Process for the disposal of aqueous sulfur and caustic-containing wastes

• US 5,466,361 A
• Filed: 10/28/1993
• Issued: 11/14/1995
• Est. Priority Date: 06/12/1992
• Status: Expired due to Fees

• Current Assignee: Mobil Oil Corporation (Exxon Mobil Corporation)
• Original Assignee: Mobil Oil Corporation (Exxon Mobil Corporation)
• Inventors: Venuto, Paul B., Reischman, P. T., Heinemann, Heinz, Heck, Roland H., Whitehurst, D. Duayne
• Primary Examiner(s): Myers, Helane
• Application Number:
  US08/118,902
• Time in Patent Office: 747 Days
• Field of Search: 208/131, 208/50, 208/126, 208/13, 48/197 R
• US Class Current: 208/131
• CPC Class Codes: C10B 55/00 Coking mineral oils, bitumen, tar, and the like or mixtures thereof with solid carbonaceous material cracking oils C10G
• CPC Class Codes: C10B 57/06 containing additives
• CPC Class Codes: C10G 9/005 Coking (in order to produce liquid products mainly)
• CPC Class Codes: C10J 2300/0946 Waste, e.g. MSW, tires, glass, tar sand, peat, paper, lignite, oil shale
• CPC Class Codes: C10J 2300/0956 Air or oxygen enriched air
• CPC Class Codes: C10J 2300/0959 Oxygen
• CPC Class Codes: C10J 2300/0976 as steam
• CPC Class Codes: C10J 2300/0986 Catalysts
• CPC Class Codes: C10J 3/06 Continuous processes

Abstract

Aqueous sulfur and caustic component-containing waste streams are disposed of in an environmentally acceptable manner employing a process featuring integrated coking and gasification operations.

Claims

1. A coking process which may be used for the disposal of an aqueous waste material, comprising the following steps:

(a) reacting a coker feedstock under coking reaction conditions in the presence of an aqueous waste material, wherein the waste material is a caustic soda, caustic potash, or a mixture of both resulting from the refining of heavy hydrocarbons to lighter hydrocarbon products, containing from 0.4 wt % to 25 wt % of at least one sulfur-containing component, wherein the sulfur-containing component is selected from the group consisting of alkaline sulfide, hydrosulfide or mixture of both, which on gasification converts to hydrogen sulfide and at least one alkali-metal containing component, wherein the component is an alkali metal oxide, to provide a sulfur-containing and alkali metal containing coke product, wherein the coker feedstock comprises a hydrocarbon fraction having a boiling point of at least about 650°

F. and wherein said coking reaction conditions include a temperature of from about 800°

F. to about 930°

F.; and

(b) gasifying the coke product under gasification conditions in the presence of a catalyst, said catalyst comprising at least one metal oxide selected from the group consisting of alkali metal oxide and alkaline earth metal oxide, in order to convert (i) the coke to gaseous products (ii) the sulfur-containing component to hydrogen sulfide and (iii) the alkali metal -containing component to a solid residue.

2. The process of claim 1, wherein at least 0.5 wt. % alkali metal and no more than 20 wt. % alkali metal is incorporated into the coke product.

3. The process of claim 2, wherein less than about 5 wt. % alkali metal compound is present in the coker feedstock.

4. The process of claim 1 wherein the coke is quenched with a alkali metal-containing aqueous stream.

5. The process of claim 1 wherein the coke is quenched with a aqueous caustic soda, a caustic potash stream or mixture thereof.

6. The process of claim 1 wherein the sulfur-containing and alkali metal-containing waste material is a caustic soda, a caustic potash stream or mixture thereof.

7. The process of claim 1 wherein the coke product, being comprised predominantly of shot coke, is of low crystallinity.

8. The process of claim 1, wherein the coke is predominantly shot coke.

9. The process of claim 1 wherein gasifying is carried out in the presence of added gasifying catalyst comprising a mixture of at least one alkali metal oxide and at least one alkaline earth metal oxide.

10. The process of claim 9 wherein gasifying is carried out in the presence of added gasifying catalyst comprising a mixture of potassium and calcium oxide.

11. The process of claim 9 wherein gasifying is carried out in the presence of added gasifying catalyst comprising a eutectic mixture of at least one alkali metal oxide and at least one alkaline earth metal oxide.

12. The process of claim 11 wherein gasifying is carried out in the presence of added gasifying catalyst comprising a eutectic mixture of potassium oxide and calcium oxide.

13. The process of claim 1 wherein coking is carried out at a pressure of from abut 0 to about 100 psig.

14. The process of claim 1 wherein gasifying is carried out in the presence of steam at a temperature of from abut 550C(1022°

F.) to about 700C(1292°

F.) and from about atmospheric pressure to about 2000 psig.

15. The process of claim 1 wherein coking is carried out under delayed coking or flexicoking conditions.

16. The process of claim 4 wherein the alkali metal containing aqueous stream is heated in a dedicated heater.

17. The process of claim 15 wherein the coker feedstock is a vacuum resid.

18. The process of claim 15 wherein the coking is carried out under delayed coking conditions and the sulfur-containing and alkali metal-containing waste material is introduced to the delayed coking drum at an elevated coking temperature.

19. A coking process which may be used for the disposal of an aqueous waste material, which comprises:

(a) coking a coker feedstock under coking reaction conditions in the presence of an aqueous waste material, wherein the waste material is a caustic soda, caustic potash, or a mixture of both resulting from the refining of heavy hydrocarbons to lighter hydrocarbon products, containing from 0.4 wt % to 13 wt % of at least one sulfur-containing component, wherein the sulfur-containing component is selected from the group consisting of alkaline sulfide, hydrosulfide or a mixture of both, which on gasification converts to hydrogen sulfide and at least one alkali-metal containing component, wherein the component is an alkali metal hydroxide, to provide a sulfur-containing and alkali metal containing coke product, wherein the coker feedstock comprises a hydrocarbon fraction having a boiling point of at least about 650°

F. and wherein said coking reaction conditions include a temperature of from about 800°

F. to about 930°

F.; and

(b) gasifying the coke product under gasification conditions in the presence of a catalyst, said catalyst comprising at least one metal oxide selected from the group consisting of alkali metal oxide and alkaline earth metal oxide, in order to convert (i) the coke to gaseous products (ii) the sulfur-containing component to hydrogen sulfide and (iii) the alkali metal-containing component to a solid residue.