CATALYTIC DEWAXING OF HYDROCARBONS USING A MOLECULAR SIEVE CATALYST

Abstract: Catalytic dewaxing of a hydrocarbon oil feedstock boiling above 176°C is effected by contacting the feedstock with a catalyst which comprises an intermediate pore size sil­ icoaluminophosphate molecular sieve and at least one Group VIII metal such as platinum.

Description: CATALYTIC DEWAXING OF:HYDROCRBONS USING A MOLECULAR SIEVE CATALYST This invention relates to the catalytic dewaxing of a hydrocarbon oil feedstock containing waxy hydrocarbons using a molecular sieve catalyst containing at least one Group VIII metal. Processes for dewaxing petroleum distillates are well known. Dewaxing is required when highly paraffinic oils are to be used. in products which need to remain mobile at low temperatures, e.g., lubricating oils, heating oils, and jet fuels. The higher molecular weight straight chain normal and slightly branched paraffins which are present in oils of this kind, are waxes which are the cause of high pour points and high cloud points in the oils. If adequately low pour points areto be obtained, these waxes must be wholly or partly removed. In the past, various solvent removal techniques were used, e.g., propane dewaxing and MEK (methylethylketone) dewaxing, but these techniques are cost and tirre consuming. Catalytic dewaxinq processes are more economical and achieve this end by selectively cracking the longer chain n-paraffins, to produce lower molecular weight products, some of which may be removed by distillation. Because of their selectivity, prior art dewaxing catalysts generally comprise an aluminosilicate zeolite having a pore size which admits the straight chain n-paraffins either alone or with only slightly branched chain paraffins, but which excludes more highly branched materials, cycloaliphatics and aromatics. Zeolites such as ZSM-5, ZSM-ll, ZSM-12, ZSM-23, ZSM-35 and ZSM-38 have been proposed for this purpose in dewaxing processes and their use is described in U.S. Patent Nos. U.S. 3,700,585; 3,894,938t 4,176,050; 4,181,598; 4,222,855; 4,229,282 and 4,247,388. Since dewaxing processes of this kind function by means of cracking reactions, a number of useful products become degraded to lower molecular weight materials. For example, waxy paraffins may be cracked down to butane, propane, ethane and methane and so may the lighter n-paraffins which do not, in any event, contribute to the waxy nature of the oil. Because these lighter products are generally of lower value than the higher molecular weight materials, it would obviously be desirable to limit the degree of cracking which takes place during a catalytic dewaxing process. A dewaxing catalyst has now been found which has superior selectivity with respect to the nature of the products obtained in a dewaxing process. By use of certain silicoaluminophosphate molecular sieve catalysts in the dewaxing process, hydrocarbon oil feedstocks may be effectively dewaxed to obtain products which are of higher molecular weight than those obtained using the prior art aluminosilicate zeolites Also, and especially with respect to lubricating oil feedstocks, the products obtained from the dewaxing process of this invention have better viscosities and viscosity indexes at a given pour point as compared to the above-described prior art process using aluminosilicate zeolites. In accordance with the present invention, the catalytic dewaxing of a hydrocarbon oil feedstock boiling above 350"F (176"C) and containing waxy hydrocarbons is effected by contacting said oil feedstock with a catalyst comprising an intermediate pore size silicoaluminophosphate molecular sieve and at least one Group VIII metal to selectively convert at least some, preferably all, of the waxy hydrocarbons to lower molecular weight non-waxy hydrocarbons. The silicoaluminophosphate molecular sieves used in the process of this invention are described, for example, in U.S. Patent NO. 4,440,871. It has been found that the present invention provides selective conVerton Of waxy n-paraffins to nonwaxy paraffins. During processin the waxy paraffins undergo mild cracking reactions to yield non-waxy products of higher molecular weight than compared to products obtained using the prior art zeolitic catalyst. At the same time, a measure of isomerization takes place, so that not only is the pour point reduced by reason of the cracking reactions described above, but in addition the n-paraffins become isomerized to iso-paraffins to form liquid range materials which contribute to a low viscosity, low pour point product. Because of the selectivity of the catalyst used in the process of this invention, the gas yield is reduced, thereby preserving the economic value of the feedstock. Hydrogen consumption using the process of this invention is less compared to prior art processes using conventional dewaxing catalysts because isomerization does not consume hydrogen and cracking to liquid range products consumes less hydrogen than cracking to gas. For a better understanding of the invention, reference will now be made, by way of exartplea to the accompanying drawings in which: FIG. 1 is a ternary diagram showing the compositional parameters 9f the silicoaluminophosphates of U.S. Patent No. 4,440,871 in terms of mole fractions of silicon, aluminum and phosphorus; FIG. 2 is a ternary diagram showing the preferred compositional parameters of the silicoaluminophosphates of mole fractions of silicon, aluminum and phosphorus; FIG. 3 is a graph showing a comparison for a crystalline silicoaluminophosphate catalyst used in the process of this invention and a ZSM-5 catalyst with respect'to lube yield at a given pour point in a dewaxing process FIG. 4 is a graph showing a comparison for a crystalline silicoaluminophosphate catalyst used in the process of this invention and a ZSM-5 catalyst with respect to viscosity index at a given pour point in a dewaxing process and and FIG. 5 is a graph showing a comparison for a crystalline silicoaluminophosphate catalyst used in the process of this invention and a ZSM-5 catalyst with respect to viscosity at a gien pour point in a dewaxing process. Feedstock The present process may be used to dewax a variety of feedstocks ranging from relatively light distillate fractions up to high boiling stocks such as whole crude petroleum, reduced crudes, vacuum tower residua, cycle oils, synthetic crudes (e.g., shale oils, tar sand oil, etc.), gas oils, vacuum gas oils, foots oils, and other heavy oils. The feedstock will normally be a C10+ feedstock boiling above 350 F (176"C) since lighter oils will usually be free of significant quantities of waxy components. However, the process is particularly useful with waxy distillate stocks such as middle distillate stocks including gas oils, kerosenes, and jet fuels, lubricating oil stocks, heating oils and other distillate fractions whose pour point and viscosity need to be maintained within certain specificati-on limits. Lubricating oil stocks will generally boil above 230"C (4500F), more usually above 315"C (600"F). Hydroprocessed stocks are a convenient source of stocks of this kind and also of other distillate fractions since they normally contain significant amounts of waxy n-paraffins. The feedstock of the present process will normally be a C10+ feedstock containing paraffins, olefins, naphthenes, aromatics and heterocyclic compounds and with a substantial proportion of higher molecular weight n-paraffins and slightly branched paraffins which contribute to the waxy nature of the feedstock. During the processing, the n-paraffins and the slightly branched paraffins undergo some cracking or hydrocracking to form liquid range materials which contribute to a low viscosity product. The degree of cracking which occurs is, however, limited so that the gas yield is reduced, thereby preserving the economic value of the feedstock. Typical feedstocks include light gas oils, heavy gas oils and reduced crudes boiling above 3500F (176 C). While the process herein can be practised with utility when the feed contains organic nitrogen (nitrogencontaining impurities), it is preferred that the organic nitrogen content of the feed be less than 50, more preferably less than 10, ppmw. Especially good results, in terms of activity and length of catalyst cycle (period between successive regenerations or start-up and first regeneration), are experienced when the feed contains less than 10 ppmw of organic nitrogen. SILICOALUMINOPHOSPHATE CATALYST COMPOSITIONS (SAPOs) Silicoaluminophosphate molecular sieves (SAPOs) suitable for use in the present invention may comprise any molecular sieve having a silicoaluminophosphate molecular framework which has an intermediate pore size and which comprises a molecular framework of corner-sharing [SiO2] tetrahedra, !A1021 tetrahedra and tPo2i tetrahedra, [i.e., (SiXAlyP)O2 tetrahedral units, and which functions to convert at effective process conditions the aforementioned .feedstock to dewaxed products and includes those silicoaluminophosphate molecular sieves described in U.S. Patent No. 4,440,871. The preferred intermediate pore size SAPOs are characterized as comprising a three-dimensional microporous crystal framework structure of [5i021, [A102] and jPO2i tetrahedral units which has a unit empirical formula on a anhydrous basis of: mR: : (Si xAl P )O2 wherein "R" represents at least one organic templating agent (hereinafter also referred to as "template") present in the intracrystalline pore system; wmw represents the moles of "R" present per mole of (SxAlyPz)O2 and has a value from zero (0) to about 0.3, with the maximum value of m being related at least in part, to the molecular dimensions of the template and the void volume of the intracrystalline pore system of the particular SAPO; "X", "y" and "z" represent the mole fractions of silicon, aluminum and phosphorus, respectively, present as tetrahedral oxide units, said mole fractions being within the pentagonal compositional area defined by points A, B, C, D and E of the ternary compositional diagram depicted by FIG. 1 of the drawings where the points A, B, C, D and E are represented by the following values for "x", "y" and "z": : Mole Fraction Point x V * z A 0.01 0.47 0.52 B 0.94 0.01 0.05 C 0.98 0.01 0.01 D 0.39 0.60 0.01 E 0.01 0.60 0.39 A preferred sub-class of the SAPOs of Formula (1), above, have a minimum value of "m" of 0.02 in the assynthesized form and have the values of Nx", "y", and "z" within the pentagonal compositional area defined by the points a, b, c, d, and e of the ternary diagram which is FIG. 2 of the drawings, wherein said points a, b, c, d, and e are represented by the following values of "x", "y" and "z": : Mole Fraction Point x y z a 0.02 0.49 0.49 b 0.25 0.37 0.38 c 0.25 0.48 0.27 d 0.13 0.60 0.27 e 0.02 0.60 0.38 The term "unit empirical formula" is used herein according to its common meaning to designate the simplest formula which gives the relative number of atoms of silicon, aluminum and phosphorus which form a is1023 and [Sio21 tetrahedral unit within a silicoaluminophosphate molecular sieve and which forms the molecular framework of the SAPO composition(s). The unit empirical formula is given in terms of silicon, aluminum and phosphorus as shown in Formula (1), above, and does not include other compounds, cations or anions which may be present as a result of the SAPO's preparation or the existence of other impurities or materials in the bulk composition not containing the aforementioned tetrahedral unit as the molecular framework. The amount of template R is reported as part of the composition when the assynthesized unit empirical formula is given, and water may also be reported unless such is defined as the anhydrous form. For convenience, coefficient wmw for template "R" is reported as a value that is normalized by dividing the number of moles of R by the total number of moles of silicon, phosphorus and aluminum. When moles of water are reported the moles of water relative to the mole fractions of silicon, aluminum and phosphorus is reported as a value that is normalized by dividing the number of moles of water by the total moles of silicon, phosphorus and aluminium. The values of x, y and z are determined by dividing the number of moles of silicon, aluminum and phosphorus individually by the total number of moles of silicon, aluminum and phosphorus. The unit empirical formula for a SAPO may be given on an "as-synthesized" basis or may be given after an "as-synthesized" SAPO composition has been subjected to some post treatment process, e.g., calcined. The term "as-synthesized* herein shall be used to refer to the SAPO composition(s) formed as a result of the hydrothermal crystallization but before the SAPO composition has been subjected to post treatment to remove any volatile components present therein. The actual value of "m" for a post-treated SAPO will depend on several factors (including: the particular SAPO, template, severity of the post-treatment in terms of its ability to remove the template from the SAPO, the proposed application of the SAPO composition, and etc.) and the value for "m" can be within the range of values as defined for the assynthesized SAPO compositions although such is generally less than the as-synthesized SAPO unless such posttreatment process adds template to the SAPO so treated. A SAPO composition which is in the calcined or other posttreated form generally has an empirical formula represented by Formula (1), except that the value. of "m" is generally less than about 0.02. Under sufficiently severe post-treatment conditions, e.g., roasting in air at high temperature for long periods (over 1 hr.), the value of "m" may be zero (0) or, in any event, the template, R, is undetectable by normal analytical procedures. The above silicoaluminophosphates are generally synthesized by hydrothermal crystallization from a reaction mixture comprising reactive sources of silicon, aluminum and phosphorus, and one or more organic templating agents. Optionally, alkali metal(s) may be present in the reaction mixture. The reaction mixture is placed in a sealed pressure vessel, preferably lined with an inert plastic material, such as polytetrafluoroethylene, and heated, preferably under autogenous pressure at a temperature of at least about 1000C, and preferably between 1000C and 2500C, until crystals of the silicoaluminophosphate product are obtained, usually for a period of from 2 hours to 2 weeks. While not essential to the synthesis of SAPO compositions, it has been found that in general stirring or other moderate agitation of the reaction mixture and/or seeding the reaction mixture with seed crystals of either the SAPO to be produced, or a topologically similar composition, facilitates the crystallization procedure. The product is recovered by any convenient method such as centrifugation or filtration. After crystallization the SAPO may be isolated and washed with water and dried in air. As a result of the hydrothermal crystallization, the as-synthesized SAPO contains within its intracrystalline pore system at least one form of-the template employed in its formation. Generally, the template is a molecular species, but it is possible, steric considerations permitting, that at least some of the template is present as a charge-balancing cation. Generally the template is too large to move freely through the intracrystalline pore system of the formed SAPO and may be removed by a post-treatment process, such as by calcining the SAPO at temperatures of between about 200wC and to about 7000C so as to thermally degrade the template or by employing some other posttreatment process for removal of at least part of the template from the SAPO. In some instances the pores of the SAPO are sufficiently large to permit transport of the template, and, accordingly, complete or partial removal thereof can be accomplished by conventional desorption procedures such as carried out in the case of zeolites. The SAPOs are preferably formed from a reaction mixture having a mole fraction of alkali metal cation which is sufficiently low that it does not interfere with the formation of the SAPO composition. Although the SAPO compositions will form if alkali metal cation are present, such reaction mixtures are not generally preferred. A reaction mixture, expressed in terms of molar oxide ratios, having the following bulk composition is preferred: aR2O:(SixAlyPz)o2 bH2o x O2:bH2O wherein "R" is a template; "a" has a value great enough to constitute an effective concentration of "R" and is within the range of from greater than zero (0) to about 3; "b" has a value of from zero to 500; "x", *y" and "z" represent the mole fractions, respectively of silicon, aluminum and phosphorus wherein x, y and z each have a value of at least 0.01. The reaction mixture is preferably formed by combining at least a portion of the reactive aluminum and phosphorus sources in the substantial absence of the silicon source and thereafter combining the resulting reaction mixture comprising the aluminum and phosphorus sources with the silicon source. When the SAPOs are synthesized by this method the value of "m" in Formula (1) is generally above about 0,02. Though the presence of alkali metal cations are not preferred, when they are present in the reaction mixture it is preferred to first admix.at least a portion of each of the aluminum and phosphorus sources in the substantial absence of the silicon source. This procedure avoids adding the phosphorus source to a highly basic reaction mixture containing the silicon and aluminum source. The reaction mixture from which these SAPOs are formed contain one or more organic templating agents (templates) which can be most any of those heretofore proposed for use in the synthesis of aluminosilicates The template preferably contains at least one element of Group VA of the Periodic Table, particularly nitrogen, phosphorus, arsenic and/or antimony, more preferably nitrogen or phosphorus and most preferably nitrogen. The template contains at least one alkyl, aryl, araalkyl, or alkylaryl group. The template preferably contains from 1 to 8 carbon atoms, although more than eight carbon atoms may be present in the template. Nitrogen-containing templates are preferred, including amines and quaternary ammonium compounds, the latter being represented generally by the formula R'4N+ wherein each R' is an alkyl, aryl, alkylaryl, or araalkyl group; wherein R' preferably contains from 1 to 8 carbon atoms or higher when R' is alkyl and greater than 6 carbon atoms when R' is otherwise, as hereinbefore discussed. Polymeric quaternary ammonium salts such as [(C14H32N2)(OH)23x wherein "x" has a value of at least 2 may also be employed. The mono-, di- and tri-amines, including mixed amines, may also be employed as templates either alone or in combination with a quaternary ammonium compound or another template. Representative templates, phosphorus, aluminum and silicon sources as well as detailed process conditions are more fully described in U.S. Patent 4,440,871, By intermediate pore size", as used herein, is meant an effective pore aperture in the range from 5.3 to 6.5 Angstroms when the molecular sieve is in the calcined form. Molecular sieves having pore apertures in this range tend to have unique molecular sieving characteristics. Unlike small pore zeolites such as erionite and chabazite, they wil allow hydrocarbons having some branching into the molecular sieve void spaces. Unlike larger pore zeolites such as the faujasites and mordenites, they can differentiate between n-alkanes and slightly branched alkanes on the one hand and larger branched alkanes having, for example, quaternary carbon atoms. The effective pore size of the molecular sieves can be measured using standard adsorption techniques and hydrocarbonaceous compounds of known minimum kinetic diameters. See Breck, Zeolite Molecular Sieves, 1974 (especially Chapter 8); Anderson et al., J. Catalysis 58, 114 (1979); and U.S. Patent No. 4,440,871 Intermediate pore size molecular sieves will typically admit molecules having kinetic diameters of 5.3 to 6.5 Angstroms with little hindrance. Examples of such compounds (and their kinetic diameters in Angstroms) are: n-hexane (4.3), 3-methylpentane (5.5), benzene (5.85), and toluene (5.8). Compounds having kinetic diameters of about 6 to 6.5 Angstroms can be admitted into the pores, depending on the particular sieve, but do not penetrate as quickly and in some cases are effectively excluded. Compounds having kinetic diameters in the range of 6 to 6.5 Angstroms include: cyclohexane (6.0), 2,3dimethylbutane (6.1), and m-xylene (6.1). Generally, compounds having kinetic diameters of greater than about 6.5 Angstroms do not penetrate the pore apertures and thus are not absorbed into the interior of the molecular sieve lattice. Examples of such larger compounds include: o-xylene (6.8), 1,3,5-trimethylbenzene (7.5), and tributylamine (8.1). The preferred effective pore size range is from about 5.5 to about 6.2 Angstroms. In performing adsorption measurements to determine pore size, standard techniques are used. It is convenient to consider a particular molecule as excluded if it does not reach at least 95% of its equilibrium adsorption value on the molecular sieve in less than about 10 minutes (p/po=0.5; 25"C). The preferred intermediate pore size silicoaluminophosphate molecular sieves which are useful in the process of this invention include SAPO-ll, SAPO-31 and SAPO-41 and are described in U.S. Patent No. 4,440,871. More specifically; SAPO-ll, as referred to herein, comprises a silicoaluminophosphate material having a three-dimensional microporous crystal framework structure of iPO2], jA1o2] and (SiO2 tetrahedral units whose unit empirical formula on an anhydrous basis is: mR: (SixAlyPz)O2 wherein "R" represents at least one organic-templating agent present in the intracrystalline pore system; "m" represents the moles af "R" present per mole of (SiXAlyPz)O2 and has a value from zero to about 0.3, "x", fly" and "z" represent respectively, the mole fractions of silicon, aluminum and phosphorus, said mole fractions being within the compositional area bounded by points A, B, C, D and E on the ternary diagram which is FIG. 1 or preferably within the area bounded by points a, b, c, d and e on the ternary diagram which is FIG. 2, and said silicoaluminophosphate having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings (as-synthesized and calcined) set forth below in Table I. When SAPO-Il is in the as-synthesized form wm" preferably has a value of from 0.02 to 0.3. TABLE I Relative 29 d Intensity 9.4-9.65 9.41-9.17 m 20.3-20.6 4.37-4.31 m 21.0-21.3 4.23-4.17 vs 22.1-22.35 4.02-3.99 m 22.5-22.9 (doublet) 3.95-3.92 m 23.15-23.35 3.84-3.81 m-s All of the as-synthesized SAPO-Il compositions for which X-ray powder diffraction data have been obtained to date have patterns which are within the generalized pattern of the Table II below. TABLE II 20 d 100 x I/Io 8.05-8.3 10.98-10.65 20-42 9.4-9.65 9.41-9.17 36-58 13.1-13.4 6.76-6.61 12-16 15.6-15.85 5.68-5.59 23-38 16.2-16.4 5.47-5.40 3-5 18.95-19.2 4.68-4.62 5-6 20.3-20.6 4.37-4.31 36-49 21.0-21.3 4.23-4.17 100 22.1-22.35 4.02-3.99 47-59 22.5-22.9 (doublet) 3.95-3.92 55-60 23.15-23.35 3.84-3.81 64-74 24.5-24.9 (doublet) 3.63-3.58 7-10 26.4-26.8 (doublet) 3.38-3.33 11-19 27.2-27.3 3.28-3.27 0-1 28.3-28.5 (shoulder) 3.15-3.13 11-17 28.6-28.85 3.121-3.094 29.0-29.2 3.079-3.058 0-3 29.45-29.65 3.033-3.013 5-7 31.45-31.7 2.846-2.823 7-9 32.8-33.1 2.730-2.706 11-14 34.1-34.4 2.629-2.607 7-9 35.7-36.0 2.515-2.495 0-3 36.3-36.7 2.475-2.449 3-4 37.5-38.0 (doublet) 2.398-2.368 10-13 39.3-39.55 2.292-2.279 2-3 40.3 2.238 0-2 42.2-42.4 2.141-2.132 0-2 42.8-43.1 2.113-2.099 3-6 44.8-45.2 (doublet) 2.023-2.006 3-5 45.9-46.1 1.977-1.969 0-2 46.8-47.1 1.941-1.929 0-1 48.7-49.0 1.870-1.859 2-3 50.5-50.8 1.807-1.797 3-4 54.6-54.8 1.681-1.675 2-3 55.4-55.7 1.658-1.650 0-2 SAPO-31, as referred to herein, comprises a silicoaluminophosphate having a three-dimensional microporous crystal framework of (PO2] , [A1o2] and [SiO2] tetrahedral units whose unit empirical formula on an anhydrous basis is: mR:(SixAlyPz)02 wherein R represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the moles of "R" present per mole of (SiXAlyPz)O2 and has a value of from zero to 0.3; "x", "y" and "z" represent respectively, the mole fractions of silicon, aluminum and phosphorus, said mole fractions being within the compositional area bounded by points A, X, C, D and E on the ternary diagram which is FIG. 1, or preferably within the area bounded by points a, b, c, d and e on the ternary diagram which is FIG. 2, said silicoaluminophosphate having a characteristic X-ray powder diffraction pattern (as-synthesized and calcined) which contains at least the d-spacings set forth below in Table III. When SAPO-31 is in the as-synthesized form "m" preferably has a value of from 0.02 to 0.3. TABLE III Relative 20 d Intensity 8.5-8.6 10.40-10.28 m-s 20.2-20.3 4.40-4.37 m 21.9-22.1 4.06-4.02 w-m 22.6-22.7 3.93-3.92 vs 31.7-31.8 2.823-2.814 w-m All of the as-synthesized SAPO-31 compositions for which X-ray powder diffraction data have presently been obtained have patterns which are within the generalized pattern of Table IV below. TABLE IV 20 d 100 x I/Io 6.1 14.5 0-1 8.5-8.6* 10.40-10.28 60-72 9.5* 9.31 7-14 13.2-13.3* 6.71-6.66 1-4 14.7-14.8 6.03-5.99 1-2 15.7-15.8* 5.64-5.61 1-8 17.05-71.1 5.20-5.19 2-4 18.3-18.4 4.85-4.82 2-3 20.2-20.3 4.40-4.37 44-55 21.1-21.1* 4.21-4.19 6-28 21.9-22.1* 4.06-4,02 32-38 22.6-22.7* 3.93-3,92 100 23.3-23.35* 3.818-S,810 2-20 25.1* 3.548 3-4 25.65-25.75 3.473-3.460 2-3 26.5* 3.363 1-4 27.9-28.0 3.198-3.187 8-10 28.7* 3.110 0-2 29.7 3.008 4-5 31.7-31.8 2.823-2.814 15-18 32.9-33.0* 2.722-2.714 0-3 35.1-35.2 2.557-2.550 5-8 36.0-36.1 2.495-2.488 1-2 37.2 2.417 1-2 37.9-38.1* 2.374-2.362 2-4 39.3 2.292 2-3 43.0-43.1* 2.103-2.100 1 44.8-45.2* 2.023-2.006 1 46.6 1.949 1-2 47.4-47.5 1.918 1 48.6-48.7 1.873-1.870 2 50.7-50.8 1.801-1.797 1 51.6-51.7 1.771-1.768 2-3 55.4-55.5 1.658-1.656 1 *Possibly contains peak from a minor impurity SAPO-41, as referred to herein, comprises a silicoaluminophosphate having a three-dimensional microporous crystal framework structure of [Pa2] , (AlO2) and [SiO2] tetrahedral units, and whose unit empirical formula on an anhydrous basis is: mR: (SixAlyPz)O2 wherein R represents at least one crganic templating agent present in the intracrystalline pore system; "m" represents the moles of "R" present per mole of (SiAlyPz)O2 and has a value of from zero to 0.3; "x", "y" and "z" represent respectively, the mole fractions of silicon, aluminum and phosphorus, said mole fractions being within the compositional area bounded by points A, B, Cs D and E on the ternary diagram which is FIG. 1, or preferably within the area bounded by points a, b, c, d and e on the ternary diagram which is FIG. 2, said silicoaluminophosphate having a characteristic X-ray powder diffraction pattern.(as-synthesized and calcined) which contains at least the d-spacings set forth below in Table V. When SAPO-41 is in the as-synthesized form "m" preferably has a value of from 0.02 to 0.3. TABLE V Relative 20 d Intensity 13.6-13.8 6.51-6.42 w-m 20.5-20.6 4.33-4.31 w-m 21.1-21.3 4.21-4.17 vs 22.1-22.3 4.02-3.99 m-s 22.8-23.0 3.90-3.86 23.1-23.4 3.82-3.80 w-m 25.5-25.9 3.493-3.44 w-m All of the as-synthesized SAPO-41 compositions for which X-ray powder diffraction data have presently been obtained have patterns which are within the generalized pattern of Table VI below. TABLE VI 20 d 100 x I/Io 6.7-6.8 13.19-12.99 15-24 9.6-9.7 9.21-9.11 12-25 13.6-13.8 6.51-6.42 10-28 18.2-18.3 4.87-4.85 8-10 20.5-20.6 4.33-4.31 10-32 21.1-21.3 4.21-4.17 100 22.1-22.3 4.02-3.99 45-82 22.8-23.0 3.90-3.87 43-58 23.1-23.4 3.82-3.80 20-30 25.2-25.5 3.5S3-3.49 8-20 25.5-25.9 3.493-3.44 12-28 29.3-29.5 3.048-3.028 17-23 31.4-31.6 2.849-2.831 5-10 33.1-33.3 2.706-2.690 5-7 37.6-37.9 2.392-2.374 10-15 38.1-38.3 2.362-2.350 7-10 39.6-39.8 2.276-2.265 2-5 42.8-43.0 2.113-2.103 5-8 49.0-49.3 1.856-1.848 1-8 51.5 1.774 0-8 When used in the present process, the silicoaluminophosphates are employed in admixture with at least one Group VIII metal, for example the noble metals such as platinum and palladium,and optionally other catalytically active metals such as, for example, molybdenum, vanadium, or zinc. The amount of metal ranges from about 0.01% to 10% and preferably 0.2 to 5% by weight of the molecular sieve. The techniques of introducing catalytically active metals to a molecular sieve are disclosed in the literature, and preexisting metal incorporation techniques and treatment of the molecular sieve to form an active catalyst are suitable, e.g., ion exchange, impregnation or by occlusion during sieve preparation. See, for example, U.S. Patent Nos. 3,236,761, 3,226,339, 3,236,762, 3,620,960, 3,373,109, 4,202,996 and 4,440,871. The Group VIII metal utilized in the process of this invention can mean one or more of the metals in its elemental state or in some form such as the sulfide or oxide and mixtures thereof. As is customary in the art of catalysis, when referring to the active metal or metals it is intended to encompass the existence of such metal in the elementary state or in some form such as the oxide or sulfide as mentioned above, and regardless of the state in which the metallic component actually exists the concentrations are computed as if they existed in the elemental state. The physical form of the silicoaluminophosphate catalyst depends on the type of catalytic reactor being employed and may be in the form of a granule or powder, and is desirably compacted into a more readily usable form (e.g., larger agglomerates), usually with a silica or alumina binder for fluidized bed reaction, or pills, prills, spheres, extrudates, or other shapes of controlled size to accord adequate catalyst-reactant contact. The catalyst may be employed either as a fluidized catalyst, or in a fixed or moving bed, and in one or more reaction stages. Process Conditions The catalytic dewaxing step of this invention may be conducted by contacting the feed to be dewaxed with a fixed stationary bed of catalyst, with a fixed fluidized bed, or with a transport bed, as desired. A simple and therefore preferred configuration is-a trickle-bed operation in which the feed is allowed to trickle through a stationary fixed bed, preferably in the presence of hydrogen. The catalytic dewaxing conditions are dependent in large measure on the feed used and upon the desired pour point. Generally, the temperature will be between 200 C and 475 C, preferably between 250 C and 450 c. The pressure is typically between 15 psig (103 kP) and 300C psig (20684 kP), preferably between 200 psig (1379 kP) and 3000 psig (20684 kP). The liquid hourly space velocity (LHSV) preferably will be from 0.1 to 20, preferably between 0.2 and 10. Hydrogen is preferably present in the reaction zone during the catalytic dewaxing process. The hydrogen to feed ratios is typically between about 500 and about 30,000 SCF/bbl (standard cubic feet per barrel), preferably 1000 to 20,000 SCF/bbl. Generally, hydrogen will be separated from the product and recycled to the reaction zone. The silicoaluminophosphate molecular sieve catalysts can be manufactured into a wide variety of physical forms. Generally speaking, the molecular sieves can be in the form of a powder, a granule, or a- molded product, such as extrudate having particle size sufficient to pass through a 2-mesh (Tyler) screen and be retained on a 40-mesh (Tyler) screen. In cases where the catalyst is molded, such as by extrusion with a binder, the silicoaluminophosphate can be extruded before drying, or, dried or partially dried and then extruded. The molecular sieve can be composited with other materials resistant to the temperatures and other conditions employed in the dewaxing process. Such matrix materials include active and inactive materials and synthetic or naturally occurring zeolites as well as inorganic materials such as clays, silica and metal oxides. The latter may be either naturally occurring or in the form of gelatinous precipitates, sols or gels including mixtures of silica and metal oxides. Inactive materials suitably serve as diluents to control the amount of conversion in the dewaxing process so that products can be obtained economically without employing other means for controlling the rate of reaction. The silicoaluminophosphates may be incorporated into naturally occurring clays, e.g., bentonite and kaolin. These materials, i.e., clays, oxides, etc., function, in part, as binders for the catalyst. It is desirable to provide a catalyst having good crush strength, because in petroleum refining the catalyst is often subjected to rough handling. This tends to break the catalyst down into powder-like materials which cause problems in processing. Naturally occurring clays which can be composited with the silicoaluminophosphate include the montmorillonite and kaolin families, which families include the sub-bentonites, and the kaolins commonly known as Dixie, McNamee, Georgia and Florida clays or others in which the main mineral constituent is halloysite, kaolinite, dickite, nacrite, or anauxite. Fibrous clays such as halloysite, sepiolite and attapulgite can also be used as supports. Such clays can be used in the raw state as originally mined or initially subjected to calcination, acid treatment or chemical modification. In addition to the foregoing materials, the silicoaluminophosphates can be composited with porous matrix materials and mixtures of matrix materials such as silica, alumina1 titania, magnesia, silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, silicaberyllia, silica-titania, titania-zirconia as well as ternary compositions such as silica-alumina-thoria, silica-alumina-titania, silica-alumina-magnesia and silica-magnesia-zirconia. The matrix can be in the form of a cogel. The silicoaluminophosphate catalysts used in the process of this invention can also be composited with other zeolites such as synthetic and natural faujasites, (e.g., X and Y) erionites, and mordenites. They can also be composited with purely synthetic zeolites such as those of the ZSM series. The combination of zeolites can also be composited in a porous inorganic matrix. The following non-limitative Examples illustrate the invention. Example 1 SAPO-li was grown according to U.S. Patent No. 4,440,871 and identified by such as X-ray diffraction analysis. Elemental analysis of the calcined sieve showed it to have the following anhydrous molar composition: 0. l6SiO2:A12O3:P2O5. The sieve was bound with 358 Catapal alumina and made into l/16-inch extrudate. The extrudate was dried four hours at 2500F (121 C), calcined in air for four hours at 8500F (454 C), then impregnated with 1 weight percent Pt (as Pt(NH3)4C12H20) by the pore-fill method. It was then dried overnight at 275 F (135 C) and calcined in air for eight hours at 850 F (454 C). Example 2 The Pt/SAPO-ll catalyst of Example 1 was tested for dewaxing a +75 F (+24 C) pour point lube oil (inspections given in Table VII) at 1 LHSV, 2200 psig (15168 kP), and 8M SCF/bbl once-through H2. The pour point could be lowered to +15 F (-9 C) at a catalyst temperature of 640 F (338 C). Pour point reduction could be increased by raising the catalyst temperature. FIG. 3 compares the 7000F+ (371 C+) lube yield for the catalyst of this invention with that for a conventional ZSM-5,catalyst containing 35% Catapal binder and run at the same space velocity, pressure, and H2 rate. Here 700 F+ (371 C+) lube yield is defined as: g 700 F+ (feed) - g 700 F+ (product) 1 - x 100% g 700 F+ (feed) The figure shows a marked advantage in terms of greater yield for the SAPO-il catalyst. A large viscosity index (VI) advantage was also found (FIG. 4) as was a lower viscosity (FIG. 5). TABLE VII +750F 824 C) Pour Point Lube Oil Gravity, API 33.9 Aniline Point, F( C) 216.6 (102.6) Sulfur, ppm 1.3 Nitrogen, ppm 0.3 Pour Point, 0F(C) +75 (+24) Viscosity, CS, 100 C 3.610 P/N/A/S, LV% 27.6/61.6/10.8/0 Simulated Distillation, LV%, F C ST/5 347/641 175/338 10/30 671/725 355/385 50 759 404 70/90 788/824 420/440 9 5/EP 839/866 448/463. Example 3 The Pt/SAPO-ll catalyst of Example 1 was used to dewax a +115 F (+46 C) pour point lube oil (inspections given in Table VI II) at 1 LHSV, 2200 psig (15168 kP), and 8M SCF/bbl H2. Table IX compares the results versus those with the same ZSM-5 catalyst described in Example 2, again showing a major advantage for the SAPO-11 catalyst. TABLE VIII +115 F (+46 C) Pour Point Lube Oil Gravity, API 36.6 Sulfur, ppm 1.5 Nitrogen, ppm 0.2 Pou-r Point, F( C ) 1115 (+46) Viscosity, CS, 1000C 5.307 Flash Point, 0F(C ) 435 (224) P/N/A/S/ LV% 37.4/57.4/5.2/0 Simulated Distillation, LV%, F C ST/S 120/716 49/380 10/30 744/803 396/428 50 849 454 70/90 893/953 478/512 9 5/EP 982/1035 528/557 TABLE IX Dewaxing +115 F(+460C) Pour Point Lube Oil at 1 LHSV, 2200 psig (15168 kP), and 8M SCF/bbl H2 Catalyst Pt/SAPO-ll (Example 1) ZSM-5 Catalyst Tempera ture, F8 C) 700 (371) 725 (383) 759 (399) 683(362) 713 (378) Pour Point, F( C) +50 (10) +25 (-3.9) +10 (-12.2) +5 (-15) -20 (-29) Viscosity, CS, 40 C 27.41 27.87 26.78 35.00 335.03 Viscosity, CS, 100 C 5.520 5.513 5.348 6.032 5.939 VI 144 139 138 118 114 700 F+(371 C+) Lube Yield, Wt% 86.5 79.3 65.0 55.4 48.0 Example 4 The following catalysts were compared for dewaxing a +100 F (+38 C) pour point lube oil (inspections given in Table X) at 1 LHSV, 2200 psig (15168 kP), and 8M SCF/bbl H2. (a) the Pt/SAPO-ll catalyst of Example 1 (b) the ZSM-5 catalyst of Example 2 (c) a ZSM-5 catalyst similar to that of Example 2 but impregnated with 0.8 wt t Pt. TABLE X +1000F (+38 C) Pour Point Lube Oil Gravity, API 34.0 Aniline Point, F( C) 244.0 (118) Sulfur, ppm 0.4 Nitrogen, ppm 0.1 Pour Point, F ( C) +100 (+38) Viscosity, CS, 100 C 6.195 Flash Point, F( C) 420 (216) P/N/A/S, LV% 25.0/62.1/12.8/0 Simulated Distillation, LV%, F C ST/5 313/770 156/410 10/30 794/841 423/449 50 873 467 70/90 908/968 487/520 95/EP 998/1061 537/572 Table XI shows advantages for the Pt/SAPO-ll in both yield and VI. It also shows this catalyst to produce much less C4- gas in the cracked product. TABLE XI Catalyst Pt/SAPO-11 ZSM-5 Pt/ZSM-5 Catalyst Temperatur- 690 (366) 725 (385) 750 (399) 650 (343) 670 (354) 580 (304) 610 (321) ature, F( C) Pour Point, F( C) +30(-1) +15(-9) +5(-15) +30(-1) +5(-15) +30(-1) +5(-15) Viscosity, CS, 40 C 34.99 36.65 35.91 45.66 50.33 46.72 49.83 Viscosity, CS, 100 C 6.234 6.372 6.272 7.124 7.491 7.235 7.419 VI 128 125 125 115 111 115 111 800 F+(427 C) Lube Yield, Wt% 79.0 77.5 68.0 77 69 78 71 P/N/A, LV% 29.3/65.3/ 14.3/78.8/ 5.4 6.9 P/N/A, ndM 77.60/22.34/ 73.21/26.79/ 0.07 0.00 Simulated Distillation, LV%, C ST/5 381/409 388/413 384/410 388/418 393/429 333/408 381/415 10/30 423/450 424/449 422/448 430/454 431/455 422/449 427/469 50 468 468 467 472 472 468 480 70/90 487/519 486/518 490/522 491/523 487/519 492/523 95/EP 535/572 537/573 535/571 537/575 539 /573 537/572 539/572 TABLE XI (Cont'd) Catalyst Pt/SAPO-11 ZSM-5 Pt/ZSM-5 Catalyst Temper- 690 (366) 725 (385) 750 (399) 650 (343) 670 (354) 580 (304) 610 (321) ature, F( C) Cracked Product Selectivity, Wt% C4- 10.7 53.4 C5-350 F(177 C) 18.7 39.7 350-550 F (177-288 C) 25.7 6.9 550-800 F (288-427 C) 0 Example 5 Another batch of SAPO-11 was prepared similarly to that of Example 1, except that the molar composition of the anhydrous sieve was: 0.4SiO2:Al2O3:P2O5. This sieve was bound with alumina and impregnated with 1 weight percent Pt as in Example 1. Example 6 The catalyst of Example 5 was used to dewax the lube oil of Table VII. The results (Table XII) again show the advantage of Pt/SAPO-ll for obtaining high lube yield and VI, as well as low viscosity. TABLE XII Dewaxing +750F(+240C) Pour Point Lube Oil at 1 LHSV, 2200 psig (15168 kP), and 8M SCF/bbl H2 Catalyst Pt/SAPO-ll (Example 5) ZSM-5 Catalyst Tempera ture, F( C) 650 (343) 675 (357) 606 (319) 621 (327) Pour Point, F( C) -10 (-23) -10(-23) +20(-7) -5(-21) Viscosity, CS, 40 C 16.79 16.88 17.33 18.26 Viscosity; CS, 100 C 3.689 3.693 3.729 3.812 VI 105 104 101 96 7000F+(3710C+) Lube YIeld, Wti 91.0 87.0 87.0 84.5 Example 7 The catalyst of Example 5 was used to dewax the lube oil of Table X. The results are shown in Table XIII. TABLE XIII Dewaxing +1000F (+30 C) Pour Point Lube Oil at 1 LHSV, 2200 psig (15168 kP), and 8M SCF/bbl H2 Catalyst Pt/SAPO-ll (Example 5) ZSM-5 Catalyst Tempera ture, F ( C) 700(371) 725(385) 650(343)670 (354) Pour Point, F ( C) +15 (-9) +5 (-15) +30 (-1) +5(.-15) Viscosity, CS, 40 C 36.94 34.54 45.66 50.33 Viscosity, CS, 100 C 6.362 6.083 7.124 7.491 VI 123 124 115 111 800 F+(427 C+) Lube Yield, Wt% 78 69 77 69

Claims: CLAIMS: 1. A method of catalytically dewaxing a hydrocarbon oil feedstock boiling above 350"F (176"C) and containing waxy hydrocarbons, which comprises contacting said oil feedstock with a catalyst comprising an intermediate pore size silicoaluminophosphate (SAPO) molecular sieve and at least one Group VIII metal to selectively convert at least some of said waxy hydrocarbons to lower molecular weight non-waxy hydrocarbons. 2. A method according to Claim 1, wherein the silicoaluminophosphate molecular sieve is SAPO-Il, SAPO-31 or SAPO-41. 3. A method according to Claim 1 or 2, wherein the Group VIII metal is platinum or palladium. 4. A method according to Claim 1, wherein the silicoaluminophosphate molecular sieve is SAPO-11 and the Group VIII metal is platinum. 5. A method according to Claim 1, 2, 3 or 4, wherein the Group VIII metal is present in the range from 0.01% to 10% based on the weight of the molecular sieve. 6. A method according to any preceding claim1 wherein the method is conducted at a temperature of from 200 to 475"C, a pressure of from 15 to 3000 psig (103 to 20684 kP), a liquid hourly space velocity of from 0.1 to 20 her , and a hydrogen circulation rate of from 500 to 30,000 SCF/bbl. 7. A method according to any preceding claim, wherein the feedstock is a middle distillate oil. 8. A method according to any one of Claims 1 to 6, wherein the feedstock is a lube oil. 9. A method according to any preceding claim, wherein the feedstock contains less than 50 ppm by weight of nitrogen. 10. A process according to any preceding claim, wherein the catalyst has a pore size in the range from 5.5 to 6.2 Angstroms.

Inventors: MILLER, STEPHEN J.
Applicants: CHEVRON RESEARCH COMPANY
Application year: 1986
Main classification: C10G45
IPC codes: B01J29, C10G45