Chelant and polar additive containing composition useful in the hydroprocessing of hydrocarbon feedstocks and method of making and use thereof

Abstract

A hydroprocessing catalyst composition that comprises a chelant treated metal containing support material having incorporated therein a polar additive. The catalyst composition is prepared by incorporating at least one metal component into a support material followed by treating the metal incorporated support with a chelating agent and thereafter incorporating a polar additive into the chelant treated composition.

Claims

1. A hydroprocessing catalyst composition, comprising: a metals incorporated shaped support, a chelating agent, and a polar additive, wherein at least 75% of the available pore volume of said metal incorporated support is filled with said polar additive.

2. The hydroprocessing catalyst composition as recited in claim 1, wherein said chelating agent is selected from the group of compounds consisting of aminocarboxylic acids, polyamines, aminoalcohols, oximes, and polyethyleneimines.

3. The hydroprocessing catalyst composition as recited in claim 2, wherein said polar additive is a heterocompound having polarity and a dipole moment of at least 0.45.

4. The hydroprocessing catalyst composition as recited in claim 3, wherein said additive impregnated composition comprises a Group 9 or Group 10 metal component selected from the group consisting of cobalt and nickel present in an amount in the range of from 0.5 wt. % to 20 wt. %, and a Group 6 metal component selected from the group consisting of molybdenum and tungsten present in an amount in the range of from 5 wt. % to 50 wt. %, wherein the weight percents are based on the weight of the dry support material with the metal component as the element regardless of its actual form.

5. The hydroprocessing catalyst composition as recited in claim 4, wherein said shaped support comprises a porous refractory oxide selected from the group of refractory oxides consisting of silica, alumina, titania, zirconia, silica-alumina, silica-titania, silica-zirconia, titania-alumina, zirconia-alumina, silica-titania and combinations of two or more thereof; and wherein said shaped support has a surface area (as determined by the BET method) in the range of from 50 m.sup.2/g to 450 m.sup.2/g, a mean pore diameter in the range of from 50 to 200 angstroms (Å), and a total pore volume exceeding 0.55 cc/g.

6. A hydroprocessing process, comprising: contacting under hydroprocessing reaction conditions the composition of claim 1.

Description

EXAMPLE 1

(1) This Example 1 describes the preparation of the alumina support particle used in the preparation of the comparative compositions A, B and an inventive composition C described in Examples 2-4.

(2) The support used in the preparation of the compositions A, B, C and D was made by forming an alumina support particle. The support particle was made by mixing alumina and water to form a mixture that was extruded into 1.3 mm Trilobe extrudates. The shaped support extrudates were dried and calcined using standard drying and calcination techniques so as to provide an alumina carrier for loading the active metals and additive components of the compositions. The properties of the shaped alumina support are presented in Table 2 below.

(3) TABLE-US-00002 TABLE 2 Properties of Shaped Support Property Value Shape 1.3 mm Trilobe Surface area (m2/g)  245 to 320 Mean pore diameter (Ang. )   80 to 100 Pore volume greater Less than 5 than 350 Ang. (%) Water pore volume (cc/g) 0.74 to 0.90

EXAMPLE 2

(4) This Example 2 describes the preparation of comparative Composition A that contains only hydrogenation metal components and had neither been treated with nor contains a chelating agent or a polar additive.

(5) An amount of the shaped support of Example 1 was impregnated with an aqueous impregnation solution (metal-containing solution) comprising a nickel component, a molybdenum component, and a phosphorous component. The aqueous impregnation solution was prepared by dissolving nickel oxide (NiO), molybdenum trioxide (MoO.sub.3) and phosphoric acid in de-ionized water with heating and stirring. A volume of the aqueous impregnation solution was used to fill the pores of the extrudate so as to load it with 4.5% nickel, 18.0 wt % molybdenum, and 3.3 wt % phosphorous, with the weight percents being on a dry basis and the metals as element. The impregnated shaped particles (extrudates) were allowed to age for two hours, and, then dried in air at a drying temperature of 100° C. to reduce the volatiles content to 7.3 wt % to thereby provide Composition A. Composition A was not treated with and did not contain a chelating agent or a polar additive.

EXAMPLE 3

(6) This Example 3 describes the preparation of comparative Composition B that has not been subject to a chelating treatment but included a polar additive.

(7) Composition A was impregnated with the polar additive dimethylformamide (DMF) to fill substantially all of the free pore volume to provide Composition B.

EXAMPLE 4

(8) This Example 4 describes the preparation of Composition C, which is one embodiment of the inventive composition, containing hydrogenation metal components and which has been treated with a chelating agent and filled with a polar additive.

(9) Composition A was impregnated with a solution comprising the chelating agent diethylenetriaminepentaacetic acid (DTPA). This solution was prepared as follows: 2726 weight parts of deionized water was mixed with 283 weight parts DTPA powder (99% concentration, BASF, Trilon C Powder). To this mixture 105 weight parts ammonium hydroxide at 29% NH.sub.3 concentration was added. Heat was used as needed to dissolve the components of the solution. The final solution had a specific gravity of approximately 1.04 g/cc and solution concentrations of 9% DTPA and 0.98% NH.sub.3. In the impregnation of Composition A with the solution comprising the chelating agent, a substantial proportion of the free pore volume was filled with the solution.

(10) Following the pore volume impregnation of Composition A with the solution of chelating agent, the chelant treated Composition A (chelant treated metal-incorporated support) was dried in air at a temperature in the range of from 120 to 130° C. for 4 hours to eliminate excess moisture and reduce the volatiles content thereof to a target LOI and to free up pore volume that could subsequently be filled with a polar additive. The dried chelant treated Composition A (dried chelant treated metal-incorporated support) was then filled by pore volume impregnation with the polar additive dimethylformamide (DMF) to at least a 90% pore volume fill to give the inventive Composition C (additive impregnated composition).

EXAMPLE 5

(11) This Example 5 describes the procedure for testing the catalytic performance of the compositions of Examples 3-4, and it presents the performance results from their use in the hydrotreating of a gas oil feedstock (activity testing).

(12) Trickle flow micro-reactors were used to test the hydrodesulfurization activity of Compositions B and C. A 50 cc volume, based on compacted bulk density of whole pellets, of each composition was used in the testing. The reactors were packed with extrudates of each composition, which were diluted with 80-60 mesh SiC in the volumetric composition-to-diluent ratio of 1:1. The compositions were conditioned and sulfided using a delayed-feed introduction procedure whereby the composition was first heated up and conditioned by contacting it with pure hydrogen at the operating pressure and at a temperature in the range of from 149° C. (300° F.) to 204° C. (400° F.) for a time period of about 12 hours. Following this hydrogen treatment, the composition was sulfided using a liquid hydrocarbon containing TNPS to provide a sulfur content of 2.5%.

(13) The activity of the compositions was tested by charging the reactors with a blended feedstock of a VGO (vacuum gas oil) boiling range. The feedstock had a sulfur content of 3.32 wt. %, a nitrogen content of 0.231 wt. %, and it was charged to the reactor, which was operated at a pressure of 1400 psig and at a rate so as to provide a liquid hourly space velocity (LHSV) of 0.75 hr.sup.−1. The hydrogen gas rate charged to the reactor was 3500 scf H.sub.2/bbl. The weight average bed temperature (WABT) was normalized for 260 ppm product nitrogen target.

(14) FIG. 1 presents the results of the testing with activity determined as the WABT required to achieve targeted 260 ppm nitrogen content in the product. It can be observed from the presented plots that the inventive Composition C exhibits a higher activity (a lower WABT for the given HDN level) than the comparative Composition B. Composition C provided 68 ppm total nitrogen in the product whereas the Composition B showed a 125 ppm total nitrogen in the product that translates into up to a 5.5° C. (10° F.) temperature advantage of the inventive Composition C.