Chemical process for sulfur reduction of hydrocarbons
Treatment of hydrocarbon streams, and in one non-limiting embodiment refinery distillates, with high pH aqueous reducing agents, such as borohydride, results in reduction of the sulfur compounds such as disulfides, mercaptans and thioethers that are present to give easily removed sulfides. The treatment converts the original sulfur compounds into hydrogen sulfide or low molecular weight mercaptans that can be extracted from the distillate with caustic solutions, hydrogen sulfide or mercaptan scavengers, solid absorbents such as clay or activated carbon or liquid absorbents such as amine-aldehyde condensates and/or aqueous aldehydes.
1. A method for removing a sulfur compound from a hydrocarbon stream containing the sulfur compound, the method comprising:
contacting the hydrocarbon stream with an amount of a reducing agent effective to react with the sulfur compound to form at least one reaction product in a treated hydrocarbon stream; and
removing the at least one reaction product from the treated hydrocarbon stream; where:
the sulfur compound is selected from the group consisting of mercaptans having the formula R—S—H where R is a linear or branched C1 to C4 alkyl group, carbon disulfide (CS 2 ), dialkyl sulfides having the formula R 1 —S—R 2 where R 1 and R 2 are independently linear or branched C1 to C4 alkyl groups, dialkyl disulfides having the formula R 1 —S—S—R 2 , and combinations thereof;
the hydrocarbon stream comprises liquid or gas hydrocarbons selected from the group consisting of C1 to C12 alkanes, C2 to C12 alkenes, liquefied petroleum gas, natural gas, fuel gas, flare gas, naphtha, gasoline, kerosene, and mixtures thereof; and
the reducing agent is selected from the group consisting of:
borane (BH 3 );
diborane (B 2 H 6 );
complexes of borane or diborane with Lewis bases selected from the group consisting of ethers, dialkyl sulfides, amines, alcohols, and mixtures thereof;
inorganic borohydride salts having the formula M 1 BH 4 where M 1 is selected from the group consisting of Li, Na, and K, or having the formula M 2 (BH 4 ) 2 where M 2 is selected from the group consisting of Mg, Ca, and Zn;
cyanoborohydrides having the formula M 1 BH 3 CN or having the formula M 2 (BH 3 CN) 2 ;
organic borohydrides having the formula M 1 BR 3 3 H and R 3 is independently selected from the group consisting of linear or branched C1 to C3 alkyl groups and a carboxylate group having the formula R 4 C(O)O—, and where R 4 is selected from the group consisting of linear or branched C1 to C9 alkyl groups; and
combinations thereof.
2. The method of claim 1 where in contacting the hydrocarbon stream with the reducing agent, the reducing agent is aqueous and has a pH ranging from about 7 to about 14.
3. The method of claim 2 where contacting the hydrocarbon stream with the reducing agent is conducted in the presence of a base selected from the group consisting of sodium hydroxide, potassium hydroxide, and combinations thereof.
4. The method of claim 1 where the effective amount of the reducing agent is up to two times the stoichiometric ratio of the reducing agent to the sulfur compound.
5. The method of claim 1 where removing the at least one reaction product from the hydrocarbon stream comprises a procedure selected from the group consisting of:
passing the treated hydrocarbon stream through a bed containing a solid absorbent selected from the group consisting of clay, carbon, a zeolite, and combinations thereof; and
washing the treated hydrocarbon stream with a liquid absorbent selected from the group consisting of amine-aldehyde condensates, aqueous aldehydes and combinations thereof.
6. The method of claim 1 where the reducing agent is in an aqueous solution.
7. The method of claim 1 where hydrocarbons in the hydrocarbon stream range from C1-C12.
8. A method for removing a sulfur compound from a hydrocarbon stream containing the sulfur compound, the method comprising:
contacting the hydrocarbon stream with an amount of a reducing agent in an amount up to two times the stoichiometric ratio to react with the sulfur compound to form at least one reaction product in a treated hydrocarbon stream, where the reducing agent is aqueous and has a pH ranging from about 7 to about 14; and
removing the at least one reaction product from the treated hydrocarbon stream; where:
the sulfur compound is selected from the group consisting of mercaptans having the formula R—S—H where R is a linear or branched C1 to C4 alkyl group, carbon disulfide (CS 2 ), dialkyl sulfides having the formula R 1 —S—R 2 where R 1 and R 2 are independently linear or branched C1 to C4 alkyl groups, dialkyl disulfides having the formula R 1 —S—S—R 2 , and combinations thereof;
the hydrocarbon stream comprises liquid or gas hydrocarbons selected from the group consisting of C1 to C12 alkanes, C2 to C12 alkenes, liquefied petroleum gas, natural gas, fuel gas, flare gas, naphtha, gasoline, kerosene, and mixtures thereof; and
the reducing agent is selected from the group consisting of:
borane (BH 3 );
diborane (B 2 H 6 );
complexes of borane or diborane with Lewis bases selected from the group consisting of ethers, dialkyl sulfides, amines, alcohols, and mixtures thereof;
inorganic borohydride salts having the formula M 1 BH 4 where M 1 is selected from the group consisting of Li, Na, and K, or having the formula M 2 (BH 4 ) 2 where M 2 is selected from the group consisting of Mg, Ca, and Zn;
cyanoborohydrides having the formula M 1 BH 3 CN or having the formula M 2 (BH 3 CN) 2 ;
organic borohydrides having the formula M 1 BR 3 3 H and R 3 is independently selected from the group consisting of linear or branched C1 to C3 alkyl groups and a carboxylate group having the formula R 4 C(O)O—, and where R 4 is selected from the group consisting of linear or branched C1 to C9 alkyl groups; and
combinations thereof.
9. The method of claim 8 where contacting the hydrocarbon stream with the reducing agent is conducted in the presence of a base selected from the group consisting of sodium hydroxide, potassium hydroxide, and combinations thereof.
10. The method of claim 8 where removing the at least one reaction product from the hydrocarbon stream comprises a procedure selected from the group consisting of:
passing the treated hydrocarbon stream through a bed containing a solid absorbent selected from the group consisting of clay, carbon, a zeolite, and combinations thereof; and
washing the treated hydrocarbon stream with a liquid absorbent selected from the group consisting of amine-aldehyde condensates, aqueous aldehydes and combinations thereof.
11. A treated hydrocarbon stream comprising:
liquid or gas light hydrocarbons selected from the group consisting of C1 to C12 alkanes, C2 to C12 alkenes, liquefied petroleum gas, natural gas, fuel gas, flare gas, naphtha, gasoline, kerosene, and mixtures thereof;
at least one sulfur compound selected from the group consisting of mercaptans having the formula R—S—H where R is a linear or branched C1 to C4 alkyl group, carbon disulfide (CS 2 ), dialkyl sulfides having the formula R 1 —S—R 2 where R 1 and R 2 are independently linear or branched C1 to C4 alkyl groups, dialkyl disulfides having the formula R 1 —S—S—R 2 where R 1 and R 2 are as previously defined, and combinations thereof; and
at least one reducing agent selected from the group consisting of:
borane (BH 3 );
diborane (B 2 H 6 );
complexes of borane or diborane with Lewis bases selected from the group consisting of ethers, dialkyl sulfides, amines, alcohols, and mixtures thereof;
inorganic borohydride salts having the formula M 1 BH 4 where M 1 is selected from the group consisting of Li, Na, and K, or having the formula M 2 (BH 4 ) 2 where M 2 is selected from the group consisting of Mg, Ca, and Zn;
cyanoborohydrides having the formula M 1 BH 3 CN or having the formula M 2 (BH 3 CN) 2 ;
organic borohydrides having the formula M 1 BR 3 3 H and R 3 is independently selected from the group consisting of linear or branched C1 to C3 alkyl groups and a carboxylate group having the formula R 4 C(O)O—, and where R 4 is selected from the group consisting of linear or branched C1 to C9 alkyl groups; and
combinations thereof;
where the reducing agent is present in an amount effective to react with the sulfur compound to form at least one reaction product.
12. The treated hydrocarbon stream of claim 11 where in contacting the hydrocarbon stream with the reducing agent, the reducing agent is aqueous and has a pH ranging from about 7 to about 14.
13. The treated hydrocarbon stream of claim 12 where contacting the hydrocarbon stream with the reducing agent is conducted in the presence of a base selected from the group consisting of sodium hydroxide, potassium hydroxide, and combinations thereof.
14. The treated hydrocarbon stream of claim 11 where the effective amount of the reducing agent is up to two times the stoichiometric ratio of the reducing agent to the sulfur compound.
15. The treated hydrocarbon stream of claim 11 where hydrocarbons in the hydrocarbon stream range from C1-C12.