Catalytic cracking with reduced emission of noxious gases

In a process for the cyclic, fluidized, catalytic cracking of hydrocarbon feedstock containing about 0.5 to about 5 weight percent sulfur as organic sulfur compounds wherein (i) said feedstock is subjected to cracking in a reaction zone in contact with fluidized solid particles comprising molecular sieve-type cracking catalyst;

• (ii) solid particles including catalytic particles which are deactivated by sulfur-containing carbonaceous deposits, are separated from reaction zone effluent and pass to a stripping zone wherein volatile deposits are removed from said solid particles by contact with a stripping gas;
• (ii) stripped, solid particles are separated from stripping zone effluent and pass to a catalyst regeneration zone and are regenerated by burning the non-stripped, sulfur-containing, carbonaceous deposits from the stripped, solid particles with an oxygen-containing gas thereby forming sulfur oxides;
• and (iv) resulting solid particles are separated from regeneration zone effluent gas and recycled to the reaction zone;
• a method for reducing emissions of carbon monoxide and sulfur oxides in the regeneration zone effluent gas which comprises:
• (a) circulating through the process cycle said solid particles comprising said catalyst and at least one metallic reactant in the same or different ones of said solid particles, which metallic reactant reacts with sulfur oxides in the regeneration zone, said metallic reactant consisting essentially of one or more members selected from the group consisting of sodium, magnesium, calcium, strontium, barium, chromium, manganese, copper, zinc, cadmium, and the rare earth metals, in free or combined form, and wherein said metallic reactant is provided to said cracking-stripping-regeneration process in non-ion-exchanged form with respect to said molecular sieve;
• (b) cracking said feedstock at a temperature from about 850.degree. to about 1,200.degree. F. and in contact with said cracking catalyst and said metallic reactant;
• (c) stripping volatile deposits from said solid particles at a temperature from about 850.degree. to about 1,200.degree. F. with a stripping gas which contains steam, wherein the ratio by weight of steam to said catalyst is from about 0.0005 to about 0.025;
• (d) burning in said regeneration zone said sulfur-containing carbonaceous deposits from the stripped, solid particles at a temperature from about 1,050.degree. to about 1,450.degree. F.;
• (e) withdrawing from said regeneration zone an effluent gas containing molecular oxygen;
• the improvement which comprises conducting said burning of the sulfur-containing carbonaceous deposits from the stripped, solid particles in the presence of at least one metallic promoter consisting essentially of one or more members selected from the group consisting of ruthenium, rhodium, palladium, osmium, iridium, platinum and rhenium, in free or combined form, wherein the metallic promoter and the metallic reactant are during said catalyst regeneration present in sufficient amounts to effect absorption by said metallic reactant of at least about 50 weight percent of the sulfur oxides produced by said burning in said regeneration zone, and wherein the metallic promoter is present in sufficient amount to enhance said absorption of sulfur oxides and the conversion of carbon monoxide to carbon dioxide in the regeneration zone;
• said burning being conducted at a temperature and with oxygen-containing gas having molecular oxygen such that at least about 50 weight percent of the sulfur oxides produced by said burning in said regeneration zone can be absorbed by said metallic reactant;
• said solid particles recycled to the reaction zone having absorbed therein at least about 50 weight percent of said sulfur oxides produced in said regeneration zone;
• said stripped, solid particles passing to said regeneration zone having said metallic reactant in an active form for absorbing at least about 50 weight percent of said sulfur oxides produced in said regeneration zone;
• said stripping being conducted at a temperature and with steam such that passage of said solid particles through said cracking and stripping zones provides said metallic reactant in an amount and active form suitable for accomplishing said absorption of at least about 50 weight percent of said sulfur oxides produced in said regeneration zone;
• and said effluent gas from said regeneration zone having a low concentration of sulfur oxides of less than about 600 ppmv;
• and substantially converting said absorbed sulfur oxides to sulfur-containing gas in said reaction and/or stripping zone.

In a process for the cyclic, fluidized, catalytic cracking of hydrocarbon feedstock containing about 1 to about 4 weight percent sulfur as organic sulfur compounds wherein (i) said feedstock is subjected to cracking in a reaction zone in contact with fluidized solid particles comprising molecular sieve-type cracking catalyst;

• (ii) solid particles including catalytic particles which are deactivated by sulfur-containing carbonaceous deposits, are separated from reaction zone effluent and pass to a stripping zone wherein volatile deposits are removed from said solid particles by contact with a stripping gas;
• (iii) stripped, solid particles are separated from stripping zone effluent and pass to a catalyst regeneration zone and are regenerated by burning the non-stripped, sulfur-containing, carbonaceous deposits from the stripped, solid particles with an oxygen-containing gas thereby forming sulfur oxides;
• and (iv) resulting solid particles are separated from regeneration zone effluent gas and recycled to the reaction zone;
• a method for reducing emissions of carbon monoxide and sulfur oxides in the regeneration zone effluent gas which comprises:
• (a) circulating through the process cycle said solid particles comprising said catalyst and at least one metallic reactant in the same or different ones of said solid particles, which metallic reactant reacts with sulfur oxides in the regeneration zone, said metallic reactant consisting essentially of one or more members selected from the group consisting of sodium, rare earth metals and magnesium, in free or combined form;
• (b) cracking said feedstock at a temperature from about 850.degree. to about 1,200.degree. F. and in contact with said cracking catalyst and said metallic reactant;
• (c) stripping volatile deposits from said solid particles at a temperature from about 850.degree. to about 1,200.degree. F. with a stripping gas which contains steam;
• wherein the ratio by weight of steam to said catalyst is from about 0.0015 to about 0.0125;
• (d) burning in said regeneration zone said sulfur-containing carbonaceous deposits from the stripped, solid particles at a temperature from about 1,050.degree. to about 1,450.degree. F.;
• (e) withdrawing from said regeneration zone an effluent gas containing at least 0.5 volume percent of molecular oxygen from the regeneration zone;
• the improvement which comprises conducting said burning of the sulfur-containing carbonaceous deposits from the stripped, solid particles in the presence of platinum, wherein the metallic reactant and platinum are present during said catalyst regeneration in sufficient amounts to effect absorption by said metallic reactant of at least about 50 weight percent of the sulfur oxides produced by said burning in said regeneration zone, and wherein the platinum is present in sufficient amount to enhance said absorption of sulfur oxides and and the conversion of carbon monoxide to carbon dioxide in the regeneration zone;
• said burning being conducted at a temperature and with oxygen-containing gas having molecular oxygen such that at least about 50 weight percent of said sulfur oxides produced by said burning in said regeneration zone can be absorbed by said metallic reactant;
• said solid particles recycled to the reaction zone containing said platinum and said solid particles having absorbed therein at least about 50 weight percent of said sulfur oxides produced in said regeneration zone;
• said stripped, solid particles passing to said regeneration zone having said metallic reactant in an active form for absorbing at least about 50 weight percent of said sulfur oxides produced in said regeneration zone;
• said stripping being conducted at a temperature and with steam such that passage of said solid particles through said catalyst and stripping zones provides said metallic reactant in an amount and active form suitable for accomplishing said absorption of at least about 50 weight percent of said sulfur oxides produced in said regeneration zone;
• said effluent gas from said regeneration zone having a low concentration of sulfur oxides of less than about 600 ppmv;
• and substantially converting said absorbed sulfur oxides to sulfur-containing gas in said reaction and/or stripping zone.

In a process for the cyclic, fluidized, catalytic cracking of hydrocarbon feedstock containing about 0.2 to about 6 weight percent sulfur as organic sulfur compounds wherein (i) said feedstock is subjected to cracking in a reaction zone in contact with fluidized solid particles comprising molecular sieve-type cracking catalyst;

• (ii) solid particles including catalytic particles which are deactivated by sulfur-containing carbonaceous deposits, are separated from reaction zone effluent and pass to a stripping zone wherein volatile deposits are removed from said solid particles by contact with a stripping gas;
• (iii) stripped, solid particles are separated from stripping zone effluent and pass to a catalyst regeneration zone and are regenerated by burning the non-stripped, sulfur-containing, carbonaceous deposits from the stripped, solid particles with an oxygen-containing gas thereby forming sulfur oxides;
• and (iv) resulting solid particles are separated from regeneration zone effluent gas and recycled to the reaction zone;
• a method for reducing emissions of carbon monoxide and sulfur oxides in the regeneration zone effluent gas which comprises:
• (a) circulating through the process cycle said solid particles comprising said catalyst and at least one metallic reactant provided to said cracking-stripping-regeneration process in different ones of said solid particles than said molecular sieve, which metallic reactant reacts with sulfur oxides in the regeneration zone, said metallic reactant consisting essentially of one or more members selected from the group consisting of sodium, magnesium, calcium, strontium, barium, scandium, titanium, chromium, molybdenum, manganese, cobalt, nickel, antimony, copper, zinc, cadmium, lead, and the rare earth metals, in free or combined form;
• (b) cracking said feedstock at a temperature from about 850.degree. to about 1,200.degree. F. and in contact with said cracking catalyst and said metallic reactant;
• (c) stripping volatile deposits from said solid particles at a temperature from about 850.degree. to about 1,200.degree. F. with a stripping gas which contains steam, wherein the ratio by weight of steam to said catalyst is from about 0.0005 to about 0.025;
• (d) burning in said regeneration zone said sulfur-containing carbonaceous deposits from the stripped, solid particles at a temperature from about 1,050.degree. to about 1,450.degree. F.;
• (e) withdrawing from said regeneration zone an effluent gas containing molecular oxygen;
• the improvement which comprises conducting said burning of the sulfur-containing carbonaceous deposits from the stripped, solid particles in the presence of at least one metallic promoter consisting essentially of one or more members selected from the group consisting of ruthenium, rhodium, palladium, osmium, iridium, platinum, vanadium, tungsten, uranium, zirconium, rhenium, and silver, in free or combined form, wherein the metallic promoter and the metallic reactant are present during said catalyst regeneration in sufficient amounts to effect absorption by said metallic reactant of at least about 50 weight percent of the sulfur oxides produced by said burning in said regeneration zone, and wherein the metallic promoter is present in sufficient amount to enhance said absorption of sulfur oxides and the conversion of carbon monoxide to carbon dioxide in the regeneration zone;
• said burning being conducted at a temperature and with oxygen-containing gas having molecular oxygen such that at least about 50 weight percent of the sulfur oxides produced by said burning in said regeneration zone can be absorbed by said metallic reactant;
• said solid particles recycled to the reaction zone having absorbed therein at least about 50 weight percent of said sulfur oxides produced in said regeneration zone;
• said stripped, solid particles passing to said regeneration zone having said metallic reactant in an active form for absorbing at least about 50 weight percent of said sulfur oxides produced in said regeneration zone;
• said stripping being conducted at a temperature and with steam such that passage of said solid particles through said cracking and stripping zones provides said metallic reactant in an amount and active form suitable for accomplishing said absorption of at least about 50 weight percent of said sulfur oxides produced in said regeneration zone;
• said effluent gas from said regeneration zone having a low concentration of sulfur oxides of less than about 600 ppmv;
• and substantially converting said absorbed sulfur oxides to sulfur-containing gas in said reaction and/or stripping zone.

In a process for the cyclic, fluidized, catalytic cracking of hydrocarbon feedstock containing about 0.2 to about 6 weight percent sulfur as organic sulfur compounds wherein (i) said feedstock is subjected to cracking in a reaction zone in contact with fluidized solid particles comprising molecular sieve-type cracking catalyst;

• (ii) solid particles including catalytic particles which are deactivated by sulfur-containing carbonaceous deposits, are separated from reaction zone effluent and pass to a stripping zone wherein volatile deposits are removed from said solid particles by contact with a stripping gas;
• (iii) stripped, solid particles are separated from stripping zone effluent and pass to a catalyst regeneration zone and are regenerated by burning the non-stripped, sulfur-containing, carbonaceous deposits from the stripped, solid particles with an oxygen-containing gas thereby forming sulfur oxides;
• and (iv) resulting solid particles are separated from regeneration zone effluent gas and recycled to the reaction zone;
• a method for reducing emissions of carbon monoxide and sulfur oxides in the regeneration zone effluent gas which comprises:
• (a) circulating through the process cycle said solid particles comprising said catalyst and at least one metallic reactant in the same or different ones of said solid particles, which metallic reactant reacts with sulfur oxides in the regeneration zone, said metallic reactant consisting essentially of one or more members selected from the group consisting of sodium, magnesium, calcium, strontium, barium, scandium, titanium, chromium, molybdenum, manganese, cobalt, nickel, antimony, copper, zinc, cadmium, lead, and the rare earth metals, in free or combined form;
• (b) cracking said feedstock at a temperature from about 850.degree. to about 1,200.degree. F. and in contact with said cracking catalyst and said metallic reactant;
• (c) stripping volatile deposits from said solid particles at a temperature from about 850.degree. to about 1,200.degree. F. with a stripping gas which contains steam, wherein the ratio by weight of steam to said catalyst is from about 0.0005 to about 0.025;
• (d) burning in said regeneration zone said sulfur-containing carbonaceous deposits from the stripped, solid particles at a temperature from about 1,050.degree. to about 1,450.degree. F.;
• (e) withdrawing from said regeneration zone an effluent gas containing molecular oxygen;
• the improvement which comprises conducting said burning of the sulfur-containing carbonaceous deposits from the stripped, solid particles in the presence of at least one metallic promoter consisting essentially of one or more members selected from the group consisting of ruthenium, rhodium, palladium, osmium, iridium, platinum, vanadium, tungsten, uranium, zirconium, rhenium, and silver, in free or combined form, said metallic promoter being combined with solid support particles other than said particles comprising said catalyst, and wherein the metallic promoter and the metallic reactant are present during said catalyst regeneration in sufficient amounts to effect absorption by said metallic reactant of at least about 50 weight percent of the sulfur oxides produced by said burning in said regeneration zone, and wherein the metallic promoter is present in sufficient amount to enhance said absorption of sulfur oxides and the conversion of carbon monoxide to carbon dioxide in the regeneration zone;
• said burning being conducted at a temperature and with oxygen-containing gas having molecular oxygen such that at least about 50 weight percent of the sulfur oxides produced by said burning in said regeneration zone can be absorbed by said metallic reactant;
• said solid particles recycled to the reaction zone having absorbed therein at least about 50 weight percent of said sulfur oxides produced in said regeneration zone;
• said stripped, solid particles passing to said regeneration zone having said metallic reactant in an active form for absorbing at least about 50 weight percent of said sulfur oxides produced in said regeneration zone;
• said stripping being conducted at a temperature and with steam such that passage of said solid particles through said cracking and stripping zones provides said metallic reactant in an amount and active form suitable for accomplishing said absorption of at least about 50 weight percent of said sulfur oxides produced in said regeneration zone;
• said effluent gas from said regeneration zone having a low concentration of sulfur oxides of less than about 600 ppmv;
• and substantially converting said absorbed sulfur oxides to sulfur-containing gas in said reaction and/or stripping zone.

In a process for the cyclic, fluidized, catalytic cracking of hydrocarbon feedstock containing about 0.2 to about 6 weight percent sulfur as organic sulfur compounds wherein (i) said feedstock is subjected to cracking in a reaction zone in contact with fluidized solid particles comprising molecular sieve-type cracking catalyst;

• (ii) solid particles including catalytic particles which are deactivated by sulfur-containing carbonaceous deposits, are separated from reaction zone effluent and pass to a stripping zone wherein volatile deposits are removed from said solid particles by contact with a stripping gas;
• (iii) stripped, solid particles are separated from stripping zone effluent and pass to a catalyst regeneration zone and are regenerated by burning the non-stripped, sulfur-containing, carbonaceous deposits from the stripped, solid particles with an oxygen-containing gas thereby forming sulfur oxides and (iv) resulting solid particles are separated from regeneration zone effluent gas and recycled to the reaction zone;
• a method for reducing emissions of carbon monoxide and sulfur oxides in the regeneration zone effluent gas which comprises:
• (a) circulating through the process cycle said solid particles comprising said catalyst and at least one metallic reactant in the same or different ones of said solid particles, which metallic reactant reacts with sulfur oxides in the regeneration zone, said metallic reactant consisting essentially of one or more members selected from the group consisting of the rare earth metals, in free or combined form;
• (b) cracking said feedstock at a temperature from about 850.degree. to about 1,200.degree. F. and in contact with said cracking catalyst and said metallic reactant;
• (c) stripping volatile deposits from said solid particles at a temperature from about 850.degree. to about 1,200.degree. F. with a stripping gas which contains steam, wherein the ratio by weight of steam to said catalyst is from about 0.0005 to about 0.025;
• (d) burning in said regeneration zone said sulfur-containing carbonaceous deposits from the stripped, solid particles at a temperature from about 1,050.degree. to about 1,450.degree. F.;
• (e) withdrawing from said regeneration zone an effluent gas containing molecular oxygen;
• the improvement which comprises conducting said burning of the sulfur-containing carbonaceous deposits from the stripped, solid particles in the presence of at least one metallic promoter consisting essentially of one or more members selected from the group consisting of ruthenium, rhodium, palladium, osmium, iridium, platinum, vanadium, tungsten, uranium, zirconium, rhenium, and silver, in free or combined form, wherein the metallic promoter and the metallic reactant are present during said catalyst regeneration in sufficient amounts to effect absorption by said metallic reactant of at least about 50 weight percent of the sulfur oxides produced by said burning in said regeneration zone, and wherein the metallic promoter is present in sufficient amount to enhance said absorption of sulfur oxides and the conversion of carbon monoxide to carbon dioxide in the regeneration zone;
• said burning being conducted at a temperature and with oxygen-containing gas having molecular oxygen such that at least about 50 weight percent of the sulfur oxides produced by said burning in said regeneration zone can be absorbed by said metallic reactant;
• said solid particles recycled to the reaction zone having absorbed therein at least about 50 weight percent of said sulfur oxides produced in said regeneration zone;
• said stripped, solid particles passing to said regeneration zone having said metallic reactant in an active form for absorbing at least about 50 weight percent of said sulfur oxides produced in said regeneration zone;
• said stripping being conducted at a temperature and with steam such that passage of said solid particles through said cracking and stripping zones provides said metallic reactant in an amount and active form suitable for accomplishing said absorption of at least about 50 weight percent of said sulfur oxides produced in said regeneration zone;
• said effluent gas from said regeneration zone having a low concentration of sulfur oxides of less than about 600 ppmv;
• and substantially converting said absorbed sulfur oxides to sulfur-containing gas in said reaction and/or stripping zone.

In a process for the cyclic, fluidized, catalytic cracking of hydrocarbon feedstock containing about 0.2 to about 6 weight percent sulfur as organic sulfur compounds wherein (i) said feedstock is subjected to cracking in a reaction zone in contact with fluidized solid particles comprising molecular sieve-type cracking catalyst;

• (ii) solid particles including catalytic particles which are deactivated by sulfur-containing carbonaceous deposits, are separated from reaction zone effluent and pass to a stripping zone wherein volatile deposits are removed from said solid particles by contact with a stripping gas;
• (iii) stripped, solid particles are separated from stripping zone effluent and pass to a catalyst regeneration zone and are regenerated by burning the non-stripped, sulfur-containing, carbonaceous deposits from the stripped, solid particles with an oxygen-containing gas thereby forming sulfur oxides;
• and (iv) resulting solid particles are separated from regeneration zone effluent gas and recycled to the reaction zone;
• a method for reducing emissions of carbon monoxide and sulfur oxides in the regeneration zone effluent gas which comprises:
• (a) circulating through the process cycle said solid particles comprising said catalyst and at least one metallic reactant in the same or different ones of said solid particles, which metallic reactant reacts with sulfur oxides in the regeneration zone, said metallic reactant consisting essentially of sodium;
• (b) cracking said feedstock at a temperature from about 850.degree. to about 1,200.degree. F. and in contact with said cracking catalyst and said metallic reactant;
• (c) stripping volatile deposits from said solid particles at a temperature from about 850.degree. to about 1,200.degree. F. with a stripping gas which contains steam, wherein the ratio by weight of steam to said catalyst is from about 0.0005 to about 0.025;
• (d) burning in said regeneration zone said sulfur-containing carbonaceous deposits from the stripped, solid particles at a temperature from about 1,050.degree. to about 1,450.degree. F.;
• (e) withdrawing from said regeneration zone an effluent gas containing molecular oxygen;
• the improvement which comprises conducting said burning of the sulfur-containing carbonaceous deposits from the stripped, solid particles in the presence of at least one metallic promoter consisting essentially of one or more members selected from the group consisting of ruthenium, rhodium, palladium, osmium, iridium, platinum, vanadium, tungsten, uranium, zirconium, rhenium, and silver, in free or combined form, wherein the metallic promoter and the metallic reactant are present during said catalyst regeneration in sufficient amounts to effect absorption by said metallic reactant of at least about 50 weight percent of the sulfur oxides produced by said burning in said regeneration zone, and wherein the metallic promoter is present in sufficient amount to enhance said absorption of sulfur oxides and the conversion of carbon monoxide to carbon dioxide in the regeneration zone;
• said burning being conducted at a temperature and with oxygen-containing gas having molecular oxygen such that at least about 50 weight percent of the sulfur oxides produced by said burning in said regeneration zone can be absorbed by said metallic reactant;
• said solid particles recycled to the reaction zone having absorbed therein at least about 50 weight percent of said sulfur oxides produced in said regeneration zone;
• said stripped, solid particles passing to said regeneration zone having said metallic reactant in an active form for absorbing at least about 50 weight percent of said sulfur oxides produced in said regeneration zone;
• said stripping being conducted at a temperature and with steam such that passage of said solid particles through said cracking and stripping zones provides said metallic reactant in an amount and active form suitable for accomplishing said absorption of at least about 50 weight percent of said sulfur oxides produced in said regeneration zone;
• said effluent gas from said regeneration zone having a low concentration of sulfur oxides of less than about 600 ppmv;
• and substantially converting said absorbed sulfur oxides to sulfur-containing gas in said reaction and/or stripping zone.