Hydrocracking process for high yields of high quality lube products
09809764 · 2017-11-07
Assignee
Inventors
- Benjamin S. UMANSKY (Fairfax, VA, US)
- Teck-Mui Hoo (Centreville, VA, US)
- Richard A. Demmin (Highland Park, NJ)
- Fengrong Chen (Spring, TX, US)
- James W. Gleeson (Magnolia, TX, US)
- Suisheng M. Dou (The Woodlands, TX, US)
- Tomas R. Melli (The Woodlands, TX, US)
- Michael C. Clark (Montgomery, TX, US)
Cpc classification
C10G65/12
CHEMISTRY; METALLURGY
C10G47/14
CHEMISTRY; METALLURGY
C10G2300/304
CHEMISTRY; METALLURGY
International classification
C10G47/14
CHEMISTRY; METALLURGY
Abstract
A process for producing high yields of higher quality (API Group II, Group III′) lubricating oil basestock fractions which allows the production of two or more types of high quality lubes in continuous mode (no blocked operation mode) without transition times and feed or intermediate product tankage segregation. Two consecutive hydroprocessing steps are used: the first step processes a wide cut feed at a severity needed to match heavy oil lube properties. The second step hydroprocesses a light oil after fractionation of the liquid product from the first step at a severity higher than for the heavy oil fraction. The two hydroprocessing steps will normally be carried out in separate reactors but they may be combined in a single reactor which allows for the two fractions to be processed with different degrees of severity.
Claims
1. A process for producing at least two lube boiling range fractions including a light oil lube fraction and a heavy oil lube fraction, which comprises: hydrocracking a hydrocarbon feed in a first hydrocracking step under a first hydrocracking regime to provide a hydrocrackate with a boiling range suitable for a heavy oil fraction, fractionating the hydrocrackate to separate at least a first portion for a light oil fraction and a second portion for the heavy oil fraction; hydrocracking the portion for the light oil fraction in a second hydrocracking step under a second hydrocracking regime, in which the first hydrocracking step and the second hydrocracking step are carried out in a common hydroprocessing reactor containing a plurality of beds in sequence, the first portion for the light oil fraction and the second portion for the heavy oil fraction being introduced at different points in the sequence, to form a second light oil hydrocrackate with a boiling range suitable for the light oil fraction, combining the hydrocrackate portion for the heavy oil and the second light oil hydrocrackate to form a combined hydrocrackate, processing the combined hydrocrackate to meet product specifications for the light oil lube fraction and the heavy oil lube fraction and form a combined stream of a finished light oil lube fraction and a finished heavy oil lube fraction, and fractionating the combined stream to separate the finished light oil lube fraction and the finished heavy oil lube fraction.
2. A process according to claim 1 in which the first hydrocracking regime of the first hydrocracking step provide a hydrocrackate with lube quality specifications comprising aromatics and cold flow properties required for the finished heavy oil lube fraction.
3. A process according to claim 1 in which the second hydrocracking regime of the second hydrocracking step provide a hydrocrackate with lube quality specifications comprising aromatics and cold flow properties required for the finished light oil lube fraction.
4. A process according to claim 1 in which the first hydrocracking step and the second hydrocracking step are carried out respectively in a first hydrocracker and a second hydrocracker.
5. A process according to claim 1 in which the first hydrocracking step provides a hydrocrackate with a boiling range suitable for both lube oil fractions.
6. A process according to claim 1 in which the first portion for the light oil fraction is introduced into the sequence before the second portion for the heavy oil fraction.
7. A process according to claim 1 in which the first and second hydrocracking steps are carried out in the presence of hydrocracking catalysts comprising a metal function having hydrogenation/dehydrogenation activity supported on a porous, refractory metal oxide support.
8. A process according to claim 7 in which the first hydrocracking step is carried out in the presence of hydrocracking catalyst comprising a base metal function of Group VI and Group VIII (IUPAC) metals.
9. A process according to claim 7 in which the first hydrocracking step is carried out in the presence of hydrocracking catalyst comprising a sulfided base metal function of Group VI and Group VIII (IUPAC) metals.
10. A process according to claim 7 in which the porous, refractory metal oxide supports of the first and second hydrocracking steps comprise alumina, silica or silica-alumina.
11. A process according to claim 7 in which the first and second hydrocracking steps are carried out in the presence of hydrocracking catalysts comprising a faujasite.
12. A process according to claim 7 in which the first and second hydrocracking steps are carried out in the presence of hydrocracking catalysts comprising zeolite Y or zeolite USY.
13. A process according to claim 1 operated as a continuous process with no intermediate product tankage.
14. A process according to claim 1 operated as a non-blocked continuous process.
15. A process for producing at least two lube boiling range fractions including a light oil lube fraction and a heavy oil lube fraction, which comprises: hydrocracking a hydrocarbon feed in a first hydrocracking step under a first hydrocracking regime to provide a first hydrocrackate with a boiling range suitable for a heavy oil fraction, fractionating the hydrocrackate to separate at least a first portion for a light oil fraction and a second portion for the heavy oil fraction; hydrocracking the portion for the light oil fraction in a second hydrocracking step under a second hydrocracking regime, to form a second light oil hydrocrackate with a boiling range suitable for the light oil fraction, combining the hydrocrackate portion for the heavy oil and the second light oil hydrocrackate to form a combined hydrocrackate, processing the combined hydrocrackate to meet product specifications for the light oil lube fraction and the heavy oil lube fraction and form a combined stream of a finished light oil lube fraction and a finished heavy oil lube fraction, and fractionating the combined stream to separate the finished light oil lube fraction and the finished heavy oil lube fraction; wherein the first hydrocrackate and the combined stream are fractionated to form the finished light oil lube fraction and the finished heavy oil lube fraction in a common divided wall fractionator.
16. A process according to claim 15 in which the first hydrocrackate is separated into the first portion for the light oil fraction and the second portion for the heavy oil fraction in one section of the divided wall fractionator on one side of the divided wall and the combined stream is fractionated on the other side of the divided wall.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
(1) In the accompanying drawings typical applications of the process configurations and process units in highly simplified schematics are shown as follows:
(2)
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DETAILED DESCRIPTION
(7) The term “about” or “approximately” means an acceptable error for a particular value as determined by one of ordinary skill in the art, which depends in part on how the value is measured or determined. All numerical values within the detailed description and the claims herein are modified by “about” or “approximately” the indicated value, and take into account experimental error and variations that would be expected by a person having ordinary skill in the art.
(8) Heavy Oil Feeds
(9) The feeds used in the present process generally comprise distillable feeds boiling above about 250° C. (about 480° F.) and extending into in the gas oil boiling range above about 345° C. (about 650° F.) with end points about 500° C. (about 930° F., possibly as high as about 600° C. (about 1110° F.) or even higher depending on the acceptable levels of high boiling feed components. The feed may be, for example, a wide cut feed extending from the heavy gasoline boiling range up to the distillable limit for the production of neutral (non-residual) lube products; narrower cut feeds are also possible if consistent with the desired lube products. Typical examples of hydrocarbon feed types from refinery operations include light gas oil, heavy gas oil, vacuum gas oil, straight run gas oil and deasphalted oils. The process is also useful for upgrading oil and/or wax produced in a synthetic fuels process such as a Fischer-Tropsch. The feed may have been processed, e.g. by hydrotreating, prior to the present process to reduce or substantially eliminate its heteroatom, metal, asphaltene or aromatic content. Asphaltenes should preferably be held at less than about 500 or 200 ppm, preferably less than about 100 ppm.
(10) An exemplary wide cut feed that may be used in the present process would be a feed as follows:
(11) TABLE-US-00001 TABLE 1 Wide Cut Feed Hydrogen Content wt % 13.5 Molecular Weight /mole 381.6 Carbon Aromaticity wt % 7.1 API Gravity 29.1 Specific Gravity @ 60 F. 0.9 Total Sulfur wt % 0.0052 Total Nitrogen ppm 10.0 Basic Nitrogen ppm 5.2 Total Aromatics, wt % 21.4 Total Paraffins, wt % 22.5 Total Olefins, wt % 0.0 Total Naphthenes, wt % 56.0 Cetane Index D976-80 43.7 Cetane Index D4737 63.2 D2887 IBP deg C. 261.3 D2887 5 wt % deg C. 322.4 D2887 10 wt % deg C. 344.2 D2887 30 wt % deg C. 392.1 D2887 50 wt % deg C. 428.7 D2887 70 wt % deg C. 466.5 D2887 90 wt % deg C. 521.6 D2887 95 wt % deg C. 547.4 D2887 FBP deg C. 606.3
Hydroprocessing Catalysts
(12) The hydroprocessing catalysts used in the present processing units will generally be of the conventional types with a metal function having hydrogenation/dehydrogenation activity supported on a porous, refractory metal oxide support such as alumina, silica, silica-alumina, thoria, titania, zirconia, normally with a binder material such as a clay. The metal function will promote the hydrogenation/dehydrogenation reactions which take place in the process to concert organic heteroatoms to inorganic form, to saturate ring systems and promote crackability in reactions such as hydrogenation, dehydrogenation, hydrodecyclization etc. The typical metal functions are based on transition metals, especially the Group VI and Group VIII (IUPAC) metals with particular examples being W—Mo, W—Ni, Co—Mo, Ni—Mo. Noble metals such as platinum and palladium may also be used in certain applications, especially in hydrodewaxing and hydrofinishing; base metals are normally preferred for hydrotreating and hydrocracking catalysts if only on grounds of cost. Metal oxide catalysts should be sulfided for optimal hydroprocessing activity. If hydrocracking catalysts are used in sweet service as in second stage service (low levels of heteroatom contaminants as with hydroprocessed feeds), the use of noble metal catalysts is an option.
(13) Hydrocracking catalysts will typically include a zeolite, especially a faujasite such as zeolite Y or USY; hydrotreating catalysts used to remove impurities such as organic sulfur and nitrogen species will normally have a lesser degree of cracking activity than the hydrocracking catalysts which are intended to promote a bulk or boiling range conversion to lower boiling species of lower molecular weight; hydrotreating catalysts will often be supported on an amorphous metal oxide support with acidic zeolite functionality. Hydrodewaxing catalysts will normally include a shape-selective zeolite component for removing waxy paraffins either by shape-selective cracking or by isomerization. Zeolites such as mordenite, erionite, and beta have been used with preference given to the synthetic intermediate pore size zeolites such as ZSM-5, ZSM-11, ZSM-23, ZSM-35 and ZSM-48. The ultimate choice of catalyst will be made by the operator given experience with the type of feeds being processed, the target product specifications and yields both for lubes and fuels, and, of course, for the characteristics of the unit.
(14) Plant Configuration
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(16) The heavy oil fraction of the desired boiling range and some specific lube properties is removed from the lower portion of the fractionator by way of line 13 leading to hydrodewaxer 14 which, in turn, passes its total effluent by way of hydrofinisher 15 to final product fractionator 16. A light oil fraction is removed higher in tower 11 at a level appropriate to the boiling range of the intended light oil product, allowing for the changes to take place in the following units. The unfinished light oil product passes by way of line 17 to light oil hydrocracker 18 where its properties, particularly boiling range, are trimmed the desired values. Light ends and recycle hydrogen can be separated prior to the hydrodewaxer if needed. The total liquid effluent from light oil hydrocracker 18 is combined with the liquid effluent from hydrocracker 11 and the combined effluents then pass to hydrodewaxer 14 and hydrofinisher 15 for control of cold flow properties and aromatic content of both light and heavy oil lube fractions. The light oil and heavy oil products are then removed from column 16 as separate fractions of differing boiling ranges; light ends, naphtha, and distillate fractions pass out higher in the column at their respective levels.
(17) The variant shown in
(18) This unit uses a single intermediate/final product fractionator 21 with a divided wall. The hydrocracking section of the unit is designated as Section A and the finishing section as Section B with the dividing wall of the fractionator marking the division line between the two sections. In
(19) The unfinished light oil fraction is withdrawn from tower 21 at approximately the top of the wall and passes to light oil hydrocracker 28 by way of line 27 for the necessary conversion and then from this second hydrocracker to hydrodewaxer 24 and hydrofinisher 25. Cold flow properties of the combined lube fractions are adjusted in hydrodewaxer 24 and aromatics content in hydrofinisher 25 as in
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(23) A wide cut feed from a fractionation column or from a first stage hydroprocessing unit is sent to a divided wall fractionation column to separate the heavy oil from light oil stream. The feed enters the intermediate side of fractionating column 50 in the A Section (left hand on diagram) of the unit and is split into a heavy oil fraction and a light oil fraction. If there is diesel/kerosene/naphtha/light ends (LE) in the wide cut feed, they will be separated out and exit the common section of the column above the top of the dividing wall. The portion of the feed suitable for making the light oil fraction is taken off at a higher level than the heavy oil portion and below the top of dividing wall 51. Assuming that the light oil stream requires the highest severity to match the product specifications (e.g. a demanding VI requirement) and for this reason, this stream will be introduced into the top portion of the hydroprocessing reactor, e.g. at bed 1 (numbering from top to bottom). The heavy oil that requires less VI uplift (lower severity processing) will be introduced in the bottom portion of the reactor (e.g. at the inlet of bed 4 in the illustrated 6-bed reactor); the bed level at which the HO stream will be introduced will depend on the type of feed and product specifications.
(24) Depending on the type of feeds (straight run, cracked stocks) and the targeted product specifications for both lube products, the beds can be loaded with hydrotreating or hydrocracking catalyst or combination of both and conditions in each bed may be varied consistent with unit operating possibilities, e.g. extent to which bed temperature can be varied by interbed quench or by external heating/cooling loops. Optionally, the stream introduced lower in the hydroprocessing reactor, shown as HO in the Figure, can be used to adjust the temperature of the lower beds. As this stream is typically at a higher temperature than the LO stream it will normally introduce heat into the lower beds in the reactor but if further temperature adjustment is required, a heat exchanger may be interposed between A in the fractionator and the hydroprocessing reactor.
(25) The total liquid effluent from reactor 52 is taken to common hydrodewaxer 53 and hydrofinisher 54 and then re-enters the product side of the fractionating column 50 at a level intermediate the heavy and light oil product levels. Light ends and converted fractions pass out at higher levels.
(26) This scheme allows a cost savings in fractionation equipment if a single fractionator with a divided wall replaces one that would otherwise be installed after a hydrotreating step and before the hydroprocessing reactor and another that fractionates the final products after the hydrofinishing reactor. This configuration also allows the unit to maximize the HO and LO yields similar to or better than commercial units operating a blocked operation mode.
(27) This configuration allows maximum flexibility for production of different type of lube products using only one hydroprocessing reactor. It will allow tuning the hydroprocessing reactor operation for different type of products by changing the severity of the operation: changing bed temperature and residence time (LHSV—bed feed introduction). Since the HO feed streams have high VI most of the time, it possible that only hydrotreating catalyst with minimum hydrocracking catalyst may be needed to meet the HO lube product quality targets (e.g., API Group II/Group III). The reactor configuration and the right operating conditions will allow the production of the highest HO lube yield while avoiding overcracking of the feed. By not overcracking, the heavy feed preserves HO yield and reduces the amount of cracked oil that can degrade the VI or saturates content of the LO. For example, this is the approximate distribution of aromatics in a commercial hydroprocessed heavy neutral lube product, after distilling into 5 approximately equal fractions according to boiling point:
(28) TABLE-US-00002 0-20% 20-40% 40-60% 60-80% 80-100% Approx wt % 5.2 4.9 4.3 3.8 3.3 aromatics
This configuration also represents the lowest capital investment since it utilizes only one hydroprocessing reactor and optionally only one fractionator.
(29) The improvement in product yields of which the configuration of
(30) TABLE-US-00003 TABLE 2 Configurations Cnvntl. FIG. 2. YIELDS Units Run #1 Run #2 H2 Cons scm/m3 liq feed 67.9 60.9 Delta H2 Consumption scm/m3 liq feed 7.0 Hydrogen Wt % produced 0.7 0.6 Water Wt % liq feed 0.0 0.0 Hydrogen Sulfide Wt % produced 0.0 0.0 Ammonia Wt % produced 0.0 0.0 Methane Wt % produced 0.1 0.1 Ethane Wt % produced 0.0 0.0 Propane Wt % produced 0.1 0.1 i-C4 Wt % liq feed 0.2 0.2 n-C4 Wt % liq feed 0.2 0.2 Light Naphtha Wt % liq feed 6.7 5.6 jet Wt % liq feed 25.9 24.2 diesel Wt % liq feed 28.1 28.1 Light Oil Wt % liq feed 24.6 25.2 Heavy Oil Wt % liq feed 14.8 17.0 Conv., 650 F.+, wt % Wt % conv 25.4 21.7 Conv., 700 F.+, wt % Wt % conv 28.3 23.7
(31) Further optimization with the type of catalyst and volume of catalyst in both reactors for the
(32) In a first embodiment at least two lube boiling range fractions including a light oil lube fraction and a heavy oil lube fraction, are produced by hydrocracking a hydrocarbon feed in a first hydrocracking step under a first hydrocracking regime to provide a hydrocrackate with a boiling range suitable for the heavy oil fraction, the hydrocrackate is fractionated to separate at least a first portion for the light oil fraction and a second portion for the heavy oil fraction; and the light oil fraction is then processed in a second hydrocracking step under a second hydrocracking regime to form a second light oil hydrocrackate; the hydrocrackates are then combined and processed to meet product specifications for the light oil lube fraction and the heavy oil lube fraction; finally, the combined stream is fractionated to separate the finished light oil lube fraction and the finished heavy oil lube fraction.
(33) In a second embodiment, the hydrocracking conditions of the first hydrocracking step provide a hydrocrackate with lube quality specifications required for the finished heavy oil lube fraction.
(34) In a third embodiment, the hydrocracking conditions of the first hydrocracking step provide a hydrocrackate in the maximum yield meeting the lube quality specifications required for the finished heavy oil lube fraction.
(35) In a fourth embodiment, the hydrocracking conditions of the second hydrocracking step provide a hydrocrackate with lube quality specifications required for the finished light oil lube fraction.
(36) In a fifth embodiment, the hydrocracking conditions of the second hydrocracking step provide a hydrocrackate in the maximum yield meeting the lube quality specifications required for the finished light oil lube fraction.
(37) In a sixth embodiment the first and second hydrocracking regimes are carried out respectively in a two hydrocrackers.
(38) In a seventh embodiment the first hydrocracking regime provides a hydrocrackate with a boiling range suitable for both lube oil fractions.
(39) In a eighth embodiment the two hydrocracking steps are carried out in a common hydroprocessing reactor containing a plurality of beds in sequence with the light oil fraction and the heavy oil fraction being introduced at different points in the sequence.
(40) In a ninth embodiment the light oil fraction is introduced into the bed sequence of a multiple bed common hydroprocessing reactor before the second portion for the heavy oil fraction.
(41) In an tenth embodiment the hydrocracking steps are carried out in the presence of hydrocracking catalysts comprising a metal function having hydrogenation/dehydrogenation activity supported on a porous, refractory metal oxide support.
(42) In a eleventh embodiment the first hydrocracking step is carried out under sour service conditions in the presence of a hydrocracking catalyst comprising a base metal function of Group VI and Group VIII (IUPAC) metals.
(43) In a twelfth embodiment the first hydrocracking step is carried out in the presence of a hydrocracking catalyst comprising a sulfided base metal function of Group VI and Group VIII (IUPAC) metals.
(44) In an thirteenth embodiment the porous, refractory metal oxide supports of the first and second hydrocracking catalysts comprise alumina, silica or silica-alumina.
(45) In a fourteenth embodiment the first and second hydrocracking steps are carried out in the presence of hydrocracking catalysts comprising a faujasite.
(46) In a fifteenth embodiment the first and second hydrocracking steps are carried out in the presence of hydrocracking catalysts comprising zeolite Y or zeolite USY.
(47) In a sixteenth embodiment the process is operated as a continuous process with no intermediate product tankage.
(48) In a seventeenth embodiment the process is operated as a non-blocked continuous process.
(49) In an eighteenth embodiment the first hydrocrackate and the combined stream are fractionated to form the finished light oil lube fraction and the finished heavy oil lube fraction in a common divided wall fractionator.
(50) In a nineteenth embodiment the first hydrocrackate is separated into the first portion for the light oil fraction and the second portion for the heavy oil fraction in one section of the divided wall fractionator on one side of the divided wall and the combined stream is fractionated on the other side of the divided wall.