IPC분류정보
국가/구분 |
United States(US) Patent
등록
|
국제특허분류(IPC7판) |
|
출원번호 |
US-0535051
(2009-08-04)
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등록번호 |
US-8409427
(2013-04-02)
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발명자
/ 주소 |
- Raybold, Troy M.
- Drnevich, Raymond Francis
- Papavassiliou, Vasilis
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출원인 / 주소 |
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대리인 / 주소 |
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인용정보 |
피인용 횟수 :
4 인용 특허 :
2 |
초록
▼
The present invention provides a method and apparatus for producing a treated hydrocarbon containing stream for use as a feed to a steam methane reformer of a hydrogen plant. In accordance with such method, amounts of olefins and organic sulfur species within an untreated feed are decreased in a rea
The present invention provides a method and apparatus for producing a treated hydrocarbon containing stream for use as a feed to a steam methane reformer of a hydrogen plant. In accordance with such method, amounts of olefins and organic sulfur species within an untreated feed are decreased in a reactor that is operated in either a hydrogenation mode to hydrogenate the olefins into saturated hydrocarbons or a pre-reforming mode in which hydrocarbon containing two or more carbon atoms including the olefins are reacted with oxygen and steam to form saturated hydrocarbons, methane, additional hydrogen and carbon monoxide. The reactor is configured and operates at a sufficiently high space velocity that olefin and organic species slip occurs that is further treated in a hydrotreater. The reactor contains a catalyst capable of promoting both hydrogenation and oxidation reactions and the hydrotreater contains a catalyst that is capable of only promoting hydrogenation reactions.
대표청구항
▼
1. A method of producing a treated hydrocarbon containing stream for use as a feed to a hydrogen plant having a steam methane reformer, said method comprising: contacting an untreated hydrocarbon containing feed stream of variable composition comprising hydrocarbons that contain two or more carbon a
1. A method of producing a treated hydrocarbon containing stream for use as a feed to a hydrogen plant having a steam methane reformer, said method comprising: contacting an untreated hydrocarbon containing feed stream of variable composition comprising hydrocarbons that contain two or more carbon atoms including olefins, organic sulfur species and hydrogen with a sulfur tolerant catalyst contained within a reaction stage and capable of promoting both hydrogenation and oxidation reactions, wherein the untreated hydrocarbon containing feed stream is a refinery off-gas that is compressed to a pressure greater than a preheated natural gas stream produced in the hydrogen plant;converting part of the olefins into saturated hydrocarbons and part of the sulfur species to hydrogen sulfide within the reaction stage, thereby to produce a first intermediate stream, through hydrogenation reactions promoted by the catalyst or by introducing sufficient oxygen and steam into the reaction stage such that oxidation reactions are promoted by the catalyst resulting in the saturated hydrocarbons, methane, additional hydrogen and carbon monoxide being produced from the hydrocarbons contained in the untreated hydrocarbon containing feed stream, combining the first intermediate stream with the preheated natural gas stream to produce a combined stream containing between about 0.5 mol percent and 6 mol percent olefins on a dry basis and less than about 25 ppm by volume of total sulfur on a dry basis;the first intermediate stream is passed through a boiler to generate saturated steam for the hydrogen plant and is thereby cooled to a temperature of between about 260° C. and about 480° C. prior to being combined with the preheated natural gas stream;prior to the hydrocarbon containing feed stream being introduced into the reaction stage, the untreated hydrocarbon containing feed stream, after compression, is: preheated to a temperature of about 230° C. through indirect heat exchange with steam generated in the hydrogen plant; preheated in a feed preheater through indirect heat exchange with a synthesis gas stream produced in the hydrogen plant to a temperature of between about 260° C. and about 400° C.; and thereafter, subjected to a pretreatment stage configured to remove incoming hydrogen sulfide from the untreated hydrocarbon containing feed stream;introducing at least the first intermediate treated hydrocarbon containing feed stream into a hydrotreater having another catalyst that is capable of solely promoting hydrogenation reactions and producing a second intermediate stream containing no greater than about 0.5 mol percent of the olefins on a dry basis and no greater than about 0.1 ppm by volume organic sulfur on a dry basis, and having a greater amount of the hydrogen sulfide than that of the first intermediate stream and lower amounts of the olefins and the organic sulfur species than that of the first intermediate stream by subjecting olefin and organic sulfur species slip in the first intermediate stream to hydrogenation reactions; andadsorbing the hydrogen sulfide in the second intermediate stream, thereby to produce the treated hydrocarbon containing stream. 2. The method of claim 1, wherein: prior to or after being compressed, the untreated hydrocarbon containing feed stream is passed into a knockout drum to separate free liquids in the hydrocarbon containing stream and thereby to produce a condensate stream; andprior to or after the untreated hydrocarbon containing feed stream being compressed, sulfur containing compounds are removed therefrom in a bulk sulfur removal stage. 3. The method of claim 1, further comprising: processing the untreated hydrocarbon containing feed in the space velocity from 40,000 hours−1 to 160,000 hours−l to reduce of the amount of catalyst required. 4. An apparatus for producing a treated hydrocarbon containing stream for use as a feed to a hydrogen plant having a steam methane reformer reactant stream to be reformed in a hydrogen plant containing a steam methane reformer, said apparatus comprising: a reactor configured to receive an untreated hydrocarbon containing feed stream of variable composition comprising hydrocarbons that contain two or more carbon atoms including olefins, organic sulfur species and hydrogen and containing a sulfur tolerant catalyst capable of promoting both hydrogenation and oxidation reactions contained within the reactor;the reactor also configured to convert part of the olefins into saturated hydrocarbons and at least part of the sulfur species to hydrogen sulfide, thereby to produce a first intermediate stream, through selective modes of operation such that in a hydrogenation mode, hydrogenation reactions are promoted by the catalyst or in a pre-reforming mode, steam and oxygen are received within the reactor, oxidation reactions are promoted by the catalyst resulting in production of saturated hydrocarbons, methane, additional hydrogen and carbon monoxide from hydrocarbons contained in the untreated hydrocarbon containing feed stream;a mixer assembly is in flow communication to the reactor and conduits supplying the steam, the oxygen and the hydrocarbon containing feed stream such that a mixture containing the hydrocarbon containing feed stream, the steam and oxygen is received in the reactor and contacts the catalyst; andcontrol valves are in flow communications with the conduits supplying the steam and oxygen to the mixer, the control valves configured to be set in open positions to allow the oxygen and steam to be received within the reactor during the pre-reforming mode of operation;a hydrotreater in flow communication with the reactor so as to receive at least the first intermediate treated hydrocarbon containing stream and to produce a second intermediate stream having a greater amount of the hydrogen sulfide than that of the first intermediate stream and lower amounts of the olefins and the organic sulfur species than that of the first intermediate stream through hydrogenation of olefin slip and conversion of the organic sulfur species slip in the first intermediate stream with the use of another catalyst capable of solely promoting hydrogenation reactions;a compressor compresses the untreated hydrocarbon containing feed stream to a pressure greater than a preheated natural gas stream produced in the hydrogen plant;anda natural gas line is in flow communication with the hydrotreater so that the first intermediate stream is combined with the preheated natural gas stream to form a combined stream and the combined stream is introduced into the hydrotreater, thereby to produce the second intermediate stream;a boiler is positioned between the reactor and the hydrotreater such that the first intermediate stream is passed through a boiler to generate saturated steam for the hydrogen plant and is thereby cooled prior to being combined with the preheated natural gas stream; anda preheater is connected to the compressor to preheat the untreated hydrocarbon containing feed stream through indirect heat exchange with steam generated in the hydrogen plant;a feed preheater is connected to the preheater to further preheat the untreated hydrocarbon containing feed stream through indirect heat exchange with a synthesis gas stream produced in the hydrogen plant; anda pretreatment stage is positioned between the feed preheater and the reactor and is configured to remove incoming hydrogen sulfide from the untreated hydrocarbon containing feed stream; anda zinc oxide bed associated with the hydrogen plant and connected to the hydrotreater to adsorb the increased hydrogen sulfide content in the second intermediate stream, thereby to produce the treated hydrocarbon containing stream. 5. The apparatus of claim 4, wherein: a knockout drum is positioned upstream of each compressor stage and receives the untreated hydrocarbon containing feed stream, thereby to separate free liquids in the untreated hydrocarbon containing feed stream and to produce a condensate stream; anda bulk sulfur removal stage is positioned between the knockout drum and the compressor or downstream of the compressor and is configured to remove sulfur containing compounds from the untreated hydrocarbon containing feed stream.
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