Adsorption desulfurization process for hydrocarbons and a reaction apparatus therefor
US-9512052-B2 · Dec 6, 2016 · US
US10689583B2 · US · B2
| Field | Value |
|---|---|
| Publication number | US-10689583-B2 |
| Application number | US-201815990500-A |
| Country | US |
| Kind code | B2 |
| Filing date | May 25, 2018 |
| Priority date | Sep 16, 2015 |
| Publication date | Jun 23, 2020 |
| Grant date | Jun 23, 2020 |
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A process is presented for the removal of contaminants like sulfur compounds from hydrocarbons. The sulfur compounds are removed from hydrocarbons that may be a feed to cracking units. A feed stream is treated with a clinoptilolite or a barium exchanged zeolite adsorbent to effectively remove carbon disulfides from the feed hydrocarbon. The adsorbent may be regenerated by a hydrogen stream, a hydrocarbon stream or a mixture thereof.
Opening claim text (preview).
The invention claimed is: 1. A process for removing CS 2 from hydrocarbon streams comprising contacting a hydrocarbon stream with a clinoptilolite adsorbent or a barium exchanged chabazite containing zeolite adsorbent and adsorbing CS 2 using size selective adsorption to produce a hydrocarbon stream having a reduced CS 2 content, and regenerating the clinoptilolite adsorbent or barium exchanged chabazite containing zeolite adsorbent with a regenerant stream comprising a hydrotreated hydrocarbon stream forming a regeneration effluent. 2. The process of claim 1 wherein the hydrocarbon stream comprises naphtha boiling range hydrocarbons and wherein size selective adsorption capacity of the adsorbent for CS 2 is not impacted by the presence of the naphtha boiling range hydrocarbons. 3. The process of claim 1 wherein the hydrocarbon stream comprises additional organic sulfur compounds and wherein size selective adsorption capacity of the adsorbent for CS 2 is not impacted by the presence of the additional organic sulfur compounds. 4. The process of claim 3 wherein the additional organic sulfur compounds comprise mercaptans, sulfides, or disulfides. 5. The process of claim 1 wherein the hydrocarbon stream comprises straight run naphtha from crude oil or natural gas condensate sources; or cracked hydrocarbons; or cracked hydrocarbons from an ethylene cracking unit; or at least one of C4 olefins, C4 dienes, C5 olefins, C5 dienes, or any combination thereof; or at least one of acetylenes, dienes, olefins, or any combination thereof. 6. The process of claim 1 wherein the clinoptilolite adsorbent or barium exchanged chabazite containing zeolite adsorbent has exchangeable cations selected from ions of Group 1A, Group 2A, Group 3A, Group 3B, the lanthanide series and mixtures of these. 7. The process of claim 1 wherein the clinoptilolite adsorbent or barium exchanged chabazite containing zeolite adsorbent is selected from natural clinoptilolite, synthetic clinoptilolite, sodium-exchanged clinoptilolite, potassium-exchanged clinoptilolite, lithium-exchanged clinoptilolite, calcium-exchanged clinoptilolite, magnesium-exchanged clinoptilolite, barium-exchanged clinoptilolite, and mixtures thereof. 8. The process of claim 1 wherein the clinoptilolite adsorbent or barium exchanged chabazite containing zeolite adsorbent is sodium-exchanged clinoptilolite or barium-exchanged clinoptilolite. 9. The process of claim 1 further comprising contacting the hydrocarbon stream having a reduced CS 2 content with a zeolite adsorbent or a promoted alumina adsorbent to remove at least one impurity selected from the group consisting of oxygenates and other sulfur compounds. 10. The process of claim 1 wherein the clinoptilolite adsorbent or barium exchanged chabazite containing zeolite adsorbent is used in a temperature swing adsorption system where an adsorption temperature is between 60° and 150° F. and a regeneration temperature is between 300° and 550° F. 11. The process of claim 1 wherein the regenerant stream is a hydrotreated naphtha stream available at a temperature of 15.5° to 287.8° C. (60° to 550° F.). 12. The process of claim 11 wherein the regenerant stream is at a temperature from about 148.9° to 287.8° C. (300° to 550° F.). 13. The process of claim 1 wherein the regenerant stream is a light hydrotreated naphtha from a naphtha splitter overhead at a temperature of 15.5° to 287.8° C. (60° to 550° F.) or 93.3° to 204.4° C. (200° to 400° F.). 14. The process of claim 1 wherein the regeneration effluent is directed to a hydrotreater at a temperature of 15.5° to 287.8° C. (60° to 550° F.). 15. The process of claim 14 wherein the regeneration effluent is at a temperature of 148.9° to 287.8° C. (300° to 550° F.). 16. A process for removing CS 2 from hydrocarbon streams comprising contacting a hydrocarbon stream with a zeolite adsorbent comprising a chabazite zeolite, an erionite zeolite, a clinoptilolite zeolite or mixtures thereof and adsorbing CS 2 using size selective adsorption to produce a hydrocarbon stream having a reduced CS 2 content, and regenerating said zeolite adsorbent with a regenerant stream comprising a hydrotreated hydrocarbon stream forming a regeneration effluent. 17. The process of claim 16 wherein said zeolite adsorbent is ion exchanged with barium. 18. The process of claim 16 wherein the hydrocarbon stream comprises naphtha boiling range hydrocarbons and wherein size selective adsorption capacity of the adsorbent for CS 2 is not impacted by the presence of the naphtha boiling range hydrocarbons or wherein the hydrocarbon stream comprises additional organic sulfur compounds and wherein size selective adsorption capacity of the adsorbent for CS 2 is not impacted by the presence of the additional organic sulfur compounds. 19. The process of claim 16 wherein the hydrocarbon stream comprises cracked hydrocarbons; or cracked hydrocarbons from an ethylene cracking unit; or at least one of C4 olefins, C4 dienes, C5 olefins, C5 dienes, or any combination thereof; or at least one of acetylenes, dienes, olefins, or any combination thereof.
Natural alumino-silicates, e.g. zeolites · CPC title
with crystalline alumino-silicates, e.g. molecular sieves · CPC title
Recovery of used adsorbent · CPC title
with ion-exchange material · CPC title
by thermal treatment not covered by groups B01J20/3441 - B01J20/3475, e.g. by heating or cooling · CPC title
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