# US 10,369,558 B2 · High activity hydrotreating catalysts

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- Number: US 10,369,558 B2
- Document ID: US10369558B2
- Status: Granted
- Kind: B2
- Application number: 14/261,346
- Filed: 2014-04-24
- Published: 2015-10-29
- Granted: 2019-08-06
- Earliest claimed: 2014-04-24
- Assignees: Advanced Refining Technologies LLC
- Applicants: Advanced Refining Technologies LLC
- Inventors: Xianghua Yu; Shuguang Zhang; Gill M. Malick; Bruno Nesci; Henry Saternus; Jifei Jia; Cecelia A. Radlowski; Theodorus Ludovicus Michael Maesen; Colleen T. Miedona
- Web page: https://patentgrep.com/patent/US10369558B2

## CPC

- B01J 31/28: of the platinum group metals, iron group metals or copper
- B01J 23/883: and nickel
- B01J 31/0209: {Esters of carboxylic or carbonic acids}
- B01J 35/615: {100-500 m2/g}
- B01J 35/635: {0.5-1.0 ml/g}
- B01J 37/0203: {the impregnation liquid containing organic compounds}
- B01J 37/20: Sulfiding
- B01J 37/28: Phosphorising
- B01J 21/12: Silica and alumina
- B01J 31/04: containing carboxylic acids or their salts {(B01J31/0277 - B01J31/0298 take precedence; multi-metal carboxylate complexes like Pd (II) acetate, i.e. Pd3 (OAc) 6 or Cr(II)acetate, i.e. Cr2(OAc)4 B01J31/2226)}
- B01J 2231/005: General concepts, e.g. reviews, relating to methods of using catalyst systems, the concept being defined by a common method or theory, e.g. microwave heating or multiple stereoselectivity
- B01J 2231/645: of C=C or C-C triple bonds
- B01J 2531/002: Materials
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS

## Abstract

This disclosure relates to supported multi-metallic catalysts for use in the hydrotreating of hydrocarbon feeds, as well as a method for preparing such catalysts. The catalysts are prepared from a catalyst precursor comprised of at least one Group VIB metal, at least one Group VIII metal and an organic acid. The catalyst precursor is thermally treated to partially decompose the organic acid, then sulfided. The catalysts have a high carbon-as-carboxyl to total carbon ratio (Ccarboxy/Ctotal) as a result of a unique post-metal calcination method employed during the manufacture of the catalyst. As a result, the hydrotreating catalysts have lower percent weight loss-on-ignition, higher activity and longer catalyst life.

## Claims

### Claim 1

A catalyst precursor composition comprising:
(a) catalytically active metal-organic complex deposited in or on an inorganic catalyst support, the support comprising a porous inorganic refractory selected from the group consisting of silica, alumina, alumina-silica, and crystalline silica-alumina, said metal-organic component partially oxidized for a time of from 1 minute to 1 hour at a temperature of 350° C. to 500° C.;
wherein (a) exhibits:
(i) a loss-on-ignition of greater than 1 wt. % and up to 10 wt. %; and
(ii) a carbon-as-carboxy to total residual carbon ratio (Ccarboxy/Ctotal) of from 0.10 to 0.19 as determined by X-ray photoelectron spectroscopy;
wherein the loss-on-ignition is determined using a test conducted by heating a sample of the partially oxidized catalyst precursor in an oxygen-containing atmosphere for 1 hour @ 1020° F. (549° C.) and measuring weight loss after such heating; and
wherein the metal portion of the partially oxidized metal organic component comprises at least one Group VIB metal and at least one Group VIII metal and wherein the organic portion of the metal-organic component, prior to partial oxidation, is a hydroxycarboxylic acid selected from the group consisting of glycolic acid, lactic acid, glyceric acid, gluconic acid, malic acid, tartaric acid, mucic acid, and citric acid.

### Claim 2 (depends on 1)

The catalyst precursor composition of claim 1, further comprising a phosphorus component.

### Claim 3 (depends on 2)

The catalyst precursor composition of claim 2, wherein the phosphorus component is present in an amount of from 1 to 10 wt. %, based on the bulk dry weight of the catalyst, calculated as P2O5.

### Claim 4 (depends on 1)

The catalyst precursor composition of claim 1, wherein the inorganic catalyst support is selected from the group consisting of alumina, silica, and alumina-silica.

### Claim 5 (depends on 1)

The catalyst precursor composition of claim 1, wherein the at least one Group VIB metal is Mo and the at least one Group VIII metal is Ni.

### Claim 6 (depends on 1)

The catalyst precursor composition of claim 1, having a loss-on-ignition of greater than 1 wt. % and up to 8 wt. %.