(12) United States Patent (10) Patent N0.: US 8,695,377 B2 Bachelier et a]. (45) Date of Patent: Apr. 15, 2014



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USOO8695377B2 (12) United States Patent (10) Patent N0.: Bachelier et a]. (45) Date of Patent: Apr. 15, 2014 (54) PROCESS AND APPARATUS FOR THE (52) us. Cl. SEPARATION OF AIR BY CRYOGENIC USPC..... 62/644; 62/643 DISTILLATION (58) Field of Classi?cation Search (75) Inventors: Frédéric Bachelier, La Chapelle la Reine (FR); Sha0_Hua sun, Shanghai USPC..... 62/644, 652, 649, 650, 647, 646 See application?le for complete search history. (CN) (56) References Cited (73) Assignee: L Air Liquide, Societe Anonyme pour l Etude et l Exploitation des Procedes U'S' PATENT DOCUMENTS Georges Claude, Pans (FR) 5,355,681 A * 10/1994 Xu..... 62/646 ( * ) _ 5,907,959 A 6/1999 Agrawal et a1. Notice: Subject to any disclaimer, the term ofthls 6,962,062 B2 11/2005 Ha et a1. patent is extended or adjusted under 35 7,533,540 B2* 5/2009 Prosser 62/645 U_S_C_ 154(b) by 572 days_ 2007/0209389 A1* 9/2007 Prosser. 62/643 2008/0134718 A1 * 6/2008 Howard ct..... 62/643 (21) Appl. No.: 12/671,798 OTHER PUBLICATIONS (22) PCT Filedl Aug- 10, 2007 Search Report for PCT/CN2007/002405. (86) PCT No.: PCT/CN2007/002405 * Cited by examiner 371 (0X1) (2), (4) Date; Jun_ 24, 2011 Primary Examiner * FrantZ Jules Assistant Examiner * Brian King (87) PCT Pub. No.: W02009/021351 (74) Attorney, Agent, or Firm * Justin K. Murray; ElWood PCT Pub. Date: Feb. 19, 2009 L Haynes (65) Prior Publication Data (57) ABSTRACT Us 2011/0259046 A1 Oct 27 2011 A process for producing a gaseous component of air under pressure by cryogenic separation is provided. (51) Int. Cl. F25] 3/04 (2006.01) 10 Claims, 1 Drawing Sheet 63 15B BB 1 173 333 i. n l

US. Patent Apr. 15, 2014 L......_1 ls 1:

1 PROCESS AND APPARATUS FOR THE SEPARATION OF AIR BY CRYOGENIC DISTILLATION This application is a 37l of International PCT Application PCT/CN2007/002405,?led Aug. 10, 2007. FIELD OF THE INVENTION The present invention relates to the separation of air by cryogenic distillation. In particular, it relates to a process for producing a gaseous component of air under pressure by cryogenic separation. BACKGROUND It is frequently required that an air separation unit produc ing a gaseous component of air under pressure should also produce a varying amount of a component of air in liquid form. It is known to supply this requirement by having an air separation unit to produce the gaseous component under pres sure, the air separation unit being associated with a lique?er to liquefy varying amounts of gas from the air separation unit to produce the liquid. This apparatus involves considerable capital expenditure. According to the invention, there is provided a new process scheme which operates ef?ciently in the gas mode and the liquid mode whilst involving only reasonable investment costs. All percentages mentioned are molar percentages. SUMMARY OF THE INVENTION According to one aspect of the invention, there is provided a process for the separation of air by cryogenic distillation in a distillation system including at least a high pressure column and a low pressure column wherein air is compressed in a main compressor, compressed air is cooled in a heat exchange line, cooled, compressed and puri?ed air is sent from the heat exchange line to the high pressure column, an oxygen enriched liquid stream is sent from the high pressure column to the low pressure column, directly or indirectly, a nitrogen enriched liquid stream is sent from the high pressure column to the low pressure column, a nitrogen rich gas is removed from the low pressure column and warmed in a heat exchange line, a component of air is removed from the distillation system in liquid form, pressurized and warmed in the heat exchange line, wherein: i) in a?rst mode of operation, at least 90% of the air divided in two, one part being lique?ed and sent to the distillation system and one part being expanded in at least one turboexpander before being sent to the high pressure column ii) in a second mode of operation, at most 70% of the air divided in two, one part being lique?ed and sent to the distillation system and one part being expanded in at least one turboexpander before being sent to the high pressure column and at least 30% of the air compressed 20 25 30 35 40 45 50 55 60 65 2 in the main compressor is sent at the outlet pressure of the main compressor to the heat exchange line, cooled and sent to the high pressure column. According to further optional aspects of the invention: the component of air is removed from the distillation sys tem in liquid form, pressurized and warmed in the heat exchange line is oxygen or nitrogen; the air compressed to the?rst pressure is compressed in at least one compressor of pair of compressors connected in parallel; the air expanded from the?rst pressure to the pressure of the high pressure column is expanded in at least one of two turboexpanders connected in parallel; during the?rst mode of operation the air is sent to both of the compressors connected in parallel and to both of the expanders connected in parallel; during the second mode of operation the air is sent to only one of the compressors connected in parallel and to only one of the expanders connected in parallel; more cryogenic liquid is produced as a?nal product during the?rst mode of operation than in the second mode of operation; a cryogenic liquid is produced as a?nal product only during the?rst mode of operation. According to a further aspect of the invention, there is provided an apparatus for the separation of air by cryogenic distillation comprising a main compressor, a heat exchange line, a distillation system comprising at least a high pressure column and a low pressure column, a conduit connecting the outlet of the main compressor with the heat exchange line and the heat exchange line with the high pressure column, adapted to transfer gaseous air to the pressure column at the outlet pressure of the main compressor, the outlet of the main compressor being connected with at least one booster com pressor, the outlet of the booster compressor being connected to the heat exchange line and the heat exchange line being connected to the distillation system via expansion means such that the air at the outlet pressure of the booster compressor is cooled at that pressure and then expanded to a pressure of one of the columns of the distillation system. Preferably the expansion means comprises two turboex panders connected in parallel and/ or the booster compressor comprises at least one pair of compressors connected in par allel. The booster compressor may comprise two pairs of com pressors connected in parallel. Whilst all four compressors of the booster compressor function in liquid mode, only one compressor of each parallel pair functions in gas mode. BRIEF DESCRIPTION OF THE FIGURES The sole FIGURE illustrates one embodiment of the present invention. DETAILED DESCRIPTION OF THE INVENTION For a further understanding of the nature and objects for the present invention, reference should be made to the detailed description, taken in conjunction with the accompanying drawing, in which like elements are given the same or analo gous reference numbers and wherein: The process will be described in more detail by referring to the FIGURE which shows an air separation unit according to the invention. The air separation unit uses a double column comprises a high pressure column 43 operating at about 5.5 bars abs. and thermally connected to a low pressure column 45.

3 According to all modes of operation, all the air for the distillation is compressed in compressor 3 to around 6 bars abs, puri?ed in puri?cation unit 7A, 7B as stream 5. Rich liquid 51, poor liquid 53 and very poor liquid are removed from the high pressure column, subcooled in exchanger 53 and sent as re?ux to the low pressure column 45. A pure nitrogen stream 63 is removed from the very top of the low pressure column minaret, warmed in subcooler 53 and then warmed in heat exchanger 41. A nitrogen waste stream 65 is removed from the bottom of the minaret of the low pressure column, warmed in subcooler 53 and then warmed in heat exchanger 41. A liquid oxygen stream 67 is removed from the low pres sure column 45, compressed in pump 69 and then vaporized in heat exchanger 41 to form a product. In gas mode, the stream 5 is divided in two. 40 mol. % of the air as stream 9 is sent to the heat exchanger 41, cooled by passing through the whole heat exchanger and then sent to the high pressure column in gaseous form as part of stream 37. The rest of the air (ie, 60 mol. % of the air) forms stream 13 and is boosted up to 50 bar abs by one ofthe two boosters 17A, 17B in parallel as stream 15A or 15B and then by one of the two boosters 23A, 23B in parallel as stream 21A or 21B. Stream 21A or 21B then forms stream 25, which is cooled in the heat exchanger to an intermediate temperature then divided in two. Stream 39 continues to be cooled in the heat exchanger 41. Stream 27 is removed, and expanded to the pressure of the high pressure column 32 in one of expanders 29A, 29B mounted in parallel. Expander 29A is coupled to booster 23A and expander 29B is coupled to booster 23B. The expanded stream 33A or 33B forms stream 35 and is sent to the high pressure column. The stream is expanded in an expander coupled to the compressor in which it was previ ously compressed. In liquid mode, all of the air from compressor 3 forms stream 13 and is boosted up to 50 bar abs by two boosters 17A, 17B in parallel as streams 15A, 15B and then by the two boosters 23A,23B in parallel as streams 21A, 21B. There is no stream 9. Streams 21A and 21B are then mixed to form stream 25, which is cooled in the heat exchanger to an inter mediate temperature then divided in two. Stream 39 contin ues to be cooled in the heat exchanger 41. Stream 27 is removed and split in two. Streams 31A, 31B are each expanded to the pressure of the high pressure column 32 in expanders 29A, 29B mounted in parallel. Expanders 29A is coupled to booster 23A and expander 29B is coupled to booster 23B. The expanded streams 33A, 33B are mixed to form stream 35 and sent to the high pressure column 43, forming the only gaseous stream sent to that column. In the liquid mode, the total amount of liquid withdrawn as a?nal product, be it as liquid oxygen 61 or liquid nitrogen 59, is greater than the amount of liquid withdrawn as a?nal product in the gas mode. The amount of liquid produced in the liquid mode can reach 50 mol % of the total products for a given air separation unit operating according to the invention. In addition to that, in either mode, high pressure gaseous nitrogen can be produced by pumping liquid nitrogen and vaporizing it (forming up to 55 mol. % of the gaseous oxygen?ow) to improve the speci?c power consumption. Variants of the process including an intermediate pressure column, a mixing column and/or an argon column can of course be envisaged. It will be understood that many additional changes in the details, materials, steps and arrangement of parts, which have been herein described in order to explain the nature of the 20 25 30 35 40 45 50 55 60 65 4 invention, may be made by those skilled in the art within the principle and scope of the invention as expressed in the appended claims. Thus, the present invention is not intended to be limited to the speci?c embodiments in the examples given above. What is claimed is: 1. A process for the separation of air by cryogenic distilla tion in a distillation system including at least a high pressure column and a low pressure column having a?rst mode of operation and a second mode of operation that are different from each other, the process comprising the steps of: purifying an inlet air stream, compressing the puri?ed air stream in a main compressor, cooling the compressed air stream in a heat exchange line, sending the cooled, compressed and puri?ed air stream from the heat exchange line to the high pres sure column, sending an oxygen enriched liquid stream from the high pressure column to the low pressure column, sending a nitrogen enriched liquid stream from the high pressure column to the low pressure column, removing a nitrogen rich gas from the low pressure column and warming the removed nitrogen rich gas a heat exchange line, removing a component of air from the distillation system in liquid form, and pres surizing and warming the removed component of air in the heat exchange line, wherein: i) in the?rst mode of operation, at least 90% of the air divided in two parts, the?rst part being lique?ed and sent to the distillation system and the second part being expanded in at least one of two turboexpanders con nected in parallelibefore being sent to the high pres sure column; in the second mode of operation, at most 70% of the air divided in two parts, the?rst part being lique?ed and sent to the distillation system and the second part being expanded in at least one of two turboexpanders con nected in parallel before being sent to the high pressure column and at least 30% of the air compressed in the main compressor is sent at the outlet pressure of the main compressor to the heat exchange line, cooled and sent to the high pressure column, wherein connected in parallel is characterized as the two turboexpanders being con?gured to receive the air at substantially the same temperature and pressure when ever air is introduced to both turboexpanders, wherein a cryogenic liquid is produced as a?nal product only during the?rst mode of operation. 2. The process of claim 1 wherein the component of air is removed from the distillation system in liquid form, pressur ized and warmed in the heat exchange line is oxygen or nitrogen. 3. The process of claim 1 wherein the air compressed to the?rst pressure is compressed in at least one compressor of a pair of compressors connected in parallel. 4. The process of claim 3 wherein during the?rst mode of operation the air is sent to both of the compressors connected in parallel.

5 5. The process of claim 1 wherein during the?rst mode of operation the air is sent to both of the turboexpanders in parallel. 6. The process of claim 3 Wherein during the second mode of operation the air is sent to only one of the compressors 5 connected in parallel. 7. The process of claim 1 Wherein during the second mode of operation the air is sent to only one of the turboexpanders connected in parallel. 8. The process of claim 1, Wherein the component of air 10 removed from the distillation system in liquid form comprises liquid nitrogen. 9. The process of claim 1, Wherein the component of air removed from the distillation system in liquid form comprises liquid oxygen. 15 10. The process of claim 1, Wherein the component of air removed from the distillation system in liquid form includes a liquid selected from the group consisting of liquid nitrogen, liquid oxygen and combinations thereof. * * * * * 20