JPS61283686A - Cracking method by molecular sieve containing aluminum, phosphorus and silicon - 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 relates to cracking reactions with aluminum, phosphorus and silicon containing molecular sieve catalysts.

US Pat. No. 4,440,871 to Lok et al. describes various molecular sieves containing aluminum, phosphorus, and silicon. Rock et al.'s patented molecular sieve is a silicoaluminum
They are called 3-nophosphates, and include A I x Os, P
It is prepared by crystallizing various sources of 2O5 and S i O2. One of the silicoaluminophosphates described in the Rock et al. patent is designated SAPO-37. This SAP○-37 has the characteristic Xfi powder diffraction pattern listed in Table 1 below: 6.1-6.3 14.49-14.03
Strongest 15.5~15.7 5.72~5.64
Weak-Medium 18.5-18.8 4.80-4.7
2 Weak - Medium 23.5~23.7 3.79~
3.75 Weak-Medium 26.9-27.1 3.
31-3.29 The X-ray powder diffraction pattern for SAPO-37 described in the Weak-Tsuku Nakaguchi et al. patent corresponds to the crystal structure of faujasite.

U.S. Pat. No. 4,504,382 to P 1ne describes a process for the modification of zeolite Y with dihydrogen phosphate or dihydrogen phosphite anions. It is stated that the obtained phosphorus-containing zeolite Y has such high cracking activity that it produces naphtha with an octane number almost the same as that obtained with comparative zeolite Y that has not been modified with phosphorus (Bin. Patent Mei It (see Book II, column 8, lines 1-17).

U.S. Pat. No. 4,30 to Chester et al.
No. 9,279, No. 4,368,114 and No. 4,
No. 416,765 describes methods of adding various additive catalysts to various cracking catalysts. Added catalyst improves octane number.

The present invention cracks hydrocarbons with a boiling point range of 232-760°C using a cracking catalyst at a temperature of 300-700°C, a pressure of 0.1-30 atm and a weight hourly space velocity of 0.1-100. In the catalytic cracking process for producing a gasoline-containing product stream, the catalyst has a faujasite type crystal structure and A I 20 s, P
The object of the present invention is to provide a catalytic cracking method characterized in that it uses a microporous crystalline molecular sieve prepared by crystallizing a source of 20 s and 5 in2.

In another embodiment, the catalyst used is a system consisting of at least the molecular sieves described above and conventional catalytic cracking components.

The molecular sieve used in the present invention is S
It can be prepared by the method for producing APO-37.

These molecular sieves contain at least 1% aluminum atoms, at least 1% phosphorus atoms, and at least 1% silicon atoms, based on the total number of aluminum atoms, phosphorus atoms, and silicon atoms in the molecular sieve. The number of aluminum atoms in the molecular sieve may exceed the number of silicon atoms in the molecular sieve, and the number of phosphorus atoms in the molecular sieve may exceed the number of silicon atoms in the molecular sieve.

The optional conventional catalytic cracking component may be a molecular sieve having a faujasite type structure. Various synthetic zeolites have a faujasite type structure, such as zeolite

The structure of these materials can be slightly modified by a number of physical and chemical treatments, such as by calcination, steaming and dealumination, to enhance the contact properties of the materials used herein. Faujasite-type structures refer to the range of structures that result when synthetic faujasites are subjected to various physical and chemical treatments that can enhance their contact properties without decomposition.

In addition to faujasite-type structures, optionally component catalysts can have other structures that are sufficiently porous to sorb large molecules much like faujasite. One such structure is disclosed in US Patent Application S,N.

No. 642.967.

Examples of structures capable of sorbing large molecules are structures with pores or openings formed by 10- or 12-membered rings of atoms. In addition to the structure of SAPO=37, SAP〇-5, SAPO-5, described in the above-mentioned U.S. Pat.
1'1 and SAPO-40 are atoms in a 10-membered ring or 12
It has a structure with pore openings formed by member rings.

The silicon, phosphorous and aluminum sites of the above-mentioned molecular sieves can be fully or partially replaced by elements of equal functionality. For example, in the field of silicon and aluminum containing zeolites, the silicon sites themselves can be replaced, for example with germanium. and the aluminum moieties themselves can be replaced with, for example, iron, chromium, vanadium, molybdenum, arsenic, antimony, manganese, gallium or boron. Regarding this, August 21, 1984
See US patent application Ser. No. 642,925, filed on no.

In addition to the crystallization of S i O 3 , A 1.03 and P 2 O 5 sources in the manner described in Locke et al. U.S. Pat. A suitable molecular sieve can be prepared. The materials described above can be prepared by impregnating a zeolite containing silicon and aluminum with a suitable phosphorus compound and then calcining it under conditions sufficient to convert the impregnated phosphorus to its oxide form. U.S. Patent No. 3,894,104; U.S. Patent No. 4.049,573;
No. 4,086,287; and No. 4,128,592; It is possible to combine aluminum phosphate with silica in a method.

The contact crabking equipment that can be used in the process of the invention can be operated at temperatures of 204 DEG to 704 DEG C. (below 400 DEG to 1300 DEG C.) and under reduced pressure, atmospheric pressure or superatmospheric pressure. Catalytic cracking processes can be carried out batchwise or continuously. Catalytic cracking processes can be fixed bed, moving bed or fluidized bed, and the hydrocarbon charge stream can be cocurrent or countercurrent with the conventional catalyst stream. The process of the invention is particularly applicable to fluid catalytic cracking (FCC) processes.

Details of specific operating parameters such as operating conditions, feedstock, etc. can be found in U.S. Pat.
No. 68,114 and No. 4,416,765.

In carrying out the cracking process of the present invention, the phosphorus-containing crystalline material and optionally the conventional cracking ingredients are combined into other materials (components) that are resistant to the temperatures and other conditions used in the operation. This is desirable. The ingredients include synthetic or naturally occurring materials as well as inorganic oxides such as clays, silicas and/or metal oxides. The material can be in the form of a gelatinous precipitate or gel containing a mixture of silica and metal oxides. Naturally occurring clays that can be used include those of the montmorillonite and kaolin families, which include subbentonite and kaolin, known as Dexie, Macnamegeorja, and Florida clays, or where raw mineral components include halloysite, kaolinite, and detskiite. , others that are Nakrite or Anauxisite. Such clays can be used in their raw, as-mined state or after prior firing, acid treatment or chemical modification.

Alumina, silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-beryria, silica-titania, as well as ternary compositions such as silica-
Alumina-thoria, silica-alumina-zirconia, silica-alumina-magnesia and silica-magnesia
Other components such as zirconia can also be used.

The dosage may be in the form of a kogel. Relative proportions, on an anhydrous basis, of the inorganic oxide gel fraction and the zeolite component, e.g., SAPO-37, as taught in U.S. Pat. The molecular sieve content ranges from about 1% to 99% by weight of the dry composite, more usually from about 5% to 99% by weight of the dry composite.
It can vary widely over 80% by weight.

Cracking conditions are conventional conditions, 300-700
Temperature of 0.1-30 atm and pressure of 0.1-100 °C
Includes space velocity of weight hourly space velocity.

The charge containing hydrocarbons to be cracked is 2
It may contain wholly or partially a gas oil (e.g. light gas oil, intermediate gas oil or heavy gas oil) having a boiling point range within the range of 32-760C (450-1400C).

1! P'=7 Phosphoric acid (85 wt 1%>12.6 parts, distilled water 13.4 parts and alumina [Catapal 5B) 1
A solution was prepared by mixing 7.5 parts. By mixing 1.4 parts of silica (Cab-0-Sil M-5), 1 part of an aqueous solution of tetramethylammonium hydroxide (25% by weight), and 52.7 parts of an aqueous solution of tetrapropylammonium hydroxide (40% by weight). After preparing the second solution, the two solutions described above were mixed under stirring until the mixture became homogeneous. Load the mixed solution into the autoclave,
0 heated to 200 °C under constant stirring for 24 h.
The resulting product was then filtered, washed and 121°C (25°C).
0) and then dried. The analysis of this material is described below in comparison to the material prepared in Example 43 of US Pat. No. 4,440,871.

N 1.7 1.8C1
4,914,2 S i O29, 79, 2 AhOt 32.5 31.8P, 0
5 29.5 31.4th order (1000
℃) 76.2 73.900゛Crystal H2035,2(12)-8) 35.3
(4,6)-A)cy~c, 20.1(2
0)-le) 23.2(60)-le)n
-Cs 18.2 (20) -2 f
: - Sodium silicate (SiOz28.7% by weight, Na2O3
Solution A containing 26.2 parts of water and 26.2 parts of water was cooled to 4-7°C (below 40-45%), and 0.0.6 part of 100% H,S was added. was gradually added and mixed using a Cowles mixer at 700-800 RPM.

In the next 1/2 hour, aluminum sulfate (17,2J11
Solution B containing 1 part of %Al2O, ) and 7.50 parts of water
was added slowly and the resulting gel was stirred at 700-800 RPM for 1/2 hour. A slurry containing 0.62 parts of the molecular sieve from Example 1 (based on 100% solids) and 2.49 parts of water was added to the gel, and the resulting slurry was then mixed for 1 hour at 700-800 RPM. .

The material was then passed through a Buchner funnel, reslurried to approximately 11% solids, homogenized, and spray dried. The spray-dried catalyst was then ion-exchanged with N )-1, NOl, washed with water, and dried at 121 °C (below 250 °C) for at least 16 hours. The obtained catalyst is amorphous S i O
2/ AI 20. Example 1 in the supplementary provisions (weight ratio 93/7)
It contained 20% of molecular sieve.

3f-:i The catalyst from Example 2 was steamed in a fluidized bed at a temperature of 677° C. (below 1250° C.) with 45% steam and 155% air at atmospheric pressure for 10 hours.

Self-” L Ko and January Yu J1 medium! b The catalyst from Example 3 above was steamed in a fluidized bed at a temperature of 788° C. (below 1450° C.) with 45% steam and 155% air at atmospheric pressure for 10 hours.

5 P , ;+ The fluidized catalyst of this example is prepared by the procedure outlined in Example 2, but with calcined RE
Use V. The obtained catalyst is amorphous S io 2/
A I20 ) 20% R in the fraction (weight ratio 93/7)
It contained EV.

6 Shishi: La1 A portion of the catalyst from Example 5 was heated at 677°C (125°C) in a fluidized bed.
0 below>, 45% steam 155% air, atmospheric pressure 1
Steamed for 0 hours.

7: ;- A portion of the catalyst from Example 5 was heated to 788°C in a fluidized bed at 1450°C.
(lower), 45% steam, 155% air, 10% at atmospheric pressure.
Steamed for an hour.

Concave-'L Example 3.4.6 and 7 catalysts in a fixed-fluidized bed apparatus using dioliet sour heavy gas oil (JS, HG○) as feedstock at 516 °C (below 960 °C), 1 .75-5.0
C10,34-12WH3V time-+ (weight time space velocity) was evaluated.

The JS HG○ charge material has the characteristics described below.

No.-U specific gravity, y/cc O, 908A
PI specific gravity 24.3 aniline point,
°C/lower 77/171 Sulfur, wt%
1.87 Nitrogen, wt%
0.10 basic nitrogen, ppm
327 Conradson residual carbon, wt% 0.28 viscosity, KV, 99°C (below 210) 3,6 bromine number
4.2R,I, 21℃ (70 below >
1.5080 hydrogen, wt%
12.3 molecular weight 3
58 pour point, "C/lower" 29.4/85 Paraffins, wt% 23.5 Naphthenes, wt% 32.0 Aromatics, wt%
44.5CA, weight% 18,
Results for the 5REV catalyst (Examples 6 and 7) and the catalyst of the present invention (Example 3)
Comparison of the results of 4) and 677°C (below 1250°C) steaming (70% conversion by volume) and 788°C (1250°C), respectively.
450) Steaming (55% conversion by volume) is described in Tables 2 and 3.

Steaming at 677°C (below 1250°C), the catalyst of the present invention has a C6+ gasoline yield of 2.2% over the RE'1/catalyst.
4 volumes? Although it decreases by 6, it improves RON+O by 4.2. In addition, the catalyst of the present invention produces a large amount of Cz(-C, olefins, and when the olefins are alkylated, an increased yield of C, 4-gasoline + alkylate can be obtained. (fuel oil) and LFO (light fuel oil) yields are approximately equal.

When subjected to more severe steam deactivation at 788°C (below 1450°C), the catalyst of the present invention reduces the C21-gasoline yield by 1.6% by volume over the REY catalyst, but the RON
Improve by 3.7. Thus, it is clear that increasing the steaming severity improves the selectivity of the catalyst of the present invention; the rate of increase in octane number per reduced volume of gasoline increases. Additionally, this more severe steaming results in the catalyst of the present invention containing 3.9% LFO by weight less than the REV catalyst.
The amount of HFO is increased by 4.2% by weight.

Daiichi-j1 677°C (below 1250), 45% steam, 755%
Transfer rate, volume % 70 70 --C5
+Gasoline, volume % 55.5 53.1 -2.
404 accounting, volume% 15.3 17.2
+1.9 dry gas, wt% 7.8 8.
8. 1.0 coke, weight% 4.6 4
．． 3 -0.311□, weight% 0.0
2 0.03 +o, otC3, weight 1%
0.5 0.5 0. OC2・, weight%
0.5 0.7) 0.2C7, volume% 2.6 2.8 +o, zC1
;, volume% 6.7 8.1 11
．． 4”-C4+vol% 1.9 1.
8-0.1i-C4, volume% 7.4
8.5 +t, tC1;, volume% 6
．． 0 6.9 +o, 9C5 + sorine + full chelate yield 77.3 78.2
)0.9RO1bO1C,)forcesolin
86.6 90.8 +4.2ftO
NIO1C9) Force (sol) 7 chelates 88.
6 91.8 +3.2LFO, weight%
27.5 26.5 -1.011FO1
Weight% 4.9 5.8 +0.9
1-1-” Round 788°C (below 1450), 45% steam 155% conversion rate, volume % 55 55 --C5+
Gasoline, volume % 47.7 46.1 -1.6
C4 total, volume% 10.1 11.4 +
i, a gas, weight% 5.1 5.8
No. 0.7 coke, weight% 2.0 2.
0 0. O11□, ffi amount%
0.01 0.03 +o, ozC3, weight%
0.3 0.4)0. IC2・、
Weight% 0.4 0.4 0°OC5, volume% 1.2 1.2
0.0C4=, volume% 4.8
5.6 to, 8n-C4, volume%
1.2 0.9 -0.3i-C4, volume %
4.3 4.2 -0. IC4: Volume % 4.6 6.3) 1,7C9
+force'Sorin t alkylate yield 63.8
68.6 +4.8RONtO1C5+force 85.9 89.6
+3.7ROM+0. C, force solubility (alkylate 87.9 91.1 +3.2
LFO, weight 1% 31.0 34
．． 9 +3゜911FO1% by weight
16.1 11.9 -4.2 The above example is
At a constant conversion, there is a yield loss of 1 to 2 volumes, indicating that the catalyst of the present invention produces a gasoline with 3 to 5 higher RON+O than the REV catalyst. This increase in octane number also produces more C3 and C, olefins, and when the olefins are alkylated, in the case of the catalyst of the present invention, a greater amount of C5 + gasoline + alkylate yield is produced. is obtained. Furthermore, R in industrial equipment
When steaming under conditions simulating the equilibrium of an EV catalyst, the catalyst of the present invention produces about 4% more LF○ by volume than REV.
, which suggests a better selectivity for residual oil cracking of the catalyst of the present invention.

Although the above examples and evaluations are of single clubking catalysts, possible applications of the catalysts of the present invention include other conventional active catalysts, such as R
EY, USY, HY, Zeolite Beta, Z S M
-5, amorphous catalysts, etc.). The amount of the catalyst of the invention in the catalyst warmer can be, for example, from 0.01 to 50% by weight or from 0.1 to 25% by weight, based on the accounting weight of the crabbing catalyst present.

Examples 9 to 11 below illustrate the effectiveness of the catalyst of the present invention when evaluated as an additive catalyst.

9-9: Defunct W R Brace End Company (W
A sample of Super-D, an industrially available fluidized cracking catalyst manufactured by Davison Division, Davison, R., Grace & Co., was steamed at 45% in a fluidized bed. , 788 using 755% air
Trap listener mining was carried out for 10 hours at a temperature of 1450° C. (below 1450° C.) and atmospheric pressure.

10 pm: Mix a portion of the steamed catalyst from tgI Example 4 with the catalyst from Example 9 to prepare Moleya from Example 4 in Super D. −
Buo 4 weight 9. Contains, compound (*f (ask.
'Takumi 11 The catalysts of Examples 9 and 10 were heated at 516°C (90°C) in a fixed-fluidized bed apparatus using a Joliet Sower heavy gas oil charge.
60 lower), catalyst/oil (C10) ratio of 1.75 to 5.0 and space velocity of 34 to 12 W T-T SV time-1.

A comparison of the catalysts of Examples 9 and 10 listed in Table 4 is RE Y
Figure 2 illustrates the effectiveness of the catalyst of Example 4 as an added catalyst in the presence of a base catalyst.

First, first, first”! 788℃ (below 1450), 45% steam 155% empty
1 point -・70%LL -ff
LL (Lu A- conversion (hi rate, volume% 70 70 --
C9+gasoline, volume% 54.9 54.4 −
0.5C1 type total, volume% 15.8 16.
0 10.2 Dry gas, weight 1% 7.9 8
．． 3 10.4 Coke, weight% 4.3
4.5 10.2H3, weight% 0.
09 0.09 0. OCz, heavy jL%
0, 5 0, 5 0, OC2
:, weight% 0.6 0.6
0. OCl, volume% 2.6
2.7 +0. IC1・, volume% 6
．． 9 7.3) 0.4l-Cn, body i%
1.6 2
．． 0 10.4i-C4, volume%
7.6 7.7 +o, t04・, volume%
6.6 6.4 -0.2C51 Sorin F alkylate yield 77.2 78.
8 -0.4RONIO1C1←Force
87.3 8L8 +1.5
RONIO5C5+Sorin (7h chelate 8
9,2 90.3 No.1. ILFO, weight 1%
25.8 25.5 -0.311F
O, weight% 7, 0 7
, 2 +-0, 2 The above results show that when 4% by weight of the catalyst of Example 4 (Molecular Jeep) is added to Super D, the C3+ gasoline yield decreases by 0.5% by volume at a constant conversion rate; This shows that an increase in RON of 1.5 is obtained. It is clear that the yields of the other major products are not affected by the addition of the catalyst of Example 4.

The phosphorus-containing catalysts of the present invention are expected to be highly resistant to metal precursors since phosphorus (P) has been shown to immobilize vanadium (V).

Current trends in the FCC indicate the need to increase gasoline octane numbers and the need to process heavier feedstocks such as atmospheric distillation bottoms or vacuum column additives.

Therefore, metal-resistant catalysts that produce octane number increase and cracking of residual oils will find widespread use throughout the petroleum industry.

As described in the examples above, the beneficial effects of the present invention, such as improved octane number, can be achieved without the addition of carbon-hydrogen cracking components as additives to the feedstock. Carbon-hydrogen decomposition components such as methanol are long
) et al., US Pat. No. 4,512,875.

Claims (1)

Claims: 1. With a boiling point range of 232-760°C using a cracking catalyst at a temperature of 300-700°C, a pressure of 0.1-30 atm and a weight hourly space velocity of 0.1-100. In the catalytic cracking process of cracking hydrocarbons to produce a gasoline-containing product stream, the catalyst has a faujasite type crystal structure and Al_2O_3, P_2O_
Catalytic cracking process characterized in that it uses microporous crystalline molecular sieves prepared by crystallizing sources of 5 and SiO_2. 2. The method of claim 1, wherein the catalyst contains a faujasite-type crystalline material and at least one conventional cracking catalyst. 3. The method according to claim 1 or 2, wherein the catalyst contains a base agent. 4. The crystalline molecular sieve contains at least 1 based on the total number of aluminum atoms, phosphorus atoms and silicon atoms.
A method according to any one of claims 1 to 3, containing % aluminum atoms, at least 1% phosphorus atoms and at least 1% silicon atoms. 5. The number of aluminum atoms is greater than or equal to the number of silicon atoms,
5. The method according to claim 4, wherein the number of phosphorus atoms is greater than or equal to the number of silicon atoms. 6. The method according to any one of claims 1 to 5, wherein the crystalline molecular sieve has an X-ray powder diffraction pattern including at least the principal diffraction lines listed in Table I. 7. The RON+O of the gasoline produced is 3 to 3-3% higher than the RON+O of the gasoline produced by cracking the same raw material at a constant conversion on a homologous crystalline material having a faujasite type structure and containing no phosphorus. 5. The method according to claim 1. 8. The residual oil fraction of the charged material cracks more at a constant conversion rate than when cracking on a homologous crystalline material that has a faujasite type structure and does not contain phosphorus. A method according to any one of claims 1 to 7. 9. The method according to any one of claims 1 to 8, wherein the cracking method is a fluid catalytic cracking method. 10. The method of claim 2, wherein the conventional catalyst is selected from the group consisting of REY, USY, HY, zeolite beta, ZSM-5 and amorphous catalysts. 11. The method of claim 2, wherein the crystalline molecular sieve constitutes 0.01 to 50% by weight of the total weight of the catalytically active ingredients. 12. The method of claim 2, wherein the crystalline molecular sieve is a separate additive composition comprising a crystalline material added to a conventional cracking catalyst. 113. Composite the crystalline molecular sieve with a conventional cracking catalyst. The method according to claim 2. 14. Crystalline molecular sieve is SAPO-5, SA
Any of claims 1 to 13 having a structure selected from the structures of PO-11, SAPO-37 and SAPO-40, and wherein the catalyst contains at least one other conventional cracking catalyst. The method described in Section 1. 15. Crystalline molecular sieve accounts for 0 of the total contact active ingredients.
．． 15. A method according to claim 14, comprising 0.01 to 50% by weight.