Desulphurisation process

• US 8,702,974 B2
• Filed: 09/02/2010
• Issued: 04/22/2014
• Est. Priority Date: 09/15/2009
• Status: Active Grant

• Current Assignee: Johnson Matthey PLC
• Original Assignee: Johnson Matthey PLC
• Inventors: Wilson, Gordon Edward, Macleod, Norman, Vass, Elaine Margaret, Lara, Antonio Chica, Canos, Avelino Corma, Lopez, Yonhy Saavedra
• Primary Examiner(s): Griffin, Walter D
• Assistant Examiner(s): PEREZ, JELITZA M
• Application Number:
  US13/395,834
• Publication Number:
  US 20120232322A1
• Time in Patent Office: 1,328 Days
• Field of Search: 208/208.R, 208/209, 208212-214, 208/217, 208/237, 208/238, 208/244, 208/264, 208/299, 208/300, 208/303, 585/820, 585/823, 585/824, 585/833, 585/841, 585/868, 585/850
• US Class Current: 208/217
• CPC Class Codes: B01D 2253/112 Metals or metal compounds not provided for in B01D2253/104 or B01D2253/106
• CPC Class Codes: B01D 2255/20 Metals or compounds thereof noble metals B01D2255/10
• CPC Class Codes: B01D 2255/20753 Nickel
• CPC Class Codes: B01D 2257/304 Hydrogen sulfide
• CPC Class Codes: B01D 2257/306 Organic sulfur compounds, e.g. mercaptans
• CPC Class Codes: B01D 2257/308 Carbonoxysulfide COS
• CPC Class Codes: B01D 2258/06 Polluted air
• CPC Class Codes: B01D 2259/40 Further details for adsorption processes and devices
• CPC Class Codes: B01D 53/52 Hydrogen sulfide
• CPC Class Codes: B01D 53/75 Multi-step processes
• CPC Class Codes: B01D 53/8603 Removing sulfur compounds
• CPC Class Codes: B01J 20/06 comprising oxides or hydroxides of metals not provided for in group B01J20/04
• CPC Class Codes: B01J 20/28004 Sorbent size or size distribution, e.g. particle size
• CPC Class Codes: B01J 20/28019 Spherical, ellipsoidal or cylindrical
• CPC Class Codes: B01J 20/2803 Sorbents comprising a binder, e.g. for forming aggregated, agglomerated or granulated products
• CPC Class Codes: B01J 20/3007 Moulding, shaping or extruding
• CPC Class Codes: B01J 20/3028 Granulating, agglomerating or aggregating
• CPC Class Codes: B01J 20/3042 Use of binding agents; addition of materials ameliorating the mechanical properties of the produced sorbent
• CPC Class Codes: B01J 20/3078 Thermal treatment, e.g. calcining or pyrolizing
• CPC Class Codes: B01J 20/3204 Inorganic carriers, supports or substrates
• CPC Class Codes: B01J 20/3236 : containing metal, other than zeolites, e.g. oxides, hydroxides, sulphides or salts
• CPC Class Codes: C01B 2203/0233 : the reforming step being a steam reforming step
• CPC Class Codes: C01B 2203/0244 : the reforming step being an autothermal reforming step, e.g. secondary reforming processes
• CPC Class Codes: C01B 2203/0811 : by combustion of fuel
• CPC Class Codes: C01B 2203/0827 : at least part of the fuel being a recycle stream
• CPC Class Codes: C01B 2203/1058 : Nickel catalysts
• CPC Class Codes: C01B 2203/1235 : Hydrocarbons
• CPC Class Codes: C01B 2203/1241 : Natural gas or methane
• CPC Class Codes: C01B 2203/1247 : Higher hydrocarbons
• CPC Class Codes: C01B 2203/127 : Catalytic desulfurisation
• CPC Class Codes: C01B 2203/148 : involving a recycle stream to the feed of the process for making hydrogen or synthesis gas
• CPC Class Codes: C01B 3/38 : using catalysts
• CPC Class Codes: C01B 3/382 : Multi-step processes
• CPC Class Codes: C10G 2300/1025 : Natural gas
• CPC Class Codes: C10G 2300/1044 : Heavy gasoline or naphtha having a boiling range of about 100 - 180 °C
• CPC Class Codes: C10G 2300/1051 : Kerosene having a boiling range of about 180 - 230 °C
• CPC Class Codes: C10G 2300/1059 : Gasoil having a boiling range of about 330 - 427 °C
• CPC Class Codes: C10G 2300/1081 : Alkanes
• CPC Class Codes: C10G 2300/202 : Heteroatoms content, i.e. S, N, O, P
• CPC Class Codes: C10G 2300/207 : Acid gases, e.g. H2S, COS, SO2, HCN
• CPC Class Codes: C10G 2300/705 : Passivation
• CPC Class Codes: C10G 45/08 : in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
• CPC Class Codes: C10L 3/10 : Working-up natural gas or synthetic natural gas
• CPC Class Codes: C10L 3/102 : of acid contaminants

Abstract

A process for desulphurizing hydrocarbons includes passing a mixture of hydrocarbon and hydrogen over a hydrodesulphurization catalyst to convert organosulphur compounds present in the hydrocarbon to hydrogen sulphide, passing the resulting mixture over a hydrogen sulphide sorbent including zinc oxide to reduce the hydrogen sulphide content of the mixture, and passing the hydrogen sulphide-depleted mixture over a further desulphurization material. The further desulphurization material includes one or more nickel compounds, a zinc oxide support material, and optionally one or more promoter metal compounds of iron, cobalt, copper and precious metals. The desulphurization material has a nickel content in the range 0.3 to 20% by weight and a promoter metal compound content in the range 0 to 10% by weight.

Claims

1. A process for desulphurising hydrocarbons comprising the steps of;

(i) passing a mixture of hydrocarbon and hydrogen over a hydrodesulphurisation catalyst to convert organosulphur compounds present in said hydrocarbon to hydrogen sulphide,

(ii) passing the resulting mixture over a hydrogen sulphide sorbent comprising zinc oxide to reduce the hydrogen sulphide content of the mixture, and

(iii) passing the hydrogen sulphide-depleted gas mixture over a further desulphurisation material,

wherein the further desulphurisation material comprises a shaped mixture of one or more particulate nickel compounds and a particulate zinc oxide support material, said desulphurisation material having a nickel content in the range 0.3 to 20% by weight, and

wherein the particulate nickel compounds are neither impregnated on nor in the form of a co-precipitate with the particulate zinc oxide support material.

2. A process according to claim 1 wherein the hydrocarbon is selected from the group consisting of natural gas, refinery off-gas, associated gas, natural gas condensates, ethane, propane, butane, liquefied petroleum gas, light naphtha, heavy naphtha, kerosene, gas oil, coke oven gas, and town (coal) gas.

3. A process according to claim 1 wherein the hydrogen content of the hydrocarbon/hydrogen mixture is in the range 1 to 30% by volume.

4. A process according to claim 1 wherein the hydrodesulphurisation catalyst is selected from the group consisting of a Ni—

Mo, Co—

Mo, Ni—

W and Co—

W catalyst.

5. A process according to claim 1 wherein the hydrogen sulphide-depleted gas mixture is passed over the further desulphurisation material at a temperature in the range 200-400°

C.

6. A process according to claim 1 wherein the further desulphurisation material comprises a promoter metal compound such that the promoter metal content of the desulphurisation material is in the range 0.3 to 10% by weight.

7. A process according to claim 1 wherein the nickel compound is selected from the group consisting of nickel oxide, nickel hydroxide, and nickel hydroxycarbonate.

8. A process according to claim 1 wherein the further desulphurisation material comprises one or more promoter metal compounds selected from compounds of copper.

9. A process according to claim 8 wherein the copper compound is selected from the group consisting of copper oxide, copper hydroxide, and copper hydroxycarbonate.

10. A process according to claim 1 wherein the zinc oxide support material is selected from the group consisting of zinc oxide and a zinc oxide/alumina mixture.

11. A process according to claim 1 wherein the further desulphurisation material further comprises an alkaline metal compound selected from the group consisting of an oxide, carbonate or hydrogen carbonate of sodium, potassium, caesium, magnesium, calcium and barium.

12. A process according to claim 1 wherein the desulphurisation material comprises 0.3 to 10% by weight nickel, 0 to 10% by weight copper, 0 to 15% by weight alumina, 0 to 10% by weight alkaline metal compound, 55 to 98% by weight ZnO and 0.5 to 10% wt binder material.

13. A process according to claim 1 wherein the further desulphurisation material comprises a shaped mixture of one or more particulate nickel compounds, a particulate zinc oxide support material, and optionally one or more particulate promoter metal compounds.

14. A process according to claim 1 wherein the desulphurisation material is provided in oxidic form and the nickel compound is reduced to elemental form by reaction with the hydrogen-containing gaseous mixture in-situ.

15. A process according to claim 1 wherein the desulphurisation material has been pre-reduced by treatment with a reducing gas and the reduced metal surfaces passivated with an oxygen-containing gas.

16. A process for reforming a hydrocarbon feed comprising the steps of subjecting a mixture of hydrocarbon and hydrogen to a desulphurisation process according to claim 1 to reduce the sulphur content to <

5 ppb volume, and then passing a mixture of the desulphurised hydrocarbon and steam over a steam reforming catalyst at elevated temperature and pressure to form a reformed gas stream comprising hydrogen and carbon oxides.

17. A reforming process according to claim 16 wherein a portion of the reformed gas stream comprising hydrogen is used as the source of hydrogen for the hydrodesulphurisation step.

18. A process according to claim 1 wherein the further desulphurisation material comprises one or more promoter metal compounds selected from compounds of iron, cobalt, copper and precious metals.

19. A process according to claim 18 wherein a promoter metal content is 10% by weight or less.

20. A process according to claim 1 wherein the zinc oxide support material is prepared from a zinc-alumina hydrotalcite.

21. A process according to claim 1 wherein the further desulphurisation material is prepared by (i) mixing a powdered nickel compound with a particulate zinc oxide support material, a binder material and optionally a powdered promoter metal compound, and/or an alkaline metal compound, in the presence of water to form a wet composition, (ii) shaping the wet composition, and, (iii) drying and calcining the shaped wet composition.