Generation of model-of-composition of petroleum by high resolution mass spectrometry and associated analytics

Abstract

A method to determine the model-of-composition of a vacuum resid wherein the resid is separated into eight fractions, saturates, aromatics, sulfides and polars by a combination of soft ionization methods.

1 . A method to determine the model-of-composition of a heavy petroleum or hydrocarbon samples comprising
 a. obtaining molecular ions or pseudo molecular ions, such as protonated ions, deprotonated ions, cation or anion adduct of parent molecule of said heavy petroleum or hydrocarbon sample by soft ionization method;   b. determining elemental formula of said molecular ions or pseudo molecular ions and quantifying corresponding concentrations using high resolution mass spectrometry; and   c. reconciling the output from step (b) with other analytical measurements that determine hydrocarbon and petroleum properties to obtain a model-of-composition.   
     
     
         2 . The method of  claim 1  wherein said heavy petroleums or hydrocarbon samples are separated into asphaltenes and deasphalted oils (DAO). 
     
     
         3 . The method of  claim 2  wherein said DAO are separated into chemical meaningful classes including saturates, aromatics, sulfides and polars to improve certainty in assigning chemical structures to the molecular formulas obtained by mass spectrometry. 
     
     
         4 . The method of  claim 3  wherein said aromatics are separated into aromatic ring class fractions including 1-ring aromatics (ARC1), 2-ring aromatics (ARC2), 3-ring aromatics (ARC3),4-ring+ aromatics (ARC4+) to improve certainty in assigning chemical structures to the molecular formulas obtained by mass spectrometry. 
     
     
         5 . The method of  claim 1  wherein said heavy petroleums or hydrocarbon samples are separated by on-line chromatography-high resolution mass spectrometry. 
     
     
         6 . The method of  claim 1  wherein ionization is performed by one or multiple ionization methods with or without chromatographic separation. 
     
     
         7 . The method of  claim 1  wherein said ionization step is a soft ionization where molecular ion or pseudo molecular ion structures remain intact after ionization. 
     
     
         8 . The method of  claim 1  wherein said ionization step is performed by electrospray ionization. 
     
     
         9 . The method of  claim 1  wherein said ionization step is performed by atmospheric pressure chemical ionization. 
     
     
         10 . The method of  claim 1  wherein said ionization step is performed by atmospheric pressure photoionization (or photon ionization). 
     
     
         11 . The method of  claim 1  wherein said ionization step is performed by matrix assisted laser desorption ionization. 
     
     
         12 . The method of  claim 1  wherein said ionization step is performed by direct laser desorption ionization. 
     
     
         13 . The method of  claim 1  wherein said ionization step is performed by field desorption ionization. 
     
     
         14 . The method of  claim 1  wherein high resolution is defined as M/ΔM FWHM >10,000. 
     
     
         15 . The method of  claim 1  wherein average resolution is preferred to be greater than 100,000. 
     
     
         16 . The method of  claim 1  wherein average resolution is preferred to be greater than 300,000. 
     
     
         17 . The method of  claim 1  wherein average resolution is preferred to be greater than 500,000. 
     
     
         18 . The method of  claim 1  wherein heavy petroleum and hydrocarbon sample is a vacuum gas oil, vacuum resid or petroleum products of similar boiling point range. 
     
     
         19 . The method of  claim 1  wherein said reconsolidation step uses lumps to normalize concentrations. 
     
     
         20 . The method of  claim 1  wherein said reconciliation step use bulk elemental properties include: hydrogen, sulfur, nitrogen, nickel and vanadium content. 
     
     
         21 . The method of  claim 1  wherein said reconciliation step use bulk composition and structural properties include: % Aromatic carbon (Ca), Average aromatic cluster size (C#), Amount of C in long chains, Degree of chain branching, organic forms of sulfur, pyrrolic, pyridinic and quaternary nitrogens. 
     
     
         22 . The method of  claim 1  wherein said reconciliation step use molecular properties include: MCR (or CCR) content, molecular weight distribution by FDMS and boiling point distribution by SIMDIS.