KR100449301B1 - Bulk improvement method of lubricant - Google Patents

Abstract

The invention relates to a process for hydrocracking, flashing and / or distilling a feedstock containing at least 50% clean oil to control the hydrogen content. The bottoms are vacuum distilled to match viscosity and volatility. The purified feedstock is dewaxed by medium pore zeolites or medium pore molecular sieves such as HZSM-5 under high pressure. After adequate flashing and distillation, the dewaxed material is simultaneously introduced into hydrogen and 230 ° C. to 330 ° C. (450 ° C.) to produce a lubricating oil product having very good light stability in the presence of high viscosity index, low aromatic content, low volatility and oxygen. Directly into the hydrofinishing stage in contact with an effective aromatic saturated catalyst having a metal hydrogenation function at a temperature of F to 575 ° F). Hydrocracking, deramping and hydrofinishing steps include multiple steps.

Description

Bulk improvement method of lubricant

The present invention relates to hydrocracking of petroleum feedstocks and to a series of catalytic dewaxing. In particular, the present invention relates to batch fuel hydrogenation process schemes that include hydrocracking, distillation, catalytic dewaxing, and hydrofinishing steps. A dewaxed product is produced with improved viscosity index, stability, color and low volatility. Hydrocrackers increase hydrogen content, decrease viscosity and lower the boiling range of hydrocracker feedstock. Catalytic dewaxers selectively degrade and / or hydroisomerize the waxy hydrocrackate. Hydrofinishing machines add hydrogen to aromatics and olefins. It reduces the ultraviolet absorption of dewaxed oil. Distillation is used to adjust volatility. The resulting lube base oil is as clear as water and has a low aromatic content, low pour point, improved low temperature flowability, high viscosity index, low volatility and excellent oxidative stability.

Mineral lubricants are derived from a variety of crude oil raw materials by a variety of refining processes directed towards obtaining lubricant base stocks with appropriate boiling point, viscosity, pour point, viscosity index (VI), stability, volatility and other properties. Generally, the basic raw materials are prepared by atmospheric or vacuum distillation of crude oil, removal of unwanted aromatics by solvent purification, and finally through dewaxing and various finishing steps. Since multi-ring aromatic compounds have poor thermal stability and light stability, poor chromaticity and extremely poor viscosity index, crude hydrogen or asphalt oil containing low hydrogen content is contained in the lubricant raw materials produced from such crude oil. Separation and removal of large amounts of aromatic compounds is undesirable because the yield of acceptable lubricant raw materials is extremely low. Therefore, paraffinic and naphthenic crude oils can be preferably used, but an aromatic treatment process is required to remove unwanted aromatic compounds from feedstocks containing polynuclear aromatics.

In the case of lubricating oil distillation fractions, commonly referred to as neutrals, for example heavy neutral, light neutral, aromatics are selected from furfural, N-methyl-2-pyrrolidone, phenol or aromatic compounds. It extracts by the solvent extraction method using the other compound extracted as a solvent. If the lubricating oil raw material is a residual raw material, asphaltene is first removed in the propane deasphaltene step and residual aromatics are removed by solvent extraction to produce a lubricating oil generally called bright stock. In both cases, however, a dewaxing step is usually required to have a lubricating oil with a satisfactory pour point and cloud point, i.e. to ensure that the low solubility paraffinic component does not solidify or precipitate even under low temperature effects. .

Lubricated base stocks with high VI can be produced by processing the bottoms of the fuel hydrocrackers. This route offers the possibility to make lubricating base stocks with VIs of 115 or more. The fuel hydrocracking scheme of the present invention not only improves VI but also provides a way to meet new international guidelines for lower volatility base stocks, such as, for example, ILSAC GF-2. The newly proposed requirement for volatility requires the removal of a low boiling point lubrication fraction, which is lighter than the vacuum distillation process currently being practiced to produce lubricating base stocks, which increases their viscosity. In conclusion, materials with higher boiling points, higher viscosities must also be removed in the midstream process to maintain the viscosity. In general, this lowers the yield, narrows the lubricating base oil fraction, and increases the viscosity. As indicated in the present invention, the distillation of the hydrocracker bottom, which circulates the non-lubricating range of materials to the hydrocracking machine (or the route to the second hydrocracker), also removes unwanted components such as polynuclear aromatics, thereby operating the hydrocracking plant. And the efficiency can be improved. The resulting lubricity range fraction is subjected to catalytic dewaxing, hydrogenation and distillation to produce the final lubricant product.

A fuel hydrocracking process that partially circulates a liquid is disclosed in US Pat. No. 4,983,273 (Kennedy et al.). Here, the input (typically VGO) or light cycle oil (LCO) is processed in a hydroprocessing reactor and then in a hydrocracking reactor before passing through the fractionator. Thereafter, a portion of the fractionator bottoms is circulated to a hydrocracking plant. However, there is no instruction in this invention for introducing the fractionator bottoms into an additional vacuum distillation step prior to the additional hydroprocessing or hydrocracking process.

Yugong Co., Ltd., in International Application No. PCT / KR94 / 00046, discloses a method for producing high quality lubricating base oil feedstock from unconverted oil (UCO) of a fuel hydrocracker operating in circulating mode. . In the present invention, the classification process is followed by a vacuum distillation process. Various UCO fractions of the vacuum distillation process are circulated to the hydrocracking reactor. In this invention, the fractions of the vacuum distillation process are not circulated to the first hydrocracker but to the second hydrocracker, or even the FCC process. The fractions of the vacuum distillation process do not need to be circulated to the hydrocracker. The application of Yugong Corporation does not disclose the need to operate a fuel hydrocracker to produce a waxy fuel hydrocracker bottom with the appropriate hydrogen content to obtain a dewaxed base stock with VI of 115 or more. . In addition, Yugong Co., Ltd. claims a general dewaxing and stabilization step, but specific contact dewaxing and subsequent hydroprocessing techniques are not described or claimed in this invention.

Catalytic dewaxing processes are preferred in the manufacture of lubricants. These processes have many advantages over conventional solvent dewaxing processes. The catalytic dewaxing process is operated to selectively degrade normal or slightly branched leaded paraffins to produce low molecular weight products which are removed from high boiling lubricating oil raw materials by distillation. The hydroisomerization process with the same or different catalysts, along with selective catalytic cracking of the leaded molecules, converts a significant amount of straight chain molecules into branched hydrocarbon structures with improved low temperature fluidity. Subsequent hydrofinishing or hydrogenation processes are commonly used for the purpose of stabilizing olefins having a boiling range as lubricating oil resulting from the selective decomposition occurring in the dewaxing process. References describing this process include US Pat. Nos. 3,894,938 (Gorring et al.), 4,181,598 (Gillespie et al.), 4,360,419 (Miller), 5,246,568 (Kyan et al.) And 5,282,958 (Santilli et al.). . Hydrocarbon Processing (September 1986) describes Mobil's lubricating oil dewaxing process and further describes the process by Catal. Rev,-Sci. Eng. 28 (283), 185-264 (1986), "Industrial Application of Shape-Selective Catalysis." See also "Lube Dewaxing Technology and Economics" in Hydrocarbon Asia 4 (8), 54-70 (1994).

In this kind of catalytic dewaxing process, the catalyst also gradually loses its activity as the dewaxing cycle proceeds. To compensate for this, the dewaxing reactor should be gradually raised in temperature to meet the pour point of the desired product. However, there are limitations to raising the temperature below the temperature at which the physical properties of the product, in particular oxidative stability, are acceptable. For this reason, contact dewaxing processes are usually end-of-cycle (EOC) at low start-of-cycle (SOC) values, typically 232 ° C to 274 ° C (450 ° F to 525 ° F). Value, typically from 354 ° C. to 385 ° C. (670 ° F. to 725 ° F.), and then the catalyst is reactivated or regenerated for a new cycle. Typically, dewaxing catalysts containing ZSM-5 as active ingredient are reactivated by hot hydrogen. Other dewaxing catalysts use cobalt or air mixed with N ₂ or flue gas to remove cokes. The catalyst containing ZSM-23 or SAPO-11 as an active ingredient has a higher SOC and EOC of 25 to 50 ° C. than the catalyst containing ZSM-5 as the active ingredient.

The use of metal hydrogenation components in the dewaxing catalyst is very desirable in extending the dewaxing cycle and improving the reactivation process, although the dewaxing reaction itself does not require hydrogen on a stoichiometric balance. It is described as convenient. U.S. Patent No. 4,683,052 discloses the use of precious metals such as platinum or palladium for this application over base metals such as nickel. U.S. Patent Nos. 5,282,958, 4,859,311, 4,689,138, 4,710,485, 4,859,312, 4,921,594, 4,943,424, 5,082,986, 5,135,638, 5,149,421, 5,246,566,138 As described, suitable catalysts for dewaxing and isomerizing or hydroisomerizing the feedstock may contain, for example, 0.1 to 0.6% by weight of platinum. In this invention, palladium is also acceptable, but 0.2 to 1% by weight of platinum is preferably used.

There is a difficulty in intimate contact between phases in the reaction between reactants of liquid and gas. These reactions are more complicated when they are catalyzed or when the two fluid phases need to contact a solid catalyst. In the operation of conventional concurent multiphase reactors, under certain circumstances, gases and liquids tend to travel different paths. The gas phase can flow in the direction of least pressure resistance: the liquid phase drops over and around the catalyst particles and flows by gravity. Under conditions where the liquid to gas ratio is low, parallel channel flow and frictional drag of the gas can make the liquid flow uneven and, due to the lack of adequate wetting, make unused portions of the catalyst bed. Under these conditions, the performance of a commercial scale reactor can be much worse than expected in laboratory studies because the flowability of small pilot units can be more uniform.

In fractionating crude oil and refining lubricating oils derived from petroleum, a series of catalytic reactions for rigorous hydrogenation, conversion and removal of sulfur and nitrogen contaminants, hydrocracking and isomerization of lubricant feedstocks are carried out in one or more catalytic reactors. Can proceed. The multinuclear aromatic feedstock is selectively hydrocracked by known techniques for ring opening the polynuclear ring. And it can be hydrodewaxed and / or hydrogenated (smooth hydrogenation) in contact with different catalysts under various reaction conditions. According to the present invention, the batch three step lubricating oil refining process disclosed by Garwood et al. In US Pat. No. 4,283,271 is applicable.

The average gas-liquid volume ratio in the catalyst zone under the process conditions of a typical multi-phase hydrogenation dewaxing reactor is about 1: 4 to 20: 1. Preferably, liquid is supplied to the catalyst bed at a rate of about 10-50% of the pore volume. As liquid feedstock and gas pass through the reactor, hydrogen is consumed, so the volume of the gas decreases. The volume is also affected by gas, adiabatic heating or expansion resulting from the production of methane, ethane, propane and butane in the dewaxing reaction.

An improved batch process has been invented for hydrocracking and hydrodewaxing liquid petroleum lubricating oil feedstock containing high boiling paraffinic beeswax. VGO, LCO or even deasphhalted oil may be hydrocracked in a fuel hydrocracker process comprising a downstream vacuum distillation unit. Contact dewaxer feedstock with at least about 13.5% by weight of hydrogen is prepared in a fuel hydrocracker followed by dewaxing, hydrofinishing and distillation. More than 50% by weight of the feedstock is converted to boiling hydrocarbons at temperatures below the initial boiling point of the feedstock. The improved process includes the following steps:

(a) A feedstock comprising VGO, LCO or deasphalted oil is subjected to hydrocracking at high pressure prior to fractionation and subsequent vacuum distillation of the fractionator bottoms to fractionate and subsequently obtain the desired viscosity and volatility. after:

(b) The distillation of the vacuum distillation unit at the same time of hydrogen injection at 425 ° C. (797) with acidic, shape-selective, medium pore molecular sieve hydrogenation dewaxing catalysts at pressures of 10,000 kPa (1450 psi) or higher. By dehydrogenation in a hydrodewaxing step in which dewaxing and hydroisomerization occur simultaneously by uniformly dispersing and contacting the liquid feedstock at a temperature elevated to < RTI ID = 0.0 > F) < / RTI >

(c) Hydrofinishing the dewaxed lubricating oil in the hydrofinishing step under aromatic saturation conditions while contacting simultaneously introduced hydrogen with an effective aromatic saturation catalyst with strong metal hydrogenation.

A hydrofinishing cycle initiation temperature of 230 ° C. (446 ° F.) to 343 ° C. (650 ° F.) and a pressure of 10,000 kPa (1450 psi) or more are applied to obtain a dewaxed lubricating oil (boiling at about 370 ° C. or higher). Subsequently, after vacuum distillation, the dewaxed lubricating oil product has an aromaticity of 5% by weight or less, and oxidative stability is improved. The product has a NOACK number of 20 or less and a viscosity index (VI) of 115 or more. Viscosity shows 3-10 cSt at 100 ° C.

Hydrogenation dewaxing catalyst containing molecular sieves having 10 oxygen atoms predominantly alternating with silicon atoms, for example aluminosilicate zeolites having the structure of ZSM-5, ZSM-23, ZSM-35 or ZSM-48 Is preferred. Non-zeolitic molecular sieves such as SAPO-11 with similar pore sizes are also suitable catalysts. Except for ZSM-5, it is preferred that the catalyst contains 0.1 to 1% by weight of precious metals. Catalysts which are preferably used for hydrofinishing following dewaxing should contain at least one VIII A group metal and one VI A metal (IUPAC) or platinum or palladium in the porous solid carrier in the porous solid carrier. A bimetallic catalyst containing nickel and tungsten in a porous alumina carrier is a good example. The carrier can be fluorinated.

Preferred feedstocks of fuel hydrocrackers are clean gas oils such as light vacuum gas oil (LVGO), VGO and heavy vacuum gas oil (HVGO). VGO and HVGO usually contain significant amounts of polycyclic aromatics. The lead material to be contacted and dewaxed after hydrocracking and vacuum distillation typically has VI of at least 125, preferably 130 or more, contains about 1 to 15% by weight of aromatic hydrocarbons, and 10% by volume of about 315 ° C (600 °). F) It has a substance having a boiling point above and contains nitrogen of 30 ppm or less. And it contains about 14.0 weight% or more of hydrogen. And it has a viscosity of 3 cSt or more at 100 ° C.

The hydrodewaxed effluent is hydrofinished and distilled and then has a kinematic viscosity of 10 to 160 cSt at 40 ° C. or 3 to 10 cSt at 100 ° C. and is separated to recover boiling lubricating oil product at 370 ° C. (698 ° F). . The lubricating oil product exhibits an UV absorbance of 0.001 L / g-cm or less and an aromatic content of 5% by weight or less at 325 nm.

The dewaxing step and the hydrofinishing step are operated under the same pressure, and the entire dewaxing oil of the dewaxing step is fed directly into the hydrofinishing step in series operation.

Units are metric units unless otherwise indicated in the following description.

Hydrocarbon feedstocks in the batch process of the present invention are lubricant raw materials having an initial boiling point and a final boiling point suitable for producing a lubricating oil raw material having suitable lubricating properties. Excellent such raw materials are hydrocarbons having a 10% distillation point above 345 ° C. (653 ° F.) and a viscosity of about 3 to 40 cSt at 100 ° C., as determined by FIG. 3 or similar correlation. Feedstocks are typically prepared by vacuum distillation of fractions from crude oil in suitable forms. Generally, crude oil is atmospheric distilled and the residue is vacuum distilled to produce an initial crude lubricating oil raw material. Clean distillate from vacuum distillate distillate stock or from "neutral" stock and vacuum distillation bottoms to deasphalate propane are used to produce products in the appropriate viscosity range. Typically, the viscosity is 4 cSt at 100 ° C. for light neutral, about 12 cSt at 100 ° C. for neutral and about 40 cSt at 100 ° C. for clean raw materials. In a conventional solvent refinery lubricating oil plant, the aromatic compounds are selectively removed using a solvent that selectively extracts aromatic compounds such as furfural, phenol or N-methyl-2-pyrrolidone to improve VI and other properties. Solvent extraction of the feedstock. In the present invention, it is necessary to hydrocrack the feedstock prior to dewaxing or hydrofinishing in order to obtain the properties of the desired product.

The crude vacuum distillate and propane deasphalted residue are purified during hydrocracking or rigorous hydrogenation to convert unwanted aromatic and heterocyclic compounds to the desired naphthenes and paraffins (see Example 3). This refined lead mixture has a low sulfur and nitrogen content and may be suitable for the viscosity described above after distillation.

The batch all-catalyst lubricating oil production process applying the hydrocracking and catalytic dewaxing process is described in U.S. Pat. 4,347,121 (Mayer et al.), 3,684,695 (Neel et al.) And 3,755,145 (Orkin et al.).

The hydrocracking process is operated with heavy hydrocarbon feedstocks such as clean LVGO, HVGO, deasphalted residues, or combinations thereof with boiling points above 340 ° C. Although such clean oils are preferred, decomposed raw materials such as light and heavy coker gas oils have a low hydrogen content (which is mostly aromatic), resulting in 20% light and heavy FCC gas oils. It is added in an amount not exceeding. Since lubricating oils are generally sold according to their viscosity and the viscosity decreases during hydrocracking, the feedstock fed into the hydrocracking process should preferably have a kinematic viscosity of 3 cSt or higher at 100 ° C. This preferably means that the boiling point is above 340 ° C (see Figure 3 which shows the relationship between the pure components and the 50% boiling point and viscosity of VGO made from Arab crude). Feedstocks having a boiling point below 340 ° C. are also included in the hydrocracker feedstock, but their light products can be removed in separator 20 of FIG. Such heavy oils contain high molecular weight long chain paraffins and high molecular weight naphthenes and aromatics. Aromatics may include some fused rings that adversely affect the stability of the lubricant. During processing, the fused ring aromatics and naphthenes are degraded by acidic catalysts, the paraffinic decomposition products are converted to iso-paraffins with the paraffinic components included in the original feedstock and some are broken down to low molecular weight materials. The catalysis of the hydrogenation component facilitates the hydrogenation of the polycyclic aromatics and facilitates the decomposition of these components. The hydrogenation of the unsaturated side chains of the monocyclic decomposition residues of the initial polycyclic aromatics provides a very preferably substituted monocyclic aromatic in the final product. The heavy hydrocarbon oil feedstock usually contains a significant amount of material having a boiling point of at least 340 ° C. and a viscosity of at least 3 cSt at 100 ° C. It usually has an initial boiling point of at least about 400 ° C. (752 ° F.) and preferably at least about 450 ° C. (842 ° F.). Boiling point ranges from 340-700 ° C (644-1292 ° F). Of course, for example, a narrow oil may be processed to a boiling point range of about 400 to 500 ° C. (about 752 to 932 ° F.). HGO is often this kind of circulating oil and other non-residues. The circulating oil from the catalytic cracking operation and the coking operation is not particularly useful for the production of lubricating oil due to its high degree of unsaturation, but the clean oil described above within the range satisfying the boiling point and viscosity required for the clean oil described above. It can be mixed in. The hydrocracker feedstock preferably contains no more than 20% of the cracked feedstock. The hydrocracker feedstock should contain 80% or more clean ingredients.

Hydrogenation pretreatment steps using conventional hydrotreatment catalysts to remove nitrogen and sulfur and to saturate aromatics with naphthene without conversion of a range of boiling points usually improve the performance of the catalyst and provide low temperature, high space velocity, low pressure or Allows you to apply a combination of conditions. In general, suitable hydrotreating catalysts include metal hydrogenation components, substantially non-acidic porous carriers such as silica-alumina or group VIB, or group VIII metals, such as cobalt-, as generally described above on alumina. Molybdenum, nickel-molybdenum. These are listed in Table 1.

Table 1:

Catalysts suitable for use in hydrogenation pretreatment

1 is a simplified diagram of a reactor system of a fuel hydrocracker preferred by the present invention. Hydrogen pretreatment steps that remove nitrogen and sulfur using conventional hydrotreatment catalysts and saturate olefins and aromatics without conversion of a range of boiling points typically improve the performance of hydrocracking catalysts and provide high space velocity, low pressure, or a combination thereof. Allows you to apply conditions. In general, suitable hydrotreating catalysts contain metal hydrogenation components such as Group VIB, or Group VIII metals, such as cobalt-molybdenum, nickel-molybdenum, on non-acidic porous carriers, such as silica-alumina or alumina. . Suitable commercial hydrogenation pretreatment catalysts suitable for use in the present invention include alumina supported nickel-molybdenum catalysts such as UOP HCH, Crossfield 594, and Criterion HDN, and USY supported nickel-molybdenum catalysts such as UOP HC-24.

The shell 10 of the vertical reactor of FIG. 1 includes and supports a series of pore hydrogenated pretreatment solid catalyst fixed beds stacked as indicated by 12A to 12B. The feedstock 6 containing VGO, LCO, deasphalted oil or a mixture thereof is mixed with a hydrogen rich gas 8 and heated by a suitable heating means 9 and then introduced into the reactor 10. The mixed gas of feedstock and hydrogen-rich gas flows downward while passing through the catalyst bed. Although five catalyst layers are shown in this example, there may be more or only two catalyst layers. Dispersion of the liquid in each catalyst layer is uniformly sprayed on the surface of the catalyst layer 12A, B, C, D, E by a conventional technique, for example, dispersion plates 13A, B, C, D, E. Is achieved by technology. Typically the gas phase and liquid phase are introduced into the reactor at the desired inlet pressure and temperature. The temperature of the gas and liquid is controlled by the addition of hydrogen-rich quench gases 14A, B, C, D between the catalyst beds or by the heat exchange of the liquid in the outer flow ring, and the temperature control independently in each catalyst bed Make it possible. Static mixers 15A, B, C, D or other suitable contacting equipment may be used to mix liquid and gas streams between the catalyst beds to create a uniform temperature.

The effluent 16 of the hydrocracker was subjected to heat exchangers (not shown), separator 18 and cleaning or fractionation equipment 20 to separate the circulating gas stream 22 and the light conversion product 24. Pass through. Here, by-product NH ₃ and H ₂ S which can poison the downstream of the hydrocracking catalyst are separated and removed. The effluent gas stream 28 is typically drawn from the circulating gas stream to remove light hydrocarbon products. Gas scrubbing facilities (not shown) are typically used to remove NH ₃ and H ₂ S from the circulating gas stream. Replenishment hydrogen 26 is added to replenish the hydrogen consumed in the hydrotreating reaction and released to the gas and liquid streams 28, 24, and 30.

The shell 34 of the vertical reactor of FIG. 2 includes and supports a series of pore hydrogenated solid catalyst fixed beds stacked as indicated by (36A) to (36E). Hydroprocessing catalysts composed of mixed or separated layers as one or more catalysts are described herein. The hydrotreatment bottoms 30 are mixed with a hydrogen-rich gas 32 and then heated by suitable heating means 33 and then introduced into a hydrocracking reactor 34. A mixture of feedstock and hydrogen-rich gas flows downwards through the catalyst bed. Although five catalyst layers are shown in this example, there may be more or only two catalyst layers. Dispersion of the liquid in each catalyst layer is uniformly sprayed on the surface of the catalyst layer 36A, B, C, D, E by conventional techniques, for example, dispersion plates 37A, B, C, D, E. Is achieved by technology. Typically the gas phase and liquid phase are introduced into the reactor at the desired inlet pressure and temperature. The temperature of the gas and liquid is controlled by the addition of hydrogen-rich quench gases 38A, B, C, D between the catalyst beds or by the heat exchange of the liquid in the outer flow ring, and the temperature control independently in each catalyst bed Make it possible. Static mixers 39A, B, C, D or other suitable contacting equipment, including quench gases, may be used to mix the liquid and gas streams between the catalyst beds to create a uniform temperature.

The outflow 38 of the hydrocracker passes through heat exchangers (not shown), separator 40 and fractionation equipment 42 to separate the circulating gas stream 44 and the conversion hydrocracking fraction 46. do. The effluent gas stream 50 is typically drawn from the circulating gas stream to remove light hydrocarbon products. Gas scrubbing facilities (not shown) are typically used to remove NH ₃ and H ₂ S from the circulating gas stream. Replenishment hydrogen 48 is added to replenish the hydrogen consumed in the hydrocracking reaction and released to the gas and liquid product streams 50 and 46. The unconverted bottoms product 2 is sent to a lubricating oil vacuum distillation unit which is one of the new features of the present invention. This distillation step adds a narrow range of lubricant fractions 56, 58, 60, 62, 64 with specific viscosity (e.g., 60N, 100N, 150N) and volatility. It is possible to manufacture. It can produce low volatility lubricant raw materials with more than 115 VI. Only five lubricant classifications are shown, but more or only two classifications are possible. As shown in FIG. 2, this lubricating oil fraction is introduced into the contact dewaxing process in the vacuum distillation unit 54. As shown in FIG.

For example, some unconverted hydrocracker bottoms product 52 or an unused fraction of this stream may be subjected to vacuum distillation units 56, 58, 60, 62, 64 with hydrocracker 34. It may be desirable to cycle to. This is indicated by flow 66. Alternatively, it is preferred to send this unconverted hydrocracker bottoms product to a second hydrocracker, FCC unit or to use it as fuel.

Tables 3 and 4 (see Example 1) show whether lubricating oil products of hydrocrackers can be processed by the addition of vacuum distillation units as described in the present invention.

The catalyst used in the hydrocracking process may be a conventional hydrocracking catalyst such as a large pore sized acid zeolite with a metal hydrogenation / dehydrogenation function added inside the porous carrier material. Specific commercial hydrocracking catalysts that can be used include UOP HC-22 and UOP HC-24. These are NiMo catalysts based on USY. IRC209, a Chevron catalyst containing palladium on a USY carrier, can also be used. Table 2 lists suitable hydrocracking catalysts. The acidic functionality of the hydrocracking catalyst is either by air-porous amorphous material such as alumina, silica-alumina or silica or by aluminosilicate zeolites such as zeolite X, Y, ZSM-3, ZSM-18, ZSM-20 or zeolite Provided by atmospheric crystalline materials such as beta. Zeolites are used in a variety of cationic and other forms, preferably in the form of high stability to withstand degradation and acid loss of functionality under hydrothermal conditions during hydrocracking processes. Thus, atmospheric pore zeolites exchanged with rare earth metals, such as REX and REY, so-called ultra stable zeolites Y (USY) and high silica zeolites, such as dealalumina Y or dealalumina mordenite Forms with improved stability are preferably used.

Zeolite ZSM-3 is disclosed in US Pat. No. 3,415,736, ZSM-18 in US Pat. No. 3,950,496, and ZSM-20 in US Pat. No. 3,972,983 for such zeolites, their properties and preparation. Zeolite USY is disclosed in US Pat. No. 3,293,192 and RE-USY is disclosed in US Pat. No. 4,415,438. Hydrocracking catalysts containing zeolite beta are disclosed in European Patent 94948 and US Patent 4,820,402. Preferably the catalyst contains silica, silica / alumina or metal oxides such as alumina, magnesia, titania as binders, typically the ratio of binder to zeolite varies from 10:90 to 90:10, more preferably, by weight To 30:70 to 70:30.

TABLE 2

Catalysts suitable for use in the hydrocracking stage prior to dewaxing

This hydrocracking process is carried out under the operating conditions used in the usual hydrocracking process. At temperatures above about 445 ° C. (833 ° F.), thermodynamics of the hydrocracking process are undesirable, so no higher temperatures are usually used, but process temperatures of about 260 to 480 ° C. may be conveniently used. In general, temperatures of 315 ° C to 425 ° C (599 ° F to 797 ° F) are used. A total pressure of 1200 to 3000 psi (8274 kPa to 20,685 kPa) is used, and preferably a pressure of 1800 psi (12,600 kPa) or more in this range is usually used. This process is operated in the presence of hydrogen, and usually the partial pressure of hydrogen is above 1200 psig (8274 kPa). The ratio of hydrogen to hydrogen feedstock (hydrogen cycle ratio) is usually 2000 to 5000 SCF / Bbl (about 18 to 980 nll ⁻¹ ). The space velocity of the feedstock is usually between 0.1 and 10 LHSV (hr ⁻¹ ), preferably between 0.5 and 5 LHSV. At low conversion, the n-paraffins in the feedstock are isomerized to iso-paraffins, and under higher stringent conditions, the iso-paraffins are converted to lighter materials at higher conversions.

The feedstock can be converted while in contact with the stationary catalyst bed. A simple configuration is a trickle-bed operation in which the feedstock drops through the stationary stop catalyst bed (shown in FIG. 1). With such a configuration, it is desirable to start the reaction at moderate temperatures when using fresh catalyst and to raise the temperature to maintain the activity of the catalyst as it is used. Hydrocracking catalysts are regenerated at high temperatures, for example by contact with hydrogen gas or by burning with a mixture of air, nitrogen and flue gas.

2 is a specific embodiment of the invention and is not intended to limit the invention. The shell 10 of the vertical reactor contains and supports a series of porous dewaxed solid catalyst fixed beds stacked as indicated by (12A) through (12C). The feedstock 6 containing beeswax liquid oil is mixed with a hydrogen rich gas 8 and heated by a suitable heating means 9 and then introduced into the reactor 10. The mixed gas of feedstock and hydrogen-rich gas flows downward while passing through the catalyst bed. Although three catalyst layers are shown in this example, there may be more or only two catalyst layers. Dispersion of the liquid in each catalyst layer is accomplished by conventional techniques, for example, by spreading the liquid evenly on the surface of the catalyst layers 12A, B, and C by the dispersion plates 13A, B, and C. Typically the gas phase and liquid phase are introduced into the reactor at the desired inlet pressure and temperature. The temperature of the gas and liquid is controlled by the addition of hydrogen-rich quench gases 14A, B between the catalyst beds or by the heat exchange of the liquid in the external flow ring, allowing for independent temperature control in each catalyst bed. Static mixers 15A, B or other suitable contacting equipment, including quench gases, may be used to mix the liquid and gas streams between the catalyst beds to create a uniform temperature.

Hydrogenation dewaxing reactor effluent 24 is heated or cooled by a heat exchanger or furnace 25 as needed and then directly introduced to hydrofinishing reactor 30. The shell 30 of the vertical reactor includes and supports a series of pore hydrogenated dewaxed solid catalyst fixed beds stacked as indicated by 32A to 32B. Liquid and gas flow downward while passing through the catalyst bed. Although three catalyst layers are shown in this example, there may be more or only two catalyst layers. Dispersion of the liquid in each catalyst layer is accomplished by conventional techniques, for example, by spreading the liquid evenly on the surface of the catalyst layers 32A, B, and C by the dispersion plates 33A, B, and C. Typically the gas phase and liquid phase are introduced into the reactor at the desired inlet pressure and temperature. The temperature of the gas and liquid is controlled by the addition of hydrogen-rich quench gases 34A, B between the catalyst beds or by the heat exchange of the liquid in the outer flow ring, allowing for independent temperature control in each catalyst bed. Static mixers 35A, B or other suitable contacting equipment, including quench gases, may be used to mix the liquid and gas streams between the catalyst beds to create a uniform temperature.

The effluent stream 36 of the hydrofinishing machine is characterized by heat exchangers (not shown), separator 40 and fractionation equipment for separating circulating gas stream 44, diverting fraction 46 and processed lubricating base stock. Pass 42. Typically the effluent gas stream 50 is withdrawn from the circulating gas to remove light hydrocarbon products. Gas scrubbing facilities (not shown) are typically used to remove NH ₃ and H ₂ S from the circulating gas stream. Replenishment hydrogen 52 is added to replenish the hydrogen consumed in the hydrowaxing and hydroprocessing reactions and released into the gas and liquid streams 50 and 46.

Continuous multistage reactor systems have been described as contacting a series of porous catalyst layers with gas and liquid phases; However, it may be desirable to have other reactor configurations with two to five catalyst beds. The catalyst composition of all catalyst beds in each reactor may be the same; However, having different catalysts and reaction conditions in separate catalyst beds is included in the inventive concept. Design and operation can be tailored to specific process needs by appropriate chemical engineering practices.

The technique is applicable to various catalytic dewaxing operations, in particular to the treatment of heavy oils in the lubricating oil range with hydrogen containing gases at high temperatures. Industrial processes applied to hydrogen, in particular petroleum refining, are applied to nonpure circulating gases containing 10 to 30 mole percent or more impurities, usually light hydrocarbons and nitrogen. Such gases are available and useful here, in particular for high temperature hydrogenation dewaxing at high pressures.

Preferably, the catalyst layer has a pore volume fraction of 0.25 or more. A pore fraction of 0.3 to 0.5 allows for loosely filled polylobe or cylindrical extrudates, spheres or pellets to provide a suitable liquid flow rate component to uniformly wet the catalyst to improve mass transfer and catalysis. To achieve. The depth of the catalyst bed is in the range of 2-6 m.

In the process of the present invention, a waxy, dewaxed product having a boiling point, typically a 321 ° C. (about 610 ° F.) lubricating oil feedstock, as a lubricating oil of low flow point (equivalent method such as ASTM D-97 or Autopour) is produced. To a medium pore size molecular sieve catalyst having the function of dewaxing and / or isomerizing or hydroisomerizing in the presence of hydrogen. For a typical lead feedstock, the hydrogen feed rate at the top of the dewaxing reactor is about 267-534 n.l.1-1 (1500-3000 SCF / Bbl). A hydrofinishing step is performed to improve the stability of the material with boiling point as dewaxed lubricant in the dewaxed effluent.

In general, when ZSM-5 is used as the active component of the catalyst, the catalytic dewaxing process step depends on the stringency of the dewaxing required to achieve the target pour point of the product, but usually at high temperature conditions, about 205 to 400 ° C. (401 to 752 ° F) And preferably in the range of about 235 to 385 ° C (455 to 725 ° F). In the case of using a weakly active catalyst, the temperature may be increased by 25 to 50 ° C. as compared with the case of using ZSM-5.

Lowering the target pour point of the product reduces the stringency of the dewaxing process by increasing the temperature of the reactor to give an effect of increasing the conversion of n-paraffins, and generally reduces the pour point of the product, thereby increasing the amount of n-paraffins in the feed. The wax yield is reduced by the dewaxing catalyst to a light product whose boiling point is outside the lubricating oil boiling range, thereby reducing the lubricating oil yield. As the pour point of the product is lowered, the VI of the product also decreases as the n-paraffins of high VI and slightly side-chain iso-paraffins are gradually converted by selective degradation.

Furthermore, the dewaxing temperature is increased during each dewaxing cycle to compensate for the degradation of the catalyst activity due to aging of the catalyst. The dewaxing cycle is usually terminated when the temperature reaches about 400 ° C. (about 750 ° F.), preferably about 385 ° C. (725 ° F.) because the viscosity and product stability at high temperatures are adversely affected. If ZSM-5 is used as the catalytically active component of a weakly active catalyst, this temperature can rise to 25-50 ° C.

Hydrogen promotes extended catalyst life by reducing the coke deposition rate on the dewaxing catalyst ("coke" is a high carbonaceous hydrocarbon that tries to accumulate on the catalyst surface during the dewaxing process). Therefore, although this process may apply a higher pressure, it is typically about 2758 to 20,685 kPa (400 to 3000 psia), preferably about 9653 to 17,238 kPa (1400 to 2500 psi), more preferably about 11032 to The hydrogen partial pressure between 15169 kPa (1600 and 2200 psia) is performed in the presence of hydrogen. The hydrogen circulation rate is typically 180 to 710 (1000 to 4000 SCF / bbl), usually 355 to 535 nl1 ^-1 (2000 to 3000 SCF / bbl), with respect to the liquid velocity at the reactor inlet, to further add hydrogen to the quench position. Add. The space velocity varies depending on the feedstock and the stringency required to achieve the target pour point, but is typically in the range of 0.25 to 5 LHSV (hr-1), preferably 0.5 to 3 LHSV (hr-1) for all catalysts. .

Recent developments in zeolite technology have provided a group of distorted mesoporous silicon materials with similar pore geometries. Preferred hydrogenation dewaxing catalysts contain porous acidic molecular sieves having pores contained with silicon atoms dominated by 10 carbon atoms alternately, such as aluminosilicate zeolites. The best of these mesoporous zeolites are ZSM-5, ZSM-23, ZSM-35 and ZSM-48, which incorporate tetrahedral coordination metals such as Al, Ga or Fe into the zeolite structure at the Bronsted acid active sites. By synthesis. Medium pore molecular sieves having a pore size of about 3.9 to 6.3 kPa are preferably used for shape selective acidic catalysis; However, the merit of the mesoporous structure is exploited by the application of crystalline molecular sieves containing high silicon materials or tetrahedral species of varying one or more acidity. Such shape-selective materials have one or more channels with pores formed by a 10-membered ring of 10 oxygen atoms that alternate with silicon and / or metal elements.

Catalysts proposed for the shape-selective contact dewaxing process usually contain a molecular sieve having a pore size that passes together straight, leaded n-paraffins alone or slightly side chained paraffins but rejects high branched and alicyclic materials. Representative medium pore molecular sieves are ZSM-5 (US Pat. No. 3,702,886), ZSM-11 (US Pat. No. 3,709,979), ZSM-22, ZSM-23 (US Pat. No. 4,076,842), ZSM-35 (US Pat. 4,016,245), ZSM-48 (US Pat. No. 4,375,573), ZSM-57 and MCM-22 (US Pat. No. 4,954,325), and SAPO-11 (US Pat. No. 4,859,311). ZSM-24 is a synthetic ferrite (see Figure 4). Those published in the patent are hereby incorporated by reference.

Molecular sieves offer advantages in contact dewaxing on amorphous catalysts. Molecular sieves are roughly classified into small, medium and atmospheric pores as shown in FIG. The pore size is determined by the ring of oxygen atoms. Small pore zeolites have windows of 8-membered rings, medium pore zeolites have 10-membered systems and atmospheric pore zeolites have 12-membered systems. Contact dewaxing performance is also influenced by the pore structure of the catalyst, such as whether it has one or two dimensional channels, the nature of the channel crossings, and the like. The severely distorted small pore zeolite has no effect on the dewaxing of the lubricant since only a small n-paraffin passes through the pore channel in the dewaxing of the lubricant. In contrast, atmospheric pore zeolites non-selectively decompose some of the desired lubricating oil components, resulting in lower yields than heavy pore zeolites.

HZSM-5 is one of many mesoporous zeolites with shape selective dewaxing ability. Other examples are ZSM-11, ZSM-22, ZSM-23, ZSM-35, ZSM-48 and ZSM-57. The pore structure of ZSM-5 provides a balance of reactant shape selectivity, reduced coking tendency and rejection of bulky nitrogen containing catalyst poisons. HZSM-5, Pt / ZSM-23, Pd / ZSM-23, Pt / ZSM-48, and Pt / SAPO-11 with appropriately controlled physicochemical properties can effectively dewax its channel system and fuel hydrocracker bottoms. It is preferably used in the present invention because of its pore structure.

Suitable molecular sieves having a coordination metal having a molar ratio of 20: 1 to 200: 1 or more relative to silica can be used. For example, in the case of HZSM-5, one having a molar ratio of 70: 1 or more can be used, but it is advantageous to use a conventional aluminosilicate ZSM-5 having a silica: alumina-molar ratio of 25: 1 to 70: 1. Exemplary zeolite catalyst components with Bronsted acid sites consist essentially of crystalline aluminosilicate with a ZSM-5 zeolite structure of 5 to 95% by weight of silica, clay and / or alumina binder. It is understood that other mesoporous acidic molecular sieves, such as salicylates, silica aluminophosphate (SAPO) materials, in particular mesoporous SAPO-11, can be used as catalysts.

U.S. Pat. No. 4,908,120 (Bowes et al.) Discloses a catalytic process useful for feedstocks having high paraffin content or high nitrogen levels. The process uses a binder free zeolite dewaxing catalyst, preferably ZSM-5.

Mesoporous zeolites are particularly useful because of their reproducibility, long life and stability under extreme operating conditions. Usually zeolite crystals have a crystal size of about 0.01 to 2 μm or more, preferably 0.02-1 μm. ZSM-5 (≥40 alpha) in the metal-free form can also be used as a selective decomposition catalyst, but other heavy pore acidic metallo-silicates described above are converted to 0.1 to 1.0% by weight of precious metals for use as hydroisomerized dewaxing catalysts. It is necessary to let.

ZSM-5 is the only medium pore zeolite or mesoporous acid molecular sieve that can be used as a selective dewaxing catalyst for practical commercial use without the addition of precious metals. Precious metals are needed to lower the rate of catalytic aging of other medium pore molecular sieves to a practical level. However, the addition of a noble metal to ZSM-5 imparts hydroisomerization activity which improves the yield of dewaxed lubricant. When precious metals were added to ZSM-23, ZSM-35, SAPO-11 and ZSM-5, product yields and VIs of ZSM-23, ZSM-35, SAPO-11 were generally found to be higher than ZSM-5. . Which catalyst is selected and used is a matter of economy.

Within the concept of the invention the size of the catalyst can vary widely depending on the process conditions and reactor structure. Preferred are catalysts processed to an average size of up to 1 to 5 mm.

The catalyst used in most of the contact dewaxing examples herein is 65 wt% ZSM-5 with an acid decomposition (alpha) value of 105 and is made of an extrudate with a diameter of 1.6 mm; However, an alpha value of about 1 to 300 can be used. The arrangement of reactors is an important consideration in the design of continuous operation systems. In its simplest form, there is a vertical pressure vessel with a series of (two or more) uniform cross-sections of stacked catalyst layers. Typically vertical reactors with a total catalyst bed height to average area ratio (L / D) of 1: 1 to 20: 1 are preferred. A series of stacked catalyst layers can be contained in one shell; However, similar results can be obtained when connecting independent reactors side by side. Reactors with a uniform horizontal cross section are preferred; However, it is also possible to use non-uniform configurations by controlling the flow rate of the bed and the corresponding circulation rate.

The present invention is particularly useful for catalytic hydrogenation dewaxing of heavy petroleum gas oil lubricating oil feedstocks having boiling points above 315 ° C (599 ° F). The catalytic dewaxing treatment may be carried out at an hourly liquid space velocity of 5 hr ⁻¹ or less, preferably about 0.5-3 hr ⁻¹ , on an extrudate catalyst layer of the irregularly filled mesoporous molecular sieve catalyst. The hydrocarbon feedstock of the catalytic dewaxer has a viscosity of 3 to 12 cSt at 100 ° C. Preferably, the liquid flow rate (including any liquid circulation) relative to the total dosing rate is 2441-17088 kg / m 2 / hr (500-3500 lb / ft ² / hr), preferably 4881-14647 kg / m 2 / hr (1000-3000 lb / ft ² / hr). The reactant gas velocity is introduced at a constant volume velocity per barrel of oil.

After contact dewaxing to improve the quality of the dewaxed lubricating oil product, the hydrofinishing step (second step) is used to obtain the effect of saturating olefins in the lubricating oil range, removing heteroatoms and pigments, and saturating residual aromatics when the hydrofinishing pressure is high enough. See also). Hydrofinishing after dewaxing is usually carried out in series in the dewaxing step. In general, at the start of the cycle, hydrofinishing after dewaxing is about 230 to 330 ° C (450 to 625 ° F), preferably 246 to 274 ° C (475 to 600 ° F), most preferably 260 to 302 ° C (500 to 575 ° F). Typical total pressures are 9653-20685 kPa (about 1400-3000 psi). Typical hourly liquid space velocity of the hydrotreater is 0.1 to 5 LHSV (hr ⁻¹ ), preferably 0.5 to 3 hr ⁻¹ . Processes employing continuous lubricant contact dewaxing-hydrofinishing are described in US Pat. Nos. 4,181,598, 4,137,148 and 3,894,938. A process employing a reactor with alternating dewaxing-hydrofinishing layers is described in US Pat. No. 4,597,854. References to these patents have been prepared for the details of such processes. The hydrofinishing step after dewaxing improves the quality of the product without particularly affecting the pour point. The metal function of the hydrofinishing catalyst is effective for saturation of aromatic components. Thus, hydrofinishing catalysts with strong desulfurization / hydrogenation functions provided by precious metals, nickel-tungsten or nickel-molybdenum are more effective than catalysts with weak metal functions such as molybdenum alone. Preferred aromatic saturation hydrofinishing catalysts contain one or more metals having a relatively strong hydrogenation function on the porous carrier. The carrier of the hydrofinishing catalyst is of low acidity because the desired hydrogenation requires little acidic functionality and no conversion to low boiling products at this stage. Amorphous or crystalline oxides such as alumina, silica and silica-alumina of low acidic properties are included in typical carrier materials. The metal content of the catalyst is often as high as about 20% by weight for non-noble metals. Precious metals are usually present in amounts up to 1.0% by weight. Hydrofinishing catalysts of this type are readily available from catalyst suppliers. Nickel-tungsten catalyst can be fluorinated.

Control of the operating factors of the hydrofinishing step provides a useful way to change the stability of the product. Hydrofinishing catalysts using a combination of Group VIIIA and Group VIA metals on the periodic table, such as Ni / W, minimize monocyclic and polynuclear aromatics at temperatures of 230-300 ° C (446-572 ° F). It also provides excellent oxidative stability, ultraviolet light stability and thermal stability. In addition, the space velocity in the hydrofinishing group provides the possibility of controlling the aromatic saturation, and the low space velocity has the effect of increasing the aromatic saturation. The hydrofinished product preferably contains up to 10% by weight of aromatics.

Example

The following examples are merely intended to illustrate the invention, not to limit the invention:

Example 1

Table 3 analyzes the atmospheric tower bottom products of a commercial two-stage hydrocracker. This hydrocracker has a hydroprocessing reactor and a hydrocracking reactor, but the vacuum distillation unit described in the hydrocracking unit of the present invention is not applied. The product is approximately 330-538 ° C. (625-1000 ° F.) fraction and has a very low hetero atom and aromatic content, especially nitrogen content. The hydrocracking catalyst used was fresh. The full range analysis of the entire drum collected at the bottom of the atmospheric tower was recorded in the section "Total Bottom". The bottoms were divided into five fractions of equal volume and the main physical properties were analyzed. The results of this analysis are also shown in Table 3.

After hydrodewaxing, including catalytic dewaxing, hydrofinishing and distillation, the final product should have the following properties:

Viscosity Index ≥ 115

NOACK> 6 ≤20

Viscosity (4 to 5 cSt at 100 ° C)

Chromaticity ≥ 20

Pour point ≤ -4 ° C (25 ° F)

Aromatic ≤ 5% by weight

The chromaticity should be stable under sunlight.

In order to obtain a final product with the above characteristics, it is desirable to start with a feedstock with as high VI and low NOACK (or high flash point) as possible. Hydrogen dewaxing lowers the pour point. In Table 3, the fraction with higher volatility showed lower pour point and the fraction with heavier, ie, the less volatile fraction, showed a higher VI. The most volatile fraction distilled from 0 to 20% exhibits low viscosity (2.77 cSt at 100 ° C.) and VI of 115 or less and therefore is not suitable for use as a lubricant.

In order to obtain the product properties described above, it was desirable to obtain a feedstock having an appropriate range of properties. In the present invention, a vacuum distillation step is applied. As shown in Table 4, even the lightest, most volatile fraction of hydrocracking and vacuum distillation bottoms exhibited a viscosity of at least 115 VI and at least 4 cSt at 100 ° C. suitable for use as lubricating oil.

Example 2

5 shows the correlation between the viscosity index and the hydrogen content of a lubricating oil (purified by solvent purification or hydrocracking) having a pour point of -7 ° C. Each of the various lead materials compared were dewaxed to have a pour point of -7 ° C. The VI improved as the weight percentage of hydrogen present in the lubricating base stock increased. VI was slightly improved over hydrocracked feedstock compared to solvent-purified feedstock. Empty circles represent lubricant raw materials prepared solely by hydrocracking, distillation and solvent dewaxing without further treatment. Circles with crossed lines represent lubricating oil raw materials prepared by fuel hydrocracking, distillation and solvent dewaxing. Squares represent lubricating oil raw materials prepared by solvent purification and solvent dewaxing. The upward triangle represents the vacuum distillate obtained from paraffin crude. The downward triangle represents the vacuum distillate obtained from naphthenic crude oil.

Fuel hydrocracking of VGO is much more stringent than lubricant hydrocracking, thus providing a lubricant raw material with a higher VI than lubricant hydrocracking or solvent purification. In the present invention, the dewaxed lubricant raw material must have a VI of at least 115. In FIG. 5, the dewaxed oil product must have a hydrogen content of at least about 14.1% by weight to obtain VI of 115. Since the dewaxing process lowers the hydrogen content, the lead oil should be about 0.2 to 0.5% by weight relative to the hydrogen content of the dewaxed oil. Therefore, a critical feature of the present invention is that the hydrocracker must supply vacuum distillation products containing at least 14.3% by weight of hydrogen. The results of PONA analysis of FIG. 5 for the hydrocracking lubrication raw material indicate that the composition contains various paraffins, some contain naphthenes, and others have moderate compositions. Therefore, infinite changes in the composition of any VI level are possible and for all VI levels the change can be expressed as a hydrogen content range. In particular, the hydrogen content of the carbon number of C ₁₇ to C 150 isoparaffins of ₅₅ was 15.1 to 14.6%. For alkylcyclohexanes it was constant at 14.37% and alkylbenzenes were in the range of 12.4 to 13.69%. From this fact the dewaxed oil product had to be rich in high hydrogen containing isoparaffins and alkylcyclohexanes. Thus, a fuel hydrocracker operated at an excess of 40% conversion to light products at 345 ° C. may produce 345 ° C. plus products with adequate hydrogen content to feed dewaxed oils with VI of at least 115.

Example 3

Figure 6 (parts a, b, c) is a demonstration of lubricating oil hydrolysis and fuel hydrocracking of heavy VGO from Stafjord crude oil. The heavy VGO was hydrocracked at various conversion rates in a pilot plant and the hydrocrackate was distilled to remove all 345 ° C. (653 ° F.) material. The leaded 345 ° C plus oil was solvent dewaxed to have a -18 ° C (0 ° F) flow point and the viscosity and VI were measured. A conversion range of 10 to about 30% was called the lubricating oil hydrocracking range and a 30% and higher conversion range was called the fuel hydrogenation range. It was apparent that the conversion rate of hydrocracking was required to be about 35% to obtain a dewaxed product with VI of 115 or greater. The degree of conversion required depends on the viscosity of the feed to the hydrocracking plant. 6 also shows how the viscosity decreases as hydrocracking proceeds. This was the reason for being limited to making products in the low viscosity range of 60 to 250 SSU at 100 ° F or 3 to 6 cSt at 100 ° C. 6 also shows a low yield of 345 ° C. ^{+ in} the fuel hydrocracker.

The data of Examples 4-12 were obtained from the catalytic dewaxing and hydrogenation process of the two reactors (see also FIG. 5 for details). The first reactor contained HZSM-5, a dedicated hydrogenation dewaxing catalyst.

The same hydrogenation dewaxing catalyst was used for high and low pressure operation. In the second reactor a commercial hydrofinishing catalyst was used. Low pressure (2.86x10 ³ - 4.2x10 ³ kPa) hydro finishing catalyst in operation was only designed for the saturation of olefins. However, some level of aromatic saturation was required for good oxidative stability and UV light stability. Hydrofinishing catalysts operating at high pressure (1.73 × 10 ⁴ kPa) were used for aromatic saturation. The hydrofinishing catalyst used at low pressure was evaluated at 1.53 × 10 ⁴ kPa for comparison.

Example 4

NOACK volatility tests (see FIGS. 7 and 8) were performed using a NOACK evaporation tester according to CEC L-40-T-87 "Evaporation Loss of Lubricating Oils" on pure (unflavored) base stocks. . In short, the method allowed the sample to stand for 60 minutes under constant air flow at 250 ° C. (482 ° F.) and measured evaporation loss (% by weight).

NOACK volatility is shown in FIG. 7 for basic raw materials prepared by contact dewaxing at high pressure and low pressure followed by hydrofinishing. In general, NOACK volatility is related to the percentage of simulated distillation according to D2887 at 399 ° C. (750 ° F.) (see FIG. 7 and Table 5). This product also had a good correlation between NOACK and 10 percentage points (see Figure 8).

In particular, when associated with 5% or 10% boiling points, the flash point and the NOACK move in opposite directions. 9 shows the correlation between the flash point and the 5% boiling point.

Example 5

Both catalyst systems (high pressure catalytic dewaxing + Arosat HDF catalyst (fluorinated NiW / Al ₂ O ₃ ) and low pressure catalytic dewaxing + HDF catalyst (Mo / Al ₂ O ₃ )) easily met the pour point specification, Lubricant yields and viscosities similar to hydrocracked low aromatic, low nitrogen feedstocks were shown. General characteristics are shown below.

Operation at 1.73 x 10 ⁴ kPa (vs. 2.86 x 10 ³ kPa) [(2500 psig vs. 400 psig)] results in aging of the dewaxing catalyst, 2.3 to 0.2 °, which greatly extends the effective cycle length and improves the unit flow factor. Lowered to F / day. The reduction of the pour point was twice that of the pour point reduction with respect to the change in contact dewaxing temperature at high pressures, making it available for the production of basic raw materials with very low pour points if desired (see FIG. 10).

Lubricant yield and VI are less sensitive to pressure (see FIG. 11): For the production of 116 SUS base stock with a pour point of -15 ° C and VI of 121, the yield is 67-72% (contrast: 129 with VI). 107 SUS yield of 82% dry beeswax basis when prepared with solvent dewaxing).

Standard low pressure contact dewaxing had little need to adjust the total aromatic level, determined by UV absorbance at 226 nm. Using an aromatic saturated catalyst at 1.73 × 10 ⁴ kPa (2500 psig) resulted in the reduction of aromatics to equilibrium levels at HDF temperatures of 274 ° C. (525 ° F.) as determined by UV absorbance. The low pressure program was conducted at a two-reactor pilot plant with on-line nitrogen cleaning capabilities. The first reactor was loaded with 225 cc of dewaxing catalyst HZSM-5. The second reactor was loaded with 225 cc of hydrofinishing catalyst (Mo / Al ₂ O ₃ ) designed for the saturation of olefins and for low desulfurization (critical for maintaining the oxidative stability of lubricating oil refined by conventional methods). Both catalysts were commercially produced 1/16 "size cylindrical extrudates.

Low pressure operation was carried out under a voltage of 400 psig using a partial pressure of hydrogen of 2.9 x 10 ³ kPa (415 psi) and a space velocity of 1 LHSV and a circulation rate of 1.73 x 10 ⁴ kPa (2500 SCF / Bbl) in each reactor. . Three HDF temperatures (241 [deg.] C., 274 [deg.] C., 288 [deg.] C.) were tested at standard pour point (-15 [deg.] C.) to address the optimum processing stringency for producing UV light stable basic raw materials.

High pressure contact dewaxing was performance tested in a two reactor pilot plant. The first reactor was loaded with 262 cc dewaxing catalyst. This catalyst was the dewaxing catalyst as used in the standard pressure test. The second reactor was loaded with 62 cc of commercial hydrofinishing catalyst (Arosat) with good aromatic saturation capability. It was a commercially available 1/16 "size lobe extrudates.

High pressure contact dewaxing has a partial pressure of 1.74 x 10 ⁴ kPa, a space velocity of 1 LHSV in each reactor, and a voltage of 1.73 x 10 ⁴ kPa (2500 psig) using a circulation rate of 445 nl1 ^-1 (2500 SCF / Bbl) Under the following conditions. Four hydrofinishing temperatures (329 ° C., 302 ° C., 274 ° C., 232 ° C.) were tested at standard pour point (-15 ° C.) to address optimum processing stringency for producing UV light stable basic raw materials. The data in FIG. 12 clearly shows that the hydrofinishing machine behind the dewaxing reactor requires a good aromatic saturated catalyst.

Example 6

Solar stability

Test Method Description

In this test, pure (unadded) basic raw materials were placed in glass bottles and exposed to natural sunlight and periodically observed for clouding, sediment, and color change. All samples were carried out simultaneously at the same place.

result

High pressure contact dewaxing and hydrogenation of the basic raw material using the aromatic saturation catalyst was excellent in light stability, and after 42 days no precipitation occurred (see FIG. 13). The products made from low pressure contact dewaxing and hydrofinishing and solvent dewaxing showed very poor photostability and similarly deteriorated badly within 2-3 days. This indicated that the light instability was not the result of anything occurring in the contact dewaxing step but due to the unstable components contained in the hydrocracker bottoms.

Such instability is generally related to 3+ ring aromatics, which can be detected by UV absorbance at 325 nm. These compounds absorb light and then oxidize to form free radical chain initiators which continue to react with other hydrocarbons to produce carboxylic acids. Such low aromatic raw materials have low solubility of these oxidation products, resulting in precipitates. The high pressure contact dewaxing and hydrofinished base stock had a lower UV absorption at 325 nm than other samples (see FIG. 12 and Table 5). It has been found that standard catalytic dewaxing hydrotreating catalysts are not suitable for removing these labile components even at 1.53 x 10 ⁴ kPa (2200 psi). The light stability results and UV results of FIG. 13 were correlated in FIG.

Example 7

Rotary Bomb Oxidation of Turbine oil (RBOT) tests for oxidative stability were performed according to ASTM D2272. The test was carried out using a sample mixed with 0.3 wt% Irganox ML 820 (commercially available as a turbine oil additive package) in the base oil. Samples were tested with water and a copper catalyst coil in a pressure bomb. The chestnut was pressurized with oxygen to 620 kPa (90 psi) and left in a bath at 150 ° C. (302 ° F.) and rotated axially on the slope. The time required for the pressure to drop to 172 kPa (25 psi) was recorded; Here, the longer time indicates that the oxidation stability is excellent (see Tables 5 and 15).

result

The RBOT performance of the high pressure contact dewaxing and low pressure contact dewaxing base stocks was comparable and excellent (see Figure 15). Induction of solvent dewaxing made from the same commercial raw material was also good, but slightly lower on average. Compared to the contact dewaxing raw material, the solvent dewaxing hydrocracking sample was bad, as the boiling point range (25% bottoms to full range hydrocracking) increased and as the hydrocracking catalyst aged (end of test versus start of test). It showed a general trend of decreasing RBOT stability.

Example 8

Table 5 shows that through the extremely low UV absorbance at 400 nm, multinuclear aromatics were removed in large quantities from lubricating oils treated with high pressure contact dewaxing and hydrofinishing. This result is related to the solar stability result of FIG.

Example 9

Aging of the dewaxing catalyst at 1.73 × 10 ⁴ kPa (2500 psi) was much lower than aging at 2.8 × 10 ³ kPa (400 psi). Also, the pour point of the lubricating oil was 2.3 times that corresponding to the change of dewaxing temperature at high pressure. This difference was due to the low coke production rate at high pressure.

Aging of the catalyst is shown in FIG. The temperature (actual and calibrated to 5 ° F pour point) and pour point of the hydrogenation dewaxing reactor (first reactor) are shown relative to the date of the stream. The aging rate was lower than that of a conventional solvent refining raw material as in the case of a low nitrogen raw material.

High pressure contact dewaxing test

The catalyst was contoured at 285 ° C. (545 ° F 0) within the first two days of the stream at 1.73 × 10 ⁴ kPa (2500 psi). The 36-day test for aging rate was negligible. In conclusion, 1.73 × 10 ⁴ kPa ( Extremely long cycle lengths could be expected.

Low pressure contact dewaxing test

At 2.8 × 10 ³ kPa (400 psi) the onset of circulation was about 530 ° F. Initial aging rate was -14 ° C (6.4 ° F / day) and shifted to a low aging rate of -15 ° C (5.65 ° F / day). Pour point to 1.3 ° F flow / 1 ° F (HDW reactor temperature change) for smoothing temperature data in HDW reactors for pour point ranges from -30 ° C to 4 ° C (-22 ° F to + 39 ° F) Letting is available.

After day 29 of the stream the pressure rose to 2200 psi. Within 4 days the catalyst recovered a significant amount of activity and the aging rate dropped to near zero. This was the result of increased aging at 2.8 x 10 ³ kPa (400 psi) and some of the coke was easily hydrogenated or desorbed when the pressure was increased.

Example 10

In general, increasing the contact dewaxing operating pressure tended to reduce the yield of distillate and increase the yield of the corresponding C5-. The yield of lubricating oil was relatively insensitive to pressure. The yield at the pour point of -15 ° C (5 ° F) was about 10% by weight relative to solvent dewaxing, 70-72% for contact dewaxing with ZSM-5 catalyst and 82% by weight for solvent dewaxing ( Dry wax). However, it should be noted that most solvent dewaxing units produce beeswax containing 10-30% oil. Therefore, the actual solvent dewaxing yield is in the range of 74 to 80%.

The product yield distribution showed that nonselective decomposition occurred on a high activity, high pressure aromatic saturated catalyst at 329 ° C. (62 ° F.). Lubricant yield dropped by 6% by weight, as shown in FIG. 16 (lubricant yield versus temperature) and 17 degrees (strictness of hydrofinishing at viscosity versus constant pour point). Most of this loss was due to an increase in distillate yield. Sudden increases in lubricating oil properties at hydrotreatment temperatures of 329 ° C (625 ° F) also indicate non-selective decomposition.

The viscosity of the low pressure and high pressure contact dewaxing lubricating oil products was similar throughout most of the hydrofinishing operating ranges tested (FIG. 18). At a pour point of −15 ° C. (5 ° F.), the viscosity at 100 ° C. was 4.6 cSt (116 SUS at 100 ° F.) and VI was 121. The viscosity of the solvent dewaxed oil was lower and VI was higher, consistent with the difference in how the two processes achieve their goals.

It was evident from the lubricating oil properties and yields discussed above that non-selective decomposition occurs on the Aroche hydrofinishing catalyst at 329 ° C. (625 ° F.). The viscosity of the lubricating oil dropped significantly, and correspondingly, the VI dropped about 3-5. (See: Figure 18)

The main differences in the properties of lubricating oils prepared by low and high pressure contact dewaxing are the result of aromatic saturation in the hydrofinishing reactor-(1) the type of hydrofinishing catalyst used and (2) the difference in hydrogen pressure. This difference was even greater for aromatic feedstocks, ie hydrocracker bottoms or end-of-cycle products of hydrocracking.

Solvent dewaxing preferentially removes heavy, high flow beeswax but preferentially degrades the small, n-paraffins, the highest VI component, in contact dewaxing with ZSM-5. As a result, the yield and VI of contact neutralized light neutral lubricating oil were low. However, the low temperature viscosity of the formulated contact dewaxing product was superior to comparable viscosity of solvent dewaxing oil.

Example 11

During the pilot plant study, the appearance of the product as well as the UV absorbance depended on the conditions of the hydrofinishing reactor. Absorbance at five wavelengths-226, 254, 275, 325 and 400 nm-was used as a qualitative indicator of the amount of aromatics with 226 nm corresponding to all aromatics. In particular, aromatics with three or more, four or more rings were well represented by absorbance at 325 and 400 nm.

The aromatics of the lubricating oil were dramatically reduced by the Arrochet HDF catalyst. Standard catalytic dewaxing HDF catalysts designed for saturation of olefins were very bad at pressures of 1.53 × 10 ⁴ kPa (2200 psi) (see FIGS. 12 and 21). As shown in FIG. 12, the UV absorbance at 226 nm (correlated with total aromatics) for the high pressure contact dewaxing catalyst at 274 ° C. (525 ° F) (represents crossover in a region dynamically limited by equilibrium limitations). Has the lowest value. This minimum should shift towards high HDF temperatures (and high UV absorbance) as the aromatics in the feedstock increase. Standard catalytic dewaxing HDF catalysts were dynamically limited in saturating aromatics over the temperature range tested.

In general, the saturation of polynuclear aromatics (400 nm) is relatively easy and the reaction is equilibrated by the usual hydrofinishing temperature range at high pressure, which means that the polynuclear aromatics decrease with increasing hydrofinishing temperature. Higher hydrogen pressures shift the equilibrium to the lower side.

19 and 20 show the correlation between the UV absorbance and aromatic content of two different hydrocracking products. One is low in aromatic content and the other is high in aromatic content. The data clearly showed that the high pressure and aromatic saturated hydrofinishing catalysts were superior to the low pressure hydrofinishing with standard hydrofinishing catalysts (Table 6).

Table 6

Comparison of product properties

Example 3

While many of the above embodiments used HZSM-5 as a dewaxing catalyst, other catalysts described above could also be used as dewaxing catalysts. This is shown in FIG. 20 where the dewaxing catalyst is platinum / ZSM-23. 18 shows that the VI and yield of the lubricating oil obtained with platinum / ZSM-23 are the same or better than those obtained with solvent dewaxing.

Example 14

A number of mesoporous molecular sieves were tested for the ability to convert n-paraffins, a representative beeswax of lead light lubricant base stocks. n-paraffins were n-hexadecane. The molecular sieves tested using this compound were ZSM-5, ZSM-23, ZSM-48 and SAPO-11. The acidic activity of the catalyst as determined by the alpha test was changed for the molecular sieve by steaming known to reduce the synthesis of the molecular sieve or the activity of the molecular sieve. To each catalyst made of powder was added a noble metal, so-called platinum. The concentration of platinum has changed in some molecular sieves. The table below lists the molecular sieves, their platinum content and alpha activity.

TABLE 7

Characteristics of Molecular Sieve

All these heavy pore molecular sieves had a high conversion to lead compounds such as n-hexadecane. The activity of the catalyst prepared with each molecular sieve could vary greatly depending on the activity of the molecular sieve in the catalyst. Platinum content also affected the activity. Product selectivity was influenced by the shape of the sieve, platinum content and alpha activity. Figure 21 shows the relationship of the conversion versus the required temperature of n-hexadecane. Figure 22 is the relationship of isomerization conversion yield to hexadecane conversion of n-hexadecane with 16 carbon atoms. This figure shows that ZSM-45 and SAPO-11 generally have the best selectivity for isoparaffins. The selectivity was very low with the high alpha ZSM-5. However, FIG. 23 shows that ZSM-23 has the best selectivity for the single-sided isomer of n-hexadecane. This type of selectivity can be very important in determining the VI of the product of the lubricant. Thus, the conversion of n-paraffins, or beeswax, to isomerized compounds of the same molecular weight requires optimization of the noble metal content, and the pore structure of the molecular sieves for each molecular sieve used to prepare the acidic activity and the processed catalyst. It is self-evident.

1 is a schematic diagram of a fuel hydrocracker suitable for use in the present invention. Hydrogenizers, hydrocrackers, separators, vacuum distillation units and hydrofinishing units are represented. The non-converting material from the fractionator unit can be sent to a vacuum distillation unit to circulate the hydrocracking unit or to make a cut suitable for input into the catalytic dewaxing reactor.

2 is a simple diagram showing a series of vertical reactors with a fixed catalyst bed and the main flow.

3 shows the correlation between the boiling point and the viscosity of pure components and vacuum gas oil (VGO) made from Arab light crude oil.

4 shows a comparison of the characteristics of small pores, mesopores, large pore zeolites and molecular sieves.

5 through 21 are graphs comparing various process coefficients and properties of lubricating oil products and products for improved processes.

Preferred reactor systems are schematically depicted in FIGS. 1 and 2.

Claims (33)

(a) Hydrocracking a feedstock boiling above 340 ° C. and containing up to 13.5% by weight of hydrogen at inlet conditions, so that at least 30% by weight of the feedstock is converted to a hydrocarbon product boiling below the initial boiling point of the feedstock. To; (b) a kinematic viscosity of 3 cSt or higher at 100 ° C., a VI (viscosity index) of waxy of 125 or more, a NOACK number of 20 or less, a hydrogen content of 14% by weight or more, a pour point of 10 ° C. or more and a nitrogen content of 30 ppm or less; A portion of the unconverted material in the excitation step (a) is distributed evenly and the material is raised to a temperature below 425 ° C. (797 ° F.) in the presence of hydrogen supplied simultaneously at a pressure of at least 10,000 kPa (1450 psi). At temperature, there is at least one channel with pores formed by a ring containing ten oxygen atoms alternating with silicon or phosphorus atoms, and a form-selective constrained intermediate having acidic functionality. Hydrogen dewaxing by contact with a catalyst containing pore molecular sieves; (c) To obtain the dewaxed lubricating oil product, the effluent of step (b) is subjected to an aromatic saturation condition at a temperature of about 230 ° C. (446 ° F.) to about 343 ° C. (650 ° F.) and at least 10,000 kPa (1450 psi). Hydrofinishing by contacting with an effective aromatic saturated hydrofinishing catalyst having simultaneously supplied hydrogen and metal hydrogenation function under pressure; (d) separating the by-product from the lubricating oil product of step (c) by flashing and distillation, By a method comprising one or more hydrocracking zones, one or more hydrodewaxing zones and one or more hydrofinishing zones, pour point below -4 ° C, hydrogen content above 13.7% by weight, flash point above 200 ° C, NOACK number below 20, 25 Prepares dewaxed lubricating oil products having at least Saybolt chromaticity, a total aromatic content of less than 10% by weight, a viscosity of at least 3.0 cSt at 100 ° C., a viscosity index (VI) of at least 115 and excellent oxidation stability, UV light stability and thermal stability. How to. The process of claim 1 wherein the hydrodewaxed unconverted material in step (b) is boiling above 315 ° C. The process of claim 1, wherein step 1 (a) is further; (a) hydroprocessing the hydrocarbon feedstock of step 1 (a) with a catalyst having hydrodenitrification and hydrodesulfurization activity in the hydroprocessing zone; (b) passing the hydrogenation effluent of step 3 (a) stepwise through a hydrocracking zone where the feed is subjected to a hydrogen partial pressure of 3448 to 17,238 kPa (500 to 2500 psi) at elevated temperature and pressure in the presence of hydrogen; , Amorphous or large pores with large pores under conditions of temperatures between 315 ° C. and 455 ° C. (600 ° F. to 850 ° F.), space velocities of 0.5 to 10 LHSV and hydrogen to oil ratios of 1000 to 5000 SCF / Bbl. Contacting a hydrocracking catalyst containing a molecular sieve and additional hydrogenation / dehydrogenation component to convert the hydrotreated effluent into a low boiling product, thereby hydrocracking the feedstock (hydrocracking effluent with 90% or more nitrogen removed). Water has a conversion of at least 30% by weight per pass here); (c) the hydrocracking effluent of step 3 (b) is passed to a separation zone for product separation, where the unconverted portion is at the bottom temperature of the tower in the range of about 300 to 380 ° C. and in the range of about 20 to 300 mm Hg. Passing through a vacuum distillation zone operating at the bottom pressure of the tower to produce a product fraction and a bottom fraction; (d) passing the product of step 3 (c) to the dewaxing zone of step 1 (b). 4. The process of claim 3, wherein at least a portion of the residue fraction in step 3 (c) is recycled to the hydrocracking zone of step 3 (b). The method of claim 1 or 2, wherein the shape-selective mesoporous molecular sieve material of step 1 (b) consists of ZSM-5, ZSM-23, ZSM-35, ZSM-11, SAPO-11, or a combination thereof. Selected from the group, wherein these catalysts are each loaded with a noble metal. The method of claim 1 or 2, wherein the shape-selective mesoporous molecular sieve of step 1 (b) is HZSM-5. 6. The method of claim 5, wherein the shape selective mesoporous molecular sieve material has an inhibition index of 0.5 to 12 and an alpha value of less than 300. 8. The method of claim 7, wherein the alpha value is less than 30. 9. The method of claim 8, wherein the alpha value is less than 10. 6. The method of claim 5 wherein 0.2 to 1.2 weight percent of the precious metal is loaded into the molecular sieve material. The process of claim 1 or 2, wherein the hydrofinishing catalyst of step 1 (c) contains at least one Group VIIIA and at least one Group VIA (IUPAC Periodic Table) metal on the porous solid support. The method of claim 1, wherein the hydrofinishing catalyst of step 1 (c) contains nickel or tungsten metal on the fluorinated porous alumina support containing alumina or a mixture of silica and alumina. The process of claim 1 wherein the dewaxing and hydrofinishing zones are operated at substantially the same pressure and the entire dewaxing oil stream from the dewaxing step is passed directly to the hydrofinishing zone. The process of claim 10 wherein the dewaxing catalyst is aged at a rate of 0.1 ° C./day or less at a pressure greater than 10,000 kPa. The process according to claim 1, wherein the hydrogenation dewaxing of step 1 (b) occurs in at least two dewaxing zones. The method of claim 1 wherein the hydrofinishing of step 1 (c) occurs in at least two dewaxing zones. The method of claim 1, wherein the dewaxed lubricant product boils at least about 370 ° C. and has a KV in the range of 4-10 cSt at 100 ° C. and a UV absorbance of less than 0.001 L / g-cm at 315 nm. 18. The method of claim 17, wherein the dewaxed lubricating oil product has a UV absorbance of less than 0.001 L / g-cm at 315 nm. The process of claim 1 or 2, wherein the heavy hydrocarbon feedstock is a vacuum gas oil, deasphalted residue, or mixtures thereof. The process of claim 1 or 2, wherein the hydrogenation dewaxing zone of step 1 (b) comprises a series of vertically arranged fixed bed catalytic reactors, wherein a hydrogen gas quench stream for use in lowering the temperature is located between the fixed beds. How to. The hydrofinishing zone of step 1 (c) comprises a series of vertically arranged fixed bed catalytic reactors, wherein a hydrogen gas quench stream for use in lowering the temperature is located between the fixed beds. Way. The method of claim 1, wherein the NOACK number is 10 or less. 23. The method of claim 22, wherein the NOACK number is 5 or less. 4. The process of claim 3, wherein the bottoms of the vacuum distillation zone in step 3 (c) have a NOACK number of 20 or less. The method of claim 24, wherein the residual oil in the vacuum distillation zone has a NOACK number of 10 or less. 26. The method of claim 25, wherein the residual oil in the vacuum distillation zone has a NOACk number of 5 or less. The method of claim 1 wherein the dewaxed lubricant and the product have an aromatic content of 2 wt% or less. The method of claim 1 wherein the dewaxed lubricating oil product exhibits chromatic stability after exposure to sunlight and air for 10 days. The process of claim 1 wherein the dewaxed lubricant product has a 10% distillation point of at least 357 ° C. 30. The method of claim 29, wherein the dewaxed lubricating oil product has a 10% distillation point of at least 413 ° C. 31. The method of claim 30, wherein the dewaxed lubricating oil product has a 10% distillation point of at least 432 ° C. The process of claim 1 wherein the dewaxed lubricant product has a pour point in the range of -50 ° C to -4 ° C. The method of claim 1 wherein the dewaxed lubricating oil product has a hydrogen content of at least 14.3% by weight and at least 120 VI.