Analysis of amines in petroleum

Abstract

SummaryAn analytical method for differentiation of primary, secondary, and tertiary amines using exhaustive trifluoroacetylation prior to GClMS has been developed. Using the conditions described in the report, most primary amines add two and secondary amines add one trifluoroacetyl group. In general, tertiary amines do not react. GC retention indices and relative GClMS total ion current response factors for 102 trifluoroacetyl derivatives are reported. Examples of the application of the method to petroleum and coal liquid products are provided. Because of the limited thermal stability of the derivatives of primary amines, the method is applicable only to distillates boiling below 370 "C (700 OF).

Application of Atmospheric Pressure Photo Ionization Hydrogen/Deuterium Exchange High-Resolution Mass Spectrometry for the Molecular Level Speciation of Nitrogen Compounds in Heavy Crude Oils

“…Nonetheless, finding elemental compositions is not enough to fully understand the chemical reactivity of the crude oil compounds. − Gaining structural information on the compounds is also very important. For example, nitrogen-containing compounds in crude oils have important implications on catalyst deactivation during oil processing. , Basic nitrogen compounds are particularly influential on catalyst deactivation. − Hence, many studies have been devoted to discerning the chemical structures of nitrogen compounds in crude oil. − ,,, However, understanding chemical structures of the nitrogen compounds in heavy crude oils, especially at a molecular level, remains a challenge .…”

“…Nonetheless, finding elemental compositions is not enough to fully understand the chemical reactivity of the crude oil compounds. − Gaining structural information on the compounds is also very important. For example, nitrogen-containing compounds in crude oils have important implications on catalyst deactivation during oil processing. , Basic nitrogen compounds are particularly influential on catalyst deactivation. − Hence, many studies have been devoted to discerning the chemical structures of nitrogen compounds in crude oil. − ,,, However, understanding chemical structures of the nitrogen compounds in heavy crude oils, especially at a molecular level, remains a challenge . The double bond equivalents (DBE) values calculated from the formulas or information derived from tandem mass spectrometry can provide some information on the chemical structures of the compounds found in crude oil. − However, specific information on the chemical structures at the molecular level cannot be provided by these methods.…”

Dynamic Control of Gas Chromatographic Selectivity during the Analysis of Organic Bases

“…To examine if analyte resolution can be controlled further, the system was applied to the analysis of a commercial gasoline sample containing amines. Analyses of this nature are routinely performed using GC and are important since such compounds can inhibit the quality of petroleum products. , Figure A demonstrates the analysis of this sample using a conventional GC column. As seen, the sample is quite complex and numerous hydrocarbons are present as evidenced from the large number of peaks eluting in the first 20 min.…”

Ni-Catalyzed Iterative Alkyl Transfer from Nitrogen Enabled by the In Situ Methylation of Tertiary Amines

“…Given the abundance of nitrogen present within chemical feedstocks, pharmaceuticals, and natural products, methods to construct carbon–carbon (C–C) bonds from amines via selective carbon–nitrogen (C–N) bond cleavage processeswhere the nitrogen atom is retained (rearranged) or excisedwould be of high value for complex-molecule synthesis and chemical diversification strategies. Indeed, multistep syntheses that incorporate a Stevens rearrangement, a strategic and predictable C–N bond cleavage method, exemplify the power of nitrogen-atom rearrangement chemistry for Csp 3 –Csp 3 bond formation .…”