JPS59133289A - Treatment of hydrocarbons under presence of catalyst based on alumina sphere formed by drip coagulation - 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 The present invention is based on (a) a matrix or support based on alumina and (6) noble metal J-3 of group (I) and at least one other metal used as a promoter. - various treatments of hydrocarbons in a heterogeneous phase in the presence of a catalyst comprising an active layer.

At least a portion of the alumina 71-lix or support is used in spherical form, the manufacture of which is unique to the present invention. Catalysts prepared in this way can be used for dehydration, hydrosulfidation, hydrodenitrification, desulfurization, hydrodesulfurization, dehydrohalogenation, reforming, steam reforming, cracking, hydrocracking, hydrogenation, dehydrogenation. oxidation, isomerization, disproportionation, oxychlorination, dehydrocyclization of hydrocarbons or other organic compounds, oxidation and/or reduction reactions, Claus reactions, treatment of internal combustion engine exhaust gas, demetallization. Suitable for carrying out reactions.

Among others, mention may be made of catalytic reforming processes (i.e. reforming) as well as catalytic aromatic hydrocarbon production processes, which include e.g. a degree, 0.1 to 5 MPa (0°1 MPa
a + 1 kg/cA) of liquid charge per hour per volume of catalyst.
This method is carried out at a hydrogen/hydrocarbon molar ratio between 1 and 20, with a space velocity between 1 and 20.

Also included are hydrocranking reactions, which are generally carried out at temperatures comprised between about 260 and 530°C and pressures comprised between about 0.8 and 25 MPa.

This catalyst is also suitable for the isomerization reaction of aromatic hydrocarbons (e.g. xylene), which usually have a
The reaction is carried out at a temperature between 0.9C and a pressure of about 0.005 to 7 MPa, with a volumetric flow rate of 0.1 to 10 times the catalyst volume per hour.

Furthermore, this catalyst is suitable for the isomerization of hydrocarbons having 4 to 7 carbon atoms in a hydrogen atmosphere at temperatures comprised between 50 and 250°C.

The catalyst is also suitable for the hydrodealkylation of aromatic hydrocarbons or the steam dealkylation of aromatic hydrocarbons, which reactions produce e.g. benzene from toluene or from other alkylbenzenes. Under known operating conditions for
It is carried out between

The catalysts used in the above-listed reactions are made of an alumina-based matrix or support;
On or in alumina it is possible to introduce so-called active phases based on at least one metal from the periodic table and, since about 20 years ago, in most cases at least two and more metals. It is something.

Catalysts consisting primarily of an alumina support and containing only one metal, e.g. of group I, without promoter metals, exhibit a marked improvement in their properties when prepared according to the method that is the subject of the invention. Well, I can't see it.

Special catalysts suitable for the process according to the invention are therefore catalysts comprising an alumina support and a critical content of various suitable metal elements (metals or metal compounds). Thus, specialized catalysts for the reforming or production of aromatic hydrocarbons or other reactions mentioned above are generally based on the weight of the alumina matrix or support (hereinafter the general term ``support j'' will be used). , a) platinum, palladium,
Iridium, Ruthenium, Rhodium and Osmium (
and preferably platinum and/or iridium).
2-1% and b) at least one additional metal or co-catalyst 0.01-1%;
2% and optionally C) 0.1 to 10% of at least one halogen, e.g. chlorine or fluorine, for reactions such as reforming, aromatic hydrocarbon formation, certain isomerizations, etc. This includes:

Catalysts considered preferred for the present invention include, more particularly, platinum, platinum and iridium, platinum and titanium, rhenium, tin, germanium, indium, thallium, manguin, nickel, iron, cobalt, zinc, copper, gold, At least one of the metals selected from the group consisting of silver, niobium, lanthanum, cerium, samarium, zirconium, 1~lium, hafnium, lead, gallium, vanadium, technetium, uranium, platinum, rhenium and platinum, iridium and at least one of each of the other metals listed above, platinum, germanium and at least one of each of the other metals listed above, platinum, Catalysts containing tin and at least one of each of the other metals listed above, platinum, indium and/or thallium and at least one of each of the other metals listed above, etc., are mentioned.

Table 1 shows in particular the advantages of the method according to the invention in increasing the pore volume of the spheres produced.

According to the invention, the alumina spheres used as carriers are formed by dropwise condensation under special conditions explained below.

According to European Patent No. 15801, the so-called "drip in oil"
) or [drop condensation j (COaQulatiOn
It is known that alumina spheres with twice the porosity can be prepared by a technique called en(]0utteS).

The method described in this European patent comprises a mixture of a sol of ultrafine boehmite or pseudo-boehmite and spherical particles of alumina at a pH below 7.5 (the proportion of alumina is between 30 and 95% by weight). Included in Boehmai 1-
The proportion of is comprised between 5 and 25%).

Oval formation and gelation from droplets of the mixture used are carried out by dropping the droplets of the mixture into a column containing an upper oil phase consisting of petroleum and an aqueous phase F consisting of an ammonia solution.

Molding takes place in the upper phase, and gelling takes place primarily in the r-oil phase. The temperature of petroleum is generally near freezing, and the ammonia solution has a pH maintained at a value of about 9 or higher. The residence time of a droplet in ammonia is several minutes,
Generally less than about 15 minutes. Under these conditions, the recovered balls are sufficiently rigid that they do not deform during subsequent manipulations.

The process for producing alumina according to the invention is an improvement on the process for producing shaped alumina spheres by dropwise condensation, which shows extremely low losses during friction and is a catalytic process that operates as a moving or ebullated bed or with catalyst recirculation. You can get a ball with a particularly right-handed flow.

Although the sphere obtained by the method of the present invention has a large total pore volume, its hardness is not significantly impaired. This feature makes its use as a catalyst or catalyst support particularly advantageous. This is because the light weight of this sphere reduces its thermal inertia and thus allows it to reach its operating temperature most rapidly.

The process for producing alumina spheres according to the invention involves forming by dropwise condensation of an aqueous suspension or dispersion of alumina or a solution of a basic salt of aluminum, followed by collection, drying and roasting of the formed spheres. Specifically, the present invention is characterized in that the aqueous alumina suspension, dispersion, or aluminum salt solution is in the form of an oil-in-water emulsion. The total f1 degree of alumina in an aqueous suspension or dispersion of alumina or a solution of a basic salt of aluminum is usually comprised between 5 and 30% at Q/1. The emulsion has a viscosity of 100 to 800 centipoise (1 c
st = mm2/s), preferably between 300 and 400 centipoise.

The increase in total pore volume appears to be due to the force of the emulsion creating porosity inside the spheres after torrefaction.

In the following, we briefly describe the main methods of the prior art by which alumina forming can be carried out by dropwise condensation: 1) from an aqueous suspension or dispersion of alumina and 2) from a solution of a basic salt of aluminum.

1) Processes for producing alumina spheres, including forming by dropwise condensation of an aqueous suspension or dispersion of alumina, recovery of the formed spheres, drying and roasting, fall into three distinct categories.

(a) The first category relates to methods based on increasing the pt-1 of aqueous suspensions or dispersions of alumina, which results in gelation of the droplets.

Such methods, using either aqueous suspensions or dispersions of alumina, are described in the literature and in particular in U.S. Pat.
No. 435379, No. 2620314, No. 3346
No. 336, No. 3096295, No. 3272!34, No. 1023, and No. 15801. The preferred technology is European Patent No. 1580.
This is what I mentioned earlier in relation to No. 1.

(b) The second category consists of forming droplets of alumina aqueous suspensions or dispersions by drying or by introducing or suspending the droplets in an immiscible liquid such that the water can be removed. Relating to a method based on removing water from. At this time, gelation of the droplets occurs. The drying or immiscible liquid extracts water from the droplet, causing it to gel into an oval shape. Examples of immiscible liquids include 2-ethyl-
1-hexanol or a long chain aliphatic alcohol may be used. The main steps of such a method are, among others
Chemical Eng, kneelingSym
posiumseries 1967.6.3, No.
80. P, A, Haas, F on pages 16-27
, G. Kitts and H. [3 entler, and ReV, Int., Hautes Temp.
1et Refract, 1972, Volume 9, 1
1 on pages 97-204. Anlat S and D, M
It is described in the paper by Artorana.

(C) The third category relates to methods based on cross-linking of polymers resulting in gelation of the droplets. □According to this method, an aqueous suspension or dispersion of alumina is
A water-soluble monomer whose non-crosslinked polymer dissolves in water or forms a gel.

The mixture obtained in the form of droplets is then dispersed in a hot fluid medium in which substantial polymerization of the monomer (eg acrylic) takes place.

The main steps of this type of process are described, inter alia, in French Patent Nos. 2,261,056 and 2,261,057.

In the case of the above three classes of processes, the aqueous suspension or dispersion of alumina used according to the invention is capable of gelling;
Also, make it clear that it must be capable of condensation.

The aqueous alumina suspensions or dispersions that can be used are inter alia of suitable sizes in the coid region, ie about 2
It is an aqueous suspension or dispersion of fine or ultrafine boehmite consisting of particles of 000A or less.

This aqueous dispersion of fine or ultrafine boehmite or @
Suspensions can be obtained by peptidation of these substances in water or in acidic water, and are described in particular in French Patents No. 1,261,182 and No. 1.
It can be obtained according to the method described in No. 381282 or European Patent No. 15196.

FR 1 261 182 describes a process for producing fine or ultrafine boehmite by heating an aqueous dispersion of alumina in the presence of monovalent acid groups.

French patent No. 1 381 282 contains up to 35% by weight of alumina calculated as Al2O3 and
0.05 for this alumino calculated as a molecule of
converting a suspension or cake of an amorphous alumina hydrate salt containing monovalent acid ions in an amount of ~0.5 at a temperature comprised between 60 and 150<0>C;
A method for producing fine or ultrafine boehmite is described.

EP 15196 discloses, inter alia, the production of at least partially ultrafine boehmite by treatment in an aqueous medium with a p l-19 or less of activated alumina powder obtained by rapid dehydration of hydrargillite in a hot gas stream. A method for producing boehmite in the form of is described.

Also, pseudoboehmite, amorphous alumina gel,
Aqueous suspensions or dispersions obtained from aluminum hydroxide or ultrafine hydrargillite can also be used.

Pseudoid boehmite is described in US Pat. No. 3,630, among others.
670, by reaction of a solution of an alkaline aluminate with a solution of an inorganic acid. This also applies to French Patent No. 13
As described in No. 57830, the dispersion width is approximately 50 c+/
Precipitation in at-19 at a temperature slightly above room temperature from l reactants yields alumina of lf'.
: You can also manufacture it in advance.

The amorphous alumina sol is, inter alia, A 1coap a
per No. 19 (1972), pages 9-12, in particular by the reaction of an aluminate with an acid, or the reaction of an aluminum salt with a base, or the reaction of an aluminate with an aluminum salt;・It can be produced by hydrolysis of alcoholade.

Aluminum hydroxide gels may be those produced by the methods described in US Pat. No. 3,268,295 and US Pat. No. 3,245,919, among others.

Ultra-fine hydragillite is an alumina gel in the form of a cake, in particular according to the method described in French patent no. may be manufactured by changing the temperature between room temperature and 60°C.

Ultra-pure boehmite or pseudo-boehmite prepared by reacting an alkaline aluminate with carbonic anhydride to form amorphous aluminum hydroxycarbonate, separating the precipitate obtained by filtration and washing it. It is also possible to use aqueous suspensions or dispersions (this process is described inter alia in US Pat. No. 3,268,299).
5).

If it is desired to produce an extremely pure alumina catalyst support, an aqueous suspension or dispersion of ultrapure boehmite or pseudoboehmite, preferably produced according to the methods described above, or U.S. Pat.
A veptized aluminum hydroxide gel prepared from the hydrolysis of aluminum alcoholade by a method of the type described in No. 8 is used.

Thus, aluminum hydroxide gels of the Boehmei type 1~ are obtained as by-products in the production of alcohols by hydrolysis of aluminum alcoholades, i.e. alkoxides (Ziegler synthesis). Ziegler's alcohol synthesis reaction is described inter alia in US Pat. No. 2,892,858. According to this process (first of all, triethylaluminum is prepared from aluminum, hydrogen and ethylene), the reaction is carried out in two stages with partial recycling of the 1-ethylaluminum.

Ethylene is added in the polymerization step, and the product obtained is then oxidized to aluminum alcoholade (X), and the alcohol is obtained by hydrolysis.

A paste of aluminum hydroxide, optionally dried and torrefied, yields a suitable alumina.

The neutralized alumina obtained as a by-product in the Daegler reaction is described inter alia in the C0N0CO report of January 19, 1971. The products described in this report are marketed under the trademark "CATAPAL". In addition, C0NDEA CHEMIE also sells such products as rPURAL and rD l5PUR.
It is commercially available under the trademark "LAL■". When these alumina hydrates are provided in gel form, they have been peptized with water or acidic solutions.

2) The method for producing alumina spheres, which involves forming by dropwise condensation of a basic solution of aluminum, is Al1(Of-1)xAy
A basic salt having the general formula is used. In the above general formula, O<x<5 and n<y<6, and n represents the number of charges on the anion A. The ion A is selected from the following. Namely, nitrate, chloride, sulfate, perchlorate, chloroacetate, dichloroacetate, trichloroacetate, bromocitate, dibromoacetate and anions having the general formula 1 -C-0- , in which R is, for example, tho, CH3, C2H5, CH3CH2CH2, (CH3
) represents a group selected from the group consisting of 20H.

It is generally preferred to use the hydroxychloride of aluminum. These basic salts of aluminum can be prepared during the digestion of metallic aluminum in HA acid or MA3 solution, electrolysis of aluminum salt solutions, base neutralization and formation of more or less basic aluminum salts. The reaction of aluminum salts with electron donors such as ethylene oxide and the removal of reaction products, the reaction of aluminum salts with long-chain aliphatic amines with water-immiscible solvents, etc. contact, followed by recovery and concentration of the aqueous phase containing basic salts, veptization of the freshly precipitated alumina gel, and erosion of the aluminum oxide or aluminum hydroxide by HAM.

According to the present invention, it has been found that an alumina-based catalyst prepared from an aqueous suspension or dispersion of alumina or a solution of a basic salt of aluminum has excellent robustness in hydrocarbon treatment reactions. . In the present invention, the aqueous alumina suspension, dispersion, or aluminum basic salt solution is made into an oil-in-water emulsion under special conditions, and then this emulsion is formed into an oil-in-water emulsion. is poured into a column containing an upper organic phase and a lower aqueous phase in order to carry out the above-mentioned shaping by dropwise condensation.

The technology of the present invention makes it possible to avoid operating during forming by drop condensation, sometimes in the presence of detergents (or water-soluble surfactants) in the lower aqueous phase. I will give an example.

This technology was developed by Nakazuku, French Patent No. 1492326.
[Hydrophilicity-lipophilicity-equilibrium J (1-N'droph
ile -L 1pophyle-Ba1ance, herein abbreviated as H, L, B).

As is well known, a water-based (or oil-in-water) emulsion is a heterogeneous system (hereinafter referred to as "organic phase") consisting of a dispersion of fine globules of a single liquid in water. has come to form a continuous phase in the presence of a surfactant or emulsifier, and this surfactant or emulsifier changes the properties of the interface between the two liquids so that the This makes it possible to achieve excellent dispersion of the J machine phase.

According to the invention, the dispersion to form the whey is carried out during stirring of an aqueous dispersion or suspension of alumina or a solution of a basic salt of aluminum in the presence of a surfactant or emulsifier. The emulsions thus prepared are between about 100 and about 800 centipoise, preferably 3.
It must exhibit a viscosity comprised between 0.00 and 400 centipoise. Viscosity, which is not shown here, is measured using the so-called "Quen 1~" method, which is a concentric cylindrical meter (1C
st==1 mm2/s).

The volume fraction of the organic phase in the aqueous phase is between about 1 and about 10% (as the aqueous phase represents the free water present in the emulsion);
Preferably it is comprised between about 4 and about 9%. This ratio affects the mechanical robustness of the alumina spheres produced by the method of the present invention (in the Suimei Book, the expression "hydrocarbon/autogenous water ratio" is used to describe the ratio in the aqueous phase). The organic phase of an emulsion is a substance that is not completely miscible with water, can be removed by combustion, and is a liquid at room temperature. We must become more and more. This organic phase is the most frequently encountered dispersed phase in industry and is comprised of the following classes: oils, crude paraffins and mineral waxes.
ses et cires), fatty substances (grileride or celite) and customary solvents. Preferably petroleum (i.e. any petroleum-based hydrocarbon charge, e.g. petroleum fraction) and/or with a density of 0.7
Use kerosene close to 8.

The surfactant or emulsifier is selected to ensure stability of the emulsion. It must also be removable by combustion and must be liquid at room temperature. Since one is attempting to prepare an oil-in-water emulsion, a surfactant that tends to be hydrophilic is selected. The choice of this reagent is well known to the person skilled in the art, inter alia [E
mulsion: theory and pract
ice by pal Becker 1957
Re1nhold Publishing Corp.
It is carried out according to the technique described in the book RationJ.

However, the selected surfactant H, L, B.

It is of paramount importance that the number of particles is close to that of the organic phase to be dispersed, ie generally comprised between 11 and 20, preferably between 12 and 18.

This particular selection of H, L, B is important in the case of catalysts containing at least two active metals (particularly bimetallic and trimetallic catalysts). The H, L, B, and indexes are, for example, W.

C, GRIFFIN's paper (Q ff1cial [)
igent28.1965, No. 377446
).

The weight proportion of emulsifier to organic phase is between 2 and 8%, preferably between about 5 and 8%.

Shaping by dropwise condensation of an aqueous suspension or dispersion of alumina or a solution in the form of an oil-in-water emulsion of a basic salt of aluminum is then carried out according to known techniques as reproduced below. The resulting spheres are subsequently collected, dried and roasted.

The suspension or dispersion of alumina or solution of a basic salt of aluminum used may contain a charge of alumina.

The proportion of the charge in the solution, dispersion or suspension is up to 90% by weight as A[203, based on the total alumina.

The size of the alumina particles making up the charge may vary within wide ranges. This generally falls between 1 and 50 microns.

The alumina charge used may consist entirely of alumina. In particular, hydrated alumina compounds such as hydrargillite, bayerite, boehmite, pseudo-boehmite and amorphous to substantially amorphous alumina gels may be used. made of transition alumina, and ρ,
Dehydrated or partially dehydrated forms of these compounds containing at least one phase taken from the group consisting of θ, δ, α in χ, η, γ can also be used.

When it is desired to produce an extremely pure alumina catalyst support, it is preferable to dry and roast an aqueous suspension or dispersion of ultrapure boehmite 1 or pseudoboehmite prepared according to each of the methods described above. or an aluminum hydroxide gel prepared from the hydrolysis of aluminum alcoholade.

According to a variant of the invention, a portion of the suspension or dispersion of alumina or the solution of the starting basic salt of aluminum is added, for example to
, VB, VIB.

m A, IVA, VA, VIA, VI class f
7) It is possible to change the nature of an element by using a sol of another element. In addition, the starting material suspension, dispersion, or solution may be treated with various salts, especially salts from IB, IB, etc. on the periodic table.
IB,IVB,,VB,'I[[A.

It is also possible to mix with salts consisting of metals of groups IVA, V8, ■■VIII, ■ and elements of group VIB.

It is also possible to mix the starting material suspension, dispersion or solution with any active or inactive compound as a catalyst. Among these compounds, 1B, I[B, 1111B, IVB, VB, , VI[B
, IA, IIA.

111A, IVA, VA, VIA, metals of groups 83, 8, and 83 J: and powders of elements of group VI salts, solid solutions and mixed oxides thereof.

The characteristics of the spheres that can be obtained by the techniques described above are extremely wide. These balls are, inter alia, 0.30-3c
Total hole volume which may be between m3/Q and 350
Specific surface area that can reach up to m2/g and 95%
As mentioned above, the 1-hole 1 mode (mono modale) or 2 mode (bi
may not exhibit a modale structure.

If the spheres are produced from a suspension or dispersion of ultrapure alumina, optionally in the presence of an ultrapure alumina feed, such spheres may be subjected to hydrodesulfurization, reforming,
It is particularly effective as a catalyst support for hydrotracking, isomerization and steam reforming reactions.

The examples listed below as non-limiting examples serve to illustrate the invention without limiting its scope.

In the examples, compressed packing density (DRT) is measured as follows. That is, agglomerates 1 to 1 of a given weight are placed in a measuring cylinder to accommodate agglomerates 1 to a given volume. The graduated cylinder is then oscillated until the compression settling is complete and a constant volume is obtained. Next, calculate the weight of the agglomerate that occupies a unit volume.

The total combined pore volume (V P ”r ) is measured as follows: Define the density and absolute density values of the particles. The density (Dq) and absolute density (Da) of the particles are mercury and helium, respectively. It is measured using the specific gravity method using

VPT is determined by the following formula.

7 people, 1,000,000 1 VPT=--□ Dg [)a Specific surface area (SBE) is measured using the B, E, T method.

Mechanical fastness (EGG) is measured using the particle-by-particle crush method. This method measures the maximum compressive force that one particle can sustain before it breaks when the product is placed between two surfaces moving at a constant speed of 5 cm/mn. In the special case of a ball, this force is denoted by 3.

Mechanical fastness (EGG) is related to total pore volume (VPT) by the 5chler law. That is, EGG=A Lop qxVPT where A and B are constants. Therefore, as the porosity of the product increases, the EGG decreases. Therefore, it is difficult to produce products that are porous and at the same time robust.

Abrasion strength (AIF) is measured as the percentage of the product that does not wear out due to friction, according to the method below. A given volume (60 cm3) of agglomerate is placed in an inverted Erlenmeyer flask of special construction connected to a metal inlet. Opening 1.168m at the bottom of the Erlenmeyer flask
A large outlet (>2.54 cm) is provided, covered with a sieve of 2.5 cm. From the inlet a strong stream of dry nitrogen is introduced, which has two effects: on the one hand, it circulates the agglomerates facing each other; , which causes its wear due to friction. On the other hand, it causes an impact of the age 1] melate against the Erlenmeyer flask, which, depending on the strength of the impact, causes its destruction. The product is tested for 5 minutes and no residual Determine the weight of the agglomerate, expressed as a percentage of the original charge.

The decrease in weight after the test indicates the abrasion strength A1. Show F.

The catalyst prepared according to the invention is particularly suitable for use as a moving bed with regeneration of the catalyst removed from the reactors and return of the regenerated catalyst into these reactors. A process considered preferred employs several moving bed reactors and operates as follows. That is, the feed flows through each reactor or reaction zone in an axial or radial direction (radial direction means from the center to the periphery,
or flow from the periphery to the center) circulate one after another.

The reaction zones are arranged in series, for example side by side or stacked. It flows sequentially through each of the reaction zones, preferably with intermediate heating of the feed between the juxtaposed reaction zones. Fresh catalyst is placed above the first reaction zone which receives fresh feed. The catalyst then flows successively from the top to the bottom of this reaction zone and is gradually removed from the bottom by any suitable means (in particular a lift in the case of side-by-side reactors). Ru. The catalyst is transported to the top of the next reaction zone,
Within it, it flows successively from top to bottom, and in the same way, it reaches the last reaction zone. In this last reaction zone the catalyst is likewise gradually removed and then sent to the regeneration zone.

Upon exiting the regeneration zone, the catalyst is progressively introduced into the upper part of the first reaction zone. To take out the catalyst several times, as shown above,
It can be done either "gradually", i.e. periodically, or continuously.

Continuous withdrawal is preferred over periodic withdrawal.

Example 1 Into a tank containing 130ml of deionized water, the following four items are added one after another with strong stirring.

63% nitric acid 27001° As a product of alcohol production by synthesis of Daegler 1
AL・037 from Condea
Boehmite-type aluminum hydroxide gel 33.3CI, commercially available under the registered trademark 5% rPtJRAL SB, J. The aforementioned gel was roasted at 650°C and had particles with an average diameter of 4 to 5 microns. Alumina charge of 9 kg, consisting of crushed alumina contained between 010 and C13 paraffinic hydrocarbons, commercially available under the trade name rsOLPAR 195-230 from P.H, L, B.

14 nonionic emulsifier rGaloryl EM■ 10” mixed with 450cm3 to 7! /.

The viscosity of the suspension after 4 hours of gentle stirring is 350 centipoise (1 cst=1 m''/s).

This suspension contains 18.5% Al2O2,
The charge ratio or percentage of torrefied alumina to total alumina is 26.5%.

The proportion of the organic phase in the aqueous phase is referred to as the "hydrocarbon/free water ratio".
It is 5% (by volume). The ratio of emulsifier to hydrocarbon is 64%.

The suspension was prepared using a tube with an inner diameter of 1.3 mm and an outer diameter of 1.8 mm, and an upper phase consisting of petroleum with a thickness of 6 cm and a concentration of 20 g/l.
of NHa is added dropwise into a column containing a lower aqueous phase consisting of an ammonia solution containing NHa.

The recovered hydrogel spheres are dried and roasted at 550°C.

The characteristics of this ball are shown in Table ■.

Example 71 Color Example IA (Comparative Example) The preparation of the suspension and the gelation of the droplets are the same as in Example 1.

However, 1 Kg of hydrocarbon and [Qa l] in the suspension.

Insert ryl EM 10■j225cm.

The hydrocarbon/free water ratio became only 75%.

The characteristics of the balls dried and roasted at 50°C are as shown in Table 3.

Example 2 Preparation of a suspension and gelation of droplets were carried out in the same manner as in Example 1 (J).

No alumina charge is introduced.

Under these conditions, the rice suspension contains 15% A[203].

The hydrocarbon/land water ratio is 5% by volume, and the ratio of emulsifier to hydrocarbon is 6.4%.

The characteristics of the dried and roasted spheres are shown in Table ■.

Example 3 The preparation of the suspension and the gelation of the droplets are carried out as in Example 1.

63% nitric acid 21 ■ Aluminum hydroxide gel f'PURAL SBJ4
01 (g Alumina charge 21.2Kg rGaloryl EM 10■J (H,L.

B, 14 > 500 cm” mixed with hydrocarbons [5olp
ado■195-230J 10Kg.

The viscosity of the suspension after 4 hours of gentle stirring is 350 centipoise.

Under these conditions, the suspension contains 25% At203, the percentage of torrefied alumina charge to total alumina is 40%, the percentage of hydrocarbon/free water is 8%, and the percentage of emulsifier to hydrocarbon is 5%. It is.

The characteristics of the dried and roasted spheres are shown in Table ■.

Example 4 ΔL20381 Cl/l and Na2061.3C
The sodium aluminate filtered solution exhibiting a temperature equal to 1/l is placed in a glass reactor equipped with an automatic stirrer, a temperature probe and an electrode for pH measurement.

A stream of CO2 gas is passed through at atmospheric pressure under strong stirring so that a small excess leaves the reactor.

The temperature is increased to 40'C and then cold water is circulated to the outside to fix the temperature at this value. 11 minutes later pl-1
When the temperature drops to 9.5, the flow of 002 is cut off and the mixture is stirred for an additional 5 minutes. The precipitate is separated by filtration and the specific resistance is 3.
The 101,050 h·cm filtrate is washed on the filter with water switched to 30°C until IG. d on the sample collected from the filter cake dried in air at 30°C.
3 and no crystal structure detected. The roasting residue (Al103) at 1000°C is 51°3% by weight.

The resulting washed hydroxycarbonate precipitate is mixed with an aqueous ammonia solution, in which the concentration of aluminum compounds, denoted by At2Q3, on the one hand is 50 g/l, and on the other hand the concentration of NH4'' ions. (Calculated assuming complete ionization of ammonia or the reaction product of ammonia and hydroxy carbonate) This amount is sufficient so that the molar ratio to the concentration of aluminum compound expressed as Al2O3 is 0.20. To carry out the mixing, the ammonia solution is gradually poured into the aqueous suspension of the hydroxycarbonate under vigorous stirring.The pH of the aqueous medium thus obtained is 10.2.

In the second step, the treatment medium originating from the first step is heated to a temperature of 85° C. for 4 hours under atmospheric pressure.

In the third step, the treatment medium from the second step is heated to 150° C. for 6 hours. A suspension of Beichimai 1 is obtained which is filtered, washed with water and dried at 100'C.

n+>Pour the following into a tank containing 9.31 ion water in order while stirring vigorously.

63% nitric acid 150 (?lI+") To boehmite obtained by the above operation 2160 Alumina charge obtained by roasting the above boehmite at 600°C 14400 f'Ga1oryl EM 10■J ('H,L
.

B, 14) Hydrocarbon rs mixed with 36 cm”.

1par ■195-3'20J 7200° The viscosity is about the same as in each of the above.

Under these conditions, a suspension is obtained containing 25% Al2O3 and having a proportion of alumina loading of 40% relative to total alumina, a proportion of hydrocarbon/free water of 8% and a proportion of hydrocarbon-resistant emulsifier of 5%.

Gelation of the droplets is carried out as in Example 1.

The characteristics of the dried and roasted spheres are shown in Table ■.

Example 5 (Comparative Example) The preparation of the suspension and the gelation of the droplets are carried out in the same manner as in Example 1.

Do not add emulsifiers to hydrocarbons.

The hydrocarbon/land water ratio is equal to zero.

The viscosity after mild stirring between 7'lII and - is 250 centipoise.

The characteristics of the dried and roasted balls at 550'C are shown in Table 1.

EXAMPLE 6 Several catalysts are prepared having an alumina support and each containing 0.4% platinum, 0.5% iridium and 1.12% chlorine by weight. Example 1 as an alumina carrier
．． Each of the three alumina supports prepared in 2.3.4 and 5 are used in turn to obtain five catalysts Δ1-A5, respectively, prepared as follows.

Examples Each aluminum boo prepared in Examples 1 to 5
100 g i , ) order 1-1c; 1 (d = 1.19) 1.96q 17 cm3 of an aqueous solution of chloroplatinic acid containing 2.35% by weight of platinum and 17 cm3 of an aqueous solution of chloroiridic acid containing 2.3ff of iridium and 11% of chloroiridic acid.
Add 100 cm" of an aqueous solution containing 4.5 Cm3.

Leave in contact for 5 hours, dehydrate, and dry at 100° C. for 1 hour. It is then roasted in dry air at 530° C. for 4 hours (drying with activated alumina).

Next, under a stream of dry hydrogen (activated alumina)
Reduce for 2 hours at °C.

The specific surface areas and pore areas of catalysts A and -A5 thus obtained are as follows.

Specific surface area Pore area (m2/g) (cm3/(])A+ 2
05 0.60 A2 195 0.53 A3 195 0.63 A/, 215 0. b9 A5 205 0.37 Example 7 In order to obtain a gasoline with a simple octane number equal to 103, naphtha with the following characteristics was treated.

ASTM distillation: 80-160℃ Composition: Aromatic hydrocarbons: 7% naphthenic hydrocarbons: 2
7% paraffinic hydrocarbons: 66% by weight 1 “Single research method” Octane number: Approximately 37 Average molecular weight
:Density at 11020℃
:0.782 This sofry passes over catalysts A, ~A5 together with recycled hydrogen.

Operate continuously in a moving bed reactor.

The operating conditions are as follows.

Pressure: 1MP
a Temperature: 530°C Hydrogen/hydrocarbon cumulative molar ratio: 8 Naphtha capacity/catalyst volume/hour: 1.65 The table ■ below shows 20
The yield of C5+ ie hydrocarbons having 5 or more carbon atoms obtained after 0 hours and the percentage of hydrogen contained in the recycle gas are shown.

When catalysts are prepared according to the invention (A+ to A4), significant gains in yield and recycled hydrogen are observed compared to catalysts not prepared according to the invention (A5).

Below is a blank table. Example 8 A series of catalysts containing platinum and chlorine containing the same catalysts A and A5 prepared in Example 6 were newly prepared.

These catalysts are made from supports prepared by the techniques of Examples 1 and 5. Instead of iridium, these
The catalyst contains 0.5% I of another cocatalyst. Catalysts B and B5 therefore contain 0.5% rhenium, but B has the support of Example 1 and B5 has the support of Example 5. Aqueous solution 100c poured onto 100Q alumina
m3 (in addition to 1.96 g of concentrated HCl with a density of 1.19 and 17 cm3 of an aqueous solution of chloroplatinic acid with a concentration of 2.35% by weight of platinum) 51 c of a solution of perrhenic acid with a concentration of 0.98% by weight of rhenium
Contains m3.

Touch tRC, and C5 contain 0.5% tin,
C1 has the carrier of Example 1, and C5 has the carrier of Example 5. 100 cm@3 of the aqueous solution poured onto the alumina contains 2.5 g of tin acetate at 20%.

Catalyst D1 and B5 contain 0.5% thallium, but catalyst D1 has the support of Example 1 and B5 has the support of Example 5. 100 cm3 of aqueous solution poured onto alumina contains 2.50 cm3 of thallium acetate solution containing 20% by weight of thallium.

Catalysts E1 and E5 contain 0.5% indium, with El having the support of Example 1 and E5 having the support of Example 5. 100 cm of water FBR poured into alumina contains 1.870 indium nitrate.

Catalysts F1 and F5 contain 0.5% titanium, while F,
F5 has the carrier of Example 1, and F5 has the carrier of Example 5. 100 cm3 of aqueous solution poured onto alumina contains 10.75 cm of titanium trichloride solution.

The catalysts obtained are dried, roasted and reduced as shown in the case of catalysts A+ to A5. All the catalysts obtained were 205 mf/
It has a specific surface area of q.

The pore areas of catalysts B+, C+, D+, E+ and F are 0.60 cm3/Q, and catalysts B2, C2, D2
, E2 and "2" is 0.37 cm3/Q.

Example 9 The catalyst prepared in Example 8 is used to obtain gasoline with a single octane number equal to 103. The feed and operating conditions are those of Example 7. The results are as shown in Table ■.

Catalysts labeled (5) are not according to the invention and show inferior results to those labeled (1).

Below is a blank table ■ Example 10 Catalysts D1 and D 5 , E prepared in Example 8
I and E5, plus F, and F5 are used in aromatic hydrocarbon production processes.

A feed having the following weight composition is passed over these catalysts with hydrogen.

Isobenkune 10-n-pentane 1.59% Isohexane 10-n-hexane 24.22% Isohebtan + n-hebutane 42.55% Copentane
0.13% medylcyclopentane 6.72
%Cyclohequinane 5.50%C7 naphthene total 15.81%C8 naphthene total
0.14% Ben U
1.68% toluene 1.66
%100 The operating conditions are as follows.

Pressure: 1 MPa Temperature: 550°C Rate of liquid feed: 3 times the volume of catalyst/Mole ratio of water/feed: 6 The results are shown in Table ■. , toluene, benzene + toluene relative to the original charge as well as the weight yield of C5+. Among other things, the touch 1sD1 according to the invention,
Superior stability is observed for E+ and Fl compared to catalysts D 5 , E 5 and F5, respectively.

Table IV Example 11 This example describes the hydrocranking of a fraction distilled between 330 and 610°C obtained by hydrotreating a blank distillation (400 to 650°C) distillate of crude oil. In the case of d3, catalysts D1 and D3 of Example 8, E+ do E5 and F
, and the use of F5. This fraction shows characteristics as shown in F.

d4.0.87 Nitrogen: 5 ppm In order to obtain a fraction of 160 to 340°C that will be an excellent diesel fuel, the reaction conditions are as follows.

Temperature = 420°C Total pressure: 12 MPa Rate (volume/volume/time): 1 Hydrogen flow rate (volume/hydrocarbon volume): 1000 With a catalyst, an effluent with the following composition is obtained. That is, C3~160℃ fraction, 23.6% of the charge Eliffi
160~340°C fraction, 48.1% of the weight of the charge 160~340°C or higher fraction, 28.3% of the weight of the charge
The 340°C fraction makes an excellent diesel fuel. Diroll index near 3 Cloud point below 30°C Freezing point below 63°C Using catalyst D5, an effluent having the following composition is obtained. Zu-Narichi 160'C C3 fraction, 23.4% of the weight of the charge 160-340'C fraction, 47°6% of the weight of the charge 340°C or higher fraction, 29% of the weight of the charge160 ~34
The 0° C. cut yields a diesel fuel with the same characteristics as that obtained with catalyst, but this fraction is now slightly smaller than that obtained with catalyst.

With catalyst E1, an effluent with the following composition is obtained. That is, the C3 fraction at ~160°C, 23.5% of the weight of the charge; the fraction between 160 and 340°C, 48°0% of the weight of the charge; the fraction above 340°C, 28.5% of the weight of the charge; 160~ The 340° C. fraction becomes a diesel fuel with the same characteristics as that obtained with a catalyst.

By touching 'JXE', an effluent of the following composition is obtained. That is, C3 fraction at ~160°C, 23.2% of the weight of the charge 160~3 /1.0°C fraction, 47°9 of the weight of the charge
% Distillate above 340℃, 28.9% of the weight of the charge 160~
The 340° C. fraction yields a diesel fuel of the same quality as that obtained with catalyst E, but in a slightly smaller quantity than that obtained with catalyst F1.

With catalyst F, an effluent of the following composition is obtained. That is, the C3 fraction at ~160°C, 23.5% of the weight of the charge, the fraction between 160 and 340°C, 48°2% of the weight of the charge, and the fraction above 340°C, 28.3% of the weight of the charge. The fraction between 160 DEG and 340 DEG C. becomes a diesel fuel of the same quality as that obtained with catalyst D1.

With catalyst F5, an effluent with the following composition is obtained. That is, the C3 fraction at ~160°C, 23.1% of the weight of the charge, the fraction between 160 and 340°C, (including 1i [(7) 47
.

8% Distillate above 340℃, 29.1% of the weight of the charge 160~
The 340'C fraction produces diesel fuel of the same quality as that obtained with each of the above catalysts, but FI11! It is slightly smaller than the fraction obtained with medium F.

Example 12 This example uses catalyst E4 in the isomerization reaction of saturated hydrocarbons.
, E5, Fl and F5.

For the modification of each of these four catalysts, each catalyst L+, E5, F, +- was previously roasted in air at 400° C. for 1 hour in a stainless steel tubular reactor.
and Fs 100Q as a fixed bed.

For the treatment of each of these catalysts, the catalyst was then
50'C with a ratio of 50% hydrogen for 11 hours.
The reactor is purged with a stream of dry smoke and water at a temperature of 200 KPa and an absolute pressure of 200 KPa. Thereafter, a solution 11 containing 0.2 mol/l AlCl2 (02Hs) in n-hebutane is injected at a rate of 500 cm@3 /h using a pump, with the effluent from the reactor being recirculated.

After 8 hours of circulation, the pump is stopped, the solvent is drained, and the solid is dried in hydrogen.

Analysis performed on each of the halogenated solids showed that each of the improved catalysts contained 11.7% chlorine by weight and 0.34% platinum.
Does not indicate that strain F1% is included. In addition, improved catalyst E1
and Est each contained 0.43% indium, and modified catalysts F and F5 each contained 0.43% titanium.

In four successive experiments, 50 cm3 of each modified reactor WE+, E5 was placed in the previously used tubular reactor as a fixed bed.
, F+ and F5. The reactor was heated to 1000 ml of carbon tetrachloride while maintaining the pressure at 150°C and 2 MPa under hydrogen circulation.
A hydrocarbon charge containing 50% by weight n-pentane and 50% by weight n-hexane with ffippm added is injected.

The hydrogen flow rate per hour is hydrogen/hydrocarbon ratio 3 mol 1
While keeping the molar ratio, the charge is 1/111 of the catalyst.
; Inject at a rate of 21 between '1 and 21.

The effluent from the reactor has the following composition shown in Table V.

Below is a blank table V. Example 13 This example relates to the use of site F5 for the isomerization reaction of aromatic hydrocarbons. Catalyst, ~F5 is catalyst D1~F5
is the same as However, they are prepared using hydrofluoric acid instead of hydrochloric acid and contain 10% by weight fluorine. The catalyst prepared in J:U is used to isomerize meta-xylene feed to para-xylene. 430°C1
It is operated under a pressure of 1.2 MPa (feed rate -5 per hour per catalytic load, hydrogen/hydrocarbon molar ratio -5).

For a weight yield of xylene of 99.9%, the following conversion to free xylene is obtained:

With a catalyst, thermodynamic equilibrium is 95.3% O; 95.2% E:
95. '1%E2
94.9% F;
95.2%r',
95.0% or more patent applicant Société Franc is de produits pour cateries 1, JII'l size 1981, γj self 1
No. 240766 If'l'a(7)IyI(f
: 'i:j, t'F 4 non-applicants 5 Benefits of hydraulic order Showa month month 6
Sleeve r1-: Invention increase 1111 7, amendment rJ image Claims column 86 Sleeve IJ content Claims +1. ) (a) at least one support based on alumina; and (1) an active phase comprising: (1) at least one noble metal from Group I of the Periodic Table of the Elements and at least one additional metal of the Periodic Table of the Elements; A process for the treatment of hydrocarbons in the presence of a solid catalyst in which alumina is used in at least some spherical form, the production of the spheres comprising an aqueous suspension or dispersion of alumina or a solution of a basic salt of aluminum. Formation by dripping condensation, collection of formed spheres,
a method comprising their drying and their roasting, in which the aqueous suspension or dispersion of alumina or the solution of base-opening groups of aluminum is in the form of an oil-in-water emulsion; The emulsion has a viscosity of 100 to 800 centipoise (1c S t = 1 m27'/s), and the emulsion is composed of an organic phase, an aqueous phase, and a surfactant or emulsifier, and the proportion of the organic phase in the aqueous phase (i.e., carbonization hydrogen/free water ratio) of 1 to 10 gff1%, and an organic phase (with an emulsifier ratio of 2 to 8% by weight), in which the organic phase contains at least one petroleum fraction and Features: Hydrocarbon treatment method.

(21-7' Lumina) ``Salt solution or dispersion or aluminum base'' [1-Salt solution contains an alumina charge and the proportion of the charge is Ae203 152. The method according to claim 151, characterized in that the content may be up to 90% by weight expressed as .

(3) Alumina coating, hydragillite, bayerite, boehmite, pseudo-boehmite, amorphous or substantially amorphous aluminum η, γ, θ, δ
3. A method according to claim 2, characterized in that the dehydrated or partially dehydrated form of these compounds has at least one phase taken from the group consisting of , α.

(4) The total concentration of alumina in an aqueous suspension or dispersion of alumina or a solution of a basic salt of aluminum is:
4. A method according to any one of claims 1 to 3, characterized in that the IJi stiffness is 5 to 30 g%.

(5) The viscosity of the emulsion is 300-4. The method according to any one of claims 1 to 4, characterized in that OO centiborezu (l c SL = l m7 azl /S) and 7 r ko (!: '\).

(6) Any one of pages 1 to 5 of the claims, characterized in that H6L and B of the surfactant are 12 to 18.
The method described in section.

(7) The catalyst contains, by weight, 0.002 to 1% platinum and 0.002 to 1% platinum, based on the alumina matrix or support.
81: The method according to any one of claims 1 to 6, containing 02 to 1% iridium.

(8) The catalyst comprises, by weight, based on the alumina matrix or support: (a) 0.02 to 1% of at least one platinum group noble metal; and (b) 1 to 2% of O,O. and one additional metal (
9) One or more additional metals include titanium, rhenium,
tin, germanium, indium, thallium, manganese,
Nickel, iron, cobalt, zinc, copper, gold, silver, niobium,
selected from the group consisting of lanthanum, cerium, samarium, zirconium, thorium, hafnium, lead, gallium, vanadium, technetium, uranium and selenium;
The method described in Clause 8 of the Patent Request.

Chemical cracking, hydrodealkylation, steam dealkylation of aromatic hydrocarbons, dehydration, hydrogen sulfidation, dehydration! 6 Halogenation, steam reforming, cracking, hydrogenation, dehydrogenation, disproportionation, oxychlorination, dehydrocyclization of hydrocarbons or other organic compounds, oxidation and/or reduction reactions, Claus reactions, internal combustion engines Special tY' applied to reactions selected from exhaust gas treatment and demetallization
The method according to any one of the ranges 1 to 9 for determining jfl.

Claims (1)

[Scope of Claims] (1) (a) at least one support based on alumina; and (b) at least one member of Group V of the Periodic Table of Elements.
and an active phase comprising at least one noble metal and at least one additional metal of the Periodic Table of the Elements. The production involves forming by dropwise condensation of an aqueous suspension or dispersion of alumina, or a solution of a basic salt of aluminum, recovery of the formed spheres, drying them and roasting them. The aqueous suspension or dispersion or solution of the basic salt of aluminum is in the form of an oil-in-water emulsion, the viscosity of the emulsion being between 100 and 800 centipoise (1 c
st = 1 mn + 2 / s), and the emulsion consisting of an organic phase, an aqueous phase and a surfactant or an emulsifier has a proportion of the organic phase in the aqueous phase (i.e. hydrocarbon/free water ratio) of 1 to 10% by volume, from 2 to 8% by weight of emulsifier to organic phase, said organic phase comprising at least one petroleum distillate kerosene and from said surfactant or emulsifier having from 11 to 20 H9L,B. A method for treating hydrocarbons, characterized in that the method is selected from the group consisting of: (2) the alumina suspension or dispersion or the solution of a basic salt of aluminum additionally contains an alumina additive;
2. A process as claimed in claim 1, characterized in that the proportion of the equipment feed may amount to up to 90% by weight, expressed as Al2O2, based on the total alumina. (3) The alumina charge is hydrargillite, bayerite, boehmite, pseudobeichimai 1~,
Dehydrated forms of these compounds consisting of amorphous or substantially amorphous alumina gels and transitional alumina and having at least one phase taken from the group consisting of ρ, χ, η, γ, θ, δ, α or a partially dehydrated type. (4) The total concentration of alumina in an aqueous suspension or dispersion of alumina or a solution of a basic salt of aluminum is 11
4. A method according to any one of claims 1 to 3, characterized in that the amount is 5 to 30 gram % per liter. (5) The viscosity of the emulsion is 300 to 400 tons (
1 cst = 1 mm 2 /s). (6) Any one of claims 1 to 5, characterized in that H, L, and B of the surfactant are 12 to 18.
The method described in section. (7) The catalyst contains 0.02 to 1% by weight of platinum d3 and
．． 7. Process according to any one of claims 1 to 6, characterized in that the iridium content is between 0.02 and 1% iridium. (8) Catalyst h (by weight, based on the alumina matrix or support, (a) at least 1% of 0.02-1%
7. A method according to any one of claims 1 to 6, comprising: (b) 0.01% to 2% of at least one additional metal. one or more additional metals include titanium, rhenium, tin, germanium, indium, thallium, manganese, nickel, iron, cobalt, zinc, copper, gold, silver, niobium, lanthanum, cerium, zamarium, zirconium,
9. The method of claim 8, wherein the metal is selected from the group consisting of ~lium, hafnium, lead, gallium, vanadium, technetium, uranium, and selenium. (10) Catalytic catalyst, production of aromatic hydrocarbons, isomerization of paraffinic rice aromatic hydrocarbons, hydrocracking, hydrodealkylation, steam dealkylation of aromatic hydrocarbons, dehydration, hydrogen sulfidation, Dehydrogenation, halogenation, steam/
Reforming, cracking, hydrogenation, dehydrogenation, disproportionation, oxychlorination, I of hydrocarbons or other organic compounds (dihydrocyclization, oxidation and/or reduction reactions, Claus reactions, internal combustion engine exhaust gases) 10. A method according to any one of claims 1 to 9, applied to a reaction selected from treatment and demetallization.