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Study on Etherification and Catalytic Distillation Process of FCC Light Gasoline

Author: HuangJing
Tutor: LiJiChun
School: Lanzhou Jiaotong University
Course: Chemical processes
Keywords: catalytic cracking light gasoline catalytic distillation dynamics etherification Aspen Plus simulation calculation
CLC: TE624.48
Type: Master's thesis
Year: 2012
Downloads: 154
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Abstract


Fluid-bed catalytic cracking (short English name:FCC) gasoline is one sources of auto-fuel, there are75%FCC gasoline in petroleum products in our country. The feature of FCC gasoline is:olefins contents and sulphur content are high, and the gasoline sability is poor, so gasoline quality cannot meet the new standards, which is the main challenge of gasoline upgrading. Recently, the main methods used by inland refining enterprises to decrease the contents of olefins and sulphur includes:adding hydrogen, catalyzing gasoline to decrease the contents of olefins and etherification, etc. Hydrotreating can reduce the contents of olefins and sulfur efficiently, but there are some shortages:the hydrogen was consumed more, the loss of octane number is great; olefins contents can be reduced efficiently by catalyzing, however, the yield of gasoline product is low; while, the etherification of light gasoline has been become one of the valid paths of gasoline upgrading. There has been a lot of studies on catalytic gasoline etherification technology, and the traits of catalytic gasoline etherification is that the tertiary carbon olefins in light gasoline can proceed etherification with methanol and produce corresponding etherate, which can reduce the olefins contents and increase the octane number of gasoline, meanwhile, about4%methanol were changed into gasoline components. The etherification of light gasoline is a gasoline increment producing process, and it is also a producing process that can transform low value methanol into high value gasoline components. As a new technology of gasoline upgrading, the reaction conditions of gasoline etherification is relaxed, the technology process is not quite complex, and the etherification efficient is outstanding, which attracted refining corporations to develop different technology of gasoline etherification all over the world. Many corporations, such as CDTECH, UOP, Neste, ARCO, IFP and BP, etc, has been exploited etherification technologies of catalytic light gasoline, and they has been exported technology to the international market.The etherification and catalytic distillation process of FCC light gasoline was mainly studied in this paper, FCC gasoline was cut into light gasoline and heavy gasoline, the tertiary carbon olefins in light gasoline can proceed etherification with methanol and produce corresponding etherate, which reduced the olefins contents and increased octane number of gasoline. The desulfuration of heavy gasoline can sulphur content of catalytic gasoline, the etherification of light gasoline and desulfuration technology were combined together to form complete technology, then the clean gasoline was obtained. The etherification technology of FCC light gasoline includes four parts:the first part is FCC light gasoline cutting part, FCC light gasoline was cut into boiling point of less than70℃light gasoline and boiling point of more than70℃heavy gasoline; the second part is selective hydrotreating, the diolefins in cutting light gasoline were removed in selective hydrotreating reactor; the third part is the beforehand etherification in fixed-bed reactor, because there are a large number of C5, C6 tertiary carbon olefins in light gasoline, which respectively happen etherification with methanol to produce methyl tertiary pentyl ether(TAME) and methyl tertiary hexyl ether(THxME); the fourth part is deep etherification, the materials from fixed-bed reactor entered into catalytic distillation column for deep etherification, the obtained mixed components, such as TAME could reach the goal of reducing olefins contents and improving the octane number.The etherification dynamics of synthesizing TAME by representative isoprene and methanol was studied in miniature fixed-bed etherification reactor. The reaction dynamics equation of isoprene and methanol was inspected, after the verification of the dynamics equation, the average relative error between experimental value and calculated value of isoprene conversion is less than5%, which improved that this equation could well describe etherification reaction process of isoprene.The cutting technology of FCC light gasoline was studied in multi-function column with the feeding scale2L/h, several factors influencing light gasoline cutting effect were investigated, which included tower plate number, feeding position, operating pressure, reflux ratio and the recovery rate of column top, based on the test results, the best operating parameters of the multi-function column:the pieces of tower board for16, feeding board for5th, feeding temperature70℃, tower bottom temperature195℃, tower top temperature67℃, tower top pressure for0.118MPa and the reflux ratio1, at this time, the C5tertiary carbon olefins recovery rate was100%, the C6tertiary carbon olefins recovery rate was95.62%, under this condition, FCC gasoline was cut into two parts:≤70℃light gasoline and heavy gasoline.Diolefins selective hydrogenation reaction happened in micro reactor in the lab, and the catalyst LNEH-1was used in the reactor. In the experimental process, the performances of removing diolefins and isomerization of LNEH-1were inspected. The results showed that the rate of removal of diolefins with LNEH-1could achieve above80%, and the isomerization performance is also better, then, took the hydrotreated light gasoline as the etherification material.The beforehand etherification in2L/h fixed-bed reactor was researched, the influenced conditions on light gasoline etherification in fixed bed reactor were investigated, which included feeding airspeed, reaction temperature and volume ration of light gasoline to methanol, after many tests and validation of the calculation, the best reaction conditions of fixed bed etherification were concluded:feeding airspeed for2h-1, reaction temperature for65℃and volume ration of light gasoline to methanol for10:1, under this condition, conversion of C5activity olefins was66.5%, and conversion of C6activity olefins was48.8%.The deep etherification in catalytic distillation column with the feeding scale2L/h was studied in the lab, the influences of reflux ration and methanol to olefins mass ration were mainly inspected, through the inspection, the best operation parameters of catalytic distillation deep etherification were obtained:feeding temperature for65℃, reflux ration1.1, column top temperature for60℃, column top pressure0.243MPa, column bottom temperature for113℃, and column bottom pressure0.286MPa, under this process operating condition, the total conversion of C5activity olefins was82.5%, also, C6activity olefins conversion was71.0%.Through analysis of the mixed gas product, gasoline index have changed:gasoline octane improved1~1.6units, the olefins levels decreased in12.8m%, and saturated steam pressure dropped in18.8kPa.After the study of the test in this paper, the100000t/a light gasoline was supposed and simulated with Aspen Plus, the theory of plate number of the catalytic distillation tower is30, the incoming board position for27, reaction period was12~26, feeding temperature range for65℃~73℃, reflux ratio range for4~5.4, the range of D/F for0.7~0.8, finally, the diameter of tower and packing layer height was simulated, the Sluzer Standard CY neat fill was used, and then, the catalytic distillation packing layer height of1.54m, the inner diameter of the tower for2.5m, which can be used as magnification basis of FCC light gasoline etherification and catalytic distillation etherification in the future.

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