استفاده از روش های آماری تحلیل سری های زمانی برای تعیین بسیار سریع و دقیق نقاط تعادلی ترمودینامیکی سامانه های گاز-آب-هیدرات در حجم ثابت
محورهای موضوعی : شیمی کاربردی
1 - استادیار مهندسی شیمی، گروه پژوهش مهندسی واکنش‌های کاتالیستی، پژوهشکده کاتالیست و نانوفناوری پژوهشگاه صنعت نفت، تهران، ایران
کلید واژه: روش هم حجم در تعیین نقاط تعادلی, نمودار سردشدن, تشخیص نقطه تغییر, روش جمع تجمعی, تحلیل سری های زمانی,
چکیده مقاله :
در این پژوهش، یک روش بسیار سریع و دقیق برای تعیین نقاط تعادلی در سامانه های گاز-آب-هیدرات ارائه شده است. در این روش فقط داده های دما و فشار در مرحله سردکردن برای تعیین نقاط تعادلی تشکیل هیدرات مورد نیاز است. با به کارگیری مفاهیم آماری تحلیل سری های زمانی و همچنین، روش جمع تجمعی در تشخیص نقطه تغییر، زمان موردنیاز برای تعیین نقاط تعادلی تشکیل/ تجزیه هیدرات به شدت کاهش می یابد و نتیجه های دقیق تری به دست می آید. با این روش، چهار آزمایش برای تعیین شرایط تعادلی دما و فشار برای گاز اتان انجام شد. درصد میانگین انحراف مطلق با داده های تجربی دیتون-فراست، معادله تصحیح کامات و نرم افزارهای AQUAlibrium و CSMHYD برای داده های تکراری به ترتیب 67/5، 49/2، 54/9 و 89/1 به دست آمد. همچنین، یکی از آزمایش های پژوهشگران دانشگاه کرتین استرالیا در باره اثر ppm 1000 از ماده سطح فعال pTSA در هیدرات متان با این روش بررسی شد. درصد انحراف مطلق نسبت به داده تجربی و تخمین مدل سازی ترمودینامیکی آماری ایشان به ترتیب 23/0 و 89/1 به دست آمد.
In this research work, a very fast and accurate new method for determining equilibrium thermodynamic conditions in gas-liquid water-hydrate systems is presented. In this method, only temperature and pressure data in the cooling trace are needed to determine the equilibrium points of hydrate formation. The required time to obtain equilibrium thermodynamic conditions for gas hydrate formation are greatly reduced and more accurate results are obtained, using statistical concepts of time series analysis as well as cumulative sum technique in change point detection. With this method, four experiments were performed to determine the equilibrium thermodynamic conditions for ethane gas hydrate. The average percentage of absolute deviations obtained with Deaton-Frost experimental data, Kamath's correction relationship, and AQUAlibrium and CSMHYD softwares were 5.67, 2.49, 9.54, and 1.89, respectively. In addition, the experimental data obtained by Curtin University researchers in Australia about the effect of 1000 ppm of pTSA surfactant in methane hydrate were investigated with this method. The absolute deviation percentage compared to the experimental data and their statistical thermodynamic modeling estimate were 0.23 and 1.89, respectively.
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