Composition having an active metal or precursor, an amine component and a non-amine containing polar additive useful in the catalytic hydroprocessing of hydrocarbons, a method of making such catalyst, and a process of using such catalyst

Abstract

A composition that comprises a support material that is loaded with an active metal or metal precursor, an amine component, and a non-amine containing polar additive. The composition is useful in the hydroprocessing of hydrocarbon feedstocks. The composition is prepared by incorporating a metal solution into a support material followed by incorporating therein an amine component and a non-amine containing polar additive.

Claims

1. A method of making a composition, wherein said method comprises: incorporating a metal-containing solution into a support material to provide a metal-incorporated support material; and incorporating both an amine component and a non-amine containing polar additive into said metal-incorporated support material to thereby provide an impregnated composition comprising said support material, said amine component, and said non-amine containing polar additive wherein the weight ratio of said non-amine containing polar additive to said amine component is in the range of upwardly to 10:1; wherein said amine component is selected from the group of compounds consisting of ether amine compounds, alkyl amine compounds, and amine oxide compounds; and wherein said amine compound has a molecular weight greater than 160 and a flash point of at least 80 C.

2. A method as recited in claim 1, further comprising: contacting said impregnated composition under suitable hydrogen treatment conditions with hydrogen to thereby provide a hydrogen-treated composition.

3. A method as recited in claim 2, wherein prior to said incorporating of said amine component and said non-amine containing polar additive into said metal-incorporated support material, said metal-incorporated support material is dried so as to contain a volatiles content in the range of from 3 to 20 wt. % LOI.

4. A method as recited in claim 1, wherein said amine component is an ether amine compound.

5. A method as recited in claim 4, wherein said ether amine compounds include those selected from the family of compounds having the following formula: RO(CH.sub.2).sub.nNH.sub.2, wherein R is an alkyl functional group comprising from 4 to 14 carbon atoms and n is an integer of ranging from 1 to 6.

6. A method as recited in claim 1, wherein said amine oxide compounds include those selected from the family of compounds having the following formula: [R1, R2 and R3] N.sup.+O.sup., wherein R1 is either a hydrogen atom or an alkyl functional group, R2 is either a hydrogen atom or an alkyl functional group, and R3 is either a hydrogen atom or an alky functional group, wherein the total number of carbon atoms included in R1 and R2 and R3 is in the range of from 8 carbon atoms to 40 carbon atoms.

7. A method as recited in claim 1, wherein said alkyl amine compounds include those selected from the group of amine compounds consisting of primary amines having from 8 to 20 carbon atoms, secondary amines having from 8 to 20 carbon atoms, and tertiary amines having from 8 to 20 carbon atoms.

8. A method as recited in claim 1, wherein said non-amine containing polar additive is selected from those compounds having a dipole moment of at least 0.45 and which are an heterocompound but excluding heterocompounds that include an amino functional group or a sulfur atom.

9. A method as recited in claim 1, wherein said active metal precursor is a metal compound that includes a Group 9 and Group 10 metal component selected from the group consisting of cobalt and nickel, and wherein said Group 9 and Group 10 metal component is present in said composition in an amount in the range of from 5 wt. % to 50 wt. %.

10. A method as recited in claim 9, wherein said support material that is loaded with said active metal precursor, said amine component, and said non-amine containing polar additive is treated with hydrogen.

11. A method as recited in claim 10, wherein said support material that is loaded with said active metal precursor, said amine component, and said non-amine containing polar additive treated with hydrogen is treated with a sulfur compound.

12. A method as recited in claim 1, wherein said support material is loaded with an active metal precursor, an amine component, and a non-amine containing polar additive in the substantial absence of a hydrocarbon oil.

13. A method as recited in claim 1, wherein said amine component is a mixture of two ether amines of 3-(octyloxy)propylamine and 3-(decyloxy)propylamine.

14. A method as recited in claim 7, wherein said alkyl amine is oleylamine.

15. A method as recited in claim 4, wherein said non-amine containing polar additive is n-formylmorpholine (NFM).

16. A method as recited in claim 13, wherein said non-amine containing polar additive is n-formylmorpholine (NFM).

Description

EXAMPLE I

(1) This Example I describes the preparation of a comparative composition that contains a prior art additive and of the inventive compositions that contain the additives, i.e., an amine component and a non-amine containing polar additive, of the invention.

(2) A commercially available alumina carrier was used in the preparation of the catalyst compositions of this Example I. The following Table 1 presents the typical physical properties of the alumina carrier that was used in the preparations.

(3) TABLE-US-00001 TABLE 1 Typical Alumina Carrier Properties Property Value Compacted Bulk Density(g/cc) 0.49 Water Pore Volume (cc/g) 0.88 BET Surface Area (m2/g) 300 Median Pore Diameter by Volume (angstroms) 91

(4) The metal components of the catalyst were incorporated into the carrier by the incipient wetness impregnation technique. The impregnation solution included 75.6 weight parts water, 11.8 weight parts phosphoric acid (H.sub.3PO.sub.4), 12.8 weight parts nickel carbonate (NiCO.sub.3), and 35.3 weight parts Climax molybdenum trioxide (62.5% Mo). 135.5 weight parts of the impregnation solution was incorporated into 100 weight parts of alumina carrier to provide a metal-incorporated support material.

(5) The impregnated carrier or metal-incorporated support material was then dried at 125 C. (257 F.) for a period of several hours to give a dried intermediate having an LOI of 7.9 wt % and a water pore volume of 0.331 cc/g.

(6) Aliquot portions of the dried intermediate were then each impregnated with a selection of one of the following four additives or additive mixtures to fill 92% of the pore volume of the dried intermediate: (1) 100% Arosurf MG-98 ether amines, which is a mixture of the two ether amines of 3-(octyloxy)propylamine and 3-(decyloxy)propylamine, wherein Arosurf MG-98 ether amines is a product marketed by Evonik Industries; (2) a mixture of 50 vol % DMF and 50 vol % NFM; (3) a mixture of 40 vol % n-formylmorpholine (NFM) and 60 vol % Arosurf MG-98 ether amines; (4) 100% dimethylformamide (DMF); (5) a mixture of 50 vol % Adogen-160 amines and 50 vol % DMF, wherein Adogen-160 amines is a mixture of amines having an average number of carbon atoms of 12 and is a product marketed by Evonik Industries; (6) a mixture of 50 vol % Tomamine AO-405 alkoxylated ether amine oxide and 50 vol % DMF, wherein Tomamine AO-405 alkoxylated ether amine oxide product is marketed by Air Products; (7) a mixture of 50 vol % Tomamine AO-455 alkoxylated ether amine oxide and 50 vol % DMF, wherein Tomamine AO-455 alkoxylated ether amine oxide product is marketed by Air Products; (8) 100% oleylamine; and (9) 50 vol % oleylamine and 50 vol % DMF. The DMF and NFM are non-amine containing polar additives.

(7) Certain of the physical properties of the individual organic additives are presented in the following Table 2.

(8) TABLE-US-00002 TABLE 2 Properties of Various Organics Ether amine Ether amine 3-(Octyloxy) 3-(Decyloxy) Andogen- Tomamine Tomamine DMF NFM propylamine propylamine 160 AO-405 AO-455 Oleyamine Flash Point ( F.) 136 235 210 242 >200 212 >212 338 Molecular Weight 79.09 115.13 187.32 215.38 See note See note See note 267.47 (g/mole) below below below Boiling Point ( F.) 307.4 458.6 514.4 577.6 498 210 210 349 Melting Point ( F.) 77.8 73.4 N/A N/A N/A 32 32 70 Formula C.sub.3H.sub.7NO C.sub.5H.sub.9NO.sub.2 C.sub.11H.sub.25NO C.sub.13H.sub.29NO See note See note See note C.sub.18H.sub.37N.sub.1 below below below Density (g/cc) 0.944 1.145 0.85 0.85 0.83 1.01 1.04 0.813 Adogen-160 is a mixture of alkylamines with a peak at C12. Tomamine AO-405 is listed as Poly[oxy(methyl-2,1-ethanediyl)], a,a-[(oxidoimino)bis(methyl-2,1-ethanediyl)]bis[w-hydroxy-, N-[3-(C9-11-isoalkyloxy)propyl] derivs., C10-rich Tomamine AO-455 is listed as Oxirane, methyl-, polymer with oxirane, ether with 2,2-(oxidoimino)bis(ethanol) (2:1), N-(3-(C9-11-isoalkyloxy)propyl) derivs., C10-rich

EXAMPLE II

(9) This Example II describes the general procedure used to test the catalytic performance of the additive impregnated compositions described in Example I, and it presents the performance results from their use in the hydrodesulfurization and hydrodenitrogenation of a typical vacuum gas oil.

(10) Each of the additive impregnated compositions of Example I was tested using reactors of a high throughput catalyst testing unit under the conditions presented in the following Table 3.

(11) TABLE-US-00003 TABLE 3 Reactor Test Conditions and Targets Hydrogen/Oil Ratio 4060 scf/bbl Pressure 1350 psig LHSV 1 hr.sup.1 Temperature 698 F. Target Nitrogen 500 ppm HDN Reaction Order 0.86 HDN Apparent Activation Energy 26 kcal/mole Target S 200 ppm HDS Reaction Order 1.3 HDS Apparent Activation Energy 33 kcal/mole

(12) The feedstock used in the testing was a typical vacuum gas oil having the physical properties as presented in the following Table 4.

(13) TABLE-US-00004 TABLE 4 Test Feedstock Properties Hydrogen (wt %) 11.65 Carbon (wt %) 85.60 Nitrogen (wt %) 0.44 Sulfur (wt %) 2.05 Nickel (ppm) 1 Vanadium (ppm) 2.5 Basic Nitrogen (ppm) 1447 API Gravity 19.29 UV Aromatics 1 4.9 2 4.2 3 5.0 4+ 3.8 Total 18.0 MCR (wt %) 0.2 HTSD 50% ( F.) 774 HTSD 95% ( F.) 980

(14) The results of the activity testing of the additive impregnated compositions are presented in the following Table 5. The catalyst activity, in this case, is defined as the temperature required to achieve a target concentration of nitrogen (500 ppm) or sulfur (200 ppm) in the treated product using a designated catalyst relative to the temperature required to achieve the same concentration of nitrogen or sulfur in the treated product using a reference catalyst. With this definition, larger negative activity numbers indicate higher activity.

(15) TABLE-US-00005 TABLE 5 Catalyst Performance Results Relative HDN Relative HDS No. Description Activity ( F.) Activity ( F.) 1 100% Arosurf MG-98 10 7 2 50/50 DMF/NFM 14 10 3 40/60 NFM/Arosurf MG-98 13 10 4 100% DMF 5 2 5 50/50 Adogen-160/DMF 14 11 6 50/50 Tomah AO-405/DMF 11 8 7 50/50 Tomah AO-455/DMF 17 10 8 100% oleylamine 3 0 9 50/50 oleylamine/DMF 10 6

(16) The performance data presented in Table 5 show that the composition which contains only ether amine as a component (#1) and the composition which contains only DMF as a component (#4) both exhibit significantly lower hydrodesulfurization (HDS) and hydrodenitrogenation (HDN) activities than the compositions that comprise a combination of the ether amine with either DMF (#2) or NFM (#3). In both these cases, the HDN and HDS activities are significantly improved over the activities exhibited by the compositions that contain either the ether amine alone (#1) or the DMF alone (#4). Likewise, the composition which contains only an primary amine as a component (#8) exhibits significantly lower HDS and HDN activities than the composition that comprises a combination of the primary amine and DMF (#9). Also, the compositions which contain a combination of both an amine oxide, or ether amine oxide, and DMF (#6 & #7) exhibit significantly better HDN and HDS activity than the composition that contains DMF alone (#4). The compositions which contain a combination of both an amine compound and DMF (#5 & #9) also exhibit significantly better HDN and HDS activity than the composition that contains DMF alone. These data suggest a synergistic effect resulting from using a non-amine containing polar additive in combination with either an ether amine compound, or an alkyl or alkenyl amine compound, or an amine oxide compound.