Hydrodechlorination of ionic liquid-derived hydrocarbon products

Abstract

Processes for the hydrodechlorination of one or more hydrocarbon products derived from ionic liquid catalyzed hydrocarbon conversion reactions provide a dechlorinated product and an HCl-containing off-gas. The dechlorinated product provides liquid fuel or lubricating base oil, and the HCl may be recovered from the off-gas for recycling to the ionic liquid catalyzed hydrocarbon conversion reaction as a catalyst promoter.

1 . An integrated hydrocarbon conversion process, comprising:
 a) contacting at least one hydrocarbon reactant with an ionic liquid catalyst in a hydrocarbon conversion zone under hydrocarbon conversion conditions to provide at least one hydrocarbon product comprising at least one halogenated component; and   b) contacting the at least one hydrocarbon product with a hydrodechlorination catalyst in the presence of hydrogen in a hydrodechlorination zone under hydrodechlorination conditions to provide: i) at least one dechlorinated product and ii) an off-gas comprising HCl, wherein a first chloride content of the at least one hydrocarbon product is greater than 50 ppm and a second chloride content of the dechlorinated product is less than 50 ppm.   
     
     
         2 . The process according to  claim 1 , wherein the first chloride content of the at least one hydrocarbon product is greater than about 100 ppm, and a second chloride content of the at least one dechlorinated product is less than about 10 ppm. 
     
     
         3 . The process according to  claim 1 , further comprising:
 c) separating the at least one dechlorinated product from the off-gas;   d) contacting the off-gas with an adsorbent under HCl adsorbing conditions such that the HCl is adsorbed by the adsorbent to provide an HCl-free off-gas; and   e) after step d), recovering the HCl from the adsorbent.   
     
     
         4 . The process according to  claim 1 , wherein the at least one hydrocarbon reactant comprises a C 4 -C 10  isoparaffin and a C 2 -C 10  olefin. 
     
     
         5 . The process according to  claim 1 , wherein the at least one hydrocarbon product is selected from the group consisting of alkylate gasoline, diesel fuel, jet fuel, base oil, and mixtures thereof. 
     
     
         6 . The process according to  claim 1 , further comprising:
 f) prior to step b), feeding the at least one hydrocarbon product to a distillation unit to provide at least one distilled hydrocarbon product, and wherein the at least one hydrocarbon product contacted with the hydrodechlorination catalyst in step b) comprises the at least one distilled hydrocarbon product.   
     
     
         7 . The process according to  claim 1 , further comprising:
 g) after step b), feeding the at least one dechlorinated product to a distillation unit.   
     
     
         8 . The process according to  claim 1 , wherein the at least one dechlorinated product comprises alkylate gasoline having a chloride content less than 50 ppm. 
     
     
         9 . The process according to  claim 1 , wherein the ionic liquid catalyst comprises a chloroaluminate ionic liquid, and the hydrodechlorination catalyst comprises an element selected from the group consisting of elements of Groups 6, 8, 9, 10, and 11, and their mixtures, present as metals, oxides, or sulfides. 
     
     
         10 . The process according to  claim 1 , wherein the adsorbent is selected from the group consisting of a molecular sieve, a refractory oxide, activated carbon, and combinations thereof. 
     
     
         11 . The process according to  claim 1 , wherein step b) comprises contacting the hydrocarbon product with the hydrodechlorination catalyst at a temperature in the range from about 300° F. to 750° F., a pressure in the range from about 100 to 5000 psig, a liquid hourly space velocity (LHSV) feed rate in the range from about 0.1 to 50, and a hydrogen supply in the range from about 50 to 8000 standard cubic feet per barrel (SCFB) of the at least one hydrocarbon product. 
     
     
         12 . The process according to  claim 3 , further comprising:
 h) feeding the HCl from step e) to the hydrocarbon conversion zone.   
     
     
         13 . The process according to  claim 3 , wherein the HCl-free off-gas comprises H 2 , and the process further comprises:
 i) recycling the HCl-free off-gas from step d) to the hydrodechlorination zone.   
     
     
         14 . The process according to  claim 3 , wherein the process is performed under anhydrous conditions. 
     
     
         15 . A hydrodechlorination and hydrogen chloride recovery process, comprising:
 a) contacting at least one hydrocarbon product with a hydrodechlorination catalyst in the presence of hydrogen under hydrodechlorination conditions to provide: i) an off-gas comprising an HCl and ii) a dechlorinated product;   b) separating the dechlorinated product from the off-gas;   c) contacting the off-gas with an adsorbent under HCl adsorbing conditions such that the HCl is adsorbed by the adsorbent; and   d) after step c), recovering the HCl from the adsorbent.   
     
     
         16 . The process according to  claim 15 , wherein the hydrodechlorination conditions comprise a reaction temperature in the range from about 300° F. to 750° F., a reaction pressure in the range from about 100 to 5000 psig, a liquid hourly space velocity (LHSV) feed rate in the range from about 0.1 to 50, and a hydrogen supply in the range from about 50 to 8000 standard cubic feet per barrel (SCFB) of the at least one hydrocarbon product. 
     
     
         17 . The process according to  claim 15 , wherein the hydrodechlorination catalyst comprises an element selected from the group consisting of elements of Groups 6, 8, 9, 10, and 11, and their mixtures, present as metals, oxides or sulfides. 
     
     
         18 . The process according to  claim 15 , wherein:
 step b) comprises separating the dechlorinated product, as a liquid, at a temperature in the range from about 50° F. to 600° F., and   step d) comprises contacting the adsorbent with a recovery carrier gas, wherein the HCl is desorbed from the adsorbent.   
     
     
         19 . The process according to  claim 15 , wherein the adsorbent is selected from the group consisting of a molecular sieve, a refractory oxide, activated carbon, and combinations thereof. 
     
     
         20 . The process according to  claim 15 , wherein the adsorbent comprises a molecular sieve selected from the group consisting of 3A, 4A, 5A, 13X, 13Y, USY, ZSM-5, ZSM-22, ZSM-23, ZSM-35, ZSM-48, MCM-22, MCM-35, MCM-58, SAPO-5, SAPO-11, SAPO-35, and VPI-5. 
     
     
         21 . The process according to  claim 15 , wherein the at least one hydrocarbon product is selected from the group consisting of alkylate gasoline, diesel fuel, jet fuel, base oil, and mixtures thereof obtained by contacting at least one hydrocarbon reactant with an ionic liquid catalyst in a hydrocarbon conversion zone under hydrocarbon conversion conditions, wherein a first chloride content of the at least one hydrocarbon product is greater than 50 ppm, and a second chloride content of the dechlorinated product is less than about 10 ppm. 
     
     
         22 . A hydrocarbon conversion and hydrodechlorination process, comprising:
 a) contacting at least one hydrocarbon reactant with an ionic liquid catalyst in a hydrocarbon conversion zone under hydrocarbon conversion conditions to provide used ionic liquid combined with a conjunct polymer;   b) regenerating at least a portion of the used ionic liquid in a catalyst regeneration zone to provide reactivated ionic liquid catalyst and a free conjunct polymer;   c) after step b), separating the free conjunct polymer from the ionic liquid catalyst; and   d) after step c), contacting the free conjunct polymer with a hydrodechlorination catalyst in the presence of hydrogen in a hydrodechlorination zone under hydrodechlorination conditions to provide a dechlorinated product.   
     
     
         23 . The process according to  claim 22 , wherein the dechlorinated product comprises middle distillate fuel having a chloride content less than about 10 ppm. 
     
     
         24 . The process according to  claim 22 , wherein the dechlorinated product comprises diesel fuel having a chloride content less than about 10 ppm. 
     
     
         25 . The process according to  claim 22 , wherein the dechlorinated product comprises base oil having a chloride content less than about 10 ppm. 
     
     
         26 . The process according to  claim 22 , wherein the hydrodechlorination catalyst comprises an element selected from the group consisting of elements of Groups 6, 8, 9, 10, and 11, and their mixtures, present as metals, oxides, or sulfides. 
     
     
         27 . The process according to  claim 22 , wherein step d) comprises contacting the conjunct polymer with the hydrodechlorination catalyst to further provide an off-gas comprising HCl, and the process further comprises:
 e) contacting the off-gas with an adsorbent in an HCl adsorption zone wherein the HCl is adsorbed by the adsorbent to provide an HCl-free off-gas; and   f) after step e), recovering the HCl from the adsorbent.   
     
     
         28 . The process according to  claim 27 , wherein the HCl-free off-gas comprises H 2 , and the process further comprises:
 g) recycling the HCl-free off-gas from step e) to the hydrodechlorination zone.