US20040108245A1 - Lube hydroisomerization system - Google Patents

Lube hydroisomerization system Download PDF

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US20040108245A1
US20040108245A1 US10/678,434 US67843403A US2004108245A1 US 20040108245 A1 US20040108245 A1 US 20040108245A1 US 67843403 A US67843403 A US 67843403A US 2004108245 A1 US2004108245 A1 US 2004108245A1
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catalyst
pt
wax
beta
lube
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Zhaozhong Jiang
Randall Partridge
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ExxonMobil Research and Engineering Co
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ExxonMobil Research and Engineering Co
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Assigned to EXXONMOBIL RESEARCH & ENGINEERING CO. reassignment EXXONMOBIL RESEARCH & ENGINEERING CO. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: PARTRIDGE, RANDALL D., JIANG, ZHAOZHONG
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/58Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
    • C10G45/60Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
    • C10G45/62Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used containing platinum group metals or compounds thereof
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/10Lubricating oil

Abstract

The present invention relates to a process for converting wax with a heavy component to high quality lube basestocks using a unidimensional intermediate pore molecular sieve with near circular pore structures having an average diameter of 0.50 nm to 0.65 nm wherein the difference between the maximum diameter and the minimum is ≦0.05 nm followed by a molecular sieve Zeolite Beta catalyst. Both catalysts comprise one or more Group VIII metals. For example, a cascaded two-bed catalyst system consisting of a first bed Pt/ZSM-48 catalyst followed by a second bed Pt/Beta catalyst improves processing of heavy lubes.

Description

    CROSS-REFERENCE TO RELATED APPLICATION
  • This application claims benefit of U.S. Provisional Patent Application Serial No. 60/416,949 filed Oct. 8, 2002.[0001]
  • FIELD OF THE INVENTION
  • The present invention relates to a process for converting waxy feeds to lube basestocks with a reduced viscosity. [0002]
  • BACKGROUND OF THE INVENTION
  • There is significant economic incentive to convert wax to high quality lube basestocks, especially base oils with properties and performance comparable to, or better than, those of polyalphaolefins (PAO). The upgrading of wax greatly relies on advanced wax isomerization technology that selectively transforms linear paraffins to multi-branched isoparaffins. [0003]
  • Processes for converting wax to paraffinic lube basestocks are known. A typical process is a two-stage process that hydroisomerizes wax to a waxy isoparaffins mixture in the first step, followed by either solvent dewaxing or catalytic dewaxing the waxy isoparaffins mixture in the second step to remove residual wax and achieve a target lube pour point. [0004]
  • The hydroisomerization catalysts disclosed previously, such as Pt supported on amorphous aluminosilicate or Zeolite Beta (Beta), normally possess large pores that allow the formation of branch structures during paraffin isomerization. Examples of other large pore molecular sieves include ZSM-3, ZSM-12, ZSM-20, MCM-37, MCM-68, ECR-5, SAPO-5, SAPO-37 and USY. However, these large pore catalysts are not selective enough to preferentially convert normal and lightly branched paraffin waxes in the presence of multi-branched isoparaffin molecules. As a result, the isoparaffin products derived from wax often contain residual wax that needs to be dewaxed in order to meet target lube cloud points or pour points. The cloud point of a lube is the temperature at which the first trace of wax starts to separate, causing the lube to become turbid or cloudy (e.g., ASTM D2500). The pour point of a lube is the temperature at which lube and wax crystallize together as a whole and will not flow when poured (e.g., ASTM D97). Dewaxing can be achieved by additionally using either a solvent dewaxing process or a catalytic dewaxing process. [0005]
  • Most selective dewaxing catalysts used in a catalytic dewaxing process have relatively small pore structures and catalyze lube pour point reduction by selectively cracking normal and lightly branched paraffin waxes. Such dewaxing catalysts usually have low paraffin isomerization selectivity. [0006]
  • Few catalysts have been reported to be efficient in catalyzing both hydroisomerization and dewaxing of paraffin wax to low pour point lubes. Also, such catalysts have difficulty to convert feeds with a high molecular weight component, as a result of which the lube products often appear hazy (or cloudy). [0007]
  • There remains a need therefore to achieve conversion of high molecular weight wax and a low enough pour point without sacrificing lube isomerization dewaxing selectivity. [0008]
  • SUMMARY OF THE INVENTION
  • The present invention relates to a process for converting wax to high quality lube basestocks by contacting the wax with a unidimensional molecular sieve catalyst with a near circular pore structure having an average diameter of 0.50 nm to 0.65 nm wherein the difference between the maximum diameter and the minimum is ≦0.05 nm (e.g., ZSM-48) followed by a second molecular sieve catalyst (e.g., Zeolite Beta). Both catalysts comprise one or more Group VIII metals (i.e., Fe, Ru, Os, Co, Rh, Ir, Pd, Pt, Ni).[0009]
  • BRIEF DESCRIPTION OF THE FIGURES
  • FIG. 1 is a plot of lube yield versus lube pour point for isomerization of C80 wax over Pt/ZSM-48 followed by Pt/Beta, and stand-alone Pt/ZSM-48 catalyst systems. [0010]
  • FIG. 2 is a plot of lube viscosity versus lube pour point for isomerization of C80 wax over Pt/ZSM-48 followed by Pt/Beta, and stand-alone Pt/ZSM-48 catalyst systems. [0011]
  • FIG. 3 is a plot of viscosity index (VI) versus lube pour point for isomerization of C80 wax over Pt/ZSM-48 followed by Pt/Beta, and stand-alone Pt/ZSM-48 catalyst systems. [0012]
  • FIG. 4 is a plot of light gas yield versus lube pour point for isomerization of C80 wax over Pt/ZSM-48 followed by Pt/Beta, and stand-alone Pt/ZSM-48 catalyst systems. [0013]
  • FIG. 5 is a plot of naphtha yield versus lube pour point for isomerization of C80 wax over Pt/ZSM-48 followed by Pt/Beta, and stand-alone Pt/ZSM-48 catalyst systems. [0014]
  • FIG. 6 is a plot of diesel yield versus lube pour point for isomerization of C80 wax over Pt/ZSM-48 followed by Pt/Beta, and stand-alone Pt/ZSM-48 catalyst systems.[0015]
  • DETAILED DESCRIPTION
  • The invention provides high isomerization and dewaxing selectivity of a wax over an unidimensional catalyst with a near circular pore structure having an average pore diameter of 0.50-0.65 nm (5.0-6.5 angstroms) wherein the maximum diameter-minimum diameter ≦0.05 nm (0.5 angstroms), followed by a molecular sieve catalyst to form a lubricant. Group VIII metals on the two catalysts are preferred and platinum is the most preferred. [0016]
  • The invention improves lube basestock products and their properties (e.g., pour point, cloud point). This method effectively reduces average lube molecular weight and potentially reduces lube product cloud point without sacrificing lube yield. This process allows improved use of the heavy end of lubes and is especially suited for waxes with 1,000° F.+ fractions and preferably 1,100° F.+ fractions. These fractions may comprise the higher molecular weight or boiling point tail of the feeds. It would be difficult to create enough branches with minimal cracking for very large molecular weight feeds if only one of the above catalysts was used. This invention is preferably used for processing heavy lube or lubes with a heavy component (e.g., with >5 wt % heavy raffinate) where the Beta catalyst selectively cracks the heavy end. This invention can give a lighter lube with yields similar to those obtained over ZSM-48 alone. [0017]
  • Preferably, wax feed is first passed over a ZSM-48 catalyst. The resulting intermediate product is then passed over a single Zeolite Beta catalyst to form the final lube. These first and second stages can be separated or preferably are integrated process steps (e.g., cascaded). [0018]
  • The unidimensional molecular sieve catalyst with near-circular pore structures does most of the dewaxing. The pores are smaller than in large pore molecular sieves thereby excluding bulkier (e.g., highly branched) molecules. Unidimensional means that the pores are essentially parallel to each other. [0019]
  • The pores of the catalyst have an average diameter of 0.50 nm to 0.65 nm wherein the difference between a minimum diameter and a maximum diameter is ≦0.05 nm. The pores may not always have a perfect circular or elliptical cross-section. The minimum diameter and maximum diameter are generally only measurements of an ellipse of a cross-sectional area equal to the cross-sectional area of an average pore. The pores can alternatively be defined by finding the center of the pore cross-section and using half of the minimum diameter and half of the maximum diameter to sweep an average cross-sectional pore shape from the center. [0020]
  • The preferred unidimensional molecular sieve catalyst is an intermediate pore molecular sieve catalyst of which the preferred version is ZSM-48. U.S. Pat. No. 5,075,269 describes the procedures for making ZSM-48 and is incorporated by reference herein. ZSM-48 is roughly 65% zeolite crystal and 35% alumina. Of the crystals, at least 90%, preferably at least 95%, and most preferably 98-99% are ideal crystals. The ZSM-48 is preferably in the protonated form though some sodium is acceptable. ZSM-48 is more robust than other catalysts with similar functions and helps to protect the second catalyst (e.g., Zeolite Beta). [0021]
  • In the first stage of the process, the unidimensional intermediate pore molecular sieve catalyst (e.g., Pt/ZSM-48) is preferably kept at 500-800° F. (260-427° C.), more preferably at 600-700° F. (316-371° C.), and most preferably at 630-660° F. (332-349° C.). ZSM-48 catalysts used in the invention preferably have an Alpha value of about 10 to about 50 prior to the Group VIII metal loading. [0022]
  • Zeolite Beta catalysts are 12 ring acidic silica/alumina zeolites with or without boron (replacing some of the aluminum atoms). Zeolite Y (USY), though less preferred than Beta, is also contemplated in the scope of the invention. Pre-sulfided Zeolite Beta is preferred when some residual sulfur in the product is acceptable. [0023]
  • Zeolite Betas used in the invention preferably have an Alpha value below 15, more preferably below 10, at least prior to metal loading. Alpha is an acidity metric that is an approximate indication of the catalytic cracking activity of the catalyst compared to a standard catalyst. Alpha is a relative rate constant (rate of normal hexane conversion per volume of catalyst per unit time). Alpha is based on the activity of the highly active silica-alumina cracking catalyst taken as an Alpha of 1 in U.S. Pat. No. 3,354,078 (incorporated by reference) and measured at 538° C. as described in the Journal of Catalysis, vol. 4, p. 527 (1965); vol. 6, p. 278 (1966); and vol. 61, p. 395 (1980). Feeds with minimal nitrogen content will require low Alpha value of this catalyst. In comparison, catalysts with high Alpha values are used for less selective cracking. Alpha values may be reduced by steaming. [0024]
  • The Beta catalyst (e.g., Pt/Beta), when contacting the intermediate product, is most preferably kept at temperatures of 400-700° F. (204-371° C.), more preferably at 500-650° F. (260-343° C.), and most preferably at 520-580° F. (271-304° C.). [0025]
  • The temperature of each catalyst is preferably controlled independently. Temperature choice partly depends on the feed liquid hourly space velocity of which 0.1-20 h[0026] −1 is preferred, 0.5-5 h−1 is more preferred, and 0.5-2 h−1 is most preferred.
  • The contact time for both catalysts is preferably similar to each other. It is understood that the space velocity can be different. The pressure for both catalysts is preferably similar to each other. Hydrogen co-feed flow rate is 100-10,000 scf/bbl (17.8-1,780 n.L.L[0027] −1), more preferably 1,000-6,000 scf/bbl (178-1,068 n.L.L−1), and most preferably 1,500-3,000 scf/bbl (267-534 n.L.L−1).
  • Each catalyst comprises 0.01-5 wt % of at least one Group VIII metal (i.e., Fe, Ru, Os, Co, Rh, Ir, Pd, Pt, Ni). Platinum and palladium are most preferred. Platinum or palladium blended with each other or other group VIII metals follow in preference. Nickel may also be blended with group VIII precious metals and is included in the scope of the invention whenever group VIII blends, alloys, or mixtures are mentioned. Platinum is the most preferred metal. Preferred metal loading on both catalysts are 0.1-1 wt % with approximately 0.6 wt % most preferred. [0028]
  • The feed preferably is a wax with a melting point over 50° C., less than 7,000 ppm sulfur, and less than 50 ppm nitrogen. The nitrogen is more preferably less than 10 ppm nitrogen if hydrogen pressure is below 500 psig (34 atm). For example, a heavy raffinate can be blended with a Fischer-Tropsch wax or similar clean waxy feed (e.g., to lower sulfur and/or nitrogen levels). [0029]
  • The feed is converted by the first catalyst to form an intermediate product which is then preferably passed directly from the first catalyst to the second catalyst. In a preferred embodiment of the invention, a cascaded two-bed catalyst system consisting of a first bed catalyst followed by a second bed catalyst allows a highly selective process for wax isomerization and lube hydrodewaxing with minimal gas formation. In cascading, the intermediate product preferably directly passes from the first bed to the second bed without inter-stage removal of light products. Optionally, light byproducts (e.g., methane, ethane) can be removed between the first and second catalysts. [0030]
  • More branching in feeds facilitates the present invention and improves final lube yield. U.S. Pat. No. 6,090,989 describes typical branching indices and is incorporated by reference. The feed is preferably mixed with hydrogen and preheated before contacting it with the first catalyst. Preferably, at least 95% of the wax is in liquid form before contacting it with the first catalyst. [0031]
  • The preferred measurements, as taught by the specification, are described in this paragraph. Where there are two values, the value in parenthesis is approximate metric conversion of the first value. The weight percent of paraffins may be measured by high-resolution [0032] 1H-NMR, for example, by the method described in ASTM standard D5292, in combination with GC-MS. This approach may also be used to determine the weight percentage of unsaturates, alcohols, oxygenates, and other organic components. The iso- to normal-paraffin ratio may be measured by performing gas chromatography (GC) or GC-MS in combination with 13C-NMR. Sulfur may be measured by XRF (X-Ray Fluorescence), as described, for example, in ASTM standard D2622. Nitrogen may be measured by syringe/inlet oxidative combustion with chemiluminescence detection, for example, by the method described in ASTM standard D4629. Aromatics may be measured as described below. As taught by the specification, olefins may be measured by using a Bromine index determined by coulimetric analysis, for example, by using ASTM standard D2710. The weight percent of total oxygen may be measured by neutron activation in combination with high-resolution 1H-NMR. If necessary, the total oxygen content may be placed on a water-free basis by measuring water content. For samples having a water content known to be less than about 200 ppm by weight, one may use known derivitization methods (e.g., by using calcium carbide to form acetylene) followed by GC-MS. For samples having a water content known to be greater than about 200 ppm by weight, one may use the Karl-Fischer method, for example, by the method described in ASTM standard D4928. The total alcohol content may be determined by high-resolution 1H-NMR, and the percentage present primarily as C12-C24 primary alcohols may be determined by GC-MS. Cetane number may be determined by using, for example, ASTM standard D613. The level of aromatics may be determined by using high-resolution 1H-NMR, for example, by using ASTM standard D5292. Dioxygenates are measured by using infrared (IR) absorbance spectroscopy. Branching characteristics of iso-paraffins may be measured by a combination of high-resolution 13C-NMR and GC with high-resolution MS.
  • Experimental
  • A cascaded two-bed catalyst system consisting of a first stage Pt/ZSM-48 catalyst immediately followed by a second stage of Pt/Beta catalyst is shown to be highly active and selective for hydroisomerization and dewaxing of waxes with high molecular weight components. [0033]
  • Example operating conditions, material balance data, lube yields and properties are summarized in Table 1. TBP x% indicates temperature below which x wt % of hydrocarbon samples boils. Time on stream (TOS) is the time during which the feed contacts the catalyst. IBP is initial boiling point. TBP is terminal boiling point. The best S.I. equivalent of standard cubic feed of hydrogen per barrel of feed (SCF/bbl) is normal liters of hydrogen gas per liter of feed (n.1.1[0034] −1. or n.L.L−1 or n.L (gas)/L (feed)). LHSV is defined as liquid hourly space velocity. WHSV is defined as weight hourly space velocity. TABLE 1 Hydroisomerization of C80 Wax Catalyzed by a Cascaded Pt/ZSM-48 Followed by Pt/Beta (1.0 h−1 LHSV for Each Catalyst) Run Number, 401- 3-3 3-11 3-16 3-20 3-22 3-24 Time on Stream, Days 3.6 15.1 21.6 26.5 28.6 31.1 ZSM-48 Temperature, ° F. 660 660 640 655 645 640 (ZSM-48 Temperature, ° C.) approximate 349 349 338 346 341 338 Beta Temperature, ° F. 560 560 540 560 560 560 (Beta Temperature, ° C.) approximate 293 293 282 293 293 293 Pressure, psig 1000 1000 1000 1000 1000 1000 (Pressure, atm) approximate 68 68 68 68 68 68 H2 Cofeeding Rate, scf/bbl 5786 6150 5575 5528 5607 5619 (H2 Cofeeding Rate, n · L · L−1) approximate 1030 1095 992 984 5607 1000 700° F.+ (371° C.) Conversion, wt % 83.5 79.4 34.6 60.7 47.7 40.4 H2 Consumption, scf/bbl 499 516 205 377 270 225 (H2 Consumption, n · L · L−1) approximate 89 92 36 67 48 40 Product Yield, wt % on Feed C1-C4 Gas 4.0 6.2 3.2 5.7 3.4 2.8 C5-330° F. (C5-166° C.) Naphtha 33.4 31.2 9.6 18.2 13.2 11.4 330-700° F. (166-371° C.) Diesel 47.0 42.9 22.1 37.5 31.6 26.6 700° F.+ (371° C.+) Lube 16.5 20.6 65.4 39.3 52.3 59.6 Total Hydrocarbon 100.9 101.0 100.4 100.7 100.5 100.4 700° F.+ (371° C.+) Lube Properties Feed KV @ 40° C., cSt 34.7 24.8 34.0 28.1 28.8 28.3 KV @ 100° C., cSt  9.4 6.31 5.06 6.91 5.77 5.98 6.00 Viscosity Index 133.5 136.0 168.7 153.4 159.8 165.2 Pour Point, ° C. 82 −60 −54 0 −33 −21 −9 Cloud Point, ° C. −60 −54 13 0 −10 4 TBP 5%, ° F. 754 702 783 723 719 716 (TBP 5%, ° C.) approximate 401 372 417 384 382 380 TBP 50%, ° F. 875 840 922 877 879 895 (TBP 50%, ° C.) approximate 468 449 494 469 471 479 TBP 95%, ° F. 1004 1006 1062 1030 1019 1028 (TBP 95%, ° C.) approximate 540 541 572 554 548 553 MB Closure, wt % 97.6 95.6 98.2 98.5 98.0 98.1
  • To obtain desirable wax isomerization results, a mild (e.g., 500-630° F. (260-332° C.)) Pt/Beta temperature should be employed during lube hydroprocessing. The mild Pt/Beta temperature should be employed with varying Pt/ZSM-48 temperature to achieve a target lube pour point. To achieve maximal lube yield, low operating pressure (<2,000 psi (272 atm) hydrogen pressure) should be used. [0035]
  • Stand-alone Pt/ZSM-48 was also evaluated for isomerizing and dewaxing C80 wax to 700° F.+ (371° C.+) lube basestocks (Tables 2). Comparison of lube yields for the two catalyst systems is illustrated in FIG. 1. FIG. 1 shows that the cascaded Pt/ZSM-48 followed by Pt/Beta gave essentially identical lube yields compared to Pt/ZSM-48 alone. The addition of Pt/Beta had minimal effects on the range of Pt/ZSM-48 operating temperature (Tables 1 and 2). [0036] TABLE 2 Hydroisomerization of C80 Wax Catalyzed by Pt/ZSM-48 Run Number, 401- 3-27 3-28 3-29 3-30 3-31 Time on Stream, Days 35.6 37.0 38.0 39.0 40.9 Temperature, ° F. 665 660 655 650 645 Temperature, ° C. approximate 352 349 352 343 341 Pressure, psig 1000 1000 1000 1000 1000 (Pressure, atm) approximate 68 68 68 68 68 LHSV, hr−1 1.0 1.0 1.0 1.0 1.0 WHSV, hr−1 1.4 1.5 1.5 1.4 1.4 H2 Cofeeding Rate, scf/bbl 5656 5643 5603 5674 5657 (H2 Cofeeding Rate, n · L · L−1) approximate 1007 1004 997 1010 1007 700° F.+ (371° C.+) Conversion, wt % 78.0 70.6 60.0 49.9 44.2 H2 Consumption, scf/bbl 544 473 377 306 261 (H2 Consumption, n · L · L−1) approximate 97 84 67 54 46 Product Yield, wt % on Feed C1-C4 Gas 8.3 6.8 5.4 4.4 3.5 C5-330° F. (C5-166° C.) Naphtha 30.0 26.1 19.6 15.6 13.7 330-700° F. (166-371° C.) Diesel 40.8 38.6 35.7 30.4 27.5 700° F.+ (371° C.+) Lube 22.0 29.4 40.0 50.1 55.8 Total Hydrocarbon 101.0 100.9 100.7 100.6 100.5 700° F.+ (371° C.+) Lube Properties Feed KV @ 40° C., cSt 14.8 34.8 31.2 32.9 34.0 KV @ 100° C., cSt  9.4 3.65 6.59 6.29 6.66 6.90 Viscosity Index 135.5 147.4 156.9 163.8 168.6 Pour Point, ° C. 82 −54 −48 −33 −24 −12 TBP 5%, ° F. 570 778 753 766 770 (TBP 5%, ° C.) approximate 299 414 400 407 410 TBP 50%, ° F. 783 899 906 918 918 (TBP 50%, ° C.) approximate 417 482 485 492 492 TBP 95%, ° F. 998 997 1007 1014 1057 (TBP 95%, ° C.) approximate 537 536 542 546 569 MB Closure, wt % 99.6 98.8 98.8 97.9 97.1
  • The viscosity and viscosity index of the nominal 700° F.+ (371° C.+) C80 wax isomerates vs. hydroprocessing severity are plotted in FIGS. 2 and 3, respectively. The two sets of data compared in the two diagrams correspond to the wax isomerates prepared using Pt/ZSM-48 followed by Pt/Beta, and stand-alone Pt/ZSM-48. [0037]
  • As shown in FIG. 2, the Pt/ZSM-48-Pt/Beta isomerates had significantly lower viscosities presumably due to the relatively high cracking activity of Pt/Beta catalyst towards multi-branched isoparaffins. Thus, this dual catalysts system provides an effective method for reducing average molecular weight of a wax feed to produce lower viscosity lube stocks without sacrificing lube yield during wax hydroisomerization process. [0038]
  • FIG. 3 shows high viscosity indices observed for the Pt/ZSM-48-Pt/Beta wax isomerates, although they are slightly lower than those of Pt/ZSM-48 isomerates. For products of the invention, a viscosity index of at least 150 at a −20° C. lube pour point and a viscosity index of at least 130 at a pour point of no more than −50° C. is preferred. [0039]
  • The spread between the lube cloud and pour points for Pt/ZSM-48-Pt/Beta is mostly less than 15° C. (Table 1). In general, the spread between the lube cloud and pour points narrows with decreasing pour point. [0040]
  • The overall light byproduct selectivity for the two catalyst systems is comparable (FIGS. [0041] 4-6). As expected, the yields of gases, naphtha, and diesel increase for both systems with increasing process severity (decreasing lube pour point) that promotes hydrocracking.
  • The following examples will serve to illustrate the invention. [0042]
  • EXAMPLE 1
  • Feedstock. The hydrotreated SASOL™ PARAFLINT™ C80 wax (C80) feed was obtained from Moore and Munger, Inc., (Shelton, Conn.) and used as received without additional pretreatment. The C80 wax was a mixture of predominantly linear paraffins with very low content of olefins and oxygenates. SASOL™ has been marketing three commercial grades of waxes: PARAFLINT™ H1, a 700° F.+ (371° C.+) full range wax; PARAFLINT™ C80 and C105, 700-1100° F. (371-593° C.) and 1100° F.+ (593° C.+) distillate fractions, respectively. The molecular weight distribution (in terms of boiling point) of the waxes is illustrated briefly in Table 3. [0043] TABLE 3 Molecular Weight Distribution of Waxes in Examples Wax Feed H1 C80 C105 Pour Point, ° C. 99 82 106 IBP-700° F. (<C24), wt % 0 3 0 700-1100° F. (C24-C60), wt % 44 89 20 1100° F. + (>C60), wt % 56 8 80
  • EXAMPLE 2
  • Preparation of Pt/Beta Catalyst. Pt/Beta catalyst was prepared by extruding a water-containing mull mix or paste containing 65 parts of Zeolite Beta with 35 parts of alumina (dry basis). After drying, the Zeolite Beta containing catalyst was calcined under nitrogen at 900° F. (482° C.) and exchanged at ambient temperature with a sufficient quantity of ammonium nitrate to remove residual sodium in the zeolite channels. The extrudate was then washed with de-ionized water and calcined in air at 1000° F. (538° C.). After air calcination, the 65% Zeolite Beta/35% Alumina extrudate was steamed at 1020° F. (549° C.) to reduce the Alpha value of the calcined catalyst to less than 10. The steamed, 65% low acidity Beta/35% Alumina catalyst was ion exchanged with a tetraammine platinum chloride solution under ion exchange conditions to uniformly produce a catalyst containing 0.6% Pt. After washing with de-ionized water to remove residual chlorides, the catalyst was dried at 250° F. (121° C.) followed by final air calcination at 680° F. (360° C.). [0044]
  • EXAMPLE 3
  • Preparation of Pt/ZSM-48 Catalyst. Pt/ZSM-48 catalyst was prepared by extruding a water-containing mull mix or paste containing 65 parts of ZSM-48 with 35 parts of alumina (dry basis). After drying, the ZSM-48 containing catalyst was calcined under nitrogen at 900° F. (482° C.) and exchanged at ambient temperature with a sufficient quantity of ammonium nitrate to remove residual sodium in the zeolite channels. The extrudate was then washed with deionized water and calcined in air at 1000° F. (538° C.). After air calcination, the 65% ZSM-48/35% Alumina catalyst was impregnated with a tetraammine platinum nitrate solution under incipient wetness conditions to uniformly produce a catalyst containing 0.6% Pt. Finally, the catalyst was dried at 250° F. (121° C.) followed by air calcination at 680° F. (360° C.). [0045]
  • EXAMPLE 4
  • Wax Hydroprocessing. The wax hydroisomerization experiments were performed using a micro-unit equipped with two three-zone furnaces and two down-flow trickle-bed tubular reactors (½″ ID) in cascade (with option to bypass the second reactor). The unit was carefully heat-traced to avoid freezing of the high melting point C80 wax. To reduce feed bypassing and lower zeolite pore diffusion resistance, the catalysts extrudates were crushed and sized to 60-80 mesh. The reactors 1 and 2 were then loaded with 15 cc of the 60-80 mesh Pt/ZSM-48 catalyst and the 60-80 mesh Pt/Beta catalyst, respectively. 5 cc of 80-120 mesh sand was also added to both catalyst beds during catalyst loading to fill the void spaces. After pressure testing of the unit, the catalysts were dried and reduced at 400° F. (204° C.) for one hour under 1 atmosphere (atm), 255 cc/min hydrogen flow. At the end of this period, the flow of pure hydrogen was stopped and flow of H[0046] 2S (2% in hydrogen) was initiated at 100 cc/min. After H2S breakthrough, the reactors 1 and 2 were gradually heated to 700° F. (371° C.) and maintained at 700° F. (371° C.) for 1 h (hour). After the completion of catalyst pre-sulfiding, the gas flow was switched back to pure hydrogen at 255 cc/min rate, and the two reactors were cooled down.
  • Hydroisomerization of the C80 wax over a cascaded Pt/ZSM-48 followed by Pt/Beta was conducted at 1.0 h[0047] −1 LHSV for each catalyst and 1000 psig (68 atm) with 5500 scf/bbl (979 n.L.L−1) hydrogen circulation rate. The wax isomerization experiments were started first by saturating the catalyst beds with the feed at 400° F. (204° C.) then heating the reactors to the initial operating temperatures. Material balances were carried out overnight for 16-24 h. Reactor temperatures were then gradually changed to vary pour point.
  • Performance of stand-alone Pt/ZSM-48 was evaluated by cooling and bypassing the Pt/Beta catalyst in the second reactor. The experiments were conducted under identical process conditions (1.0 LHSV, 1000 psig (68 atm), 5500 scf/bbl (979 n.L.L[0048] −1) H2) and according to similar procedures used for testing the cascade Pt/ZSM-48 and Pt/Beta combination.
  • EXAMPLE 5
  • Product Separation and Analysis. Off-gas samples were analyzed by GC using a 60m DB-1 (0.25 mm ID) capillary column with FID detection. Total liquid products (TLP's) were weighed and analyzed by simulated distillation (Simdis, such as D2887) using high temperature GC. TLP's were distilled into IBP-330° F. (IBP-166° C.) naphtha, 330-700° F. (166-371° C.) distillate, and 700° F.+ (371° C.+) lube fractions. The 700° F.+ (371° C.+) lube fractions were again analyzed by Simdis to ensure accuracy of the actual distillation operations. The pour point and cloud point of 700° F.+ (371° C.+) lubes were measured by D97 and D2500 methods, and their viscosities were determined at both 40° C. and 100° C. according to D445-3 and D445-5 methods, respectively. [0049]

Claims (13)

1. A process for converting a wax, having hydrocarbons primarily within C24-C110 with essentially no sulfur or nitrogen content, to an isoparaffinic lube basestock, comprising:
first, passing the wax and a hydrogen co-feed over a unidimensional molecular sieve catalyst comprising a unidimensional intermediate pore molecular sieve with near circular pore structures having an average diameter of 0.50 nm to 0.65 nm wherein the difference between a maximum diameter and a minimum diameter is ≦0.05 nm and one or more Group VIII metals to form an intermediate product; and
second, passing the intermediate product over a Beta catalyst comprising a Zeolite Beta and one or more Group VIII metals; to form the isoparaffinic lube basestock.
2. A process according to claim 1, wherein
the wax comprises about 5 wt % to about 80 wt % of a 1,100° F.+ fraction, based on the total weight of the wax;
the unidimensional molecular sieve catalyst is kept at a temperature of 500 to 800° F. (260 to 427° C.);
the Beta catalyst is kept at a temperature of 400 to 700° F. (204 to 371° C.);
the wax is passed over the unidimensional molecular sieve catalyst at a feed liquid hourly space velocity of 0.1 to 10 h−1;
the intermediate product is passed over the Beta catalyst at a feed liquid hourly space velocity of 0.1 to 10 h−1; and
the process further comprises less than about 1,500 psig (102 atm) hydrogen, wherein the hydrogen is circulated at 100 to 10,000 scf/bbl (18 to 1780 n.L.L−1).
3. A process according to claim 2, wherein
the unidimensional molecular sieve catalyst is kept at a temperature of 600-700° F. (316 to 371° C.);
the Beta catalyst is kept at a temperature of 500-600° F. (260 to 316° C.);
the wax is passed over the unidimensional molecular sieve catalyst at a feed liquid hourly space velocity of 0.5 to 2 h−1;
the intermediate product is passed over the Beta catalyst at a feed liquid hourly space velocity of 0.5 to 2 h−1; and
the process further comprises less than about 1,500 psig (102 atm) hydrogen, wherein the hydrogen is circulated at 1,000 to 6,000 scf/bbl (178 to 1068 n.L.L−1).
4. A process according to claim 3, wherein the Group VIII metal on said catalysts is at least one member selected from the group consisting of Pt and Pd; and the unidimensional molecular sieve catalyst is ZSM-48 with a Alpha value of 10 to 50 prior to the metal incorporation.
5. A process according to claim 3, wherein
the wax has a 1,000° F.+ high temperature tail;
the ZSM-48 is loaded with about 0.5 wt % to about 1 wt % of the Group VIII metal, based on the total weight of the ZSM-48;
the Zeolite Beta has an Alpha value less than about 15 prior to loading with the Group VIII metal;
the Zeolite Beta is loaded with about 0.5 wt % to about 1 wt % of the Group VIII metal, based on the total weight of the Zeolite Beta; and
the Group VIII metal is at least one member selected from the group consisting of Pt and Pd.
6. A process according to claim 5, wherein
the Beta catalyst is Pt/Beta; and
the Pt/ZSM-48 and the Pt/Beta are in a cascaded two-bed catalyst system comprising a first bed followed by a second bed, wherein the first bed comprises the Pt/ZSM-48 catalyst and the second bed comprises the Pt/Beta catalyst.
7. A process according to claim 6, wherein
the temperature of the first bed and the temperature of the second bed are controlled independently; and
the intermediate product is cascaded directly to the second bed.
8. An isoparaffinic lube basestock made by the process according to claim 1, wherein
the isoparaffinic lube basestock has a viscosity index of at least 150 at a −20° C. lube pour point and a viscosity index of at least 130 at a pour point of no more than −50° C.
9. An isoparaffinic lube basestock made by the process according to claim 1, wherein the isoparaffinic lube basestock has less than 1 wt % aromatic content.
10. A lubricant with a viscosity index of at least 150 at a −20° C. lube pour point and a viscosity index of at least 130 at a pour point of no more than −50° C. made by the process according to claim 1.
11. A lubricant with a viscosity index of at least 150 at a −20° C. lube pour point and a viscosity index of at least 130 at a pour point of no more than −50° C. made by the process according to claim 6.
12. A process according to claim 1, wherein the passing of the wax and the intermediate product over said catalysts is conducted under conditions sufficient to form an isoparaffinic lube basestock with a viscosity index of at least 150 at a −20° C. lube pour point and a viscosity index of at least 130 at a pour point of no more than −50° C.
13. A process according to claim 5, wherein the passing of the wax and the intermediate product over said catalysts is conducted under conditions sufficient to form an isoparaffinic lube basestock with a viscosity index of at least 150 at a −20° C. lube pour point and a viscosity index of at least 130 at a pour point of no more than −50° C.
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