JPH0712433B2 - An improved catalyst for heavy hydrocarbon hydrotreating. - Google Patents

Description

Detailed Description of the Invention

This invention relates to an improved hydrotreating catalyst containing useful alumina particles as a catalyst support and a process for hydrotreating hydrocarbon liquids.

The catalyst carrier particles of the present invention are made by flashing hydrated alumina such as Bayer process alumina.
Made from partially dehydrated, rehydratable alumina produced by calcining. In a method of forming shaped alumina particles, partially dehydrated alumina is rehydrated to solidify and cure the particles and then calcined to convert the alumina into essentially anhydrous alumina, such as gamma and eta alumina. . A method of forming rehydrated spherical spherical beads of alumina from an aqueous slurry of partially dehydrated alumina is described in US Pat.
65,407. After the partially dehydrated alumina is ground and dispersed in water to make an aqueous slurry of about 50-60% solids, drops of the aqueous slurry are introduced into the build medium where the drops are shaped, It is heated to shape, rehydrate and harden. In one embodiment, droplets are formed by forcing the slurry through an orifice, from which droplets of the slurry are dropped into a hot oil bath where the droplets are spherically shaped and rehydrated. It is cured at a moderately suitable temperature. After curing in a hot oil bath for several hours to complete rehydration, the spherical alumina beads were separated, dried and calcined to finish the alumina particles.

The described prior art method of introducing drops of an alumina slurry into a hot oil shaping and hardening medium is very suitable, but very small, for making beads with an average particle size of 1-5 mm. Limited by the ability to pass the slurry through a diameter tube or orifice. As a practical matter, such techniques are unsuitable for producing beads with diameters smaller than 1 mm due to the low throughput per orifice. An additional difficulty is the frequent clogging of the required small diameters and waste due to particle agglomeration on the surface of the hot oil bath. This prior art is more suitable for producing beads of large diameter, i.e. 1 mm to 5 mm in diameter.

In accordance with the present invention, a volume of aqueous alumina slurry is combined with a large volume of immiscible hot oil and the slurry and oil are agitated together with sufficient shear to produce
The process was improved by dispersing the aqueous slurry in the continuous phase of hot oil as small droplets. When the drops of aqueous slurry are suspended in the immiscible oil phase, the surface tension of the interface causes the drops to be shaped into spherical beads. In hot oil,
The beads are cured to at least partially rehydrate the alumina and cure. The average particle size of the beads is determined by the drop size, and the drop size is determined by the degree of agitation used to disperse the drops of the aqueous slurry in the oil phase. Excellent yields of beads within a selected, rather narrow size range can be obtained by this method, and this method is for forming spherical beads of rehydratable alumina having a diameter of less than 1 mm. Is preferred.

Dispersion of the aqueous slurry droplets in the continuous oil phase can be accomplished by several agitating means, such as a rotating blade agitator mixer. However, it is preferred to use an in-line static mixer, which is placed online in the conduit immediately downstream, in view of the conduit into which the separate streams of immiscible aqueous slurry and oil component are introduced in selected proportions. Several different designs of static mixers are commercially available. Some types of in-line static mixers are known from European Patent Application Publication No. 0.0000.
5,619 (Application No. 79,300,825.1). The combined flow of the two immiscible components is fed through the conduit to the in-line static mixer at a sufficient linear velocity to provide sufficient shearing force due to the agitation of the components in the mixer, as desired when the liquid crosses the mixer. Disperse drops of an aqueous slurry of size in a continuous oil phase. The two phase dispersion is conducted from an in-line mixer into a relatively stationary hot oil bath. Aqueous drops in the hot oil bath gradually settle to the bottom when held by the interfacial tension in the desired spherical particle shape. The drops harden rapidly in hot oil by rehydration of the alumina in the drops. Thus, the spherical shape of each formed particle is fixed by rehydration as the dispersed drops harden in hot oil.

The advantage of this is that with a given mixer, the average bead size can be varied within the effective range of sizes by controlling the flow rate of fluid through the mixer, and controlling the flow rate. This means that the size can be maintained at the selected size. The bead size decreases as the flow rate through the mixer increases.

Other factors affecting bead size are the diameter of the mixer, the number of mixing elements in the mixer, the slurry to oil ratio, and the viscosity, density and interfacial surface tension properties of the selected fluid.

A suitable slurry of partially dehydrated, rehydratable alumina powder is prepared by mixing the powder with water. The rehydratable alumina powder is preferably
The loss on ignition at 650 ° C. is about 7-15% and the median particle size is 5-15 microns.
It can contain Na ₂ O of 0.1 to 0.8 wt%.
Such powders are described in previous U.S. Pat. No. 4,065,407.
It can be prepared by flash firing an alumina hydrate, such as the Bayer alumina, as detailed in US Pat. When it is necessary to reduce the sodium content of the finished beads for a particular application, soda can be easily leached from the powder prior to bead formation or from the beads after formation. The level of soda in the powder can be reduced by cold water, sodium leaching with dilute acid, or by the use of ion exchange resins, as described in the patent. When soda has not been extracted from the powder, the slurry should be neutralized with a preferably small amount of acid. Aqueous slurries of rehydratable alumina powder have no significant effect on the final rehydrated bead product and can be used at low temperatures (eg,
15 ° C) for several hours.

The concentration of alumina solids in the slurry used in the present invention is about 40 to about 60 in the slurry.
It is in the range of solids by weight, preferably about 42-55% by weight. The advantages of this method are the total pore volume of the finished alumina beads, and the macropore volume (ie, the volume of pores with a pore radius greater than 105 Å).
Can be varied within a range by varying the concentration of solids in the slurry, and the desired pore volume can be obtained by selecting the appropriate slurry concentration. In order to obtain a large pore volume and a low density, choose a solids concentration at the lower end of this range. The microporosity of the bead product, ie, the volume of pores with a pore radius of less than 105 angstroms, is largely unaffected by variations in the solids concentration of the slurry, and generally ranges from about 0.3-.
Within the range of 0.6 ml / g, macroporosity will be affected by changes in solids concentration in the slurry.
A preferred slurry with 47.5% solids has a total pore volume of about 1 ml / g and has macropores, ie 10
It has been found to produce alumina beads with a pore volume of about 0.6 ml / g in the range of pores with radii greater than 5 Å.

In order to produce spherical alumina beads with a diameter of less than 1 mm, the process of the present invention introduces drops of slurry into the hot oil by dropping it from an orifice plate or hollow needle above the hot oil bath. It has been found that such beads can be effectively produced with less mechanical difficulty, higher production rates, and less waste.

In-line mixers, preferably used to disperse the drops of the slurry in the continuous immiscible phase, are commercially available in a variety of sizes. In essence, such a mixer is a tube lined with a series of several radial spiral blade stators, the interior of which is fixed along the axis of the tube, with each stator blade pitch being in-line. Opposite the next adjacent stator blade pitch. The two-phase liquid flow across the length of the mixer
Directed by the constantly changing facing blades, it causes a strong shear agitation, which causes the aqueous phase to disperse into the continuous oil phase as drops. Other mixers can be used to disperse the aqueous phase in the oil.

Because of the feeding of the two components to the mixer, the oil to water phase ratio is always greater than 2 volumes to 1, preferably about 5 to 5.
It is in the range of about 20. The water immiscible component is necessarily immiscible with the aqueous slurry. Other properties of immiscible liquids,
For example, viscosity, density and interfacial tension should be within a range that produces the desired slurry drop size and shape. Various mineral oils could be used effectively. It is most convenient, if not necessary, to use the same oil component for the mixing step and the hot oil bath so that the composition of the oil bath does not change when the dispersion is fed from the mixer to the bath. Also, after preheating the oil component, introduce it into the mixer,
When feeding the dispersion from the mixer to the bath, it is most convenient to help maintain the desired use temperature in the hot oil bath.

The preferred use temperature for the hot oil curing bath is
It is the highest temperature that can be maintained without boiling the water in the aqueous drops, and strives to maintain the bath temperature at about 90-95 ° C. At temperatures below this, hydration and therefore curing of spherical beads will take a long time.

The beads may be removed from the hot oil bath as soon as they have been sufficiently hardened to retain their spherical shape, or the beads may be allowed to harden in the hot oil bath for a time sufficient to complete hydration. it can. Subsequent curing steps with steam or hot water should be used when the beads are removed prior to completion of hydration.

The oil can be largely removed from the beads prior to calcination by simple filtration or centrifugation, or by washing with steam or hot water. A small amount of residual oil will burn off during the subsequent firing process. When sodium ion removal is required, this can be done by leaching the spherical beads with water or dilute acid before or after firing.

[0016]

EXAMPLES Next, the present invention will be described in more detail by way of examples.
To do. Note that Examples 1, 2, 3, 6 and 7 are the touch points of the present invention.
A production example of spherical alumina beads, which is a carrier of a medium, is also shown.
Of. Example 1 Flash firing with a median particle size of about 10 microns, loss on ignition (LOI) of 7.8%, rehydration index (RHI) of 63, and about 0.15% Na ₂ O. Alumina powder prepared in dilute nitric acid
3.2 lbs (6.0 kg) of rehydratable alumina /
16 pounds (7.3 kg) of ice chips plus 24 pounds (10.9 kg) of water / 76 ml of concentrated HN
Slurry at a ratio of O ₃ (70%). The terms LOI and RHI are defined in US Pat. No. 4,065,407. That is, loss on ignition (LO
I) is 2% powdered alumina at 1800 ° F (982 ° C).
What is required from the measurement of weight loss when heated for hours
And the rehydration index (RHI) is present in the powder
It expresses the amount of alumina that can be rehydrated.
It is calculated. After leaching for 1.5 hours, the alumina is separated by filtration and residual salts are washed off with deionized water. Filter cake containing about 57% solids in water at 20 pounds (9.1k).
Thaw again with the cake of g) to about 3 pounds (1.4 kg) of pure water to form a slurry with a solids content of 47.5%. The slurry is stored at 15 ° C until use.

[0017] 1 part of mineral oil (Sontex ^R 35) and 1 part of polyterpene resin (Zonarey ^R 7070) 9
Approximately 3 through a 1 inch (2.5 cm) diameter Kenics 12 element static mixer heated to 5 ° C.
Pump at gallons per minute GPM (11.4 l / min). This about 15 ° C. aqueous slurry is about 0.3 GPM
It is introduced into the oil stream at the inlet of the mixer at a rate of (1.1 l / min) and dispersed in the oil phase during the passage of the mixer as drops of average diameter of about 500 microns. The conduit from the mixer has the same composition as the oil phase used to disperse the drops,
Directly to oil bath heated to ℃. The drops solidify rapidly as they cure in the bath. After curing in a hot oil bath for 0.5 hours, the beads are separated from the oil by sieving and hydrothermally treated with hot water. During this treatment, strength is improved, additional soda is removed, and adhering oils are washed away from the surface of the beads. The beads are dried, calcined at 650 ° C. for 3 hours and then classified to give the desired mesh size. The classification yield from a typical sample is 20% of 50%.
40 mesh, 6% +20 mesh, and 44% -40 mesh. The pressed bulk density (CBD) was 0.48 g / ml. Beads are 0.99ml / g
It has a pore volume of water. The pore size distribution, determined by mercury porosimetry, was 0.96 ml / g total pore volume, 0.39 ml / g micropore volume and 0.57 m.
The volume of the macropore is 1 / g.

Example 2 Fixation of a slurry substantially as described in Example 1 but using different rehydratable alumina powders and introduced into a Kenics mixer, as shown in Table I. The concentration is varied in some experiments to produce beads. In all cases, the finished alumina beads had 0.44-0.4 measured by mercury injection.
It has a micropore volume of 8 ml / g. This is a property derived from the selected alumina powder. The total pore volume is
It changed as shown in Table I. It was found that other similar products had micropore volumes that were substantially unaffected by solids concentration, but that there is substantially the same relationship between total pore volume and slurry solids concentration. I understood. This relationship is represented schematically by:

[0019]

[Equation 1]

Thus, it is expressed as ml / g. The total pore volume in the final alumina beads equals approximately 90% of the volume (ml) of water in the precursor slurry drop divided by the mass of alumina solids (g) in the slurry drop. Thus, the total pore volume is about 42% to 55% slurry concentration.
By controlling between% solids, about 0.7
It can be controlled between 5 and about 1.3 ml / g.

[0021]

TABLE I Solid% in Slurry in Slurry Total Pore Volume in Final Alumina Beads ml / g 45.0 1.10 47.5 0.99 50.0 0.92 Example 3 Median Particle Size 11.4 Micron, 0.25 for Na ₂ O
A bead forming slurry is prepared by mixing 6.77 kg of rehydratable alumina powder with wt% and LOI of 10.2% with 3 kg ice, 3 kg water and 85 ml acetic acid. This slurry is 1.54
It has a specific gravity of g / ml, a solids content of 47.1% and a viscosity of 17 seconds in a Zahn # 2 cup.

This cooled slurry was applied to Kenics with a diameter of 1 inch (2.5 cm) × 18 elements.
At the inlet of the in-line mixer, 1 part by volume of slurry to 10 parts by volume of hot (95 ° C.) mineral oil (Sont
ex ^R 35) at a rate of 2.2 gallons / min (8.3 l / min)
Min) is introduced at the total flow rate. This mixture of slurry drops in hot oil is collected in a heated vessel and cured at 90 ° C overnight. After removing the oil from the beads with a centrifuge in a perforated basket, the beads are calcined at 650 ° C for 2 hours. Here, the soda is washed off in acidic water. The same procedure is repeated to reveal how the bead size changes as a function of the total flow rate through the static mixer using different flow rates; see Table II. The pore size distribution does not depend on the flow rate through the mixer. In all cases, the total pore volume is about 1.0 ml / g, the micropore volume is about 0.42 ml / g, and the macropore volume is about 0.58 ml / g.

[0023]

Table II Table II Effect of Flow Rate on Median Particle Size Total Flow Rate Mineral Oil + Slurry, Median Bead Diameter, Gallon / min (l / min) Micron 2.2 (8.3) 600 2.5 (9.5) ) 500 3.5 (13.2) 375 4.5 (17.0) 300 The pore volume and pore size characteristics of the above rehydrated and calcined alumina beads are characterized by the hydrocarbon liquid catalytic hydrogen. These beads are particularly suitable for use as carriers for catalysts used in various methods of treatment. Petroleum fractions or residues or other hydrocarbons in the presence of alumina supported catalysts for hydrodesulfurization, removal of nitrogen compounds, or removal of metals, or for conversion of hydrocarbons, for example refuming or cracking, or their Contacting with hydrogen under suitable conditions for the combination of functions,
A number of methods have been described. The majority of such catalysts consist of at least one catalyst metal selected from Group VI of the Periodic Table, usually molybdenum, and also at least one promoter metal selected from Group VIII of the Periodic Table.
It can contain seeds, usually cobalt or nickel. As catalyst support particles for such catalysts, the spherical beads of the present invention offer several advantages. They are readily prepared in very small and uniform particle size, which is particularly suitable for use in, for example, a backflow ebullated bed process of the type described in US Pat. No. 3,622,500. Due to the particle size and pore size distributions described above, these catalysts have been extended in processes for hydrotreating heavy petroleum residues, such as those described in US Pat. No. 3,630,888. Suitable for use. In addition to the catalytic hydrotreating of petroleum fractions or residues, the hydrotreating catalysts of the present invention may be used with other hydrocarbon liquids such as US Pat.
Coal derived residue according to the method described in No. 933,
Or it can be used for hydrotreating other hydrocarbons derived from oil shears, gravel sandstone, etc.

Example 4 Shaped from slurry droplets of rehydratable alumina as described in Example 1 above, solidified in a hot oil bath, then steam cured and calcined at 650 ° C. The catalyst beads are manufactured by impregnating the spherical alumina beads manufactured by the above method. Use a classification fraction of 20/40 mesh. The impregnation solution is prepared in two parts in order to impregnate 1700 g of these calcined carrier particles. First
Part dissolves 40 g citric acid in water, 116.4 g
Of _{Co (NO 3) 2 · 6H} 2 O and 116.4g of Ni
(NO ₃₎ prepared by adding ₂ · 6H ₂ O.
The second part is that molybdenum oxide (grade L) is dissolved in an aqueous solution of ammonium hydroxide so that the molar ratio of MoO ₃ : NH ₄ OH is 1: 1 and the concentration of MoO ₃ in 1 ml of the solution is 0.2.
Prepared by weighing 32 g. Immediately before impregnation, the first
A portion is combined with 1034 ml of the second portion while stirring and the mixture is diluted with water to make 1785 ml of impregnating solution. This amount of solution is sprayed onto 1700 g of beads for impregnation. The wet beads are aged for 1-2 hours, then dried and calcined at 650 ° C for 1 hour. The calcined catalyst contains, by analysis, 1.5% CoO, 1.5% NiO and 12.8% MoO ₃ . The measured pore volume of water is 0.86 ml / g. The impregnated and calcined catalyst has a macropore volume of 0.57 ml of macropores with a radius of 105 Å or more measured by mercury injection.
/ G, and the micropore volume is 0.31 ml / g. The large pore volume, compared with other hydrotreating catalysts,
It is relatively large and is particularly advantageous for hydrotreating heavy oil fractions.

The catalyst was recalcined at 450 ° C. for 1 hour,
It is then loaded into a graded density trickle bed reactor using sand as a diluent to help maintain an isothermal bed. The catalyst in this reactor is presulphided at 400 ° C. for 75 minutes with a 10% by volume gas solution of H ₂ S in hydrogen.

After sulfurization, 27 ° API specific gravity and 350 ° C.
An oil feedstock blend of a light cycle oil fraction with a distillation end point of
IG reactor with 500 SCF at a weight hourly space velocity of 5
/ BBL with hydrogen at a flow rate of BBL. Sulfur in the feed was reduced from 1.4 wt% to 0.40 wt% in a single pass through the reactor.

Example 5 150 g of stainless steel cylindrical locking autoclave in a container 285 cc with inlet and thermowell.
And 2 g of the bead catalyst prepared as in Example 4 above. This catalyst has a surface area of 150 m ² / g, a total pore volume of 0.86 ml / g, 0.57 m
It has a macropore volume of 1 / g and a particle size of 20-40 mesh. Flush the reactor with hydrogen to remove air,
Then pressurize with hydrogen to 750 psi. The reactor is brought to a working temperature of 380 ° C. for about 2 hours and the pressure is 1
Raise to 500 psi and then control to this pressure. When the reactor temperature reaches 380 ° C., the gas in the reactor is purged by aeration to reduce the internal pressure to 500 psi. The pressure is then restored to 1500 psi with hydrogen. The reactor was maintained at 380 ° C. and continuously
In a circular arc of °, rock at a frequency of about 60 cycles / minute. After operating for 1 hour at the working temperature, the gas is reapplied to
Vent to 0 psi and repressurize the reactor with hydrogen as before. This is also repeated at the end of the second, third and fourth hours. At the end of the 20.5 hour working time, heating is stopped, the reactor is cooled to about 200 ° C. in about 1 hour and gas is bubbled through. Open the reactor, separate the liquid contents from the solids and analyze for sulfur, metals and asphaltene. The analytical values of the products are shown in Table III.

The procedure just described is repeated in a series of experiments, but in the experiments of use, the catalyst used, the residual oil treated and the reaction time are varied, as shown in Table III. It is carried out with no catalyst and with comparable sizes of particles of crystalline aluminum oxide of Alundum brand, using a control experiment. These particles have a surface area of less than 10 m ² / g, a pore volume of less than 0.1 ml / g and 20-4.
It has a size of 0 mesh. Aero HDS, a commercially available hydrodesulfurization catalyst with comparable catalytic metals supported on alumina extrudate support particles.
Comparative experiments are conducted using 1442B brand catalyst. This commercial catalyst was crushed to a comparable size (20-4
0 mesh) and it has a comparable total pore volume (0.85 ml / g) but a low macropore volume (0.
31 ml / g) and large surface area (greater than 250 m ² / g). The content of catalytic metal in the aerocatalyst is 15% by weight MoO ₃ and 3% CoO. In the bead catalyst, the content of catalytic metal is 12% by weight of MoO ₃ ,
1.5% CoO and 1.5% NiO.

The two types of Parsian used in the experiment
Persian Gulf residual oil (untreated) is shown in Table III. Safaniy
aResid) residue is 642 when 20% is distilled
Boil at ° F (339 ° C) and boil at 995 ° F (535 ° C) when 50% distilled, 13.9 °
It is a distillation residue with API gravity. 9. Kuwait Resid boiled at 793 ° F (423 ° C) when distilled 10% and 981 ° F (527 ° C) when distilled 30%, 9.
Heavy oil with 3 ° API gravity.

[0030]

[Table 3]

As is evident from the data in Table III,
The rehydrated alumina-supported catalyst is used for hydrodesulfurization of residual oil.
It has activities comparable to those of the extruded alumina carrier supported catalysts which are known to be effective. The bead catalyst had a significantly smaller surface area and had equal effectiveness. The beaded alumina support has a relatively large macropore pore volume, which allows it to absorb more metal from the residual oil being treated before the catalyst is deactivated by the metal. Thus, the life of the catalyst in continuous processing of resids and other metal-containing feedstocks is longer than known catalysts.

Example 6 A beading slurry was prepared as in Example 1 by suspending the rehydratable alumina powder in ice water containing about 1 part concentrated nitric acid per 100 parts alumina. Prepare. After leaching for 1 hour, the slurry is filtered and washed with 4 displacements of deionized water. Reslurry the filter cake to a solids concentration of 47%. Molybdenum oxide (Amax purity grade L) was added to this slurry to give 6
100 parts by weight of MoO ₃ to 100 parts by weight of alumina, and mixed while stirring. Adjust pH to 6-7 with ammonia. The beads are formed by pipetting drops of the slurry into hot mineral oil at about 90 ° C. This mineral oil is Son
a 30:70 mixture of tex ^R 35 mineral oil Zonarez ^R 7070 polyterpene resins, beads in this slow sedimentation, followed by overnight cure at 90 ° C.. After dripping the oil, the beads are fired at 650 ° C.

Instead of molybdenum oxide, 1 silica is used.
5 parts by weight of SiO ₂ per 00 parts of alumina and as an additive, Linde HNa-Y-
1 molecular sieve was used at a ratio of 10 weights of sieve per 100 parts of alumina, and without additives,
Beads are similarly prepared. In all cases very uniform size beads were produced. As is evident from the physical properties listed in Table IV, strong beads with large total pore volume are produced with admixture prior to bead formation. 70-100 parts by weight of partially dehydrated rehydratable alumina and up to 30 parts by weight of other solids (which may include other aluminas and other solid fillers)
Beads made in the same manner as above can be made by the method described herein.

[0034]

Table IV Additive Bead Diameter mm Total Pore Volume ml / g Crush Strength lb (kg) None 4.3 1.0 10 (4.5) Molybdenum Oxide 4.3 1.0 10 ( 4.5) Silica 4.3 1.1 12 (5.4) Molecular Sieve 4.8 1.0 39 (17.7) In the above description and claims, the word "spherical" has two phases. Used to define the shape formed by surface tension in a fluid system. The term includes shapes that can vary from a true sphere, such as pear-shaped, flat sphere, and the like.

In a variation of the bead forming process described herein, the droplets of the slurry are dispersed in a low melting point thermal paraffin wax, liquefied and the paraffin is removed as in other water immiscible oils. It is then cooled to a low temperature at which the paraffin solidifies sufficiently to hold the drops in suspension indefinitely. In this state, the drop remains in its shape for a time sufficient to set by rehydration, which is slow at this low temperature. The paraffin is heated again to remove the hardened beads and separated by filtration.

In addition to rehydratable alumina, other alumina in the aqueous dispersion can be formed into spherical beads by the method of the present invention. There are several known aluminas in the aqueous dispersion that have properties that make them suitable for use in the present invention. Aqueous alumina slurries (the term slurry as used herein includes sol or other dispersions of alumina in water) must be dispersed in drops by agitation with a water immiscible liquid, and It must be fluid and droplets can be shaped into beads by interfacial surface tension in an oil bath. Further, the alumina must be sufficiently hardened in the bath to be able to retain the particle shape formed in the bath, so that the particles agglomerate and stick after they have been removed from the bath. must not.

In aqueous dispersions with non-rehydratable alumina, these properties are, for example, those at which the pH of the aqueous dispersion is increased by adding a base to the pH at which the alumina thickens and solidifies.
It can be obtained by setting it in the range of about 4 to 7. Basic substances can be added by using an ammoniated oil bath, from which drops absorb basic ammonia when dispersed in the oil or the base decomposes by the heat of the bath to release the base. Can be generated by adding a compound such as hexamethylenetetramine to the aqueous slurry.

US Pat. No. 4,179,408 describes a method of forming spherical particles from drops of an alumina slurry, which drops fall into a bath of water immiscible liquid,
Then, when descending the bath containing ammonia, it is shaped and solidified in a water immiscible bath. The shaped and thickened particles are then further cured in an aqueous alkaline bath. The present invention can be used as an alternative to the oil dripping method to disperse drops of the same aqueous alumina slurry in the continuous phase of the same ammoniated oil. In this dispersion, the drops are shaped and solidify as they settle out of the dispersion. Aqueous alumina drops are water immiscible liquids (kerosene) with alumina slurry.
Are fed together into an in-line mixer to distribute the aqueous phase as a dispersed aqueous phase (droplets) in the continuous phase immiscible liquid. The dispersion immediately flows into an ammonified kerosene bath in which drops gradually settle down. Kerosene can be ammonified in the bath, or preferably before being fed to the mixer.

US Pat. No. 4,250,058 further describes another method of making spherical alumina particles by the oil drop method. Alumina hydrogel, containing an ammonia precursor that hydrolyzes or decomposes to ammonia when heated, is prepared in a slurry and dropped as drops from a nozzle into an oil bath heated to a temperature of about 95-100 ° C. Prepare by At this temperature, the ammonia precursor reacts to release the ammonia, which raises the pH of the droplets, which causes the droplets to harden while still in the oil bath. Instead of dispersing the droplets into the oil bath by dropping the slurry through a nozzle, the present invention disperses the alumina slurry droplets into the oil with a stir mixer.

Example 7 An alumina sol is prepared by aging an alumina pellet in dilute hydrochloric acid at 102 ° C. Cool this sol,
Combined with the hexamethylenetetramine solution, a thermoset alumina hydrosol containing about 12% by weight hexamethylenetetramine and about 8% by weight aluminum is prepared. The slurry stream is combined with the oil stream and the mixture is dispersed as drops in kerosene by feeding through a static in-line mixer. The slurry to oil ratio is 1:10 volume / volume. The flow rate through this mixer produces beads of about 500 microns in diameter at 5 gallons per minute (18.9 l / min) through an 18 element Kenics mixer with a diameter of 1 inch (2.5 cm). To adjust. No significant gelation occurs before the dispersion leaves the mixer. A dispersion of aqueous drops in oil is fed to an oil-filled molding tower maintained at about 95 ° C., at which temperature gelation of the drops into beads is induced by the decomposition of tetramine into ammonia. The beads were further aged in a 100 ° C. oil bath for 19 hours, then 9
Aging in a buffered ammonium chloride solution at 5 ° C for 15 minutes,
Finally, it is aged in an aqueous ammonia solution for 7 hours. The beads are dried in air at 650 ° C. for 2 hours and calcined. The spherical particles are ready for use.

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Claims (14)

[Claims] 1. Alumina 70-10 rehydrated from partially dehydrated alumina upon particle formation and then calcined to convert this alumina to essentially anhydrous alumina.
0% by weight, wherein the particles have an average particle size of 0.1 to 1 mm
, And the total pore volume is 0.75-1.3
ml / g in the range of 0.3 to 0.3 of the pore volume in the pores.
0.6 ml / g has a pore radius less than 105 angstroms, and 0.3 to 0.95 ml / g in the pores has a pore radius greater than 105 angstroms, consisting essentially of spherical alumina beads At least one catalyst metal selected from Group VI of the periodic table supported on catalyst carrier particles consisting of
A catalyst for hydrotreating a hydrocarbon liquid containing at least one promoter metal selected from Group III. 2. A hydrotreating catalyst according to claim 1 wherein said catalyst metal is molybdenum and said promoter metal is cobalt, nickel or both. 3. The hydrotreating catalyst according to claim 1, wherein the spherical alumina beads have an average particle size smaller than 1 mm. 4. The hydrotreating catalyst according to claim 1, wherein the beads have a particle size of 20 to 40 mesh. 5. Alumina 70-10 rehydrated from partially dehydrated alumina during particle formation and then calcined to convert this alumina to essentially anhydrous alumina.
0% by weight, wherein the particles have an average particle size of 0.1 to 1 mm
, And the total pore volume is 0.75-1.3
ml / g in the range of 0.3 to 0.3 of the pore volume in the pores.
0.6 ml / g has a pore radius less than 105 angstroms, and 0.3 to 0.95 ml / g in the pores has a pore radius greater than 105 angstroms, consisting essentially of spherical alumina beads At least one catalyst metal selected from Group VI of the periodic table supported on catalyst carrier particles consisting of
Hydrotreating conditions for the removal of sulfur compounds, nitrogen compounds or metals from hydrocarbon liquids in the presence of hydrotreating catalysts containing at least one promoter metal selected from Group III. A method of hydrotreating a hydrocarbon liquid, which comprises contacting the liquid with hydrogen. 6. A method according to claim 5, wherein said contacting is carried out in a boiling bed of said catalyst particles. 7. A method according to claim 5 wherein the hydrocarbon liquid to be treated is heavy resid. 8. A method according to claim 5 wherein the hydrocarbon liquid to be treated is an oil derived from coal. 9. A method according to claim 5 wherein the hydrocarbon liquid to be treated is an oil derived from Sierre. 10. A method according to claim 5 wherein the hydrocarbon liquid to be treated is an oil derived from gravel sandstone. 11. One part by volume of an aqueous slurry containing 40-60% by weight of finely divided solids, wherein the partially dehydrated rehydratable alumina powder constitutes 70-100% by weight,
Combining with at least 2 parts by volume of a water immiscible liquid; and agitating the combined liquids to disperse the aqueous slurry as a dispersed phase of aqueous slurry droplets in a continuous phase of the water immiscible liquid; Is dispersed into the spherical beads due to the interfacial tension in the dispersion, the dispersed drops in the dispersion are at least partially rehydrated of the rehydratable alumina in the dispersed drops. To heat and cure; the beads are hardened to rehydrate the alumina in the dispersion or in another contact with water vapor or water by heat sufficient to rehydrate the alumina. A spherical alumina bead produced by a method comprising: calcining the rehydrated alumina bead to convert the alumina into a substantially anhydrous alumina. A et consisting catalyst support particles, the particles
Rehydrated from partially dehydrated alumina during the formation of
And then calcined the alumina to yield a substantially anhydrous
70-100% by weight of alumina converted to mina, where
The particles have an average particle size in the range of 0.1 to 1 mm.
And the total pore volume is in the range of 0.75-1.3 ml / g
Yes, 0.3-0.6 ml / g of the pore volume in the pore is 1
Has a pore radius smaller than 05 angstroms, and
0.3 to 0.95 ml / g in the hole is 105 angstrom
Having over beam above pore radius, the sphere-shaped Al which consists essentially of
Supported on catalyst support particles consisting essentially of mina beads
And at least a catalytic metal selected from Group VI of the periodic table
Also selected from Group VIII, if desired
Hydrocarbons containing at least one of the following promoter metals
A method for producing a liquid hydrotreating catalyst. 12. Periodic particles supported on catalyst carrier particles consisting of spherical alumina beads prepared by the method of dispersing an aqueous slurry drop in an oil phase by an in-line static mixer according to claim 11. Table group VI from selected at least one catalytic metal, and optionally, range to Ru formed claims containing at least one promoter metal selected from group VIII first
1. A method for producing a catalyst for hydrotreating a hydrocarbon liquid according to item 1.
Law. 13. A partially dehydrated rehydratable alkyl
Mina powder makes up 70-100% by weight of fine solids
1 part by volume of an aqueous slurry containing 40 to 60% by weight,
Combined with at least 2 parts by volume of a water immiscible liquid; and
By stirring the combined liquid, the aqueous slurry
Of the aqueous slurry droplets in the continuous phase of the water-immiscible liquid.
Dispersed as a dispersed phase; and said droplets at the interface in the dispersion
When molded into spherical beads by tension, in the dispersion
Redispersible droplets of the
At least partial rehydration of the alumina has occurred and
And heat the beads to cure;
In the dispersion with sufficient heat to rehydrate
Cure in separate contact with water or steam or water
Complete rehydration of the alumina; and rehydrated alumina
Calcining the Lumina beads to remove the alumina from the
Turning into Mina; spheres manufactured by a method consisting of
A catalyst carrier particle comprising spherical alumina beads,
Rehydrated from partially dehydrated alumina during the formation of
And then calcined the alumina to yield a substantially anhydrous
70-100% by weight of alumina converted to mina, where
The particles have an average particle size in the range of 0.1 to 1 mm.
And the total pore volume is in the range of 0.75-1.3 ml / g
Yes, 0.3-0.6 ml / g of the pore volume in the pore is 1
Has a pore radius smaller than 05 angstroms, and
0.3 to 0.95 ml / g in the hole is 105 angstrom
Spherical spherical radius
Supported on catalyst support particles consisting essentially of mina beads
And at least a catalytic metal selected from Group VI of the periodic table
Also selected from Group VIII, if desired
Hydrocarbons containing at least one of the following promoter metals
Manufactured by a method for manufacturing a liquid hydrotreating catalyst
In the presence of a catalyst, a hydrocarbon liquid is subjected to hydrotreating conditions to remove sulfur compounds, nitrogen compounds or metals,
A method of hydrotreating a hydrocarbon liquid comprising contacting with hydrogen. 14. A partially dehydrated rehydratable alcohol.
Mina powder makes up 70-100% by weight of fine solids
1 part by volume of an aqueous slurry containing 40 to 60% by weight,
Combined with at least 2 parts by volume of a water immiscible liquid; and
By stirring the combined liquid, the aqueous slurry
Of the aqueous slurry droplets in the continuous phase of the water-immiscible liquid.
Dispersed as a dispersed phase; and said droplets at the interface in the dispersion
When molded into spherical beads by tension, in the dispersion
Redispersible droplets of the
At least partial rehydration of the alumina has occurred and
And heat the beads to cure;
In the dispersion with sufficient heat to rehydrate
Cure in separate contact with water or steam or water
Complete rehydration of the alumina; and rehydrated alumina
Calcining the Lumina beads to remove the alumina from the
Turning into Mina; spheres manufactured by a method consisting of
A catalyst carrier particle comprising spherical alumina beads,
Rehydrated from partially dehydrated alumina during the formation of
And then calcined the alumina to yield a substantially anhydrous
70-100% by weight of alumina converted to mina, where
The particles have an average particle size in the range of 0.1 to 1 mm.
And the total pore volume is in the range of 0.75-1.3 ml / g
Yes, 0.3-0.6 ml / g of the pore volume in the pore is 1
Has a pore radius smaller than 05 angstroms, and
0.3 to 0.95 ml / g in the hole is 105 angstrom
Spherical spherical radius
Supported on catalyst support particles consisting essentially of mina beads
And at least a catalytic metal selected from Group VI of the periodic table
Also selected from Group VIII, if desired
Hydrocarbons containing at least one of the following promoter metals
Aqueous slurry in a method for producing a liquid hydrotreating catalyst.
-Disperse the drops into the oil phase with an in-line static mixer.
Made of spherical alumina beads produced by the
Selected from Group VI of the periodic table supported on the catalyst carrier particles.
At least one selected catalytic metal , and optionally
And at least a promoter metal selected from Group VIII
Manufactured by a method for manufacturing a hydrotreating catalyst containing one kind
A hydrocarbon liquid in the presence of a sulfurized compound,
A method of hydrotreating a hydrocarbon liquid comprising contacting with hydrogen under hydrotreating conditions to remove nitrogen compounds or metals.