Upgrading of peroxide treated petroleum streams

Abstract

This invention relates to a method for upgrading petroleum streams which have been treated with peroxide, extracted to remove oxidized sulfur and nitrogen compounds, dewaxed and hydrofinished. More particularly, peroxides are generated in-situ by combining the petroleum stream with a high neutralization number (HNN) crude and adding an oxygen-containing stream. Alternatively, the oxidation of sulfur and nitrogen compounds may be accomplished by adding peroxides in the presence of oil soluble metal catalysts. The peroxides oxidize nitrogen and sulfur compounds in the petroleum stream to more polar compounds which are solvent extracted.

1 . An upgrading process for upgrading a petroleum feed containing sulfur and nitrogen compounds which comprises: 
 (a) combining the petroleum feed with a high neutralization number crude having a total acid number (TAN) greater than 1.0 to produce a mixture of feed and high neutralization crude,    (b) adding an oxygen-containing gas to the mixture from step (a) for a time sufficient to generate peroxides in a concentration sufficient to oxidize at least a portion of the sulfur and nitrogen compounds in the mixture,    (c) solvent extracting oxidized sulfur and nitrogen compounds from step (b) under solvent extraction conditions to separate a raffinate containing less than 100 wppm, based on raffinate of sulfur compounds and less than 5 wppm of nitrogen compounds,    (d) contacting the raffinate with a catalytic dewaxing catalyst under catalytic dewaxing conditions to form a dewaxed raffinate and    (e) hydrofinishing the dewaxed raffinate under hydrofinishing conditions.    
   
   
       2 . An upgrading process for upgrading a petroleum feed containing sulfur and nitrogen compounds which comprises: 
 (a) combining the petroleum feed with a high neutralization number crude having a total acid number (TAN) greater than 1.0,    (b) adding an oil soluble metal catalyst to produce a mixture of feed, high neutralization crude and oil soluble metal catalyst,    (c) adding an oxygen-containing gas to the mixture from step (b) for a time sufficient to generate peroxides in a concentration sufficient to oxidize at least a portion of the sulfur and nitrogen compounds in the mixture,    (d) solvent extracting oxidized sulfur and nitrogen compounds under solvent extraction conditions to separate a raffinate containing less than 100 wppm, based on raffinate of sulfur compounds and less than 5 wppm of nitrogen compounds,    (e) contacting the raffinate with a catalytic dewaxing catalyst under catalytic dewaxing conditions to form a dewaxed raffinate and    (f) hydrofinishing the dewaxed raffinate under hydrofinishing conditions.    
   
   
       3 . An upgrading process for upgrading a petroleum feed containing sulfur and nitrogen compounds which comprises: 
 (a) combining the feed with a catalytically effective amount of an oil soluble metal catalyst to produce a mixture of feed and oil soluble metal catalyst,    (b) adding at least one peroxide to the mixture in a concentration sufficient to oxidize at least a portion of the sulfur and nitrogen compounds in the mixture,    (c) solvent extracting oxidized sulfur and nitrogen compounds under solvent extraction conditions to separate a raffinate containing less than 100 wppm, based on raffinate of sulfur compounds and less than 5 wppm of nitrogen compounds,    (d) contacting the raffinate with a catalytic dewaxing catalyst under catalytic dewaxing conditions to form a dewaxed raffinate and    (e) hydrofinishing the dewaxed raffinate under hydrofinishing conditions.    
   
   
       4 . The process of  claim 1  wherein the petroleum feed has a TAN less than 1.0.  
   
   
       5 . The process of  claim 2  wherein the petroleum feed has a TAN less than 1.0.  
   
   
       6 . The process of  claim 1  wherein the oxygen-containing gas is air.  
   
   
       7 . The process of  claim 2  wherein the oxygen-containing gas is air.  
   
   
       8 . The process of  claim 2  wherein the oil soluble metal catalysts include metals from Groups 4-12 of the Periodic Table based on the IUPAC format having Groups 1-18.  
   
   
       9 . The process of  claim 3  wherein the oil soluble metal catalysts include metals from Groups 4-12 of the Periodic Table based on the IUPAC format having Groups 1-18.  
   
   
       10 . The process of  claim 1  wherein the oxygen-containing gas is added to the mixture from step (a) for a time sufficient to generate peroxides in a concentration of at least about 1 wt. %, based on mixture.  
   
   
       11 . The process of  claim 2  wherein the oxygen-containing gas is added to the mixture from step (b) for a time sufficient to generate peroxides in a concentration of at least about 1 wt. %, based on mixture.  
   
   
       12 . The process of  claim 3  wherein the peroxide includes hydrogen peroxide, inorganic peroxide compounds, salts of peracids, and organic peroxides.  
   
   
       13 . The process of  claim 1  wherein the dewaxing catalyst is a crystalline material containing at least one zeolite including ZSM-5, ZSM-11, ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-57, ferrierite, EU-1, NU-87, ITQ-13, MCM-71, ECR-42, SAPO-11, SAPO-41, zeolite beta, ZSM-12, MCM-68 SAPO-5, SAPO-31, MAPO-36, ZSM-18, mordenite, faujasite and offretite.  
   
   
       14 . The process of  claim 2  wherein the dewaxing catalyst is a crystalline material containing at least one zeolite including ZSM-5, ZSM-11, ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-57, ferrierite, EU-1, NU-87, ITQ-13, MCM-71, ECR-42, SAPO-11, SAPO-41, zeolite beta, ZSM-12, MCM-68 SAPO-5, SAPO-31, MAPO-36, ZSM-18, mordenite, faujasite and offretite.  
   
   
       15 . The process of  claim 3  wherein the dewaxing catalyst is a crystalline material containing at least one zeolite including ZSM-5, ZSM-11, ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-57, ferrierite, EU-1, NU-87, ITQ-13, MCM-71, ECR-42, SAPO-11, SAPO-41, zeolite beta, ZSM-12, MCM-68 SAPO-5, SAPO-31, MAPO-36, ZSM-18, mordenite, faujasite and offretite.  
   
   
       16 . The process of  claim 13  wherein the zeolite is ZSM-48.  
   
   
       17 . The process of  claim 14  wherein the zeolite is ZSM-48.  
   
   
       18 . The process of  claim 15  wherein the zeolite is ZSM-48.  
   
   
       19 . The process of  claim 1  wherein the hydrofinishing catalyst contains Group 6 metals, Groups 8-10 metals or mixtures thereof.  
   
   
       20 . The process of  claim 2  wherein the hydrofinishing catalyst contains Group 6 metals, Groups 8-10 metals or mixtures thereof.  
   
   
       21 . The process of  claim 3  wherein the hydrofinishing catalyst contains Group 6 metals, Groups 8-10 metals or mixtures thereof.  
   
   
       22 . The process of  claim 1  wherein the hydrofinishing catalyst is MCM-41 containing a Group 6-8 noble metal.  
   
   
       23 . The process of  claim 2  wherein the hydrofinishing catalyst is MCM-41 containing a Group 6-8 noble metal.  
   
   
       24 . The process of  claim 3  wherein the hydrofinishing catalyst is MCM-41 containing a Group 6-8 noble metal.  
   
   
       25 . The process of  claim 1  wherein oxidized sulfur compounds from step (b) are thermally decomposed.  
   
   
       26 . The process of  claim 3  wherein oxidized sulfur compounds from step (b) are thermally decomposed.  
   
   
       27 . The process of  claim 2  wherein oxidized sulfur compounds from step (c) are thermally decomposed.