Production of liquids and reduced sulfur gaseous products from sour natural gas

Patent metadata

Field	Value
Publication number	US-10759722-B2
Application number	US-201815867902-A
Country	US
Kind code	B2
Filing date	Jan 11, 2018
Priority date	Jan 11, 2018
Publication date	Sep 1, 2020
Grant date	Sep 1, 2020

Abstract

Aspects of the invention are associated with the discovery of approaches for the conversion of sour natural gas streams, by conversion to liquid hydrocarbons. Particular processes and their associated apparatuses advantageously combine (i) dehydroaromatization (DHA) of methane in a gaseous feedstock, to produce aromatic hydrocarbons such as benzene, with (ii) the reaction of H2S and methane in this feedstock, to produce organic sulfur compounds such as carbon disulfide (CS2) and thiophene (C4H4S). A gaseous product having a reduced concentration of H2S is thereby generated. The aromatic hydrocarbons and organic sulfur compounds may be recovered in a liquid product. Both the gaseous and liquid products may be easily amenable to further upgrading. Other advantages of the disclosed processes and apparatuses reside in their simplicity, whereby the associated streams, including a potential gaseous recycle, generally avoid high partial pressures of H2S.

First claim

The invention claimed is:

1. A methane dehydroaromatization (DHA) process comprising:
contacting a feedstock comprising methane and H 2 S with a DHA catalyst comprising MoS 2 or sulfided CoMo to produce a DHA effluent,
recovering from the DHA effluent a liquid product comprising one or more aromatic hydrocarbons and one or more organic sulfur compounds including CS 2 , and
hydroprocessing the liquid product to convert at least a portion of the CS 2 to H 2 S,
wherein the methane is present in the feedstock at a concentration of at least about 50 vol-%,
wherein the H 2 S is present in the feedstock at a concentration from 1 vol-% to about 25 vol-%, and
wherein the contacting is carried out under DHA conditions including a temperature from about 900° C. to about 1000° C., an absolute pressure from about 30 kPa to about 2.1 MPa, and a weight hourly space velocity from about 0.05 to about 5 hr −1 .

2. The process of claim 1 , wherein the one or more aromatic hydrocarbons include benzene and the one or more organic sulfur compounds further include thiophene.

3. The process of claim 1 , wherein the feedstock comprises sour natural gas.

4. The process of claim 3 , wherein the feedstock further comprises a methane-containing gaseous recycle.

5. The process of claim 1 , wherein a methane-containing gaseous product is recovered from the DHA effluent.

6. The process of claim 5 , wherein the DHA catalyst is contained in a DHA reactor, the process further comprising:
withdrawing the DHA effluent from the DHA reactor and feeding at least a portion of the DHA effluent to a separator to produce the liquid product and the methane-containing gaseous product.

7. The process of claim 5 , further comprising separating H 2 S from the methane-containing gaseous product to provide an H 2 S-depleted methane product.

8. The process of claim 5 , wherein the DHA catalyst is contained in a DHA reactor, the process further comprising:
withdrawing the DHA effluent from the DHA reactor and feeding at least a portion of the DHA effluent to an ethylene oligomerization (EO) reactor containing an EO catalyst,
withdrawing an EO effluent from the EO reactor, and
feeding at least a portion of the EO effluent to a separator to produce the liquid product and the methane-containing gaseous product.

9. The process of claim 1 , wherein a single pass yield of CS 2 in the DHA reaction stage is from about 1% to about 15%.

10. The process of claim 1 , wherein the DHA catalyst comprises greater than about 30 wt-% MoS 2 .

11. A process for sweetening of a feedstock comprising methane and H 2 S, the process comprising:
in a dehydroaromatization (DHA) reaction stage, contacting at least a portion of the feedstock with a DHA catalyst to provide a DHA effluent,
in a separation stage, separating at least a portion of the DHA effluent to provide
(i) a liquid product comprising one or more aromatic hydrocarbons and one or more organic sulfur compounds including CS 2 , and
(ii) a methane-containing gaseous product,

in a gas purification stage, separating H 2 S from the methane-containing gaseous product to provide
(iii) a sweetened methane product and
(iv) a methane-containing gaseous recycle comprising said H 2 S

recycling at least a portion of said methane-containing gaseous recycle to said DHA reaction stage, and
hydroprocessing the liquid product to convert at least a portion of the CS 2 to H 2 S,
wherein the DHA reaction stage is carried out at an absolute pressure from about 100 kPa to about 300 kPa, and
wherein H 2 S is present in the feedstock at a concentration from 1 vol-% to about 25 vol-%.

12. The process of claim 11 , wherein the overall H 2 S conversion in the process is from about 50% to about 99%.

13. A process for sweetening of a feedstock comprising methane and H 2 S, the process comprising:
in a dehydroaromatization (DHA) reaction stage, contacting at least a portion of the feedstock with a DHA catalyst to provide a DHA effluent;
in a separation stage, separating at least a portion of the DHA effluent to provide
(i) a liquid product comprising one or more aromatic hydrocarbons and one or more organic sulfur compounds including CS 2 , and
(ii) a sweetened methane-containing gaseous product, and

Hydroprocessing the liquid product to convert at least a portion of the CS 2 to H 2 S,
wherein the DHA reaction stage is carried out at an absolute pressure from about 100 kPa to about 300 kPa, and
wherein the H 2 S is present in the feedstock at a concentration from 1 vol-% to about 25 vol-%.

14. A methane dehydroaromatization (DHA) process comprising:
contacting a feedstock comprising methane and H 2 S with a DHA catalyst to produce a DHA effluent,
recovering from the DHA effluent a liquid product comprising one or more aromatic hydrocarbons and one or more organic sulfur compounds including CS 2 , and
hydroprocessing the liquid product to convert at least a portion of the CS 2 to H 2 S,
wherein the methane is present in the feedstock at a concentration of at least about 50 vol-% and the H 2 S is present in the feedstock at a concentration from 1 vol-% to about 25 vol-%.

15. The process of claim 14 , further comprising blending the liquid product with a refinery hydrodesulfurization feedstock before hydroprocessing.

16. The process of claim 14 , wherein the one or more aromatic hydrocarbons include benzene and the one or more organic sulfur compounds further include thiophene.

17. The process of claim 14 , wherein a methane-containing gaseous product is recovered from the DHA effluent.

18. The process of claim 17 , wherein the DHA catalyst is contained in a DHA reactor, the process further comprising:
withdrawing the DHA effluent from the DHA reactor and feeding at least a portion of the DHA effluent to a separator to produce the liquid product and the methane-containing gaseous product.

19. The process of claim 17 , wherein the DHA catalyst is contained in a DHA reactor, the process further comprising:
withdrawing the DHA effluent from the DHA reactor and feeding at least a portion of the DHA effluent to an ethylene oligomerization (EO) reactor containing an EO catalyst,
withdrawing an EO effluent from the EO reactor, and
feeding at least a portion of the EO effluent to a separator to produce the liquid product and the methane-containing gaseous product.

Assignees

• Gas Technology Inst

Inventors

• Marker Terry
• Wangerow Jim
• Boysen Dane
• Linck Martin B
• Ortiz-Toral Pedro

Classifications

• C10L3/103

  Sulfur containing contaminants · CPC title

• C07C2/76 Primary

  by condensation of hydrocarbons with partial elimination of hydrogen · CPC title

• Y02P20/52

  using catalysts, e.g. selective catalysts · CPC title

• C10L2290/548

  Membrane- or permeation-treatment for separating fractions, components or impurities during preparation or upgrading of a fuel · CPC title

• C07C2523/882

  and cobalt · CPC title