hourly space velocity, calculated on a moisture-free basis, dried at 1100°F, weighed, and then heated to about 25°C and (using clean catalyst conditioned for at least 8 hours at 50% relative humidity) and ASTM D-
3C10 according to 32MAT test method D-3907-80 (
The percentage by volume of the standard feed that is converted to a 430° F. end point gasoline (catalyst to oil ratio), plus lighter products and coke.

The standard feedstock has the following analytical values and properties: API Gravity at 60°F, Degrees 31.0 Specific Gravity at 600F, g/cc O, 8708 Lumspotom Carbon, wt% 0.09 Conradson Carbon, wt% (approximately) ) 0.04 carbon, weight % 84. ．． 92 hydrogen, wt%
12.94 Sulfur, wt%
0.68 Nitrogen, ppIn305 Viscosity at 100”F, centistokes 10.36 Watson factor 11.93 Aniline point
182 Bromine number 2.2 paraffin,
Capacity% 31.7 Olefin, Capacity%
1.6 naphthene, volume % 44.
0 aromatic compounds, volume % 22.7 average molecular weight
284 Nickel Trace Vanadium Trace Iron Trace Sodium Trace Chloride Trace BS and W Trace Distillation ASTM D-1160 IBP 445 10% 601 30% 664 50% 701 70% 734 90% 787 Davison with FBP 834 (Davison), Division of W.R. Brace (Divisio)
There are sweet light primary gas oils such as those used by W, R, Grace).

The boiling temperature-volume % relationship between the end point of gasoline and the product produced in the MAT conversion test can be determined using a simulated distillation method, such as a gas chromatograph [Sim-D (Sim-D)].
) It can be determined by an improved method of J method, ASTM D-2887-73.

The results of such simulsion are in fairly good agreement with those obtained by subjecting large quantities of sample material to standard laboratory distillation procedures.

Conversion is calculated by subtracting from 100 the volume percent (based on fresh feed oil) of products heavier than gasoline remaining in the recovered product.

Haugen and Watson
Son)'s Chemical Process Principles
les) (John Wiley & Sons, Inc.)
John Wiley & 5ons, inc.) New York (N, Y.).

No. 11947, pages 935 to 937, the contents of "factors of activity" are discussed.

This concept has led to the use of "relative activity" to compare the effectiveness of a working catalyst to a standard catalyst.

Measurements of relative activity make it easy to discern how the requirements of various catalysts differ from each other.

Relative activity is thus obtained by dividing the weight of the standard or reference catalyst required or deemed necessary to give a given conversion level under the same or equivalent conditions. operating catalyst (
The ratio compared to the weight of the catalyst (whether proposed or actually used).

Although this ratio of catalyst weights can be expressed as a numerical ratio, it is preferably converted to a percentage basis.

The standard catalyst is preferably selected from among the catalysts useful in carrying out the invention, such as zeolite fluid cracking catalysts, and whose capabilities are determined with respect to temperature, WH8V, catalyst to oil ratio conditions and MAT conversion test. The above description and AST
MD-32 is selected to produce a predetermined conversion level in a standard feedstock under the other conditions described in MAT test D-3907-80.

Conversion is the volume percentage of feedstock oil that is converted to gasoline, lighter products, and coke at a 430°F endpoint.

For standard feedstock oils, the light primary gas oils described above or equivalent oils may be used.

In order to make measurements of relative activity, a "standard catalyst curve", i.e. a conversion rate (
A chart or graph of the reverse WH8V (as defined above) may be prepared.

A sufficient number of experiments were conducted under ASTM D-3907-80 conditions (improved method above) at various WH8V levels using standard feedstock oils to determine the exact conversion vs. WH8V for standard feedstock oils. Create a "curve".

This curve should traverse all or substantially all of the various conversion levels at which the operating catalyst is tested, including the expected conversion range.

From this curve, a standard value of inverse wnsv can be determined for the standard WH8V for comparison of the test and its conversion level chosen to represent 100% relative activity on the standard catalyst.

For purposes of this invention disclosure, the inverse WH8V and conversion levels are 0.0625 and 75%, respectively.

When testing a working catalyst of unknown relative activity, the D-
A sufficient number of experiments are conducted with the catalyst under 3907-80 conditions (improved method above) to determine the conversion level obtained, or expected to be obtained, with the operating catalyst at standard msv.

Next, using the standard catalyst curve above, determine the hypothetical reverse WH8V that constitutes the required reverse WH8V when using the standard catalyst, and determine the obtain the same conversion level that would be expected.

Next, calculate the relative activity by converting the assumed inverse WH8V to the inverse standard WH8
Calculated by dividing by V.

Its value is 1/16, or 0.0625.

The result is a relative activity expressed as a decimal, which can then be converted to a percentage relative activity by multiplying by 100.

When applying this measurement result, 0.5, i.e. 50%
The relative activity of means that twice the amount of working catalyst is required to give the same conversion as the standard catalyst, ie, the production catalyst is 50% of the activity of the reference catalyst.

The catalyst can be introduced into the process in its virgin form or, as described above, in a form other than virgin form.

For example, equilibrium catalyst taken from other equipment can be used, such as catalyst used in the cracking of another feedstock oil.

Preferred catalysts, whether characterized on a basis of MAT conversion activity or on a basis of relative activity, are based on their activity as "introduced" to the process of this invention. or in terms of the "as-drawn" activity, ie, equilibrium activity, in the process of the invention, or in terms of both criteria.

Preferred activity levels for fresh and non-virgin catalysts "as introduced" into the process of this invention are at least about 60% in MAT conversion, and preferably at least about 20% in terms of relative activity; More preferably at least about 40%, still more preferably at least about 60%.

However, lower activity levels are acceptable, especially with non-virgin catalysts fed at high addition rates.

The catalyst used in the process of this invention has an acceptable
The activity level "at the time of withdrawal," or equilibrium activity level, is at least about 20% or more, although about 40% or more, preferably about 60% or more, is a preferred value on a relative activity basis. , and activity levels of 60% or greater on a MAT conversion basis are also contemplated.

More preferably, it is desirable to use a catalyst that establishes an equilibrium activity at or above the above-mentioned level under the conditions of use in the device.

The activity of the catalyst is determined using a catalyst with coke of 0.01 or less, for example, a regenerated catalyst.

Any hydrocarbon cracking catalyst having the above-mentioned conversion ability can be used.

A particularly preferred group of catalysts are those having a pore structure through which molecules of the feed oil material can enter for sorption and/or for contact with active catalyst sites within or adjacent to the pores.

Various types of catalysts are available that fall into this category, including, for example, scrap silicates, such as green clays.

Although the most widely available catalysts within this class are the well-known zeolite-containing catalysts, non-zeolite catalysts are also contemplated.

Preferred zeolite-containing catalysts may contain any zeolite, be it natural, semi-synthetic or synthetic zeolite, as long as the resulting catalyst has the activity and pore structure mentioned in the penalty notes, and may contain zeolite alone or as a catalyst. It can be included in admixture with other substances that do not significantly impair suitability.

For example, when the fresh catalyst is a mixture, the zeolite component can be included in conjunction with or dispersed within a porous refractory inorganic oxide carrier.

In such cases, the catalyst may contain, for example, from about 1% to about 60% by weight of zeolite, based on its total weight (water-free basis).
More preferably, it may contain from about 15% to about 50%, and most typically from about 20% to about 45%, with the remainder being the porous refractory inorganic oxide alone or as desired. or its inorganic oxides in combination with known auxiliaries that promote or inhibit undesired reactions.

July 26, 1978 and 1977 for a general description of the class of zeolites that are molecular sieve catalysts useful in this invention.
Chemical Week Magazine (C
Refinery Catalyst Tour Fluid Business (RefineryCatalyst
s Area Fluid Business) J and [Making Cat Crackers Work
On Vaired Daiichi (MakingCat
Crackers Work On Varied D
Attention is drawn to the disclosure of a paper entitled iet) J.

The descriptions of these publications are incorporated herein by reference.

The zeolite component of the zeolite-containing catalyst is mostly one that has been found to be useful in FCC cracking processes.

In general, these zeolites are crystalline aluminosilicates typically made up of tetracoordinated aluminum atoms linked to adjacent silicon atoms via oxygen atoms in their crystal structure.

However, the term "zeolite" as used in this disclosure contemplates not only aluminosilicates, but also materials in which aluminum has been partially or fully replaced, for example by gallium and/or other metal atoms; It also includes substances in which all or part of silicon is replaced with atoms such as germanium.

Substitutions of titanium and zirconium can also be made.

Most zeolites are either synthetic or naturally occurring in sodium form.

In the sodium form, the sodium cation is associated with electronegative sites in the crystal structure.

Sodium cations tend to render zeolites inert and highly unstable when exposed to hydrocarbon conversion conditions, especially when exposed to high temperatures.

Thus, the zeolite is ion-exchanged, but if the zeolite is a component of the catalyst composition, such ion exchange can occur before or after incorporation of the zeolite as a component of the catalyst composition.

Suitable cations to replace sodium in the crystal structure of the zeolite include ammonium (which can be decomposed to hydrogen), hydrogen, rare earth metals, alkaline earth metals, and the like.

A variety of suitable ion exchange operations and cations that can be exchanged into the zeolite crystal structure are well known to those skilled in the art.

Examples of naturally occurring crystalline aluminosilicate zeolites that can be used or included in the catalysts of this invention are faujasite, mordenite, clinobutyrolite, chabazite, analzite, kryonite, and lewyite. , datyalgite, poringite, analone, ferriolide, volatilite, angiolite, huanganhua, bijurite, greyscale, briuskuite, fullerite, butolite, gmelinite, comnite, leucite, alanite, They are scaprite, mesozeolite, butrite, nephrin, matrolite, olephrite, and sodalite.

Examples of synthetic crystalline aluminosilicate zeolites that are useful as catalysts for practicing this invention are Zeolite X of U.S. Pat. No. 2,882,244, Zeolite Y of U.S. Pat. Zeolite A1 of US Patent No. 2,882,243 and Zeolite B of US Patent No. 3.008.803, Canadian Patent No. 6
Zeolite I-D of No. 61.981, Canadian Patent No. 614
．． 495 Zeolite L1 U.S. Patent No. 2.996
, 358 Zeolite L1 U.S. Patent No. 3,010
, 789 Zeolite L1 U.S. Patent No. 3,011
, 869 Zeolite J, Belgian Patent No. 575,1
No. 77 Zeolite L1 U.S. Patent No. 2,995,4
No. 23 Zeolite L1 U.S. Patent No. 3,140.2
524 Zeolite 0, U.S. Patent No. 2.991,1
No. 51 Zeolite L1 U.S. Patent No. 3,054,6
No. 57 Zeolite S1 U.S. Patent No. 2,950,9
No. 52 Zeolite T.

Zeolite W of U.S. Patent No. 3,012,853;
Zeolite Z of Canadian Patent No. 614,495 and Zeolite Omega of Canadian Patent No. 817.915.

Also, ZK-4HJ, Alphabeter and ZSM
-type zeolites are also effective.

Furthermore, U.S. Patent No. 3,140,249;
No. 140,253, No. 3,944,482 and No. 4
, 137.151 are also effective, and the disclosures of these patent specifications are cited and referred to in the specification of this invention.

Crystalline aluminosilicate zeolites having a faujasite type crystal structure are particularly preferred for use in this invention.

This includes especially the natural faujasite and zeolite
and Zeolite Y.

Synthetic crystalline aluminosilicate zeolites, such as faujasite, crystallize under standard conditions as regularly shaped, loose particles of about 1 micron to about 10 micron in size, and therefore are commercially available which can be used in this invention. This is the size often found in catalysts.

Preferably, the particle size of the zeolite is from about 0.1μ to about 10μ
and more preferably from about 0.1μ to about 2μ or less.

For example, zeolite produced in situ from calcined kaolin is characterized by smaller crystals.

Crystalline zeolites have internal and external surface areas,
The latter was defined as the "portal surface area."

The largest portion of the total surface area is the internal surface area.

The outer surface of the zeolite crystal is referred to as the portal surface area, and it is believed that the reactants pass through the outer surface and are converted to lower boiling point products.

For example, blockage of internal channels due to the formation of coke,
Blockage of the entrance to the internal channels by coke deposition on the portal surface area and contamination by catalyst poisoning of metals greatly reduces the total surface area of the zeolite.

Therefore, to minimize the effects of contamination and pore clogging, crystals larger than the above standard sizes are preferably not used in the catalysts of this invention.

Commercially available zeolite-containing catalysts include a variety of zeolite-containing catalysts, including, for example, silica, alumina, magnesia, and mixtures thereof, and mixtures of such oxides with clays, such as those described in U.S. Pat. No. 3,034,948. Available with carriers containing metal oxides and combinations thereof.

For example, any zeolite-containing molecular sieve fluid cracking catalyst suitable for the production of gasoline from vacuum gas oil can be selected.

However, certain advantages can be obtained by judicious selection of catalysts with significant resistance to metals.

Metal-resistant zeolite catalysts are described, for example, in U.S. Pat. It is a refractory metal oxide with a volume and size distribution.

Other catalysts described as "metal resistant" are described in the Sinhalo et al. paper cited above.

It is generally preferred to use catalysts having a total particle size of from about 5 microns to about 160 microns, more preferably from about 40 microns to about 120 microns, and most preferably from about 40 microns to about 80 microns.

For example, useful catalysts can have a skeleton size of about 150 pounds per cubic foot and an average particle size of about 60 to 70 microns, and where less than 10% of the particles have a particle size of about 40 microns or less and 80 % or less have a particle size of about 50-60 microns or less.

The table below is an example of commercially available catalysts that can be used in the practice of this invention, although a wide variety of other catalysts can be used in the practice of this invention, including both zeolite-containing and zeolite-free catalysts. be.

AGZ-290, GRZ-1 mentioned above.

CCZ-220 and Super DX are manufactured by W, R, Grace and Co.
) products.

F-87 and FCC-90 are Filtr
ol) products, while HFZ-20 and HEZ-
55 is Engelh Rehard/Howdry
It is a product of ard/Houdry).

The above table is of virgin catalyst properties and, except for zeolite content, is adjusted to a water-free basis, ie, based on material ignited at 1750°F.

The zeolite content is determined by the ``determination of the fajasite content of the catalyst'' (Dete.
rm 1na-tion of the Fauja
Site Content of aCatalyst
) 19 of the proposed ASTM standard method entitled J.
This was derived from a comparison using draft #6 dated January 9, 1978.

Among the commercially available catalysts mentioned above, super D family and especially GR
Particularly preferred is the catalyst designated Z-1.

For example, Super DX has given particularly good results with Arabian Light crude oil.

Although GRZ-1 is currently substantially more expensive than Super DX, it appears to be slightly more resistant to metals.

Although not yet commercially available, the best catalyst for carrying out this invention was developed by Dr. William B. Hitzteinger, Jr.

William P., Hettinger, Jr.
) and Dr. James E. Lewis (Dr.
James E., Lewis) proposed that the matrix has a feeder bow with a large minimum diameter and a large mouth to facilitate the diffusion of high molecular weight molecules through the matrix to the portal surface area of the molecular sieve particles within the matrix. It is thought that there is.

Such a matrix also preferably has a relatively large pore area to absorb the non-volatile portions of the carbon-metal oil feedstock.

Thus, a significant number of liquid hydrocarbon molecules form the matrix,
and the droplet particles on the surface of the Mal-IJ rack.

Generally, the catalyst has a feeder hole of about 40μ to about 6,000μ.
Preferably, it is used with a matrix having a diameter ranging from about 1,000 to about 6,000 people.

The process of this invention is performed in the substantial absence of tin and/or antimony, or in the absence of any of these metals.
Alternatively, it has the advantage that it can be carried out in the presence of a catalyst substantially free of both.

Although the process of the invention can be operated with the carbon-metal oil and the catalyst as substantially the only material charged to the reaction zone, the charge of additional materials is not excluded.

The charging of recycled oil to the reaction zone has already been described.

Still other materials can be incorporated that serve a variety of functions, as described in more detail below.

In such cases, the carbon-metal oil and catalyst usually represent a majority by weight of all materials charged to the reaction zone.

Some of the additional materials that can be used accomplish functions that provide significant advantages over the process when achieved with carbon-metal oil and catalyst alone.

These features include:

i.e., controlling the effects of heavy metals and other catalyst contaminants; improving catalyst activity; absorbing excess heat from the catalyst taken from the regenerator; treating contaminants or removing further heat from the product. Conversion of contaminants into one or more forms that can be easily separated or treated; controlling catalyst temperature to dilute carbon-metal oil vapors to lower their partial pressure and produce the desired product. increasing the yield of products; adjusting the feed oil/catalyst contact time; e.g., the Geo.
rgeD, Myers) to provide hydrogen to a hydrogen deficient carbon-metal oil feedstock to aid in the dispersion of the feedstock oil, as disclosed in a U.S. patent application filed March 23, 1981 in the name of ; and possibly also distillation of the product.

In the accumulation of heavy metals on catalysts, some of the metals are more desirable when they are in elemental metal form than when they are produced in oxidized form by contact with oxygen in the catalyst regenerator. It is active against reactions that do not occur and promotes them.

However, in past conventional catalytic cracking, the contact time between the catalyst and the feed oil and product vapors was such that the hydrogen released in the cracking reaction reconverted a significant portion of the less harmful oxides. It was long enough that it could be converted back to more harmful elemental heavy metals.

This situation can be made advantageous by introducing additional substances in gaseous form (including vapor form) into the reaction zone in a mixture with the catalyst and feed oil and product vapors. .

The increased volume of material in the reaction zone due to the presence of such additional material increases the rate of flow through the reaction zone and tends to correspondingly reduce the residence time of the catalyst and the resulting oxidized heavy metals. be.

Because of this reduced residence time, there is less opportunity for reduction of oxidized heavy metals to elemental form, and thus less hazardous elemental metals are available for contacting the feed oil and product.

Additive materials can be introduced into the process in any suitable manner.

Some examples are as follows.

For example, they can be mixed with the carbon-metal oil feedstock prior to contacting the feedstock with the catalyst.

Alternatively, the additives can optionally be mixed with the catalyst prior to contacting the catalyst with the feedstock oil.

The additives can also be divided into separate portions and mixed separately with both the catalyst and the carbon-metal oil.

Additionally, the feed oil, catalyst, and additional materials may be combined substantially simultaneously, if desired.

A portion of the additive material is catalyzed and/or
Alternatively, it can be mixed with a carbon-metal oil while additional portions can be mixed subsequently.

For example, a portion of the additive material can be added to the carbon-metal oil and/or to the catalyst before they reach the reaction zone, while another portion of the additive material is introduced directly into the reaction zone.

The additive material can also be introduced at multiple spaced locations in the reaction zone, ie along the length of the reaction zone, if the reaction zone is long.

The amounts of feed oil, catalyst, or additional materials that may be present in the reaction zone to perform the above and other functions can be varied as desired, but the amounts do not substantially thermally balance the process. Preferably, the amount is sufficient.

These materials may be present in the reaction zone, for example, in a weight ratio to the feedstock oil of up to about 0.4, preferably from about 0.02 to
in the range of about 0.4, more preferably about 0.03 to about 0
．． 3 and most preferably from about 0.05 to about 0.3.
It can be introduced at a ratio in the range of 25.

For example, many or all of the desirable features described above may include providing H2O to the reaction zone in the form of steam, or in the form of liquid water, or in the form of a combination thereof, as a weight ratio to the feed oil of about 0.04. or more, more preferably in a weight ratio ranging from about 0.05 to about 0.1 or more.

Without wishing to be bound by any theory, it is believed that the use of H2O promotes the condensation-dehydrogenation reaction of catalyst-produced oxides, sulfites and sulfates, thereby increasing coke and hydrogen yields, There appears to be a tendency to suppress the reduction to free metal forms that would concomitantly deplete the product.

Additionally, H2O can also reduce metal deposition on the catalyst surface to some extent.

There is also some tendency to adsorb nitrogen-containing molecules and other heavy contaminant-containing molecules from the surface of the catalyst particles, ie, at least some tendency to inhibit their adsorption by the catalyst.

It is also believed that the addition of H20 tends to increase the acidity of the catalyst through the formation of Brønsted acids, which in turn tends to improve the activity of the catalyst.

Assuming that the H2O supplied is cooler than the temperature of the regenerated catalyst and/or reaction zone, the sensible heat involved in raising the temperature of the H2O as it contacts the catalyst in the reaction zone or elsewhere will increase the temperature of the catalyst. can absorb excess heat from

H2O is, for example, about 500 ppm to about 5,000 pl)
I [l] of recycled water containing dissolved H2S;
or its inclusion, a number of additional benefits result.

The ecologically generated H2S does not need to be released into the atmosphere, the recycled water does not need any further treatment to remove the H2S, and the H2S is reduced by passivation of heavy metals, i.e. from free metals. Conversion of heavy metals to sulfide forms, which have less tendency to enhance coke and hydrogen production, can help reduce coking of the catalyst.

In the reaction zone, the presence of H2O can dilute the carbon-metal oil vapors, thus lowering their partial pressure and tending to increase the yield of the desired product.

H2O has been reported to be effective in combination with other substances in the production of hydrogen during decomposition.

Thus, H2O could act as a hydrogen donor to the hydrogen-deficient carbon-metal oil feedstock.

H2O also promotes atomization or dispersion of the feedstock, competes with higher molecular weight molecules for adsorption on the catalyst surface, and thus impedes coke formation: vaporizability from non-vaporized feedstock materials. Steam distillation of the product:
and bringing together H2O, catalyst and carbon-metal oil substantially simultaneously, which may also serve some purely mechanical function, such as desorption of products from the catalyst at the end of a cracking reaction. is particularly preferred.

For example, mixing H2O and feedstock oil in an atomizing nozzle;
The resulting mist can be immediately directed towards and contacted with the catalyst at the downstream end of the reaction zone.

The addition of steam to the reaction zone is often mentioned in the literature on fluid catalytic cracking.

The addition of liquid water to the feed oil is less well studied than the direct introduction of steam into the reaction zone.

However, in accordance with the present invention, it is particularly preferred that liquid water be thoroughly mixed with the carbon-metal oil in a weight ratio of from about 0.104 to about 0.25 during or prior to the introduction of the carbon-metal oil into the reaction zone. , whereby water (in the form of liquid water or water vapor produced by vaporization of liquid water on contact with oil) enters the reaction zone as part of the feed stream entering the reaction zone.

While not wishing to be bound by any theory, the above is believed to be advantageous in promoting feedstock dispersion.

Also, the heat of vaporization of water--which heat is absorbed from the catalyst or feed oil, or both--makes water a more efficient heat sink than water vapor alone.

Preferably, the weight ratio of liquid water to feedstock oil is about 0.0.
4 to about 0.2, more preferably about 0.05 to about 0.1
It is 5.

Of course, liquid water can be introduced into this process in the manner described above or in other ways, but in any case the introduction of liquid water can be in the same or different parts of the reaction zone.
It can also be achieved by introducing additional amounts of water as steam to the catalyst and/or feedstock oil.

For example, the amount of additional steam can range from about 0.01 to about 0.25 as a weight ratio to feedstock oil;
The weight ratio of total H20 (as steam and liquid water) to feedstock oil is then about 0.3 or less.

In such combinations of liquid water and steam, the charge weight ratio of liquid water to steam can range, for example, from a presently preferred value of about 15 to about 0.2.

Such ratios may be held at a predetermined level within the above ranges, or may be varied as necessary or desired to adjust or maintain thermal balance.

Other materials can be added to the reaction zone to accomplish one or more of the above functions.

For example, the dehydrogenation-polymerization activity of heavy metals can be inhibited by introducing hydrogen sulfide gas into the reaction zone.

Hydrogen can be extracted from heavy naphtha or, for example, light paraffin; low molecular weight alcohols and other compounds that enable or favor intermolecular hydrogen transfer; and carbon monoxide and water,
Relatively low molecular weight carbon-hydrogen fragments, including compounds that chemically combine to produce hydrogen in the reaction zone by reaction, such as with alcohols, olefins, or other substances or mixtures mentioned above. fragment contributor
) can be made effective against hydrogen-deficient carbon-metal oil feedstocks by introducing any of the conventional hydrogen donor diluents into the reaction zone.

All of the additional substances (including water), alone or in combination with each other or in combination with other substances such as nitrogen or other inert gases, light hydrocarbons, etc., may increase the partial pressure of the feedstock oil. They may accomplish any of the foregoing functions for which they are suitable, including without limitation acting as a diluent to reduce the can.

The foregoing is a discussion of some of the functions that can be accomplished by materials other than the catalyst and carbon-metal oil feedstock introduced into the reaction zone, and other materials may be added without departing from the spirit of the invention. It should also be understood that other functions can be achieved.

The invention can be implemented in a wide variety of devices.

However, the preferred equipment is to rapidly vaporize as much of the feedstock as possible, efficiently mix the feedstock and catalyst (although not necessarily in this order), and provide the resulting mixture in a progressive flow format. It flows as a dilute suspension and includes means for separating the catalyst from the cracked products and uncracked feedstock or partially cracked feedstock at the end of a predetermined residence time.

In this case, it is preferred that all or at least a substantial part of the product should be rapidly separated from at least a portion of the catalyst.

For example, the apparatus may include one or more carbon-metal feedstock introduction points, one or more catalyst introduction points, and one or more additional material introduction points along its long reaction chamber. , one or more product withdrawal points, and one or more catalyst withdrawal points.

Means for introducing the feedstock oil, catalyst and other materials can range from open pipes to sophisticated jets or atomizing nozzles, but it is preferred to use means that can break the liquid feedstock oil into fine droplets.

Catalyst, liquid water (if used) and fresh feedstock oil are described in U.S. Patent Application No. 969.601, filed December 14, 1978, by George Dee Meyer et al.
Preferably, they are combined in a device similar to that disclosed in that patent.

The entire disclosure of the above US patent application is incorporated by reference in this specification.

Mr. Stephen M. Kovac
According to a particularly preferred embodiment based on the proposal found to have originated from M. Kovach),
The liquid water and carbon-metal oil are processed before their introduction into the riser using a propeller perforated disk or a "homogenization" system containing finely divided droplets of oil and/or water with the oil and/or water present as the continuous phase. through suitable high shear agitation means to form a "mixed mixture".

Preferably, the reaction chamber, or at least a major portion thereof, is substantially more vertical than horizontal and has a length to diameter ratio of at least about 10, more preferably about 20 or 25 or more.

Preference is given to using a vertical riser type reactor.

If tubular, the reactor can be of uniform diameter throughout, or it can be of continuously or stepwise increasing diameter to maintain or vary the flow rate along the flow path. It may be something like that.

Typically, the feed means (for the catalyst and feedstock oil) and the arrangement of the reactor are such as to provide relatively high flow rates and a dilute suspension of catalyst.

For example, the steam or catalyst velocity in the riser will usually be at least about 25 feet/second, more typically at least about 35 feet/second.

The velocity of the vapor at the top of the reactor can be greater than at the bottom, for example about 80 feet/second at the top and about 40 feet/second at the bottom.

The rate capability of the reactor is generally sufficient to prevent substantial deposition of catalyst bed at the bottom or other portions of the riser, such that the amount of catalyst loading in the riser is lower than that at the upstream end of the riser (e.g., the bottom). and at the downstream end (e.g., top) an amount of no more than about 4 pounds/cu. ft. or 5 lb./cu.ft., such as about 0.5 lb./cu.ft., and, e.g., 0.8 lb./cu. ft., respectively. It can hold less than about 2 pounds per cubic foot.

Gradual flow involves, for example, flowing the catalyst, feed oil, and product as one stream in an actively controlled and maintained direction defined by the elongated structure of the reaction zone.

This is not to suggest, however, that the flow must be strictly straight.

As is well known, turbulence and catalyst "slippage" can occur to some extent, especially over a range of steam speeds and certain catalyst loadings, but at low enough catalyst loadings to limit shearing and backmixing. It has been reported that it is a good idea to use

The reactor abruptly separates a substantial portion or all of the vaporized cracking products from the catalyst at one or more points along the riser, and preferably removes substantially all of the vaporized cracking products from the catalyst and into the riser. Most preferred are those that separate at the downstream end of.

A preferred type of reactor provides ballistic separation of catalyst and product.

That is, the catalyst is injected in the direction defined by the riser tube and its movement continues in the general direction thus defined, while the products (with lower momentum) undergo a sharp change of direction and are removed from the catalyst. of the product results in a rapid, virtually instantaneous separation.

In a preferred embodiment, referred to as a vented riser, the riser tube is provided at its downstream end with a substantially unobstructed discharge opening for catalyst discharge.

An outlet drilled in the side of the tube adjacent its downstream end receives the product.

The discharge opening communicates with the catalyst flow path extending to a conventional stripper and regenerator, while the outlet opening communicates with the catalyst (
separation means for separating the product from a relatively small portion of the catalyst which is substantially or completely separated from the ME and controlled to allow the product, if any, to enter the outlet section; It communicates with the leading product flow path.

Examples of ballistic separation devices and methods described above are U.S. Pat. No. 4,066,533 and U.S. Pat.
, 070,159.

The disclosures of these patent specifications are incorporated herein by reference in their entirety.

Paul W. Walters (Paul W.

Wslters), Roger M. Bensley (
Roger M, Ben5lay) and wide
Dwight F. Barger
In accordance with a particularly preferred embodiment based on a proposal known from ), the ballistic separation step includes an at least partial reversal of direction by the vapor of the product upon discharge from the riser tube.

That is, the product vapor is at the outlet of the riser tube at 9
Change direction by more than 0°.

This can be achieved, for example, by providing a cup-like member surrounding the riser pipe at its upper end, in which case the ratio of the cross-sectional area of the cup-like member to the cross-sectional area of the riser pipe outlet is small. i.e. 1
smaller, preferably less than about 0.6.

The lip of the cup is slightly downstream of the riser tube or
or on the downstream end or top, and preferably the cup is concentric with the riser tube.

The riser tube is controlled by a product vapor conduit having an inlet located within the cup interior in the upstream direction of the riser tube outlet, communicating with the interior of the cup but not with the interior of the riser tube. Product vapor exiting the cup and pivoting in direction is transferred from the cup to a catalyst and product separation device.

Such an arrangement allows for a highly complete separation of the catalyst from the product vapor at the riser tube outlet, thereby significantly reducing the number of auxiliary catalyst separation devices such as cyclones, and thus Significant savings in capital investment and operating costs are achieved as a result.

Preferred operating conditions for this method are described below.

These include feedstock, catalyst and reaction temperatures, reaction and feedstock pressures, residence times, and levels of conversion, coke formation, and coke deposition on the catalyst.

In normal FCC operations with VGO, the feedstock oil is often preheated to a temperature sufficiently higher than that required to render the feedstock sufficiently fluid for feed introduction into the reactor. It's normal.

For example, preheat temperatures as high as about 700° to 800°F have been reported.

However, in the process of the present invention as currently practiced, the preheating of the feedstock oil is such that the feedstock oil absorbs a large amount of heat from the catalyst while the catalyst heats the feedstock oil to the conversion temperature and at the same time Preferably, the use of external fuels to heat the oil is limited to a minimum.

Thus, if the properties of the feedstock oil permit, it can be fed at ambient temperature.

Heavier feedstocks up to about 600°F, typically about 20°F.
Preheat temperatures of 0 T to about 500°F can be provided, although higher preheat temperatures are not necessarily excluded.

The catalyst fed to the reactor is, for example, at about 1,100'F.
~about 1,600”F, more preferably about 1,200°
F to about 1500'F, and most preferably about 1,30'F
Temperatures can vary widely from 0°F to about 1,4000°F, and from about 1.325°F to about 1,375°F
temperature is currently considered optimal.

As noted above, the conversion of carbon-metal oil to lower molecular weight products occurs at temperatures ranging from about 900'F to about 1,400F as measured at the exit of the reaction chamber.
It can be carried out at a temperature of 'F.

The reaction temperature measured at this outlet is more preferably about 9
It is maintained in the range of 65°F to about 1,300°F, more preferably about 975°F to about 1.200°F, and most preferably about 980'F to about 1,150°F.

Depending on the temperature selected and the nature of the feedstock oil, the feedstock oil may or may not be completely vaporized in the riser.

Although the pressure within the reactor can range from about 10 psia to about 50 psia as described above, a preferred and more preferred pressure range is about 15 psia.
psia to about 35 psia and about 20 psia to about 3
5 psia.

Generally, the partial pressure (or total pressure) of the feedstock oil is approximately 3 psi.
a to about 30 psia, more preferably about 7 psia to
about 25 psia, and most preferably about 10 psi
a to about 17 psia.

The partial pressure of the feedstock oil can be controlled or suppressed by the introduction of gaseous substances (including vaporous substances) into the reactor, such as steam, water, and other additional substances mentioned above.

The method of the present invention provides, for example, a ratio of the partial pressure of the feedstock oil to the total pressure in the riser from about 0.2 to about 0.8, more typically from about 0.3 to about 0.7, or even more typically is operating at a ratio in the range of about 0.4 to about 0.6, and correspondingly the added gaseous material to the total pressure in the riser (which is in the form of water vapor and/or liquid water to the riser). (which may include recycle gas and/or water vapor resulting from the introduction of H2O at a ratio of approximately 0.
8 to about 0.2, more typically about 0.7 to about 0.3,
Still more typically in the range of about 0.6 to about 0.4.

In the above illustrative operation, the ratio of the partial pressure of the additive gaseous material to the partial pressure of the feedstock oil is from about 0.25 to about 4.
0, more typically from about 0.4 to about 2.3, and even more typically from about 0.7 to about 1.7.

The residence time of the feedstock oil and product vapor in the riser can range from about 0.5 seconds to about 10 seconds, as described above, with preferred and more preferred values of about 0.5 seconds each. - about 6 seconds and about 1 second to about 4 seconds, and about 1.5 seconds to about 3.0 seconds is currently considered to be optimal.

For example, the process was operated with a vapor residence time in the riser of about 2.5 seconds or less by introducing a large amount of gaseous material into the riser.

The amount of gaseous material is, for example, sufficient to provide a partial pressure ratio of the added gaseous material to the hydrocarbon feedstock of about 0.8 or greater.

In yet another example, the process was operated with a residence time of about 2 seconds or less.

In this case, the above ratio ranged from about 1 to about 2.

The combination of low partial pressure of the feedstock oil, very short residence time, and ballistic separation of the product from the catalyst is believed to be particularly advantageous for carbon-to-metal oil conversion.

An additional advantage is the addition of gaseous substances, especially when H2O
can be obtained in the above combinations when is present in substantial partial pressure.

Depending on whether there is a offset between the catalyst and the hydrocarbon vapor in the riser, the residence time of the catalyst in the riser may or may not be the same as the residence time of the vapor.

Thus, the ratio, or deviation, of the average catalyst reactor residence time to vapor reactor residence time ranges from about 1 to about 5, more preferably from about 1 to about 4, and most preferably from about 1 to about 3. and a ratio of about 1 to about 2 is currently considered optimal.

In practice, there is usually a small deviation, e.g. at least about 1.05
It seems that there is a deviation of ~1,2.

In some operating systems, for example, there may be an offset of about 1.1 at the bottom of the riser and about 1.05 at the top.

One type of known FCC unit includes a riser that discharges the catalyst and product vapors together into an expansion chamber that is normally considered part of the reactor.

In the reactor, the catalyst is desorbed and collected from the product.

Continuous contact of the catalyst, uncracked feedstock (if present), and cracked products in such an expanded chamber results in a total catalyst-feedstock contact time that significantly exceeds the riser tube residence time of the vapor and catalyst.

When carrying out the process of this invention by ballistic separation of the catalyst and steam at the downstream (e.g., upper) end of the riser, as taught in the aforementioned Myers et al. patent, the riser residence time and catalyst contact time are substantially the same for the main portion of the feed oil and product vapors.

The riser residence time and steam catalyst contact time of the steam is at least about 80% by volume of the total feed oil and product vapor passing through the riser, more preferably at least about 90% by volume.
, and most preferably substantially the same for at least about 95% by volume.

By eliminating catalyst desorption, continuous contact of the vapors with the catalyst in the collection chamber, the trend toward re-cracking and loss of selectivity can be repeated.

Generally, the combination of catalyst to oil ratio, temperature, pressure and residence time should be such as to achieve substantial conversion of the carbon-metal oil feedstock.

The advantage of the process of the invention is that very high conversions can be obtained in a single pass, e.g.
% or more, and can range from about 90% or more.

Preferably, the conditions are maintained at a level sufficient to maintain conversion levels in the range of about 60% to about 90%, more preferably about 70% to about 85%.

The above conversion level increases the liquid volume of the new feedstock oil to 430°
F and above 430 F (tbp
, standard atmospheric pressure) is calculated by subtracting from 100% the percentage obtained by dividing by 100 times the volume of the boiling liquid product.

These substantial conversion levels typically range from, for example, about 4% to about 14% by weight, more commonly about 6% to about 13%, and most often about 10%, based on fresh feedstock oil.
A relatively large amount of coke is produced, such as ~13%.

This coke formation can be deposited more or less quantitatively on the catalyst.

At the intended catalyst-to-oil ratio, the resulting coke deposits are approximately 0.05% based on the weight of regenerated catalyst without moisture.
More than 3% by weight, more commonly more than about 0.5%, and more than about 1% are very often found.

Such coke deposits can range as high as about 2% or about 3%, or even higher.

Similar to conventional FCC operations for VGO, the process of this invention also includes sl-IJ spiking of the depleted catalyst after desorption of the catalyst from the product vapors.

Although those skilled in the art are familiar with suitable stripping agents and depletion catalyst stripping conditions, in some cases the present invention requires slightly more severe conditions than are commonly used.

This is due, for example, to the use of carbon-metallic oils whose components do not vaporize under the prevailing conditions in the reactor and which themselves are at least partially deposited on the catalyst.

Such sorbed non-vaporized substances are troublesome from at least two perspectives.

The first is that such a If there is a deposit of catalyst in the chamber, vaporization of these unvaporized hydrocarbons in the stripper can occur subsequent to absorption onto the catalyst bed in the chamber.

More specifically, as the catalyst in the Sl-IJ collar is stripped from the sorbed feedstock, the resulting feedstock material vapor is deposited in the catalyst collection and/or desorption chamber. and deposit coke and/or condensate on the catalyst in the bed.

As the catalyst with such deposits moves from its bed to the stripper and then from the stripper to the regenerator,
The condensation products create a need for greater stripping capacity, while coke tends to require increased regeneration temperatures and/or greater regeneration capacity.

For the above reasons, it is preferred to prevent or limit contact between the stripping vapor and the catalyst deposits in the catalyst desorption chamber or collection chamber.

This can be done, for example, essentially out of circulation and in desorption chambers and/or
or other than a certain amount of catalyst remaining at the bottom of the collection chamber, which can be done, for example, by preventing such deposits from forming, and when the catalyst under circulation settles to the bottom of the chamber. It can be quickly removed from the room.

Additionally, to minimize regeneration temperature and regeneration capacity requirements, the potentially volatile hydrocarbon material carried by the stripped catalyst should be approximately 10% by weight of the total carbon deposited on the catalyst or It is desirable to use sufficient time, temperature and ambient conditions in the stripper to reduce the temperature below that level.

Such stripping operations include, for example, catalyst reheating, extensive stripping with steam, FCC/VG
Other refined oils such as flue gas from regenerators and by-product gases of hydrorefineries (containing H2O), hydrogen and other gases, such as flue gases from regenerators and by-product gases (containing H2O) Including the use of in-situ stream gas.

For example, a stripper uses water vapor at a temperature of about 350'F, a pressure of about 150 psig and a pressure of about 0.00
It can be operated with a steam to catalyst weight ratio of 2 to about 0.003.

On the other hand, the stripper can also be operated at temperatures of about 1025'F or higher.

Substantial conversion of carbon-metallic oils to light products by this invention tends to produce sufficiently large coke yields and deposition of coke on the catalyst that some care is required in catalyst regeneration. .

To maintain adequate activity for zeolite and non-zeolite catalysts, the weight percent of carbon remaining on the catalyst must be
It is desirable to regenerate the catalyst under temperature and ambient conditions for a sufficient time to reduce the % to about 0.25% or less.

Therefore, the amount of coke that must be burned off from the catalyst when processing a ferro-metallic oil is typically substantially greater than the amount when cracking VGO.

The term coke used to describe this invention1
Go is to be understood to include any residual unvaporized feedstock oil or cracked products when such stripping is also present on the catalyst.

Catalyst regeneration, i.e., burning off coke deposited on the catalyst during feedstock conversion, is carried out at any suitable temperature between about 1,100°F and about 1,600°F as measured at the catalyst outlet of the regenerator. It can be carried out at any temperature.

This temperature is preferably from about 1,200°F to about 1.500°F.
°F1 more preferably from about 1,275 °F to about 1.42 °F
5°F1 and optimally about 1325°F to about 1.375
in the °F range.

This process is carried out, for example, when the temperature of the dense phase of the catalyst is approximately 1.3
00F to about 1,400F.

According to the invention, regeneration takes place in one or more fluidization chambers while maintaining the catalyst in one or more fluidized beds.

Such fluidized bed operations can be carried out, for example, by ebullient particles (fluidized over a fixed area).
ing particles) having a bed density of, for example, from about 25 pounds per cubic foot to about 50 pounds per cubic foot.

Fluidization involves passing various gases, including combustion sustaining gases, through the bed at a velocity sufficient to keep the particles in a fluid state, but low enough so that the gas is substantially free of entrainment of the particles. It is maintained by

For example, the linear velocity of the fluidizing gas ranges from about 0.2 ft/sec to about 4 ft/sec, preferably from about 0.2 ft/sec to about 4 ft/sec.
It can be in the range of about 3 feet/second.

The total average residence time of particles in one or more beds is a substantial amount of time, such as from about 5 minutes to about 30 minutes, preferably from about 5 minutes to about 20 minutes, and more preferably from about 5 minutes to about 20 minutes.
The duration is approximately 10 minutes.

The heat released by the combustion of coke in the regenerator is absorbed by the catalyst and can easily be retained in the catalyst until the regenerated catalyst is contacted with fresh feedstock oil.

When processing carbon-metallic oils to the relatively high conversion levels provided by this invention, the amount of regenerator heat transferred to the feedstock by recycling the regenerated catalyst is transferred to the feedstock in the riser. The level of heat input that is adequate to heat and vaporize oil and other materials, to provide the endothermic reaction heat of decomposition, to compensate for heat losses in the equipment, etc. can be substantially exceeded.

Thus, the amount of regenerator heat transferred to fresh feedstock can be controlled or limited within some suitable range if necessary.

The amount of heat so transferred may range, for example, from about 500 BTU to about 1,200 BTU, particularly about 60 BTU per pound of feedstock.
0BTU to about 900BTU1 and especially about 650B
It can range from TU to about 850 BTU.

The above range is for each pound of fresh feedstock oil transferred by the catalyst to the feedstock oil and reaction products to provide the heat of reaction (e.g., cracking) and the enthalpy difference between the products and the feedstock oil. Refers to total heat expressed in BTU.

This total heat includes the heat made available in the reactor by the adsorption of coke on the catalyst, as well as the heat from the recycle stream,
and does not include heat dissipated by heating, vaporizing or reacting additive substances such as water, steam, naphtha and other hydrogen donating substances, flue gases and inert gases, or by radiation and other losses. .

A method or a combination of methods can be used to control or limit the amount of regeneration heat transferred to fresh feedstock oil through the catalyst.

For example, a combustion modifier can be added to the cracking catalyst to reduce the temperature at which the coke is combusted to carbon dioxide and/or carbon monoxide in the regenerator.

Furthermore, for example, a heat exchanger (RI 1
First, heat can be removed from the catalyst via heat exchange means, including a steam coil (steam coil), thereby extracting heat from the catalyst during regeneration.

A heat exchanger can be integrated into a catalyst transfer line, such as a catalyst return line from the regenerator to the reactor, so that heat can be removed from the catalyst after its regeneration.

The amount of heat imparted to the catalyst in the regenerator, especially when processing feedstocks with a very high potential for coke formation, can be reduced by reducing the amount of insulation in the regenerator and transferring some of the heat to the surrounding atmosphere. can be restricted by letting it escape.

Such heat dissipation into the surrounding atmosphere is generally considered to be less economically desirable than some of the other methods described above.

It is also possible to inject a cooling fluid, e.g. The amount can also be increased.

Another suitable and preferred method of controlling or limiting the heat transferred to fresh feedstock oil through the recycled regenerated catalyst is to reduce the heat transfer between carbon dioxide and carbon monoxide formed in the regenerator. A method of maintaining the ratio at a defined ratio while the gases are in heat exchange contact or relationship with the catalyst undergoing regeneration.

Yet another particularly preferred method of controlling or limiting the regeneration heat imparted to the fresh feedstock via the recycled catalyst is to transfer a portion of the heat imparted by the recycled catalyst to the reactor by adding an additive, For example, water, steam, naphtha, other hydrogen donating substances, flue gas, inert gases, and other gaseous or vaporizable substances that can be introduced into the reactor.

In most cases, it is important to ensure that unabsorbed oxygen-containing gas is carried to the riser by the recycled catalyst.

Thus, the catalyst exiting the regenerator can be stripped with a suitable stripping gas to remove oxygen-containing gases whenever such action is deemed necessary.

Such stripping may be carried out at relatively high temperatures, for example.
For example, it can be carried out using water vapor, nitrogen or other inert gas as the stripping gas at a temperature of about 1.350<0>F to about 1,370<0>F.

The use of nitrogen and other inert gases is advantageous in that it avoids the tendency for hydrothermal deactivation of the catalyst that would result from the use of steam.

The following comments and considerations regarding metal management, carbon management and thermal management will assist in achieving the best results when practicing this invention.

It will be clear that the present invention is not limited to the particular operating modes discussed below, as these findings are mostly directed to what is considered to be the best operating mode.

Moreover, since some of these comments are necessarily based on theoretical considerations, there is no guarantee that any such comments, whether stated here or implicit in the driving suggestions below, There is no way to connect it to theory.

Although discussed separately below, it is readily apparent that metal management, carbon management, and thermal management are interrelated and interdependent subjects in both theory and practice.

Although coke formation and coke deposition on the catalyst is primarily a result of the relatively large amounts of pre-coke precursors found in the carbon-metal oil, coke formation is exacerbated by the high accumulation of metals; And it can also significantly affect the performance of the catalyst.

Furthermore, the degree of success experienced in metal management and carbon management has a direct impact on the degree of thermal management required.

Additionally, some of the processes thought to aid in metal management have proven very useful with respect to carbon and thermal management.

As mentioned above, the accumulation and presence of large amounts of heavy metals on the catalyst tends to exacerbate dehydrogenation and aromatics condensation problems, and for a given Ramsbottom carbon value feedstock oil, gas and Increase coke production.

Introducing substantial amounts of H2O into the reactor in the form of either steam or liquid water maintains the heavy metals in a less harmful form, i.e., in the oxide form rather than the metal form. From this point of view, it seems extremely advantageous.

This helps in maintaining the desired selectivity.

Additionally, the system components and residence times are chosen to reduce the ratio of the light blue time of the catalyst in the reactor to the residence time of the catalyst in the regenerator. There is a tendency to lower the ratio at certain times.

This can also help maintain the desired level of selectivity.

Whether the metal content of the catalyst is well controlled can be observed by monitoring the total amount of hydrogen and methane produced in the reactor and/or the ratio of hydrogen to methane thus produced.

Generally, the molar ratio of hydrogen to methane is about 1, preferably about 0.
．． 6 or less, and a molar ratio of 0.4 or less is believed to be approximately optimal.

In practical practice, the molar ratio of hydrogen to methane is approximately 0.
5 to about 1.5, with an average of about 0.8 to about 1.

Careful carbon management can improve both selectivity (the ability to maximize production of valuable products) and thermogenicity.

In general, the metal control methods described above also aid in carbon management.

The effectiveness of the addition of water with respect to carbon control has already been discussed in considerable detail in the explanatory section of the specification regarding the addition of substances for introduction into the reaction zone.

In general, methods of improving the dispersion of feedstock oil in the reaction zone may also prove useful.

These methods include, for example, the use of atomization or atomization devices to assist in dispersing the feedstock oil.

The catalyst to oil ratio is also a factor in thermal management.

■ As with conventional FCC implementations for (3), the reactor temperature in the practice of this invention also limits the flow of thermally regenerated catalyst to the reactor to the reactor temperature, typically of riser type 1. It can be controlled by increasing or decreasing the temperature at the outlet of the reactor, respectively.

If the automatic controller is set to maintain an excessive catalyst-to-oil ratio for catalyst introduction, the rate of carbon production and heat release will be proportional to the weight of fresh feedstock oil fed to the reaction zone. It seems to be unnecessarily large.

Relatively high reactor temperatures are also advantageous from a carbon management perspective.

Such high temperatures promote more complete vaporization of the feedstock oil and desorption of products from the catalyst.

Carbon management can also be facilitated by appropriate limits on the reactor total pressure and feed oil partial pressure.

Normally, at a given conversion level, relatively small reductions in pressure can substantially reduce coke formation.

This is because limiting the total pressure improves the vaporization of high-boiling components of the feedstock, favors cracking, and desorption of both unconverted feedstock and higher-boiling cracked products from the catalyst. This may be due to the fact that it tends to promote

This may also help limit the pressure drop in downstream equipment communicating with the reactor.

However, when it is desirable or necessary to operate the system under a higher total pressure, e.g. due to operational limitations (e.g. pressure drop in downstream equipment), the above advantages can be applied to the feedstock oil. can be obtained by limiting the partial pressure of .

The appropriate range for the total pressure of the reactor and the partial pressure of the feedstock oil is as described above, but it is generally desirable that the pressure be at its lowest within this range.

Rapid separation of the catalyst from the product vapor and unconverted feedstock (if any) is also of great help.

For this reason, U.S. Pat. Nos. 4,070,159 and 4,066, et al.
The so-called vented riser apparatus and method disclosed in No. 533 is the preferred type of apparatus for carrying out the method of this invention.

For similar reasons, the separation of the catalyst from the product vapor and the
- It is advantageous for the elapsed time between the start of IJ tubbing to be as short as possible.

Vented risers and rapid stripping tend to reduce the chance of coking of unconverted feed oil and higher boiling cracked products sorbed onto the catalyst.

A particularly desirable mode of operation from a carbon management point of view is to carry out the process in a bench riser, using a hydrogen donor if necessary, while keeping the partial pressure of the feed oil and the total pressure of the reactor as low as possible. and provides a number of advantages discussed in detail above.

Relatively large amounts of water, steam, and optionally other diluents are incorporated.

Furthermore, when feeding liquid water, steam, hydrogen donating substances, hydrogen and other gaseous or vaporizable substances to the reaction zone, the feeding of these substances provides an opportunity for additional control of the catalyst to oil ratio.

Thus, for example, implementing an increase or decrease in the catalyst-to-oil ratio for a given increase or decrease in reactor temperature may result in a moderate decrease or increase in the charge ratio of water, steam, and other gaseous or volatile substances, or This can be reduced or eliminated by either a moderate reduction or increase in the ratio of other gaseous substances introduced into the reaction zone.

Thermal management includes actions taken to control the amount of heat released in various parts of the method and/or to manage such heat that is released.

Normal FC using VGO, which usually has time to generate enough heat to thermally balance the reactor during regeneration
Unlike the C process, large amounts of heat are generally generated in carbon-metal oil processing and therefore careful thermal management is required.

Thermal management can be facilitated by a variety of methods related to the materials introduced into the reactor.

Thus, heat absorption by the feedstock can be maximized with minimal preheating of the feedstock, where the temperature of the feedstock is adjusted to be sufficiently fluid for good dispersion in the feed and reactor. It only needs to be high enough to

The high degree of conversion and high selectivity obtained when the catalyst is kept highly active and inhibits coking (metal control) to achieve higher conversions can increase the absorption of the heat of reaction.

In general, higher reactor temperatures favor conversion activity of the catalyst in terms of more refractory, higher boiling, high coking potential components.

Therefore, although the rate of catalyst deactivation increases, higher operating temperatures tend to offset this loss in activity.

Higher temperatures in the reactor also contribute to improving the octane number, thus supplementing the octane number reduces the effects of high carbon deposition.

Other methods of absorbing heat have already been discussed above in connection with the introduction of water, steam and other gaseous or vaporizable substances into the reactor.

As noted above, the invention can be practiced in the manner described above and in many other ways.

One illustrative, non-limiting example will now be described with reference to the accompanying schematic drawings and the following description of these figures.

To explain in detail with reference to the drawings, in FIG. It is then mixed with the thermally regenerated catalyst.

The feedstock oil is catalytically cracked as it ascends riser 2 and its product vapors are separated from the depleted catalyst in vessel 8.

The catalyst particles move upward from the riser 2 into the space of the vessel 8 and descend into a dense bed 16.

The decomposition products enter cyclone 5 through horizontal line 4 together with some finely divided catalyst.

The gas is separated from the catalyst in a cyclone and exits through line 6.

The fine catalyst falls through the depending foot 19 to the bed 16.

The depleted catalyst coated with coke and reduced vanadium passes through line 7 into the upper dense fluidized bed 18 in regenerator 9 .

This depleted catalyst is fluidized by a mixture of air, CO and CO2 coming from the lower zone 20 through the perforated plate 21.

The depleted catalyst is partially regenerated in bed 18 and in line 1
1 and enters the lower part of the vented riser 13.

Air is introduced through line 12 into riser 13 where it is mixed with the partially regenerated catalyst.

The catalyst is forced rapidly upward through the riser,
It then falls into a dense sedimentary bed 17.

Line 14 is a source of reducing gas to bed 17, such as CO, to maintain the regenerated catalyst in a reducing atmosphere and thus maintain the vanadium present in a reduced oxidized state.

The regenerated catalyst is returned to the user reactor 2 through line 3, which is provided with a source of reducing gas, such as CO, sent through line 12.

In FIG. 2, the depleted catalyst coated with coke and reduced vanadium enters the dense fluidized bed 32 of the regenerator 31 through an inlet line 33.

Air for burning the coke and flowing the catalyst is introduced through line 34 into an air distribution device 35.

The coke is burned and directed upwards into the riser regenerator 36.
to go into.

The partially regenerated catalyst reaching riser 36 is routed through line 3
7 and comes into contact with the air that completes the regeneration.

The regenerated catalyst exits upwardly from the top of riser 36 and descends into a dense settling bed 37.

The dense bed 37 into which the regenerated catalyst falls and the zone above bed 37 are supplied with a reducing gas such as CO through lines 40 and 41.The regenerated catalyst is passed through line 38 to the cracking reactor. It will be returned.

The CO-rich flue gas exits the regenerator through line 39.

The present invention has been described above, and the present invention will be explained in further detail in the following examples.

EXAMPLE Carbon-metal feedstock oil at a temperature of about 400° F.
00 lb/hr to the bottom of a vented riser reactor where the zeolite catalyst and approximately 1,275'
Mix at a temperature of F and a catalyst to oil weight ratio of about 11.

The carbon-metal feedstock oil, including the three Lords vanadium, is approximately 5.
It has a heavy metal content of nickel equivalent of ppI 11 and a Conradson carbon content of about 7%.

About 85% of the feedstock oil boils above 650°F and about 20% boils above about 1,025°F.

The temperature inside the reactor is about 1,000'F and the pressure is about 27
It is psi.

Approximately 75% of the feedstock oil is converted to fractions boiling at temperatures below 430°C and approximately 53% is converted to gasoline.

Approximately 11% of the feedstock oil is converted to coke during conversion.

A catalyst containing about 1% by weight coke has about 12.00% coke.
It contains about 20,000 ppm nickel equivalent including vanadium at QppH.

The catalyst is stripped with steam to remove volatiles at a temperature of about 1.0 OOOF, and the stripped catalyst is placed in the upper zone of the regenerator shown in FIG.
000 lb/hr, and air, CO
and CO□; thus partially regenerated to a coke concentration of approximately 0.2%.

The CO/Co□ ratio in the fluidized bed in this upper zone is approximately 0.
．． It is 3.

The partially regenerated catalyst had little interparticle adhesion, likely due to the stickiness of the five vanadias.

The partially regenerated catalyst is passed to the bottom of the riser reactor where it is contacted with a sufficient amount of air to force the catalyst up to the riser with a residence time of about 1 second.

The regenerated catalyst with a coke content of about 0.05% exits the top of the riser and falls into a dense catalyst bed with a reducing atmosphere of Co.

This regenerated catalyst is recycled to the riser reactor for contact with additional feed membranes.

[Brief explanation of the drawing]

1 and 2 are schematic diagrams of a catalyst regeneration system and associated cracking system that can be used in practicing the present invention. 2... Riser reactor, 5... Cyclone, 9.31... Regenerator, 13...
...vented riser, 16...catalyst bed, 1
7,37...Settled bed of catalyst, 18,32...
... Catalyst fluidized bed, 21 ... Perforated plate, 35.
... Air distribution device, 36 ... Riser regeneration device.

Claims (1)

Claims: 1. Contacting a vanadium-containing hydrocarbon oil feedstock with a cracking catalyst under conversion conditions to form light products and coke to deposit vanadium in an oxidation state less than +5 and coke on the catalyst. separating the light products from an exhaustion catalyst carrying vanadium in an oxidation state below 5 and coke; burning the exhaustion catalyst with coke on the catalyst;
Regenerating the catalyst by contacting it with an oxygen-containing gas under conditions that form gaseous products consisting of CO and CO□, with regeneration occurring under conditions in which the vanadium is maintained in an oxidation state below +5. and recycling said regenerated catalyst to a reactor for contact with fresh feedstock oil. 2. The feedstock oil contains material at 650° F. with a pyrolytic carbon residue of at least about 1 and a heavy metal nickel equivalent content of at least about 4. The method described in section. 3. The 650°F+ material is at least about 70% by volume of said feedstock and includes at least about 10% by volume of material that does not boil below about 1.000°F. The method described in section. 4. The feed oil contains at least about 0.1% vanadium.
The method according to claim 1, containing ppm. 5. The feedstock oil contains vanadium at least about I l
1l) The method according to claim 1, containing In. 6 The feedstock oil contains from about 1 ppIn to about 5 ppIn of vanadium.
The method according to claim 1, containing ppm. 7. The method of claim 3, wherein the feedstock oil contains about 5 pIMII or more of vanadium. 8. The method of claim 1, wherein the cracking catalyst comprises a zeolite molecular sieve catalyst containing from about 1% to about 60% by weight molecular sieve. 9. The method of claim 1, wherein the cracking catalyst comprises a zeolite molecular sieve catalyst containing from about 15% to about 50% by weight molecular sieve. 10. The method of claim 1, wherein the cracking catalyst comprises a zeolite molecular sieve catalyst containing from about 20% to about 45% by weight molecular sieve. 11. The method of claim 1, wherein the concentration of deposited vanadium on the cracking catalyst is greater than or equal to about 0.05% by weight of the catalyst. 12. The method of claim 1, wherein the concentration of deposited vanadium on the cracking catalyst is greater than or equal to about 0.1% by weight of the catalyst. 13. The method of claim 1, wherein the concentration of deposited vanadium on the cracking catalyst is greater than or equal to about 5% by weight of the catalyst. 14. The method of claim 1, wherein the concentration of deposited vanadium on the cracking catalyst is from 0.1% to about 5% by weight of the catalyst. 15. The method of claim 1, wherein coke is deposited in an amount of 0.3 to 3% by weight relative to the cracking catalyst. 16＠Exhaust catalyst from about 1.100°F to about 1.600°
2. A method according to claim 1, wherein the method is regenerated at a temperature of F. 17＠Exhaust catalyst from about 1.200°F to about 1.500°
2. A method according to claim 1, wherein the method is regenerated at a temperature of F. 18 The depleted catalyst is heated between about 1.275° F. and about 1.425° F.
2. A method according to claim 1, wherein the regeneration is carried out in a temperature range of F. 19＠A sufficient amount of coke is retained on the regenerated catalyst,
A method as claimed in claim 1 in which the deposited vanadium of the catalyst is provided with a non-oxidizing environment. 20 The concentration of coke on the regenerated catalyst is at least about 0.
．． 05%. 21 The concentration of coke on the regenerated catalyst is about 0.05%
15. The method of claim 1 in the range of 0.15% to about 0.15%. 22 The regeneration is carried out in at least two stages, and at least one stage reduces CO and CO2 to at least about 0.
．． Claim 1 containing in a molar ratio of 25
The method described in section. 23@) The depleted catalyst is regenerated in at least two stages, the first of which involves contacting the depleted catalyst with a gas containing a substoichiometric amount of oxygen in a dense fluidized bed to regenerate the depleted catalyst above the catalyst. Converting the hydrogen in the coke to H2O and its carbon to CO2, and in a final step contacting the partially regenerated catalyst with an excess stoichiometric amount of oxygen for a time of no more than about 2 seconds. The method described in paragraph 1. 24. The method of claim 23, wherein the catalyst in the final stage comprises a dispersed bed having a density of less than about 4 pounds per cubic foot. 25. The method of claim 23, wherein the residence time of the catalyst in the dense fluidized bed of claim 25 is at least about 5 minutes. 26＠The liquid powder is approximately 25 lbs./cubic foot to approximately 50 lbs./cubic foot.
24. The method of claim 23 having a degree of pounds per cubic foot. 27. Contacting the partially regenerated catalyst with at least a stoichiometric amount of oxygen in a riser regenerator, the residence time of the catalyst in the riser regenerator is about 2 seconds or less, and the regenerated catalyst 24. A method as claimed in claim 23 in which the gaseous products are separated from the gaseous products. 28. The method of claim 27, wherein the residence time of the catalyst in the riser regenerator is about 1 second or less. 29. A method according to claim 27, in which the separated regenerated catalyst is brought into contact with a reducing gas. 2. A method as claimed in claim 2. 31. Claim 27, wherein the density of the catalyst in the riser regenerator is less than or equal to about 4 pounds per cubic foot.
The method described in section. 32. The method of claim 27, wherein the density of the catalyst in the riser regenerator is less than or equal to about 2 pounds per cubic foot. 33. Separate the regenerated catalyst from the gaseous products by injecting it in the direction defined by the riser regenerator or in the direction of its extension, and during which the gaseous products are subjected to a sudden drop of the gaseous products from the regenerated catalyst. 2. A method as claimed in claim 2.gamma., which produces an abrupt change in direction resulting in a substantially instantaneous ballistic separation.