Low pressure drop purifier for nitrogen, methane, and argon removal from syngas
An apparatus for purifying a raw syngas stream containing excess nitrogen and an ammonia process plant for manufacturing ammonia from syngas with excess air for reforming and nitrogen removal with low pressure losses is disclosed. Auto-refrigeration for cooling the syngas for cryogenic hydrogen enrichment is provided by expansion of a hydrogen-lean waste fluid stream from a distillation column
The present application is a divisional to co-pending U.S. patent application Ser. No. 10/604,404, filed on Jul. 17, 2003.
FIELDThe present embodiments relate generally to methods and apparatus to improve production of synthesis gas for manufacturing ammonia. The present embodiments reduces pressure losses in a nitrogen-wash purifier unit
BACKGROUNDProcesses for manufacturing ammonia from a hydrocarbon and air, via a hydrogen/nitrogen synthesis gas (syngas), are well known. Extraneous syngas components typically include inert gases from the air and/or the hydrocarbon feed, such as argon and methane. When excess air is used in the syngas production, nitrogen is also present in stoichiometric excess, and must be removed from a raw makeup syngas stream or purged from an ammonia synthesis loop to maintain a desired ammonia synthesis reactor feed composition.
In the prior art, some syngas production methods use excess air and cryogenic syngas purification, which relies on a syngas pressure drop upstream of purification for refrigeration. The pressure drop is subsequently made up in a compressor that raises the syngas to ammonia synthesis loop pressure. This type of method also reduces the rate of recycle or purge gas flow from the ammonia reactor loop due to the upstream removal from the makeup syngas of inerts such as argon and methane in the syngas purification.
Other methods of ammonia synthesis use high-activity catalyst in the ammonia synthesis reactor. Purge gases are eliminated via a hydrogen enrichment process operating on a sidestream of the syngas recycled to the synthesis loop compressor. The total recycle flow is roughly three times the volumetric flowrate of the makeup syngas.
Other methods use air separation to provide oxygen-enriched air such that reforming produces a synthesis gas with higher hydrocarbon slip than in other ammonia manufacturing systems. A higher concentration of nonreactive gas in the ammonia synthesis is managed by purging from a residual syngas stream following recovery of ammonia product. This type of method unloads front-end gas reforming reactors, at the expense of including air separation, but ostensibly enables a smaller purge stream process after ammonia synthesis.
Other methods are centered on an integrated process system for synthesizing methanol and ammonia that uses a nitrogen wash by cryogenic fractionation to purify ammonia syngas, with refrigeration supplied externally and providing no recovery of expansion power in the process.
The present embodiments meet these needs.
BRIEF DESCRIPTION OF THE DRAWINGSThe detailed description will be better understood in conjunction with the accompanying drawings as follows:
The present embodiments are detailed below with reference to the listed Figures.
DETAILED DESCRIPTION OF THE EMBODIMENTSBefore explaining the present embodiments in detail, it is to be understood that the embodiments are not limited to the particular embodiments and that they can be practiced or carried out in various ways.
The present embodiments provide methods to purify syngas. Syngas, as an example, occurs in ammonia manufacturing processes. The methods use cryogenic distillation to purify syngas, and obtain refrigeration for the distillation from waste fluid expansion using a liquid expander to recover mechanical work from the waste fluid. These methods reduce the pressure losses in the syngas stream and concomitantly reduce compression costs and power relative to similar prior art ammonia processes utilizing nitrogen and inerts removal.
The methods are applicable in grassroots plant design, and can also be applied to retrofit existing synthesis gas systems to improve process performance and economics. In the retrofit, for example, the lower pressure drop of the present embodiments can allow process modification for reforming with excess air and nitrogen removal from the makeup syngas without expensive modification or replacement of the synthesis loop and/or makeup gas compressors.
In an embodiment, the present embodiments provide methods to purify syngas, including: (a) introducing a raw syngas stream containing excess nitrogen to a feed zone in a distillation column; (b) expanding a liquid bottoms stream from the distillation column through a liquid expander with a work output to form a cooled waste fluid stream; (c) rectifying vapor from the feed zone in the distillation column to form an overhead vapor stream of reduced nitrogen and inerts content; (d) cooling the overhead vapor stream in indirect heat exchange with the cooled waste fluid stream to form a partially condensed overhead stream and a relatively warm waste fluid stream; (e) separating the partially condensed overhead stream into a condensate stream and a purified syngas vapor stream of reduced nitrogen and inerts content; and (f) refluxing the distillation column with the condensate stream. The method can also include cooling the raw syngas stream by expansion across a Joule-Thompson (J-T) valve in advance of the introduction to the feed zone. Additionally, the method can include cooling the raw syngas stream in cross-exchange against the warm waste fluid stream and against the purified syngas vapor stream. In this embodiment, adjusting the flow to the liquid bottoms stream expansion controls liquid level in the distillation column.
The methods can further include producing the raw synthesis gas by reforming a hydrocarbon, wherein the reforming includes autothermal or secondary reforming with excess air. The purified syngas vapor stream can be supplied to an ammonia synthesis loop for manufacturing ammonia.
In an embodiment, the present embodiments provide an ammonia process. The process embodiments include reforming a hydrocarbon to form syngas. The reforming can include autothermal or secondary reforming with excess air to form a raw syngas stream containing excess nitrogen for ammonia synthesis. The process embodiments include cooling the raw syngas stream in a cross-exchanger and expanding the cooled raw syngas stream. The expanded raw syngas stream is introduced to a feed zone in a distillation column. The liquid bottoms stream from the distillation column is expanded through a liquid expander to form a cooled waste fluid stream. The process embodiments include rectifying vapor from the feed zone in the distillation column to form an overhead vapor stream of reduced nitrogen and inerts content. The overhead vapor stream is cooled in indirect heat exchange with the cooled waste fluid stream to form a partially condensed overhead stream and a partially warmed waste fluid stream. The partially condensed overhead stream is separated into a condensate stream and a purified syngas vapor stream of reduced nitrogen and inerts content. The distillation column is refluxed with the condensate stream and the purified syngas vapor stream and the partially warmed waste fluid stream are heated in one or more cross-exchangers. The purified syngas vapor stream is supplied from the cross-exchanger to an ammonia synthesis loop.
In an embodiment, the present embodiments can be applied to improve an ammonia process that includes the steps of reforming a hydrocarbon with excess air to form a raw syngas stream, removing nitrogen and inerts from the raw syngas stream by distillation. The cooling can be provided by process fluid expansion through an expander-generator, wherein an overhead stream is partially condensed against a waste stream cooled by expanding bottoms liquid from a distillation column, and supplying syngas with reduced nitrogen and inerts content from the distillation to an ammonia synthesis loop. The process embodiments can include optionally expanding the raw syngas stream across a Joule-Thompson valve upstream of the distillation column; and/or expanding the bottoms liquid through a liquid expander with a work output.
In an embodiment, the present embodiments provide for a purification apparatus for purifying a raw syngas stream containing excess nitrogen. The embodied apparatus, can include means for introducing the raw syngas stream to a feed zone in a distillation column; means for expanding a liquid bottoms stream from the distillation column to form a cooled waste fluid stream; means for rectifying vapor from the feed zone in the distillation column to form an overhead vapor stream of reduced nitrogen and inerts content; means for cooling the overhead vapor stream in indirect heat exchange with the cooled waste fluid stream to form a partially condensed overhead stream and a relatively warm waste fluid stream; means for separating the partially condensed overhead stream into a condensate stream and a purified syngas vapor stream of reduced nitrogen and inerts content; and means for refluxing the distillation column with the condensate stream.
In an embodiment, the present embodiments provide for an ammonia process plant. The embodied an ammonia process plants can include means for reforming a hydrocarbon to form syngas, wherein the reforming means includes an autothermal or secondary reformer and means for supplying excess air to the autothermal or secondary reformer, to form a raw syngas stream containing excess nitrogen for ammonia synthesis; cross-exchanger means for cooling the raw syngas stream; means for expanding the cooled raw syngas stream from the cross-exchanger; means for introducing the expanded raw syngas stream to a feed zone in a distillation column; means for expanding a liquid bottoms stream from the distillation column through a liquid expander to form a cooled waste fluid stream; means for rectifying vapor from the feed zone in the distillation column to form an overhead vapor stream of reduced nitrogen and inerts content; means for cooling the overhead vapor stream in indirect heat exchange with the cooled waste fluid stream to form a partially condensed overhead stream and a partially warmed waste fluid stream; means for separating the partially condensed overhead stream into a condensate stream and a purified syngas vapor stream of reduced nitrogen and inerts content; means for refluxing the distillation column with the condensate stream; means for heating the purified syngas vapor stream in the cross-exchanger; means for heating the partially warmed waste fluid stream in the cross exchanger; and means for supplying the purified syngas vapor stream from the cross-exchanger to an ammonia synthesis loop
With reference to the figures,
The waste gas stream 26 is discharged from the distillation column 20 as bottoms stream 28, flashed across level control valve 30, and used as a coolant in a heat exchanger 32 integral with the distillation column 20. The heat exchanger 32 cools and partially condenses overhead vapor from the column 20 to obtain syngas liquid to reflux the column 20. The makeup syngas stream 24 is compressed for conversion in ammonia synthesis reactors (not shown) that operate at higher pressures. Thus, a pressure drop incurred by the raw syngas 10 in the purification PA must be recouped downstream by consuming additional power for compression.
A bypass J-T valve 50 is included for gas or two-phase flow, e.g. at startup. In operation, expansion of the bottoms stream 28 is preferably a primary source of auto-refrigeration in the syngas purification process 34 of the present embodiments, whereas the expansion across the bypass J-T valve at valve station 38 is a relatively minor source. The bypass J-T valve can be a significant refrigeration source during startup.
From liquid expander 46, the chilled waste fluid stream 28 enters a coolant inlet 52 of an indirect heat exchange zone 32 integral to the column 20. The flow rate to the liquid expander 46 controls the liquid level in the holdup zone 42 and also, in part, regulates conditions in the column 20, based on feedback from a syngas analyzer 56. Conditions in the column 20 determine the composition of the purified syngas stream 24. For example, more refrigeration reduces the nitrogen content; less refrigeration increases the nitrogen content. The chilled waste fluid stream 28 passes through the heat exchange zone 32, discharging from the column 20 via coolant outlet 56. During transit through the heat exchange zone 32, the bottoms stream 28 cools and partially condenses overhead vapor from the column 20.
From the inlet zone 40, syngas vapor flows upward through a contact zone 58 in contact with liquid flowing downward through the contact zone 58 to absorb nitrogen and enrich the hydrogen content of the vapor. At the upper end of the contact zone 58, the vapor enters a vapor riser 60 and flows to a vapor inlet zone 62 at an upper end of the heat exchange zone 32. The vapor passes tube-side through the heat exchange zone 32 for partial condensation against the waste fluid stream 28, further enriching the vapor in lower-boiling components. Vapor and condensate exit the heat exchange zone 32 and are separated in a knockout zone 64. Vapor exits the column 20 as the purified syngas stream 24, discharging via syngas outlet 66. The condensate collects in a liquid seal well 68 below the knockout zone 64 and in communication with the contact zone 58. The condensate overflows from the seal well 68 to flow downward through the contact zone 58 to the liquid holdup zone 42 as described previously.
In an embodiment, expansion of a liquid byproduct stream of purged gases (such as, the column bottoms stream 28) can generate a major portion of the auto-refrigeration required for the purification process. This generation avoids a major part of the syngas pressure loss incurred in the prior art configuration of
Referring to
Referring to
The purification process of
The purification method of the present invention embodiment of
Operation of the low-ΔP process of
The data in Table 2 show that the flow rates and temperatures are similar, but the pressure drop for the syngas between the purification process inlet and outlet is considerably lower in the
As seen in the data presented above, the purification process of
The embodiments are described above with reference to non-limiting examples provided for illustrative purposes only. Various modifications and changes will become apparent to the skilled artisan in view thereof. All such changes and modifications are intended within the scope and spirit of the appended claims and shall be embraced thereby.
Claims
1) An apparatus for purifying a raw syngas stream containing excess nitrogen comprising:
- means for introducing the raw syngas stream to a feed zone in a distillation column;
- means for expanding a liquid bottoms stream from the distillation column through a liquid expander with a work output to form a cooled waste fluid stream;
- means for rectifying vapor from the feed zone in the distillation column to form an overhead vapor stream of reduced nitrogen and inerts content;
- means for cooling the overhead vapor stream in indirect heat exchange with the cooled waste fluid stream to form a partially condensed overhead stream and a relatively warm waste fluid stream;
- means for separating the partially condensed overhead stream into a condensate stream and a purified syngas vapor stream of reduced nitrogen and inerts content; and
- means for refluxing the distillation column with the condensate stream.
2) The apparatus of claim 1, further comprising means for cooling and expanding the raw syngas stream across a Joule-Thompson valve in advance of the introduction to the feed zone.
3) The apparatus of claim 2, wherein the means for expanding the liquid bottoms stream comprises a hydraulic turbine.
4) The apparatus of claim 1, wherein the relatively warm waste fluid stream from the overhead vapor cooling consists of a vapor phase.
5) The apparatus of claim 1, wherein the relatively warm waste fluid stream from the liquid expander comprises mixed vapor and liquid.
6) The apparatus of claim 1, wherein a liquid level in the distillation column is controlled by adjusting flow the expansion to the liquid bottoms stream.
7) The apparatus of claim 1, further comprising means for producing the raw synthesis gas by reforming a hydrocarbon, wherein the means for producing the raw synthesis gas comprises autothermal or secondary reforming with excess air.
8) The apparatus of claim 1, further comprising means for supplying the purified syngas vapor stream to an ammonia synthesis loop to form ammonia.
9) An ammonia process plant comprising:
- means for reforming a hydrocarbon to form syngas, wherein the reforming means include an autothermal or secondary reformer and means for supplying excess air to the autothermal or secondary reformer to form a raw syngas stream containing excess nitrogen for ammonia synthesis;
- cross-exchanger means for cooling the raw syngas stream;
- means for expanding the cooled raw syngas stream from the cross-exchanger;
- means for introducing the expanded raw syngas stream to a feed zone in a distillation column;
- means for expanding a liquid bottoms stream from the distillation column through a liquid expander with a work output to form a cooled waste fluid stream;
- means for rectifying vapor from the feed zone in the distillation column to form an overhead vapor stream of reduced nitrogen and inerts content;
- means for cooling the overhead vapor stream in indirect heat exchange with the cooled waste fluid stream to form a partially condensed overhead stream and a partially warmed waste fluid stream;
- means for separating the partially condensed overhead stream into a condensate stream and a purified syngas vapor stream of reduced nitrogen and inerts content;
- means for refluxing the distillation column with the condensate stream;
- means for heating the purified syngas vapor stream in the cross-exchanger;
- means for heating the partially warmed waste fluid stream in the cross exchanger;
- means for supplying the purified syngas vapor stream from the cross-exchanger to an ammonia synthesis loop.
10) The ammonia process plant of claim 9, further comprising means for cooling and expanding the raw syngas stream across a Joule-Thompson valve in advance of the introduction to the feed zone.
11) The ammonia process plant of claim 10, wherein the means for cooling of the raw syngas stream includes cross-exchange against the partially warmed waste fluid stream and against the purified syngas vapor stream.
12) The ammonia process plant of claim 9, wherein the means for expanding the liquid bottoms stream comprises a hydraulic turbine.
13) The ammonia process plant of claim 9, wherein the partially warmed waste fluid stream from cooling of the overhead vapor stream consists of a vapor phase.
14) The ammonia process plant of claim 9, wherein waste fluid from the liquid expander comprises mixed vapor and liquid.
15) The ammonia process plant of claim 9, wherein a liquid level in the distillation column is controlled by adjusting flow the expansion to the liquid bottoms stream.
16) The ammonia process plant of claim 9, further comprising means for producing the raw synthesis gas by reforming a hydrocarbon, wherein the means for producing the raw synthesis gas comprises autothermal or secondary reforming with excess air.
17) The ammonia process plant of claim 9, further comprising means for supplying the purified syngas vapor stream to an ammonia synthesis loop to form ammonia.
Type: Application
Filed: Jun 22, 2006
Publication Date: Oct 26, 2006
Inventors: Avinash Malhotra (Sugar Land, TX), Tufail Ahmad (Houston, TX), Bradley Welter (Houston, TX)
Application Number: 11/472,590
International Classification: B32B 27/04 (20060101); B32B 27/12 (20060101);