Process for the production of LPG rich in olefins and high quality gasoline

• US 5,326,465 A
• Filed: 03/12/1993
• Issued: 07/05/1994
• Est. Priority Date: 10/22/1992
• Status: Expired due to Term

• Current Assignee: China Petroleum & Chemical Corporation and Research Institute of Petroleum Processing Sinopec
• Original Assignee: China Petrochemical Corporation, Research Institute of Petroleum Processing Sinopec
• Inventors: Yongqing, Huo, Yamin, Wang, Zeyu, Wang, Yukang, Lu
• Primary Examiner(s): Breneman, R. Bruce
• Assistant Examiner(s): Yildirim, Bekir L.
• Application Number:
  US08/030,578
• Time in Patent Office: 480 Days
• Field of Search: 208/113, 208/120, 208/71, 208/70, 208/122, 502/62, 502/65, 502/64, 502/67, 585/517, 252/455 Z
• US Class Current: 208/120.15
• CPC Class Codes: B01J 2229/42 Addition of matrix or binder particles
• CPC Class Codes: B01J 29/088 Y-type faujasite
• CPC Class Codes: B01J 29/40 of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
• CPC Class Codes: B01J 29/80 Mixtures of different zeolites
• CPC Class Codes: C10G 11/05 Crystalline alumino-silicates, e.g. molecular sieves
• CPC Class Codes: C10G 11/18 according to the "fluidised-bed" technique

Abstract

A process for producing LPG rich in propylene, butylenes and high octane number gasoline by catalytic conversion which comprises contacting the preheated hydrocarbon feedstock with a solid acidic catalyst which contains rare-earth-containing high silica zeolite having the structure of a pentasil (ZRP), rare-earth-Y zeolite (REY) and high silica Y zeolite in a riser or a fluidized bed reactor, at a temperature in the range of from about 480° C. to about 550° C., a pressure in the range of from about 130 KPa to about 350 KPa, a weight hourly space velocity in the range of 1 to 150 hr-1, a catalyst-to-oil ratio in the range of 4 to 15, and a steam-to-feedstock ratio in the range of 0.05 to 0.12:1 by weight.

Claims

1. A process for producing LPG rich in propylene, butylenes and high octane number gasoline by catalytic conversion which comprises:

(1) contacting in a riser or a fluidized bed reactor a preheated hydrocarbon feedstock with a solid acidic catalyst which contains three zeolitic active components including rare-earth-containing high silica zeolite having the structure of a pentasil (ZRP), rare-earth-Y zeolite (REY) and high silica Y zeolite, and

(2) converting said feedstock in the reactor at a temperature in the range of from about 480°

C. to about 550°

C., a pressure in the range of from about 130 KPa to about 350 KPa, a weight hourly space velocity in the range of 1 to 150 hr-1, and a catalyst-to-oil ratio in the range of 4 to 15.

2. The process of claim 1, wherein said catalytic conversion is carried out at a temperature in the range of from 500°

C. to 535°

C., a pressure in the range of from 130 KPa to 250 KPa, a weight hourly space velocity in the range of 3 to 80 hr^-1, and a catalyst-to-oil ratio in the range of 5 to 10.

3. The process of claim 1, wherein said three zeolitic active components comprise 10 to 40 wt% of said catalyst, and the remainder of said catalyst comprises a matrix containing silica or silica/alumina binders.

4. The process of claim 3, wherein the said matrix is an amorphous silica/alumina or silica/magnesia gel containing not more than 70 wt% SiO₂.

5. The process of claim 1, wherein said ZRP zeolite is characterized by having:

A. the following anhydrous state formula

space="preserve" listing-type="equation">0.01-0.30 RE.sub.2 O.sub.3 . 0.4-1.0 Na.sub.2 O . Al.sub.2 O.sub.3 . 20-60 SiO.sub.2,

B. X-ray diffraction patterns as follows;

space="preserve" listing-type="tabular">______________________________________ d(Å

) 100 l/l.sub.o ______________________________________ 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 4.090 5 4.010 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 ______________________________________

and

c. a 2-4 times higher ratio of adsorption capacity for normal-hexane to cyclohexane than HZSM-5.

6. The process of claim 1, wherein said ZRP zeolite is in hydrogen-exchanged form.

7. The process of claim 1, wherein said hydrocarbon feedstocks are straight run fractions, including naphtha, light gas oil, vacuum gas oil and resids;

or mixtures of two or more of the above fractions mixed in any desirable proportions.

8. The process of claim 7, wherein said resid feeds are heavy hydrocarbons with high nickel content.

9. The process of claim 7, where said straight run fractions are blended with coker gas oil, deasphalted oil, other secondary processed fractions, or mixtures thereof, or crude oils.

10. The process of claim 9, wherein said coker gas oil, deasphalted oil, other secondary processed fractions, or mixtures thereof, blended with said straight run fractions make up not more than 30 wt% of said feed.

11. The process of claim 1, wherein said catalyst in an equilibrium state allows 20,000 ppm of Nickel equivalent or higher.

12. The process of claim 1, wherein the bottoms or the bottoms together with the light cycle oil fraction in the products are recycled to the reactor to be reconverted.

13. The process of claim 1, which further comprises stripping and regenerating the catalyst after the catalytic conversion and returning the stripped and regenerated catalyst to the reactor for reuse.

14. The process of claim 1, wherein a gas is added to said feedstock to promote atomization of said feedstock.

15. The process of claim 14, wherein said gas is steam which is added to said feedstock at a steam-to-feedstock ratio between 0.05-0.12:

1 by weight.

16. The process of claim 1, wherein 5-19% of said REY zeolite is in the form of RE₂ O₃, and the crystallite size of said REY zeolite is 0.5-10 microns.

17. The process of claim 1, wherein the Na₂ O content of said high silica Y zeolite does not exceed 4 wt%, and the crystallite size of said high silica Y zeolite is 0.5-10 microns.

18. A process for producing LPG rich in propylene, butylenes and high octane number gasoline by catalytic conversion which comprises:

(1) contacting in a riser or a fluidized bed reactor a preheated hydrocarbon feedstock with a solid acidic catalyst which contains a matrix and three zeolithic active components including rare-earth-containing high silica zeolite having the structure of a pentasil (ZRP), rare-earth-Y zeolite (REY) and high silica Y zeolite, and

(2) converting said feedstock in the reactor at a temperature in the range of from about 480°

C. to about 550°

C., a pressure in the ranger of from about 130 KPa to about 350 KPa, a weight hourly space velocity in the range of 1 to 150 hr-1, a catalyst-to-oil ratio in the range of 4 to 15, and a steam-to-feedstock ratio between 0.05-0.12;

1 by weight;

wherein said catalyst is characterized as follows;

(1) the anhydrous state formula of said ZRP zeolite is 0.01-0.30 RE₂ O₃ . 0.1-1.0 Na₂ O . Al₂ O₃ . 20-60 SiO₂ ;

(2) said ZRP zeolite is in hydrogen-exchanged form;

(3) 5-19% of said REY zeolite is in the form of RE₂ O₃, and the crystallite size of said REY zeolite is 0.5-10 microns.

(4) the Na₂ O content of said high silica Y zeolite does not exceed 4 wt%, and the crystallite size of said high silica Y zeolite is 0.5-10 microns; and

(5) said matrix is an amorphous silica/alumina or silica/magnesia gel containing not more than 70 wt% SiO₂.