Multi-stage fractionation of FCC naphtha with post treatment and recovery of aromatics and gasoline fractions
10774276 · 2020-09-15
Assignee
Inventors
Cpc classification
C10G45/02
CHEMISTRY; METALLURGY
C10G7/02
CHEMISTRY; METALLURGY
C10G67/04
CHEMISTRY; METALLURGY
C10G69/04
CHEMISTRY; METALLURGY
C10G29/205
CHEMISTRY; METALLURGY
C10G2300/1044
CHEMISTRY; METALLURGY
C10G2300/104
CHEMISTRY; METALLURGY
C10G45/32
CHEMISTRY; METALLURGY
International classification
C10G45/02
CHEMISTRY; METALLURGY
C10G7/02
CHEMISTRY; METALLURGY
Abstract
A stream of cracked naphtha is fractionated into at least four specified fractions defined by their respective boiling point ranges. The lightest fraction, IBP to 50 C., is treated in a selective etherification or alkylation process to reduce its RVP value and increase its RON. The second fraction, 50 C. to 150 C., is selectively hydrogenated to treat and convert the diolefins present and the treated stream is sent directly to the gasoline blending pool since it has the desired RON and low sulfur content. The third, and optionally a fourth fraction, boiling in the range of 50 C. to 180 C., in an embodiment, are utilized for the production of aromatics and the raffinate stream, after aromatic extraction, is sent to the gasoline blending pool. A fraction of this latter stream can optionally be recycled for further cracking to produce additional aromatics and gasoline blending components. The heaviest fraction, 180 C. to MBP, constitutes a relatively small volume and is hydrotreated at high pressure, and one portion of the hydrotreated stream is recycled to the FCC unit for further processing and the remaining hydrotreated portion is sent to the gasoline blending pool.
Claims
1. A process for treating a feedstream of cracked naphtha to produce aromatics and gasoline blending components, the process comprising: a. introducing the feedstream into a fractionating column and fractionating the cracked naphtha into five fractions based on boiling point ranges in which i. a first fraction has a boiling point ranging from the initial boiling point (IBP) of the feed up to 50 C., contains no or substantially no aromatics and comprises a substantial proportion of the olefins present in the original cracked naphtha feed, ii. a second fraction has an initial boiling point that is the final boiling point of the first fraction and a final boiling point of 100 C., iii. a third fraction has an initial boiling point that is the final boiling point of the second fraction and a final boiling point of 150 C., iv. a fourth fraction has an initial boiling point that is the final boiling point of the third fraction and a final boiling point of 180 C., and v. a fifth fraction has an initial boiling point that is the final boiling point of the fourth fraction and a final boiling point that is the maximum boiling point (MBP) of the cracked naphtha feed entering the fractionation column; b. passing the first fraction for processing to reduce the RVP value by subjecting the fraction to a selective etherification or alkylation process and directing the treated stream to a gasoline blending pool; c. passing the second fraction to a selective hydrogenation processing zone to catalytically convert diolefins to mono-olefins and light sulfur components into heavier sulfur-containing components; d. passing the selectively hydrogenated product stream of step (c) to the gasoline blending pool; e. optionally passing the third fraction to a selective hydrogenation unit to catalytically convert diolefins to mono-olefins and passing the selectively hydrogenerated stream or the untreated third fraction to an aromatics extraction unit; f. passing the fourth fraction to a hydrotreating unit and passing the hydrotreated stream and the third fraction to the aromatics extraction unit; g. recovering from the aromatic extraction unit an aromatic rich stream, which is directed for further aromatic processing, and an aromatic-lean stream composed mainly of paraffins, isoparaffins, and olefins, and passing the aromatic-lean stream to a hydrotreating unit, and passing the hydrotreated stream to the gasoline blending pool; and h. passing the fifth fraction to a hydroconverting unit and passing all or a predetermined portion of the hydroconverted product stream to an FCC unit as a recycle stream and passing any remaining portion to the gasoline blending pool.
2. The process of claim 1, wherein the boiling cut point of the second fraction is 75 C., whereby the boiling range of the second fraction is from 50 to 75 C. and the boiling range of the third fraction is from 75 to 150 C.
3. The process of claim 1, wherein the third fraction is passed to a common hydrotreating unit with the fourth fraction without further hydrotreating downstream of the aromatic extraction unit.
4. The process of claim 1, wherein the third fraction is sent directly to the aromatic extraction unit.
5. The process of claim 1, wherein the final boiling point of the first fraction is 50 C.
6. The process of claim 1, wherein the selectively hydrogenated stream is hydrotreated to reduce its sulfur content.
7. The process of claim 1, wherein the third fraction is sent to a common hydrotreating unit with the fourth fraction prior to the aromatics extraction unit.
8. The process of claim 1, wherein all of the fifth fraction is recycled to FCC unit after the hydroconverting unit.
9. The process of claim 1, wherein all of the fifth fraction is sent to the gasoline pool after the hydroconverting unit.
10. The process of claim 1, wherein the third fraction is passed to a separate hydrotreating unit before it is mixed with the hydrotreated fourth fraction upstream of the aromatics extraction unit.
11. A process for treating a feedstream of cracked naphtha to produce aromatics and gasoline blending components comprising: a. fractionating the cracked naphtha into four fractions based on boiling point in which: i. the first fraction having a boiling point below 50 C. that contains no or substantially no aromatics and a substantial proportion of olefins present in the original cracked naphtha feed, ii. a second fraction having an initial boiling point that is the final boiling point of the first fraction and a final boiling point of 150 C. that contains a substantial proportion of the aromatics and olefins present in the original feed, iii. a third fraction having an initial boiling point that is the final boiling point of the second fraction and a final boiling point of 180 C., and iv. a fourth fraction with an initial boiling point that is of the final boiling point of the third fraction and a final boiling point that is the maximum boiling point (MBP) of the feed entering the fractionation column; b. optionally passing the first fraction for processing to reduce the Reid vapor pressure (RVP) value and increase the research octane number (RON) by subjecting the fraction to a selective etherification or alkylation process and directing the treated stream or untreated first fraction to a gasoline blending pool; c. passing the second fraction to a selective hydrogenation process to catalytically convert the corresponding diolefins to mono-olefins; d. passing the selectively hydrogenated product to a splitter operating under predetermined conditions to divide the product into two streams based on boiling point, and recovering from the splitter a first light stream having a boiling not exceeding 100 C. and a second heavy stream boiling up to the final boiling point of the selectively hydrogenated product, wherein the first light stream is sent directly to the gasoline blending pool without further hydrotreatment, and the second heavy stream is sent to an aromatic extraction unit; e. passing the third fraction to a hydrotreating unit, recovering and combining the hydrotreated third fraction with the second heavy stream from the splitter prior to passing the combined streams to the aromatic extraction unit; f. recovering from the aromatic extraction unit an aromatic-lean stream comprising as a major proportion paraffins, isoparaffins and olefins, the aromatic-lean stream being passed to a hydrotreating unit, and passing the hydrotreated stream to the gasoline blending pool, where the hydrotreating unit care be placed upstream or downstream of the aromatic extraction unit; and g. passing the fourth fraction to a hydroconverting unit and passing all or a portion of the hydroconverted stream to either an FCC unit as a recycle stream or to the gasoline blending pool.
12. The process of claim 11, wherein the Reid vapor pressure value of the first fraction is decreased by passing the first fraction for treatment to an alkylation unit or a selective etherification unit.
13. The process of claims 11 or 12, wherein the first fraction is subjected to a selective etherification process.
14. The process of claim 13, wherein the selective etherification process employs an alcohol under acidic conditions and reaction temperatures ranging from 20 to 80 C.
15. The process of claim 14, wherein the alcohol is methanol.
16. The process of claim 11, wherein the splitter in step 11(d) separates the selectively hydrogenated stream into a light stream boiling in the range of 50-75 C. and a heavy stream boiling in the range of 75-150 C.
17. The process of claim 16, wherein the light stream from the splitter contains sulfur compounds and is hydrotreated to reduce the sulfur content.
18. The process of claim 11, wherein the aromatic extraction unit utilizes a solvent extraction process operated in the range of 50-150 C., wherein the solvent is selected from the group comprising sulfolane, mono-ethylene glycols and/or multi-ethylene glycols, and dimethyl sulfoxide, alone and in combination.
19. The process of claim 18, wherein the solvent extraction process is operated at 120 C.
20. The process of claim 18 wherein the multi-ethylene glycols are diethylene glycols and tetraethylene glycols, alone and in combination.
21. The process of claim 11, wherein the aromatic-lean fraction recovered in step 11(f) is further split into two fractions at a cut point of 150 C. to provide a light stream and a heavy stream, and the light stream is passed to a hydrotreating unit and the hydrotreated stream is passed to the gasoline blending pool.
22. The process of claim 21, wherein the heavy stream derived from the aromatic-lean fraction is mixed with the hydroconverted stream of step 11(g).
23. The process of claim 22, wherein the cracked naphtha is produced in an FCC unit and all or a predetermined portion of the two mixed streams are recycled to the FCC unit and any portion remaining is sent to the gasoline blending pool.
24. The process of claim 23, wherein all of the mixed streams are combined and recycled to the FCC unit.
25. The process of claim 23, wherein all of the mixed streams are combined and sent to the gasoline blending pool.
26. The process of claim 11, wherein the fourth fraction is subjected to a hydroconversion process selected from hydrotreating, partial hydrogenation and mild hydrocracking.
27. The process of claim 11, wherein all or a predetermined portion of the hydroconverted fourth fraction is recycled to an FCC unit and any remaining portion is sent to the gasoline blending pool.
28. The process of claim 27, wherein all of the hydroconverted fourth fraction is recycled to the FCC unit.
29. The process of claim 27, wherein all of the hydroconverted fourth fraction is passed to the gasoline blending pool.
30. The process of claim 11, wherein the selective hydrogenation product is admixed directly with the third hydrotreated fraction and the mixed stream is passed to the aromatics extraction unit.
31. The process of claim 11, wherein the hydrotreating of the aromatic lean stream of step 11(f) occurs in a hydrotreating unit upstream of the aromatic extraction unit.
32. The process of claim 11, wherein the hydrotreating of the aromatic lean stream of step 11(f) occurs in a hydrotreating unit downstream of the aromatic extraction unit.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
(1) The invention will be described in further detail below and with reference to the attached drawings in which the same or similar elements are identified by the same numeral, and where:
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DETAILED DESCRIPTION OF THE INVENTION
(12) An embodiment of the disclosure will be described with reference to the simplified schematic flow diagram of
(13) The first and lightest fraction (322) includes material boiling from the initial boiling point (IBP) up to 50 C. and is passed to processing zone (330) where it undergoes a selective etherification or alkylation process to reduce its Reid vapor pressure (RVP) value and to increase its research octane number (RON). The treated product (332) is then passed to the gasoline blending pool (390).
(14) The second fraction (324), boiling in the range of from 50 C. to 100 C. is passed to the selective hydrogenation zone (340) where it is subjected to selective catalytic hydrogenation using appropriate catalysts to convert diolefins, or dienes, to mono-olefins after which the treated stream is sent directly to the gasoline blending pool (390). For reasons that will be discussed in more detail below, this second fraction (324) has an excellent RON value and a relatively low sulfur content.
(15) The third fraction (326), boiling in the range of from 100 C. to 150 C. is passed to an aromatic extraction zone (370) which can comprise a solvent extraction unit which includes means for separating the aromatics from the solvent and recovery of the aromatics (372) for further processing in a downstream unit (376). The aromatic-lean raffinate stream (374) which is composed principally of paraffins, isoparaffins and olefins is passed to a hydrotreating zone (380B) and the hydrotreated product (382) is passed to the gasoline blending pool (390). Also shown in
(16) The fourth fraction (328) boiling from 150 C. to 180 C. is passed to a hydrotreating zone (350) and the hydrotreated stream (352) is passed to the aromatic extraction zone (370) where it is processed with the third fraction (326). This fourth fraction is high in aromatic content, with more than 30% of the weight percent of aromatics present in the 100 C. to 150 C. fraction (326).
(17) The fifth and final fraction (329) comprises those components boiling at 180 C. and up to the maximum boiling point (MBP) of the cracked naphtha feed. The final fraction which is passed to high pressure hydroprocessing zone (360) for appropriate treatment depending upon the composition of the fraction. A portion of the hydrotreated material can be sent to the gasoline blending pool (390), and the remaining stream (364) recycled to the FCC unit (310) where it is combined with the fresh feed to the unit.
(18) Referring now to
(19) With continuing reference to
(20) Another embodiment of the process and system of the present disclosure will be described with reference to
(21) A further embodiment of the process and system in the present disclosure will be described with reference to
(22) The third fraction (528) from the distillation unit (520) boiling from 150 C. to 180 C. is passed to hydrotreating zone (550) and the hydrotreated stream (552) is introduced into the aromatic extraction zone (570) for processing with the 100 C. to 150 C. component stream (548) from splitter (545). Subsequent treatment of these components streams (572, 574) in the embodiment of system (500) is the same as previously described for system (300) in conjunction with
(23) An additional embodiment of the process and system of the present disclosure will be described with reference to
(24) As will be understood from the above descriptions, the processes of
(25) Each of the splitters described in the several embodiments of the process function in a manner that is similar to a distillation tower where the heating is provided by a bottom boiler and which has a number of plates in order to ensure the desired degree of separation between the top and bottom product streams. As is shown in the schematic flow diagrams, only two products are withdrawn from the splitter, e.g., one from the top and the other from the bottom. The operating temperature and pressure of each splitter are based on the predetermined cutting temperature, which is, by definition, implied in the respective stream temperature ranges.
(26) Thereafter, the subsequent processing and passage of the treated streams are substantially as previously described in conjunction with the earlier embodiments.
(27) The following discussion and description of the composition and characteristics of the fractions cut from the FCC naphtha stream in accordance with the invention will be best understood with reference to
(28) Referring to the chart of
(29) The calculated Research Octane Number (RON) and Motor Octane Number (MON) for each of the six cracked naphtha fractions are graphically plotted in
(30) Referring to Table 1, data is provided for the density, nitrogen and sulfur content obtained from the analysis of seven (7) distillation cuts taken at 25 C. temperature intervals after the initial IBP-50 C. cut and up to 150-180 C. and the final cut of 180 C.+. The analysis of the complete FCC naphtha stream from which the distillation data was obtained is also provided. As shown in Table 1, the nitrogen content of the 150 C.-180 C. fraction was significantly greater than the lower boiling fractions. The sulfur content of all of the fractions of this naphtha stream exceeded the common regulatory benchmark of 10 ppm with a greater than 100-fold increase in the 150 C.-180 C. cut. However, in an embodiment of the process, the lightest fraction with a sulfur content in the low double digit range can be sent directly to the gasoline blending pool for blending with lower sulfur content components so that the blended components withdrawn from the pool for distribution as motor vehicle fuels will not exceed the regulatory maximum sulfur value.
(31) TABLE-US-00001 TABLE 1 Normalized Yield of Nitrogen Sulfur Fraction Density Content Content Fraction (wt %) (g/mL) (ppm) (ppm) IBP-50 10.2 0.6547 1 13 50-75 13.7 0.6891 1 200 75-100 11.0 0.723 1 300 100-125 15.1 0.7532 1 750 125-150 11.9 0.7846 1 1100 150-180 17.7 0.8168 6 1400 180+ 20.4 0.8735 68 14500 FCC Naphtha 100 0.7648 14 4000
(32) As is clearly shown by the analytical data presented in Table 1, the most problematic fraction in terms of nitrogen- and sulfur-containing compounds is that boiling above 180 C. which accounts for only about 20 weight % of the feed and yet contains the most sulfur- and nitrogen-containing compounds.
(33) Aromatics can be recovered to maximize the value of the FCC naphtha and adhere to any regulatory or other limitations on the content of benzene and/or other aromatic compounds in the blended gasoline. The process of the present disclosure maximizes the amount of aromatics extracted by increasing the range of the boiling points of the fraction of the feed sent to the aromatic extraction unit, and by recycling the heaviest fraction after the hydrotreating and/or mild hydrocracking of the fraction. By recycling the stream after hydrotreating, hydrogenation and mild hydrocracking, more extractable aromatics are produced in the desired range which results in a better quality raffinate for the gasoline blending pool. The benefits and advantages of separating the various process treatment steps in accordance with the present disclosure are to minimize the cost of hydrotreating and/or decrease the size of the reactor vessels since the most refractory fraction treated is relatively small as compared to the volume of the initial feedstream.
(34) The lightest fraction is optionally processed in an alkylation or selective etherification step to reduce the RVP value and to increase the RON of this stream prior to sending it to the gasoline blending pool when these characteristics require modification to meet specifications for the pool.
(35) In summary, the present improved integrated refinery process for treating cracked naphtha to produce aromatics and components for gasoline blending comprise the steps of fractionating the cracked naphtha into five, or alternatively, four fractions based on boiling points to provide: a first light fraction that has no aromatics and a substantial amount of olefins which can typically range from greater than 50 weight % up to about 60 weight % and that can include C4-C7 components with a boiling point below 50 C., a second fraction with an initial boiling point in the range that is the final boiling point of the first fraction and up to either 100 C. or 150 C. containing a substantial proportion of aromatics and olefins, a third fraction with an initial boiling point which is the same as final boiling point of the second fraction and a final boiling point that is either 150 C. or 180 C. a fourth fraction with an initial boiling point which is the same as the final boiling point of the third fraction and a final boiling point that is either 180 C. or the MBP of the feed entering the fractionation column, and in the alternative, a fifth fraction that with an initial boiling point that is the final boiling point of the fourth fraction and a final boiling point that is the MBP of the feed.
(36) As will be understood from the above descriptions, the present process differs from the prior art Timken et al and Mehlberg et al processes by increasing the number of fractions and specify the temperature ranges of the fractions, or cuts, for the purpose of maximizing the recovery of aromatics. The lightest fraction with a maximum boiling point cut off of 50 C. is optionally directed to a selective etherification process or an alkylation process to reduce the RVP value and to maintain or increase the RON value of the fraction. The heaviest fraction is hydrotreated and/or mildly hydrocracked prior to recycling a portion to the FCC unit and/or sending a portion directly to the gasoline blending pool. The embodiments described above provide additional benefits and offer alternative means to achieve the advantages of increasing the value of the cracked naphtha stream.
(37) The process can also be distinguished by the further splitting of the heavier products to maximize the production of aromatics by further cracking of the 180 C.+ fraction and recovering a portion of the cracked products for use in the gasoline pool.
(38) From the above description, it will also be understood that the hydrotreating step is improved by segmenting the product stream, e.g., by fractionation and/or use of the splitter, into those portions that require hydrotreating in order to maximize efficient utilization of the equipment to its design capacity and optimize utilization of the hydrogen supply.
(39) In addition, the selective partial recycling of the heaviest fraction of 180 C. and above further enhances the recovery of gasoline and gasoline blending components to maximize the value of the original cracked naphtha stream.
(40) In retrospect from the vantage provided by the present disclosure, the main disadvantage of Timken et al. is that the fraction identified for aromatic production is narrow, i.e., between 150-300 F./77-150 C. The range was widened by Mehlberg et al. to reference it to carbon chain lengths of at least C6-C9, which would result in an aromatic yield comparable to the present disclosure prior to the partial recycling of the heavy stream to the FCC unit. However, the present process differs significantly with respect to (1) the processing of the very light first fraction, (2) the separate hydrotreating of the different fractions, and (3) by the partial recycling of the heavy ends of the specified fraction to the FCC unit for further processing. This latter distinction is in contrast to the processes of both Timken et al and Mehlberg et al which send the heavy fraction after hydrotreating directly to the gasoline blending pool.
(41) The process of the present disclosure maximizes the aromatics extracted by increasing the range of the boiling points of the fractions sent to the aromatic extraction unit and also by recycling the heaviest fraction remaining after the hydrotreating and/or mild hydrocracking unit. Further processing of the remainder of these fractions after hydrotreating, hydrogenation and mild hydrocracking produces more extractable aromatics in the desired range and provides a better quality raffinate for gasoline blending. As explained above, by separating the fractions for treatment, the cost of hydrotreating is minimized by reducing the hydrogen requirement and the capital cost for the hydrotreating vessel in the case of new construction, since the most refractory fraction is relatively small compared with the initial feed of cracked naphtha from the FCC unit. Moreover, the very light first fraction can optionally be upgraded to increase the value of the product prior to sending it to the gasoline blending pool. The light fraction can be passed to an alkylation or selective etherification unit to reduce the RVP value and further increase its RON. The cumulative outcome is increased value for the FCC naphtha compared with prior art processes and current commercial practices.
(42) Although the invention has been described in detail above and in the embodiments illustrated in the attached drawing, modifications and variations of the process will be apparent to those of skill in the art, and the scope of the invention is to be determined by the claims that follow.