Process and zeolitic catalyst for the catalytic cracking of unconventional light crude oil type shale/tight oil and its blends with vacuum gas oil

Abstract

The present invention deals with a process for catalytic cracking of hydrocarbons comprising vacuum gas oil, hydrotreated vacuum gas oil, unconventional light crude oil, preferably unconventional light crude oil type shale/tight oil and its blends with conventional vacuum gas oil, in order to generate products of major commercial value in the field of fuels, getting improved gasoline and coke yield, as well as the procedure for the preparation of a catalyst with essential physical properties of density and particle size to uphold it in a fluidized bed under the operation conditions in the catalyst evaluation unit at micro level, wherein the catalyst particles achieve a catalytic performance similar to fluidized microspheres in a reactor, without appreciable generation of fine particles.

Claims

1. A catalytic system, comprising: a heterogeneous solid acid catalyst based on a formulation with at least one active zeolite comprising Faujasite Y zeolite and a coke selective active matrix; wherein the active matrix is selected from a group consisting of gamma phase alumina, silica-alumina or silicon oxide, kaolin, aluminum chlorohydrate, or mixtures thereof and avoids the use of phosphate; and hydrocarbon feedstocks consisting of vacuum gas oil (VGO), conventional vacuum gas oil, hydrotreated vacuum gas oil, unconventional light crude oil, or unconventional light crude oil type shale/tight oil and its blends with conventional vacuum gas oil, in a percentage range of from 0 to 100% by volume of unconventional light crude oil, wherein the hydrocarbon feedstocks are placed in contact with the heterogeneous solid acid catalyst.

2. A catalytic system, comprising: a heterogeneous solid acid catalyst based on a formulation with at least one active zeolite comprising Faujasite Y zeolite and a coke selective active matrix; wherein the active matrix is selected from a group consisting of gamma phase alumina, silica-alumina or silicon oxide, kaolin, aluminum chlorohydrate, or mixtures thereof and avoids the use of phosphate; and hydrocarbon feedstocks consisting of vacuum gas oil (VGO), conventional vacuum gas oil, hydrotreated vacuum gas oil, unconventional light crude oil, or unconventional light crude oil type shale/tight oil and its blends with conventional vacuum gas oil, in a percentage range of from 0 to 100% by volume of unconventional light crude oil, put in contact with the heterogeneous solid acid catalyst.

3. The catalytic system of claim 2, wherein the active zeolite further comprises a REY zeolite and a ZSM-5 zeolite.

4. The catalytic system of claim 3, further comprising a binder comprising a peptized alumina.

5. The catalytic system of claim 2, wherein the total surface area of catalyst is in the range from 350 m.sup.2/g to 450 m.sup.2/g, the zeolite surface area is in the range from 280 m.sup.2/g to 350 m.sup.2/g, the matrix area is in the range from 60 m.sup.2/g to 75 m.sup.2/g and the pore volume in the range of from 0.25 cm.sup.3/g to 0.35 cm.sup.3/g obtained by the Nitrogen desorption method.

6. The catalytic system of claim 2, wherein the active zeolite comprising Faujasite Y zeolite further comprising a stabilizing metal selected from a group consisting of lanthanum (La), Cerium (Ce), or its mixtures.

7. The catalytic system of claim 2, wherein the active zeolite comprising Faujasite Y zeolite further comprising a stabilizing metal; wherein the stabilizing metal comprises from 2.5% to 5.1% by weight of the catalyst.

Description

BRIEF DESCRIPTION OF THE DRAWINGS OF THE INVENTION

(1) The description of the invention refers to the following figures:

(2) FIG. 1 shows the total conversion as a function of the C/O ratio for catalyst CAT-1, at different ratios of vacuum gas oil/shale oil blends in the feed stream to the FCC catalytic cracking reactor.

(3) FIG. 2 shows the gasoline yield as a function of the total conversion for catalyst CAT-1, at different ratio of vacuum gas oil/shale oil blends in the feed stream to the FCC catalytic cracking reactor.

(4) FIG. 3 shows the coke yield as a function of the total conversion for catalyst CAT-1, at different ratio of vacuum gas oil/shale oil blend in the feed stream to the FCC catalytic cracking reactor.

(5) FIG. 4 shows the total conversion as a function of the C/O ratio for the catalyst CAT-2, with different ratio of shale/tight oil blend in the feed stream to the FCC micro reactor.

(6) FIG. 5 shows the gasoline yield as a function of the total conversion for the catalyst CAT-2, at different ratio of shale/tight oil blend in the feed stream to the FCC micro reactor.

(7) FIG. 6 shows the coke yield as a function of the total conversion for the catalyst CAT-2, at different shale/tight oil ratio in the feed stream blend to the FCC micro reactor.

EXAMPLES

Example 1

(8) A catalyst (designated CAT-1) was prepared using 38% of an Ultrastable Y Faujasite Zeolite (USY) containing from 8 to 8.5% by weight of rare earth oxide (RE.sub.2O.sub.3) and maximum 1.2% by weight of Na.sub.2O. Catalyst CAT-1 also contains 2.0% by weight of ZSM-5 zeolite. As a binder, 15% by weight of alumina from boehmite, formic acid and water were used; the aforementioned boehmite was obtained according to the method described in the Mexican patent MX 245842. In the preparation, 10% by weight of silicon oxide from colloidal silica AS-40 and kaolin were also used. With these materials a suspension with a 30% solids content was calculated.

(9) In a container containing distilled water, each component was added and mixed at a stirring speed of 1000-4000 rpm for 15 minutes until all the components were integrated and a complete homogenization was achieved in the mixture. The material obtained was dried at a temperature between 50-200° C., preferably between 110-180° C. for 6 to 8 hours. The paste obtained by the way above indicated, was fed to a stainless steel hand extruder in order to form extrudates. The extrudates were dried for 4 hours at 100-120° C., then calcined for 3 hours at 600° C., and finally milled to have a particle size between 74 and 250 microns, using 60 and 200 mesh sieves.

Example 2

(10) For the catalyst (named CAT-2) a composition of 35% of Ultrastable Y (USY) Faujasite zeolite was considered, containing 8 to 8.5% by weight of rare earth oxide (RE.sub.2O.sub.3) and maximum 1.2% by weight of Na.sub.2O. Catalyst also contains 2.0 wt % zeolite ZSM-5. As a binder, 1.5% by weight of an alumina from aluminum chlorohydrate, 13.5% by weight of alumina from boehmite, formic acid and water were used; the aforementioned boehmite was obtained according to the method described in the Mexican patent registration MX 245842. The catalyst CAT-2 also contains 10% by weight of silicon oxide from colloidal silica AS-40 and kaolin. With these materials and conditions, a suspension with 30% solids was calculated. This catalyst was prepared and heat-treated following the protocols described in Example 1.

Example 3

(11) The catalyst CAT-1 described in example 1 was deactivated at a temperature of 816° C. for 5 hours within an ambient of 100% water vapor, according to the following procedure:

(12) The catalyst is introduced into a quartz tubular reactor provided with a porous plate of the same material. An upflow nitrogen stream is connected. The flow of nitrogen gas is set at a rate of 100 ml/min and heating is started from room temperature to 816° C., at a heating rate of 3-5° C./min. Upon reaching the temperature of 816° C., the nitrogen flow is slowly closed and a 100% steam is introduced. These conditions of steam and temperature are maintained for 5 hours. At the end of the period, the steam flow is suspended, changed for nitrogen and cooled.

Example 4

(13) Catalyst CAT-2 was hydrothermally treated at 860° C. for 5 hours with 100% steam under the same deactivation protocol described in Example 3. Table 2 shows the physical properties of the catalysts before and after the deactivation protocol with steam. The surface area reported in this document was measured using the Nitrogen desorption method in an ASAP-2405 Surface Area Analyzer of Micromeritics. The Surface Area was determined according to ASTM D-4222-03 (R2008) method. The Micropore Volume and the Zeolite Area were determined the ASTM D-4365-95 (R-2008) method. The unit cell size in zeolite was determined using X-ray diffraction (XRD) by comparing each catalyst with a silicon reference material based on IMP 05LA-34080109-AAEC-MP-01 method (subsection F).

(14) TABLE-US-00002 TABLE 2 Physical properties of the catalysts before and after deactivation by steam. Physical properties CAT-1 CAT-2 Surface Area, m.sup.2/g 413 360 Zeolite area, m.sup.2/g 338 292 Matrix Area, m.sup.2/g 75 67 Pore Volume, cm.sup.3/g 0.30872 0.283 Unit Cell Size (UCS), Å 24.579 24.563 CATALYST DEACTIVATED BY STEAM Deactivation temperature, ° C. 816 860 Surface Area, m.sup.2/g 255 175 Zeolite area, m.sup.2/g 203 122 Matrix Area, m.sup.2/g 52 53 Unit Cell Size (UCS), Å 24.280 24.223 Rate of remaining total area 62% 49% Rate of remaining zeolite area 60% 42% Rate of remaining Matrix Area 70% 79%

Example 5

(15) The catalytic cracking catalyst named CAT-1 is introduced into a suspended and confined bed reactor by using feedstock 1 comprising vacuum gas oil (100% volume) in order to have a comparative baseline to analyze the own catalyst performance when processing unconventional light crude oil type shale/tight oil and blends of vacuum gas oil with shale/tight oil.

(16) Table 3 shows the catalyst CAT-1 performance as a function of the catalyst/oil ratio. The catalyst/oil ratios performed were of 4.5, 6, 7.5 and 10% weight/weight. Dry gas, LP gas, gasoline, LCO, HCO, coke and total feed conversion, expressed in % by weight of product yields are shown. The effect of the catalyst/oil ratio for 100% volume of vacuum gas oil, was emphasized. Using the catalyst CAT-1, the gasoline yield obtained was from 45.8 to 46.6% by weight, the conversion was from 74.7 to 78.6% by weight and the coke selectivity form 6.8 to 9% by weight. These results were obtained carrying out the evaluation procedure described in the Detailed Description of the Invention Section above and using feedstocks with properties shown in Table 1.

(17) TABLE-US-00003 TABLE 3 Reaction products distribution for catalyst CAT-1 when evaluated in a suspended bed reactor using vacuum gas oil feedstock 1 (100% volume), as a function of the catalyst/oil ratio. Catalyst/Oil Ratio 4.5 6 7.5 10 Dry Gas, % by weight 2.7 2.4 2.5 2.7 LP Gas, % by weight 19.7 18.6 19.0 20.0 Gasoline, % by weight 45.8 46.4 46.6 46.6 LCO, % by weight 15.9 16.1 15.3 13.8 HCO, % by weight 8.2 9.0 8.3 7.5 Coke, % by weight 7.0 6.8 7.7 9.0 Conversion, % by weight 75.7 74.7 76.2 78.6

Example 6

(18) CAT-1 catalytic disintegration catalyst is introduced into an ebullient bed reactor, with feedstock 2 comprising the blend of 90% volume of vacuum gas oil (VGO)+10% volume of domestic light shale/tight oil, with the properties presented in Table 1. The CAT-1 catalyst showed gasoline yield values from 46.2 to 46.8% by weight, with total feed conversion values of 76.3 to 78.5, % by weight, and coke selectivity of 6.8 to 8.7% b weight, these results are shown in Table 4.

(19) TABLE-US-00004 TABLE 4 Reaction Products distribution for the catalyst CAT-1 in an ebullient bed reactor as a function of the ratio catalyst/oil, using feedstock 2 consisting of vacuum gas oil (90% by volume) + crude shale/tight oil (10% by volume), Catalyst/Oil Ratio 4.5 6 7.5 10 Dry Gas, % by weight 2.8 2.6 2.8 2.8 LP Gas, % by weight 20.4 19.6 20.3 20.6 Gasoline, % weight 46.5 46.8 46.5 46.2 LCO, % by weight 15.6 15.3 14.4 14.3 HCO, % by weight 8.0 8.3 7.6 7.1 Coke, % by weight 6.8 6.7 7.8 8.7 Conversion, % by 76.2 76.3 77.8 78.5 weight

Example 7

(20) The catalytic cracking catalyst CAT-1 is introduced into an ebullient bed reactor and evaluated using feedstock 3 comprising the blend of 70% volume of vacuum gas oil (VGO)+30% volume of light crude oil type domestic Shale Oil, with the properties presented in Table 1. The catalyst Cat-1 showed gasoline yield values from 46.6 to 48% by weight, total conversion of feed number 3 from 77.3 to 80.4, % by weight and selectivity to coke from 6.5 to 8.8% by weight. These results are shown in Table 5.

(21) TABLE-US-00005 TABLE 5 Reaction Products distribution for CAT-1 in an ebullient bed reactor with feedstock 3 consisting of vacuum gas oil (70% by volume) + 30% by volume of shale/ tight oil, as a function of the catalyst/ratio oil. Catalyst/Oil Ratio 4.5 6 7.5 10 Dry Gas, % by weight 2.8 2.6 2.7 2.9 LP Gas, % by weight 21.0 19.6 20.5 22.0 Gasoline, % by weight 46.9 48.0 47.3 46.6 LCO, % by weight 15.1 15.1 14.5 13.3 HCO, % by weight 6.9 7.4 7.1 6.1 Coke, % by weight 6.6 6.5 7.3 8.8 Conversion, % by 77.8 77.3 78.3 80.4 weight

Example 8

(22) Catalyst testing of catalyst CAT-1 was carried out using feedstock 4 consisting of a blend of 50% by volume of vacuum gas oil+50% by volume of shale/tight oil, with properties presented in Table 1. Catalytic performance of catalyst CAT-1 in the catalytic cracking reaction showed gasoline yield values from 48.3 to 49.5% by weight, with total feedstock conversion from 79.3 to 81.8% by weight and selectivity to coke from 6.1 to 7.9% by weight, these Results are shown in Table 6.

(23) TABLE-US-00006 TABLE 6 Reaction Products distribution for CAT-1 catalyst in an ebullient bed reactor with feedstock 4 consisting of vacuum gas oil (50% by volume) + 50% by volume of light shale/tight oil, as a function of the catalyst/oil ratio Catalyst/Oil Ratio 4.5 6 7.5 10 Dry gas, % by weight 2.9 2.6 2.6 2.8 LPG, % by weight 22.3 20.6 21.1 22.7 Gasoline, % by weight 48.3 49.5 48.9 48.2 LCO, % by weight 14.0 14.4 14.0 12.9 HCO, % by weight 5.6 6.1 5.8 5.1 Coke, % by weight 6.3 6.1 6.8 7.9 Conversion, % by weight 80.3 79.3 80.0 81.8

Example 9

(24) Catalyst testing of catalyst CAT-1 was carried out using feedstock 5 consisting of 100% by volume of shale/tight oil, with properties presented in Table 1. Catalytic performance of catalyst CAT-1 in the catalytic cracking reaction showed gasoline yield values from 48.8 to 51% by weight, with total feedstock conversion from 79.3 to 81.8% by weight and selectivity to coke from 6.4 to 8.0% by weight. The products distribution is showed in Table 7. The gasoline yield, LPG yield and total conversion are notably increased compared to Example 5 results.

(25) TABLE-US-00007 TABLE 7 Reaction Products distribution for catalyst CAT-1 in an ebullient bed reactor with feedstock 5 consisting of 100% by volume of light shale/tight oil, as a function of catalyst/oil ratio. Catalyst/Oil Ratio 4.5 6 7.5 10 Dry gas, % by weight 2.9 2.6 2.6 2.8 LPG, % by weight 24.7 22.6 23.1 25.0 Gasoline, % by weight 49.2 51.0 50.1 48.8 LCO, % by weight 12.4 12.6 12.5 11.3 HCO, % by weight 4.0 4.1 4.0 3.7 Coke, % by weight 6.4 6.4 7.0 8.0 Conversion, % by weight 83.4 83.1 83.3 84.8

(26) According to the examples 5 to 9, FIGS. 1, 2 and 3 show representative results of the behavior of catalyst CAT-1 activity for the total conversion of feedstock and the gasoline and coke yield. FIG. 1 shows the conversion as a function of the catalyst/oil ratio (R=C/O), when the feedstocks 1 to 5 are used in the catalytic cracking reactor.

(27) FIG. 2 shows the gasoline yield as a function of the total conversion of feedstock in % by weight, when feedstocks 1 to 5 of Table 1 are used in the catalytic cracking reactor with catalyst CAT-1.

(28) FIG. 3 shows the coke production as a function of the total feedstock conversion (% by weight), when feedstocks 1 to 5 of table 1 are used in the catalytic cracking reactor with catalyst CAT-1. At constant coke content (7% by weight) in the catalyst when VGO vacuum gas oil is processed, the conversion is from 75.8% by weight; when feedstock processed is a blend consisting of 50% by volume of VOG+50% by volume of shale/tight oil, the conversion increases 5% by weight, up to 80.8% by weight. If 100% by volume of unconventional crude oil is processed, the total conversion increases 8% by weight.

Example 10

(29) The catalytic cracking catalyst CAT-2 was evaluated in the fluidized bed reactor with feedstock 1 consisting of 100% volume vacuum gas oil VGO, following the evaluation procedure described above. The feedstock properties are shown in Table 1. As a result of the microactivity conversion, gasoline yield values are between the range of 45.3 to 45.9% by weight, total conversion is in the range of 71 to 74,% by weight, and selectivity to coke is in the range from 5.6 to 7.4% weight.

(30) Table 8 shows the reaction products distribution for the catalyst CAT-2, the dry gas, LP gas, gasoline, LCO, HCO and coke yields, as well as microactivity conversion expressed in % by weight, based on the catalyst/oil ratio for a feedstock consisting of vacuum gas oil at 100% volume.

(31) TABLE-US-00008 TABLE 8 Reaction Products distribution for catalyst CAT-2 with a feedstock consisting of 100% by volume of vacuum gasoil VGO, as a function of the catalyst/oil ratio. Catalyst/Oil Ratio 4.5 6 7.5 10 Dry gas, % by weight 2.1 2.0 2.1 2.2 LPG, % by weight 17.8 16.9 17.8 18.3 Gasoline, % by weight 45.3 45.7 45.9 45.7 LCO, % by weight 18.0 17.9 17.0 16.6 HCO, % by weight 9.9 11.3 10.0 9.3 Coke, % by weight 6.2 5.6 6.6 7.4 Conversion, % by weight 71.9 72.3 72.9 74.0

Example 11

(32) The microactivity of the catalytic cracking catalyst CAT-2 was evaluated in an ebullient bed reactor with feedstock 2 consisting of a blend 90% by volume of vacuum gas oil VGO+10% by volume of shale/tight oil, with properties presented in Table 1. As a result of the catalyst testing, gasoline yield values on the range from 46.3 to 46.6% by weight, total conversion from 72.4 to 73, % by weight and selectivity to coke from 5.9 to 6.7% by weight, were obtained.

(33) Table 9 shows the performance of the catalyst CAT-2 in terms of yield to dry gas, LP gas, gasoline, LCO, HCO, coke and total feedstock conversion in % by weight, as a function of the ratio of catalyst/oil for said feedstock.

(34) TABLE-US-00009 TABLE 9 Reaction Products distribution for catalyst CAT-2 in an ebullient bed reactor with feedstock 2 consisting of a blend 90% by volume of vacuum gasoil VGO + 10% by volume of shale/tight oil, as a function of the catalyst/oil ratio. Catalyst/Oil Ratio 4.5 6 7.5 10 Dry gas, % by weight 2.1 2.0 2.1 2.2 LPG, % by weight 17.4 16.2 16.8 17.2 Gasoline, % by weight 46.3 46.5 46.6 46.6 LCO, % by weight 18.0 18.3 18.0 17.8 HCO, % by weight 9.4 10.6 9.8 9.2 Coke, % by weight 6.1 5.9 6.5 6.7 Conversion, % by weight 72.4 72.4 72.5 73.0

Example 12

(35) The catalytic activity of the heterogeneous catalyst CAT-2 was evaluated using feedstock 3 with the highest content of shale/tight oil, consisting of a blend 70% by volume of vacuum gas oil VGO+30% by volume of shale/tight oil, with the properties shown in Table 1. The CAT-2 catalyst presented gasoline yield values in a range from 46.6 to 47.5% by weight, total conversion from 72.3 to 75.2% by weight, and coke selectivity from 5.2 to 7.0% by weight.

(36) Table 10 shows the product distribution for the catalyst CAT-2, dry gas yield, LP gas yield, gasoline yield, LCO, HCO and coke yields, as well as total conversion, expressed in % by weight, as a function of the catalyst/oil ratio

(37) TABLE-US-00010 TABLE 10 Reaction Products distribution for catalyst CAT-2 in an ebullient bed reactor with feedstock consisting of a blend 70% by volume of vacuum gasoil VGO + 30% by volume of shale/tight oil, as a function of the catalyst/oil ratio. Catalyst/Oil Ratio 4.5 6 7.5 10 Dry gas, % by weight 2.1 2.0 2.1 2.3 LPG, % by weight 17.2 16.5 17.3 18.2 Gasoline, % by weight 46.6 47.3 47.4 47.5 LCO, % by weight 18.9 18.9 17.8 16.8 HCO, % by weight 8.7 9.5 9.0 7.9 Coke, % by weight 6.0 5.2 5.8 7.0 Conversion, % by weight 72.3 72.6 73.0 75.2

Example 13

(38) The catalytic performance for catalyst CAT-2 was carried out used feedstock 4, consisting of a blend of 50% by volume of vacuum gas oil VGO+50% volume of shale/tight oil, with the properties shown in Table 1.

(39) The evaluation of the catalytic cracking reaction showed gasoline yield values in a range of 47.8 to 48.3% by weight, total conversion from 73.1 to 75.7% by weight, and coke selectivity from 5.0 to 6.2% by weight, these results are shown in Table 11

(40) TABLE-US-00011 TABLE 11 Reaction products distribution for catalyst CAT-2 in an ebullient bed reactor with feedstock 4 consisting of a blend 50% by volume of vacuum gasoil VGO + 50% by volume of shale/tight oil, as a function of the catalyst/oil ratio. Catalyst/Oil Ratio 4.5 6 7.5 10 Dry gas, % by weight 2.1 1.9 2.1 2.2 LPG, % by weight 17.6 16.6 17.5 18.1 Gasoline, % by weight 47.8 48.1 48.2 48.3 LCO, % by weight 18.9 19.3 18.7 17.6 HCO, % by weight 8.1 9.0 8.5 7.9 Coke, % by weight 5.5 5.0 5.4 6.2 Conversion, % by weight 74.0 73.1 73.5 75.7

Example 14

(41) The catalyst CAT-2 is evaluated using feedstock 5, which consists of 100% by volume of shale/tight oil, whose properties are shown in Table 1. The reaction conditions to which the catalyst was subjected, allowed obtaining gasoline yield values in a range of 47.8 to 49% by weight, total conversion from 74.8 to 76.6, and coke selectivity in a range of 5.0 6.4% by weight. These results are shown in Table 12

(42) TABLE-US-00012 TABLE 12 Reaction Products distribution for catalyst CAT-2 in an ebullient bed reactor with feedstock 5 consisting of 100% by volume of shale/tight oil, as a function of the catalyst/oil ratio. Catalyst/Oil Ratio 4.5 6 7.5 10 Dry gas, % by weight 2.1 2.0 2.0 2.1 LPG, % by weight 19.9 18.7 19.5 20.1 Gasoline, % by weight 48.2 49.0 48.7 47.8 LCO, % by weight 18.7 18.6 18.4 18.2 HCO, % by weight 5.8 6.4 5.6 5.1 Coke, % by weight 5.0 5.1 5.6 6.4 Conversion, % by weight 75.4 74.8 75.9 76.6

(43) For the examples 10 to 14, the representative results of catalyst CAT-2 activity behavior are shown in FIGS. 4 to 6, included feedstock conversion as well as gasoline and coke production.

(44) FIG. 4 shows the total conversion as a function of the catalyst/oil ratio (R=C/O) with values or 4.5, 6, 7.5 and 10, for the different feedstocks (feedstock 1 to 5) shown in table 1, which comprise blends of vacuum gas oil VGO with shale/tight oil in proportions of 0, 30, 50 and 100% by volume.