JPH09324182A - Production of lpg having high olefin concentration and high quality gasoline - Google Patents

Abstract

PURPOSE: To produce LPG having high propylene and butylene concentrations and gasoline having high a octane number by catalytic conversion.

CONSTITUTION: This method for producing the LPG and the gasoline comprises bringing a pre-heated hydrocarbon raw mateiral into contact with an acidic solid catalyst containing high silica zeolite (ZRP) containing rare earth elements and having pentasil structure, rare earth element-Y zeolite (REY) and high-silica Y zeolite, at approximately 480-550°C, under approximately 130-350 Kpa pressure, at 1-150/hour weight space velocity, in 4-15 ratio of catalyst/oil and in (0.05:1) to (0.12:1) weight ratio of vapor to the rare material in a riser or a fluid bed reactor.

COPYRIGHT: (C)1997,JPO

Description

Detailed Description of the Invention

The present invention relates generally to a novel process for producing high quality gasoline and liquefied petroleum gas (LPG) having a high olefin concentration, and more particularly to the catalytic conversion of petroleum hydrocarbons to obtain high octane gasoline with high total yield. And LPG with high propylene and butylene concentrations.

Conventionally, propylene, butylenes and gasoline are produced by catalytic or thermal cracking of petroleum fractions, such as fluid catalytic cracking (FCC) or thermal cracking.
Pyrolysis is aimed at the production of ethylene but has some drawbacks. The catholine fraction of the product is generally of poor quality and has a high concentration of aromatics and diolefins. Moreover, pyrolysis requires expensive materials for reactor fabrication due to its high temperature decomposition (above 700 ° C.). Moreover, pyrolysis requires purification and a high degree of separation of gaseous products. Fluid catalytic cracking can be carried out at temperatures well below the temperature of thermal cracking and can also produce low carbon olefins. As an example, in the German Democratic Republic Patent No. 152,356, gasoline or vacuum gas oil is used as a raw material, and amorphous silica-alumina is used as a catalyst so that a reaction temperature in a fixed-bed or moving-bed reactor is increased. At 600 to 800 ° C. and a contact time of 0.1 to 1.5 seconds, 50% by weight of C ₂ -C ₄ olefins are obtained.

Japanese Patent Application Publication No. 60-222,42
In No. 8, C _{5 to} C ₂₅ paraffinic hydrocarbons or naphtha is used as a raw material, and ZSM-5 zeolite is used as a catalyst. Approximately 30% by weight at reaction temperatures below 600-700 ° C and LHSV of 20-300 / hour.
C ₂ -C ₄ olefins have been obtained. U.S. Pat. No. 4,980,053 and Chinese Patent No. 1004878.
More examples are described in B, where various boiling range petroleum fractions, residual oils or crude oils are used as feedstocks. ZSM-5 and rare earth element type Y
Composites of (REY) zeolites or composites of ZSM-5 and ultrastable Y (USY) zeolites have been used as catalysts. By this method, using a fluidized bed or moving bed reactor, 500 ° C-600 ° C, 1.5-
3.0 × 10 ⁵ Pa, weight space velocity (WHSV) 0.2
Under conditions of .about.2.0 / hour and catalyst / oil ratio of 2-12, the total yield of propylene and butylene can reach about 40% by weight.

The conventional FCC manufacturing method can produce 50% by weight or more of gasoline, but the LPG yield is 8 to 13% by weight or less, and the total yield of propylene and butylene is less than 10% by weight. Moreover, the octane number of gasoline is usually
Cannot meet the requirements for mixed gasoline products.

For over 10 years, the patent document has been ZSM
It has been shown that the use of the -5 additive in combination with a catalytic cracking catalyst can increase the octane number of cracked gasoline and increase the yield of alkylate. US Patent No. 4,
No. 368,114 uses Joliet sour heavy gas oil (boiling range 212 to 513 ° C.) as a raw material. The catalyst composition comprises 25% ZSM-5 zeolite containing additive and Su.
per D decomposition catalyst (Grace-Davison product, its composition is 1
It is a mixture of 7% RENaY / clay.SiO ₂ ). The mixture is
When 0.1 to 0.5% by weight of ZSM-5 zeolite is contained in Super D, at a reaction temperature of 574 ° C., WHSV of 20 / hour, and a catalyst / oil ratio of 3, the yield of C ₅ ⁺ gasoline obtained is 47. The research octane number (RONC) is 90.1 to 91.4 at ˜53.7% by volume. Besides, L
The PG yield is 30.4-37.1 vol% and the total yield of propylene and butylene is 15.2-19.6 vol%.

US Pat. No. 4,522,705 also uses the above-mentioned Joliet sour heavy gas oil as a raw material. The catalyst used is a HEZ-53 decomposition catalyst (Enge
products of Lhard Corpp., including Y zeolite) and Z
It is a mixture of SM-5 zeolite containing additives. This mixture contains 0.25 to 2.0% by weight of ZSM-5 zeolite. The reaction is carried out at 515 ° C. and WHSV of 15.5 / hour. The yield of C ₅ ⁺ gasoline obtained is 39.5.
˜46.6% by volume, RONC is 90.1-92.0, total yield of propylene and butylene is 15.1-2.
It is 4.2% by volume.

In US Pat. No. 4,818,738, the raw materials used are the same as above. The catalyst used is a mixture of REY cracking catalyst and ZSM-5 zeolite containing additive, containing 25% ZSM-5 zeolite. This mixture was prepared with a ratio of additive to REY cracking catalyst of 1:50 by weight. Under normal operating conditions of FCC process, the yield of C ₅ ⁺ gasoline is 47.5% by volume.
The RONC is 90.8, and the total yield of propylene and butylene is 23.9% by volume.

In European Patent No. 229,609,
Light oil having a boiling range of 204 to 538 ° C is used as a raw material. The catalyst was a mixture of ZSM-5 zeolite containing additive and Octacat decomposition catalyst (active ingredient 40% USY, matrix kaolin clay and silica-alumina sol binder), 1.25-1.5 wt% Z.
Includes SM-5 zeolite. Reaction temperature 493-498 ° C
The product yield is 53.1 to ₅ for C ₅ ⁺ gasoline.
At 5.4% by volume, RONC is 92.6-93.0%, LPG is 19.6-21.4% by volume, and propylene and butylene are 14.8-14.9% by volume.

Adding the ZSM-5 additive to the FCC catalyst not only increases the octane number of the product gasoline, but also increases the yield of propylene and butylene in LPG. As described in U.S. Pat. No. 3,758,403, the ZSM-5 additive is added to a cracking catalyst containing a zeolite having a pore size greater than 7 Angstroms to obtain gasoline octane number and total propylene and butylene yields. Both rates are higher. Especially 5-10% H
When a REY cracking catalyst containing ZSM-5 is used, light oil having a boiling range of 204 to 316 ° C., 482 to 486 ° C., L
Treated with a HSV of 4 / hour and a catalyst / oil ratio of 1.5, C ₅
⁺ A mixture of gasoline and alkylate from 97.3 to 98.
6 RON (+3 ml TEL), C ₅ ⁺
The yield of gasoline is 46.4 to 55.3% by volume, and the total yield of propylene and butylene is 19.8 to 24.7% by volume.

An object of the present invention is to use a composite material catalyst containing three kinds of zeolites, and to use petroleum fractions having different boiling ranges,
It is an object of the present invention to provide a method for catalytically converting a residue, or a raw material of crude oil, into LPG having a high concentration of propylene and butylene, and high-quality C ₅ ⁺ gasoline in a high yield.

Further objects of the invention will be apparent from the following description and claims.

The present invention provides a novel process for catalytic conversion of hydrocarbons for producing LPG having a high concentration of propylene and butylene and for producing high octane gasoline. In this new process, a preheated hydrocarbon feedstock is heated in a riser or fluidized bed reactor,
It is contacted with a solid acidic catalyst containing three zeolite components. The zeolite component of the catalyst is (1) a high silica zeolite having a pentasil structure and containing a rare earth element (hereinafter Z
RP), (2) REY zeolite, and (3)
Includes high silica Y zeolite. The hydrocarbon raw material is 480 ° C to 550 ° C, 130 to 350 KPa, WHS in the reactor.
V 1-150 / hour, catalyst / oil ratio 4-15, steam-to-hydrocarbon feed weight ratio 0.05-0.12: 1. After the reaction, the used catalyst is taken out and sent to a regenerator, where it is regenerated by contacting with air. The regenerated catalyst returns to the reactor and the process is repeated.

(1) Catalyst The catalyst of the present invention comprises 10 to 40% by weight of an active ingredient consisting of three zeolites, namely (1) ZRP, (2) REY and (3) high silica Y zeolite.
The rest of the catalyst is formed by the catalyst matrix. The matrix is 10 to 40% by weight as a binder.
Consisting of fully synthetic or semi-synthetic silica-alumina containing natural kaolin or halloysite containing silica (relative to the catalyst) and / or alumina. The weight percentages of active components in the catalyst are 3 to 50 wt% for ZRP zeolite, 12 to 75 wt% for REY zeolite, and 12 to 75 wt% for high silica Y zeolite.

The ZRP zeolite used in the present invention has been described by the applicant in US patent application Ser. No. 07 / 820,385,
It is a high silica zeolite having a pentasil structure and containing a rare earth element as described in January 14, 1992 or in European Patent Application No. 922000611.7, filed January 10, 1992. The chemical formula of ZRP is 0.01 to 0. (in moles of oxide) in the anhydrous state.
30 RE ₂ O ₃ · 0.4 to 1.0 Na ₂ O · Al ₂ O ₃ · 20 to 6
It can be displayed as 0 SiO ₂ . Table 1 shows the X-ray diffraction data of ZRP zeolite.

Table 1 X-ray diffraction pattern of zeolite ZRP ZRP H-ZRP ^* d (Å) 100 I / I ₀ d (Å) 100 I / I ₀ 11.17 40 11.18 18 37 10.01 35 10.01 40 9 .76 12 9.75 10 7.45 4 7.44 3 7.08 1.5 7.09 1.5 6.71 6 6.72 3.5 6.37 8 6.37 7 6.01 11 6 .00 11 5.72 10 5.71 8 5.58 10 5.58 9 5.37 3 5.38 2 5.15 3 5.14 3 5.04 5 5.05 5 4.985 8 4.983 8 4.621 6 4.620 6 4.366 10 4.369 7 4.267 13 4.265 12 4.090 5 4.085 2 4.010 9 4.010 7 3.861 100 3.856 100 3 .819 74 .817 72 3.755 41 3.752 36 3.720 49 3.719 39 3.650 28 3.652 2 3.591 7 3.593 4 3.481 29 3.479 6 3.447 13 3.447 11 * H-ZRP hydrogen exchange type The ratio of the adsorption of n-hexane by ZRP to the adsorption of cyclohexane by ZRP is 2 times the ratio of the adsorption by HZSM-5.
Since it is ~ 4 times, the pore size of ZRP is smaller than that of HZSM-5. The rare earth element component of zeolite is ZR
It is derived from the rare earth element-containing faujasite used as a seed crystal in the synthesis of P zeolite. In the present invention, it is preferable to use H type ZRP having a crystallite size of 2 to 3 microns.

The REY zeolite used in the present invention is N
It is produced by exchanging aY with a rare earth element cation. Following this exchange reaction, it may or may not be calcined. 5 to 5 contained in the obtained REY zeolite
19 wt% rare earth elements are in the form of RE ₂ O ₃ . REY
The size of the zeolite crystallites is 0.5 to 10 microns, preferably 0.8 to 2 microns.

The high silica Y zeolite can be prepared by various chemical and / or physico-chemical methods. Examples of such methods include hydrothermal treatment, acid extraction,
Skeleton dealumina and silica enrichment, and SiCl ₄ treatment,
Etc. In the present invention, using such a method, Na ₂ O
A stabilized product of zeolite Y is obtained whose content does not exceed 4% by weight, preferably less than 1% by weight. further,
The unit cell size of the crystals should not exceed 24.5Å and the silica / alumina ratio (mole) should be in the range of 8 to 15 or higher. Moreover, the crystallite size of high silica Y zeolite is 0.5-10.
Micron, preferably 0.8-2 microns.

The synthetic matrix which can be used according to the invention is amorphous silica / SiO ₂ content below 70% by weight.
Alumina or silica / magnesia gel. Synthetic matrices are produced by co-gelation or stepwise precipitation. A suitable amount of clay can be mixed with the synthetic matrix composite to increase the bulk density of the catalyst.

The semi-synthetic matrix that can be used in the present invention is a composite of clay and binder. Clays conventionally used as matrices for cracking catalysts can be used, such as kaolin clay and halloysite clay. As the binder, a binder such as sol or gel alumina, silica or silica-alumina is used.

(2) Raw material The hydrocarbon raw material used in the present invention is a petroleum fraction, residue or crude oil having different boiling ranges. In particular, these feedstocks may be straight run fractions containing naphtha, light gas oil, vacuum gas oil and residues, etc., or mixtures of two or more of the above materials in the desired ratios. Alternatively, the feedstock may be a mixture of the above materials with an amount, preferably less than 30% by weight, of coker gas oil, deasphalted oil or other secondary treated fractions. The catalyst of the present invention can contain a high concentration of nickel in the raw material, and can process a residue having a nickel content of up to 15 ppm and a heavy oil mixed with a treated fraction.

(3) Method and Operating Conditions The novel method of the present invention will be described below. The preheated hydrocarbon feedstock is fed into the riser or fluidized bed reactor in a Z
Contact with a solid acidic catalyst including RP, REY and high silica Y zeolite. The catalytic conversion has a temperature of 480 to 550.
° C, preferably 500-535 ° C, reaction pressure 130-3
50KPa, preferably 130-250KPa, WHSV
It is carried out under the conditions of 1-150 / hour, preferably 3-80 / hour, and a catalyst / oil ratio of 4-15, preferably 5-10. To efficiently atomize the feedstock, steam or other gas is used, with a steam to hydrocarbon feedstock ratio of 0.0 by weight.
It can be mixed by blowing it into the raw material so that it becomes 5 to 0.12: 1. The mixture of converted product and coke-deposited spent catalyst is separated from each other during passage through a series of cyclones. The spent catalyst then passes through a stripper where the hydrocarbons adsorbed are removed and introduced into the regenerator. 580 in the playback device
The contact of the spent catalyst with air at a temperature of ˜730 ° C., preferably 650 to 700 ° C., burns and removes the coke deposited on the used catalyst. The regenerated high temperature catalyst returns to the reactor where it contacts the hydrocarbon feedstock where the reaction and regeneration are repeated. The product is
Rectification column and absorption - as a stabilizing mechanism, H ₂ -C _2, L
It is separated into PG, gasoline, light cycle oil and heavy residual oil. The heavy residue can be recycled to the reactor and converted. Alternatively, both the heavy residue and the light cycle oil can be returned to the reactor and recycled for conversion. In this method, the catalyst is at equilibrium 20,
Nickel above 000 ppm can be tolerated.

The above operating conditions are for the general case. The conditions can be adjusted depending on the feed characteristics and the desired yield distribution of the expected product. The novel method of the present invention may be a specially designed device similar to a conventional FCC device, or an improved (existing LPG separator, condenser, and compressor capacity, etc.) existing FCC device. But you can do it too.

By the method of the present invention, LPG having a high concentration of propylene and butylene can be produced in high yield, and at the same time, gasoline with enhanced antiknock ability and stability can be produced in high yield. It is also possible to produce a diesel fraction. Moreover, the quality of the product produced by the method of the present invention is comparable to that of the product produced by the conventional fluid catalytic cracking process.

The results obtained in the riser pilot plant were as follows: LPG yield 30-40% by weight, of which 67-75
Parts by weight are propylene and butylene (ie the total yield of propylene and butylene is 20-30% by weight), C ₅ ⁺ gasoline yield 45-55% by weight, RON
C is 91-95, motor method octane number (MONC) 8
0-84, induction period 500-1000 minutes, and yield of real gum 0-3 mg / 100 ml (based on raw material). The sum of LPG and total liquid product amounts to 90% by weight. The weight ratio of LPG to-H ₂ -C ₂ 8 to 13: up to 1. The following examples further illustrate the novel catalytic conversion processes provided by this invention, but do not limit the scope of this invention.

The raw material properties associated with the following examples are shown in Table 2.
Shown in Table 2: raw material properties A B C D E F Density (20 ℃) 0.8560 0.8871 0.8572 0.8995 0.8672 0.8612 (g / cm 3) Conradson 0.22 0.22 0.17 0.22 3.81 2.12 Carbon (wt%) UOP (K) 12.11 12.0 12.1 11.7 11.9 12.6 H (wt%) 13.24 --- 13.57 11.70 --- 13.94 C (wt%) 86.52 --- 85.92 85.95 --- 85.76 Basic nitrogen 420 --- 357 693 --- 600 (ppm) Ni (ppm) ) 0.49 --- 0.1 3.6 11.3 3.3 V (ppm) 0.03 --- <0.1 <0.1 0.1 <0.1 Boiling range 319-504 243-507 243-490 224-482>308> 291 (℃) * Paraffin base crude oil

The catalyst A used in the examples was prepared as follows. 1. As a matrix slurry, 1200 g of alumina hydrogel (20% by weight of Al ₂ O ₃ ) was thoroughly mixed with 950 g of halloysite clay (solid content of 50% by weight). 2. A. H-ZRP zeolite (US patent application No. 07 /
820,385 or European Patent Application No. 9220
Manufactured by the procedure of Example 8 described in No. 611.7) 7
1 gram, B. REY 214 grams, C.I. DASY zeolite (high silica Y zeolite produced by hydrothermal dealumina method, SiO ₂ / Al ₂ O ₃ = 8-9) 1
43 grams, and D. 514 grams of decations were mixed to form a homogeneous slurry. 3. The above two slurries were mixed, homogenized, spray dried, then washed and flash dried.

Example 1 This example demonstrates that the process of the present invention is suitable for converting gas oils obtained from various crude oils, or mixtures of gas oils and other processed fractions.
Catalytic conversion was carried out in a laboratory scale fluidized-fixed bed system using catalyst A.
With various hydrocarbon raw materials shown in Table 3
C., 130 KPa, WHSV 14 / hr, catalyst / oil ratio 8 and steam to feed hydrocarbon weight ratio 0.07: 1. The results are shown in Table 3. Table 3 percentage by weight of product from Example 1 distribution products \ material _{A B D G H 2 -C 2} 2.45 2.65 2.76 2.86 LPG 32.43 22.82 22.50 29.05 C 3 = 10.30 7.15 6.55 8.02 C 4 = 7.87 5.55 5.19 7.12 Gasoline (C ₅ ⁺ -205 ° C) 46.99 48.43 46.68 42.89 205-330 ° C 9.16 13.34 14.74 10.85> 330 ° C 4.62 7.41 6.98 5.93 Coke 5.35 5.35 6.34 8.42 conversion, wt% 86.22 79.25 78.28 83.22

Example 2 This example demonstrates that the process of the present invention is suitable for catalytic conversion of various petroleum fractions and crude oils. Catalytic conversion is carried out in a laboratory scale fluid-fixed bed apparatus using 3600 ppm nickel-contaminated catalyst A and various types of hydrocarbon feedstocks and under the same operating conditions as described in Example 1. It was The results are shown in Table 4. Table 4 Weight Percentage Distribution Product of Product from Example 2 \ Raw Material Direct Run Straight Run Gasoline Light Gas Oil F E H H ₂ -C ₂ 1.74 2.55 2.45 2.45 3.17 LPG 29.37 30.96 29.90 27.78 28.63 C ₃ ⁼ 6.76 7.09 9.32 9.00 8.20 C ₄ ⁼ 5.39 5.92 7.43 9.73 6.42 Gasoline (C ₅ ⁺ -205 ° C) 61.44 38.05 46.52 45.26 42.34 205-330 ° C 3.29 19.32 9.56 8.56 10.75 ＞ 330 ° C 0.00 3.84 4.45 4.80 Coke 4.16 9.12 7.73 11.50 10.31 Conversion, wt% 96.71 80.68 86.60 86.99 84.45 The straight- run gasoline in Table 4 is a fraction having a boiling point of less than 200 ° C, and the light gas oil is a fraction having a boiling range of 200 to 330 ° C. The catalyst was artificially polluted with nickel. The procedure is described below. 1. 2.564 kilograms of nickel naphthenate was dissolved in 50 liters of light gas oil. 2. The nickel naphthenate / light gas oil mixture obtained in step 1 was pumped into the feed system at a constant rate for 24 hours. 3. Fifty kilograms of catalyst was placed in the riser reactor and the weight ratio of catalyst to nickel naphthenate (7.8% nickel) was 50: 2.564. 4. The nickel naphthenate / light gas oil mixture pumped into the feed system contacted and reacted with the catalyst, resulting in nickel deposits on the catalyst. 5. The pure feedstock hydrocarbon was then contacted with the catalyst for another 24 hours under the same conditions as above. The catalyst obtained is 3
Contaminated with 600 ppm nickel.

Example 3 This example demonstrates that the process of the present invention is suitable for catalytic conversion of high nickel content hydrocarbon feedstocks. Catalytic conversions were carried out using a catalyst A contaminated with 3600 ppm nickel and uncontaminated with a pressure of 1 at the riser pilot plant test rig.
Performed at 99 KPa, catalyst / oil ratio 8. Table 5 shows the results. Table 5 Weight Percentage Distribution of Products Obtained from Example 3 Raw Material FFE Ni on Catalyst A, ppm 0 3600 3600 Reaction Temperature, ° C 515 514 515 WHSV, hr ^-1 73 74 74 Steam / raw material (weight / weight ) 0.101 0.099 0.100 Product distribution, wt% H ₂ -C ₂ 3.27 2.86 2.86 LPG 35.60 33.91 31.91 C ₃ ⁼ 11.41 11.17 10.92 C ₄ ⁼ 13.94 13.51 17.93 C ₅ ⁺ gasoline 44.18 44.52 43.99 205-330 ° C 10.55 10.45 10.46> 330 C 0.35 1.92 2.27 Coke 6.05 6.34 9.51 Conversion, wt% 89.10 87.63 88.27 Two hydrocarbon feedstocks with nickel content were used. Raw material E has a nickel content of 11.3 ppm, and raw material F has a nickel content of 3.3 ppm.

Example 4 This example demonstrates that in the method of the present invention, the product distribution can be adjusted by changing the operating conditions. Contact conversion is 3600ppm
Catalyst A and feed F from Example 5 (from Example 5) were used in the riser pilot plant test equipment described in Example 3 at a pressure of 199 KPa and a catalyst / oil ratio of 8. Table 6 shows the results. Table 6 Weight Percentage Distribution of Products Obtained from Example 4 Reaction Temperature, ° C 500 514 529 WHSV, hr ^-1 78 74 71 71 Steam / Raw Material (weight / weight) 0.103 0.099 0.104
Product distribution, _{wt% H 2 -C 2 2.25 2.86 4.49} LPG 31.69 33.91 36.87 C 3 = 9.72 11.17 13.47 C 4 = 13.10 14.51 15.18 C 5 + gasoline 44.85 44.52 41.24> 200 ℃ 16.06 12.37 11.95 Coke 5.15 5.34 5.45 Conversion, wt % 83.94 87.63 88.05

Example 5 This example demonstrates that the method of the present invention is suitable for various modes of operation. Catalytic conversion was carried out using catalyst A and feed F contaminated with 3600 ppm nickel in the riser pilot plant test apparatus described in Example 3 at 515 ° C., 130 KPa, catalyst / oil ratio 8. Table 7 shows the results. Table 7 Weight Percentage Distribution of Products Obtained from Example 5 Operating Mode Single Flow Residue Circulation Residue + LCO Circulation WHSV, hr ^-1 73 74 76 Steam / Raw Material (wt / wt) 0.101 0.105 0.102 Product Distribution, wt% H ₂ -C ₂ 2.86 3.17 3.65 LPG 33.91 33.70 34.91 C ₃ ⁼ 11.17 11.20 11.41 C ₄ ⁼ 13.95 13.63 14.22 C ₅ ⁺ gasoline 44.85 44.34 53.97 205-330 ° C 10.41 11.05 --- ＞ 330 ° C 1.63 --- --- coke 6.34 6.74 7.47 conversion, wt% 87.96 88.95 100.00

Example 6 This example demonstrates that the process of the invention can be used for the production of LPG in high yield and gasoline with good antiknock properties and stability. Catalytic conversion was carried out using catalyst A contaminated with 3600 ppm nickel and various types of feedstocks in a riser pilot plant test apparatus described in Example 3 and a laboratory scale fluid-fixed bed apparatus described in Example 1. I did. These tests were run at a catalyst / oil ratio of 8 and different reaction temperatures and various operating modes. The results are shown in Table 8
Shown in Table 8 Weight Percentage Distribution Tester for Product Obtained from Example 6 Riser Pilot Plant Laboratory Scale Fixed-Fluidized Bed Feed F AC B Mode of Operation Residue Residue Single Flow Single Flow Single Flow Single Flow Single Flow Single Flow Circulation + LCO Circulation Reaction Temperature (℃) 500 500 515 530 515 530 515 Product distribution, (wt%) LPG 29.8 32.1 35.6 36.9 32.4 29.4 22.3 Gasoline 45.9 54.1 44.2 41.2 47.0 46.1 48.2 Gasoline characteristic RON (C) 92.6 9.14 94.2 93.0 92.7 95.1 93.9 MON ( C) 80.9 80.7 81.6 81.2 81.2 82.6 82.5 Induction period (min) 825 1110 735 525 Real gum 2 202 mg / 100ml

Example 7 In this example, the LPG product obtained by the novel method of the present invention is propylene, n-
Demonstrate high butylene and iso-butylene concentrations. Catalytic conversions were carried out in the riser pilot plant test equipment described in Example 3 at a pressure of 199 KPa and a catalyst / oil ratio of 8 using catalyst A and feed F contaminated with 3600 ppm nickel. The results are shown in Table 9. Table 9 Weight Percentage Distribution of the Product Obtained from Example 7 Reaction Parameter Reaction Temperature, ° C 500 515 530 500 WHSV, hr ^-1 63 84 81 84 Steam / Raw Material (weight / weight) 0.108 0.099 0.104 0.105 Operating Mode Single Flow Single Flow Single flow Residual circulation Product distribution C ₃ ⁼ Yield, wt% 9.72 11.17 13.47 9.83 C ₃ ⁼ / LPG, wt% 30.70 32.94 36.53 32.18 C ₃ ⁼ / (C ₃ ⁰ + C ₃ ⁼ ), wt% 86.4 86.1 88.4 84.7 total C ₄ ⁼ yield, wt% 12.34 12.90 14.51 11.36 iC ₄ ⁼ yield, ^{_{wt% 3.93 4.67 4.73 4.35 C 4 =}} / LPG, ^{_{wt% 41.33 39.84 41.17 38.40 C 4 =}} / (C 4 0 + C 4 ⁼ ),% By weight 64.50 65.30 70.81 62.41

Example 8 This example demonstrates the low yield of dry gas obtained by the method of the present invention.
Catalytic conversion, catalyst A contaminated with 3600 ppm nickel
And feedstock F were used in the riser pilot plant test equipment described in Example 3 at a pressure of 199 KPa and a catalyst / oil ratio of 8. The results are shown in Table 10. Table 10 Weight percentage distribution of the product obtained from Example 8 Reaction temperature, ° C 500 514 529 500 515 WHSV, hr ^-1 78 84 81 87 86 Steam / raw material (weight / weight) 0.103 0.099 0.104 0.101 0.102 Mode of operation Single flow single flow per pass residue + LCO residue + LCO circulated circulating product distribution, _{wt% H 2 -C 2 2.25 2.86 4.49} 3.55 3.65 LPG 1.69 33.91 36.87 32.69 34.91 gasoline 44.85 44.52 41.24 53.84 53.97 LPG / H 2 -C 2 14.1 11.9 8.2 9.2 9.6

Example 9 This example shows that the method of the present invention results in a lower yield of dry gas and coke, as compared with the conventional catalytic cracking method using an additive ((1) 2) Demonstrate production of gasoline products with higher yields of LPG, propylene and butylene, and (3) improved properties. To compare the two methods, catalytic cracking and catalytic conversion of the present invention were carried out using feedstock E on the riser pilot plant test equipment described in Example 3. The difference is that in catalytic decomposition, additive B
The conventional cracking catalyst LWC-33 mixed with is used while catalyst A is used in the catalytic conversion. The ratio of ZRP in catalyst A is the same as the ratio of ZSM-5 in the mixture of LWC-33 and additive B. The results are shown in Table 11. Weight of product obtained from Table 11 Example 9 percentage distribution catalyst A LWC-33 + B reaction temperature, ° C. 500 500 520 product distribution, _{wt% H 2 -C 2 2.77 3.00 3.61} LPG 30.52 20.40 21.49 C 3 = 9.80 6.91 7.11 C ₄ ⁼ 11.85 8.42 9.61 Gasoline (C ₅ ⁺ -205 ℃) 45.05 47.40 48.00 205-330 ℃ 13.14 18.30 16.80 ＞ 330 ℃ --- --- --- Coke 8.52 10.90 10.10 Loss 1.00 --- --- Conversion % By weight 86.86 81.70 83.20 RON (C) 92.8 --- --- MON (C) 81.5 77.6 79.3 induction period of gasoline , min 825 485 421 Additive B above in this example is HZSM-5,
It is a composite material of pseudo-boehmite and halloysite,
It was produced by the same method as a conventional semi-synthetic cracking catalyst by slurry formation, mixing, homogenization, spray drying, and the like. The composition could be expressed as 20% HZSM-5 / 15% Al ₂ O ₃ .65 wt% halloysite. LWC-
33 is a conventional REY catalyst manufactured and sold by Lan Zhou Refinery.

[Procedure amendment]

[Submission date] May 30, 1997

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─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical indication location C10L 3/10 CST 6958-4H C10L 3/00 CSTD (72) Inventor Yogin Huo People's Republic of China. Beijing, Haidian District, Sueyuan Road 18 (72) Inventor Zeyu Wan People's Republic of China. Beijing, Haidian District, Sueyuan Road 18 (72) Inventor Yamin Wang, People's Republic of China. Beijing, Haidian District, Sueyuan Road 18 (72) Inventor Yukan Lu People's Republic of China. Beijing, Haidian District, Sueyuan Road 18

Claims (18)

[Claims] 1. A method for producing LPG having a high concentration of propylene and butylene, and high octane gasoline by catalytic conversion, which comprises: (1) converting a hydrocarbon raw material preheated in a riser or a fluidized bed reactor into pentasil Contacting with a solid acidic catalyst having a structure and comprising three types of zeolitic active components including a high silica zeolite containing a rare earth element (ZRP), a rare earth element-Y zeolite (REY) and a high silica Y zeolite, and (2) The raw material is placed in a reactor at a temperature of about 480 ° C. to about 550 ° C. and a pressure of about 130 KPa to about 35.
0 KPa, weight hourly space velocity 1-150 / hour, and contact-
A process characterized in that it is converted at a ratio of oil to oil of 4 to 15. 2. The catalytic conversion is carried out at a temperature of 500 ° C. to 535 ° C.
℃, pressure 130 KPa ~ 250 KPa, weight space velocity 3 ~ 8
Process according to claim 1, characterized in that it is carried out at 0 / h and a contact-to-oil ratio of 5-10. 3. The zeolitic active component comprises 10 to 40% by weight of the catalyst, the remainder of the catalyst comprising a matrix containing silica or a silica / alumina binder. The method of claim 1, wherein 4. The characteristics of the ZRP zeolite are as follows: 0.01 to 0.30 (in moles of oxide) RE ₂ O ₃
0.4 to 1.0 Na ₂ O.Al ₂ O ₃ 20 to 60 SiO ₂ formula in anhydrous state, B. The following X-ray diffraction pattern: d (Å) 100 I / I ₀ 11.17 40 10.01 35 9.76 12 7.45 4 7.08 1.5 6.71 6 6.37 8 6.01 11 5 .72 10 5.58 10 5.37 3 5.15 3 5.04 5 4.985 8 4.621 6 4.366 10 4.267 13 4.0090 5 4.0010 9 3.861 100 3.819 74 3.755 41 3.720 49 3.650 28 3.591 7 3.481 29 3.447 13 C.I. The method of claim 1 having a ratio of the adsorption capacity of n-hexane to cyclohexane that is 2 to 4 times higher than HZSM-5. 5. The method of claim 1, wherein the ZRP zeolite is in a hydrogen exchanged form. 6. The hydrocarbon feedstock is naphtha, light gas oil,
The process according to claim 1, which is a straight-run fraction containing vacuum gas oil and a residue, or a mixture of two or more of the above fractions mixed in a desired ratio. 7. The method of claim 6 wherein the residual feedstock is a heavy hydrocarbon with a high nickel content. 8. The method of claim 1 wherein the catalyst is acceptable at equilibrium with a nickel equivalent of 20,000 ppm or greater. 9. Process according to claim 1, characterized in that the residue, or the light cycle oil fraction in the product, is recycled together with the residue into the reactor. 10. The method of claim 1, further comprising stripping and regenerating the catalyst after catalytic conversion and returning the stripped and regenerated catalyst back to the reactor for reuse. 11. The method of claim 1, wherein a gas is added to the raw material to promote atomization of the raw material. 12. The method of claim 1 wherein said gas is steam and said steam is added to said feedstock in a steam-to-feedstock weight ratio of 0.05 to 0.12: 1. 13. The straight run fraction is mixed with coker gas oil, deasphalted oil, other secondary treated fractions, or mixtures thereof, or crude oil.
the method of. 14. The coker gas oil, deasphalted oil, other secondary treated fraction, or a mixture thereof mixed with the straight-run fraction is 30% by weight or less of the raw material. 14. The method of claim 13, wherein 15. 5 to 19% of said REY zeolite is R
The method of claim 1 in the form of E ₂ O ₃ , wherein the crystallite size of the REY zeolite is 0.5-10 microns. 16. The high silica Y zeolite has a Na ₂ O content not exceeding 4% by weight, and the high silica Y zeolite has a crystallite size of 0.5 to 10 microns. the method of. 17. The method of claim 3 wherein the matrix is an amorphous silica / alumina or silica / magnesia gel containing up to 70% by weight of SiO ₂ . 18. A method for producing LPG having a high concentration of propylene and butylene and high octane number gasoline by catalytic conversion, which comprises: (1) converting a hydrocarbon raw material preheated in a riser or a fluidized bed reactor into pentasil Contacting with a solid acidic catalyst having a structure and containing three types of zeolitic active components including high silica zeolite (ZRP) containing rare earth elements, rare earth element-Y zeolite (REY) and high silica Y zeolite and a matrix And (2) the raw material in a reactor at a temperature of about 480 ° C to about 550 ° C, a pressure of about 130 KPa to about 350 KPa, and a weight hourly space velocity of 1 to 150 /.
Conversion over time and contact-to-oil ratio of 4 to 15 and steam-to-feed ratio of 0.05 to 0.12: 1, wherein the characteristics of the catalyst are: (1) The formula in the anhydrous state is 0.01 to 0.30 RE ₂ O ₃ · 0.4
1.0 Na ₂ O · Al ₂ O ₃ · 20-60 SiO ₂ ,
(2) The ZRP zeolite is in the form of hydrogen exchange, (3) 5 to 19% of the REY zeolite is in the form of RE ₂ O ₃ , and the crystallite size of the REY zeolite is 0.5 to 10 microns. And (4) the high silica Y
The Na ₂ O content of the zeolite does not exceed 4% by weight, and the high-silica Y zeolite has a crystallite size of 0.5 to 10
Micron and (5) the matrix is an amorphous silica / alumina or silica / magnesia gel containing 70% by weight or less of SiO ₂ .