Treatment of mercaptan-containing streams utilizing nitrogen based promoters

An improved method of sweetening a sour hydrocarbon distillate having mercaptan compounds therein by the extraction of said mercaptan compounds from said distillate, wherein said distillate is contacted with a caustic solution for a period of time sufficient to extract at least a portion of said mercaptan compounds into said caustic solution, the improvement comprising contacting said distillate and said caustic solution in the presence of from about 1 ppm to about 50 ppm by weight, based upon said distillate, of a nitrogen-based promoter, wherein said nitrogen-based promoter comprises a non-electrolytic, substantially sulfur free organic compound having at least one nitrogen atom, said nitrogen-based promoter being selected from the group consisting of:

• heterocyclic compounds, wherein the ring or rings of said heterocyclic compounds consist of carbon and nitrogen atoms, said heterocyclic compounds being selected from the group consisting of pyridine, picolene, nicotinonitrile, 1-phenylpyrrole, 2,2-bipyridine, quinoline, 2,2-biquinoline, triazine, melamine, methenamine, 3,4-diaminopyridine, 3-aminopyridine, acridine, quinaldine, isoquinoline, 3-aminoquinoline, 7-azaindole, 5-triazolo[4,3-a]quinoline, 4-azabenzimidazole, L-histidine, aminopiperidine, benzotriazole, 1,2,4-triazole, 5-aminoindazole, aminopyrazole, 5,10,15,20-tetraphenyl 21H,23H porphine, nicotine, 2-analinopyridine, 4-dimethylaminopyridine, benzimidazole, N-methyltolyimidazole, tolyimidazole, pyrrole, pyrrolidine, 4-methylpiperidine, 2,5 dimethylpyrrole, piperidine, 1-ethylpiperidine, 2-ethylpiperidine, pyrazole, indole, 3-methylindole, 5-methylindole, indoline, polyvinyl piperidine, azabicyclo[3,2,2]nonane, phthalocyanine, 1,4,8,12 tetraazacyclopentadicane, 5-aminoindole, carbazole, imidazole, N-alkylate imidazole, skatole, quinalidine, 2,3-cyclopentenepyridine and penanthroline;
• substituted homocyclic compounds, wherein at least one substituent attached to the ring or rings of said homocyclic compounds comprises at least one nitrogen atom;
• aliphatic compounds comprising at least one nitrogen atom;
• and
• mixtures thereof.

An improved method for regenerating a spent caustic stream having mercaptide compounds therein by the catalytic oxidation of said mercaptide compounds to disulfide compounds and extraction thereof from said caustic solution, wherein said spent caustic solution is contacted with a hydrocarbon distillate in the presence of an oxidizing agent and a metal chelate mercaptan oxidation catalyst for a period of time sufficient to oxidize at least a portion of said mercaptide compounds to disulfide compounds and to extract at least a portion of said disulfide compounds into said hydrocarbon distillate, the improvement comprising contacting said distillate and caustic stream in the presence of said oxidizing agent and said metal chelate mercaptan oxidation catalyst and also in the presence of from about 1 ppm to about 50 ppm by weight, based upon said distillate, of a nitrogen-based promoter, comprising a non-electrolytic, substantially sulfur free organic compound having at least one nitrogen atom, said nitrogen-based promoter being selected from the group consisting of:

• heterocyclic compounds, wherein the ring or rings of said heterocyclic compounds consist of carbon and nitrogen atoms, said heterocyclic compounds being selected from the group consisting of pyridine, picolene, nicotinonitrile, 1-phenylpyrrole, 2,2-bipyridine, quinoline, 2,2-biquinoline, triazine, melamine, methenamine, 3,4-diaminopyridine, 3-aminopyridine, acridine, quinaldine, isoquinoline, 3-aminoquinoline, 7-azaindole, 5-triazolo[4,3-a]quinoline, 4-azabenzimidazole, L-histidine, aminopiperidine, benzotriazole, 1,2,4-triazole, 5-aminoindazole, aminopyrazole, 5,10,15,20-tetraphenyl 21H,23H porphine, nicotine, 2-analinopyridine, 4-dimethylaminopyridine, benzimidazole, N-methyltolyimidazole, tolyimidazole, pyrrole, pyrrolidine, 4-methylpiperidine, 2,5 dimethylpyrrole, piperidine, 1-ethylpiperidine, 2-ethylpiperidine, pyrazole, indole, 3-methylindole, 5-methylindole, indoline, polyvinyl piperidine, azabicyclo[3,2,2]nonane, phthalocyanine, 1,4,8,12 tetraazacyclopentadicane, 5-aminoindole, carbazole, imidazole, N-alkylate imidazole, skatole, quinalidine, 2,3-cyclopentenepyridine and penanthroline;
• substituted homocyclic compounds, wherein at least one substituent attached to the ring or rings of said homocyclic compounds comprises at least one nitrogen atom;
• aliphatic compounds comprising at least one nitrogen atom;
• and
• mixtures thereof.

A method of regenerating a caustic stream or sweetening a hydrocarbon stream having mercaptan or mercaptan-based compounds therein, comprising the steps of:

• introducing said caustic stream onto the upstream end of a fiber bundle positioned within a conduit, wherein the downstream end of said fiber bundle extends out of said conduit into a collection vessel;
• flowing said hydrocarbon stream cocurrently through said conduit in contact with said caustic stream in the presence of from about 1 ppm to about 50 ppm by weight, based upon said hydrocarbon stream, of a nitrogen-based promoter, wherein said nitrogen-based promoter comprises a non-electrolytic, substantially sulfur free organic compound having at least one nitrogen atom, said nitrogen-based promoter being selected from the group consisting of:
• heterocyclic compounds wherein the ring or rings of said heterocyclic compounds consist of carbon and nitrogen atoms, said heterocyclic compounds being selected from the group consisting of pyridine, picolene, nicotinonitrile, 1-phenylpyrrole, 2,2-bipyridine, quinoline, 2,2-biquinoline, triazine, melamine, methenamine, 3,4-diaminopyridine, 3-aminopyridine, acridine, quinaldine, isoquinoline, 3-aminoquinoline, 7-azaindole, 5-triazolo [4,3-a] quinoline, 4-azabenzimidazole, L-histidine, aminopiperidine, 2,2'-biquinoline, benzotriazole, 1,2,4-triazole, 5-aminoindazole, aminopyrazole, 5,10,15,20-tetraphenyl 21H,23H porphine, nicotine, 2-analinopyridine, 4-dimethylaminopyridine, benzimidazole, N-methyltolyimidazole, tolyimidazole, pyrrole, pyrrolidine, 4-methylpiperidine, 2,5 dimethylpyrrole, piperidine, 1-ethylpiperidine, 2-ethylpiperidine, pyrazole, indole, 3-methylindole, 5-methylindole, indoline, polyvinyl piperidine, azabicyclo [3,2,2] nonane, phthalocyanine, 1,4,8,12 tetraazacyclopentadicane, 5-aminoindole, carbazole, imidazole, N-alkylate imidazole, skatole, quinalidine, 2,3-cyclopentenepyridine and penanthroline,
• substituted homocyclic compounds wherein at least one substituent attached to the ring or rings of said homocyclic compounds comprises at least one nitrogen atom,
• aliphatic compounds comprising at least one nitrogen atom, and
• mixtures thereof;
• receiving said hydrocarbon stream and said caustic stream in said collection vessel, wherein said hydrocarbon stream forms an upper layer in said collection vessel, and wherein said caustic stream forms a lower layer in said collection vessel;
• withdrawing said hydrocarbon stream from said collection vessel;
• and
• withdrawing said caustic stream from said collection vessel.

A method of regenerating a caustic stream or sweetening a hydrocarbon stream having mercaptan or mercaptan-based compounds therein, comprising the steps of:

• introducing said caustic stream onto an upstream end of a fiber bundle positioned within a conduit, wherein said fiber bundle has a downstream end extending from said conduit into a collection vessel having an upper and lower portion;
• introducing into the upper portion of said collection vessel said hydrocarbon stream at a sufficient rate and pressure to flow said hydrocarbon stream countercurrently through said conduit, in contact with said caustic stream in the presence of from about 1 ppm to about 50 ppm by weight, based upon said hydrocarbon stream, of a nitrogen-based promoter, wherein said nitrogen-based promoter comprises a non-electrolytic, substantially sulfur free organic compound having at least one nitrogen atom, selected from the group consisting of:
• heterocyclic compounds wherein the ring or rings of said heterocyclic compounds consist of carbon and nitrogen atoms, said heterocyclic compounds being selected from the group consisting of pyridine, picolene, nicotinonitrile, 1-phenylpyrrole, 2,2-bipyridine, quinoline, 2,2-biquinoline, triazine, melamine, methenamine, 3,4-diaminopyridine, 3-aminopyridine, acridine, quinaldine, isoquinoline, 3-aminoquinoline, 7-azaindole, 5-triazolo [4,3-a] quinoline, 4-azabenzimidazole, L-histidine, aminopiperidine, benzotriazole, 1,2,4-triazole, 5-aminoindazole, aminopyrazole, 5,10,15,20-tetraphenyl 21H,23H porphine, nicotine, 2-analinopyridine, 4-dimethylaminopyridine, benzimidazole, N-methyltolyimidazole, tolyimidazole, pyrrole, pyrrolidine, 4-methylpiperidine, 2,5 dimethylpyrrole, piperidine, 1-ethylpiperidine, 2-ethylpiperidine, pyrazole, indole, 3-methylindole, 5-methylindole, indoline, polyvinyl piperidine, azabicyclo [3,2,2] nonane, phthalocyanine, 1,4,8,12 tetraazacyclopentadicane, 5-aminoindole, carbazole, imidazole, N-alkylate imidazole, skatole, quinalidine, 2,3-cyclopentenepyridine and penanthroline,
• substituted homocyclic compounds wherein at least one substituent attached to the ring or rings of said homocyclic compounds comprises at least one nitrogen atom,
• aliphatic compounds comprising at least one nitrogen atom and
• mixtures thereof;
• receiving a first portion of said caustic stream and a first portion of said hydrocarbon stream in said collection vessel, wherein said hydrocarbon stream forms an upper layer in said collection vessel and said caustic stream forms a lower layer in said collection vessel, and wherein said caustic stream is withdrawn from said lower portion of said collection vessel;
• withdrawing a second portion of said hydrocarbon stream and a second portion of said caustic stream after contact with said upstream end of said fiber bundle;
• and
• receiving in a separator said second portion of said hydrocarbon stream and said second portion of said caustic stream, wherein said hydrocarbon stream forms an upper layer and said caustic stream forms a lower layer in said separator, and wherein said hydrocarbon stream and said caustic stream are withdrawn from said separator.

A method of sweetening sour hydrocarbon distillate having mercaptan compounds therein by the catalytic oxidation of said mercaptan compounds to disulfide compounds, comprising the steps of:

• contacting said hydrocarbon distillate with a caustic stream in the presence of a fixed bed carrying a metal chelate mercaptan oxidation catalyst and further in the presence of an oxidizing agent and from about 1 ppm to about 50 ppm by weight, based upon said hydrocarbon stream, of a nitrogen-based promoter for a time sufficient to oxidize at least a portion of said mercaptan compounds to disulfide compounds, wherein said nitrogen-based promoter comprises a non-electrolytic, substantially sulfur free organic compound having at least one nitrogen atom, selected from the group consisting of:
• heterocyclic compounds wherein the ring or rings of said heterocyclic compounds consist of carbon and nitrogen atoms, said heterocyclic compounds being selected from the group consisting of pyridine, picolene, nicotinonitrile, 1-phenylpyrrole, 2,2-bipyridine, quinoline, 2,2-biquinoline, triazine, melamine, methenamine, 3,4-diaminopyridine, 3-aminopyridine, acridine, quinaldine, isoquinoline, 3-aminoquinoline, 7-azaindole, 5-triazolo[4,3-a]quinoline, 4-azabenzimidazole, L-histidine, aminopiperidine, benzotriazole, 1,2,4-triazole, 5-aminoindazole, aminopyrazole, 5,10,15,20-tetraphenyl 21H,23H porphine, nicotine, 2-analinopyridine, 4-dimethylaminopyridine, benzimidazole, N-methyltolyimidazole, tolyimidazole, pyrrole, pyrrolidine, 4-methylpiperidine, 2,5 dimethylpyrrole, piperidine, 1-ethylpiperidine, 2-ethylpiperidine, pyrazole, indole, 3-methylindole, 5-methylindole, indoline, polyvinyl piperidine, azabicyclo[3,2,2]nonane, phthalocyanine, 1,4,8,12 tetraazacyclopentadicane, 5-aminoindole, carbazole, imidazole, N-alkylate imidazole, skatole, quinalidine, 2,3-cyclopentenepyridine and penanthroline, substituted homocyclic compounds wherein at least one substituent attached to the ring or rings of said homocyclic compounds comprises at least one nitrogen atom,
• aliphatic compounds comprising at least one nitrogen atom, and
• mixtures thereof;
• receiving said hydrocarbon stream and said caustic stream in a collection vessel, wherein said hydrocarbon stream forms an upper layer in said collection vessel, and wherein said caustic stream forms a lower layer in said collection vessel;
• withdrawing said hydrocarbon stream from said collection vessel;
• and
• withdrawing said caustic stream from said collection vessel.

A method of sweetening a sour hydrocarbon distillate having mercaptan compounds therein by the catalytic oxidation of said mercaptan compounds to disulfide compounds, comprising the steps of:

• introducing a first caustic stream onto an upstream end of a fiber bundle positioned within a conduit, wherein the downstream end of said fiber bundle extends out of said conduit into a collection vessel;
• flowing said hydrocarbon distillate through said conduit, in contact with said first caustic stream in the presence of an oxidizing agent, a metal chelate mercaptan oxidation catalyst, and from about 1 ppm to about 50 ppm by weight, based upon said hydrocarbon distillate, of a nitrogen-based promoter for a time sufficient to oxidize at least a portion of said mercaptan compounds to disulfide compounds, wherein said nitrogen-based promoter comprises a non-electrolytic, substantially sulfur free organic compound having at least one nitrogen atom, selected from the group consisting of:
• heterocyclic compounds wherein the ring or rings of said heterocyclic compounds consist of carbon and nitrogen atoms, said heterocyclic compounds being selected from the group consisting of pyridine, picolene, nicotinonitrile, 1-phenylpyrrole, 2,2-bipyridine, quinoline, 2,2-biquinoline, triazine, melamine, methenamine, 3,4-diaminopyridine, 3-aminopyridine, acridine, quinaldine, isoquinoline, 3-aminoquinoline, 7-azaindole, 5-triazolo,[4,3-a] quinoline, 4-azabenzimidazole, L-histidine, aminopiperidine, benzotriazole, 1,2,4-triazole, 5-aminoindazole, aminopyrazole, 5,10,15,20-tetraphenyl 21H,23H porphine, nicotine, 2-analinopyridine, 4-dimethylaminopyridine, benzimidazole, N-methyltolyimidazole, tolyimidazole, pyrrole, pyrrolidine, 4-methylpiperidine, 2,5 dimethylpyrrole, piperidine, 1-ethylpiperidine, 2-ethylpiperidine, pyrazole, indole, 3-methylindole, 5-methylindole, indoline, polyvinyl piperidine, azabicyclo[3,2,2]nonane, phthalocyanine, 1,4,8,12 tetraazacyclopentadicane, 5-aminoindole, carbazole, imidazole, N-alkylate imidazole, skatole, quinalidine, 2,3-cyclopentenepyridine and penanthroline,
• substituted homocyclic compounds wherein at least one substituent attached to the ring or rings of said homocyclic compounds comprises at least one nitrogen atom,
• aliphatic compounds comprising at least one nitrogen atom, and
• mixtures thereof;
• receiving said hydrocarbon distillate and said first caustic stream in said collection vessel;
• and
• further contacting said hydrocarbon distillate with a second caustic stream in the presence of said oxidizing agent and nitrogen-based promoter and further in the presence of a fixed bed catalyst for a time sufficient to oxidize a portion of the remaining mercaptan compounds to disulfide compounds, wherein said fixed bed catalyst comprises a supported metal chelate mercaptan oxidation catalyst.