JPS5918098B2 - Hydroconversion catalyst and its production and usage method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to catalysts, particularly catalysts useful in hydroconversion processes, more preferably hydrocracking processes, methods for producing catalysts,
and a method of using the catalyst.

PRIOR ART The prior art is replete with methods for producing catalysts consisting of metals entrained on the surface of porous inorganic oxide supports.

According to the prior art, the catalyst is prepared, for example, by impregnating a preformed inorganic oxide support with a metal.
Alternatively, it can be prepared by co-precipitating the metal as an oxide or hydroxide with a material forming a porous inorganic oxide support, e.g. in a solution containing dissolved silica, alumina and palladium. The pH is such that silica and alumina co-precipitate and palladium, primarily in the form of soluble palladium hydroxide and/or soluble palladium salts, is chemisorbed onto the resulting silica-alumina co-precipitate to a certain extent. It can be adjusted to the desired point.

Since palladium is a cation, it does not co-precipitate with silica and alumina; more specifically, palladium hydroxide is soluble within the pH range where silica and alumina co-precipitate.

U.S. Patent Nos. 1280314, 1282296, and 12
No. 82297 teaches impregnating powders with nickel by precipitation with nitrogenous organic colloids.

In U.S. Pat. No. 2,662,861, an alumina slurry 1 is prepared, washed, an accelerator is added, and hydrogen sulfide is bubbled through a solution 2 of chloroplatinic acid hexahydrate.
It teaches that a catalyst can be made by mixing and drying 2 and 2.

US Pat. No. 2,898,305 teaches mixing silica in slurry form with insoluble inorganic compounds, drying and calcining.

U.S. Pat. No. 2,688,603 discloses the process of dispersing a potentially catalytically active metal-containing organic compound onto the surface of a suitable support and decomposing the precursor to remove the organic component of the molecule. He teaches catalyst production.

In U.S. Pat. No. 3,210,296, alcohol,
The use of noble metal compounds dissolved in ethers, aldehydes, ketones or mixtures thereof is taught to impregnate inorganic oxides.

When a catalyst consisting of a metal associated with a porous inorganic oxide support is prepared by the process of the invention, it is surprising that the metal, preferably palladium, intended to be bound into the catalyst is It has been found that a greater proportion is actually bound therein than is obtained with prior art combined coprecipitation and chemisorption catalyst preparation methods.

It has also been found that, surprisingly, when preparing catalysts according to the present invention, the resulting catalysts have higher hydrogenation catalyst stability than do prior art catalysts.

The higher hydrogen soot stability found for catalysts prepared according to the present invention achieves a more uniform dispersion of metals on the surface of porous inorganic oxide supports than obtained by prior art catalyst preparation methods. This is thought to be the result of

The present invention comprises: (a) intimately mixing a solution of a palladium compound in an aqueous medium containing a gelatinous precipitate of an inorganic oxide of silica and alumina or a precursor thereof to form a mixture; (b) By intimately mixing a solution of an organic precipitant for gravimetric analysis in the mixture, the palladium compound is reacted with the precipitant, and a finely powdered organic palladium compound precipitate is uniformly distributed on the surface of the gelatinous precipitate. (C) dispersing the catalyst precursor at about 260-982.2°C to form a catalyst precursor comprising an intimate mixture of the gelatinous precipitate and the organopalladium compound precipitate; A method for producing a hydrocarbon conversion catalyst, characterized in that the catalyst precursor is converted into a catalyst by performing at least a step of heating for 48 hours.

Porous Inorganic Oxide Support The catalyst of the present invention can be prepared on any suitable inorganic oxide support.

Porous inorganic oxide supports useful in the present invention include a number of materials that can include transition metals.

The inorganic oxide support for the present invention must be porous, i.e. with a surface area of 50 to 7007712/
9 s, more preferably 150 to 700 m/g.

Amorphous silica-alumina supports having an alumina content of 40 to 95% by weight are preferred supports for hydrocracking catalysts.

Metals Any suitable catalytically active metal can be used in the unique catalyst preparation method of the present invention.

Suitable catalytic metals are metals that do not substantially completely coprecipitate with the inorganic oxide at the pH at which precipitation of the inorganic oxide occurs.

The suitability of the metal for use in the present invention is not diminished by the fact that the metal may be chemisorbed to some extent onto the gelatinous precipitate of the inorganic oxide.

Suitably catalytically active metals include transition metals (
Duffle You M Latimer (W, M.

Latimer) and Reference Book of Inorganic Chemistry by J.H. Heldebrand.
Revised version of Inorganic Chemistry),
See page 378 and below, which are three series transition metals as follows: first series, atomic number 2;
2-30 metals, second series metals with atomic numbers 40-48, third series metals with atomic numbers 72-80).

Group 8 transition metals are preferred, and more preferred are noble metals belonging to the Group 8 transition metals, namely ruthenium, rhodium, palladium, osmium, iridium and platinum, of which palladium is most preferred.

The method of the invention uses relatively small amounts, e.g. about 0.0% of the total composition.
01 to about 3% by weight, more preferably about 0
．． Particularly useful are metals preferably blended with the catalyst in amounts ranging from 0.02 to about 1.0% by weight.

When the metal is present in the catalyst in relatively small amounts, it is highly preferred that the metal be in finely divided form and distributed as uniformly as possible over both the internal and external surfaces of the support.

This ensures that more available metal surface area is present in the catalyst.

The catalytically active metal component used in the present invention is preferably a metal component having hydrogenation-dehydrogenation activity.

The most preferred hydrogenation-dehydrogenation metal component is palladium among Group 8 noble metals, and palladium is 0.01 to 3% by weight, more preferably 0.02 to 1.0% by weight.
present in the composition in an amount of

Metals that promote the activity of Group 8 noble metals for hydrogenation-dehydrogenation, such as rhenium, technesium, lead, tin and germanium, are also more preferably present in amounts of 0.01 to 3% by weight of the catalyst composition. is preferably present in the range of about 0.02 to about 1.0% by weight.

These promoters are also generally advantageously incorporated into the catalyst by the method of the invention.

Particular preference is given to producing promoter-added palladium-containing catalysts by the process of the invention.

The term "metal" is used herein to describe the catalysts produced by the process of the invention, which means that the metal or metal component is present in the final catalyst as a metal, as an inorganic compound thereof, or as a metal. It is understood that it can exist as one or several compounds thereof.

Thus, metals of the ζ group can exist as oxides, chlorides, sulfides, etc.

Organic Precipitating Agents Organic compounds suitable for use as gravimetric reagents for the subject metal compounds generally in aqueous media are suitable and anticipated for use in the practice of this invention. .

Suitable gravimetric organic reagents are generally organic compounds that do not have carbon-metal bonds and have at least moderate solubility in water.

In their use, the organic compound reacts or interacts with the transition metal compound by one or more reaction mechanisms including complex compound formation and metathesis and formation of water-insoluble compounds.

Typical reactions are as follows: As shown in particular, the precipitate formed by the reaction of an organic gravimetric reagent with a transition metal compound generally consists of a metal cation and one or more non-metallic compounds of the organic compound. Bonds between electron rich components (such as oxygen, nitrogen and sulfur) are considered to include polar and/or coordination complexes.

For convenience and definition, these are referred to herein as organometallic compounds.

The suitability of a gravimetric reagent depends on the degree to which precipitation of metal components from aqueous solution is desired.

Generally, reagents have a solubility product (Ksp, i.e., (molar concentration of an organic gravimetrically analyzed compound in an aqueous solution) (molar concentration of a metal component in an aqueous solution)) at the precipitation temperature.
fh written by A. A. Noyes,
Qualitative Chemical Analysis
10-3 or less, preferably less than 10-5 in the case of expensive metals, such as Group 8 noble metals.

In a speculative sense, generally above, a satisfactory organic gravimetrically analyzed compound has a water solubility of at least 0.01 molar (moderate water solubility), preferably a solubility of at least about 0.1 molar.
It is necessary to have a mole.

Representative organic gravimetric reagents suitable for use herein include 1,2,3-benzotriazole, nioxime, 1, 10-phenanthroline, α-nitroso-β
-Naphthol, 2-hydroxy-1-naphthaldehyde, dimethylphenylbenzylammonium chloride, phenyl semicarbazide, phenothiazine, thiourea, 2
-Mercaptobenzothiazole, thiophenol, dimethylglyoxime, α-furyldioxime, thionalide, thioacetamide, β-mercaptopropionic acid, 2
, 3-dimercapto-1-propatur, strychnine sulfate, acridine, 2-phenylbenzothiazole, thiobarbic acid, 2-mercaptobenzoxazole,
Thioacetanilide, ammonium p-aminophenyldithiocarbamate, 1-nitroso-2-naphthol,
Salicylaldoxime, benzoylmethylglyoxime, β-furfuraldoxime, α-benzoinoxime, oxalenediamide oxime, 2-thiophene-trans-aldoxime, 2-o-hydroxyphenylbenzoxazole, N-phenyl-N-phenylazo- Hydroxylamine, 6-nitroquinoline, 5-methyl-
8-hydroxyquinoline, quinaldic acid, quinolinic acid,
β-amine becolic acid, α-becolic acid, heselenol, 1,3-dimethyl-4-imino-5-hydroxyiminoaloxane, α,β-bis(hydroxyimino)acetoacetyl-0-t-luidide, 3-hydroxy- 1-
(p-Tolyl-3-phenyltriazine, p-thiocyanatoaniline, p-amine salicylic acid, p-amino-acetophenone, phthalamic acid, 1-naphthylphthalanilic acid, p-tolylphthalanilic acid, 0-carboxyisonitroso - acetanilide, α,β-dioxyimide acetoacetanilide, 2-mercaptobenzimidazole, phenylthiohydantoic acid, diethyldithiophosphoric acid, and similar organic gravimetric analysis reagents (F.
Written by A. Beamish CF, E. Beamish),
The Analytical Chemistry of Precious Metals
hemistry of the NobleMet
als)s, published by Pergamon).

Special types of organic gravimetric reagents, oximes, azoles,
Among the sulfides and analides, azoles are preferred for use in the present invention.

Among the latter, azoles containing aromatic rings, such as 1,
2,3-Benzol-I) azoles, their conventional types and their derivatives with inert substituents are particularly useful for Group 8 noble metals, since they allow efficient precipitation of Group 8 noble metals. Most preferred for use.

Inert related to substituents refers to substituents that do not reduce the catalytic metal component of the transition metal compound to the metal.

It goes without saying that precipitation of transition metal compounds in aqueous media with organic gravimetric reagents is common and that this practice itself is not the subject of the present invention.

Gelatinous Precipitation It is essential for the practice of the present invention to prepare a new gelatinous precipitate of inorganic oxides.

Before forming and intimately mixing the organometallic compound,
If the inorganic gelatinous precipitate is allowed to ripen for some time, a catalyst of inferior quality results.

While not wishing to be bound by this explanation, the longer the delay allows the gelatinous precipitate to develop further, forming "cross-links" which eventually form over the entire surface of the support. This prevents uniform distribution of precipitated metal compounds on the top.

Preferably, substantially immediately prior to precipitation of the organometallic compound, a new gelatinous precipitate of the inorganic oxide is prepared and the precipitated organometallic compound is intimately mixed therewith.

Thus, it is preferred that no more than 2 hours, preferably no more than 1 hour, elapse after the formation of the gelatinous precipitate of the mineral oxide before intimate mixing is carried out.

Intimate mixing is preferably carried out as follows: preparing an aqueous medium consisting of (1) dissolving the gelatinous precipitate precursor and (2) dissolving the metal.

The pH of the solution is adjusted by adding base or acid to it until a gelatinous precipitation results.

An organic precipitant, such as benzotriazole or dimethylglyoxime, is then added to the aqueous slurry of the freshly prepared gelatinous precipitate of the inorganic oxide, while stirring the slurry to convert the dissolved metal into a finely powdered organometallic compound. Precipitate.

Most of this precipitate is formed in situ in the aqueous gel (hydrogel), and the remainder is substantially (at least 95% effective) mixed into the gel by intimate mixing, if any.

Although it is preferable to form a gelatinous precipitate prior to precipitation of the organometallic compound, the method for producing the catalyst of the present invention involves first precipitating the organometallic compound, followed by precipitation of the inorganic oxide or its precursor. This can be done by precipitating.

In this case, it is preferable to use a suitable stabilizer such as casein, polyacrylic acid, etc. to stabilize the finely powdered organometallic compound and prevent particle agglomeration.

The term "intimately mix" is used to mean uniformly distributing the finely divided organometallic compound over the surface of the gelatinous precipitate of fresh inorganic oxide.

It is generally highly preferred to use agitation to more thoroughly achieve intimate mixing.

Stirring may be continuous or intermittent.

Once the finely powdered organometallic compound has been intimately mixed with the fresh inorganic oxide gelatinous precipitate, the resulting mixed organic oxide-gelatinous precipitate can then be processed in conventional manner to produce a practical product. In addition, catalyst particles of useful particle size can be produced.

Generally, the mixed organometallic compound-gelatinous precipitate is prepared into particles, such as by extrusion, and the particles are then heated at about 500° to about 1° C. for about 1 to about 48 hours.
Heat to a temperature within the range of 800°F (approximately 510-982.2°C).

Heating helps break down organic residues.

The heating temperature varies depending on the organic precipitant selected, but is selected to be at least the decomposition temperature of the organic residue.

The heating also serves to calcinate and activate the catalyst composition.

For hydrocracking catalysts, the heating is from about 950° to about 1
Preferably, the process is carried out at a temperature within the range of 800°F (about 510-982.2°C) for about 2 hours to about 8 hours.

The product produced according to the invention, after the heating step,
Within the range of about 100 m/QC to about 500 m/CC, and more preferably from about 200,771"/CG to about 5, especially when the catalyst is a hydrocracking catalyst.
It is preferred to indicate a parameter consisting of a product with a bulk density of 9/cc particles and a surface area of rn'/g particles falling within the range G).

Generally, the method of making the catalyst of the present invention results in at least 95% of the metal being intimately mixed with the gelatinous precipitate slurry to form an organometallic compound-gelatinous precipitate mixture.

The catalysts of the present invention are effective in converting a wide variety of hydrocarbon feedstocks, including petroleum output, petroleum distillation residues, and various recycle stocks.

Hydrocarbon feedstocks are about 400°F to about 1050°
F (about 204.4 to 565.6 °C), more preferably about 500 °F to about 950 °F (about 260 to 510 °C)
It is preferable to boil within the range of C).

The catalysts of the present invention are useful in a number of hydrocarbon hydroconversion processes, including hydrogenation, dehydrogenation, and reforming processes, but are particularly useful when used in hydrocracking processes.

When the method of the present invention is used to produce a hydrocracking catalyst, the organic nitrogen content of the hydrocarbon feed to be hydrocracking is less than about 0.05% by weight, preferably about 0.
．． It should be less than 0.02% by weight, more preferably less than about 10 ppI11.

The organic sulfur content of the feed should also be less than about 0.05 weight percent, preferably less than about 0.02 weight percent, and more preferably less than about 10% by weight.

If desired, the hydrocarbon feedstock may be subjected to conventional hydrorefining pretreatment steps prior to conversion in the presence of the catalyst of the present invention.

The conditions for the hydrocracking method are normal conditions, for example about 450°
Temperature within the range of F to about 859 F (about 2322-465 C), about 500 psig to about 3500 psig
(about 35.2 to 246.1 kg/crir gauge), a liquid hourly space velocity of about 0.5 to about 3.0, and about 1 hydrogen per barrel of feedstock.
00O8CF to approximately 20,0OO8CF (approximately 28.3
~566.3 Nm3), preferably about 200O8C
F to about to, oooSCF (about 56.6 to 283.
2Nm).

When the catalyst is contacted with the hydrogen used in the hydrocracking reaction, some reduction of any metal oxides present to the metal occurs.

This is not harmful, and in fact at the start of the operation the temperature is appreciably higher than the reaction temperature, i.e. high enough to cause smelting of the metal on the catalyst and at the same time a reduction in the metal surface area. is necessary to exert the catalytic hydrogenation activity of the catalyst, as long as hydrogen does not come into contact with the catalyst.

The invention will be better elucidated with reference to the following examples.

Reference Example A prior art catalytic silica-alumina co-gel was prepared according to the following general procedure.

AlCl3・6H201130,? H20! A first solution was prepared by dissolving in M and adding 125 ml of glacial acetic acid.

A second solution is prepared by dissolving 450 g of sodium silicate in 2.5 parts of water.

The first and second solutions are combined to form a mixed solution, and the pH of the mixture is determined.
was adjusted to 6.5 by adding a solution 31 of 2 parts H2O and 1 part NH40H.

The resulting mixture in suspension form was heated to 150'F (approximately 65.6
℃), the pH is readjusted to 6.5, and the mixture is filtered to form a co-gel paste filter cake.

drying the filter cake at 95°F (approximately 35°C);
The solids content is 30%.

The solids were washed four times in approximately 1 ol of a 1% solution of ammonium acetate at 150°F (approximately 65.6°C).

The washed gel was contacted with a solution containing 0.66 g of palladium tetraamine dinitrate in an open book 570d for about 1 hour.

The solution was removed, the co-gel was shaped into 10 to 16 meshes, dried, and a portion was incubated at 450° F. for 4 hours at 100° C. in substantially dry air.
8 hours at 0°F and 1400°F
(approximately 760°C) for 4 hours.

This catalyst was used to hydrocrack a feed having the properties shown in Table 1 below.

The feedstock was hydrocracked in a recirculation operation under the following conditions, total pressure, psi g (kg/crj.

gauge) 1200 (approximately 846) hourly space velocity of liquid, volume/volume/hour 4.0 conversion,
550°F (about 287.8°C) - % of liquid to 60 Recycled Gas Percentage SCF /bbl Feedstock 5600 Boiling Range of Liquid Product to be Recirculated 550°F (about 287.8°C)
) + Catalyst inspection and test results are shown in Table 2.

EXAMPLE Catalyst of the Invention A catalyst according to the invention for precipitating palladium as an organometallic compound was prepared as follows (all parts are by weight unless otherwise specified): solution A was 483 parts of water;
There were 100 parts of glacial acetic acid and 1295 parts of an aluminum chloride solution containing 4.9% by weight of aluminum.

Solution B was 278 parts of sodium silicate solution (containing 28.7% by weight of SiO□) and 1000 parts of water.

Solution B was gradually combined with solution A with rapid stirring.

Obtain a clear solution.

The combined solution was adjusted to pH with a solution of 3 volumes of water to 1 volume of concentrated NH40H.
It was titrated to 6.0 to form a gelatinous precipitate.

Pd (N 03 ) 2 and (Pd (N
A solution containing 0.441 parts of palladium dissolved as H3)4)(NO3)2 is added to the gel.

Stir the mixture rapidly for about 15 minutes to ensure that the palladium is evenly distributed throughout the gel.

Next, 83 parts of a fishing rod containing 1.49 parts of 1°2.3-benzotriazole dissolved therein was added to the gel.

Addition of dissolved palladium and benzotriazole was completed within about 40 minutes after completion of the gel precipitation step.

The mixture was stirred rapidly for 15 to 20 minutes to ensure that the benzotriazole was evenly dispersed throughout the gel.

Benzotriazole reacted with palladium to form an insoluble inorganic metal compound.

■ 3 parts of 3A After aging, the slurry is heated to 140°F (approx.
0 °C), adjust the pH to 6.4, and filter and incompletely dry the slurry to reduce the volatile content to about 70%.
I made it.

17.6 parts of this cake was molded and dissolved in about 55 parts of water containing 1% by weight ammonium acetate and having a pH of 6.0 at 150°F (about 65.6°C) for 5% hourly.
I had it replaced twice.

After exchange, the catalyst was washed once in water and incompletely dried to a volatile content of 32.5% by weight.

This material was heated to 950°F (approximately 510°C) for 3% of the time at 400°F (approximately 2044°C) in a substantially chemical atmosphere.
) for 5 hours and 1400°F (about 760°C) for 2 hours to produce a finished catalyst.

The initial F solution contained 0.4 to 0.5 ppm palladium.

The P solution yielded about 3250 parts, so it contained about 0.6 to 0.75 g of palladium.

More than 99.5% of the palladium thus added remained in the filter cake.

Analysis of the final catalyst confirmed that essentially all of the added palladium was in the finished catalyst.

This catalyst was tested using the same charging and testing conditions as in Example 1.

The inspection and test results of the catalyst are shown in Table 2.

Langres obtained with this catalyst (length of continuous operation period)
was 50% longer than obtained with the corresponding prior art catalyst.

This was achieved without sacrificing product selectivity.

Additionally, the hydrogenated component is added during the normal manufacture of the silica-alumina component, thereby eliminating the need for costly steps associated with impregnation with the hydrogenated component.

As in the examples above, it is usually more preferred to intimately mix the metal compound into the gel-like precipitate, followed by introduction of the organic gravimetric reagent and ensure precipitation of the organometallic compound.

The order of introducing reactants, soluble metal compounds and organic gravimetric reagents may be reversed.

In this case, the gravimetric analysis reagent is intimately mixed with the gel and a substantial portion thereof is incorporated therein, and the water-soluble transition metal is then similarly incorporated into the gel.

Again, the desired insoluble organometallic compounds, complex compounds and/or insoluble metathesis products are formed substantially in situ in the gelatinous precipitate and produce useful catalyst precursors.

In view of the above, it should be clear that the method of the present invention is generally an effective method for producing transition metal compound catalysts.

It is evident that many widely different embodiments of the invention may be made without departing from the scope and spirit of the invention, and therefore no limitations are intended other than as disclosed in the claims.

Claims (1)

Claims: 1(a) intimately mixing a solution of a palladium compound in an aqueous medium containing a gelatinous precipitate of an inorganic oxide of silica and alumina or a precursor thereof to form a mixture; (b) By intimately mixing a solution of an organic precipitant for gravimetric analysis in the mixture, the palladium compound is reacted with the precipitant, and a finely powdered organic palladium compound precipitate is deposited on the surface of the gelatinous precipitate. (c) dispersing the catalyst precursor uniformly over the mixture to form a catalyst precursor comprising an intimate mixture of the gelatinous precipitate and the organopalladium compound precipitate; 1
By performing at least the step of heating for ~48 hours,
A method for producing a hydrocarbon conversion catalyst, comprising: converting the catalyst precursor into a catalyst.