JPS61204043A - Spray drying additive for immobilizing vanadium - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Zeolite brought about a life-changing change in oil refining.

Uniform cells of hydrothermally stable acidic zeolite, high boiling point,
It is an ideal site for the selective catalytic cracking of long silver hydrocarbon fractions into more valuable low-boiling hydrocarbons. It is believed that a relatively small amount of the amorphous silica alumina cracking catalyst converts the amorphous silica alumina cracking catalyst into a catalyst that exhibits a younger and improved activity and selectivity. Unfortunately, for every 7, it is stable (/r
There is a '65 (iF= M) that collapses into a homogeneous network of cells or an inert amorphous structure.

, the stability of zeolite, the resistance to the collapse of the crystal structure, the stability of the zeolite structure.
The X cation can be replaced with other more desirable cations (by replacing r1), such as dilute ions or anthenium ions. For example, rare earth-exchanged Y-neusi p+night (Y-fa
Ujasite) is a relatively stable 41'° biolyte 1- that is widely used in fluid catalytic cracking catalysts.
For example, seven-sume aite or pastnezite (bastn)
alzite) is derived from naturally occurring mixtures such as those found in sand.

However, although the rare-type 12-constituted phonp+Jite has improved hydrothermal stability, it is still criticized for causing disruption of the cell structure of the zeolite due to the formation of low melting point eutectics. It is likely to support the harmful effects of vanadium compounds. For example, a new high-activity compound that can withstand heavy hanging vanadium, typically up to about 5 m, as commonly found in the feedstock of conventional fluid catalytic cracking technology a/\. Zeolite 1 ~ catalysts have been developed. However, Kasuura Gyoko is often used by hand in many cases, from about 20 to about 4
001) Requires the ability to decompose raw material 1 containing residual oil dyed with vanadium -F7.

Although these catalysts tolerate most metals, they have problems at these concentrations of vanadium. It may be desirable to mix these highly active catalysts with particulate additives to adjust their activity levels. However, in many cases, particulate additives have been found to reduce the inherent vanadium resistance of the catalyst.

Recent successes in fluid catalytic cracking technology have shown that relatively high percentages of dilute class 1-exchanged Y-noses (containing I-reite and correspondingly reduced silica) Flumina matrices containing 6
i and reduced microporosity v1 to promote a highly active catalyst. These new catalysts are
Application No. 06/469,765''; However, the high school fl
l'l! l! Since the activity of the catalyst is too high for many applications, it is desirable to mix the catalyst particles with relatively catalytically inert additive particles.1. For many applications, the nature of the additive is not particularly necessary, especially for raw materials containing up to about 5 ppm of vanadium in medium quantities, but if it contains metals.

The affinity of many additives for vanadium is unexpectedly low compared to that of the zeolite component, resulting in the transfer of vanadium from the additive to the zeolite.
There is a possibility that concentration of the light-emitting diam- um may occur. It has been observed that inactivation is accelerated with the transfer of the vanadium rum initially present on the additive to the zeolite 1~ particles. It seems that this vanadium, which migrates from the additive to the zeolite, promotes the deactivation of the catalyst (although such a transition from the zeolide to the additive rarely occurs). The operating conditions of fluid catalytic cracking affect the speed and speed of this redistribution. For example, i + 1't = When the partial pressure of steam and oxygen in the vessel is large, the sheath is good + ] I distribution (1). Vanodium species in the +5 oxidation state are the main species, 1 and 11 species. It appears that the operating conditions, which favor the additives, result in both inactivation of the catalyst in the absence of additives and an increase in the migration of vanadium rum from the additives to the zeolite component in the presence of vanadium ram. It will be done.

This problem has a BE surface of less than about 20 m2/q and a microporosity of about 0.02 to about 0.06 CC/Q.
It has been found that rare Mnu can be reduced to a fine particle form consisting of microspheres of calcium oxide and roasted calcium chloride by the use of 1J]1. Preferably, the majority of the particles are between 20 and 150 microns in diameter. In a preferred embodiment, microspheres of roasted kaolin viscous are impregnated with a calcium or dilute hexaoxide precursor (in an E-11 filtrate solution) and the precursor is then smoldered by smoldering. The appropriate calcined 1, 1, and A phosphorus microspheres to be converted to the respective oxides can be formed by methods known in the art. For example, such microspheres can be made by spray drying an aqueous slurry of hydrated kaolin containing a small amount of tetrasodium pyro-v4ate to form hydrated kaolin microspheres, and then subjecting the microspheres to a substantial production of mullite. It can be prepared by roasting until the characteristic exotherm at least substantially ceases. It is also possible to use kaolin or a mixture of roasted kaolin and other clays including bentite and attapulgite. The impregnation with salt may be used to dry the microspheres at a suitable time and temperature to form rare earth and/or calcium oxides. .

Microspheres impregnated with both rare earth and calcium oxides immobilize vanadium on additive particles, whereas catalysts containing calcium oxide-coated microspheres surprisingly reduce coke formation. Seem. It is believed that calcium oxide not only immobilizes vanadium but also nickel compounds. Calcium salts impregnated onto smoked aluminum dog particles of a specific surface area appear to immobilize vanodium as well as nickel1, whereas clay-based microspheres1
In contrast to the results shown in Table 9, the desired surface area for calcining calcium oxide bearing aluminum particles appears to range up to about 10 m², with surface areas of less than about 8°1/9 being preferred. To provide a desirable compromise between selectivity and badge lam immobilization properties, the surface area of the calcium-supported alumina should be between about 301112/g and about 60 m'/(J (
It is preferable that DH[ff[[ru. With a surface area comparable to that of substantially pure alumina, this 30-60 m
'/.

Calcium oxide-supported aluminas, with surface areas in the range of , provide both good selectivity and good vanadium immobilization, whereas substantially pure aluminas have reduced selectivity at relatively high surface areas. It exhibits vanadium immobilization with low F properties and relatively low surface area.

It is highly desirable that the surface area of clay-based additives not exceed about 2 om2/g, because relatively high Additives with high surface areas reduce the overall selectivity of the cracking process by promoting non-selective racking that results in the formation of undesirable dark coke and light gases in the dissolution of the desired products. It is C because it may cause the value to drop significantly.

Although the additives used in the present invention can help improve the resistance of many IfL initial cracking catalysts, they are 100% aquatic at 1450°C.
After 4 hours of steam treatment at J3 in C, the standard mid-continent gas oil feedstock i! Test using l, sometimes the US special of r4ff:? + Please write the dimensions in the application 41△S IM D, 3907-90 C11
J, U4 exhibiting a micro-activity of more than about 2.5 (hereinafter referred to as 1. water-inactivation-inactivation-microactivity).
It is especially useful in highly active catalysts.

A relatively high percentage of additive IJ11 is used in a relatively active catalyst.
Since it is desirable that the unmixed zecontaining microspheres exhibit a steam deactivation microactivity of greater than about 6, the present invention particularly provides that the microspheres are either rare earth or an[nium] exchanged forms. 40% of the haiku's greatest and least acclaimed heron,
It preferably contains about 50 to about 70% Y-faujasite and has a pore volume in the range of 2 to 1 nm (hereinafter referred to as Tomiku O pore volume) or about 0.20 cc, 'Q less than,
θ adjustment is approximately less than 0.15cc/g (if any,
In particular, in the publication 1, this unique method for making microspheres (9A, which has not yet been described in US Pat.

According to the present invention, microspheres of a mixture of phosphorus clay, which has been smoked, or a mixture of phosphorus clay, which is at least partially kaolin, are oxidized. Tunorsium, rare earth oxides, mixtures thereof,
Or they can be formed by their precursor v't. Generally, egg-fried microspheres are about 51~F) 8102.41 of 3% (Φ suspension). ~
It contains 45% Δ1203 and 0-1% 1-120, with the remainder being minor hard A1 impurities, especially iron, titanium and alkaline earth metals. Generally, the iron content (F
The titanium content (expressed as TiOz) is about 0.5%, and the titanium content (expressed as TiOz) is about 2%. The rare earth oxide, calcium oxide, or their precursors can be combined with the clay component before, during, or after the formation of the microspheres. The use of rare earth oxides, lucium oxide and mixtures thereof or their precursors may also provide additives with desirable selectivity and small hookability.

Preferably, the microspheres are prepared by spray drying an aqueous suspension of a phosphorus clay or a mixture of aqueous and pre-fired clay. The term ° means that its main mineral components are kaolinite,
including clays that are ano-kyrites and mixtures thereof. With suitable mechanical strength, microspheres are produced, in which the plastic aqueous phase viscosity of fine particle size is less than 1 micron, with a substantial row 1. Preference is given to using clay containing particles of particle size.

To facilitate spray drying, powdered hydrated viscous or aqueous uncalcined clay mixtures may be prepared such as 1-lium silicate or condensed notrium phosphate salts such as tetrasodium pyrophosphate. Dispersion in water in the presence of a thickening agent is preferred. The use of peptizers makes it possible to carry out spray drying at relatively high solids contents and to obtain products that are usually relatively hard. If a peptizer is used, a slurry of hydrated kaolin containing about 55-60% solids can be prepared.

These high solids slurries do not contain deflating agents40
-50% slurry.

Various methods can be used to mix the ingredients to form the slurry. for example.

A method can be used in which the finely divided solid components are dry blended, water is added, and then the peptizer is incorporated.

Each component can be mechanically processed together or individually to produce a slurry with desirable viscosity properties.

Microspheres can be produced using a spray dryer with countercurrent, cocurrent, or mixed countercurrent and cocurrent slurry flow and hot air. The air can be heated directly or indirectly, electrically or by other convenient means. Combustion gas obtained by burning hydrocarbon fuel in air may also be used.

250-600°F when using a parallel flow dryer
Air inlet humidity up to 1200° F. may be used if the clay stock is charged at a rate sufficient to provide an air outlet temperature within the range of 1200° F. At such a degree, free water is removed from the slurry without removing water of hydration (water of crystallization) from the raw clay components. It is expected that some or all of the raw clay will evaporate during spray drying. By fractionating the spray dryer effluent, microspheres of the desired particle size can be recovered. generally having a diameter in the range 20-150 microns, preferably 20-70 microns,
Collect the particles for smoking.

Smoking can be performed during the manufacturing operation or by adding the spray-dried particles to the regenerator of a fluid catalytic cracker.

In some cases, the microspheres are smoldered at a temperature in the range of about 1600-2100 degrees Fahrenheit to produce particles of maximum hardness.
Although preferred, the microspheres are dehydrated by smoking at lower temperatures, such as in the range of 1000-1600°F, thereby converting the hydrated clay fraction to ``metakaolin''.

It is possible to convert it into a material known as After smoking, the microspheres are cooled and, if necessary, separated.
By doing so, it is possible to recover a portion of the desired particle size range.

The pore volume of the microspheres varies slightly depending on the smoldering temperature, the duration of smoldering, and the ratio of smoldering clay to hydrated viscosity. Digisorb 250 from Micromertics Instrument Corporation, Norcross, Georgia.
Pore size distribution analysis of a representative sample obtained using nitrogen desorption with a zero analyzer shows that the majority of pores have diameters in the range of 15-60 nm.

The maximum surface area of the smoked microspheres is about 10 to about 20 m as measured according to the known BET method using nitrogen absorption.
It is preferably in the range '/q. It should be noted that the surface areas of commercially available zeolite fluidized catalysts and common additives are much higher, typically having values in excess of 1001/lj as measured by the BET method.

The particle size of these microfluids must be such that the microspheres flow with the intended fluidized cracking catalyst. In order to achieve optimal results, it is essential that the microspheres have at most minimal catalytic cracking activity, which is why the 201
The surface area should be less than /q, as this leads to undesirable high rates of coke and light gas formation.

After forming smoldering kaolin microspheres, by contacting the microspheres with a mixture of a volatile fluid medium and a compound that provides the desired oxide upon smoldering.
A vanadium passivating agent can be applied. For example, mixed rare earth oxides can be deposited by impregnating the microspheres with an aqueous solution containing a sufficient amount of mixed nitrates to provide the desired rare earth oxide loading. Similarly, calcium can be deposited as an aqueous solution of acetate. Other suitable water-soluble compounds are known in the art and include hydrated rare earth halides and nitric acid, formic acid, calcium thiosulfate, and others. Calcium hydroxide can be deposited as a suspension.

The most preferred water-soluble rare earth compounds are chlorides, while the most preferred water-soluble calcium compounds are calcium chloride or calcium nitrate.

After impregnation, the passivating agent precursor is smoldered at a temperature high enough to drive out most of the solvent present therein;
. Although it is often advantageous to smolder at a temperature high enough to convert the passivating agent precursor to the desired passivating agent, it may also be possible to accomplish this when used as a catalyst. The additive particles pass through the regenerator in the first cycle. In this case, counterions may be selected that will cause harmful fumes, such as nitrogen oxides, to be generated when the additive is smoked during use.

The optimum amount of immobilizer to use depends primarily on the amount of vanadium in the feedstock to be cracked; resulting over the total equilibrium catalyst;
Depends on the vanadium loading; the mixing ratio between the zeolitic particles and the vanadium immobilized particles; the distribution of vanadium present; and the operating conditions of the device. However, knowing the requirements for lowest drug costs, it is possible to specify simplified guidelines. When the weight ratio of additive to catalyst particles is about 2=1, the rare earth oxide content on the particles is generally lower for applications with vanadium contents of 5 oppm to 2000 ppm on equilibrium catalysts. , about 2.5% to about 3.
Must be 5% rare earth oxide.

For vanadium contents of about 3000 pl) to about 7000 ppm, the rare earth oxide content on the particles is generally optimal in amounts of about 5 to about 7%. Approximately 7000
For vanadium content exceeding ppm, supply;
The optimum amount of additive should be sufficient to provide about 2.5 to about 3.5 moles of mixed rare earth oxide per mole of vanadium on the equilibrium catalyst. Mixing ratios and rare earth oxide contents outside such ranges also provide substantial benefits. The degree of benefit depends primarily on the condition of the particular metal and
Depending on the operating conditions of the equipment, such as the partial pressures of steam and air in the regeneration mold, as well as the relative amounts of vanadium present in the various oxidation states. For most applications involving residual oils or mixtures containing substantial amounts of residual oils, about 3
It is desirable to use zeolite-containing particles and additive particles in a heavy water ratio of from about 1:1 to about 1:3. Approximately 40% by weight
In the above-mentioned highly active catalysts containing more than Y-faujasite, it is preferred that the weight ratio of zeolite-containing particles to additive particles does not exceed 3:2. In more preferred applications with high zeolite catalysts, the weight ratio of zeolade-containing particles to additive particles is less than 1:1. When the weight ratio of additive to zeolite-containing catalyst particles is about 2:1, the content of calcium oxide on the additive particles is generally between 50 ppm and 2.0 ppm above the equilibrium catalyst.
For applications involving vanadium contents of 00 ppn+, it should be from about 0.5% to about 25%. Approximately 3.
0001) E) m to about 7. For a vanadium content of OOppm, the calcium oxide content on the particles is generally optimally from about 0.5 to about 40% Ca 2 O. Although effective alumina-based additive particles typically contain from about 0.5 to about 40% CaO by weight, preferred additive particles contain from about 5 to about 30% CaO by weight.
Contains O. The most preferred alumina-based additive particles consist essentially of about 10 to about 25% CaO;
The rest is alumina. It is advantageous to introduce a large excess of calcium oxide into the reactor, usually more than 10 moles, preferably more than 30 moles, per mole of vanadium.

Different laboratory test methods have been found to yield different quantitative results on the effectiveness of vanadium immobilizers. We note that although several laboratory-scale tests give similar or comparable results, which should achieve good prediction of industrial performance, the presence of oxygen during the hydrothermal deactivation step I discovered that I had to. This effect is due to the fact that vanadium in the 5+ oxidation state is a mobile species, whereas vanadium in lower oxidation states is less mobile or immobile, and therefore
In order to better simulate a typical fluid catalytic cracking regenerator and result in the production of mobile species, the presence of conditions favoring V (V), such as steam treatment in the presence of oxygen, is desirable. This seems to be caused by a reason. Other variables such as the amount of coke on the catalyst affect the distribution of vanadium oxidation states and the exact amount of vanadium that can be migrated. Sulfur oxides may also affect migration in some cases. Thus, depending on the test conditions, different degrees of adverse effects of vanadium are observed. Laboratory tests that have been found to be particularly useful are described below. During testing of mixtures of zeolite-containing particles and additive particles, the vanadium retention composition was applied separately to the unmixed zeolite-containing particles and the unmixed additive particles rather than to the preblended mixture. impregnate,
In some cases, it has been found that even more meaningful results are obtained. The separately impregnated particles are then dried in air at 600°F, baked at 1100°F, and then mixed. After baking and mixing, the vanadium-impregnated catalyst composition is treated with water, commonly referred to as steam treatment. Apply a heat inactivation step. Suitable vanadium-containing solutions are vanadium naphthenate or a mixture of vanadium naphthenate and nickel in an organic solvent. Simultaneous impregnation of a mixture of zeolite-containing particles and additive particles gives significantly less valuable results.

Conventional steam treatments for stability can be made more significant for these mixture compositions if from about 1 to about 20% oxygen is included in the atmosphere during the process. Generally, suitable steaming conditions are about 13% in the presence of 10% air and at least 20% water vapor.
001" to about 1500° F. After steam treatment, the activity and selectivity of the steam treated catalyst was determined in comparison to a control sample that did not contain vanadium using a known microactivity test. Alternatively, the blend components can be separated after steaming and analyzed separately for nickel and vanadium.

An alternative method to the above test involves contacting a premixed blend with a high metal content resid fraction under catalytic cracking conditions in a fixed fluidized bed reactor and subsequently simulating metal deactivation. This includes periodic tracking and regeneration to be performed. The samples are then removed and exposed to the steam treatment conditions described above and evaluated for microactivity. Other modifications are also possible and are detailed in the examples.

Preparation IA High zeolite catalyst microspheres were prepared as described in Example 1 of U.S. patent application Ser. It was prepared as follows.

Preparation IB The procedure of Preparation IA was repeated, except that after completion of crystallization the microspheres were thoroughly washed with hot water, thereby removing soluble silicates from the pores of the microspheres.

After separation of the crystallized microspheres from the mother liquor, the microspheres are washed, rare earth exchanged, dried, and then heat treated in air at about 1050° F. for about 2 hours. , the method of Preparation IB was repeated. By subjecting the smoked microspheres to an ammonium exchange step, the sodium content was reduced to approximately 0.28 on a volatile free basis.
% NazO.

Manufacture ■ U.S. Patent Nos. 3,647.718 and 4,263.12
By spray-drying an aqueous suspension of kaolin clay as described in No. 8 and baking the obtained microspheres, a layer with a silica content of about 52%, an alumina content of about 43% and a small amount of others is obtained. Additive microspheres were prepared containing impurities, particularly water, iron, titanium, and alkaline earth metals.

After collection, the microspheres had an average particle size of about 69 microns and a BET surface area of about 8°5 Ins/Q.

A number of additive microspheres were prepared derived from ta' m clay and alumina and containing a vanadium immobilizing component. This example describes one exemplary method for the production of additive microspheres containing a mixture of rare earths as the vanadium immobilization component.

One hundred milliliters of a lanthanum-enriched mixed rare earth nitrate aqueous solution containing 25-27% mixed rare earth oxides was diluted by the addition of 33 ml of deionized water. Using this diluted solution, proceed as in Preparation ① above,
400a (as-made) smoked clay microspheres made from kaolin clay only were impregnated. After thorough mixing, the sample was dried in a drying mold at approximately 200°F and heated to 60°C.
Heat treated at 0°F for 1 hour, then in a Matsufuru furnace at T: 1100°F for 2 hours. Replicate analysis of the microspheres thus obtained showed 0.045% CeO2, 0.045% 5111203.6.94% la! 03.0゜0
1% Y20s, 2.28% Nd20z, and 0.
10% pr60u, total 9.41% mixed rare earth oxides (57 mmol/100 IJ additive microspheres (A
M) + vanadium immobilization component).

Microspheres impregnated with various rare earth contents by appropriate dilution of a concentrated rare earth nitrate solution, pH adjusted to prevent precipitation of the desired species, while maintaining a constant ratio of total impregnated volume to microsphere weight. was prepared. Other microspheres containing different ratios of clay and alumina can be used to prepare other additive microspheres containing vanadium immobilization components.

Production IV 7200 Ca (N03
Add an aqueous solution containing 2.4H20 to 1000q of additive microspheres prepared as in Preparation ①,
The resulting initially wet mixture was air-dried overnight and then heated to 600°
It was kept in air at F for 1 hour.

After sooting the microspheres at 1100°F for 1 hour, chemical analysis showed a calcium oxide content of 10.34% on a volatile free basis.

Preparation V This example illustrates the preparation of additive microspheres impregnated with vanadium immobilizer. Calcined kaolin clay microspheres were prepared as described in Preparation (1) and used to make additive microspheres carrying a vanadium immobilized component consisting of TfO2.

A three neck, 1 liter round bottom flask was fitted with a stirrer, an isobaric collapse funnel and a septum cap into which a syringe needle was inserted to relieve pressure buildup. Pre-dried toluene (1
34 ml) into the dropping funnel, and 500 g of +32
5 mesh vacuum-dried soot-fired clay microspheres (AM)
was put into the flask. Titanium tetrachloride (approximately 351) was injected into degassed toluene to form a bright red solution. This solution was gradually added to the solid with stirring. Approximately 4 On+I additional toluene was added to bring the solid to initial wetness. reached it.

The solid was transferred to a dry open beaker in a hood to evaporate the toluene and hydrolyze the T i C+ 4 in humid air. Add a small amount of ethanol (approximately 5-10 ml), being careful not to add too much to remove a significant amount of TiCl from the pore structure.
It helped the hydrolysis of a. The sample was left exposed to the atmosphere overnight and then sooted in air at 1100° F. for 2 hours to yield an off-white solid. Chemical analysis showed approximately 4% Tl02 (based on free volatiles) in excess of titanium impurities inherent in clay microspheres.

Manufacturing ■ 2.0g of zirconium chloride (Zr OCI □・4H
The additive microspheres were impregnated with zirconium oxide by dissolving 20) in 100 ml of cold deionized water. This solution was added to 300(+) microspheres prepared according to the method of Preparation H to obtain an initially wet mixture. After air drying, the impregnated microspheres were kept in air at 600° F. for 1 hour. , 1 hour at 1100° F. On the specimen, the microspheres were found to be impregnated with about 0.30% by weight ZR.

'VI-AM+CeO2 Additive microspheres were impregnated with ceria in the same manner as in Preparation 1 except that a cerium nitrate solution of the appropriate concentration was used instead of the mixed rare earth nitrate solution. After recovery, the additive microspheres were found to have approximately 6% by weight cerium oxide.

Manufacture ■ Additive microspheres were impregnated with P 4 Hw by contacting with phosphoric acid to incipient wetness, then air dried and then fired at about 1100°F. The microspheres produced by repeating this procedure several times have approximately 6.5
% by weight of P4 HIO.

Production IX AM+La2O3 Additive microspheres were impregnated with lanthana in the same manner as in Production (1) except that a lanthanum nitrate solution of an appropriate concentration was used in place of the rare earth nitrate.

Preparation

Approximately 6519 M per liter of deionized
A nearly saturated solution of magnesium acetate (hydrated) was prepared by dissolving (02H302)2.4H20. The fired clay microspheres (1kc+) were transferred to the Aeromatic AG experimental fluidized bed coating equipment, 5TREA.
It was placed in a type I fluidization chamber and fluidized by a stream of hot air at 90-100°C. The aqueous solution was introduced intermittently as a fine spray at a rate of approximately 20 ml/min, with drying between additions of liquid. Liquid addition and air drying cycles were performed using 125-170 ml of liquid between each addition. After removing the dry powder, it was heated in a packed bed at 600°F for 1 hour at 1100°C for 2 hours.
Soot-roasted for hours. Chemical analysis of the product was 11 on a non-volatile basis.
．． It showed 0% MgO.

, ' REO on Xl Al2O3 Particle size from 45 microns to about 63 microns and about 89111
Mixed rare earth oxides were deposited on particles of alumina, having a BET surface area of 2/(l), by a method similar to that of preparation 2. Upon recovery, the particles had a BET surface area of It was observed that 80 mmol of mixed rare earth oxide was retained.

Preparation X MIJ on Al2O3 Alumina powder having the properties described in Preparation Upon recovery, the alumina particles were found to contain about 0.5% magnesia by weight.

Manufactured xm 54.7% CaO, 0.6% MaOlo.

4% S! 2.0.64 kO crushed limestone (average particle size 4.2 microns) with an approximate composition of 0.02% AlpOt and 0.1% Fe5O3 and a loss on ignition of 43.1%. Mixed with 36 ka kaolin clay, U.S. Pat.
10 per ton of solids using the procedure described in No. 128.
Bond's [60 using tetratetrasodium as a dispersant]
Calcium oxide impregnated alumina-silica microspheres were prepared by forming an aqueous suspension having a solids content of 1.5%. The C slurry was then spray dried using an inlet temperature of 130°C and an outlet temperature of 340°C. The microspheres thus obtained were then calcined in a Matsufuru furnace for 1 hour at about 996°C to give an average particle size of about 64 microns and, on a non-volatile basis, Cab, 15°6%; A+ 203.38°2%; Si 0243.6%: Na 20,0.78
%:Fe! 203.0.45% and Ti0i, 1°3%
Microspheres with the composition were obtained. The microspheres can be used as an additive to both highly active commercial catalysts and high zeolite catalysts to provide effective vanadium immobilization with advantageous low coke and hydrogen production. .

Example 1 uses zeolitic microspheres as a blend component with smoked clay microspheres in the absence of a vanadium immobilizing component and uses the blend for the treatment of metal-containing feedstocks. We illustrate the concentration of vanadium on zeolitic microspheres when used, and in particular, when manufacturing zeolite-containing microspheres, vanadium is added to the zeolite when diluted with roasted kaolin microspheres of manufacture. This illustrates that the undesirable effects of vanadium on the catalyst are increased due to preferential migration to the containing particles.

For example, a fractionated high-activity commercial catalyst <HACC> such as Ultrasib 260 sold by Engelhard Corporation or a high zeolite test catalyst (H2C) prepared as described in the manufacturer's manual and fractionated smoky kaolin. 1:1 with clay additive microspheres (AM) (
Weight) The mixture was composited. After blending, Midcontinent gas oil or 20% high metal Mayan residual oil/80% pre-fertilized with nickel naphthenate and vanadium.
Using any of the Midcontinent light oil blends,
These metals were applied during repeated cycles in a fixed fluidized bed Taratuki leg/regeneration reactor.

After the samples were removed after the regeneration cycle and the carbonaceous deposits were heated away, a small portion of each sample was fractionated and subsequently analyzed for nickel and vanadium. Alternatively, samples were prepared and analyzed by impregnating the mixed matchstick with vanadium and nickel naphthenate in cyclohexane, followed by drying and sooting. The portion of each sample remaining after analysis was steamed in a fluidized bed reactor with 100% steam at 1400°F for 4 hours. The distribution of metals between blend components of different particle sizes was determined by performing nickel and vanadium analysis after fractionation. The results of metal distribution before and after steam treatment are shown in Table 1. These results indicate a significant transfer of vanadium species from the additive to the zeolite particles. These data also indicate that the initial vanadium distribution produced by simultaneous impregnation methods that apply the metal directly to the blend is not equivalent to the distribution produced by cracking of metal-contaminated feedstocks.

Table 1 (40 cycles 1/100°F/4 hours/100% steam height in a fixed fluidized bed reactor) This example illustrates the effect of the steam processing environment on vanadium migration. The blend was prepared by adding 1 part by weight (clean) 200-325 mesh high zeosite test catalyst (clean) which was separately impregnated with vanadium naphthenate and smoked before mixing.
H2C) and 1 part by weight of 100-170 mesh smoked kaolin clay microspheres. The "low loading" microspheres had 4280 ppm vanadium at ff1ffi, while the "high loading" microspheres had 8450 ppm vanadium by weight. The blend was divided into 8 portions and each portion was steamed in a different environment. After steam treatment, each portion was sieved into separate fractions and each component was analyzed for vanadium. The results are shown in Table 2.

Table 2 Vanadium distribution after steam treatment for Example 2
Cloth (+7 on H2C) V/v on AM) Low loading after hot air treatment High loading (4280ppm V) (8450ppm V
) 1450”F/4 hours steam treatment atmosphere 100% steam
0.8 0,599% water vapor + 1% air 3.1-90% water vapor +
10% air 3.8
2,899.9% water vapor + 0.1% SOt
1.7 -9
9% 9% water vapor + 1O12,43,389,9% water fi
Qi + 10% air + 0.1% SOz 2.8
-89% water vapor + 10% air + 1%
SOs 2.4 3.
Pre-coking to 03% C, then 100% steam then dry smoking 0
．． 3-These results show that in the presence of air or S02, vanadium tends to migrate preferentially to zeolite-containing particles, whereas when pre-coking zeolite-containing particles, vanadium tends to transfer preferentially to zeolite-containing particles. This indicates that the tendency is likely to decrease as the particles shift to smaller particles.

Example 3 Blends containing zeolite cracking catalysts and additives prepared according to the manufacturing procedure described above were investigated for selectivity and activity characteristics in laboratory microactivity tests in the presence of metals. The cracking catalyst component and the vanadium immobilization additive component were each separately fractionated and impregnated to incipient wetness on equivalent metal charges with a mixture of vanadium naphthenate and nickel naphthenate in cyclohexane. After drying and heat treating in a Matsufuru oven at 600°F for 1 hour, then at 1100°F for 2 hours,
The contaminated additive was blended with the appropriate amount of contaminated zeolite catalyst. The blend ratio was chosen to approximate the activity of a comparative high activity commercial catalyst (HACC). High zeolite test catalyst (H2CA, H2CBS, respectively) prepared as in Preparation IA, IB or IC -
jZCC) was used as the gelaite blend component. A variety of additives were used, including additive microspheres (AM) that did not contain immobilizing components. A blended mixture of high zeolite test catalyst and additive microspheres plus vanadium immobilizer (VIC) was placed into a periodic fixed fluidized bed catalytic cracking reactor. The reactor was operated at 950° F. during the 75 second cracking portion of the cycle and then up to about 1350° F. during the 26 minute regeneration portion of the cycle. Each blend was cranked and regenerated using a high sulfur residue/gas oil mixture containing approximately 3% sulfur with a Conradson carbon content of approximately 6.95% and an API gravity of approximately 24. It was exposed to 10 cycles between The regenerated blend sample was then removed and subjected to 10 vol.% air, 0.1 vol.% SOz, in a fixed fluidized bed reactor.
and steaming for 4 hours at 1450°F using a flowing gas consisting of 89.9% water vapor by volume. After this treatment, a portion of the sample was prepared using a Midcontinent gas oil feedstock (having the properties shown in Table 3).
The standard microactivity (MAT) test established in all of our experiments operating at a catalyst/oil weight ratio of 5 and a weight hourly space velocity of 15 hr-λ
The relative activities and selectivities were determined by testing in a modification of the ASTM method as described in No. 469.765. In experiments using a blend of high zeolite test catalyst of one particle size distribution and vanadium immobilizer-loaded microspheres with a different particle size distribution, a separate portion of each sample removed from the fixed fluidized bed apparatus was sieved by sieving. Fractionation separated the high zeolite test catalyst (H2C) from the additive microsphere (AM) component loaded with vanadium immobilizer (V I C). These fractions were then separated for nickel and vanadium content, respectively.

The resulting data on activity, selectivity and vanadium migration are shown in Table 4, and the relationship between vanadium migration and activity of the catalyst blend is shown in FIG.

These results demonstrate improved persistence of activity for samples containing vanadium immobilizer-loaded additive microsphere components above the minimum level. Experiments 4 and 5 showed that the effective loading of MgO on the additive microspheres under these conditions was 100
170 per g of vanadium immobilizer-loaded additive microspheres
This shows that it exceeds millimoles of MqO. Experiment 6~
10 shows the effect of rare earth magnide (REO) loading on performance.

10% 550°F 20% 609°F 30% 659°F 40% 101) 50% 756°F 60% 807°F70%
864°F 80% 932F 90% 1030'7”92%
1066°FNi
1ppHlV

I Dp1 System Value 22 Example 4 Additives prepared by the above manufacturing procedure were further tested as blends with zeolite cracking catalysts in the presence of metals in order to more fully characterize their activity and selectivity properties. The tartarking catalyst component and the additive component were each impregnated to incipient wetness to approximately equivalent metal loadings with a mixture of vanadium naphthenate and nickel in cyclohexane. 600 in Matsufuru Furnace
After drying and smoking for 1 hour at 100°C and then 2 hours at 1100°F, the contaminated additives were blended with the appropriate amount of contaminated zeolite catalyst.

The blending materials used were either highly active commercial catalysts or high zeolite test catalysts. The blended catalyst and additive mixture was then treated at 1450°F for 4 hours with a flowing gas mixture consisting of 10% air and 90% water vapor by volume at 1450°F in a fixed fluidized bed. After repeated steam treatments, each sample was tested in the cyclic microactive cranking test described in Example 3. This test is a standard laboratory procedure conducted using a midcontinent gas oil feedstock at a catalyst/oil ratio of 5 and a weight hourly space velocity of 15 hr-x. Conversion as weight percentage, relative selectivity and amount of hydrogen produced as weight percent of feed were reported. Comparative experiments were performed with uncontaminated blends containing the specified additives and with metal-contaminated blends prepared with additive microspheres containing no immobilizing component. The results of these tests are shown in Table 5.

1 ・ ′1 o , □ , to 0
'D 0 Tomoe B man --- f --- heart) -to the gate -to l
7 - 0 - - -
-a, 100 (additive loading expressed as mmol per liter) HACC is a highly active commercially available tuffing compound; H2CA, H2CB and H2CO are as specified in Preparation IA, IB or IC A high zeolite test catalyst was prepared as follows.

AM is additive microspheres.

All C1 compositions were prepared from the full range of mesh sizes for each component unless stated to the contrary.

d. Each component was impregnated separately before blending.

e. Mat < MAT) test results repeated 3 times, catalyst/oil = 5, W) - ISV = 15 h -1, Midontinent light oil listed in Table 3 was used. The data in Table 5 was for immobilization addition. The results show that the conversion and, in some cases, the selectivity towards Lund products with additives are clearly improved compared to blends with no immobilizing component added. There is. The indicated selectivity coefficient is the ratio of the weight percent yield obtained with the indicated catalyst to the weight percent yield obtained with the unpolluted HFZ-20'' catalyst at the same conversion.

Example 5 This example demonstrates the improvement in vanadium tolerance imparted by using REO-containing additive microspheres instead of additive microspheres alone for a 1:1 blend with a highly active commercial catalyst. ing.

The procedure of Example 4 was followed by substituting a high activity commercial catalyst for the high zeolite test catalyst and blending with the REO-imparting additive microspheres or only the additive microspheres. The results are shown in Table 6, with RE as a blend component.
O-loaded additive microspheres have been shown to be advantageous over additive microspheres alone.

Table 6 (for Example 5) (1450°F, / 4 hours / 10% air + 90% hot water) V/Ni (nominal Dpm) OL5000/250
0REO loading (mmol/100(+) Conversion rate (wt%) 37.8 5
0.5 50.5 gasoline
27.5 38.5 38.7LCO (wt%) 27.2 25.6
25.3 Residual oil (wt%) 34.7
23,6 23.9 coke coefficient
1.8 1.5 1.5hh (weight%)
0.63 0.59'
0.55a The particles were contaminated separately with metals before blending.

This example demonstrates the advantageous use of a vanadium immobilizing component on alumina. Fractions of 325 mesh to 200 mesh of H2C (J-made IA) were treated using the metal naphthenate method to prepare 50001)I)m (nominal) and 25001
) I) Impregnated to III (nominal) nickel and smoked. 150 m2/g using 100% steam flow in a fixed fluidized bed reactor to give a BET surface area of 62 m2/g.
A 170-100 mesh fraction of presteamed gibbzite trihydrate alumina (type C-30, commercially available by Aluminum Corporation of America, Pittsburgh, Pennsylvania), which had been treated for 4 hours at 0°F, was Impregnated with calcium loading and similarly impregnated with metal. preparing a blend containing, by weight, 38% metal-contaminated high zeolite test catalyst (H2C) component and 62% metal-contaminated calcium-loaded alumina component;
4 at 1450°F with 90% water vapor and 10% air
After steaming for an hour, repeat MAT analysis was performed using standard Midcontinent gas oil.

The results are shown in Table 7.

The results in Table 7 demonstrate the improvements in conversion and selectivity observed with the use of vanadium immobilization components on alumina. Results from the evaluation of additives based on such alumina are also included in the table to illustrate the negative effects of using relatively high surface area alumina. This sample had a steam treatment temperature of 1200"F and a final BET surface area of 12
It was prepared in the same manner as above except that 11'/g was taken.

Preparation The high zeolite catalyst prepared as described in IB was blended with the additive microspheres prepared as described in Preparation 1. Additive 1 of rare earth oxide onto additive microspheres
It was impregnated in an amount of 28 mmol of rare earth per g. The amounts of metals indicated in Table 7 were impregnated onto the separate components and also onto a commercially available high activity catalyst. After drying, smoking and analysis as described above, each blend of high zeolite catalyst and additives was
Each was subjected to 10 cracking and regeneration cycles in a fixed fluidized bed using a high sulfur residual oil feedstock. For comparison, a highly active commercial catalyst was subjected to the same aging procedure. Each catalyst was then steamed for 4 hours at 1450° F. in 10% air + 90% steam, and activity and selectivity were determined by the microactivity test described above. The results shown in Table 8 illustrate that blends of high zeolite catalysts and rare earth-impregnated microspheres exhibit higher conversions, lower coking, and lower hydrogen production than commercial high-activity catalysts subjected to comparable aging. are doing.

The average ppI on a single composition! 1 Standard Coke Composition V Ni Mesh Conversion Coefficient Formation %H/C/AM +28) (EO45222856 Total Ck60.9
+, 2 0.45HA CQ
4670 2675 Total 52.6
1.9 0.73a, total mesh is 1
00/325 or a powder size ranging from 44 to 749 microns.

b. Vanadium immobilization component concentration represents millimoles of vanadium immobilization component per 1000 additives.

The procedure of Example 7 was repeated using the catalyst shown in Table 9, except that the aging cycle in the fixed fluidized bed was omitted. The results of the matte analysis are shown in Table 9, which shows that when the additive microspheres have a vanadium immobilization component,
Although completely equivalent conversions were not obtained, in many cases the results obtained were similar to those obtained using highly active commercial catalysts, especially rare earth catalysts, which showed higher conversions, increased gasoline conversion, and lower coke and hydrogen production. The results were generally comparable to those obtained with oxide-containing catalysts.

Example 9 The performance of the catalyst of the present invention when the metal concentration is not significant is
In order to compare the performance of high zeolite content catalysts blended with additive microspheres that do not contain a vanadium immobilizing component, the catalyst compositions shown in Table 10 were combined with 90% water vapor and 1
Subjected to steam treatment for 4 hours at 1450° F. in 0% air and then subjected to microstability testing. 10th
The results shown in the table demonstrate that satisfactory performance is obtained with all three catalysts. These results in the absence of metal should be contrasted with those of Example 8 (Table 9), which clearly shows that high metal concentrations significantly reduce the performance of catalysts that do not contain vanadium immobilization components. It is.

The catalyst composition shown in Table 11 was subjected to the above-described suitable metal impregnation treatment and then heated to 1450 ml in 90% steam + 10% air.
Analyzed for metals and tested for microactivity after 4 hours of steam treatment at 7".
The results shown in the table demonstrate that tin and bismuth are significantly less effective than rare earths and calcium in inhibiting vanadium migration.

a) 33%200/325H2C; 67%170/1
00 additive metals were impregnated separately for the same components.

4000-5000 ppmV 2O00-25001) DIIN i Steaming conditions: 4 hours at 1450°F/90% steam + 10% air b) ISA = initial surface area at the time of impregnation C) Migration values measured under different experimental conditions: 1450 °F / 4 hours / 89% water vapor / 10% air / 1% SO2 Figure 2 illustrates the advantageous improvement in friability provided by the addition of a vanadium passivator compound compared to smoked kaolin microspheres or alumina alone, respectively. Samples were prepared according to the method described above and tested using the Engelhard Abrasion Index test.

The results, shown in Table 12, demonstrate that the addition of various vanadium immobilizing species improves the wear resistance after soot burning by significantly reducing the wear rate. .

Additive composition % per FAl l AM 0.96AM+25
6Mg0 O, 54AM+257Mg0
O,33AM+11REO0,68 AM+35REO0,49 AM+64REO0,42 AM+86REO0,54 1201/(J Al 203 0."7780
mi /Q Al 2 03
0. 64AM+247.9Ca
0. 20a, Engelhard wear index AM-100% Kakiyaki-smoking additive microspheres AM+ x
Y - [X mmol of Y per calcined kaolin microspheres + 1001 J of impregnated additive microspheres

[Brief explanation of drawings]

FIG. 1 shows the relationship between vanadium migration and catalyst blend activity. Patent Applicant Engelhard Corporation-j FIG, I Dium 1; v. T) Hyakuma Ki

Claims (1)

Claims: 1. Consisting of a fluidizable mixture of additive particles including (a) highly active zeolite-containing particles and (b) a vanadium passivating agent that is relatively inert to the catalyst of the cracking reaction. , the highly active zeolite particles consist essentially of Y-faujasite dispersed in a matrix containing at least partially silica-alumina, and the additive particles are essentially baked past their exothermic It consists of a calcium oxide agent dispersed in microspheres that at least partially include kaolin, the total BET surface area of the microspheres is less than about 20 m^2/g, and the calcium oxide is about 0.5 m^2/g by weight of the additive particles. present in an amount of 5 to about 30%;
and 90% by volume flowing water vapor plus 10%
After steaming the zeolite-containing particles for 4 hours at 1450° F. in a fluidized bed reactor with an air atmosphere, the zeolite-containing particles meet ASTM D. 3907-80
In a microactivity test, the reactor was operated at 910° F., a catalyst to oil weight ratio of 5, and a weight hourly space velocity of 15 h^-^1, using the feedstocks in Table 3. The microspheres are obtained by slurrying a mixture of crushed limestone and kaolin in water, spray drying the slurry thus obtained and calcining the microspheres obtained. A catalyst composition for fluid catalytic cracking of hydrocarbon fractions, characterized in that it is formed by: 2. The catalyst composition of claim 1, wherein the zeolite-containing particles contain at least about 40% Y-faujasite by weight and have a microporosity of 0.2 cc/g or less. 3. The catalyst composition of claim 1, wherein the additive particles contain from about 0.5 to about 15% calcium oxide by weight. 4. Additive particles are at least about 20% by weight of the total composition
The catalyst composition of claim 1, wherein the zeolite-containing particles represent from about 10 to about 80% by weight of the total composition. 5. The catalyst composition of claim 4, wherein the zeolite-containing particles contain at least about 40% Y-faujasite by weight and have a microporosity of 0.2 cc/g or less. 6. The catalyst composition of claim 5, wherein the additive particles contain from about 0.5 to about 15% calcium oxide by weight. 7. The catalyst composition of claim 4, wherein the additive particles contain from about 2.5 to about 7.5% calcium oxide by weight. 8. The catalyst composition of claim 1, wherein the additive particles include from about 10% to about 30% calcium oxide by weight. 9. The catalyst composition of claim 8, wherein the zeolite-containing particles contain at least about 40% Y-faujasite by weight and have a microporosity of 0.2 cc/g or less. 10. The additive particles are at least about 20 by weight of the total composition.
% to about 90%, and the zeolite-containing particles account for about 10% to about 80% by weight of the total composition. 11. A petroleum fraction is subjected to catalytic cracking conditions in a cracking zone consisting of a fluidizable mixture of highly active zeolite-containing particles and relatively catalytically inert additive particles including calcium oxide and silica-alumina. contact with a catalyst composition; the highly active zeolite particles consist essentially of at least about 20% by weight Y-faujasite dispersed in a silica-alumina matrix; ASTM
D. 3907-80, the reactor was operated at 910°F, the weight ratio of catalyst to oil was 5, and the weight hourly space velocity was 15 h^-^1, and the feedstocks of Table 3 were used. When tested with a weight loading of at least 70%, the additive particles essentially consist of microspheres consisting primarily of calcined kaolin through which the exotherm has passed, and the total BET surface area of the microspheres is Approximately 20
m^2/g, and the amount of calcium oxide dispersed with the additive particles and introduced into the cracking zone is at least about 10% per mole of vanadium present in the petroleum introduced into the cracking zone. mol of calcium oxide, and the microspheres are formed by slurrying a mixture of crushed limestone and kaolin in water, spray-drying the slurry thus obtained, and calcining the microspheres obtained. 100 in weight
A process for fluid catalytic cracking of petroleum fractions containing at least about 5 parts per million vanadium. 12. The zeolite-containing particles are at least about 14% by weight
12. The method of claim 11, comprising Y-faujasite of 0.2 cc/g or less and having a microporosity of 0.2 cc/g or less. 13. The method of claim 11, wherein the additive particles contain from about 2.5 to about 7% rare earth calcium oxide by weight. 14. The additive particles are at least about 20 by weight of the total composition.
12. The method of claim 11, wherein the zeolite-containing particles represent from about 10% to about 80% by weight of the total composition. 15. The zeolite-containing particles are at least about 40% by weight
15. The method of claim 14, comprising Y-faujasite of 0.2 cc/g or less and having a microporosity of 0.2 cc/g or less. 16. The method of claim 15, wherein the additive particles contain from about 2.5 to about 7.5% calcium oxide by weight. 17. The method of claim 14, wherein the additive particles contain from about 2.5 to about 7.5% calcium oxide by weight. 18. The method of claim 11, wherein the additive particles include about 10 to 30% calcium oxide by weight. 19. The zeolite-containing particles are at least about 40% by weight
19. The composition of claim 18, comprising Y-faujasite of 0.2 cc/g or less and having a microporosity of 0.2 cc/g or less. 20, the additive particles are at least about 20 by weight of the total composition.
% to about 90%, and the zeolite-containing particles make up about 10% to about 80% by weight of the total composition.