Sorbent useful in a visbreaking treatment of carbo-metallic oils

• US 4,515,900 A
• Filed: 06/30/1983
• Issued: 05/07/1985
• Est. Priority Date: 07/09/1981
• 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): DEES, CARL
• Application Number:
  US06/509,100
• Time in Patent Office: 677 Days
• Field of Search: 502/80, 502/84, 502/87, 502/439, 502/63, 502/521
• US Class Current: 502/63
• 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 solid sorbent particulate, its method of preparation and use is disclosed for the treatment of a residual hydrocarbon oil feed, etc. comprising metal contaminants and high carbon forming constituents with a high pore volume solid sorbent material of at least 0.4 cc/g in a visbreaking zone in which operation the effectiveness of the high pore volume sorbent material is further improved by a metal additive to immobilize low melting point vanadium compounds. The sorbent pore volume, sorbent to oil ratio and operating conditions are such that the volume of sorbent pores filled with oil feed is limited to the range of 1/4 to 2/3 and along with carbonaceous material and metal contaminants are encouraged to deposit within the pores rather than on the exterior surface of the solid sorbent in a hydrothermal visbreaking operation in the absence of added molecular hydrogen.

Claims

1. A composition of matter comprising a clay of at least 0.4 cc/g pore volume prepared by slurring kaolinite clay with a high pore volume producing dispersant material which will thermally decompose, spray drying the slurry of clay and dispersant to form microspherical solids, heating said microspherical solids to an elevated temperature over a time period up to about 3 hours and thereafter slowly cooling the heated solids to about 300°

F. over a time period up to about 16 hours.

2. The composition of claim 1 wherein the thermally decomposable dispersant material is a material selected from the group of materials comprising, sugar, carbon black, a thermally decomposable organic material, a thermally decomposable inorganic material such as salts of a molecular weight and structure providing desired pore size upon decomposition.

3. The composition of claim 1 wherein the thermally decomposable dispersant material comprises carbon black.

4. A method for preparing a solid sorbent clay particles of at least 0.4 cc/g pore volume which comprises,

forming a slurried mixture of kaolinite and sodium pyrophosphate in water,

adding alpha monhydrate alumina to said slurry during agitated mixing of the slurry,

adding sulfuric acid and water slowly to the stirred slurry to provide the slurry with a pH of about 3, spray drying the pH adjusted slurry at a temperature up to about 750°

F. to form microspherical solids, heating the microspherical solids to an elevated temperature, and recovering a cooler clay sorbent particle material comprising an alumina binder and a pore volume of at least 0.5 cc/gm.

6. The solid clay sorbent particles of claim 4 to which one or more metals for immobilizing vanadium is added during preparation of the solids.

5. A method for preparing a solid clay sorbent particle material of at least 0.4 cc/gm pore volume which comprises, forming a slurry of water, lignin and carbon black, adding kaolinite clay to said slurry with stirred agitation, spray drying the slurried clay at a temperature up to about 750°

F., heating the spray dried material up to a temperature of about 1850°

F., slowly cooling the heated and calcined spray dried material, and recovering a clay particle material depleted of carbon black and comprising a pore volume of at least 0.4 cc/gm.

7. A method of preparing solid sorbent particulate material comprising a pore volume of at least 0.4 cc/g which comprises, forming a homogenized slurry mix of water, sodium pyrophosphate and very small particle kaolinite clay,

adding sodium metasilicate to the clay slurry with stirring to produce a thick clay slurry, dilute the thick clay slurry with water while mixing at a temperature of 125°

F., spray drying the diluted clay slurry at a temperature within the range of 250°

F. to about 750°

F. to produce microspherical solid products,

heating the microspherical particles to an elevated temperature for an extended period of time, cooling the heated material, and recovering fluidizable clay adsorbent particles containing 5 weight percent of silica binder and 93 wt % of clay providing a pore volume of at least 0.41 cc/g and a surface area of at least 14 m² /g.

8. A composition of matter for demetallizing and decarbonizing high boiling residual oils comprising vanadium and asphaltenes which comprises

a clay sorbent material provided with a pore volume in the range of 0.4 cc/g to 0.5 cc/g and a pore opening of at least 500 Angstroms, and

said clay sorbent provided with from 1 to 20 wt % of a metal or compounds of metals selected from the group consisting of silica, alumina, titanium, zirconium, barium, magnesium, calcium and mixtures thereof.