# US 4,395,329 A · Catalyst and process for hydrorefining hydrocarbon charges with high contents of metals, resins and/or asphaltenes

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- Number: US 4,395,329 A
- Document ID: US4395329A
- Status: Granted
- Kind: A
- Application number: 06/279,637
- Filed: 1981-07-02
- Granted: 1983-07-26
- Earliest claimed: 1980-07-02
- Assignees: Societe Francaise des Produits pour Catalyse
- Inventors: Jean-Francois Le Page; Alain Billon; Yves Jacquin
- Web page: https://patentgrep.com/patent/US4395329A

## CPC

- B01J 37/0018: {Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)}
- B01J 23/85: Chromium, molybdenum or tungsten
- B01J 35/60: characterised by their surface properties or porosity
- 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}
- C10G 2300/107: Atmospheric residues having a boiling point of at least about 538 °C
- 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

Hydrorefining of a hydrocarbon charge of high metal content with a catalyst containing alumina, a metal from group VI and a metal from the iron group, of a specific surface from 120 to 200 m.sup.2 /g, a total pore volume from 0.8 to 1.2 cc/g and a pore distribution as follows: 0 to 10% of pores smaller than 100 A 35 to 60% of pores from 100 to 600 A 35 to 55% of pores greater than 600 A, including 10 to 25% of pores greater than 10,000 A, said catalyst optionally containing additionally an alkaline-earth metal.

## Claims

### Claim 1

A process for hydrodemetallizing a hydrocarbon charge of high metal content, comprising passing said charge, in the presence of hydrogen, in contact with a catalyst comprising (a) alumina, (b) at least one metal from group VI and (c) at least one metal from the iron group; wherein said catalyst has all of the following characteristics:
specific surface: 120 to 200 m.sup.2 /g
total pore volume (.sup.V.sub.T): 0.8 to 1.2 cc/g
% of .sup.V.sub.T in pores of a diameter lower than 100 A: 0-10
% of .sup.V.sub.T in pores of a diameter from 100 to 600 A: 35-60
% of .sup.V.sub.T in pores of a diameter greater than 600 A: 35-55
% of .sup.V.sub.T in pores of a diameter greater than 10,000 A: 10-25.

### Claim 2 (depends on 1)

A process according to claim 1, wherein the catalyst further comprises an alkaline-earth metal.

### Claim 3 (depends on 2)

A process according to claim 2, wherein the alkaline-earth metal is magnesium, whose proportion in the catalyst is from 1 to 10%, expressed as MgO.

### Claim 4 (depends on 3)

A process according to claim 3, wherein the catalyst further comprises 1 to 10% by weight of phosphorus, expressed as P.sub.2 O.sub.5.

### Claim 5 (depends on 1)

A process according to claim 1, wherein the catalyst comprises a total of from 5 to 30% by weight of molybdenum, tungsten, nickel and/or cobalt oxides, the atomic ratio: ##EQU2## being from 0.15 to 1.

### Claim 6 (depends on 1)

A process according to claim 1, wherein the catalyst has all of the following characteristics:
______________________________________ specific surface: 120 to 200 m.sup.2 /g total pore volume: 0.85 to 1.15 cc/g pore diameter distribution in % of the total volume: 0-100 A 0-8 0-200 A 20-55 0-300 A 35- 60 0-600 A 45-65 0-1,000 A 60-70 >600 A 35-55 >10,000 A 10-20 specific gravity: 0.4-0.6 g/cc. ______________________________________

### Claim 7 (depends on 1)

A process according to claim 1, wherein the catalyst is prepared by depositing at least one metal of group VI and at least one metal of the iron group on a roasted alumina carrier prepared by agglomeration of an alumina monohydrate with a pore-generating agent, said agglomeration being followed with a drying and roasting step under conditions promoting decomposition of the pore-generating agent.

### Claim 8 (depends on 7)

A process according to claim 7, wherein the roasted alumina carrier has the following characteristics:
______________________________________ specific surface: 120 to 200 m.sup.2 /g total pore volume (V.sub.T): 0.85 to 1.25 cc/g % of V.sub.T in pores of a diameter smaller than 100 A: 0-10 % of V.sub.T in pores of a diameter from 100 to 600 A: 35-60 % of V.sub.T in pores of a diameter greater than 600 A: 35-55 % of V.sub.T in pores of a diameter greater than 10,000 A: 10-25. ______________________________________

### Claim 9 (depends on 7)

A process according to claim 7, wherein the roasting of the agglomerate of alumina monohydrate with the pore-generating agent is effected in at least two stages, a first stage at 420.degree.-480.degree. C. for 1 to 20 hours, and a second stage at 500.degree.-600.degree. C. for 1 to 20 hours, said roasting being followed with a treatment in a saturated steam atmosphere at 150.degree.-300.degree. C. for 1 to 20 hours, and completed with a roasting at 550.degree.-750.degree. C. for 1 to 20 hours.

### Claim 10 (depends on 1)

A process according to claim 1, wherein the catalyst further exhibits the following pore diameter distribution in % of total pore volume:
______________________________________ 0-1000 A 60-70% 0-3000 A 67-80% 300-3000 A 20-45%. ______________________________________

### Claim 11 (depends on 1)

A process according to claim 1, wherein the catalyst is presulfided.

### Claim 12 (depends on 1)

A process according to claim 1, which is effected at a temperature of 365.degree.-450.degree. C., a pressure of 80-200 bars, a space velocity of 0.3-3 VVH, and a ratio of hydrogen to hydrocarbon of 200-5,000 m.sup.3 /m.sup.3.

### Claim 13

A process of preparing a catalyst suitable for use in hydrodemetallization of a hydrocarbon charge of high metal content, said process comprising the steps of:
(1) shaping, drying and roasting a moistened mixture of (a) alumina monohydrate and (b) an organic pore-generating agent capable of decomposing when roasted, the roasting being effected at a temperature sufficient to decompose the pore-generating agent, thereby producing an alumina carrier having a specific surface of 120-200 m.sup.2 /g, a total pore volume (.sup.V.sub.T) of 0.85-1.25 cc/g, and a pore diameter distribution, in % of .sup.V.sub.T of:
______________________________________ 0-100 A 0-10% 100-600 A 35-60% >600 A 35-55% >10,000 A 10-25%; and ______________________________________
(2) impregnating the carrier with (a) at least one group VIA metal compound and (b) at least one group VIII metal compound, and drying and roasting the impregnated carrier, thereby producing a catalyst having a specific surface of 120-200 m.sup.2 /g, a total pore volume of 0.8-1.2 cc/g, and substantially the same pore diameter distribution as the alumina carrier, and comprising 5-30% by weight, as oxides, of said group VIA and group VIII metals.

### Claim 14 (depends on 13)

The process of claim 13, wherein the amount of said pore-generating agent in said mixture, prior to moistening, is 1-15% by weight.

### Claim 15 (depends on 13)

The process of claim 13, wherein the shaped mixture is dried at about 100.degree. C. in an air stream, and roasted at 400.degree.-700.degree. C.

### Claim 16 (depends on 15)

The process of claim 15, wherein said roasting is effected in two stages, a first stage at 420.degree.-480.degree. C. in an air stream, said first stage being continued for 1-20 hours until the pore-generating agent has been decomposed, and a second stage at 500.degree.-600.degree. C. in an air stream for 1-20 hours.

### Claim 17 (depends on 16)

The process of claim 16, wherein the catalyst is further treated in a saturated steam atmosphere at 150.degree.-300.degree. C. for 1-20 hours, and then roasted at 550.degree.-750.degree. C.

### Claim 18 (depends on 13)

The process of claim 13, wherein the group VIA metal is molybdenum or tungsten, and the group VIII metal is cobalt or nickel, and the atomic ratio ##EQU3## is 0.15-1.

### Claim 19 (depends on 13)

The process of claim 13, wherein an amount of a magnesium compound is deposited by impregnation on said roasted alumina carrier sufficient to produce 1-10% by weight of MgO on the final catalyst, and the magnesium-impregnated carrier is roasted, prior to impregnation with the group VIA and group VIII metal compounds.

### Claim 20 (depends on 13)

The process of claim 13, wherein a phosphoric acid is added to the impregnation solution is an amount such that the final roasted catalyst has 1-10% by weight of phosphorus, expressed as P.sub.2 O.sub.5.

### Claim 21 (depends on 13)

A hydrodemetallization catalyst prepared by the process of claim 13.

### Claim 22

A hydrodemetallization catalyst, comprising (a) an alumina carrier, and (b) at least one pair of metals, being Co-Mo, Ni-Mo, Ni-W or Co-W, in a total amount of 5-30%, expressed as metal oxides, the atomic ratio ##EQU4## being 0.15-1; wherein said catalyst has a specific surface of 120-200 m.sup.2 /g, a total pore volume of 0.8-1.2 cc/g, and a pore diameter distribution, as a percentage of total pore volume of:
______________________________________ 0-100 A 0-10% 100-600 A 35-60% >600 A 35-55% >10,000 A 10-25%. ______________________________________

### Claim 23 (depends on 22)

A catalyst according to claim 22, which further comprises 1-10% by weight of magnesium, expressed as MgO.

### Claim 24 (depends on 23)

A catalyst according to claim 23, which further comprises 1-10% by weight of phosphorus, expressed as P.sub.2 O.sub.5.

### Claim 25 (depends on 22)

A catalyst according to claim 22, having a total pore volume of 0.85-1.115 cc/g, a specific gravity of 0.4-0.6 g/cc, and a pore diameter distribution as a percentage of total pore volume of:
______________________________________ 0-100 A 0-8 0-200 A 20-55 0-300 A 35-60 0-600 A 45-65 0-1,000 A 60-70 >600 A 35-55 >10,000 A 10-20. ______________________________________

### Claim 26 (depends on 22)

A catalyst according to claim 22, wherein said pore diameter distribution in percentage of total pore volume is:
______________________________________ 0-1000 A 60-70% 0-3000 A 67-80% 300-3000 A 20-45%. ______________________________________