Zeolite catalysis process for conversion of diene-containing olefins to aromatic hydrocarbons

• US 4,751,339 A
• Filed: 01/23/1987
• Issued: 06/14/1988
• Est. Priority Date: 01/23/1987
• Status: Expired due to Term

• Current Assignee: Mobil Oil Corporation (Exxon Mobil Corporation)
• Original Assignee: Mobil Oil Corporation (Exxon Mobil Corporation)
• Inventors: Beech, James H. Jr., Tabak, Samuel A.
• Primary Examiner(s): NOT, DEFINED
• Application Number:
  US07/006,089
• Time in Patent Office: 508 Days
• Field of Search: 585/533, 585/415
• US Class Current: 585/415
• CPC Class Codes: C07C 15/00 Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
• CPC Class Codes: C07C 2/00 Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms redistribution reactions involving splitting C07C6/00
• CPC Class Codes: C07C 2529/40 of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
• CPC Class Codes: Y02P 20/584 Recycling of catalysts

Abstract

A technique for continuous conversion of diene-containing aliphatic hydrocarbon feedstock to heavier hydrocarbon products wherein the feedstock is contacted at elevated temperature under endothermic high severity reaction conditions with a fluidized bed of acidic zeolite fine catalyst particles, comprising methods and means for:

maintaining the fluidized catalyst bed in a vertical reactor having a turbulent reaction zone by passing vapor upwardly through the reaction zone at a velocity greater than dense bed transition velocity to a turbulent regime and less than transport velocity for the average catalyst particle;

feeding a continuous stream of feedstock into the reaction zone, said feedstream comprising sufficient C₃⁺ alkanes to require net endothermic reaction conditions;

withdrawing a portion of coked catalyst from the reaction zone, oxidatively regenerating the withdrawn catalyst, heating the catalyst substantially above process temperature in the fluidized bed reactor, and returning hot regenerated catalyst to the reaction zone at a rate to control catalyst activity and reaction temperature under conditions of reaction severity to effect feedstock conversion to an aromatics-rich hydrocarbon effluent stream; and

separating an aromatics-rich product from the fluidized bed effluent stream.

Aromatics yield is increased by recovering a recycle stream comprising C₅⁺ aliphatic hydrocarbons from the fluidized bed effluent stream for further conversion in the fluidized bed to increase aromatics product yield.

Claims

1. A process for converting lower olefinic hydrocarbon feedstock to aromatics-rich product by contacting the feedstock with acidic siliceous zeolite conversion catalyst particles at elevated temperature between about 200 degrees C. to 650 degrees C. under aromatization conditions to produce heavier hydrocarbons including aromatic hydrocarbons comprising:

introducing lower olefinic feedstock comprising at least one C₄ -C₆ diene component into a bed of catalyst particles to convert feedstock to heavier hydrocarbon rich in aromatics;

separating an aromatics-rich C₅⁺ liquid stream from fluidized bed reaction effluent;

extracting aromatics components from the liquid stream and recovering a product stream comprising at least 50 wt% C₆ -C₁₀ aromatic hydrocarbons.

2. The process of claim 1 wherein the olefinic feed comprises about 5 to 90 wt.% C₄⁺ mono-olefin and 1 to 50 wt.% conjugated unsaturated diolefins;

and wherein the net yield of aromatic product comprises at least 15 wt% of the olefin components of the feedstock.

3. The process of claim 2 wherein said feedstock consists essentially of liquid pyrolysis gas byproduct of hydrocarbon pyrolysis, wherein the catalyst comprises zeolite having the crystalline structure of ZSM-5.

4. In the process for catalytic conversion of lower olefinic hydrocarbon feed to heavier hydrocarbons wherein the olefinic feedstock is contacted under conversion conditions at elevated temperature with an acidic medium pore shape selective metallosilicate catalyst, the improvement which comprises:

cofeeding at least one C₂ -C₄ mono-alkene with at least one C₄ -C₆ conjugated diene for concurrent conversion to an aromatics-rich C₅⁺ liquid product at a temperature between about 200 degrees C. to 650 degrees C. whereby an improved yield of aromatics is produced.

5. The process of claim 4 wherein aromatics produced in the conversion are substantially greater than that produced by the equivalent mono-alkenes without diene cofeeding.

6. The process of claim 4 wherein the catalyst comprises aluminosilicate ZSM-5, the diene comprises 1,3-butadiene and the mono-alkenes comprises either, butene and/or propene.

7. The process of claim 5 wherein the aromatics content of C₅⁺ liquid product is at least 15 wt.%.

8. In the process for producing benzenoid hydrocarbons from aliphatic hydrocarbon feed by contacting with a medium pore shape selective acid zeolite catalyst at elevated reaction temperature, the improvement which comprises feeding a conjugated di-ethylenically unsaturated diene with the aliphatic hydrocarbon feed under aromatization conditions between about 200 degrees C. and 650 degrees C. in an amount to increase C₆ -C₈ monocyclic benzenoid production substantially above that produced by diene-free aliphatic feed.

9. The process of claim 8 wherein the feed consists essentially of aliphatic hydrocarbons having up to six carbon atoms, including about 5 to 50 wt.% diene and 5 to 95 wt.% mono-alkene;

the reaction temperature is at about 200°

C. to 650°

C.;

the catalyst comprises an aluminosilicate having the crystalline structure of ZSM-5; and

reaction effluent contains at least 15 wt.% total C₆ -C₈ benzenoid hydrocarbons.

10. The process of claim 8 wherein the reaction temperature is maintained in the range of about 200°

to 650°

C. at a partial olefin pressure of at least 50 kPa.