Catalysts based on silicoaluminophosphate SAPO-11 and uses thereof

Abstract

The invention provides a process for preparing SAPO-11, that comprises combining in an aqueous solution alumina source, P 2 O source and a silica source in the presence of a crystallization template and a surfactant to form a gel, which is then subjected to hydrothermal crystallization and calcination. The so-formed SAPO-11, which possesses unique silicon distribution, high resistance to hydrothermal degradation (desilication) and high surface area, forms another aspect of the invention. Hydroprocessing of a vegetable oil in the presence of a catalyst comprising the Pt and SAPO-11 of the invention is also demonstrated.

Claims

1. SAPO-11 possessing a silicon distribution, wherein the distribution of silicon atoms among the five silicon sites, indicated by the notation (0Si,4Al); (1Si,3Al), (2Si,2Al), (3Si,1Al) and (4Si,0Al), identifying the composition of the four nearest neighbor positions of a silicon atom in terms of the silicon and aluminum atoms filling said neighbor positions, is determined by a deconvoluted .sup.29Si-NMR spectrum of said SAPO-11, said spectrum exhibiting five peaks centered at 90 ppm (2), 97 ppm(2), 103 (2) ppm, 108 (2) ppm and 112 (2) ppm, assigned to (0Si,4Al); (1Si,3Al), (2Si,2Al), (3Si,1Al) and (4Si,0Al) sites respectively, wherein said .sup.29Si-NMR spectrum indicates the predomination of aluminum-rich silicon sites (0Si,4Al) and (1Si,3Al), with the peaks assigned to (0Si,4Al) and (1Si,3Al) sites being the first and second most intense peaks, respectively, such that the major peak assigned to the (0Si,4Al) site indicates that the molar concentration of said site is not less than 60 molar % of the total number of silicon sites, wherein said SAPO-11 has an external surface area of above 200 m.sup.2/g, and wherein said SAPO-11 is hydrothermally stable in a hydrous environment formed in hydroprocessing of a lipid feedstock at 370 C.

2. SAPO-11 according to claim 1, wherein the sum of the molar concentrations of the (0Si,4Al) and (1Si,3Al) sites constitutes not less than 75% of the total number of silicon sites, as indicated by the deconvulated results of the .sup.29Si-NMR spectrum of said SAPO-11.

3. SAPO-11 according to claim 1, wherein the ratio of the concentration of the (0Si,4Al) site to the concentration of the (1Si,3Al) is greater than 3:1, as indicated by the deconvulated results of the .sup.29Si-NMR spectrum of said SAPO-11.

4. SAPO-11 of claim 1, possessing silicon distribution, based on the deconvoluted results of .sup.29Si-NMR spectrum, as tabulated: TABLE-US-00007 site (0Si, 4Al) (1Si, 3Al) (2si, 2Al) (3Si, 1Al) (4Si, 0Al) NMR peak 90 ppm 97 ppm 103 ppm 108 ppm 112 ppm centered at (2) (2) (2) (2) (2) Molar % 60-75 10-20 7-12 6-8 4-6.

5. SAPO-11 according to claim 1, wherein the external surface area is from 200 m.sup.2/g to 250 m.sup.2/g.

6. A catalyst Pt/(SAPO-11+Al.sub.20.sub.3), wherein the SAPO-11 component of said catalyst is as defined in claim 1.

7. A process for producing a liquid fuel composition, comprising hydroprocessing a feedstock in the presence of a catalyst according to claim 6, wherein said feedstock comprises oxygen-containing compounds.

8. A process according to claim 7, comprising: providing a feedstock oil selected from the group consisting of vegetable oil, animal oil, and mixtures thereof, and hydrodeoxygenating and hydroisomerizing the oil.

9. A process according to claim 8, comprising: (i) hydrodeoxygenating, hydroisomerizing and aromatizing the feedstock oil in the presence of the catalyst Pt/(SAP0-11+Al.sub.20.sub.3), wherein the SAPO-11 component of said catalyst posesses a silicon distribution, wherein the distribution of silicon atoms among the five possible silicon sites, indicated by the notation (nSi,(4-n)Al), 0n4, identifying the composition of the four nearest neighbor positions of a silicon atom in terms of the silicon and aluminum atoms filling said neighbor positions, is determined by a deconvoluted .sup.29Si-NMR spectrum of said SAPO-11, said spectrum exhibiting five peaks centered at 90 ppm (2), 97 ppm(2), 103 (2) ppm, 108 (2) ppm and 112 (2) ppm, assigned to (0Si,4Al); (1Si,3Al), (2Si,2Al), (3Si,1Al) and (4Si,0Al) sites respectively, wherein said .sup.29Si-NMR spectrum indicates the predomination of aluminum-rich silicon sites (0Si,4Al) and (1Si,3Al), with the peaks assigned to (0Si,4Al) and (1Si,3Al) sites being the first and second most intense peaks, respectively, such that the major peak assigned to the (0Si,4Al) site indicates that the molar concentration of said site is not less than 60 molar % of the total number of silicon sites to obtain a gas-liquid mixture, wherein the gaseous component of said mixture comprises unreacted hydrogen and light hydrocarbons and the liquid component of said mixture comprises water and an organic liquid; (ii) separating said gaseous component from said liquid component; (iii) separating said liquid component into an organic and aqueous phases, and collecting at least said organic phase; and (v) optionally subjecting said organic phase, or a portion thereof, to hydrocracking in the presence of hydrogen and one or more catalysts.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 schematically illustrates the local arrangement of Si atoms in SAPO-11 framework.

(2) FIG. 2 shows XRD patterns of pure SAPO-11 materials synthesized according to Examples #1 (1), #5 (2) and #7 (3).

(3) FIGS. 3A, 3B and 3C show the .sup.29Si MAS NMR spectra of catalysts of Examples 1, 3 and 5, respectively.

(4) FIG. 4A schematically illustrates an apparatus for conducting hydrodeoxygenation reaction employing SAPO-11 of the invention.

(5) FIG. 4B displays the experimental setup for catalysts testing: (1) packed reactor, (2) thermowell, (3) heat dispersion mantle, (4) heating jacket, (5) thermal insulation, (6) balance, (7) feed tank, (8) high pressure pump, (9) Brooks flow meter controller, (10) high pressure cylinders, (11) back pressure regulator, (12) GC (13) cooler, (14) low-temperature gas-liquid separator, and (15) high temperature gas-liquid separator.

(6) FIGS. 5A, 5B and 5C illustrate variations of SAPO-11 component phase content in 1 wt. % Pt/(SAPO-11+10% Al.sub.2O.sub.3) catalyst with time on stream in catalytic runs of hydrotreating of soybean oil with catalysts synthesized according to Examples #1 (FIG. 5A), #2 (FIG. 5B) and #5 (FIG. 5C).

(7) FIG. 6 shows variations of the pour point of the hydrotreating product of soybean oil obtained in testing the catalyst as a function of time on stream: catalyst according to examples #1-3 and 5.

(8) FIG. 7 shows distillation curves of jet fuel fraction formed from soybean oil with the aid of SAPO-11 of the invention.

(9) FIG. 8 shows distillation curves of jet fuel fraction formed from soybean oil with the aid of SAPO-11 of the invention.

(10) FIG. 9 shows distillation curves of jet fuel fraction formed from soybean oil with the aid of SAPO-11 of the invention.

EXAMPLES

(11) Methods

(12) X-Ray Diffraction (XRD)

(13) The X-ray diffraction (XRD) patterns were obtained with a Phillips 1050/70 powder diffractometer fitted with a graphite monochromator, at 40 kV and 28 mA. Software developed by Crystal Logic was used. The data were collected in a range of 2 values between 5 and 80 with a step size of 0.05. Phase identification was performed by using BEDE ZDS computer search/match program coupled with the ICDD (International Center for Diffraction Data) Powder Diffraction File database (2006). The relative content of SAPO-11, SAPO-41, APO-11 and amorphous phases represented in X-ray diffractograms by a wide reflection centered at 2=22 was obtained by Rietveld refinement of the XRD profile by using the DBWS-9807 program.

(14) Surface Area and Pore Volume Measurements

(15) Surface area and pore volume were derived from N.sub.2 adsorption-desorption isotherms using conventional BET and BJH methods (Barrett-Joyner-Halenda method, Journal of American Chemical Society, 73, 373, 1951). The samples were degassed under vacuum at 250-70 C., depending on their thermal stability. Isotherms were measured at liquid nitrogen temperature with a NOVA-2000 Quantachrome, Version 7.02 instrument.

(16) Energy Dispersive X-Ray Spectroscopy (EDAX)

(17) The total elemental composition of catalysts was measured by EDAX method using Quanta-200, SEM-EDAX, FEI Co. instrument. The contents of Si, P and Al atoms in the SAPO-11 framework were calculated averaging the data obtained from five different points of the material crystals.

(18) .sup.29Si MAS NMR

(19) .sup.29Si cross polarization (cp) MAS NMR spectra were acquired on Bruker Avance III 500 MHz spectrometer using a 4 mm VTN CPMAS probe, covering the necessary frequency range, using MAS at 8 kHz.

Example 1

(Comparative, Based on U.S. Pat. No. 6,294,081) SAPO-11 Prepared at HDA/Al2O3=0.29, 24 h

(20) Aluminum oxide-hydroxide AlOOH with pure pseudobohemite structure and crystal size of 4.5 nm was used as alumina source. 24.5 g water, 26.0 g phosphoric acid (85%, Sigma Aldrich) and 22.0 g pseudobohemite (73% Al.sub.2O.sub.3, crystal size 4.5 nm; Disperal P2, Sasol Ltd., Germany) were stirred together for h. 13.4 g DPA (Sigma Aldrich) was added and the gel was stirred for 2 h. 59.4 g hexanol (Sigma Aldrich) and 10.4 g hexadecylamine (Fluka) were stirred in a separate vessel for about 30 min, following which 24.5 g water was added and stirred together for 5 min, and then added to the reaction mixture. This was followed by addition of 13.8 g TEOS (tetraethylorthosilicate) and 24.5 g water. The final gel was stirred for another 2 h reaching the final pH of 4.7. The weight ratio between three portions of water added at three different steps of preparation of crystallization gel was 1:1:1. The gel containing Al.sub.2O.sub.3:P.sub.2O.sub.5:DPA:0.5TEOS:0.288 hexadecylamine:4.4 hexanol:35H.sub.2O was introduced into a Teflon-coated 350 cm.sup.3 autoclave and heated statically for 24 h at 195 C. (heating rate 2 C./min). Then the mixture was quenched to room temperature, centrifuged and washed several times with ethanol and water with interim and final centrifugations. The recovered white powder was dried at 40 C. overnight and then calcined in nitrogen flow (130 ml/min) for 1 h at 550 C. (heating rate 2 C./min) followed by calcination in an air flow (130 ml/min) for additional 2 h. The calcined material did not contain other phases besides silicoaluminophosphate SAPO-11 (XRD, FIG. 2, pattern no. 1) and its framework included Si, Al and P in atomic ratio of Si:P:Al=0.30:0.74:1.0 corresponding to Si content of 6.9 wt. % (EDAX).

(21) The total surface area of calcined SAPO-11 material was 187 m.sup.2/g, external surface area 60 m.sup.2/g, micropore volume 0.025 cm.sup.3/g and mesopore volume 0.235 cm.sup.3/g. The Pt/SAPO-11-Al.sub.2O.sub.3 catalysts pellets were prepared by combining of SAPO-11 zeolite with alumina binder. For this purpose the same pseudobohemite powder used for zeolite synthesis was mixed with the powder of obtained zeolitic material at weight ratio corresponding to SAPO-11/Al.sub.2O.sub.3=9/1, homogenized in a ball mill for 10 min and peptized with an aqueous solution of Al(NO.sub.3).sub.3 salt (Riedel de Haen) reaching the rheological characteristics suitable for its forming by extrusion. After drying at 120 C. for 2 h and calcination in air at 500 C. for 2 h, the extrudates having diameter of 1.5 mm were cut into pellets of 6.5-7.5 mm length. Platinum (1 wt %) was loaded into these extrudates by incipient wetness impregnation with H.sub.2PtCl.sub.6 aqueous solution. The Pt-loaded extrudates were dried at room temperature for 15 h, then at 110 C. for 3 h and calcined according to following program: 180 C.:1 C./min, 300 C.:1 C./min for 3 h, 400 C.:1 C./min for 2 h and 500 C.:1 C./min for 2 h. The final catalyst pellets were reduced in a tubular reactor in H.sub.2 flow of 250 cm.sup.3/min at temperature of 300 C. for 16 h.

Example 2

(Comparative, Based on U.S. Pat. No. 4,310,440 and U.S. Pat. No. 4,440,871) SAPO-11 without Surfactant

(22) The catalyst was prepared according to Example 1 but with no addition of hexadecyl-amine and hexanol at the preparation of crystallization gel, while water was added only in two portions of 24.5 g excluding the second portion. The gel composition was Al.sub.2O.sub.3: P.sub.2O.sub.5:DPA:0.5TEOS:23.5H.sub.2O. The calcined material did not contain other phases besides silico-alumino-phosphate SAPO-(XRD) and its framework included Si, Al and P in atomic ratio of Si:P:Al=0.19:0.80:1.0, corresponding to Si content 4.5 wt. % (EDAX). The total surface area of calcined SAPO-11 material was 150 m.sup.2/g, external surface area 45 m.sup.2/g, micropore volume 0.025 cm.sup.3/g and mesopore volume 0.096 cm.sup.3/g.

Example 3

(Comparative, Based on U.S. Pat. No. 6,294,081) SAPO-11 Prepared at HDA/Al2O3=0.5; 24 h

(23) The catalyst was prepared according to Example 1, but the amount of added hexadecylamine for preparation of crystallization gel was 18.0 gram corresponding to HDA/Al.sub.2O.sub.3 molar ratio of 0.50. The gel composition was Al.sub.2O.sub.3:P.sub.2O.sub.5:DPA:0.5TEOS:0.50 hexadecylamine:4.4 hexanol:35H.sub.2O. The calcined material did not contain other phases besides silicoaluminophosphate SAPO-11 (XRD) and its framework included Si, Al and P in atomic ratio of Si:P:Al=0.24:0.79:1.0 corresponding to Si content 5.5 wt. % (EDAX). The total surface area of calcined SAPO-11 material was 219 m.sup.2/g, external surface area 189 m.sup.2/g, micropore volume 0.028 cm.sup.3/g and mesopore volume 0.252 cm.sup.3/g.

Example 4

SAPO-11 Prepared at HDA/Al2O3=0.55; 24 h

(24) The catalyst was prepared according to Example 1 but the amount of added hexadecylamine for preparation of crystallization gel was 20.0 gram corresponding to HDA/Al.sub.2O.sub.3 molar ratio of 0.55, and the amount of water combined with the hexanol and hexadecylamine was 12.25 g. The gel composition was Al.sub.2O.sub.3:P.sub.2O.sub.5:DPA:0.5TEOS:0.55 hexadecylamine:4.4 hexanol:35H.sub.2O. The calcined material did not contain other phases besides silicoaluminophosphate SAPO-11 and its framework included Si, Al and P in atomic ratio of Si:P:Al=0.31:0.74:1.0 corresponding to Si content 7.0 wt. % (EDAX). The total surface area of calcined SAPO-11 material was 228 m.sup.2/g, external surface area 190 m.sup.2/g, micropore volume 0.024 cm.sup.3/g and mesopore volume 0.240 cm.sup.3/g.

Example 5

SAPO-11 Prepared at HDA/Al2O3=0.58; 24 h

(25) The catalyst was prepared according to Example 1 but the amount of added hexadecylamine for preparation of crystallization gel was 21.0 g corresponding to HDA/Al.sub.2O.sub.3 molar ratio of 0.58, and the amount of water combined with the hexanol and hexadecylamine was 12.25 g. The gel composition was Al.sub.2O.sub.3: P.sub.2O.sub.5:DPA:0.5TEOS:0.58 hexadecylamine:4.4 hexanol:35H.sub.2O. The calcined material did not contain other phases besides silicoaluminophosphate SAPO-11 (XRD, FIG. 2, pattern no. 2) and its framework included Si, Al and P in atomic ratio of Si:P:Al=0.31:0.72:1.0 corresponding to Si content 7.2 wt. % (EDAX). The total surface area of calcined SAPO-11 material was 240 m.sup.2/g, external surface area 205 m.sup.2/g, micropore volume 0.035 cm.sup.3/g and mesopore volume 0.205 cm.sup.3/g.

Example 6

SAPO-11 Prepared at HDA/Al2O3=0.65; 24 h

(26) The catalyst was prepared according to Example 1 but the amount of added hexadecylamine for preparation of crystallization gel was 23.5 g corresponding to HDA/Al.sub.2O.sub.3 molar ratio of 0.65, and the amount of water combined with the hexanol and hexadecylamine was 12.25 g. The gel composition was Al.sub.2O.sub.3: P.sub.2O.sub.5:DPA:0.5TEOS:0.65 hexadecylamine:4.4 hexanol:35H.sub.2O. The calcined contained two zeolitic phases90 wt. % SAPO-11 and 10 wt. % SAPO-41. Its framework included Si, Al and P in atomic ratio of Si:P:Al=0.33:0.72:1.0 corresponding to Si content 7.6 wt. % (EDAX). The total surface area of calcined SAPO-11 material was 285 m.sup.2/g, external surface area 239 m.sup.2/g, micropore volume 0.033 cm.sup.3/g and mesopore volume 0.282 cm.sup.3/g.

Example 7

(Comparative) SAPO-11 Prepared at HDA/Al2O3=0.72; 24 h

(27) The catalyst was prepared according to Example 1 but the amount of added hexadecylamine for preparation of crystallization gel was 26.2 g corresponding to HDA/Al.sub.2O.sub.3 molar ratio of 0.72, and the amount of water combined with the hexanol and hexadecylamine was 12.25 g. The gel composition was Al.sub.2O.sub.3: P.sub.2O.sub.5:DPA:0.5TEOS:0.72 hexadecylamine:4.4 hexanol:35H.sub.2O. The calcined material contained two zeolitic phases50 wt. % SAPO-11 and 50 wt. % SAPO-41 (FIG. 2, pattern no. 3). Its framework included Si, Al and P in atomic ratio of Si:P:Al=0.40:0.72:1.0 corresponding to Si content 8.9 wt. % (EDAX). The total surface area of calcined SAPO-11 material was 272 m.sup.2/g, external surface area 235 m.sup.2/g, micropore volume 0.018 cm.sup.3/g and mesopore volume 0.281 cm.sup.3/g.

Example 8

SAPO-11 Prepared at HDA/Al2O3=0.58, 48 h

(28) The catalyst was prepared according to Example 5 but the crystallization time of the gel in preparation of SAPO-11 material was 48 h. The calcined material did not contain other phases besides silicoaluminophosphate SAPO-11 (XRD) and its framework included Si, Al and P in atomic ratio of Si:P:Al=0.31:0.73:1.0 corresponding to Si content 7.1 wt. % (EDAX). The total surface area of calcined SAPO-11 material was 264 m.sup.2/g, external surface area 241 m.sup.2/g, micropore volume 0.012 cm.sup.3/g and mesopore volume 0.266 cm.sup.3/g.

Example 9

SAPO-11 Prepared at HDA/Al2O3=0.58, 72 h

(29) The catalyst was prepared according to Example 5 but the crystallization time of the gel in preparation of SAPO-11 material was 72 h. The calcined material did not contain other phases besides silicoaluminophosphate SAPO-11 (XRD) and its framework included Si, Al and P in atomic ratio of Si:P:Al=0.3:0.71:1.0 corresponding to Si content 7.0 wt. % (EDAX). The total surface area of calcined SAPO-11 material was 266 m.sup.2/g, external surface area 240 m.sup.2/g, micropore volume 0.013 cm.sup.3/g and mesopore volume 0.192 cm.sup.3/g.

Example 10

SAPO-11 Prepared at HDA/Al2O3=0.58, 96 h

(30) The catalyst was prepared according to Example 5 but the crystallization time of the gel in preparation of SAPO-11 material was 96 h. The calcined material did not contain other phases besides silicoaluminophosphate SAPO-11 (XRD) and its framework included Si, Al and P in atomic ratio of Si:P:Al=0.3:0.71:1.0 corresponding to Si content 7.0 wt. % (EDAX). The total surface area of calcined SAPO-11 material was 264 m.sup.2/g, external surface area 214 m.sup.2/g, micropore volume 0.025 cm.sup.3/g and mesopore volume 0.181 cm.sup.3/g.

Example 11

SAPO-11 Prepared at HDA/Al2O3=0.58 24 h; 0.5% Pt in SAPO-11, 1% Pt in Al2O3

(31) The catalyst prepared according to Example 5, but the platinum loading was done in two steps. The first portion of 0.5 wt % was loaded directly on SAPO-11 powder by incipient wetness impregnation with aqueous H.sub.2PtCl.sub.6 solution followed by calcination and Pt reduction. Additional 1% of Pt was loaded on extrudates of SAPO-11/0.5% Pt+10% Al.sub.2O.sub.3 and reduced as described in Example 5.

(32) The distributions of silicon atoms among possible silicon sites in some of the SAPO-11 materials prepared in the foregoing examples and derived from .sup.29Si-NMR spectra shown in FIGS. 3A, 3B and 3C are tabulated in Table 1.

(33) TABLE-US-00002 TABLE 1 Si Environment 4Al, 0Si 3Al, 1Si 2Al, 2Si 1Al, 3 Si 0Al, 4 Si Chemical 89 to 97 103 108 110 to shift in ppm 91 113 according to .sup.29Si NMR spectra Example 1 47.3 22.1 16.2 10.2 4.2 (comparative) Example 3 52.0 30.1 10.5 4.3 3.1 (comparative) Example 5 71.8 15.5 11.4 0.4 0.9

Example 12

(34) The catalysts prepared according to Examples 1-11 were tested in hydrotreating of soybean oil (Miloumor) containing <0.1% free fatty acids in an experimental rig equipped with a fixed-bed reactor (a scheme of the experimental set-up is shown in FIG. 4B). The bench-scale reactor consisted of a 1.1-cm ID and 45-cm long, stainless-steel, electrically heated tube and contained 20-40 cm.sup.3 of pelletized catalyst mixed with 10-20 cm.sup.3 of 300-500-m SiC inert particles. The bench-scale system was equipped with a feed tank, gas cylinders, a high-pressure gas-liquid separator, Brooks mass flow meters and high pressure. The system pressure was maintained by a back-pressure regulator. Temperature and pressure controllers and proper safety instrumentation ensured safe operation of the system.

(35) The catalysts were tested in continuous runs at 30 atm, 370 C., LHSV=1 h.sup.1 and H.sub.2/oil ratio at the reactor inlet 700 NL/L. The products density, cloud point, aromatics content and total acidity were measured after periods of run according to ASTM D1217, ASTM D2500, ASTM D6379 and ASTM D3242.

(36) The testing results obtained after 200 h of run are presented in Table 2.

(37) TABLE-US-00003 TABLE 2 Testing results in hydrotreating of soybean oil Aromatic Total Cloud content acidity point Density Organic Catalyst (%) (mgKOH/g) ( C.) (g/cm.sup.3) liquid according to ASTM ASTM ASTM ASTM yield example # D6379 D3242 D2500 D1217 (%) 1 (compar- 16 0.15 20 0.811 84 ative) 2 (compar- 14 0.04 5 0.784 83 ative) 3 (compar- 15 0.30 22 0.797 83 ative) 4 (of the 14 0.20 23 0.798 83 invention) 5 (of the 15 0.12 33 0.807 84 invention) 8 (of the 14 0.03 37 0.794 83 invention) 9 (of the 14 0.04 40 0.791 82 invention) 10 (of the 14 0.03 42 0.791 83 invention) 11 (of the 12 0.02 30 0.794 83 invention)

(38) The results indicate that after 200 h on stream, the catalysts prepared according to the present invention (Examples 4-5 and 8-11) displayed higher isomerization activity of normal hydrocarbons produced through hydrodeoxygenation of triglycerides of the vegetable oil. This is indicated by the low cloud point (below 30 C. during a 200 h run) of the products formed with the aid of the catalysts of the invention.

(39) The improved stability of the catalyst of the invention is further illustrated in the graphs shown in FIG. 5. The variation of the SAPO-11 content in the catalysts of Examples 1, 3 and 5 with time on stream was measured and the results are graphically presented in FIGS. 5a, 5b and 5c, respectively. The content of the SAPO-11 component in the comparative catalysts of Examples 1 and 3 decreases sharply with time on stream. This is due to the desilication of SAPO-11 framework of comparative catalysts at hydrothermal conditions, leading to the formation of crystalline aluminophosphate APO-11 and amorphous silica phases. In contrast, the content of SAPO-11 phase in the catalyst prepared according to the present invention (Example 5) is stable during the catalytic run for a period of 1000 h (see FIG. 5c).

(40) In the graph shown in FIG. 6, the cloud points of liquid products obtained with the aid of several catalysts were measured periodically during a run of 1000 hours, and the results are plotted against the time on stream. The catalyst of Example 5 (marked in the graph with black triangles) leads to formation of products displaying cloud points lower than 30 C., from the very beginning of run, all the way around to the end of the run. In contrast, the cloud point of the hydrocarbon products obtained with the catalysts of Examples #1 and 3 rises steeply with time (marked in the graph with empty triangles and X, respectively). It is also noted that the performance of the catalyst of Example 2 (black circles) is especially poor.

(41) The deoxygenation extent of the vegetable oil in all cases exceeds 99% yielding low acidity of <0.5 mgKOH/g. The product contains 10-20% aromatic hydrocarbons and has density of 0.790-0.810 g/cm.sup.3. So, the liquid product obtained with catalyst according to the present invention is an excellent feedstock for production of diesel and jet fuels in long continuous runs conducted in trickle-bed reactors.

Example 13

Production of Aromatic Jet Fuel from Soybean Oil

(42) Refined soybean oil was fed to a fixed-bed reactor with a granulated 1% Pt/(SAPO-11+Al.sub.2O.sub.2) catalyst of Example 5 at LHSV=1.0 h.sup.1, T=370-385 C., P=30 atm and H.sub.2/oil ratio=700 NL/L. The run was carried out for >1000 h. The gas phase contained, besides hydrogen, CO.sub.2, CO and light products, mainly C.sub.1 to C.sub.3 hydrocarbons. The total liquid flow was separated into two phases, water and organics.

(43) To improve the properties and increase yield of jet fuel fraction, the organic liquid obtained from the first stage was subjected to mild hydrocracking step. The liquid was fed to a fixed-bed reactor with two catalytic layers: (1) Ni.sub.2P/HY catalyst as mild hydrocracking step at 315 C. and (2) the catalyst of Example 5 at 350 C. Each layer was functioned under LHSV=4.0 h.sup.1, 30 atm and H.sub.2/oil ratio=600 NL/L. The run was carried out for >100 h. The gas phase contained, besides hydrogen, other light products, mainly C.sub.1 to C.sub.4 hydrocarbons. Yield (based on oil feedstock) and properties of the jet fuel fraction collected are set out in Table 3.

(44) TABLE-US-00004 TABLE 3 Method Property (ASTM) Limits Jet fuel Yield of fraction to oil, wt % 58 Acidity, total mg KOH/g D3242 0.10 0.010 Aromatics, vol % D1319 8-25 8.2 Distillation temperature, C.: D86 Initial boiling point, C. Max. 205 132 10% recovered, report 143 20% recovered, report 160 30% recovered, report 175 40% recovered, report 175 50% recovered, report 190 60% recovered, report 207 70% recovered, report 225 80% recovered, report 244 90% recovered, report 280 Final boiling point,, C. Max. 300 289 T50-T10, C. Min. 15 47 T90-T10, C. Min. 40 137 Distillation residue, % Max. 1.5 1.5 Distillation loss, % Max. 1.5 1.1 Flash point, C. D56 Min. 38 44 Density at 15 C., kg/m.sup.3 D1298 0.775-0.840 0.780 Freezing point, C. D2386 Max. 47 50 Viscosity 20 C., mm2/s D445 Max. 8 4.58 Existent gum, mg/100 mL D381 Max. 7 1

(45) FIG. 7 shows distillation curves of organic products from the 1st step (i.e., the product of the simultaneous hydrodeoxygenation and hydroisomerization of a refined soybean oil; indicated by empty rhombuses), the 2nd step (i.e., the product of the mild hydrocraking step; indicated by solid squares), the final product (obtained by additional isomerization step; indicated by solid triangles) and the biojet product obtained after distillation (marked by the empty squares).

Example 14

Production of Aromatic Jet Fuel from Soybean Oil

(46) Refined soybean oil was fed to a fixed-bed reactor with a granulated 1% Pt/(SAPO-11+Al.sub.2O.sub.3) catalyst of Example 5 at LHSV=1.0 h.sup.1, 370-385 C., 30 atm and H.sub.2/oil ratio=600 NL/L. The run was carried out for >1000 h. The gas phase contained, besides hydrogen, other light products, mainly C.sub.1 to C.sub.3 hydrocarbons. The total liquid flow was separated into two phases, water and organics.

(47) To improve the properties of the jet fuel fraction, the organic liquid obtained from the first stage was passed fractionation to light naphtha (<130 C.), jet (135-260 C.) and heavy (>260 C.) fractions. The heavy fraction was passed mild-hydrocracking over Ni.sub.2P/HY at 315 C. and then additional isomerization over the catalyst of Example 5 at 350 C., LHSV=4.0 h.sup.1, 30 atm and H.sub.2/oil ratio=700 NL/L, respectively. The run was carried out for >100 h. The gas phase contained, besides hydrogen, other light products, mainly C1 to C4 hydrocarbons. Yield (based on the oil feedstock) and properties of the jet fuel fraction collected are set out in Table 4.

(48) TABLE-US-00005 TABLE 4 Property Method Limits Jet fuel Yield of fraction to oil, wt % 69 Acidity, total mg KOH/g D3242 0.10 0.010 Aromatics, vol % D1319 8-25 8.4 Distillation temperature, C.: D86 Initial boiling point, C. Max. 205 140 10% recovered, report 185 20% recovered, report 215 30% recovered, report 235 40% recovered, report 255 50% recovered, report 263 60% recovered, report 271 70% recovered, report 276 80% recovered, report 280 90% recovered, report 282 T50-T10, C. Min. 15 123 T90-T10, C. Min. 40 142 Final boiling point,, C. Max. 300 300 Distillation residue, % Max. 1.5 1.2 Distillation loss, % Max. 1.5 0.8 Flash point, C. D56 Min. 38 48.5 Density at 15 C., kg/m.sup.3 D1298 0.775-0.840 0.776 Freezing point, C. D2386 Max. 47 50 Viscosity 20 C., mm2/s D445 Max. 8 3.3 Existent gum, mg/100 mL D381 Max. 7 1

(49) FIG. 8 shows distillation curves of the organic products from the 1st step (i.e., the product of the simultaneous hydrodeoxygenation and hydroisomerization of the refined soybean oil; indicated by the solid triangles), the heavy fraction above 260 C. (indicated by the upper smooth curve), the mild hydrocracking product (indicated by crosses), additional isomerization product and the final aromatic BioJet product (indicated by rhombuses).

Example 15

Production of Paraffinic Jet Fuel from Soybean Oil

(50) Refined soybean oil was fed to a fixed-bed reactor with a granulated Ni.sub.2P/SiO.sub.2 catalyst at LHSV=1.0 h.sup.1, 330-370 C., 30 atm and H.sub.2/oil ratio=1000 NL/L. The run was carried out for >1000 h. The gas phase contained, besides hydrogen, other light products, mainly C.sub.1 to C.sub.3 hydrocarbons. The total liquid flow was separated into two phases, water and organics.

(51) To enrich the distillation range and properties of jet fuel, the organic normal paraffinic liquid obtained from the first stage was subjected to mild hydrockracking and isomerization steps. The liquid was fed to a fixed-bed reactor with two catalytic layers: (1) Ni.sub.2P/HY catalyst as mild hydrocracking step at 325 C. and (2) 1% Pt/(SAPO-11+Al.sub.2O.sub.2) of Example 5 at 350 C. Each layer was functioned under LHSV=4.0 h.sup.1, 30 atm and H.sub.2/oil ratio=350 NL/L. The run was carried out for >100 h. The gas phase contained, besides hydrogen, other light products, mainly C.sub.1 to C.sub.4 hydrocarbons. Yield (based on oil feedstock) and properties of the jet fuel paraffinic fraction collected are set out in Table 5.

(52) TABLE-US-00006 TABLE 5 Property Method Limits Jet fuel Yield of fraction to oil, wt % 56 Acidity, total mg KOH/g D3242 0.015 0.010 Aromatics, vol % D1319 Max. 0.5 0.0 Distillation temperature, C.: D86 Initial boiling point, C. Max. 205 142 10% recovered, report 178 20% recovered, report 194 30% recovered, report 216 40% recovered, report 235 50% recovered, report 250 60% recovered, report 262 70% recovered, report 269 80% recovered, report 274 90% recovered, report 278 T50-T10, C. Min. 22 72 Final boiling point,, C. Max. 300 280 Distillation residue, % Max. 1.5 1.5 Distillation loss, % Max. 1.5 1 Flash point, C. D56 Min. 38 46 Density at 15 C., kg/m.sup.3 D1298 0.775-0.840 0.766 Freezing point, C. D2386 Max. 47 55 Viscosity 20 C., mm2/s D445 Max. 8 7.62 Existent gum, mg/100 mL D381 Max. 7 3

(53) FIG. 9 describes distillation curves of organic products from 1st, 2nd stage and the final paraffinic BioJet fraction. It is noted that in this example, where the catalyst employed in the first step is not the catalyst of the invention, the jet fuel composition collected is free of aromatic compounds.