JPS5949275B2 - Immobilization of vanadia deposited on catalyst materials during processing of extracted crude oil - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides an improved catalyst, one or more methods for its preparation, one or more processing methods thereof, and a fuel for transporting and/or heating liquids from prefixed crude oil or crude oil. How to use this when converting to .

More particularly, the present invention provides catalytic activity homogeneously dispersed in a matrix containing a metal additive as a selected metal, its oxide or salt, to immobilize vanadium oxide deposited on the catalyst during processing. The present invention relates to a catalyst composition comprising a crystalline aluminosilicate zeolite.

Another embodiment of the present invention is to add metal additives for vanadia immobilization during catalyst production either by impregnation after spray drying or at any point during the processing cycle of the prefixed crude oil.

The introduction of catalytic cracking to the petroleum industry in the 1930s was a major advance over previous technologies aimed at increasing the yield of gasoline and its quality.

Early fixed bed, moving bed and fluidized bed catalytic cracking FCC
The law includes vacuum gas petroleum obtained from crude oil that was considered sweet and light.
soils, VGO) was used.

The term sweet refers to a low sulfur content and the term light refers to the amount of material that boils below about 1.000-1.025''F.

Early homogeneous dense fluidized bed
The catalyst used in ed) was of an amorphous siliceous material made synthetically or from natural materials activated by acid leaching.

In the 1950s, metallurgy, processing equipment,
Significant advances have been made in regeneration and new, more active and more stable amorphous catalysts.

However, increasing demands on gasoline quality to meet the new high-horsepower, high-compression engines subsidized by the automobile industry, as well as increased demands on octane, have resulted in stricter production capacity and operation requirements for the FCC method. Severe pressure on the oil industry to increase the 7JD
I got it.

Major advances in FCC catalysts occurred in the early 1960s.
This was achieved by introducing molecular sieves or zeolites.

These were incorporated into the amorphous material and/or amorphous/kaolin material matrix that constituted the FCC catalyst at the time.

These new zeolite catalysts containing crystalline aluminosilicate zeolites in matrices such as amorphous materials, amorphous/kaolin materials, silica, alumina, silica-alumina, kaolin, etc., are superior to earlier zeolite catalysts containing silica-alumina catalysts. At least 1.00 for cranking hydrocarbons over amorphous materials, amorphous/kaolin materials
The surnames were 0 to 10,000 times higher.

The introduction of this zeolite cracking catalyst brought about a revolution in fluid catalytic cracking.

New modifications to handle these high activities, such as riser cranking, reduced contact time, new regeneration methods,
New and improved zeolite catalysts have been developed.

The overall economic result of the development of these zeolite-based catalysts is to significantly increase throughput and conversion of feedstocks without the need for expansion or construction of new units using the same unit. and offered the petroleum industry the possibility of increasing selectivity.

Newer catalysts have been developed, centering on the development of various zeolites such as X, Y, and faujasite types.

By incorporating rare earth ions or ammonium through ion exchange technology, heat-steam stability has been increased and a material with greater wear resistance has been developed.

After the introduction of catalysts containing zeolitic materials, the petroleum industry began to struggle with the availability of crude oil in terms of quantity and quality as the demand for higher octane gasoline increased.

The world crude oil supply situation changed from the late 1960s to the early 1970s.

The supply situation has changed from an abundance of light-sweed crude oil to a more scarce supply situation with constant boosters of heavier crude oils with higher sulfur content.

These heavier and higher sulfur content crude oils are difficult to refine in that these heavier crude oils always also have higher amounts of metals and Conradson carbon numbers, with significant increases in asphalt content. I raised the issue of force with the contractor.

The fractionation of the total crude oil to obtain the catalytic cracking feedstock also needed to be better controlled to ensure that the metals and Conradson carbon numbers were not transferred throughout and mixed into the FCC feedstock.

The effect of metals and Conradson carbon on FCC catalysts containing zeolitic materials is that they have a significant detrimental effect reducing catalyst activity and selectivity for gasoline production, as well as an equally detrimental effect on catalyst life. It has been described in the literature that this is the case.

In particular, we have found that the presence of vanadia in high concentrations in the feedstock is particularly detrimental to catalyst life.

As noted above, these heavier crude oils also contained higher amounts of heavier fractions, resulting in lower amounts of good quality FCC feedstocks.

FCC feedstocks typically boil below 1025'F and typically have a metal content of less than 1 ppm, preferably 0. 1 ppm or less and the Conradson carbon number is substantially 1 or less.

This increased supply of heavier crude oils means lower gasoline yields and increased demand for liquid transportation fuels, leading the oil industry to convert these heavier crudes into gasoline. We have begun to pursue a processing plan for use in the production of .

Most of these plans are described in the literature.

These include Gulf's Galfining and Union Oil's Unifying processes for treating kettle residue, UOP's Aurabon process for producing pyrolysis gasoline and coke; These include Research's H-oil method, Exxon's flexi-coking method, H-Oil's dynacracking method, and Philips' heavy oil cranking method (I(O(,')).

These methods employ pyrolysis or hydrotreating followed by FCC or hydrocracking operations to produce relatively high metal content (Ni-V-Fe-Cu-Na) and high Conradson carbon of 5-15. It processes value.

The disadvantages of this type of processing method are as follows.

In other words, the coking method yields pyrolyzed gasoline with a significantly lower octane number than catalytic cracked gasoline.
This process is also unstable due to the production of rubber from diolefins and requires further hydrotreating and reforming to obtain high octane products.

Thermal reactions reduce the quality of the gas oil and result in products containing refractory polynuclear aromatics, and the high Conradson carbon number is highly unsuitable for catalytic cracking.

Hydrogen processing also requires expensive high-pressure hydrogen, multiple reactor clusters made of special alloys, expensive operations, and expensive separate equipment for hydrogen production.

In order to better understand why the industry has progressed with the UO engineering program described above, it is important to note that contaminant metals (N i -V-F e -Cu-Na ) and the confirmed and known effects of Conradson carbon.

Metal content and Conradson carbon are determined by the FCC unit or prefixed crude conversion (Reduced Cru).
deConves 1on) are two very significant restraints on operating for high conversion, selectivity and longevity.

Although there is only enough hydrogen to produce only toluene and pentane if a highly selective catalyst is devised, the operating capacity and efficiency of the FCC unit will be large due to the metal and Conradson carbon boosters. affected and ultimately adversely affected or rendered inoperable.

The effect of the Conradson carbon booster is that more feed oil is converted to carbon that is deposited on the catalyst.

For typical VGO operations using zeolite-containing catalysts in FCC units, the amount of coke deposited on the catalyst averages about 4-5% by weight of the feed.

This coke formation was due to four types of coking mechanisms.

That is, contaminated coke (from metal deposits), catalytically cracked coke (cracking in acidic sites), and entrained hydrocarbons (
Pore structure adsorption - poor stripping) and Conradson carbon.

High-boiling fractions, e.g. reduced cr.
When focusing on residual fractions such as ude, topped crude, etc., the amount of coke produced relative to the amount of feed is determined by the above four components present during VGO, UI], high Conradson carbon number, high boiling point hydrocarbons that are not stripped, and coke associated with nitrogen-rich molecules irreversibly adsorbed on the catalyst.

Therefore, when processing a prefixed crude oil, the amount of coke produced on a clean catalyst is about 4% by weight plus the Conradson carbon number of the feedstock.

Therefore, it has been hypothesized that in addition to the four coking sources present in VGO, there are two other coking sources in the extracted crude oil.

They are: 1) adsorbed and absorbed high-boiling hydrocarbons that cannot be removed by stripping at normal capacity;
and 2) a high molecular weight hydrocarbon compound containing nitrogen adsorbed on the acidic sites of the catalyst.

These two new types of coke formation phenomena add significantly to the complexity of kettle bottom oil production.

The spent catalyst that produced coke is brought back to equilibrium activity by burning off the deactivating coke in the presence of air in a regeneration zone and recycled to the reaction zone.

The heat generated during regeneration is removed by the catalyst and transported to the reaction zone for vaporization of the feedstock and to provide heat for the endothermic reactivity of the cranking reaction.

The temperature in the regeneration zone is kept within conventional limits due to metallurgical limitations and thermal-steam stability of the catalyst.

The thermal-steam stability of zeolite-containing catalysts is determined by the temperature and water vapor partial pressure at which the zeolite rapidly begins to lose its crystalline structure to an amorphous material of low activity.

The presence of water vapor is very important and is generated by the combustion of adsorbed carbonaceous material with a high hydrogen atomic content.

This carbonaceous material is mainly boiling point 1 with moderate hydrogen content.
Adsorbed high boiling hydrocarbons from 500 to 1700'F or higher, and high boiling hydrocarbons containing nitrogen;
and related porphyrins and asphaltenos.

Coke production increases as the Conradson carbon number of the feedstock increases, and this increased loading will increase regeneration temperatures.

The unit is therefore limited in terms of the amount of stock it can process due to its Conradson carbon content.

Relatively early VGO units had a regenerator of 1150
Operated at ~1250°F.

A newly developed method has been developed in the power of prefixed crude oils, namely Ashland Oil's "Prefixed Crude Conversion Method" (pending patent application USSN 094,216).
) can be operated at regenerative temperatures ranging from 1350 to 1400 degrees Fahrenheit.

However, even this high regeneration temperature is limited by the feedstock's Conradson carbon number of about 8.

This level will be the regulation unless significant amounts of water are introduced to further control the temperature (which the RCC method does).

The metal-containing fraction of the prefixed crude oil contains N i -V-Fe-Cu present in porphyrins and asqualtene.

These metal-containing hydrocarbons are deposited on the catalyst during processing, cranked in the riser to deposit metals, or left intact by the used catalyst as metal-porphyrins or asphaltenes to form metal oxides during regeneration. can be changed to

According to the literature, the adverse effect of these metals is to cause non-selective or vacuum ranking and dehydrogenation of coke and light gases (e.g. hydrogen,
methane and ethane), resulting in a decrease in the yield and quality of gasoline and gas oil.

Increased production of light gases compromises the yield and selectivity structure of the process, while also increasing demands on compressor capacity.

In addition to its negative impact on yield, increased coke production also affects catalyst activity and selectivity, significantly increasing regenerator air demand and compressor capacity, and potentially uncontrollable and dangerous regenerator temperatures. increase to

These problems of the prior art have been greatly reduced by the development of the Prefixed Crude Compancon process at Enyuland Oil Company (see pending patent applications USSN 094,092 and 094.216).

This new method allows handling of prefixed crude oils or crude oils with high metal contents and Conradson carbon numbers that previously could not be directly targeted.

Thus, these crude oils require expensive vacuum distillation to separate the appropriate feedstocks and produce vacuum still bottoms with high sulfur content as a by-product.

The RCC method avoids all of these.

Prefixed crude oil with high nickel to vanadium levels has a high metal content relative to the catalyst (e.g. 5,000 to 10,0
It was early recognized that elevated regeneration temperatures (00 ppm) exhibited fewer problems with catalyst deactivation.

However, when prefixed crude oils with high vanadium to nickel levels are processed over zeolite-containing catalysts, especially at high vanadium contents relative to the catalyst, rapid deactivation of the zeolite-containing catalysts is observed.

This inactivation ranges from 5.000 ppm to 10,000 ppm.
Enhanced regeneration with vanadium levels up to ppm? sW
It has been shown that the zeolite structure is rapidly lost at high temperatures.

According to the published commentary, for this factor l O,00
It has been reported that it is not possible to operate with vanadium levels above 0 ppm.

To date, this rapid inactivation by vanadium at high vanadium levels has only been suppressed by lowering the regenerator temperature and increasing the fresh catalyst addition rate.

These problems of the prior art are solved in a process using the catalyst and selected metal additives according to the invention, whereby a prefixed crude oil with high metal content (high vanadium/nickel ratio) and high Conradson carbon number is Or you can power loe the crude oil.

A prefixed crude oil or crude oil having a high metal content and a high Conradson carbon number is contacted with a zeolitic material-containing catalyst in a high humidity region of about 950 or below.

The residence time of the crude oil in the riser is 5 seconds or less, preferably 0.5 to 2 seconds.

The particle size of the catalyst is approximately 20~20 to ensure proper fluidity.
The dimensions are 150 microns.

Prefixed Crude Oil - Crude oil is introduced into the bottom of the riser and 1200 to 1
Contacting the catalyst at a temperature of 400'F results in a temperature of about 950-1100F at the exit of the reactor riser.

Water, steam, naphtha, flue gas, etc. are introduced along with the prefixed crude oil or crude oil to assist in evaporation and to provide lift gas (
xirt gas) to control residence time and obtain other advantages as shown in patent application USSN 094.216.

The spent catalyst is rapidly separated from the hydrocarbon vapors at the exit of the riser by employing the vented riser concept developed by Unjland Oil.

During the reaction in the riser, metals and Conradson carbon compounds are deposited on the catalyst.

The spent catalyst is separated in a vented riser and deposited in a dense but fluffy layer at the bottom of the reactor, transferred to a stripper and then to a regeneration zone.

The used catalyst is brought into contact with an oxygen-containing gas and burned to form carbon oxides, thereby removing carbonaceous material and regenerating the carbon content to 0.1% by weight or less, preferably 0.05% by weight or less. A catalyst is obtained.

The regenerated catalyst is then recycled to the bottom of the riser where it is again combined with the high metal content and Conradson carbon content feedstock to repeat the cycle.

Vanadium deposited on the catalyst converts to oxides of vanadium, particularly vanadium pentoxide, at the elevated temperatures encountered in the regeneration zone.

The melting point of vanadium pentoxide is much lower than the temperatures encountered in the regeneration zone.

It therefore becomes mobile and flows over the surface of the catalyst, plugging the pores, fusing the particles, and more importantly entering the pores of the zeolite, where, according to our studies, the crystals become immobilized. It has been shown that o'J mediates the reverse decay into an amorphous substance.

The present invention can be applied by incorporating specific metals, metal oxides or their salts into the catalyst matrix during production or by impregnation after spray drying, or at specific times in the unit during production. The addition represents a novel means to immobilize vanadium through the formation of compounds or complexes and to counteract the adverse effects of vanadium pentoxide.

These compounds or complexes of vanadia and metal additives are
It acts to immobilize vanadia by forming a complex or compound of vanadia with a melting point higher than the temperatures encountered in the regeneration zone.

Particular catalysts of the invention include clays, kaolins, silicas, aluminas, smectites, and other bilayer plate silicates,
Included are solids with high catalytic activity, such as zeolites, in matrices such as silica-alumina.

The surface area of these catalysts is preferably greater than or equal to ioom/, 9, with a pore size of 0.2
+711/ E1 or higher, and ASTM test method Atsushi D3
It has a microactivity value or companion value of at least 60 or more, preferably 65 or more, as measured by 907-80.

Metal additives are mixed into an aqueous slurry of raw material and zeolite, and the amount of metal additives is about 1 to 20% relative to the final catalyst.
Concentration in weight%.

The metal proboscis can be added in the form of water-soluble compounds such as nitrates, halides, sulfates, carbonates, and/or as oxides or hydrates.

Spray drying this mixture provides the promoted final catalyst as microspherical particles with dimensions of 10 to 200 microns containing active metal additives deposited within the matrix and/or on the outer surface of the catalyst particles.

Since the concentration of vanadia in the used catalyst may be up to 4% by weight of the weight of the particles, in order to always maintain at least an 1 to 1 atomic ratio of vanadium to n of the metal part,
The metal additives will range from 1 to 6% by weight as metallic elements.

The catalyst may be impregnated with metal additives after spray drying using techniques well known in the art, or an active gelatinous precipitate (e.g. titania or silconyl or other r) can be added to the matrix r.

Although it is not intended to determine the exact mechanism of vanadium immobilization, it is likely that the metal additives of the present invention form compounds or complexes with vanadia that have higher melting points than those encountered in the regeneration zone.

A 1:1 atomic ratio is chosen as the minimum.

However, if the catalyst is to contain metal before use, the metal loading proboscis may initially be much higher than this ratio.

The ratio of additive to vanadium will then decrease as vanadium is deposited on the catalyst.

Therefore, at this 1:1 ratio (50% vanadium-50% metal additive) the melting point of the two-component reaction product is generally well above the operating conditions.

Alternatively, metal additives can be added at a ratio equal to the metal content of the feedstock to maintain a 1:1 atomic ratio.

This experimental method involves finding a suitable metal-metal oxide that can form a two-component reaction mixture with vanadium pentoxide to give a solid compound with a melting point of about 1800°F or higher in this one-to-one ratio. It was actually adopted to confirm.

The search for this high melting point reaction product was initiated to gain confidence that vanadia would not melt and flow and enter the zeolite cage structure and disrupt the zeolite crystal structure as described above.

The metal-metal oxide in the present invention includes the following groups of the periodic table of elements and their active elements.

The reaction of Panadia with metal additives generally results in a two-component reaction mixture.

According to the present invention, mixtures of vanadia with these additives can produce high melting point ternary and quaternary reaction mixtures (e.g. barium vanadium titanate); It was also confirmed that metals can occur together with metals not included in the above groups.

Additionally, the present invention includes vanadium pentoxide as well as lower oxidation states of vanadium.

However, during processing of sulfur-containing feedstocks, oils, and regeneration in the presence of oxygen-containing gases, vanadium also appears to form compounds such as vanadium sulfides, sulfates, and oxysulfides; Also, together with the metal additives in the present invention, there is a possibility of forming binary, ternary, etc. reaction mixtures in the form of mixed oxides and mixed sulfides.

If a metal additive is not added to the catalyst during V forming, it can be added to the spray-dried microspherical catalyst particles by an impregnation method.

Additionally, the metal part, 710, can be added as an aqueous solution, a hydrocarbon solution, or a volatile compound at any time the catalyst moves through the processing unit during the recycling cycle.

This includes the riser 7 junction 11 along the riser length 4, the dense catalyst bed 9 of the reactor 5, the strippers 10 and 15, the regenerator population 14, the dense catalyst bed 12 of the regenerator. Alternatively, the methods include, but are not limited to, adding an aqueous solution of an inorganic metal salt or a hydrocarbon solution of an organometallic compound to the regenerated catalyst standpipe 16.

Certain catalysts of the present invention (with or without metals) can be used in the prefixed crude oil conversion system (with or without metals) as shown schematically in FIG.
Charge into Re(,') type unit.

Catalyst particle circulation and operating parameters are tailored to the desired conditions in a manner well known to those skilled in the art.

The equilibrium catalyst contacts the prefixed crude oil of high metal content and Conradson carbon number in riser 7 junction 11 at a temperature below 1100-1400°C.

The crude oil is prefixed with steam and/or flue gas injected in section 2, water and/or injected in section 3, to assist in evaporation, fluidization of the catalyst, and control the contact time in riser 4. Alternatively, it may contain naphtha.

The catalyst and vaporous hydrocarbons rise up the riser 4 with a contact time of 0.5 to 5 seconds, preferably 1 to 2 seconds.

The catalyst and vaporous hydrocarbons are heated at a final reaction temperature of -950 to 11
00, and the hydrocarbon vapors are separated via a transfer line 8 to a vented riser outlet 6.

The vaporized hydrocarbons are transferred to the cyclone 7, where any entrained catalyst fine particles are sent to the back mold.

The spent catalyst is then transferred to a stripper 10 for removal of entrained hydrocarbon vapors and then transferred to a regenerator 11 to form a dense catalyst bed 12.

An oxygen-containing gas, such as air, may enter the bottom of the dense catalyst bed 12 of the regenerator 11 to combust the coke to oxides of carbon.

The resulting flue gas is processed through a cyclone and exits the regenerator 11 via line 13.

The dried catalyst is transferred to the stripper 15 to remove all entrained combustion gases, and then transferred to the riser pipe 17 via line 16 to repeat this cycle.

At this point, the metal level on the catalyst becomes too high and the activity and selectivity of the catalyst decreases, so add additional catalyst at 77[] and add the deactivated catalyst at 77[1-take-off position 18]. It is taken out into the high-density catalyst bed 12, and taken out at the loading point = take-out position 19 into the regenerated catalyst standpipe 1.
6. Move to inside.

Addition 71 JO positions 18 and 19 can also be used for addition of catalyst promoted by metal addition proboscis.

In the case of unpromoted catalysts, metal additives in the form of aqueous solutions or organometallic compounds in aqueous or hydrocarbon solvents are added at the addition points 18 and 19 and on the charge line 1. 1 position 2 and 3, riser 4
Addition position 20 in the reactor 5 at D position 21
can be added 77[] into the dense catalyst bed 9 at the bottom of the catalyst.

Addition of metal additives is not limited to these locations and can be made at any point in the crude oil-to-catalyst processing process.

The regenerator shown in FIG. 1 is a simple, single zone, dense catalyst bed type.

Regenerative sections are not limited to this example, but may be of two or more zones with internal and/or external circulating transfer lines from zone to zone, in a car or side-by-side fashion. There may be.

In some conventional prefixed crude oil processing methods, the use of prefixed crude oils containing low levels of metal impurities and high nickel/vanadium ratios as feedstocks provides acceptable catalyst life and selectivity. You will be able to do it.

However, as the vanadium content of the catalyst increases or when prefixed crude oils with high vanadium/nickel ratios are used, catalyst activity and selectivity decrease rapidly and become economically unacceptable. This can only be corrected by increasing the catalyst addition rate by a certain amount.

The observed deleterious effects of vanadium and nickel, the catalyst of the present invention, the metal additive proboscis promoter, and the method of the present invention were discussed in Ogihi.

The following specific examples are presented to illustrate the action of vanadia to flow and deactivate the catalyst by disrupting the crystalline structure of the zeolite, and the steps taken to prevent this from occurring.

EXAMPLE Panagia deposited on a fluidized catalytic cracking catalyst enters the zeolite under elevated temperature conditions in the amphiphilic zone, destroying its crystal structure and forming a more active amorphous material (lower activity and selectivity). The determination that mediating (accompanying) was observed in our prefixed crude oil demonstration unit.

This phenomenon was then determined in the laboratory by individually depositing vanadium and nickel on specific canadidate catalysts to examine the catalyst's resistance to harsh temperature and cooking conditions.

As can be seen in Figures 2-5 and Tables 1 and 2 (the overall effect of nickel is to neutralize acidic sites and increase the production of coke and gas), the zeolite cage Little or no structural failure was observed.

In contrast, Panajiu 11 was irreversibly destructive.

As the vanadium content increases under moderately harsh conditions, at a level of about 1% vanadium, the crystalline structure of the zeolite is destroyed after 5 minutes in steam at 1450 °C, resulting in a completely inactivated catalyst. The zeolite content was relatively reduced until the point when the zeolite content was relatively low.

Three methods were used to determine whether vanadium deposited on the catalyst flows and causes fusion between catalyst particles at the regenerator temperature, and whether vanadium-forming elements and their salts inhibit this process. I did this.

agglomeration or agglomeration methods, diffusion of vanadium with metal additives in alumina-ceramic crucibles or formation of compounds with metal additives, and spectroscopic studies and differential thermal analysis of vanadium-metal additive mixtures. .

Agglomeration Test Various concentrations of vanadium were deposited on clay that had been spray dried into microspherical particles ranging in size from 20 to 150 microns.

placing a vanadium-free clay and a clay containing various concentrations of vanadium in separate ceramic crucibles;
Baked in air at 14,000F for 2 hours.

At the end of this period, the crucible was removed from the Matsufuru furnace and allowed to cool in the chamber.

The surface texture and fluidity of these samples were confirmed and the results are shown in Table 3.

Table 3: V, O, Concentration (ppm) Surface Texture Flow Age Outside 0
Independent Free Flow 1.
000-5,000 Surface agglomeration
Partial shell - free flow 5,000-20,00
0 Surface agglomeration General agglomeration - no flowability As shown in Table 3, Vanadia clay does not form crusts or agglomerates or fused particles at the temperatures encountered in the regenerator section of the present invention.

At vanadia concentrations above 5,000 ppm, the clay begins to agglomerate and becomes severely bonded and completely non-flowing.

Although liquid in operating conditions, the manifestation of this phenomenon is that it lowers the freezing point in the melting hole or operating unit to facilitate entry into the unit for cleaning out clogged material (di pi egs) or for other repairs. Explained by findings.

Since this material has to be scraped away, this phenomenon also causes multiple redirections to take place in time.

Diffusion in a Crucible - Compound Formation The extended flocculation test uses a ceramic aluminum crucible to determine whether vanadia reacts with a particular metal additive.

If panadia does not react with the metal loading proboscis, or if only a small amount of the compound is formed, vanadia will diffuse through the porous alumina wall onto the wall surface and form a yellow to orange deposit on the outer wall of the crucible. Deposition was observed.

On the other hand, when the compound is formed, there is little or no vanadia deposit on the external surface of the crucible outer wall.

Two series of tests were conducted.

In the series shown in Table 4, a 1:1 (weight ratio) mixture of vanadium pentoxide and metal additive proboscis was placed in a crucible and heated at 1500°F in air for 12 hours.

Formation of compounds or diffusion of panagia was observed.

Table 4 ■ 20.1 parts 1,000 Metal additives 1 part 1,500 parts - Air - 12 hours Metal additives Diffusion of vanadium
Compound formation titania none
Yes Magnesium acetate No
Yes lanthanum oxide
Yes No Alumina Yes
No barium acetate
Yes No Copper oxide Yes
In a partial second series of tests, vanadia-containing materials were tested in a similar manner.

The vanadia-containing material and metal part 7JO material (1:1 weight ratio) were heated in air to 1500'F for 12 hours.

The results are shown in Table 5. Table 5 ~ 1205-1 part of catalyst 10 Metal part nose 1500'F
- Air - 12 hours Panaji γ concentration (ppm) Metal additives
Particle generation 24.000 None
Yes 24,000 Calcium oxide No 24,000
Magnesium oxide None 24,000
Manganese oxide Studies on the ability of certain elements to fix vanadium dioxide have been conducted using DuPont Differential Thermal Analysis (DTA), X-ray Diffraction (XRD)
) and scanning electron microscope direct SEM).

In examining metal additives based on DTA, titania, barium oxide, calcium oxide, iron oxide, and indium oxide are all excellent additives for the production of high melting point metal vanadates with melting points below 1800 or higher. It was shown that

Copper and manganese produced compounds that melted below about 1500, giving intermediate results.

Lead oxide, molybdena, tin oxide, chromia, zinc oxide,
Poor results were obtained for cobalt oxide, cadmium oxide, and some of the rare earths.

1500 ppm of vanadia on the product shown in Table 5, i.e. 24,000 ppm of clay without metal additives.
It was examined by SEM after combustion at ``'F.

The fused particles initially exhibited the state of fused particles.

However, as the material continued to be bombarded, the fused particles separated due to the heat generated by the bombarded electrons.

The vanadia was observed to melt and flow, with the initial single fused particle separating into two separate microspherical particles.

An example of an XRD study is the identification of the compound formed when manganese acetate reacts with vanadium pentoxide.

This compound has been tentatively identified as Mn2V207.

The matrix material for the catalyst of the invention must have good hydrothermal stability.

Examples of materials exhibiting relatively stable pore customization are alumina, silica-alumina, silica, clays such as kaolin, metakaolin, halloysite, dietschite, macrite, and combinations of these materials.

Other clays, such as montmorillonite, can also be added to increase the acidity of the matrix.

Clays can be used in their natural state or in their heat-modified state.

The preferred matrix of US Pat. No. 3,034,994 is a semi-synthetic combination of clay and liquor alumina.

The clay is predominantly kaolinite, preferably in combination with synthetic silica-alumina hydrols or hydrosils.

The synthesis components preferably represent about 15-75% by weight of the produced catalyst;
More preferably, it accounts for about 20-25%.

The proportion of clay is preferably about 10 to 7 after the catalyst is formed.
It contains 5% by weight of clay, more preferably 30 to 50% by weight.

The most preferred matrix compositions contain about twice as much clay as synthetically derived silica-alumina.

The synthetically derived silica-alumina should contain 55-95%, preferably 65-85% and most preferably about 75% silica (S+02) by weight.

However, the catalyst includes a gamma matrix or a catalyst made entirely of silica.

After introducing zeolite and/or metal additives 1
Preferably, the composition is slurried and spray dried into catalyst microspheres.

The particle size of spray-dried 7 Trix is generally about 5 ~
60 microns, preferably in the range 40-80 microns.

General E-terminal catalysts are both X- and Y-type molecular sieves (
(replaced with rare earth or ammonia) 5-50% by weight, preferably 15-45% by weight, most preferably 20% by weight
It will also contain up to 40% by weight.

To further increase the catalytic activity, the rare earth exchanged sieve can be calcined and further exchanged with rare earth or ammonia to produce an extremely stable molecular sieve.

A variety of methods can be used to produce synthetic phosphorescent liquor alumina, such as those described in U.S. Pat. No. 3,034,994.

One of these methods involves the oxidation of alkali metal silicates with inorganic acids while maintaining the pH on the alkaline side.

An aqueous solution of the acidic aluminum salt is then intimately mixed with the silica hydrogel, filling the pores of the silica hydrogel with the aluminum salt solution.

The aluminum is then precipitated as alumina by addition of an alkali compound.

As a special example of this process, solicahydride oryl is prepared by adding sulfuric acid to a sodium silicate solution under vigorous stirring and under controlled conditions of temperature, time and concentration.

Aluminum sulfate in water is then added to the silica hydrol under vigorous stirring, and the pores of the rol are filled with the aluminum salt solution.

An ammonium solution is then added to the above-mentioned roll under vigorous stirring to precipitate aluminum as water-containing alumina into the pores of the silica hydrogel.

Thereafter, by removing some of the water, for example on a vacuum filter, and then drying, or more preferably by removing the hydrated γ
The hydrated pellets are processed by spray drying the pellets to form microspheres.

The dried product is then washed with water or a very weak acid solution to remove the ions and sulfate ions.

The resulting product is then dried to a low moisture content, usually below 25% by weight, for example 10-20% by weight, to obtain the final catalyst product.

The silica hydrodel slurry with or without alumina in the hydrated state can be purified by roll filtration and washing to remove dissolved salts.

This will promote the formation of a continuous phase in the spray dried microspherical particles.

If the slurry has been previously filtered and washed and it is desired to spray dry the filter, the filter can be reslurried with sufficient water to prepare a mixture that can be pumped for spray drying. can.

The spray-dried product can then be washed again and finally dried by the means described above.

M&, C are used as metal additives to immobilize vanadia.
a, Sr, Ba, Sc, Y, La, Ti, Zr, Hf.

Nb, Ta, Mn, Fe, In, Tt, Bi, Te)
Included are metals such as rare earths and elements of the actinide and ranknide series, their oxides and salts, or organometallic compounds.

These promoters or elemental metal additives (1) are used in concentrations ranging from about 0.5 to 20% by weight of the final catalyst, more preferably from about 1 to 5% by weight.

The catalytic promoter in the preferred catalyst composition is a crystalline aluminosilicate zeolite, commonly known as a molecular sieve.

Molecular sieves are initially formed as alkali metal aluminosilicates.

It is a dehydrated form of crystalline hydrated siliceous zeolite.

However, since the alkaline form has no appreciable activity and alkali metal ions are detrimental to the cracking process, the aluminosilicate is ion-exchanged to replace the sodium with one of the other ions, such as ammonium and /or Substitution with rare earth metal ions.

Of zeolite? The silica and alumina that form the sacrifice are
They are arranged in a crystalline pattern that includes a large number of uniform holes interconnected by smaller uniform grooves or pores.

The pore size of these pores is typically about 4A to 12A.

Zeolites that can be used according to the invention include both natural and synthetic zeolites.

Natural zeolites include Damerisite, Krynobutiteikulite, Chi'yabazite, and Butyardite (dechia).
rditel faujasite, hyurandite, erionite, analgite, levynite, sodalite, canculinite, nephelin, rutulite (1cy
ur i te), scolicite (5 col 1 cit)
e), nato-Olite, offretite, menrite, mordenite, bluesterite, ferrierite, etc.

Suitable synthetic zeolite zeolite, y2A
, L, ZK 4BtB y E > Fy H > J
2M, Q, T 7 W > X, Z > ZSM-
Includes types, alpha, beta and omega.

The "zeolite" used in the present invention includes not only aluminosilicates, but also substances in which aluminum or gallium is substituted, and substances in which silicon is substituted with Ilumanium.

The so-called pillars (pi 1lar) have been introduced relatively recently.
ed) Also means clay.

The zeolitic materials used in preferred embodiments of the invention have a silica/alumina ratio in the range of about 2.5 to 7.0, preferably 3.0 to 6.0 and most preferably 4.5 to 6.0. It is a synthetic faujasite.

Synthetic faujasite is a widely known crystalline aluminosilicate zeolite, and a common example of synthetic faujasite is W., R-Grace, &.

Types X and Y are commercially available from the Davison Division of Union Carbide, Inc. and the Linde Division of Union Carbide, Corporation.

Zeolites substituted with ultrastable hydrogen, e.g. Z-]
, 4XS and Z-14US (Davison) are also particularly suitable.

Besides faujasite, other preferred types of zeolite materials are mordenite and erionite.

A preferred synthetic fauja guide is Zeolite Y, which is described in U.S. Pat. Nos. 3,130,007 and 4,0
No. 10,116, each of which is incorporated herein by reference.

The latter patent's aluminosilicates are high silica (S+
02 )/alumina (At203) molar ratio (preferably 4 or more) and provides high thermal stability.

Below are examples of zeolites produced by silicification of clays.

Reaction from a mixture of sodium silicate, sodium hydroxide and sulfur chloride prepared to contain 2527 mol% S+0, 5 mol% Na2O3, 1.7 mol% chloride and water (remainder) Get a mixture.

12.6 parts of this solution are mixed with 1 part of calcined kaolin clay.

The reaction mixture is held at about 60-75'F for about 4 days.

After this low temperature aging step, the mixture is heated to about 190''F with vigorous steam until crystallization of the material is complete (eg, about 72 hours).

Filtration and washing of this crystalline material yields a silicided crezeolite having a silica/alumina ratio of about 4.3 and containing about 13.5% by weight Na2O while being free of volatile components. can get.

Varying the ingredients and time and temperature as is commonly practiced in commercial operations will produce zeolites with silica/alumina molar ratios varying between about 4 and 5.

Molar ratios greater than about 5 can be obtained by increasing the amount of 8102 in the reaction mixture.

The Na2O content is then reduced to less than about 5% by weight, preferably less than 1.0% by weight, by exchanging the sodium form of the zeolite with polyvalent cations.

Methods for removing alkali metals and forming zeolites into suitable types are described in U.S. Pat. No. 3,293,192;
No. 996, No. 3,446,727, No. 3,449,0
No. 70 and No. 3,537,816, which are well known in the art and are incorporated herein by reference.

Zeolites and/or metal additives are dispersed in the matrix used as cracking catalyst by methods well known in the art.

These methods are described, for example, in U.S. Pat. No. 3,140,249.
No. 3,140,253 (Blank et al.), U.S. Pat. No. 3,660,274 (Brine et al.), U.S. Pat.
．． No. 94,4,482 (Mitschel et al.), as well as US Pat.

For the hot final product, the amount of zeolitic material dispersed in the matrix should be at least about 10% by weight, preferably about 25-50%, most preferably about 35-45%. be.

Crystalline aluminosilicates exhibit acidic sites on both the inner and outer surfaces and have the largest proportion to the total surface area.

The cranking site is within the crystalline microspheres inside the particle.

These zeolites are crystallized as discrete particles of regular shape, typically 0.1 to 10 microns in size, and thus this is the size range commonly offered by catalyst suppliers.

In order to increase the portal surface area, the particle size of the zeolite for the main purpose/invention is preferably 0.1~
It should be in the range of 1 micron or less, more preferably 0.1 micron or less.

Preferred zeolites are heat treated with hydrogen and/or rare earth ions and are steam resistant up to about 1.650°F.

Examples of the effectiveness of the metals of this invention in immobilizing vanadium and reducing its destructive properties on crystals of zeolite structures are shown in Table 6.

The FCC catalyst was cooked in the presence and absence of panagia as shown in Experiments 1 and 2.

Due to the presence of vanadium, the zeolite content varies from 9.4 to 3
．． Reduced to 1X strength.

Experiments 3 and 4 demonstrate the effectiveness of titania and the necessity of its presence as vanadia is deposited on the catalyst.

As shown in Experiment 4, titanium and vanadium are deposited as organometallic compounds and are oxidized to remove the hydrocarbon portion of these organometallic compounds and oxidize the elements to their corresponding oxides.

Then steam for 5 hours at 1450°F.

During oxidation and cooking, titanium is present at a ratio of at least 1 to 1 due to the formation of titanium vanadate (see Table A), a high-melting solid.
It is present in a proportion of %.

[Brief explanation of the drawing]

Figure 1 shows the prefixed crude oil converter used in this invention:
An example of a /(RCC) type unit is shown. FIG. 2 is a graph showing the change in catalyst activity as the amount of vanadium on the catalyst increases. FIG. 3 is a graph showing the change in catalyst activity as the amount of nickel on the catalyst increases. FIG. 4 is a graph showing the loss of crystalline aluminosilicate zeolite as the amount of vanadium on the catalyst increases by 7 JDi. FIG. 5 is a graph showing the loss of crystalline aluminosilicate zeolite as the amount of nickel on the catalyst increases. Figure 6 shows the total daily savings of T I) T and TiCt4. The symbols in FIG. 1 represent the following. 4... riser pipe, 5... reactor, 6...
...rising pipe outlet, 7...cyclone, 8.
...transfer line, 9...high density catalyst bed,
io, is... stripper, 11...
・Regenerator, 12... High-density catalyst bed, 14...
... Regenerator inlet, 15 ... Stripper, 1
6... Regenerated catalyst vertical pipe, 1γ... Soil riser pipe Y-junction, 18, 19... Addition and removal position, 2
0,21...Addition position.

Claims (1)

Claims: 1. A process for converting prefixed crude oil or crude oil into a liquid transportation and light heating petroleum fuel having a substantial metal content and Conradson carbon content, comprising: (593-760℃)
Mg7Ca,S in the riser flow transfer zone at a temperature of
r, Ba, Sc, Y, La. Ti, Zr, Hf, Nb, Ta) Mn, Fe, Co, N
i, In. The activity is promoted by the addition of a metal additive selected from the group consisting of Tt, Bi, Tc, rare earth, actinide and lanthanide series elements, their oxides or salts, or organometallic compounds thereof. The vanadium compound is immobilized by contacting with a zeolite-containing catalyst, the gaseous product and the spent catalyst are then immediately separated, the spent catalyst is regenerated in the presence of an oxygen-containing gas, and the regenerated catalyst is added to fresh prefixed crude oil. or an improved method in recirculating crude oil to the riser transfer zone for convergence. 2. The method according to claim 1, wherein the prefixed crude oil or crude oil contains 200 ppm or less of a metal consisting of nickel, vanadium, iron or copper and has a Conradson carbon number of 10% by weight or less. 3. The method of claim 1, wherein the prefixed crude oil or crude oil contains 200 ppm or less of vanadium and has a Conradson carbon number of 12% by weight or less. 4. The method of claim 1, wherein the prefixed crude oil or crude oil contains 1100 pp or less vanadium and has a Conradson carbon number of 10% by weight or less. 5. The prefixed crude oil or crude oil contains vanadium compounds in pm or less and has a Conradson carbon number of 10% by weight or less,
A method according to claim 1. 6 Crystalline aluminosilicate zeolite 10-40 dispersed in an amorphous inert solid oxide matrix in which the catalyst contains metal additives for vanadium compound immobilization
% by weight. 2. The method of claim 1, wherein the gamma metal additive is a water-soluble inorganic metal salt or a hydrocarbon-soluble organometallic compound. 8 The metal additives that immobilize the vanadium compound deposited on the catalyst are Mg, ea, Sr, Ba, Sc, Y, and La. Ti, Zr, Hf, Nb, Ta, Mn, Fe, In, T
2. A method according to claim 1, comprising elements of the lanthanide series and the actinide series. 9. The claimed metal additives can react with vanadium compounds to form binary vanadate metal salts and react with mixtures thereof to form ternary and quaternary compounds or complexes. The method described in Scope 1. 10. The method of claim 1, wherein the metal additive is present in the catalyst in an amount of about 1-20%, preferably 1-6% by weight of the final catalyst. 11. The method of claim 1, wherein the vanadium compounds deposited on the catalyst include vanadium oxides, sulfides, sulfites, sulfates and oxysulfides. 12. The method of claim 1, wherein the aqueous slurry of catalyst components includes a metal additive prior to spray drying. 13. The method according to claim 1, wherein the metal part is characterized by impregnating the spray-dried catalyst. 14. The method according to claim 1, wherein the metal additive is incorporated into the crystalline aluminosilicate zeolite by ion exchange. 15. The method according to claim 1, characterized in that metal additives are used during the production of the crystalline silica-metal zeolite. 16. The method of claim 1, characterized in that the crystalline silica dicinate zeolite or the crystalline silica-zirconate zeolite is made using titanium or zirconium. 17. The method of claim 1, wherein 7) D is added as an aqueous solution of a metal salt or a hydrocarbon solution of an organometallic compound at any point in the prefixed crude catalyst processing cycle. 18 The vanadium concentration of the catalyst is 0.1 to 5 of the catalyst weight
% by weight. 19 Claim 1, wherein the vanadium/nickel ratio in the prefixed crude oil or crude oil is in the range of 5/1-1/3.
The method described in section. 20. The method according to claim 1, wherein the proportion of vanadium in the total metal content in the raw pot residual oil is greater than 50%. 21 7 The atomic ratio of the metal additives added to the JO Ecocycle is at least 0.5 of the vanadium present in the feedstock.
2. A method according to claim 1, wherein the ratio is preferably at least 1:1. 22 Water-soluble metal additives include halides, nitrates,
The method according to claim 1, wherein the salt is a sulfate, a sulfite, or a carbonate. 23. The method according to claim 1, wherein the hydrocarbon-soluble metal additive is an alcoholate, ester, ferulate, naphthinate, carboxylate, or genyl-based sandinth compound. 24. The method of claim 1, wherein the metal additive for immobilizing the vanadium compound is tetraisopropyl titanate. 25. The method according to claim 1, wherein the metal additive for immobilizing the vanadium compound is titanium tetrachloride. 26. The method according to claim 1, wherein the metal additive for immobilizing the vanadium compound is MMT. 2. The method of claim 1, wherein the metal additive for immobilizing the 2γ vanadium compound is a titanium-containing clay. 28 The titanium-containing clay has a titania content of at least 1
．． 2. The method of claim 1, wherein the kaolin content is 5% by weight. 29. The method of claim 1, wherein 0.1 to 20% by weight of the metal part 710 is present as a gelatinous precipitate in the spray-dried roll within the pores. 30 The catalyst promoted by the metal additive is 1
containing up to 40% by weight of concreting aluminosilicate zeolites consisting of one or more different zeolites;
A method according to claim 1. 31 The catalyst composition used in 7) D processing of raw pot residue with high metal content consists of silica-alumina, kaolin clay and crystalline aluminosilicate zeolite, which further contains 1-5% titania gal. The method according to claim 1. 32 A catalytic composition used in the processing of feedstock residues with high metal content consists of silicate alumina, kaolin clay, and crystalline aluminosilicate zeolite, which is further characterized by ~5% zirconia gamma. A method according to claim 1. 33 Patent in which the catalyst composition used in the processing of raw kettle residues with high metal content is silica or solicar alumina, kaolin clay and crystalline aluminosilicate zeolite, further featuring 1-5% alumina catalyst. The method according to claim 1.