Immobilization of vanadia deposited on sorbent materials during visbreaking treatment of carbo-metallic oils

• US 4,469,588 A
• Filed: 09/29/1982
• Issued: 09/04/1984
• Est. Priority Date: 03/30/1981
• Status: Expired due to Fees

• Current Assignee: Ashland Oil, Inc. (Ashland Global Holdings, Inc.)
• Original Assignee: Ashland Oil, Inc. (Ashland Global Holdings, Inc.)
• Inventors: Hettinger, William P. Jr., Beck, Hubert W.
• Primary Examiner(s): Gantz, Delbert E.
• Assistant Examiner(s): CHAUDHURI, OLIK
• Application Number:
  US06/427,355
• Time in Patent Office: 706 Days
• Field of Search: 208/251 R, 208/253, 208/120, 208/91, 208/68, 208/77, 208/106, 208/126, 208/127
• US Class Current: 208/77
• CPC Class Codes: C10G 25/00 Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
• CPC Class Codes: C10G 25/003 Specific sorbent material, not covered by C10G25/02 or C10G25/03
• CPC Class Codes: C10G 25/09 according to the "fluidised bed" technique
• CPC Class Codes: Y10S 502/521 Metal contaminant passivation

Abstract

A high pore volume solid sorbent material of low cracking activity and comprising a select group of metal additives to immobilize accumulated vanadium compounds deposited on the sorbent material in a heavy oil feed visbreaking zone is described and the conditions employed to effect demetallization and decarbonization of the heavy oil feed to produce vaporous products boiling up to about 1000° F. Deposition of metal contaminants within the pores of the high pore volume material is encouraged by restricting the volume of the sorbent pores filled with oil feed to within the range of 1/4 to 2/3.

Claims

1. A method for demetallizng and decarbonizing high boiling portions of crude oils comprising metal contaminants, and highly viscous high molecular weight hydrocarbons boiling above 1000°

F. which comprises, contacting said high boiling portion of crude oil with solid sorbent particulate material provided with a metal additive material selected from one or more of Mg, Ca, Sr, Ba, Sc, Y, La, Ti, Ar, Hf, Nb, Ta, Mn, Ni, In, Te, Bi, and elements in the lanthanide or actinide series to form a compound with deposited vanadium and substantially immobilize flow of vanadium during high temperature use of said sorbent material, said sorbent providing a high pore volume in the range of 0.4 cc/g up to about 0.8 cc/g at

elevated temperature conditions above 900°

F. and a contact time equal to or less than 5 sec. providing a vaporous product of thermal visbreaking, said conditions limiting production to lower boiling naphtha containing products, said contacting with such high pore volume sorbent material effected under conditions of sorbent to oil feed ratio for particularly imbibing metal contaminants and some high boiling highly viscous high molecular weight hydrocarbons of said crude oil at said visbreaking conditions, and recovering a vaporous product of said thermal visbreaking operation boiling up to about 1000°

F. comprising less than about 100 ppm of nickel plus vanadium.

2. The method of claim 1 wherein the solid sorbent material of high pore volume is obtained by mixing one or more temperature decomposable materials comprising carbon black, an organic material, a polymeric material or an inorganic salt with a slurried clay before spray drying thereof.

3. The method of claim 1 wherein the solid sorbent material has a MAT activity less than 20.

4. The method of claim 1 wherein the solid sorbent particulate material is employed under contact conditions sufficient to provide a demetallized vaporous hydrocarbon product comprising less than 50 ppm Ni+V.

5. The method of claim 1 wherein a high boiling vaporous oil product comprising less than 100 ppm Ni+V of said thermal visbreaking is thereafter catalytically converted to lower boiling products comprising gasoline employing a crystalline zeolite containing cracking catalyst.

6. The method of claim 1 wherein the solid sorbent material is of a fluidizable particle size selected from within the range of 20 to 150 micron particle size.

7. The method of claim 1 wherein the solid sorbent is prepared from one or more clays such as bentonite, kaolin, montmorilonites, smectites, 2-layered lamellar silicates, mullite, pumice, silica, laterite, and pillared interlayered clays.

8. The method of claim 1 wherein a naphtha product is obtained from said thermal visbreaking operation which is thereafter upgraded by contact with a crystalline zeolite conversion catalyst.

9. The method of claim 1 wherein vanadium is deposited on said sorbent and comprises one or more of vanadium oxides, sulfides, sulfites, sulfates or oxysulfides.

10. The method of claim 9 wherein the metal additive and the temperature decomposable material are added to an aqueous slurry of of the clay before being spray dried to obtain said sorbent particle material.

11. The method of claim 1 wherein the metal additive is added following preparation and use of the sorbent material in a cyclic system comprising visbreaking demetallization and regeneration of sorbent material.

12. The method of claim 1 wherein the high boiling oil comprises a residual oil.

13. The method of claim 1 wherein the high boiling oil portion is charged to a moving solids visbreaking zone with atomizing steam to reduce the partial pressure of the oil and effect atomized contact with said sorbent particle material.

14. The method of claim 1 wherein the high boiling portion of crude oil has a higher level of vanadium than nickel.

15. The method of claim 1 wherein the sorbent material is provided with a metal or metal compound which will complex with vanadia to provide a material melting above a regeneration temperature for the sorbent material.

16. The method of claim 1 wherein the sorbent material is regenerated by burning hydrocarbonaceous deposits at a temperature below about 1500°

F. and accumulated vanadium is precluded from flowing by forming a complex with an addition material having a melting point above 1500°

F.

17. The method of claim 1 wherein said solid sorbent material is a clay sorbent material providing pore openings of at least 500 Angstroms, said clay sorbent is provided with from 1 to 20 weight percent of one or more metals and compounds thereof selected from the group consisting of silica, alumina, titanium, zirconium, barium, magnesium and calcium.