EP3322979A1 - Analyse d'amines par chromatographie ionique - Google Patents

Analyse d'amines par chromatographie ionique

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Publication number
EP3322979A1
EP3322979A1 EP16744976.8A EP16744976A EP3322979A1 EP 3322979 A1 EP3322979 A1 EP 3322979A1 EP 16744976 A EP16744976 A EP 16744976A EP 3322979 A1 EP3322979 A1 EP 3322979A1
Authority
EP
European Patent Office
Prior art keywords
acid
gradient
eluent
ion
eluting
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP16744976.8A
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German (de)
English (en)
Inventor
Timothy Mark Sivavec
Nathan Mclean
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
General Electric Co
Original Assignee
General Electric Co
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Filing date
Publication date
Application filed by General Electric Co filed Critical General Electric Co
Publication of EP3322979A1 publication Critical patent/EP3322979A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/96—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation using ion-exchange
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
    • B01D15/08—Selective adsorption, e.g. chromatography
    • B01D15/10—Selective adsorption, e.g. chromatography characterised by constructional or operational features
    • B01D15/16—Selective adsorption, e.g. chromatography characterised by constructional or operational features relating to the conditioning of the fluid carrier
    • B01D15/161—Temperature conditioning
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
    • B01D15/08—Selective adsorption, e.g. chromatography
    • B01D15/10—Selective adsorption, e.g. chromatography characterised by constructional or operational features
    • B01D15/16—Selective adsorption, e.g. chromatography characterised by constructional or operational features relating to the conditioning of the fluid carrier
    • B01D15/166—Fluid composition conditioning, e.g. gradient
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
    • B01D15/08—Selective adsorption, e.g. chromatography
    • B01D15/26—Selective adsorption, e.g. chromatography characterised by the separation mechanism
    • B01D15/36—Selective adsorption, e.g. chromatography characterised by the separation mechanism involving ionic interaction, e.g. ion-exchange, ion-pair, ion-suppression or ion-exclusion
    • B01D15/361—Ion-exchange
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
    • B01D15/08—Selective adsorption, e.g. chromatography
    • B01D15/26—Selective adsorption, e.g. chromatography characterised by the separation mechanism
    • B01D15/36—Selective adsorption, e.g. chromatography characterised by the separation mechanism involving ionic interaction, e.g. ion-exchange, ion-pair, ion-suppression or ion-exclusion
    • B01D15/361—Ion-exchange
    • B01D15/362—Cation-exchange
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/26—Conditioning of the fluid carrier; Flow patterns
    • G01N30/28—Control of physical parameters of the fluid carrier
    • G01N30/34—Control of physical parameters of the fluid carrier of fluid composition, e.g. gradient
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/26—Conditioning of the fluid carrier; Flow patterns
    • G01N30/28—Control of physical parameters of the fluid carrier
    • G01N30/34—Control of physical parameters of the fluid carrier of fluid composition, e.g. gradient
    • G01N2030/342—Control of physical parameters of the fluid carrier of fluid composition, e.g. gradient fluid composition fixed during analysis
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
    • G01N2030/8809—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 analysis specially adapted for the sample
    • G01N2030/8813—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 analysis specially adapted for the sample biological materials
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/26—Conditioning of the fluid carrier; Flow patterns
    • G01N30/28—Control of physical parameters of the fluid carrier
    • G01N30/30—Control of physical parameters of the fluid carrier of temperature
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/26—Conditioning of the fluid carrier; Flow patterns
    • G01N30/38—Flow patterns
    • G01N30/46—Flow patterns using more than one column

Definitions

  • This disclosure relates generally to methods for monitoring ionic species in a mixture, particularly to monitoring ionic species in an industrial fluid.
  • Salt fouling and associated corrosion in crude unit overhead systems are complex phenomena that impact refinery reliability, flexibility, and ultimately, profitability. Establishing an appropriate balance of physical, mechanical, and operational parameters, unique to each unit, is critical to minimizing fouling and corrosion throughout the crude unit. Factors such as amine chloride salt points, optimum accumulator pH, and overhead water ICP (initial condensation point, also referred to as water dew point) are interrelated and all affect the potential for system fouling and corrosion. There is a need for methods of monitoring, identifying, and/or quantifying ionic species in an industrial fluid.
  • amines present in industrial fluids can come from a variety of sources (e.g., neutralizers, original crude source, upstream additives, hydrogen sulfide scavengers) and over time the mix of amines present changes. Therefore, there is a need for methods of monitoring, identifying, and/or quantifying a plurality of amines in an industrial fluid, wherein the methods are not affected by the presence of common interfering species (including cations, anions, crude oil). The methods disclosed herein address these and other needs.
  • the methods can be used to separate, monitor, identify, and/or quantify a plurality of amines in a mixture.
  • the method can include a first chromatography step, a second chromatography step, and optionally, a third chromatography step.
  • the first chromatography step and second chromatography step can be performed simultaneously, for example in a dual channel apparatus.
  • the methods described herein can be performed in an amount of time of less than about 24 hours, less than about 10 hours, less than about 5 hours, or less than about 3 hours.
  • the first chromatography step can comprise introducing a sample of the mixture onto a first ion-exchange chromatography matrix, and eluting at least one first eluate from the first ion- exchange chromatography matrix under a first gradient eluting condition, using a first gradient eluent at a first elution temperature.
  • the first gradient eluent can comprise an acid selected from citric acid, glycine, 2(N-moipholino)ethanesulfonic acid, methanesulfonic acid, acetic acid, formic acid, phosphoric acid, hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, oxalic acid, tartaric acid, benzoic acid, phthalic acid, and combinations thereof.
  • the first gradient eluting condition used in the methods can include an acid concentration gradient between about 1 mM to about 100 mM.
  • the first gradient eluent can further comprise a polar aprotic solvent such as acetonitrile.
  • the first gradient eluent used in the methods can include acetonitrile in an amount of from about 0.05% to about 25% by volume, based on the volume of the first gradient eluent.
  • the first elution temperature can be from about 15°C to about 45°C.
  • the first gradient eluting condition includes a multistep gradient.
  • the first multistep gradient can include a first step, wherein the first gradient eluent comprises an acid concentration of from about 1 mM to about 10 mM; a second step, wherein the first gradient eluent comprises an acid concentration of from about 50 mM to about 100 mM; and a third step, wherein the first gradient eluent comprises an acid concentration of from about 1 mM to about 10 mM.
  • the first multistep gradient can include a first step, wherein the first gradient eluent comprises an acid at a concentration of from about 2 mM to about 5 mM and acetonitrile in an amount of from about 0.05% to about 5% by volume, based on the total volume of the first gradient eluent.
  • the first multistep gradient can further include a second step, wherein the first gradient eluent comprises an acid at a concentration of from about 25 mM to about 100 mM and acetonitrile in an amount of from about 5% to about 20% by volume, based on the total volume of the first gradient eluent.
  • the first multistep gradient can also include a third step, wherein the first gradient eluent comprises an acid at a concentration of from about 2 mM to about 5 mM and acetonitrile in an amount of from about 0.05% to about 5% by volume, based on the volume of the first gradient eluent.
  • the second chromatography step can comprise introducing a sample of the mixture onto a second ion-exchange chromatography matrix under a second gradient eluting condition, and eluting at least one second eluate from the second ion-exchange chromatography matrix, using a second gradient eluent at a second elution temperature.
  • the second gradient eluent can comprise an acid as described herein.
  • the second gradient eluting condition used in the methods can include an acid concentration gradient between about 5 mM to about 100 mM.
  • the second gradient eluting condition includes a multistep gradient.
  • the second multistep gradient condition can include a first step, wherein the second gradient eluent comprises an acid concentration of from about 3 mM to about 15 mM; a second step, wherein the second gradient eluent comprises an acid concentration of from about 50 mM to about 100 mM; and a third step, wherein the second gradient eluent comprises an acid concentration of from about 3 mM to about 10 mM.
  • the second chromatography step can comprise introducing a sample of the mixture onto a second ion-exchange chromatography matrix under a first isocratic eluting condition, and eluting at least one second eluate from the second ion-exchange chromatography matrix, using a first isocratic eluent at a second elution temperature.
  • the first isocratic eluent used in the methods can include an acid concentration of from about 5 mM to about 20 mM or from about 8 mM to about 15 mM.
  • the first isocratic eluent can comprise acetonitrile in an amount of from about 0.5% to about 5% or about 2% to about 4% by volume, based on the volume of the first isocratic eluent.
  • the second elution temperature can be from about 15°C to about 70°C.
  • the optional third chromatography step can comprise introducing a sample of the mixture onto a third ion-exchange chromatography matrix, and eluting at least one third eluate from the third ion-exchange chromatography matrix under a second isocratic condition, using a second isocratic eluent at a third elution temperature.
  • the second isocratic eluent can comprise an acid as described herein, having a concentration of from about 5 mM to about 20 mM.
  • the third elution temperature can be from about 35°C to about 45°C.
  • the mixture of ionic species that can be analyzed using the methods described can include amines, metal ions, sulfides, sulfates, phosphates, nitrates, nitrites, halides, organic acids, perchlorates, selenates, cyanides, borates, and combinations thereof.
  • the mixture can include a plurality of cationic species.
  • the mixture can include a plurality of amines such as from about 5 to about 25 amines.
  • the mixture can include at least 5 amines, at least 10 amines, or at least 20 amines.
  • the method can include identifying and/or quantifying the separated ionic species using any suitable apparatus. Suitable apparatuses can include a mass spectrometer, a nuclear magnetic resonance spectrometer, a surface enhanced Raman spectrometer, a ultra-violet
  • the minimum detection level of each ionic species in the mixture can be about 10 ppb.
  • industrial fluids can include a refinery fluid, a production fluid, cooling water, process water, drilling fluids, completion fluids, production fluids, crude oil, feed streams to desalting units, outflow from desalting units, refinery heat transfer fluids, gas scrubber fluids, refinery unit feed streams, refinery intermediate streams, finished product streams, and combinations thereof.
  • Disclosed herein are also methods for efficiently operating a refinery.
  • Figure 1 is a graph showing an ion-exchange chromatogram of early eluting amines from a mixture.
  • Figure 2 is a graph showing an ion-exchange chromatogram of mid eluting amines from a mixture.
  • Figure 3 is a graph showing an ion-exchange chromatogram of late eluting amines from a mixture.
  • Figure 4 is a graph showing an ion-exchange chromatogram of early eluting amines from a mixture.
  • Figure 5 is a graph showing an ion-exchange chromatogram of late eluting amines from a mixture.
  • the methods provide for analysis of a plurality of amines in a mixture.
  • the method can include a multi-step ion-exchange
  • the method can include two or more ion-exchange chromatography steps.
  • the ionic species can be identified and/or quantified, following separation, using any suitable method known in the art.
  • Ion-exchange chromatography refers to a chromatographic process in which an ionizable solute(s) of interest (e.g., an amine) interacts with an oppositely charged ligand linked (e.g., by covalent attachment) to a solid phase ion- exchange material under appropriate conditions of pH, temperature, eluent, and/or conductivity, such that the solute(s) of interest interacts non-specifically with the charged ligand as a function of their net surface charge. As a result, the solute(s) of interest separates according to differences in their net charge.
  • Ion-exchange chromatography includes cation-exchange chromatography, anion-exchange chromatography, and mixed mode chromatography.
  • ion-exchange chromatography systems include, but are not limited to, ICS-5000 single channel or dual channel apparatuses supplied by DionexTM or a 940 Professional IC Vario apparatus available from MetrohmTM.
  • the ion-exchange can be carried out using commercially available columns known in the art and used in ion
  • a cation-exchange column comprising a
  • the chromatography matrix can comprise carboxylic acid groups, phosphonic acid groups, sulfonic acid groups, or combinations thereof.
  • Suitable examples of commercially available cation-exchange columns include, but are not limited to, CS 1 1, CS 12, CS14, CS 15, CS 16, CS17, CS 18, and CS 19 supplied under the tradename IonPac by DionexTM; TSKgel IC- Cation or TSKgel IC-Cation I/II HR supplied by TOSOH Corporation; Shodex YK-421 supplied by Showa Denko K.K; and C6 supplied by MetrohmTM under the tradename MetrosepTM.
  • the eluent (also referred to herein as an "elution buffer”) can include any suitable eluent known in the art for eluting an ionic species from an ion-exchange chromatography matrix.
  • Suitable eluents can include citric acid, glycine, 2(N-morpholino) ethanesulfonic acid, methanesulfonic acid, acetic acid, formic acid, phosphoric acid, hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, oxalic acid, tartaric acid, benzoic acid, phthalic acid, and combinations thereof.
  • the methods described herein can include gradient and/or isocratic flow of the eluent.
  • the eluent can further include a polar aprotic solvent.
  • polar aprotic solvents include solvents comprising an amide, ketone, nitrile, sulfoxide, sulfone, or alkylene carbonate.
  • the polar aprotic solvent can be selected from acetonitrile, tetrahydrofuran, dimethylacetamide, methyl ethyl ketone, butyronitrile, dimethyl sulfoxide, sulfolane, propylene carbonate, and butylene carbonate.
  • the methods for separating the ionic species can be carried out at any suitable temperature for improved selectivity of ion-exchange reactions and efficiency of the ion- exchange column, thus influencing the quality of the separation.
  • changes in the temperature of a column can cause changes in the thermodynamic functions (free energy, enthalpy, and entropy) of the column that results in increased or decreased retention of the species depending on, for example, the acidity of cation-exchange functional groups and the eluent used.
  • the elution temperature (including the temperature of the column(s) including the eluent and the chromatography matrix) can be from about 10°C to about 80°C.
  • the elution temperature can be from about 15°C to about 70°C, about 25°C to about 70°C, about 30°C to about 70°C, about 35°C to about 70°C, about 15°C to about 45°C, or about 15°C to about 35°C.
  • Suitable ionic species can include amines, metal ions, sulfides, sulfates, phosphates, nitrates, nitrites, halides, organic acids, perchlorates, selenates, cyanides, borates, and combinations thereof.
  • ionic species can include primary, secondary, tertiary, and quarternary amines such as methylamine, ethylamine, ethanolamine, cyclohexylamine, morpholine, monoethanolamine, dimethylethanolamine, and pyridines; ammonia; alkali and alkaline metals such as sodium, potassium, magnesium, and calcium; and combinations thereof.
  • the methods provide for separation and/or quantification of a plurality of amines in a mixture.
  • the mixture can comprise at least 5 amines, at least 10 amines, or at least 20 amines. In some embodiments, the mixture can comprise from about 5 to about 25 amines.
  • the mixture can be an industrial fluid, including liquids and gases.
  • Industrial fluids also include materials that may be solid at ambient temperatures but are liquid during an industrial process.
  • the industrial fluid can include aqueous and non-aqueous fluids, including emulsions and other multiphase fluids which are admixtures of aqueous and non-aqueous fluids and which are present in the exploration for or production of oil and gas, during the refining of crude oil, and during the production of chemical products.
  • the industrial fluid can include a refinery fluid, a production fluid, cooling water, process water, oil field drilling and completion fluids, oil and gas well production fluids, crude oil, feed streams to desalting units, outflow from desalting units, refinery and chemical plant heat transfer fluids, gas scrubber fluids, chemical plant and refinery unit feed streams, refinery and chemical plant intermediate streams, and refinery and chemical plant production and finished product streams, and combinations thereof.
  • a refinery fluid a production fluid, cooling water, process water, oil field drilling and completion fluids, oil and gas well production fluids, crude oil, feed streams to desalting units, outflow from desalting units, refinery and chemical plant heat transfer fluids, gas scrubber fluids, chemical plant and refinery unit feed streams, refinery and chemical plant intermediate streams, and refinery and chemical plant production and finished product streams, and combinations thereof.
  • the industrial fluid or an industrial fluid stream can be introduced directly into the ion- exchange chromatography apparatus.
  • the mixture can be pre-treated prior to ion-exchange chromatography.
  • particulate matter can be removed from the sample by filtration prior to introducing the sample into the ion-exchange chromatography apparatus.
  • the pH of the mixture can be altered to for example, improve separation or increase interaction between the ionic species and the chromatography matrix, depending on the nature of the ionic species.
  • an industrial fluid can be treated with a pre-concentrator to increase the relative concentration of an ionic species of interest, reducing the presence of an undesirable fluid.
  • the industrial fluid can be subjected to a chemical treatment or derivatization.
  • the industrial fluid can be subjected to an extraction process or heating prior to being introduced into the ion- exchange chromatography apparatus.
  • the methods for separating the ionic species can include a first chromatography step, a second chromatography step, and optionally, a third chromatography step.
  • Each chromatography step can be particularly carried out under conditions such that separation of the respective ions in the separation column is optimized. Such conditions can include, for example, the
  • eluate refers to a combination of the eluent and ionic species exiting the chromatography matrix. As discussed herein, the various compositions of the ionic species travel at different speeds allowing separation of the ionic species. In some embodiments, the eluate can be collected as one or more fractions, using any suitable method known in the art, to obtain one or more pure or substantially pure eluates for further analysis. “Substantially pure” as used herein, refers to an eluate, for example, with greater than 95 wt% of the desired ionic species, based on the total weight of solute in the eluate.
  • the eluate contains low amounts of undesirable species and can include less than 5 wt%, less than 3 wt%, less than 2 wt%, less than 1 wt%, or less than 0.5 wt% undesirable species, based on the total weight of solute in the eluate.
  • the first chromatography step can include introducing a sample of the mixture onto a first ion-exchange chromatography matrix.
  • the first ion-exchange chromatography matrix can include a carboxylate-functionalized resin.
  • the first ion-exchange chromatography matrix can be suitable for separating adjacent eluting cations including metal ions such as sodium, potassium, and calcium; ammonium; and/or short-chained amines, including alkylamines and alkanolamines.
  • a high capacity column that provides high loadability and resolution, while also suitable for disparate concentrations of species in a variety of sample matrices can be used as the first ion-exchange chromatography matrix.
  • an IonPacTM CS14, IonPacTM CS15, IonPacTM CS16, or MetrohmTM Metrosep C6 column can be used as the first
  • the first chromatography step can include eluting at least one early eluting eluate (also referred to herein as "first eluate") from the first ion-exchange chromatography matrix under a first gradient eluting condition.
  • the first gradient eluting condition can include using a first gradient eluent at a first elution temperature.
  • a plurality of early eluting eluate fractions, comprising separated or substantially separated ionic species can be obtained.
  • the first gradient eluent can include any one of the eluents described herein.
  • the first gradient eluent can comprise an acid, for example, methanesulfonic acid or oxalic acid.
  • the first gradient eluent can have a pH of less than about 7, for example, about pH 6 or less, about pH 5 or less, about pH 4 or less, about pH 3 or less, or about pH 2 or less.
  • the concentration of acid in the first gradient eluent can be from about 0.5 mM to about 100 mM.
  • the first gradient eluting condition uses an acid concentration gradient (i.e., the change in concentration of the acid in the eluent over time), encompassing any gradient from about 0.5 mM to about 100 mM.
  • the acid concentration gradient can be from about 1 mM to about 100 mM, about 1 mM to about 80 mM, or about 3 mM to about 70 mM.
  • the first gradient eluting condition includes a multistep gradient (or a "first multistep gradient").
  • the first multistep gradient can include two or more steps.
  • the first multistep gradient can include a first step, a second step, and optionally a third step.
  • the first multistep gradient can include a first step, wherein the first gradient eluent comprises an acid concentration of from about 1 mM to about 10 mM; a second step, wherein the first gradient eluent comprises an acid concentration of from about 50 mM to about 100 mM; and a third step, wherein the first gradient eluent comprises an acid concentration of from about 1 mM to about 10 mM.
  • the first gradient eluent can further comprise a polar aprotic solvent, for example, acetonitrile.
  • the polar aprotic solvent in the first gradient eluent can be in an amount of from about 0.05% to about 25% by volume, based on the total volume of the first gradient eluent.
  • the polar aprotic solvent in the first gradient eluent can be in an amount of about 0.05% or greater, about 0.1% or greater, about 0.2% or greater, about 0.25% or greater, about 0.5%) or greater, about 1% or greater, about 2% or greater, about 3% or greater, about 5% or greater, about 6% or greater, about 7% or greater, about 8% or greater, about 9% or greater, about 10%) or greater, about 1 1% or greater, about 12% or greater, about 15% or greater, about 18%) or greater, about 20% or greater, about 22% or greater, or about 25% or greater by volume, based on the volume of the first gradient eluent.
  • the polar aprotic solvent in the first gradient eluent can be in an amount of about 30% or less, about 25% or less, about 20%) or less, or about 15% or less by volume, based on the volume of the first gradient eluent. In some embodiments, the polar aprotic solvent in the first gradient eluent can be in an amount of about 0.1% to about 25%, about 0.1% to about 20%, or about 0.1% to about 15% by volume, based on the volume of the first gradient eluent. In some examples, the first gradient eluent does not include a polar aprotic solvent. In some examples, the first gradient eluent does not include acetonitrile.
  • the first multistep gradient can include a first step, wherein the concentration of acid in the first gradient eluent is from about 2 mM to about 5 mM or from about 3 mM to about 4 mM.
  • the polar aprotic solvent such as acetonitrile, can be in amount of from about 0.05% to about 5% or about 0.1% to about 1% by volume, based on the volume of the first gradient eluent.
  • the first multistep gradient can include a second step, wherein the concentration of acid in the first gradient eluent is from about 25 mM to about 100 mM or from about 40 mM to about 60 mM.
  • the polar aprotic solvent such as acetonitrile
  • the polar aprotic solvent can be in amount of from about 5% to about 25% or about 5% to about 15% by volume, based on the volume of the first gradient eluent.
  • the first multistep gradient can include a third step, wherein the concentration of acid in the first gradient eluent is from about 2 mM to about 5 mM or from about 3 mM to about 4 mM.
  • the polar aprotic solvent, such as acetonitrile can be in amount of from about 0.05% to about 5% or about 0.1% to about 1% by volume, based on the volume of the first gradient eluent.
  • the first elution temperature can be about 15°C or greater. In some embodiments, the first elution temperature can be from about 15°C to about 45°C, about 20°C to about 45°C, about 25°C to about 45°C, about 20°C to about 40°C, about 37°C to about 45°C, about 37°C to about 43°C, or about 38°C to about 42°C.
  • the first elution temperature can be about 20°C, about 22°C, about 24°C, about 25°C, about 26°C, about 28°C, about 30°C, about 32°C, about 34°C, about 35°C, about 36°C, about 37°C, about 38°C, about 39°C, about 40°C, about 41°C, about 42°C, about 43°C, about 44°C, or about 45°C.
  • the first chromatography step can be performed within about 120 minutes or less. In some embodiments, the first chromatography step can be performed from about 5 minutes to about 100 minutes, about 10 minutes to about 90 minutes, about 10 minutes to about 60 minutes, about 20 minutes to about 60 minutes, about 20 minutes to about 50 minutes, or about 20 minutes to about 40 minutes. For example, the first chromatography step can be performed within about 110 minutes or less, about 100 minutes or less, about 90 minutes or less, about 80 minutes or less, about 75 minutes or less, about 70 minutes or less, about 60 minutes or less, or about 50 minutes or less.
  • the second chromatography step can include introducing a sample of the mixture onto a second ion-exchange chromatography matrix.
  • the second ion-exchange chromatography matrix can include a carboxylate-functionalized resin.
  • the second chromatography matrix can be the same as the first chromatography matrix.
  • an IonPacTM CS14, IonPacTM CS15, IonPacTM CS16, or MetrohmTM Metrosep C6 column can be used as the second chromatography matrix.
  • the second chromatography step can be performed sequential to or simultaneously with the first chromatography step.
  • the second chromatography step is performed simultaneously with the first chromatography step.
  • a dual channel ion- exchange chromatography system can be used, wherein the mixture can be injected via a single injection (i.e., one injection into two different eluent streams) or two injections (one injection per eluent stream).
  • the first channel can carry out the first chromatography step and the second channel carry out the second chromatography step, simultaneously.
  • the second chromatography step is performed sequential to the first chromatography step.
  • the second chromatography step can include eluting at least one mid-eluting eluate (also referred to herein as "second eluate") from the second ion-exchange chromatography matrix under a second gradient eluting condition.
  • the second gradient eluting condition can include using a second gradient eluent at a second elution temperature.
  • a plurality of mid-eluting eluate fractions, comprising separated or substantially separated ionic species can be obtained.
  • the second gradient eluent can include any one of the eluent described herein.
  • the second gradient eluent can comprise an acid, for example, methanesulfonic acid or oxalic acid.
  • the second gradient eluent can have a pH of less than about 7, for example, about pH 6 or less, about pH 5 or less, about pH 4 or less, about pH 3 or less, or about pH 2 or less.
  • the concentration of acid in the second gradient eluent can be from about 5 mM to about 100 mM.
  • the second gradient eluting condition uses an acid concentration gradient encompassing any gradient from about 5 mM to about 100 mM.
  • the acid concentration gradient can be from about 5 mM to about 90 mM, about 5 mM to about 80 mM, about 5 mM to about 70 mM, or about 8 mM to about 70 mM.
  • the second gradient eluting condition includes a multistep gradient (or a "second multistep gradient").
  • the second multistep gradient can include two or more steps.
  • the second multistep gradient can include a first step, a second step, and optionally a third step.
  • the second multistep gradient can include a first step, wherein the second gradient eluent comprises an acid concentration of from about 3 mM to about 20 mM or from about 3 mM to about 10 mM; a second step, wherein the second gradient eluent comprises an acid concentration of from about 25 mM to about 100 mM or from about 40 mM to about 60 mM; and a third step, wherein the second gradient eluent comprises an acid concentration of from about 1 mM to about 10 mM or from about 1 mM to about 5 mM.
  • the second gradient eluent can further comprise a polar aprotic solvent as described herein. In some examples, the second gradient eluent does not include a polar aprotic solvent. In some examples, the second gradient eluent does not include acetonitrile.
  • the second chromatography step can include eluting at least one eluate from the second ion-exchange chromatography matrix under a first isocratic eluting condition.
  • the first isocratic eluting condition includes using a first isocratic eluent at a second elution temperature.
  • the first isocratic eluent can include any one of the eluent described herein.
  • the first isocratic eluent can comprise an acid, for example,
  • the first isocratic eluent can have a pH of less than about 7, for example, about pH 6 or less, about pH 5 or less, about pH 4 or less, about pH 3 or less, or about pH 2 or less.
  • the concentration of acid in the first isocratic eluent can be from about 5 mM to about 20 mM or from about 5 mM to about 15 mM.
  • the first isocratic eluent can further comprise a polar aprotic solvent, for example, acetonitrile.
  • the polar aprotic solvent in the first isocratic eluent can be in an amount of from about 0.5% to about 5% by volume, based on the total volume of the first isocratic eluent.
  • the polar aprotic solvent in the first isocratic eluent can be in an amount of about 0.5% or greater, about 1% or greater, about 1.5% or greater, about 2% or greater, about 2.5%) or greater, about 3% or greater, about 4% or greater, or about 5% or greater by volume, based on the volume of the first isocratic eluent.
  • the polar aprotic solvent in the first isocratic eluent can be in an amount of about 5% or less, about 4% or less, or about 3%) or less by volume, based on the volume of the first isocratic eluent. In some embodiments, the polar aprotic solvent in the first isocratic eluent can be in an amount of about 1% to about 5%> or about 2% to about 5% by volume, based on the volume of the first isocratic eluent.
  • the second elution temperature can be about 15°C or greater. In some embodiments, the second elution temperature can be from about 15°C to about 70°C, 15°C to about 65°C, 15°C to about 50°C, 15°C to about 30°C, 20°C to about 30°C, 60°C to about 70°C, about 62°C to about 67°C, or about 63°C to about 67°C.
  • the second elution temperature can be about 15°C, about 20°C, about 25°C, about 30°C, about 35°C, about 40°C, about 45°C, about 50°C, about 55°C, about 56°C, about 57°C, about 58°C, about 59°C, about 60°C, about 61°C, about 62°C, about 63 °C, about 64°C, about 65°C, about 66°C, about 67°C, about 68°C, about 69°C, or about 70°C.
  • the second chromatography step can be performed within about 100 minutes or less. In some embodiments, the second chromatography step can be performed from about 5 minutes to about 100 minutes, about 10 minutes to about 90 minutes, about 10 minutes to about 60 minutes, about 20 minutes to about 60 minutes, or about 20 minutes to about 50 minutes. For example, the second chromatography step can be performed within about 90 minutes or less, about 80 minutes or less, about 75 minutes or less, about 70 minutes or less, about 60 minutes or less, or about 50 minutes or less.
  • the methods described herein can include a third chromatography step.
  • the third chromatography step can include introducing a sample of the mixture onto a third ion- exchange chromatography matrix.
  • the third ion-exchange chromatography matrix can include a carboxylate-functionalized resin.
  • the third chromatography matrix can be suitable for separating polar amines and moderately hydrophobic and polyvalent amines.
  • a high capacity column that provides for acidic gradient separation can be used as the third ion-exchange
  • an IonPacTM CS17, IonPacTM CS18, or IonPacTM CS19 column can be used as the third chromatography matrix.
  • the third chromatography step can be performed sequential to the second chromatography step.
  • the third chromatography step can include eluting at least one late eluting eluate (also referred to herein as "third eluate") from the third ion-exchange chromatography matrix under a second isocratic eluting condition.
  • the second isocratic eluting condition includes using a second isocratic eluent at a third elution temperature.
  • a plurality of late eluting eluate fractions, comprising separated or substantially separated ionic species can be obtained.
  • the second isocratic eluent can include any one of the eluent described herein.
  • the second isocratic eluent can comprise an acid, for example, methanesulfonic acid or oxalic acid.
  • the second isocratic eluent can have a pH of less than about 7, for example, about pH 6 or less, about pH 5 or less, about pH 4 or less, about pH 3 or less, or about pH 2 or less.
  • the concentration of acid in the second isocratic eluent can be about 5 mM or greater. In some embodiments, the concentration of acid in the second isocratic eluent can be from about 5 mM to about 20 mM, about 5 mM to about 15 mM, or about 10 mM.
  • the third elution temperature can be from about 35°C to about 45°C.
  • the third elution temperature can be from about 37°C to about 45°C, about 37°C to about 43°C, or about 38°C to about 42°C. In some examples, the third elution temperature can be about 36°C, about 37°C, about 38°C, about 39°C, about 40°C, about 41°C, about 42°C, about 43°C, about 44°C, or about 45°C.
  • the third chromatography step can be performed within about 60 minutes or less. In some embodiments, the third chromatography step can be performed from about 5 minutes to about 60 minutes, about 10 minutes to about 60 minutes, about 10 minutes to about 50 minutes, or about 20 minutes to about 60 minutes. For example, the third chromatography step can be performed within about 50 minutes or less, or about 45 minutes or less.
  • the method for separating and/or monitoring a plurality of ionic species such as a plurality of amines in a mixture can include (a) a first chromatography step comprising (i) introducing a sample of the mixture onto a first ion-exchange chromatography matrix; and (ii) eluting at least one first eluate from the first ion-exchange chromatography matrix under a first multistep gradient eluting condition, using a first gradient eluent at a first elution temperature; and (b) a second chromatography step comprising (i) introducing a sample of the mixture onto a second ion-exchange chromatography matrix; and (ii) eluting at least one second eluate from the second ion-exchange chromatography matrix under a first isocratic condition, using a first isocratic eluent at a second elution temperature.
  • the mixture comprises at least five amines and
  • the method for separating and/or monitoring a plurality of ionic species such as a plurality of amines in a mixture can include (a) a first chromatography step comprising (i) introducing a sample of the mixture onto a first ion-exchange chromatography matrix; and (ii) eluting at least one first eluate from the first ion-exchange chromatography matrix under a first gradient eluting condition, using a first gradient eluent at a first elution temperature; (b) a second chromatography step comprising (i) introducing a sample of the mixture onto a second ion-exchange chromatography matrix; and (ii) eluting at least one second eluate from the second ion-exchange chromatography matrix under a second gradient eluting condition, using a second gradient eluent at a second elution temperature; and (c) a third chromatography step comprising (i) introducing a first ion
  • the eluates can be identified and/or quantified using any suitable apparatus know in the art and used to identify and/or quantify ionic species.
  • apparatuses for mass spectrometry, nuclear magnetic resonance, surface enhanced Raman scattering, ultra-violet spectrophotometry, fluorescence, conductivity, and combinations thereof can be used for identifying and/or quantifying the ionic species of interest.
  • a hybrid apparatus incorporating the ion-exchange chromatography system can be used in the methods described herein, for monitoring, separating, identifying, and/or quantifying the ionic species in a mixture. For example, an ICS-5000 + TSQ Quantum Access Max triple quad or an ICS-5000 +
  • CD Conductivity Detector supplied by Thermo ScientificTM and DionexTM can be used in the methods described herein.
  • the minimum detection level of each ionic species in the mixture can be about 10 ppb or greater. In some embodiments, the detection level of each ionic species in the mixture can be about 1 ppm or greater, about 2 ppm or greater, about 3 ppm or greater, about 4 ppm or greater, about 4 ppm or greater, or about 10 ppm or greater.
  • the methods described herein can be performed and provide results in a short time. As a result, the methods can be employed in automated process control applications.
  • a "short time,” as used herein generally refers to "sufficiently fast enough to be employed in controlling an industrial process” and specifically less than about 24 hours.
  • the method can be performed and produce results in less than about 10 hours, less than about 8 hours, less than about 6 hours, less than about 5 hours, less than about 4 hours, or less than about 3 hours.
  • Described herein are also methods for controlling an industrial device or an industrial process using the results of the output from the ion-exchange apparatus and/or the apparatus for identifying and/or quantifying the ionic species in the mixture.
  • the output may be employed directly to control a parameter of a process.
  • Parameters related to, for example an industrial fluid that may be altered based on the results or data obtained related to the identified ionic species and the respective amount of the identified ionic species within the industrial fluid can include temperature, amount of the composition, pressure, and combinations thereof.
  • the temperature of a process may be altered in order to avoid the formation or deposition of solid amine hydrochloride salts within the process equipment if the
  • concentration of a particular amine is determined to be above a pre-determined threshold value.
  • the amount of specific amines or inorganic ions may be used to optimize process parameters of the desalter.
  • the parameter may be altered upstream or downstream of the location of the analyzed sample.
  • contaminant removal technology may be applied at the desalter (upstream) based on the quantitation of amines in a water sample from the overhead system of the atmospheric distillation tower (downstream).
  • the output from the ion-exchange apparatus and/or the apparatus for identifying and/or quantifying the ionic species can also be used to speed up or slow down a specific process stream in response to the concentration of the undesirable compound.
  • the output can be used to change the pH of a process stream, optimize the dosage of additives such as corrosion inhibitors, hydrate inhibitors, anti-fouling agents, antifoaming agents, anti-scaling agents, demulsifiers, and the like.
  • the output from the ion-exchange apparatus and/or the apparatus for identifying and/or quantifying the ionic species can be employed as input into a computer model of a process. This may be used to indicate changes to feed stream rates, temperature, and/or pressures for efficient operation of a refinery.
  • IC column CS16 plus CGI 6 guard column
  • IC column CS16 plus CGI 6 guard column
  • IC column CS19 plus CGI 9 guard column
  • IC column MetrohmTM Metrosep C6 IC column dimension: 250 mm long x 4 mm inner diameter
  • First Eluent 3.4 mM oxalic acid and 0.25% acetonitrile.
  • the first eluent was prepared by adding oxalic acid dihydrate (0.857g +/- 0.001 g) into a 2 L glass container followed by addition of acetonitrile (5 ml). The mixture was diluted to 2 L with deionized or distilled water. The resulting mixture was mixed for -10 minutes to ensure dissolution of oxalic acid and degassing of the acetonitrile.
  • Second eluent 50 mM oxalic acid 10% acetonitrile.
  • the second eluent was prepared by adding oxalic acid dihydrate (12.6g +/- 0.1 g) into a 2 L glass container followed by addition of acetonitrile (200 ml). The mixture was dilute to 2 L by adding deionized or distilled water. The resulting mixture was mixed for -10 minutes to ensure dissolution of oxalic acid and degassing of the acetonitrile.
  • Eluent 10 mM oxalic acid and 2.5% acetonitrile.
  • the eluent was prepared by adding oxalic acid dihydrate (2.52g +/- 0.01 g) into a 2 L glass container followed by addition of acetonitrile (50 ml). The mixture was diluted to 2 L with deionized or distilled water. The resulting mixture was shaken for -10 minutes to ensure dissolution of oxalic acid and degassing of the acetonitrile.
  • Eluent Flow Rate 1.0 ml/min
  • compositions and methods of the appended claims are not limited in scope by the specific compositions and methods described herein, which are intended as illustrations of a few aspects of the claims and any compositions and methods that are functionally equivalent are intended to fall within the scope of the claims.
  • Various modifications of the compositions and methods in addition to those shown and described herein are intended to fall within the scope of the appended claims.

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Abstract

L'invention concerne des procédés pour séparer, surveiller, identifier et/ou quantifier une pluralité d'espèces ioniques dans un mélange. Les espèces ioniques peuvent comprendre une pluralité d'amines dans un fluide industriel. Les procédés peuvent comprendre une première étape de chromatographie, une deuxième étape de chromatographie, et éventuellement, une troisième étape de chromatographie. La première étape de chromatographie et la deuxième étape de chromatographie peuvent être effectuées simultanément, par exemple dans un appareil à double canal, de telle sorte que le procédé peut être effectué en moins d'environ 24 heures. L'invention concerne également des procédés pour faire fonctionner efficacement une raffinerie.
EP16744976.8A 2015-07-13 2016-07-05 Analyse d'amines par chromatographie ionique Withdrawn EP3322979A1 (fr)

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