ATR-FTIR Model Development and Verification for Qualitative And
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energies Article ATR-FTIR Model Development and Verification for Qualitative and Quantitative Analysis in MDEA–H2O–MEG/TEG–CO2 Blends Usman Shoukat , Eva Baumeister and Hanna K. Knuutila * Department of Chemical Engineering, Norwegian University of Science and Technology (NTNU), 7491 Trondheim, Norway * Correspondence: [email protected] Received: 26 June 2019; Accepted: 20 August 2019; Published: 26 August 2019 Abstract: A Fourier transform infrared (FTIR) spectroscopy method was developed to identify and quantify various components in an amine-based combined acid gas and water removal process. In this work, an attenuated total reflectance (ATR) probe was used. A partial least-squares (PLS) regression model was also developed using up to four components (methyl diethanolamine (MDEA)-H2O-CO2-ethylene glycol/triethylene glycol (MEG/TEG)), and it was successfully validated. The model was applied on thermally degraded CO2-loaded MDEA blends to predict the weight percentages of MDEA, H2O, CO2, and MEG or TEG to test the performance spectrum. The results confirmed that FTIR could be used as a simpler, quicker and reliable tool to identify and quantify various compounds such as MDEA, MEG/TEG, H2O and CO2 simultaneously in a combined acid gas and water removal process. Keywords: Fourier transform infrared (FTIR) spectroscopy; acid gas removal; N-Methyldiethanolamine; monoethylene glycol; triethylene glycol 1. Introduction Norway produced 124.16 million Sm3 oil equivalents of natural gas (NG) in 2017, which is 5.96% higher than in 2016 (Source: The Norwegian Petroleum Directorate (https://www.norskpetroleum. no/en/facts/production/)). Natural gas has impurities such as acid gases (hydrogen sulfide (H2S) and carbon dioxide (CO2)), water vapor, and mercury, etc. CO2 in the presence of water vapors can cause corrosion, and it can also reduce the heating value of natural gas [1–3]. H2S is a poisonous gas and can cause instant death at concentrations over 500 parts per million (ppm) [4,5]. Moreover, water vapor and methane can form ice-like solids called hydrates, increasing the corrosion rate and/or plug gas pipelines [6]. Conventionally, acid gases and water vapor are removed separately from natural gas before its use; this two-step process increases the investment and operational costs [7,8]. Absorption by using alkanolamines is the most commonly used technology for natural gas sweetening and CO2 capture processes, while tertiary amines (like methyldiethanolamine) are known to absorb H2S selectively [9]. Ethylene glycol (MEG) and triethylene glycol (TEG) are used for H2O removal and hydrate control [10]. Norway natural gas production mostly comes from offshore facilities. Therefore, developing combined subsea selective acid gas (H2S/CO2) removal along with water vapor will reduce both the environmental footprint and the operational costs. Hutchinson, McCartney, and Chapin studied combined acid gas and water removal [11–14]. A blend of MEA and diethylene glycol was the first system used for combined acid gas removal and dehydration, but it is no longer considered competitive due to high amine degradation and severe corrosion at a high reboiler temperature [9]. Tertiary amine systems, like a blend of methyl diethanolamine (MDEA) with glycols (MEG/TEG), Energies 2019, 12, 3285; doi:10.3390/en12173285 www.mdpi.com/journal/energies Energies 2019, 12, 3285 2 of 15 have lower amine degradation and corrosion rates [9,15]. Therefore, MDEA blends with MEG/TEG were also recently explored for simultaneous acid gas and water removal [16,17]. Fourier transform infrared (FTIR) spectroscopy has previously been used as an analytical technique to monitor online reaction chemistry [18]. Molecules’ dipole movements due to molecular deformations 1 are measurable in the mid-IR region (4000–400 cm− ), which allows many chemical compounds to be identified and quantified [19]. FTIR with a partial least-squares (PLS) model has been used as an alternative calibration technique for real-time performance monitoring. It requires calibration and validation datasets, which cover a full range of process gas pressures and amine concentrations, Energies 2019, 12, x FOR PEER REVIEW 2 of 16 however, this combinationEnergies does 2019 not, 12, x FOR provide PEER REVIEW accurate results outside the calibration and validation2 of 16 Energies 2019, 12, x FOR PEER REVIEW 2 of 16 dataset [19]. The FTIR andandEnergies PLS corrosion 2019 combination, 12, xrates FOR PEER[9,15]. REVIEW hasTherefore, been MDEA used blends successfully with MEG/TEG to extract were also process recently explored information2 of for 16 simultaneousand corrosion acidrates gas [9,15]. and Therefore,water removal MDEA [16,17]. blends with MEG/TEG were also recently explored for data from the CO2 absorptionsimultaneousand corrosion system acidrates gas [[9,15].20 and] and Therefore,water also removal MDEA from [16,17]. blends the with simultaneous MEG/TEG were absorption also recently explored of the for CO 2 and corrosionFourier transform rates [9,15]. infrared Therefore, (FTIR) MDEA spectroscopy blends with has MEG/TEG previously were been also used recently as an explored analytical for simultaneousFourier transform acid gas and infrared water removal(FTIR) spectroscopy [16,17]. has previously been used as an analytical and SO2 in a pilot plant [21techniquesimultaneous]. Furthermore, to monitor acid gas online and FTIRwater reaction removal was chemistry used [16,17]. 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FT IRMolecules’ with a partial dipole–1 least-squares movements due(PLS) to model molecular has an ammonia-based CO capturecompoundsdeformations process to are be identifiedmeasurable [25]. Also,and in quantifiedthe itmid-IR was [19]. region used FT IR(4000–400 to with measure a partial cm ), least-squareswhich the concentrations allows (PLS) many model chemical has in the 2 beendeformations used as anare alternative measurable calibration in the mid-IR technique region for (4000–400real-time performancecm–1), which monitoring.allows many It chemicalrequires beencompounds used as to an be alternative identified calibrationand quantified technique [19]. FTforIR real-time with a partial performance least-squares monitoring. (PLS) Itmodel requires has simultaneous absorption ofcalibrationcompounds CO2 and and to be Hvalidation 2identifiedS in the datasets, and aqueous quantified which methyldiethanolaminecover [19]. 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Handojo et al. [28] processandconcentrations, validation information dataset.however, data [19]. thisfrom The combination the FTIR CO and absorption 2 doesPLS notcombination providesystem accurate [20]has andbeen results also used from outsidesuccessfully the thesimultaneous calibration to extract process information data from the CO2 absorption system [20] and also from the simultaneous absorption of the CO2 and SO2 in a pilot plant [21]. Furthermore, FTIR was used to measure both processand validation information dataset. data [19]. from The the FTIR CO and2 absorption PLS combination system [20]has andbeen alsoused from successfully the simultaneous to extract used FTIR to identify thermalabsorption degradation of the CO2 and byproducts SO2 in a pilot in plant aqueous [21]. Furthermore, MDEA FTIR degradation was used to atmeasure 120 ◦bothC with inorganicprocess information and organic data compounds from the in CO amine-based2 absorption post-combustion system [20] and carbon also capturefrom the (PCCC) simultaneous in flue inorganicabsorption and of theorganic CO2 andcompounds SO2