JPS596944A - Catalyst for treating heavy oil and preparation thereof - Google Patents

Abstract

PURPOSE:To obtain a catalyst used in a fluidized catalyst layer available in the catalytic cracking of heavy oil, by baking a slurry in which alophene with a specific particle size and silica alumina hydrogel are mixed in a specific ratio. CONSTITUTION:Alophene is dispersed in a wet system to make an alophene slurry containing a alophene with an average particle size of about 5mum or less and a silicate solution and an acidic Al liquid are added to said slurry to form silica alumina therein. In the next step, after the volume of the slurry is reduced to about 1/2-1/10 by dehydration and concentration to remove impurities, water is added to the concn. slurry to adjust the slurry concn. to about 15-25% and the diluted slurry is spray dried. In this case, the ratio of an alophene and the aforementioned gel may be adjusted in such a manner that alophene content occupies 5-80% of a final catalyst. Thus obtained catalyst is treated so as to bring the specific surface area thereof to about 35-250m<2>/g and the specific gravity thereof to about 0.45-0.95 and, when it is used in the catalytic cracking of heavy oil, dehydrogeneration reaction and dehydrocyclization reaction are remarkably promoted.

Description

[Detailed description of the invention] A fluidized catalyst bed effective for the catalytic cracking of heavy oils such as commercial distillation residual oil, reduced kingship distillation oil, oil sand oil, oil oil, or similar heavy hydrocarbons. Regarding the touch 11l^ and its manufacturing method, it is extremely safe against water vapor and heat, and has excellent resistance to wear and tear.
Heavy oil processing catalysts and catalysts that produce high yields of so-called middle distillates such as stale oil and nail oil, and which significantly promote dehydration, unreacted dehydration, and dehydrogenation reactions. The purpose is to propose a manufacturing method for i4cm.

It has been known for some time that the quality of hydrocarbons (petroleum-based hydrocarbons) can be improved by processing them under appropriate operating conditions, and many sacrificial projects have been proposed. Then, the flow contact outside 1'l'i! method (Ii' C
(Method 3) uses a synthetic alumina amorphous gel catalyst or a synthetic alumina gel catalyst. A catalyst with relatively high activity, such as a catalyst containing zeolite, is required, and a reaction width of 115°C is achieved using carbons such as kerosene and arsenic, which have a relatively narrow boiling point range, as raw materials. 1 core time 20
The purpose is to obtain a ganolin distillate f) 'l''y< by a single contact treatment in a short period of time.Such FCC! However, the reaction unsaturated components undergo thermal condensation, producing tar-like heavy oil as a by-product, and the yield of middle distillates below heavy oil is low, and the thermal stability of the catalyst is poor. This has not made up for the shortage of middle distillates for jet oil, kerosene, diesel oil, and AFJF oil, which are expected to have a potential increase in future demand.

In order to obtain a middle distillate of 11V from the catalytic cracking of heavy oil, the present applicant first carried out a catalytic cracking process using natural allophane and rM''R as a catalyst, and achieved a cracked oil yield of more than 80%. A means to become a thing?I proposed, but this proposal 11 1-1
−． 1) The decomposition of the catalyst into the precious fluid #F was successful.) 1. +C<<, and 1 has the disadvantage that the catalyst life is relatively short, so it is not completely satisfactory.

The present invention proposes an effective catalyst in the method of catalytic cracking of heavy oil proposed in the above-mentioned prior art (disclosed in Japanese Patent Application Laid-Open No. 56-127687). The catalyst used in No. 127687 (No. and significantly promote dehydrogenation reactions 17,
]11 P(-Al
203, Or203-Al2203, Mo03-Δ
R, (, ),, circle 11c - A Q, high R by using an expensive catalyst such as 201: product similar to the decomposition number d product produced in the device, 4z-, ) Jffi contact It also has great features that can be obtained through decomposition.

Allophane used in wood invention has the nickname Kurito, 1
Unexpanded soil, water, soil, or floating stones, it's one thing! Stem alpha soil, central body id mineralogical VcAfV, L+ph
Its physicochemical properties 1 are different from other clays, and it has an extremely interesting adsorption capacity, and is about to become the first adsorbent in Japan. For example, there is a deposit of 100 million tons in the center of the 1 Kanto Lom layer, and it is famous that it is produced in the Kanuma region of Tochigi Prefecture.This allophane is 011
It is assembled from fine particles of 1 m or less to form porous giant particles, and the general formula of its structure is J203 ・(1-
2) Si02 ・(2~3) 1120-1- (0
-2) It is represented by Ag203 (1120) and is a mixture or ii: composite of amorphous hydrated aluminum silicate and the same Irl' alumina gel 2.
The components of the dry product (d, Sin, , are 34.91■, AQ2
(,)3ka'22.7K@%,O;IOf)r
O, 9% by weight, MgO 0.9% by weight, Na20 06
10, K2O is 05 weight i%, Fc203 is 561■, 1
．． g-Ross has a weight of 32.6, an apparent specific gravity of 25, a bulk specific gravity of 0.43, and an evaporation rate of 75.

The wood invention is based on this allophane 'i'F-average particle size 5/4
One of the features is that the wet dispersion machine is used to perform as fine a grinding process as possible to less than the TI, that is, the basic particles with an allophane ID of less than 0.114n are only agglomerated. The interparticle strength was weak, the abrasion resistance was poor, and there were many problems as a single catalyst for flow l111 catalytic cracking, but allophane was dispersed close to the basic particles so that the average particle size was 51bn or less, and the interparticle gaps were By reacting and producing a silica alumina hydrogel with the same composition as allophane, thoroughly mixing it, and then molding this gel as a binder, allophane is
Contains 0% shirashi with a specific surface area of 35-250 m”7g
We have created a product with a cap specific gravity of 045 to 095 that does not impair the properties of allophane in any way (and is rich in abrasion resistance (F)).

It is generally said that the cracking catalyst 1 has a higher activity as the specific surface area and pore volume of the catalyst are larger. As shown in the figure, the molecular weight of the decomposition product is relatively thick @tn, lμ combined i/rc is the pore diameter of the catalyst - h5 on the larger side, - that is, I Fl Fl
A catalyst with a majority of pores larger than O'A is required,
Koyun 40 equipped with silica alumina hydrogel
The pores with a diameter of about 100 mm are blocked by the carbonaceous material produced by a single contact reaction; Alofuenwo average 5/l according to the present invention
■ 1000 to 5 obtained by dispersing below
A pore size of 000 x is considered to be effective for heavy oil processing.

Silica alumina M containing silica alumina catalyst or zeolite! There are various methods for preparing the aluminosilicate used in medium II etc. ΔNo.1. For example, glue kneading method and gel kneading method of kneading alumina hydrokel, 7II
A gel deposition method in which silica gel is produced and alumina is produced in this slurry, and alumina is deposited on silica gel particles. Silica xerogel powder or silica hydrogel is impregnated with a salt aqueous solution of alumina, and silica alumina xerogel is evaporated to dryness. an impregnation method to obtain a silica-alumina hydrogel, a kell milling kneading method to obtain a silica-alumina hydrogel by grinding silica and alumina xerogel powder and dry chemical mixing, and a co-gelation method to obtain a silica-alumina hydrogel by simultaneously gelling alumina and warping force. Although there are various methods, since the silica alumina hydrogel 1 of the catalyst C in the present invention is only considered to have a role as a binder, the simplest cokelization method is suitable for its production method. However, rather than making a silica alumina hydrogel and then mechanically mixing allophane, a method in which allophane and sodium silicate liquid are mixed in the first step,
Next, adding aluminum sulfate or aluminum nitrate solution, which is an alumina source, to react and generate silica alumina hydrogel in the allophane slurry can solve the problem of adhesion between the cough kelp and allophane. . It should be noted that the co-gelation method is said to be inferior to the stability of silica alumina gel, but as in the present invention, it is possible to ripen the gel at a low temperature in one container, to form a gel, and to use the gel as a binder. The instability of tL-i could not be ameliorated.

Additionally, fluidized bed catalysts are particularly desirable for wear resistance.
In particular, allophane alone has a problem of 1r1, 100% corrosion resistance, and in other words, due to the strict public regulations, it is difficult to discharge it from the chimney from the Zyclone of the regeneration tower used during regeneration. Even if worn catalyst fine powder becomes a problem,
For these reasons, catalysts with even better wear resistance are available. Catalysts containing dry I-based materials were generally considered to have poor wear resistance, but the catalyst of the present invention has excellent wear resistance comparable to that of conventional silica-alumina catalysts. ing.

The method for producing such a catalyst is as follows: (1) Allophane, which has been ground in advance to a size of +00 mesh or less, is mixed with water to create a slurry containing 2 to 50 allophane particles, and the average number of allophane particles is 5.
/#nl: Under J, homogeneous dispersion is carried out using a wet separator until the large particle size is about 1010n or less, and the final catalyst contains about 5 to 80% allophane, especially preferably I, <(Ii30
(2) Mix and stir a 0.5 M or less sodium silicate aqueous solution to the slurry, (3) Add 0.5 M or less of acidic aluminum to this slurry. Add a salt solution, react and generate silica-alumina cokel in the slurry at a pH range of 3 to 10, and age with stirring, (4)
Then, the slurry is concentrated and dehydrated to remove impurities produced by a centrifugal separator, etc. (5) After adjusting the water content so that the slurry has an unusual viscosity, it is spray-dried, (6) IT acid It is produced by ion-exchanging and washing impurities that are produced as a by-product during the production of solica alumina hydrogel with ammonia solution or ammonia water, (7) re-drying, and then firing.

In the above process, sodium silicate,
As the alumina source, aluminum sulfate or aluminum nitrate, and ammonium IL1+I acid or aqueous ammonia for cleaning are used, and industrial chemicals according to JIS standards can be used as these.

For example, sodium silicate is 1. IIS No. 1 5in
2/Na2O molar ratio of about 2 or January 83 Sin, /Na2O molar ratio of about 3 can be used, and diluted with water to a concentration of 0.5 M or less. It was in January. When using IIS No. 3 sodium silicate, there was a problem that the flocs became large and soggy when creating a high concentration gel, but no problems were observed when gelling at a low concentration. Ta. In addition, when creating a co-gel, the amount of sodium silicate and acidic aluminum are adjusted and determined so that the pH at the time of gel formation is in the range of 3 to 10, so that good strength as a catalyst can be obtained. A co-gel was created with Further, the ratio of the amount of allophane to the cogel may be adjusted so that the amount of allophane contained in the final catalyst is 5 to 80% -Fl, is 80%
In the second case, the particle strength becomes low and it is not possible to obtain a particle strength that can withstand industrial use for a month.In addition, below 5%, the catalytic properties of Id allophane cannot be fully exhibited. . Further, when the co-gel is produced for 1.7 seconds, the solid content concentration of the gelling slurry is preferably 10 parts or more, more preferably 5 parts or less. This is because co-gel flocs of silica-alumina hydrogel grew too quickly, resulting in insufficient mixing, which adversely affected mixing with allophane, making it impossible to obtain a dense and hard catalyst.

Furthermore, dehydration using a centrifugal separator can reduce the amount of sodium sulfate and sodium nitrate that are produced as by-products during gelation, which increases the strength of the shaped particles after the spray drying process. When drying, adding as little water as possible to the concentrated cake to achieve the highest slurry concentration that can be sprayed by the nozzle will reduce particle shrinkage during drying and yield dense spherical particles. and tc
Ru. The sulfur (II) 7.0 in the dry particles can be removed by conventional means, such as ion exchange with an ammonia sulfate solution or aqueous ammonia, and washing. Then, for example, dry at 110°C for several hours J, '61. ．． By carrying out 'l1lIj15' at 750°C, heavy 2I11
1 November 1 catalyst is obtained, but drying is next -f
This is just a way to easily carry out firing in the shoulder joints, and regarding firing, the dehydration condensation of silica alumina hydrogel is 6
Since it is carried out up to about 50℃, it is less than 7': C at least 6.
#1 in the range of 970'Ci where (7) d,,03(Si02)n in silica alumina hydrogel and allophane undergoes a thermal phase transition and becomes sintered. It is necessary to carry out the process at a temperature of about 700 to 80° C. A good catalyst for treating heavy oil can be obtained by firing at a temperature of about 700 to 80°C.

The catalyst obtained in this way can be brought into contact with the reaction conditions that are normally used for the decomposition of petroleum hydrocarbons, for example, in a fluidized manner. It selectively promotes dehydrogenation reactions and dehydrocyclization reactions, lightens the oil, and at the same time produces cracked oil rich in middle distillates.The temperature during this fluid catalytic cracking is approximately 350℃.
The process may be carried out at ~500°C for several seconds to several minutes, and the catalyst ratio (catalyst/heavy oil) may be in the range of 01 to I5.
As the catalyst ratio increases, the cracked oil yield tends to decrease slightly, the cracked gas density increases, and the hydrogen in the cracked gas increases.
A catalytic dehydrogenation reaction is observed. The amount of dehydrogenation is comparable to that of the brat forming method known as a catalytic reforming method, and the reaction depending on temperature is also similar, and the aromatization reaction increases as the temperature rises. However, the cracked oil has a lower specific gravity than the heavy feedstock oil in all fractions, and the non-reactive fraction in the cracked oil causes thermal condensation, as seen in conventional CC catalysts. There is no generation of tar or pitch by-products, and the decomposition residue is recovered in a non-viscous state with carbon deposited evenly on the catalyst surface.This waste catalyst can be easily regenerated in a fluidized manner, improving decomposition performance through regeneration. The decrease was almost negligible.

As described in -4- below, the present invention involves micronizing soil mainly composed of allophane, which is abundantly produced in nature and available in large quantities, into particles of a specific size, and forming silica alumina hydrogel. ! A granulated composition containing i and lr in a certain range is treated in a specific manner. There is less spherical A, C, and when such a catalyst is used in the catalytic cracking of heavy oil (7), a high yield of middle distillates (8) and dehydrogenation reaction, dehydrogenation The reaction is significantly accelerated,
(Buddha)' Become a sign.

Specific examples of the present invention will be described below.

Real Noi! IV/]lI Place several sheets of Shika I (Ganseiro 11 Ginseng Ju) allophane (Ganseiro 11 Ginseng Ju), which has been crushed in advance to less than 100 Metsuyu (40014), into a 50% slurry liquid by adding water (7) f The agitator shaft with a disc is rotated to stir the steel ball beads filled in the container to 60-80%, and the allophane particles are dispersed at the bottom of the container. The average particle size is 211m or less, the maximum particle size IQ/1m
Wet fractionation is performed to obtain the following (7) to obtain an allofene dispersion slurry, and 600/(7) of water is further added to obtain a 20-circulation slurry.

Add 1.5 M sodium silicate to this slurry liquid, which is obtained by diluting JlSl: 4-grade 1-digit sodium silicate (SiO, 37%, 5i02/Na□0 molar ratio 209) with water. Add 25 m3 of an aqueous solution, mix well with a mixer at 11', then add 028 m3 of a 05M aluminum sulfate aqueous solution prepared by diluting JIS solid special issue aluminum sulfate with water, stir vigorously for 1 hour, and then continue stirring. Mix and mature for one day and night. Note that ptr at this time is 45.

Then, this slurry liquid is separated into a concentrated slurry with a solid content concentration of 30% and a -L wrinkle liquid using a horizontal continuous car core separator.
This concentrated slurry is taken out and water is added to give a solid content concentration of 20.

Then, add this 20% slurry to 1" gas temperature 1 phase 30
Spray-dry in an atmosphere with a gas temperature of 110°C,
The obtained dried product was mixed with 05% 1fift ammonia aqueous solution,
After washing with 05 ammonia water, it is dried in an oven at 110°C for 16 hours, and then baked at 750°C.

The composition of the catalyst according to the present invention obtained in this way is S
10263.6%, AQ20324.0%, C;
+02.5%, Mgol, 7%.

Nh201.4%, K2(') 0.7%, 5O10
, 4%, l'c: 32%, and the specific gravity is 0779,
Specific surface area ++smF/g, pore volume 0.21 an”/
, q, wear resistance rate was 0.93, and the fluidity evaluation and jetting property evaluation are as shown in Tables 1 and 2.

Example 2 Si() 227.1%, A flood 203227, Oao
03%, Mg00.2%, Na2006, +(20
0.2%, I'c2031.8%, 1. g −1 ns
s46', 4% allophane dried at 105°C,
Fruit) Strain and disperse in the same manner as in Example I to an average particle size of 2 μm or less.1. JIS standard: No. storium silicate (,'1
i0229%, 5i027N; +20 E/l/ratio +1
)+7) +1.5% Sodium silicate solution 23m
3 and mix, further add and mix 0.5M 1l aluminum peroxide water and sex liquid 0281i3, and ripen by stirring gently for one skin, then dehydrate, adjust water content, and spray in the same manner as in Example 1. Dry, wash, re-dry, and fire.

The composition of the catalyst according to the investigation obtained in this way is 1/l
j, Sin,, 664%, 8ρ20321.2%,
(EaO2, 4%, Mg01.2%, Na201.2
%, K200.6%, 8030.4%, Fc 2.5%
, specific gravity 0.775, specific surface edge +osm”/
g, thinning volume 0.23 (1n3/g, wear resistance rate 090
The fluidity evaluation and the jet property evaluation are as shown in Tables 1 and 2.

Table 1 Table 2 As can be seen from these results, Catalyst 1 according to the present invention is slightly inferior to the FCC zeolite catalyst in terms of surface area and atomization volume (if compared to allophane frozen soil, the surface area of Tohi is However, in 1, the pore diameter is concentrated in the 40 to 70 λ range in the zeolite catalyst, whereas in I7, the pore diameter in the present invention is often in the range of several hundred to several thousand years. The wear resistance rate is much lower than that of allophane frozen soil, and it is similar to the zeolite catalyst, and has a high strength. The evaluation shows that the catalyst of the present invention has very good fluidity as a flowing catalyst and forms a uniform fluidized bed.The catalyst of the present invention has a small collapse angle and a very spherical particle shape. It is close to 1/lC, and the taste IF
F: There is a C with high l.

Next, the catalyst according to the present invention, the zeolite catalyst, and the allophane frozen soil catalyst were tested in a continuous fluidized catalytic cracking test furnace with a specific gravity of 957, a pour point of 10°C, and a flash point of 1.
78°C, kinematic viscosity ri (50°C) 2315C8I, residual carbon 89%, S content 32%, A, sl + min 0015% Middle Eastern atmospheric residual oil was treated under heavy-duty oil treatment IR/reaction conditions.
h, catalyst ratio 10. Regeneration temperature 650℃, decomposition temperature 450℃
When the decomposition test was carried out, the results were as shown in Table 3.

υ From the results, the catalyst of the present invention 1. C. The zeolite catalyst (l-1) exhibits mild cracking characteristics, and the fraction of cracked oil is also lighter than the feedstock oil, and the heavy oil fraction is similar to that of heavy oil A. Furthermore, the yield of the middle distillate is extremely high, and the dehydrogenation reaction is remarkable, with a large amount of 112 min in the cracked gas.Furthermore, the naphtha fraction has an aromatic content of 25 to 26%. It shows a remarkable dehydrocyclization reaction, and the gas oil fraction also contains a large amount of olefins, of which 1 part is α-olefin, and can be used as a raw material for higher alcohols, etc. It has f features such as.

Claims (1)

[Claims] ■ A slurry containing allophane with an average particle size of about 5 μm or less in a ratio of about 5 to 8 degrees, and the remaining main component being alumina hydrogel, is fired, and has a specific surface area of about 35 ~25
0Tn2/! ;/de,ka/]Kasada type is approximately 045~o9
A certain 1 immortal who is characterized by having 5Cs. ■Wet-fraction allophane to make an allophane slurry consisting of particles with an average particle diameter of approximately 5 μm or less. Kawai allophane slurry, silicic acid 1@liquid and 1'l! 2. Aluminum liquid? In addition, the paste is produced in a slurry of alumina gel, and then the slurry is dehydrated and concentrated to remove impurities, and then water is added to make the slurry concentration about 15 to 25%, and the slurry is sprayed. 1. A method for producing a catalyst for beating oil, which is characterized by drying and then calcination.