Капиллярные колонки, приготовленные на основе модифицированного органическими основаниями поли(1-триметилсилил‑1-пропина), для анализа товарного (целевого и технического) н-бутана

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Abstract

Разработан способ газохроматографического анализа примесей углеводородов и метанола в н-бутане (содержание более 99%) с использованием капиллярных колонок, приготовленных на основе модифицированного поликатионным полиэтиленимином (ПЭИ) поли(1-триметилсилил- 1-ропина) (ПТМСП). Исследована селективность разделения определяемых компонентов и показано, что разрешающая способность для пиков углеводородов С3–С4 и метанола на пористослойных капиллярных колонках размером 30 м × 0.32 мм (ПТМСП032-ПЭИ) и 25 м × 0.53 мм (ПТМСП053-ПЭИ) с модифицированным полиэтиленимином слоем ПТМСП существенно выше, чем для предложенной ранее капиллярной колонки размером 30 м × 0.32 мм с поли(1-триметилсилил-1-пропином) (ПТМСП032). Метанол на колонках ПТМСП032-ПЭИ и ПТМСП053-ПЭИ элюируется в виде симметричного пика отдельно от всех компонентов, включая пропан, пропилен, 1-бутен, н-бутан. Рассчитанные пределы детектирования с использованием пламенно-ионизационного детектора находятся в диапазоне 1.51–7.95 × 10–12 г/с для углеводородов и 6.47 × 10–12 г/с для метанола.

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About the authors

Елена Юрьевна Яковлева

Институт катализа им. Г. К. Борескова СО РАН; Новосибирский государственный университет

Author for correspondence.
Email: yakovl@catalysis.ru
ORCID iD: 0000-0002-8284-7832

к. х. н.

Russian Federation, Новосибирск, 630090; Новосибирск, 630090

Юрий Валерьевич Патрушев

Институт катализа им. Г. К. Борескова СО РАН; Новосибирский государственный университет

Email: yakovl@catalysis.ru
ORCID iD: 0000-0002-2078-5488

к. х. н.

Russian Federation, Новосибирск, 630090; Новосибирск, 630090

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2. Fig. 1. Structure of the modifier - polyethyleneimine (PEI) used in the work.

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3. Fig. 2. Thermogravimetry (a) and differential thermogravimetry (b) curves for PTMSP (solid line), PEI (dashed line).

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4. Fig. 3. Chromatogram of model mixture I of extreme, unsaturated, aromatic hydrocarbons and methanol on a 30 m × 0.32 mm PTMSP032-PEI column. Temperature programme: 40°C for 3 min, then heating at a rate of 7°C/min to 220°C, evaporator and detector temperatures 240°C; sample volume 1.0 µl; carrier gas - nitrogen at 0.7 bar, detector - flame ionisation.

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5. Fig. 4. Chromatogram of model mixture I of extreme, unsaturated, aromatic hydrocarbons and methanol on a 30 m × 0.53 mm PTMSP053-PEI column. Temperature programme: 40°C for 3 min, then heating at a rate of 7°C/min to 220°C, evaporator and detector temperatures to 240°C; sample volume 1.0 µl; carrier gas - nitrogen at 0.35 bar, detector - flame ionisation.

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6. Fig. 5. Chromatogram of model mixture I of extreme, unsaturated, aromatic hydrocarbons and methanol on a 30 m × 0.32 mm PTMSP032 capillary column. Temperature programme: 40°C for 11 min, followed by heating at a rate of 7°C/min to 220°C; evaporator and detector temperatures, 240°C; sample volume, 1.0 µl; carrier gas, helium (0.7 bar), detector, PID.

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7. Fig. 6. Chromatogram of the components of extreme, aromatic hydrocarbons and methanol of model mixture II (n-butane content > 99.97%); superimposition of three consecutive chromatograms recorded on a 30 m × 0.32 mm PTMSP032-PEI column. Temperature programme: 40°C for 3 min, then heating at a rate of 7°C/min to 220°C, evaporator and detector temperatures to 240°C; sample volume 250 µl; carrier gas - nitrogen at 1.2 atm, detector - flame ionisation.

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