JPS60152592A - Hydrogenation of hydrocarbon - 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 Industrial Application The present invention generally relates to alumina containing an active phase containing at least one metal from Group I of the Periodic Table and at least one additional metal used as a cocatalyst. The present invention relates to a method for hydrotreating hydrocarbons, including the presence of catalysts based on

Prior art and its problems In general, in the prior art, "C" means that this type of catalyst has 21
Prepared on the floor. i.e. a) prepare or purchase the support, 1)) then generally (α) often belonging to group I of the Periodic Table of the elements and mostly in metallic form, for example in the form of oxides or sulfides; At least one metal present in the catalyst and (β) optionally in the form of an oxide or sulfide, for example, generally in the form of an oxide or sulfide (%”Q). 1'), an active phase containing a so-called additional metal (or co-catalyst) is supported on a support.

According to the prior art, several methods can be used to add the active phase of the catalyst into the support. In general, each metal, either individually or all at the same time, can be prepared by any suitable method, such as co-precipitation with a sub-porous carrier or simultaneous gelling or gelling with a gelling carrier. It can be incorporated before or after drying and calcination of this carrier by ion exchange or impregnation with 11.

However, the catalysts prepared by the prior art described above were still unsatisfactory in terms of reaction yield and selectivity, as well as catalyst stability and life.

The present invention aims to overcome the above-mentioned drawbacks of the prior art catalysts.Means for solving the problems The present invention provides a solution to the problems by: (a) a support consisting mostly of alumina; Hydrogenation of hydrocarbons in the presence of a catalyst comprising at least one metal from group 1 of the Table of Contents and an active phase comprising at least one additional or promoter metal
! X-buried, hydrogenated Oi2 metal or hydrodesulfurization,
the support used in the preparation of the catalyst is obtained by mixing a predominantly alumina-based binder with a predominantly alumina-based charge, shaping said mixture, drying and optionally calcination; The weight proportion of the binder represents 15-40% of the total carrier, and the fffffi of the charge
If the proportion is 60 to 85% of the total carrier and the alumina binder itself is a thick part of the dispersed alumina, then J:
The alumina charge itself consists of a small portion of non-dispersed alumina (with the portion of dispersed alumina representing at least 70% by weight of said binder), and the alumina charge itself may contain a large portion of non-dispersed alumina. a part of dispersed alumina (where the dispersed alumina part represents less than 10% by weight of said charge), and the dispersion rate of the composition resulting from the mixing of the binder and the charge is from 10 to 60%.
It is characterized in that at least a part of the active phase or its precursor is introduced into the charge during the manufacture of the support or into the binder during the mixing operation of the binder and the charge.

In general, the present invention relates to a method for producing a catalyst comprising an active phase consisting of at least one metal of an autochthonous ore and at least one additional metal, and an Ic support obtained by mixing a binder and a charge. .

The method includes the following steps: 1) mixing at least a portion of the charge, binder and active phase; 3) shaping the mixture; 3) drying and optionally calcination; 4) optionally Introduction of the remaining part of the active phase followed by drying and activation.

In this process J3, the majority of the platinum ore metal and/or the additional metal is also introduced into the binder or charge during the first step.

The present invention also uses a catalyst having a support prepared from an aqueous composition of alumina. The carrier comprises a binder which essentially constitutes the dispersed part and a charge which essentially constitutes the non-dispersed part of the composition. Preferably, the composition resulting from mixing the binder and charge has a dispersity in water of about 10-60%.
In addition, the particle size of the non-dispersed portion of the composition is such that the alumina particles comprising it have an average diameter of 1 to 15 microns; at least 70% of the particles are half the average diameter
It is appropriate that the average diameter be 218 mm.

The dispersion rate is determined after the composition is centrifuged and completely 4
1 It is expressed as the percentage of alumina in colloidal suspension. This dispersion rate can be measured as follows. The aqueous composition of alumina is diluted to obtain a total alumina concentration of 100 (1//).

This solution at 100 rfn' was stirred vigorously for 10 minutes (1
vinegar. This solution is then centrifuged for 10 minutes at a speed of 3000 revolutions per minute. Separate the decanted 1= portion from the undecantated portion consisting of a colloidal suspension of alumina 7. Calculate and weigh the decanted portion.

The dispersion rate is expressed as the ratio of the initial total Meibus graded alumina amount of alumina in the composition to the initial total amount of alumina in the composition.

Within the framework of the invention, the dispersion rate in water of the aqueous composition of alumina is preferably between 10 and 100%, more particularly 15%.
~40%, and the particle size of the non-dispersed portion of the composition is preferably such that the average diameter of the alumina particles constituting it is between 1 and 15%.
Micron C. It is like that.

The non-dispersed portion of the composition consists of the ligneous charge. A small portion of this may come from the binder.

The weight proportion of the binder in the composition (total carrier m) is preferably 10 to 60%, and more than 1] <G7↓
It is 15-/10%. As a result, the weight proportion of the charge in the composition is therefore /IO·-90%, J, more specifically 6
The result is 0-85%.

Within the framework of the present invention, the alumina binder consists of a woody, dispersed alumina portion and optionally a small portion of non-dispersed alumina.

11 pieces (preferably at least 7 pieces of binder)
Indicates 0% hanging. In the following description of specification n), the dispersed part is called a binder (not all the binders are necessarily dispersed = b>, and the non-dispersed part is the original product of the equipment (
Even if a part of the charge, less than 10% of the charge, is dispersed and b) has thorns.

The present invention relates to a process for hydrotreating hydrocarbons in the presence of (a) a support J3 consisting predominantly of alumina and (1) a catalyst comprising an active phase. The alumina support used for the production of the catalyst is obtained by mixing a nonormina binder and an alumina charge, shaping, drying J3 and calcination. Production of catalyst 1. J, at least a portion of the active phase is 1F1
This active phase is introduced during the manufacture of the body and is present mostly in the binder, or is present mostly in the charge, or directly in the equipment before mixing with the binder; αJ exists in the same n'7 in the binder and 1% l during mixing.
RuJ, Characterized by Uni Riko. For example, this method is
, 1.1; consisting of introducing at least a portion of the sexual phase into the bulk binder or during the mixing of the charge and the binder (into the two-part charge).

Variations of this method include aluminum alloys (to improve their thermal stability), magnesium, calcium, strontium, barium, scandium, yttrium, rank nitrides, gallium, indium, thallium, Boron, titanium, zirconium, octane, thorium, germanium, tin, lead, vanadium, 2A, tantalum, chromium, butene, tungsten,
an oxide selected from the group consisting of oxides of rhenium, iron, cobal 1~, nickel, copper, zinc J3 and bismuth;
Please replace at least part of it.

The present invention relates to various hydroprocessing of petroleum products such as hydrodesulfurization, hydrodemetalization, hydrodenitrification, etc.

According to the present invention, an alumina binder (in powder form) is used.

The alumina binder used is J
: Must be capable of gelling or hardening.

Gelation or solidification by the action of heat is well known to those skilled in the art and can be accomplished by entrainment of water in an aqueous suspension or dispersion of alumina forming the binder. Gelation or solidification by chemical action - also well known to those skilled in the art;
Aqueous L of alumina that forms and covers the binder! This can be done by increasing 1) II of the suspension or aqueous dispersion to a value of 9 or more, which corresponds to the isoelectric point of alumina.

Alumina binder (,↓,
In particular, the size within the T10 id range, that is, approximately 2000 Å
Microparticles consisting of particles having the following dimensions are ultrafine Boehmai (aqueous N, suspension or aqueous dispersion).

Aqueous dispersion of fine or ultrafine boehmite or 1 q of water
Suspensions can be obtained by bedilation of these substances in water or acidified water, as is well known to those skilled in the art. Or ultra-fine boehmite is particularly suitable for those described in French Patent Application Nos. 1.262, 182 and 1,381,282 or European I (I was able to do it.

France Special R'1 No. 1,262.1 ε32 is characterized by the presence of monovalent acid groups [fine particles J, or ultrafine particles J], The manufacturing method is described in -C. The alumina water 11J dispersion is
Basic rafluminium chloride, aluminum nitrate, aluminum hydroxide, alumina gel or colloid.

This product, sold under the trade name 1'Baym%lj by De'Yu Bons of C Nemours, is generally priced at 250
Fine or ultrafine boehmite is ground from fibrils with a specific surface area of ~350 m2/g.

France Special No. 6'1 No. 1,381,282 is -△ρ2
Calculated as 03 and up to 35% aluminum,
This alumina calculated by UBI as l\/203 molecules is
fil: A suspension or gel cake of amorphous hydrated alumina containing a matrix of acid ions, 1! '＞
A method for producing fine or ultra-fine grains consisting of developing at a temperature of 60 to 150'C is particularly described ()C.

This dark was obtained from a solution of ptrium aluminate and nitric acid at p Ll 8-9), drying of precipitated I/reminaglu, washing J5 and filtration membrane. The specific surface area of these products generally varies from 200 to 600 m 2 /g.

European Patent Application No. 15.196 specifically describes hot squid YQ
Middle Tee 17) Mizudon stone (1) ydrag i I l
1q of activated alumina can be obtained by rapid dehydration of IC).
A process is described for the production of bezee, at least partially in the form of ultrafine boehmite, by treating the powder in an aqueous medium with an atom temperature of less than at-19.

Similarly, an aqueous suspension or dispersion obtained from pseudo-boehmite 1 to amorphous alumina gel, aluminum hydroxide, or ultrafine water V (soil and stone gel) can be used as the alumina binder.

Pseudo-boehmite is particularly described in U.S. Patent No. 3,360.67.
IC0 can be prepared by reaction of a solution of an aluminate aryl salt with a solution of an inorganic acid according to the method described in IC0, which is also French Patent No. 71S1.3.
57. As it was classified as ε330, in pl-19,
Approximately 50
To obtain alumina of g/ρ', 'K'Ifd from the reactant of degree! 11Jtl lC0 Amorphous alumina gel is especially suitable for PA △l G O1f1)
apcr No. 19 (1972), No. 9~
According to the method described in the article on page 12 - C1, especially aluminates and acids, or aluminum salts and salts, or aluminates and aluminum salts in anti-1δ, or aluminum basics in 1B and lcμ C was prepared by hydrolysis of aluminum alcohol-1- obtained by reaction between aluminum and alcohol.

Aluminum hydroxide gels are particularly useful in U.S. Pat.
68.295 and 3.245.919.

Ultra-fine water cloud clay (in particular, French Patent No. 1゜373
．． By the method described in No. 808, △120a120
The alumina gel in the form of Cook containing 0.10 monovalent acid ions with respect to alumina was prepared by exfoliation at room temperature to 60°C.

According to a variant of the method of the invention, an alumina binder (
It may be replaced, at least in part, by a Silino J suspension or dispersion exhibiting the same characteristics as the alumina binder.

In the present invention, the alumina charge comprises a dispersible alumina portion and optionally a small group of dispersible alumina molecules dispersed throughout the composition. The non-dispersible portion represents at least 90% by weight of the charge. The particle size of the undispersed portion of the composition, and thus essentially the portion consisting of equipment, is preferably such that the average diameter of the alumina particles constituting it is between 1 and 15 microns.

The alumina charge used may consist entirely of alumina exhibiting the characteristics indicated above.

In particular, alumino-water 11 compounds can be used.

This is, for example, water, earth, stone, bayerite, bei7, i1~
, pseudobeams 1 to 33, and amorphous or woody amorphous alumina gels. Similarly) dehydration or part of these compounds consisting of U-transferred alumino and containing at least one phase taken from the group consisting of ρ, χ, η, γ, θ, δ, α Dehydrated forms can be used.

In particular, optionally the grinding of the particles and the sieving fraction could be followed by the use of an alumino charge obtained by one of the following methods: * Precipitation of an aqueous aluminum solution with a solution of an alkali aluminate salt. let The obtained precipitate was atomized () and then pl-14, 5-7
The resulting lζ alumina slurry is dried, and the product is then washed, dried and calcined (method described in US Pat. No. 3.520.654).

*Precipitation of alumina glue at p l-17, 5-11, washing, drying, resuspension, rapid addition of the product in hot gas liquid to 112 water at an inlet temperature of about 350-10'00 °C. (The method described in French Patent No. 2.221.405).

Precipitation of alumina glu at $111-17~10.5,
Aging of the precipitate at p l-110-11, homogenization of the resulting slurry at 2.50-5 EtO' (/), atomization and subsequent calcination by calcination.
72).

* Precipitation of alkali aluminate salts with inorganic acids at temperatures of 30-75 °C, 1) aging in the second reactor of N7 (= J near C, 1) in the mixing reactor ■-4
Recirculation of the slurry produced, filtration, washing, drying of the product by atomization and subsequent calcination (US [iSl Patent No. 3,63]
No. 0,670 (1,000,000 people).

: F, hydroxide of aluminum or A-hydroxide; This dehydration is carried out in any suitable apparatus with a stream of hot gas. The inlet temperature of the gas in the 'JA unit generally varies from about 400 to 1200°C. The contact time of the hydroxide or A-oxyhydroxide with the hot gas generally ranges from a fraction of a second to 4-5 seconds.

This process for the preparation of activated alumina powder is described in particular in French Patent R'l No. 1,108,0112.

In a hot gas flow, water (by rapid 1B2 water, atomization of soil and stone) * By drying and calcination, and by treatment of the obtained activated alumina powder in an aqueous medium of 1TH9 or less ( (method described in European 'farγI Application No. 15,196).

Alumina charges obtained by various methods can be divided into two groups. The first group shows a certain proportion of dispersion J1 drying and in case J, and C relates to the charge obtained after calcination.

These products, as is, are optionally -(1!
5) Used as a charge after crushing J3 and sieving. The second group has a dispersion rate J of the charge of the first group,
The present invention relates to a device that is ICi-treated after drying due to its low dispersion rate. These ￥i1 genuine items are used for I-kome,
: Requires a firing step at a temperature of 3°C or higher. These charges, if any, can then be used in the present invention after crushing and sieving.

In the method of the present invention, the binder J3 and/'t(y)lumina loading comprises at least one oxide of this group of metals referred to above as J3-C cocatalyst metals or additional metals. 12-C can be at least partially replaced by an oxide selected from

According to the prior art, the mixing operation of the charge and the binder may be carried out in powder form. The binder in powder form consists of various materials: Boehmite 1~, pseudo-boehmite, Bi-1 light, amorphous alumina gel, aluminum hydroxide gel, ultrafine water-bearing soil in a non-peptided state. The powder mixture is then contacted with water or acidified water. The charge, binder, and water are mixed in proportions such that the final composition has a dispersion rate of 10 to 60%, and the final composition has a p I-1 of No. 4 and below.

According to another method of use, the dispersion rate of the composition is from 10 to
60% and the r+lt of the final composition is 4 or less, the charge in powder form and the binder in the form of an alumina suspension or dispersion may be mixed under stirring.

Therefore, the present invention relates to the use of one catalyst.

The production of this catalyst is characterized in that at least part of the active phase or its precursor is introduced during shaping of the support, ie during mixing of binder and charge. The active phase generally comprises at least one metal of group I, which is generally present in the catalyst in metallic form, particularly when the catalyst is a negative metal of the platinum group, and optionally an active promoter of the first metal. At least one Doshi-C generally used in oxide or sulfide form
Also contains two other metals. At least a portion of the active phase may optionally be incorporated into the binder of the support or into the charge of the support or into the charge and the binder, as specifically described below. It's okay. If not all of the active phase is introduced during the preparation of the carrier, the activity 411
The supplement is later introduced into the carrier according to conventional techniques 14j. J, or precisely at least said portion of the active phase or its precursor, is introduced (α) into the charge (β) into the binder (γ) simultaneously into the charge and into the binder.

During mixing of the charge and the binder, said portion of the active phase may be added to the binder and/or the charge.

Regarding the addition of the active phase in the binder, C can be written as follows:

(1) Regarding the impregnation treatment of the binder by a conventional (dry or wet) method using a metal salt or compound or an acidic aqueous solution of at least one metal in the active phase.

For example, one method involves impregnating the support with a solution of the desired metal compound;
Consists of. A common solution for these metals or a different solution for each metal or metal synthesis is used.

A first method of preparation consists of impregnating the binder or charge of the support with an aqueous solution of a nitrate R salt or other compound of a metal other than the group I metal, for example. This is then followed by a second impregnation treatment using a solution containing at least one metal of group (I).

Another method consists of coating the C support with a solution containing, for example, the following in the same pot.

α〉 1゛In other words, lJ is a plurality of metals of the first class, β) One or more of the first metals of the third class and (, another metal, for example) a compound of a metal, bromide, fluoride. compound, (dicyonate or acetate or any other salt of selected metals that is soluble in water.

Yet another method consists of introducing metal elements by carrying out impregnation treatments as many times as there are metal elements in the catalyst. one metal of Group VlI or (if the catalyst contains more than one metal) using a solution containing it; - finally introducing one or more additional metals.

-The above order of impregnation with Suraron is not mandatory.
<' may be different.

(2) Due to the simultaneous gelation between the alumina powder forming the binder and the active phase introduced in the form of a Uoid suspension.

(3) Or by co-precipitation between alumina salts and active phase salts during binder production. The binder is advantageously 30
Dry at a temperature below 0°C.

In order to introduce the active phase preferentially into the binder or into the equipment Q and add the active phase between the charge and the binder, a) in multiple steps or b) in a single step C1 operation. Even if I do it, it's okay.

a) In the case of multiple steps: If it is desired to introduce the active phase preferentially into the binder, the method preferably first introduces the binder in the form of an aqueous solution;
The salt of the active phase is then pre-saturated with a suitable salt and the TC charge is introduced, ensuring that the salt of the active phase does not get into the charge (this salt therefore becomes part of the charge). Volatile salts such as nitrates, chlorides, sulfates, ammonium salts, amines, human[1-xyamines, hydroxyamine chloride, ammonium acetate, etc.]
(C is also good).

If the active 1g phase is preferentially introduced into the charge, then preferably the method
c consists of introducing a binder suppressed by J: salts described above with multiple salts. (1)) In the case of a single step: the active phase is preferentially introduced into the binder or charge. To do this, - suppress the charge or binder using a suitable salt, as described above. The +ir+(:l phase is thus either fixed in the binder if the charge is suppressed, or fixed in the charge if the binder is suppressed.

In order to preferentially introduce the active phase into the binder, about 15
0~600m2. Although a binder with a specific surface area of /9 and a charge with some specific surface area can be used, the ratio of the specific surface area of the binder to the charge is such that it is about 1.5 or more C. In this case, the salt of the active phase (, non-preferentially immobilized on the binder).

Conversely, if the active phase is preferentially introduced into the charge, a charge with a specific surface area of about 100 to 600 m2/g can be used. The binder has a J, U4C specific surface area such that the ratio of the specific surface area of the binder directly to the device is about 1.5 or more.

If the active ↑:l: 1] contains multiple metals, then the above-mentioned thx IC (J)
It is also possible C' to introduce each of the metals separately into the binder or charge.

Simultaneously with the introduction of a small portion of the active phase in one or more steps, the binder and the charge may be processed by any suitable means, such as a) extrusion b) the so-called rotary tabletting process (rotary ball or rotary molding). (grains, etc.) C) Molded by the so-called oil drop method (or drop in oil method).

Then, after shaping the support, parts of the active phase which have not yet been introduced into the catalyst mass may optionally be added.
.

In general, the introduction of a portion of the active phase or the T1 bamboo phase into the equipment material can give the J1 Saihiragi catalyst improved catalytic properties (selectivity, yield) ＼Also, the introduction of part of the active phase into the binder (,↓) is also required in the Ju-terminated catalyst (in particular in the case of the use of a moving bed C).
ME has been found to provide higher than normal mechanical durability and therefore a longer lifespan.

According to the invention, therefore, an IFI body of a catalyst based on alumina (for example For example, preferably the extrusion method or the so-called tableting or rotary granulation (or equivalent method such as rotary hole etc.)
In addition, one method of production is such that at least a portion of the active phase is present in the charge or in the binder, or in the charge and the binder. It is characterized by being added in the same amount.

Generally, the active phase comprises at least one metal of Group I and, on the other hand, at least one promoter metal.

In that case, during the manufacture of the support, for shaping of the binder and/or charge and the said part of the active phase, said part of the active phase contains a group II metal r15J: and/or a cocatalyst metal. Depending on the situation, three methods can be considered for θf.

In this specification, the majority of the 1-oxides of the co-catalyst used (or, if there are more than one, the "plurality of W oxides" of the co-catalyst used) or the metal of Group 1 or if there is a small number of them in the catalyst, the 1st-Mth
The edict "Multiple metals of Group I" shall be used.

“Mostly” means the oxide (if more than one, then multiple oxides)
Total small 1 C means at least 55% by weight of the total metal.

All of one or more cocatalyst metal oxides:
This means that if C is not introduced, then C is not shown. d in the sense that one or more of these cocatalyst oxides which are not introduced by Ich, are introduced into the charge later (by any suitable method C) after the preparation of the support.
Uri, on the other hand t'-LL means that one or more of these metals of group I, which are not introduced by the indicated method, are introduced in the charge or subsequently (i.e. after the preparation of the support) - 〔·be.

During the formation of the carrier, a portion of the active phase 11 is simultaneously added to the binder or the charge in order to warm up the binder and the charge, and during this warming. Various techniques described above are possible.

(2) The molding method of the charge/bariender mixture is an oil casting method. Group I metals may be introduced into the binder as a charge. However, later on (after the preparation of the carrier mixed with part of the active phase), it may be added by any suitable conventional method, e.g. by an impregnation process. You can also The so-called co-catalysts or additional metals are generally introduced in the form of one of their oxides, either in the binder or in the charge or in the binder and the charge, or alternatively, generally. When the small portions or the active phase mixture have been prepared, they are added in any suitable manner, for example by impregnation.

Preferably, the operation method is divided into six steps (1 to 6) below.
.

Method 1 A major portion of one or more cocatalyst gold m oxides is introduced into a binder, and at least a portion, e.g. a major portion, of one or more group Ru.

Method 2 A majority of the one or more promoter metal oxides is introduced into the charge and at least a portion, eg, a majority, of the one or more Group I metals is introduced into the binder. In some cases, one or more cocatalyst metal oxides and one or more co-catalyst metal oxides are incorporated into
Group I metals are introduced in the binder or after the preparation of the support for one or more promoter metal oxides and in the charge or after preparation of the catalyst for one or more Group I metals. Be careful of the introduction of Liebe.

This kind of thing was done about the 165th and 2nd method? :t
Since @ is also valid for other methods 3 to 6, it will not be repeated in the following Book I. 'Thus, even if a small portion of U, one or more cocatalyst oxides or one or more Group I metals is not introduced according to the method indicated, one or more of this portion can be introduced by any other method. T:S
1. Method 3 A major portion of one or more cocatalyst metal oxides is introduced into a binder, and at least a portion, e.g. a major portion, of one or more Group I metals introduced into the charge.

Method 4 A major portion of one or more □ promoter metal oxides is introduced into the B charge, and at least a portion, eg, a major portion, of one or more Group I metals is introduced into the charge.

Method 5 The majority of the IJ promoter metal oxides are introduced into the binder and one or more Group I metals are removed after the manufacture of the support, e.g. after a conventional impregnation process. Introducing
Ru.

Method 6 The bulk of the promoter oxide or oxides is introduced into the charge and the Group I metal or metals are introduced later after the production of the Jp body, for example by a conventional impregnation process.

The H,tl'ii compound is obtained by a rotary tablet type process.

In this case, two methods No. 7 and 8 are adopted for the main and introduction.

The first method 7 consists of introducing the bulk of one or more so-called promoter metal oxides into the binder.

The second h method 8 consists of introducing at least a portion, eg a major portion, of the promoter metal oxide or metal oxides into the charge.

For these two h-methods, one or tc is
After the preparation of the support, e.g. impregnation treatment -
Introduced by Cover. - (1) A carrier/active phase mixture is obtained by an extrusion type method.

Several methods are possible, including the first of the six same methods described for the oil drop method.
~6.

The application of the catalyst prepared as described above to the hydrocarbon IV purification reaction, the shaping of the catalyst is carried out - by the "oil drop method" - preferably by the "rotary tabletting" method or by "extrusion".

More specifically, regarding the dropping method in oil, C may be preferably carried out as described below.

According to the M1 method, droplets of binder and R11i are introduced into a water-immiscible liquid such that the droplets form substantially unispherical particles. These particles,
Solidification occurs simultaneously with and/or after shaping into spheres by means of a gelling agent which removes stabilizing ligands. At the same time, at least a portion of the active phase of the catalyst is also added into the binder, or into the charge, or simultaneously with the charge and binder.

A liquid that does not have a mixed phase with water will cause the droplet to fall (the density of the liquid is lower than the density of the droplet) or rise (the density of the liquid is higher than the density of the droplet J) in the processing liquid. C of
Atte bJ: Yes. Examples of water-immiscible liquids suitable for the purpose of the process of the invention include, inter alia, petroleum, casin, dodecylbenzone, 1-lichloro1]ethylene, perchlor1
Mention may be made of coethylene, organic solvents, hydrocarbons J5 and generally mineral oils.

Gluing agents that remove stabilizing ligands include, among others, ammonia,
It may also be aqueous ammonia, ammonium carbonate, long-chain amines (especially those sold under the trademark Prim?: nc), hexyrimethylenetetramine, urea.

This is how it is processed! , : droplets are collected from their medium v1 of shaping and/or solidification.

According to a preferred method of use, droplets of the mixture are mixed with petroleum 1. s
into the interior of a column containing an upper phase consisting of + and a lower aqueous phase consisting of ammonia solution. Shaping takes place in the upper phase and gelation essentially takes place in the upper phase. is generally close to room temperature. The aqueous ammonia solution must be maintained above about 9 and have an Ip l-1. The residence time of the droplets in aqueous ammonia ranges from a few minutes to generally less than about 15 minutes. Under these conditions, the recovered spheres are sufficiently rigid that they are not deformed during subsequent handling. Two new advantages of the method appear particularly in the case of this sphere-forming and gelling process: shaping is carried out at room temperature, and besides the gelling takes place very rapidly, so that according to this method basic A subsequent ripening of the C spheres in solution is not necessary at all, since these spheres exhibit sufficient hardness after a short residence time of the C in the ammonia phase.

According to a second method, the droplets of the mixture are introduced (suspended) into an immiscible liquid that is capable of removing the water of the 'zJs droplets. This immiscible liquid (J-0, e.g. 2-upper chill-1-
Hekylinol or octyl
It is possible to use a long-chain aliphatic alcohol sold under the trade name (Ol).

According to the 30th Tsunokai, this mixture is soluble in water (・
i-
and at least one water-soluble salt. −)
The mixture in the form of droplets is poured into a hot fluid medium. In this medium, substantial polymerization of the heptamer occurs. The monomer has the general formula;
3 or NR3R/1 group (in the formula R3J3J and 1 or 1'' or I denotes a hydrophilic group), especially a hydroalkyl group containing 1 to 2 carbon atoms or There may also be an acrylic compound C that shows the following. The main steps of this method are especially the French characteristic π′1 negative]2,261
．． It is described in No. Q-56 and No. 21.261.057.

Regardless of the method used, the resulting spheres are then separated from their gluing medium and then dried to a
Calcinate at a temperature of 0 to 1100°C.

Obtained 1=sphere is approximately 0.30-1.7 cm"'/g 1
8 The micropore volume of those with a diameter of less than η1, 0.06 μl is approximately 0.
145 to 1cll13/g, O, Q6 Miku1]
It consists of pores with a diameter of
”?’) IN Inn 'JL tF M L3
, about 0.05 to 0.7 CII13/g, the average diameter of the 7 pores is 0°1 to 10 microns [1 C, and the specific surface area of these spheres is about 80 to 350 Il12/g. (
BET iodine oxides) dried at 110° C. and their fracture resistance (11×9 or higher).

Regarding the extrusion method or rotary granulation method (, L
In more detail, the catalyst is produced as follows.

1. During the optional first step, wash the carrier and the used material.

2. In the 21st culm, the material used as carrier is dried by any suitable IN method, for example in a dryer, having the same structure as the starting culm I and having -C1 about 15 to 1000 °C after drying.
] ~ 40% combustion weight loss Q4j)

3. During the third step, wash and dry the tofu.

1. At this stage, it is often preferred to at least partially calcine the dried powder before continuing with any other steps. 20 to 630% σ) of alumina
The powder may be mixed with the calcined powder at a temperature of 00 to 800°C.

The advantage here is that the two-phase product can provide 1 q;゛ is 1 to 50 after mixing the fired powder and the unfired powder.
The particle diameter is on the order of microns, and the critical pore size is approximately 600 Å or more in diameter. - 191 attempts to create a powder characterized by particles with pores.

5. Molding of the obtained powder is carried out by a) extrusion or I+) rotary tablet making, or by equivalent means. This shaping is carried out at the level of the binder (dispersed alumina) and also at the level of the charge (non-dispersed alumina) and at least a portion of the active phase. '
The addition of J is called the J sign.

If the extrusion operation is to be carried out as follows: add the powder to water or acidified water for a period of about 5 minutes to 5111 minutes. There will be 11 buildings.

The water or acidified water contains at least a portion of the active phase of the catalyst (liphatic metal oxides and/or metal oxides).

To water a certain seedling, use the acidified water in (a). This represents 50-89% by weight based on the powder material.

The base plate obtained can be processed by any suitable method, e.g.
It is extruded through a spinneret in a twin or double twine or any other type of extruder.

The resulting extrudate is generally dried at a temperature below 350°C, resulting in a loss on combustion of the resulting solid of approximately 15-40%.

It is at this step, in some cases and usually, that portions of the active phase which have not yet been mixed into the IJI form are introduced. For example, it is finished by drying at a temperature of 350°C or less.
:stomach.

Optionally, the extrudate is then heated to 80-500"C.
At a temperature of C, 1/1 or I is acidic: l' 7. : What is the hot water treatment for 63 tj in 1 Fukudon medium, amorphous 41
Be My I-S+:/:, 1. 11. (Changed to boehmite-like texture 11 and improved mechanical properties.)

Calcining of the extrudate obtained is generally carried out at a temperature of 350 to 00°C.

You can also reverse the order of these last steps.

If the operation is performed using a rotary granulation method or a similar method (tablet making machine, two-rotating plate, rotary ball (rotary 1), etc.), proceed as follows. On the one hand, the powder is passed through a granulator, and on the other hand, an aqueous solution or an acidified IC aqueous solution containing at least a portion of the 15-phase (Zunawara metal oxide J5 and/or (1-membered metal) of the catalyst) is poured into a granulator. The powder is poured or pulverized and simultaneously introduced into the granulator. Generally, the tablet machine or pulverizer is moistened while the powder is rotated.

The powder will be applied to the adhesion of the distal condyle, and will be placed above the hole. By Torihata's method, for example, by centrifuging 11+L, the particles are made into a tablet (a few degrees are discharged and removed, and then they are dried, as explained above in the so-called extrusion method).
The parts of the active phase that have not been introduced onto the support are then calcined (introduced) as described above.

Improvements to this method and the use of an aqueous solution or better an acid 1
! In an aqueous solution of I? A portion of the diluted powder (approximately 0~/1.0% of this V powder) is sent to the granulator (
It is therefore possible to dilute some of the powder in acid. This acid disperses the acidified aqueous solution).

The catalysts prepared according to the invention are therefore suitable for use in refining processes, in particular hydrodesulphurization processes and/or hydroprocessing processes, such as the hydrogenation of crude oil, liquefied coal, heavy hydrocarbon fractions as well as petroleum residues. It can be used in the conversion method of J:.Petroleum residue means the distillation residue of petroleum ()C, shale oil d':3 and earth i1M blue sand/)W1 min extracted from the grains. It also means.

For example, the feed used may be any hydrocarbon oil with a high boiling point, for example above 350°C. first 81
1 ft1i 4J, may be any hydrocarbon deposit of ancient origin. These include, in addition to crude oil, materials such as oily sand or oily sand-like materials or liquid coal arsenic resulting from coal liquefaction.

Petroleum and petroleum fractions are non-X+:) complex mixtures. In this mixture, in addition to hydrocarbons, there are various compounds containing primarily sulfur, nitrogen, oxygen as well as metals.

The number and types of these compounds vary depending on the origin of the crude oil and the fraction considered. These are generally harmful impurities that cause pollution, corrosion, odor, stability and high quality petroleum products. Among the numerous methods recommended for their removal, the most widely used is a contact treatment in the presence of hydrogen.

This technology (4) shows the advantage of being able to extract high quality products from crude oil and residues with high impurity content.

The difficulty in processing this charge is related to the presence of carbon asphaltenes and metals. These lead to deactivation of the catalyst under conditions of insufficient treatment.

Metal contaminants can exist in oxide or sulfide form. However, usually these are in the form of trimetallic compounds such as porphyrins J'j and their derivatives.

The hydrocarbon feed treated according to the present invention contains hydrocarbons,
There is a liquid hydrocarbon mixture C containing contaminant components, which may be of very different types.

Particularly interesting applications include relatively heavy materials such as crude oil or spill residues containing impurities such as sulfur compounds and/or nitrogen compounds, asfnormetal compounds, metal compounds or (', L-gold-white compounds). It is possible to treat high quality 4F feedstocks.The reactions used are those aimed at this type of heavy trade feedstock, especially desulfurization, denitrification, hydrocracking, hydrogenation A3 and demetallization. There is.

Another type of reaction is "hydrogenation" or the treatment with hydrogen of bituminous shale coal dissolved or dispersed in a circulating hydrocarbon solvent.

Another type of reaction removes additives and organometallic particles from used oils! , :Me, and J2 for hydrogenation,
Improved lubricity and stability against oxidation J5 and σ temperatures.
This is the process by which this oil is turned into hydrogen.

The reaction conditions described above are typically at a temperature of -270'
-/175°C, pressure -20-300 bar d'3, J
: The hourly circulation rate of the 1-body solvent - 0.1 to 15 volumes of catalyst - (although these values are not necessarily limiting and depend on the type of feed and the treatment being carried out) It depends on the degree of severity required.

The catalyst may be of the known type used in analogous reactions, especially those used as such or supported on an alumino support. -jvIIbx metal compound.

Examples of metal compounds include molybdenum, tungsten,
Oxides such as nickel,] Pal 1- and/or iron,
Preferred examples include sulfides.

Fixed bed, moving bed, or expanding bed (e.g.) 111 bed and l
Perform the operation with .

In general, in the prior art J5, in order to prepare a catalyst based on the metal No.
It is made of transition alumina in the form of, for example, spheres, extrudates, crushed products, belene, etc., and has an area of 100 to 500 m2.
Starting from a support having a specific surface area of 0.2-Q, 9cm'' 7g and a total combined pore volume of 0.2~Q, 9cm''7g. Nickel or 1 [was impregnated with a solution of a soluble salt of cobalt, and on the carrier thus impregnated,
-itn nickel or cobal in oxide form
-1 to 1011% to 1 [J: Sea urchin Juru. Konni・)
The crushed solid is then dried in the presence of air, e.g. 1- or under a stream of air, preferably 4;
It is baked at 850° C. for, for example, 0.5 to 6 hours.

After cold N], compounds of the metals of VIA hX are incorporated in any suitable manner, for example by impregnation, kneading or coprecipitation, such as ammonium ribdate or ammonium tungstate. The total weight proportion of the supported lζ metal oxides (N10 or I = 4.t CoO, MOOI or WO3) is preferably 5 to 3.
There is 0% C. The relative proportions of metal oxides of Group Vl and Group II are, for example, as follows: For Group I metal oxides, it is 10 to 50% by weight, and for Group VIA hX metal oxides, it is 50 to 90% by weight. The catalyst obtained in this manner is then dried, and then
Cover baking at a temperature of ~600 °C.

Similarly, some prior art also describes the introduction of molybdenum and/or tungsten during the first calcination step at 300-550°C. The second step then consists of introducing nickel J3 and/or =lpal1-, with a final temperature of 400-600°C. When the catalyst is used in the hydrogenation, it may advantageously also undergo an in-situ presulfidation. This pre-treatment may be carried out in addition to hydrogen and/or inert shinai gas such as nitrogen or methane or 1 to 10%
200°C ~ using a waste stream containing 1% hydrogen sulfide.
At 500° C., at least a large portion of the metal oxides of Groups C1 and VIA are converted to the corresponding sulfides, such as NIO and COO, N03S2 and CO! IS 13
Then Moo will wait for enough time to convert WO3 to MOS2 or WS2.

The final catalyst will generally have a smaller specific surface area (j'g) than the starting alumina J.

The present invention is constructed as described above, and the catalyst obtained according to the present invention has the following effects: □ Yield of the reaction, b
and selectivity as well as stability of the catalyst.
In the hydroprocessing reactions of hydrocarbons, significant effects are achieved with respect to the introduction of a part of the talkative phase or active phase into the charge, which improves the catalytic properties ( selectivity, yield) is imparted to the final catalyst, and the introduction of part of the talkative phase or active phase into the binder (also particularly required in the case of use in moving beds) Normally, a higher I range durability and therefore a better lifespan is observed in the final catalyst. increases the yield d5 and selectivity of the reaction to which is applied,
This can increase the stability and life of the catalyst. These improvements are due to the special preparation of the catalyst. Therefore, -C, for example, in reforming reactions, shows an improvement in yield (by just 0.1 m% (L)) and a significant increase in gasoline yield.

EXAMPLES In order to demonstrate the effectiveness of the catalyst according to the present invention, examples of the present invention were provided.

Example 1 A number of alumina-based catalysts containing cobalt and molybdenum are prepared and then tested for suitability for use in hydrogen-1 arsenic reactions.

Seven catalysts (containing 3% cobalt oxide and 14% molybdenum oxide) were prepared according to the following method.

Catalyst A: (No 1 in accordance with the invention) 250 m2/g of (B F 1- > specific surface area and 09 (
Forty bodies of transition alumina having a total pore volume of 3 cm"/(I) were impregnated with 3% by weight of cobal oxide l- from an aqueous solution of (IlI acid) pal l-. The catalyst was dried and then calcined for 2 hours at 500'C'U.The catalyst was then impregnated with 14% molybdenum oxide from a solution of ammonium paramolybdate.The catalyst was then dried and calcined at 500C. Ru.

Catalyst B: (does not meet the invention) Prepare ultrafine particles as follows.

The preparation of alumina gel is carried out by three consecutive precipitations of a solution of 1 helium aluminate. This putrium aluminate solution exhibited a weight ratio of Al 203 /Na2O of about 1.08, and the suspension had a
1, titrate about 50 (+/ρ) of alumino-, and NOa, /A/203 molecules of ffl tail, 1ζ
Ratio Jfi 0, 16 T'h') J:U'6
m1ia with nitric acid solution △/20; expressed as 1 and 10
0g// of watermelon is shown. The pl-1 of the precipitate is then approximately 9, and the gelcook prepared in this way is dried, filtered and washed. The mixture was treated in a stirred autoclave for 2/1 hour at 115°C. The resulting 7j product was treated with Al2O3 to give 12% alumina.
This shows the shape of the paste containing the .

B [E
The specific surface area measured by the 'l-method is approximately 30Qm
2/g, and the tC geometric surface measured after drying of this product, which was removed by azeotropic distillation and evaporation of isopropanol, was approximately 55
It is 0m2/g. Photographs of the product obtained by electron microscopy show that the product consists of long, very narrow, rod-shaped single crystals, often bound together in bundles.
It is made up of ultra-fine boehmite, which is completely made up of small fibers. The single crystal has a vertical size reaching about 500 to 1000 people. According to the other two directions, C1 If we consider these single crystals to be the same as cylinders, then B E
From the specific surface area determined by the T'' method, it can be inferred that these single crystals have an average diameter of 55 people.

l) el+yO-3cl+crrCr of this product
(Debye Sierra) Grano is old without reflection 1)
, Halation (0'12) J3J: Shows clear reflection (200>).

In this way, the sol forming the binder is treated with a certain acidified sol, selected so that the pl-1 of the final composition is less than 4 and the dispersion rate of the composition is 30%. I. Contact with water. The par ink is mixed with a gamma alumina charge in powder form.

The binder charge of 'ch fm was chosen so that the carrier thus produced contained 30% by weight binder and 70% by weight device genuine.The mixture of the charge and binder was as follows: It is done like c b.

A droplet of the mixture of dispersed alumina (binder) and non-dispersed alumina (charge) is formed by means of a 2.5111111 g diameter tube. Floating on an ammonia solution with a concentration of about 209/? A droplet falls into a column of diameter 600 nv containing a >6 cm oil layer.

The 811 residence time of particles in ammonia solution is approximately 2 minutes. The droplets curl up in petroleum and gel in ammonia solution. The balls recovered are very hard and can be transferred without deformation, and the balls are then dried and calcined at 950° C. for 1 hour.

This diameter exhibits a diameter of approximately 2-4 mm. - On the support thus prepared by the oil drop method, 1-cobal and 2-molybutylene are added to the catalyst according to the technique shown in "C", so that the metal content is 1q equal to that of the catalyst .DELTA.

Catalyst C: (Conforms with the present invention) Touch! I! ! Repeating the production of B, Lee added ammonium paramolybdate solution at the beginning and during the oil drop process. This solution is introduced into the binder (dispersion vessel 1~). Cobalt I~ is introduced into J in the case of catalyst B, sea urchin, and then C is introduced J8.

Catalyst 1): (Not in accordance with the invention) An ultrafine Per-My-1 sol is prepared according to the technique used for Catalyst B. Binder (dispersed permy 1-)
and the charge (non-dispersed Boehmai 1-) with water and 9
1"J acid and C paste 1 to Iζ and then extrusion". In this way 5 (,) Ofll's alumina on the one hand, and on the other'
? 25.0 cm3 of 2 distilled water and 20 can3 of 0,0
Add a solution containing 0.01M nitric acid to 13 o'clock [! 1. After mixing, prepare a uniform base.

Extrude C1 base (-) through a piston-shaped extruder C diameter 1.5111111 spun 11-karat gold.

The extrudates are dried at 300° C. and covered in such a way that the burnout nl of the resulting Iζ solid is about 20%.

To the catalyst 114 thus obtained, 11% molybdenum is then added using the technique used in the preparation of catalyst A.

Catalyst E: (Compatible with the invention) The preparation of the catalyst is repeated, but during extrusion, a solution containing balamolybutan nq ammonium is added to the binder (from 1 to 1 per minute).

As in the case of catalyst Da'), C cobal (.) is added afterwards.

Touch'A! F Knee (the present invention (3 does not match), touch the knee v!;' B @Used to dress up j this technique (ai
L: 2-) to prepare an ultrafine Permy 1-sol. A mixture of a binder (dispersed permy 1-) and a charge (non-dispersed permy 1-) was agglomerated into one batch using a rotary granulator.

Pour 500q of powder into the granulator, and at the same time pour 250q of powder into the granulator.
An aqueous solution containing m'' of distilled water and 20 cm3 of O,OOIMIl'1 acid is introduced in a granulation manner.

In this way, while the powder is rotating, the tablet making machine is
The first year of the Seiraku era).

The powder grows due to adhesion of the rice particles present.

Centrifugation removes particles as they exit the tablet machine. This is then dried at 300° C., and the resulting solid is dried so that the loss on combustion of the obtained solid is about 20%.

To the catalyst mass thus obtained, cohal oxide E~ and molybdenum oxide are added, according to the technique used for the preparation of 1Δ.

Catalyst G: (according to the invention) The preparation of catalyst F is carried out again, but during granulation a solution of paramolybdenum ammonium is added to the binder (dispersed boehmite).

Cobalt is added post-C as in catalyst F.

Catalyst B~[1 is presulfurized like catalyst A.

Example 2 Catalysts A-G are tested to determine their activity and stability in A5 hydroprocessing reactions. Catalysts Δ to G are presulfided before use according to the known h method. Processes heavy Iranian-type atmospheric distillation residue L! l! Zuru. The characteristics of this residue are shown in Table ■. Various tests were conducted using J-3 catalysts with the same diameter and different hydrocarbons at the same flow rate. A3 on the boiling 11jj bed (, the operation is carried out in only one step.

(Left below) Table 1 The reactor used in the test had an I-1/I) ratio (
The height relative to the white diameter is -13. All L1 [(
There is 90 bar C at the outlet of the reactor. The operation is carried out using a hydrogen gas flow Qi of gas 1480a under standard conditions at 15°C for feed 11. All of the gas is mixed with the feed and drips to the bottom of the reactor. The average temperature used in the test was 390'0 (-) with added catalyst/
'Freshly charged material is O, Gk++/t'' (there is. Newly prepared material/heavy Fυ ratio of can opening 1 with heavy catalyst suspension (, upper 0, 8
5, / l'l T exists.

The results are shown in Table ■. The catalyst prepared by the prior art (
A, B, D A3 J: and F) are less active than the catalysts (C, E, J, and G) prepared according to the present invention.

Continuation of page 1

Claims (1)

[Claims] (1) (a) A carrier 6 consisting mostly of alumina and (b)
) hydrotreating, hydrogenation of hydrocarbons in the presence of a catalyst comprising at least 1 metals from group 1 of the Periodic Table of the Elements and an active phase comprising at least one additional or promoter metal. Demetallization or hydrodesulphurization, in which the support used for the preparation of the catalyst comprises mixing a binder that is predominantly alumina-based with a charge that is predominantly alumina-based, shaping said mixture, drying and optionally It is obtained by performing calcination, and the dosage ratio of the binder is 15% of the total carrier.
~40%, and the ff11 proportion of the loading was 6% of the total carrier.
0 to 85%, and the alumina binder itself consists of a large portion of dispersed alumina and a small portion of non-dispersed alumina (where the portion of dispersed alumina represents at least 70% by weight of said binder). , the alumina charge itself consists of a large part of undispersed alumina and possibly a small part of dispersed alumina (the dispersed alumina part represents less than 101% of said charge), resulting from the mixing of binder and charge. The dispersion rate of the composition is 10-6
0% of the active phase or its precursors'
A method characterized in that at least part of the It is introduced into the charge during the manufacture of the support, and the Mlc is introduced into the binder during the mixing operation of the binder and the charge. (2) The mixing operation of the binder and the charge may be performed by an oil drop method,
The method according to claim 1, which is selected from the extrusion method and the rotary one-tablet method. (3) At least said portion of the active phase or its precursor is introduced during the mixing of the charge and the binder, mostly into the binder, or mostly into the charge. The method described in Section 2. (/I) When mixing the charge and the binder, first add the aqueous binder, then the active phase salt, and then add the appropriate salt.
According to the method, at least said portion of the active phase is introduced, preferably into a binder, in order to prevent the salts of the active phase from penetrating into the charge. The method according to claim 3, wherein: (5) When mixing the charge and the binder, first introduce the charge in the form of an aqueous solution, then the active phase salt, and then introduce the binder that has been pre-saturated with a suitable salt to prevent the active phase salt from penetrating into the binder. (6) Part of the active phase, binder d5. and the charge are simultaneously introduced, preferably by suppressing the charge with a suitable salt to introduce said part of the active phase into the binder, or preferably by suppressing the binder with a suitable salt to introduce said part of the active phase into the binder. Part 3 is introduced into the charge.
The method described in section. (7) Introducing a major portion of one or more additional metals into the binder using an oil drop method or an extrusion method, and introducing a major portion of one or more Group I metals into the binder or charge. The method according to claim 3, wherein: (8) Using an oil drop method or an extrusion method, introduce a major portion of one or more additional metals into the charge; 4. The method according to claim 3, wherein the method is introduced into (9) Using an oil drop method or an extrusion method, a major portion of one or more additional metals is introduced into the binder or charge, and a major portion of the Group I metal or metals is removed later. 4. The method according to claim 3, wherein the method is introduced into a carrier. (Hl) Using a rotary tablet machine method, introducing the bulk of one or more additional metals into the charge or binder;
4. A method according to claim 3, wherein the majority of the Group I metal(s) is subsequently introduced into the carrier.