# US 2014/0190871 A1 · Hydrocarbon oil desulfurization adsorbing agent, production and use thereof

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- Number: US 2014/0190871 A1
- Document ID: US20140190871A1
- Status: Published application
- Kind: A1
- Application number: 14/235,037
- Filed: 2012-07-27
- Published: 2014-07-10
- Earliest claimed: 2011-07-28
- Assignees: Research Institute of Petroleum Processing, Sinopec; China Petroleum & Chemical Corporation
- Inventors: Wei Lin; Huiping Tian; Zhenbo Wang
- Web page: https://patentgrep.com/patent/US20140190871A1

## CPC

- B01J 20/18: Synthetic zeolitic molecular sieves
- B01J 20/0222: {Compounds of Mn, Re}
- B01J 20/0225: {Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt}
- B01J 20/06: comprising oxides or hydroxides of metals not provided for in group B01J20/04
- B01J 20/103: {comprising silica}
- B01J 20/2803: {Sorbents comprising a binder, e.g. for forming aggregated, agglomerated or granulated products}
- B01J 20/3007: {Moulding, shaping or extruding}
- B01J 20/3042: {Use of binding agents; addition of materials ameliorating the mechanical properties of the produced sorbent}
- B01J 20/3078: {Thermal treatment, e.g. calcining or pyrolizing}
- B01J 20/3085: {Chemical treatments not covered by groups B01J20/3007 - B01J20/3078}
- B01J 20/3204: {Inorganic carriers, supports or substrates}
- B01J 20/3236: {containing metal, other than zeolites, e.g. oxides, hydroxides, sulphides or salts}
- B01J 29/061: {containing metallic elements added to the zeolite}
- B01J 29/072: Iron group metals or copper
- C10G 25/05: Removal of non-hydrocarbon compounds, e.g. sulfur compounds
- C10G 45/12: containing crystalline alumino-silicates, e.g. molecular sieves
- C10G 2300/202: Heteroatoms content, i.e. S, N, O, P
- 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

This disclosure provides an adsorbing agent which, on the basis of the total weight of the adsorbing agent, comprises the following components: 1) a Si—Al molecular sieve having a BEA structure, in an amount of 1-20 wt %, 2) at least one binder selected from the group consisting of titanium dioxide, stannic oxide, zirconium oxide and alumina, in an amount of 3-35 wt %, 3) a silica source, in an amount of 5-40 wt %, 4) zinc oxide, in an amount of 10-80 wt %, and 5) at least one promoter metal selected from the group consisting of cobalt, nickel, iron and manganese, based on the metal, in an amount of 5-30 wt %, wherein at least 10 wt % of the promoter metal is present in a reduced valence state. The adsorbing agent exhibits improved activity and stability, and at the same time, is capable of significantly improving the octane number of the product gasoline.

## Claims

### Claim 1

A desulfurization adsorbing agent for hydrocarbon oil, on the basis of the total weight of the adsorbing agent, comprising the following components,
1) a Si—Al molecular sieve having a BEA structure, in an amount of 1-20 wt %,
2) at least one binder selected from the group consisting of titanium dioxide, stannic oxide, zirconium oxide and alumina, in an amount of 3-35 wt %,
3) a silica source, in an amount of 5-40 wt %,
4) zinc oxide, in an amount of 10-80 wt %, and
5) at least one promoter metal selected from the group consisting of cobalt, nickel, iron and manganese, based on the metal, in an amount of 5-30 wt %, wherein at least 10 wt % of the promoter metal is present in a reduced valence state.

### Claim 2 (depends on 1)

The adsorbing agent according to claim 1, wherein the Si—Al molecular sieve having a BEA structure is in an amount of 2-15 wt %, the binder is in an amount of 5-25 wt %, the silica source is in an amount of 10-30 wt %, the zinc oxide is in an amount of 25-70 wt %, the promoter metal is in an amount of 8-25 wt %.

### Claim 3 (depends on 1)

The adsorbing agent according to claim 1, wherein the Si—Al molecular sieve having a BEA structure is in an amount of 2-10 wt %, the binder is in an amount of 8-15 wt %, the silica source is in an amount of 12-25 wt %, the zinc oxide is in an amount of 40-60 wt %, the promoter metal is in an amount of 12-20 wt %.

### Claim 4 (depends on 1)

The adsorbing agent according to claim 1, wherein the silica source is selected from the group consisting of silica or a natural mineral having a silica content of more than 45 wt %.

### Claim 5 (depends on 1)

The adsorbing agent according to claim 1, wherein the Si—Al molecular sieve having a BEA structure is a Beta-molecular sieve.

### Claim 6 (depends on 1)

A process for producing the desulfurization adsorbing agent for hydrocarbon oil according to claim 1, comprising the steps of:
(1) contacting at least one binder selected from the group consisting of titanium dioxide, stannic oxide, zirconium oxide and alumina with a silica source, a Si—Al molecular sieve having a BEA structure and zinc oxide, to obtain a carrier,
(2) contacting the carrier with a promoter metal-containing compound, to obtain a precursor of the adsorbing agent, and
(3) under a condition sufficient to present at least 10 wt % of the promoter metal in a reduced valence state, treating the precursor of the adsorbing agent, to obtain the desulfurization adsorbing agent for hydrocarbon oil.

### Claim 7 (depends on 6)

The process according to claim 6, wherein the step (1) further comprises the following steps,
(1a) mixing the binder or a binder precursor with an acid to form a slurry, and
(1b) mixing the slurry, the silica source, the Si—Al molecular sieve having a BEA structure and zinc oxide to form a mixture and subject the mixture to molding, drying, and calcination to obtain the carrier.

### Claim 8 (depends on 6)

The process according to claim 6, wherein the step (1) further comprises the following steps,
(1a′) mixing at least a part of the silica source and the binder or a binder precursor with an acid to form a slurry, and
(1b′) mixing the slurry, the rest part of the silica source, the Si—Al molecular sieve having a BEA structure and zinc oxide to form a mixture and subject the mixture to molding, drying, and calcination to obtain the carrier.

### Claim 9 (depends on 7)

The process according to claim 7, wherein the binder precursor is at least one selected from the group consisting of halides, alkoxylates, carboxylic acid salts, hydrated oxides, hydroxides, hydrated hydroxides and oxyhalides, of titanium, tin, zirconium and/or aluminum.

### Claim 10 (depends on 7)

The process according to claim 7, wherein the acid is at least one selected from the group consisting of a water soluble inorganic acid and a water soluble organic acid, and the amount of the acid to be used is such that the pH value of the slurry reaches 0.5-6.

### Claim 11 (depends on 1)

A hydrocarbon oil desulfurization process, comprising the step of obtaining the desulfurization adsorbing agent for hydrocarbon oil according to claim 1; and contacting a sulfur-containing hydrocarbon oil with the desulfurization adsorbing agent under a condition sufficient to remove at least a part of sulfur from the sulfur-containing hydrocarbon oil.

### Claim 12 (depends on 11)

The hydrocarbon oil desulfurization process according to claim 11, wherein the Si—Al molecular sieve having a BEA structure is in an amount of 2-15 wt %, the binder is in an amount of 5-25 wt %, the silica source is in an amount of 10-30 wt %, the zinc oxide is in an amount of 25-70 wt %, the promoter metal is in an amount of 8-25 wt %.

### Claim 13 (depends on 11)

The hydrocarbon oil desulfurization process according to claim 11, wherein the Si—Al molecular sieve having a BEA structure is in an amount of 2-10 wt %, the binder is in an amount of 8-15 wt %, the silica source is in an amount of 12-25 wt %, the zinc oxide is in an amount of 40-60 wt %, the promoter metal is in an amount of 12-20 wt %.

### Claim 14 (depends on 11)

The hydrocarbon oil desulfurization process according to claim 11, wherein the silica source is selected from the group consisting of silica or a natural mineral having a silica content of more than 45 wt %.

### Claim 15 (depends on 11)

The hydrocarbon oil desulfurization process according to claim 11, wherein the Si—Al molecular sieve having a BEA structure is a Beta-molecular sieve.

### Claim 16 (depends on 8)

The process according to claim 8, wherein the binder precursor is at least one selected from the group consisting of halides, alkoxylates, carboxylic acid salts, hydrated oxides, hydroxides, hydrated hydroxides and oxyhalides, of titanium, tin, zirconium and/or aluminum.

### Claim 17 (depends on 8)

The process according to claim 8, wherein the acid is at least one selected from the group consisting of a water soluble inorganic acid and a water soluble organic acid, and the amount of the acid to be used is such that the pH value of the slurry reaches 0.5-6.