# US 2015/0144532 A1 · Resid hydrotreating catalyst containing titania

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- Number: US 2015/0144532 A1
- Document ID: US20150144532A1
- Status: Published application
- Kind: A1
- Application number: 14/409,560
- Filed: 2013-06-20
- Published: 2015-05-28
- Earliest claimed: 2012-06-20
- Assignees: Advanced Refining Technologies LLC
- Applicants: Advanced Refining Technologies LLC
- Inventors: Rong He; Stanislaw Plecha; Meenakshi S. Krishnamoorthy; Bharat M. Patel
- Web page: https://patentgrep.com/patent/US20150144532A1

## CPC

- B01J 27/19: Molybdenum
- B01J 21/04: Alumina
- B01J 21/063: {Titanium; Oxides or hydroxides thereof}
- B01J 23/755: Nickel
- B01J 23/883: and nickel
- B01J 35/615: {100-500 m2/g}
- B01J 35/635: {0.5-1.0 ml/g}
- B01J 35/638: {more than 1.0 ml/g}
- B01J 35/647: {2-50 nm}
- B01J 35/651: {50-500 nm}
- B01J 35/653: {500-1000 nm}
- B01J 35/657: {larger than 1000 nm}
- B01J 37/0009: {Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst}
- B01J 37/0045: {Drying a slurry, e.g. spray drying}
- B01J 37/0201: {Impregnation}
- B01J 37/03: Precipitation; Co-precipitation
- B01J 37/031: {Precipitation}
- B01J 37/08: Heat treatment {(B01J37/0009, B01J37/0018 take precedence)}
- B01J 37/12: Oxidising
- B01J 37/16: Reducing
- B01J 37/28: Phosphorising
- C10G 45/00: Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G 45/08: in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
- C10G 2300/10: Feedstock materials
- C10G 2300/107: Atmospheric residues having a boiling point of at least about 538 °C
- C10G 2300/1077: Vacuum residues
- C10G 2300/70: Catalyst aspects
- C10G 2300/708: Coking aspect, coke content and composition of deposits
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C10G: CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION (cracking to hydrogen or synthesis gas C01B; cracking or pyrolysis of hydrocarbon gases to individual hydrocarbons or mixtures thereof of definite or specified constitution C07C; cracking to cokes C10B); RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES

## Abstract

Improved catalyst supports, supported catalyst, and method of preparing and using the catalysts for the hydrodesulfurization of a residuum hydrocarbon feedstock are disclosed. The catalyst supports comprise titania alumina having 5 wt % or less titania and have greater than 70% of their pore volume in pores having a diameter between 70 and 130 and less than 2% in pores having a diameter above 1000. Catalysts prepared from the supports contain Groups 6, 9 and 10 metals or metal compounds, and optionally phosphorus, supported on the titania alumina supports. Catalysts in accordance with the invention exhibit improved sulfur and MCR conversion in hydrotreating processes.

## Claims

### Claim 1

A process for preparing a porous support material for supporting catalytically active metals suitable for the hydrodesulfurization of residuum hydrocarbon fractions under hydrotreating conditions, which process comprises:
(a) preparing a co-precipitated titania alumina powder having wt % or less titania, based on the total weight of the titania alumina powder;
(b) peptizing the titania alumina powder;
(c) extruding the titania alumina powder to form a titania alumina extrudate; and
calcining the extrudate at a temperature from about 500° C. to about 900° C. for about 1 hour to about 3 hours to obtain a titania alumina support having 5 wt % or less titania, based on the total weight of the support, wherein the support is characterized as having:
(i) a total pore volume from about 0.5 to about 1.1 cubic centimeters per gram;
(ii) at least 70% of the total pore volume in pores having a diameter of about 70 Å to about 130 Å;
(iii) less than 5% of the total pore volume in pores having a diameter above 300 Å, as determined by nitrogen porosimetry; and
(iv) less than 2% of the total pore volume in pores having a diameter above 1000 Å, as determined by mercury penetration porosimetry.

### Claim 2 (depends on 1)

The process of claim 1 wherein the support comprises at least 90 wt % of co-precipitated titania alumina.

### Claim 3 (depends on 1)

The process of claim 1 wherein the co-precipitated titania alumina powder is formed by co-precipitating aluminum sulfate and titanium sulfate with sodium aluminate while using an amount of titanium sulfate sufficient to provide a final support comprising titania alumina.

### Claim 4 (depends on 1)

The process of claim 1 wherein the support is calcined at a temperature from about 650° C. to about 870° C.

### Claim 5 (depends on 1)

A catalyst support prepared by the process according to claim 1.

### Claim 6

A catalyst support comprising a co-precipitated titania alumina having 5 wt % or less titania based on the total weight of the titania alumina, said support having a total pore volume in the range of from about 0.5 to about 1.0 cubic centimeters per gram, at least 70% of the total pore volume in pores having a diameter between about 70 Å and about 130 Å, less than 5% of the total pore volume have pores in a diameter above 300 Å, as determined by nitrogen porosimetry, and less than 2% of the total pore volume in pores having a diameter above 1000 Å, as determined by mercury penetration porosimetry.

### Claim 7 (depends on 6)

The support of claim 6 wherein the amount of titania present in the titania alumina is an amount less than 5 wt %, based on the total weight of the titania alumina.

### Claim 8 (depends on 7)

The support of claim 7 wherein the amount of titania present in the titania alumina is an amount from about 0.3 to about 4.5 wt % titania, based on the total weight of the titania alumina.

### Claim 9 (depends on 6)

The support of claim 6 wherein the support comprises at least 90 wt % co-precipitated titania alumina.

### Claim 10 (depends on 6)

The support of claim 6 wherein: (a) at least 79% of the total pore volume is in pores having a diameter between about 70 Å and about 130 Å; or (b) from about 0.40% to about 1.5% of the total pore volume is in pores having a diameter above 1000 Å; or both (a) and (b).

### Claim 11

(canceled)

### Claim 12

(canceled)

### Claim 13 (depends on 1)

A method for preparing a catalyst for hydrodesulfurization of residuum hydrocarbon feedstocks which method comprises: impregnating a porous extruded support with an aqueous solution comprising at least one catalytic agent or catalytic agent precursor selected from the group consisting of a compound of Group 6 metals of The Periodic Table, Group 9 metals of the Periodic Table, Group 10 metals of The Periodic Table, and combinations thereof, and optionally phosphorous, said compounds being thermally decomposable to their corresponding metal oxides, and thereafter drying and calcining the resulting impregnated support to provide a supported catalyst, said support having been prepared by the process of claim 1.

### Claim 14 (depends on 13)

A catalyst produced by the method according to claim 13.

### Claim 15

A catalyst suitable for use in hydrodesulfurization of residuum hydrocarbon feedstocks comprising:
(a) a support comprising a co-precipitated titania alumina having 5 wt % or less titania based on the total weight of the titania alumina; and
(b) at least one catalytic agent comprising a metal selected from the group consisting of a Group 6 metal of The Periodic Table, a Group 9 metal of The Periodic Table, a Group 10 metal of The Periodic Table, and combinations thereof, and optionally phosphorous;
wherein the support is characterized as having:
(i) a total pore volume of from about 0.5 to about 1.0 cubic centimeters per gram;
(ii) at least 70% of the total pore volume in pores having a diameter between about 70 Å and about 130 Å;
(iii) less than 5% of the total pore volume in pores having a diameter above 300 Å, as determined by nitrogen porosimetry; and
(iv) less than 2% of the total pore volume in pores having a diameter above 1000 Å, as determined by mercury penetration porosimetry.

### Claim 16 (depends on 15)

The catalyst of claim 15 wherein the calcined support comprises at least 90 wt % of the co-precipitated titania alumina.

### Claim 17 (depends on 15)

The catalyst of claim 15 wherein the amount of titania present in the co-precipitated titania alumina is an amount less than 5 wt %, based on the total weight of the titania alumina.

### Claim 18 (depends on 17)

The catalyst of claim 17 wherein the amount of titania present in the co-precipitated titania alumina is an amount from about 0.3 to about 4.5 wt % titania, based on the total weight of the titania alumina.

### Claim 19 (depends on 15)

The catalyst of claim 15 wherein: (a) at least 79% of the total pore volume of the support is in pores having a diameter between about 70 Å and about 130 Å; or (b) from about 0.40% to about 1.5% of the total pore volume is in pores having a diameter above 1000 Å; or both (a) and (b).

### Claim 20

(canceled)

### Claim 21 (depends on 15)

The catalyst of claim 15 wherein said at least one catalytic agent comprises a metal selected from the group consisting of cobalt, nickel, molybdenum, and combinations thereof, and optionally phosphorous.

### Claim 22

(canceled)

### Claim 23 (depends on 15)

A process for hydrotreating residuum hydrocarbon feedstocks comprising at least one of sulfur or microcarbon residue (MCR), which process comprises contacting said residuum feedstocks with a catalyst of claim 15 under hydrodesulfurization process conditions and producing a hydrotreated residuum hydrocarbon fraction having a reduced sulfur content or a reduced MCR content or both a reduced sulfur and a reduced MCR content compared to the residuum hydrocarbon feedstock.

### Claim 24 (depends on 23)

The process of claim 23 wherein the residuum hydrocarbon feedstock is contacted with the catalyst at a reaction temperature from about 300° C. to about 450° C., a hydrogen pressure of about 120 bar to about 200 bar, a H2:oil ratio ranging from about 250 Nl/l to about 1400 N1/1, and a space velocity from about 0.2 hr−1 to about 2.0 hr−1.

### Claim 25

(canceled)

### Claim 26

(canceled)

### Claim 27

(canceled)