(12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT) (19) World Intellectual Property 3 Orgai Z ANOKA A {ntematona] Barca = (10) International Publication Number (43) International Publication Date = So December 2012 (20.12.2012) WIPO|PCT Ree (1) International Patent Classification (74) Common Representative; HALDOR TOPSOE AVS; BOLD S/00(2006.01) CIB 17/80 (2006.01) ‘Nymalleve) 55, DK-2800 Kgs. Lyngby (DK). 21) International Application Number: (81) Designated States (uriess otherwise indicated, for every PCT/EP2012/060514 kind of national protection available): AE, AG, AL, AM, AO, AT, AU, AZ, BA, BB, BG, BH, BR, BW, BY, BZ, CA, CH, CL, CN, CO, CR, CU, CZ, DE, DK, DM, DO, DZ, EC, FE, EG, ES, Fl, GB, GD, GE, GH, GM, GT, HN, @ 4 June 2012 (04.06.2012) 25) Filing Language: English HR, HU, 1D, TL, IN, IS, JP, KE, KG, KM, KN, KP. KR, KZ, LA, LC, LK, LR, LS, LT, LU, LY, MA, MD, ME (26) Publication Language: English MG, MK, MN, MW, MX, MY, MZ, NA, NG, NI, NO, NZ, (00) Priority Da OM, PE, PG, PI, PL, PT, QA; RO, RS, RU, RW, SC, SD, PA 2011 00451 15 June 2011 (15.06.2011) pK SE SY, TH, TS, TM, TN, TR, (71) Applicant: HALDOR TOPSOE_ A/S [DK/DK]; Nymol- leve} $5, DK-2800 Kgs. Lyngby (DK). (84) Designated States (urless otherwise indicated, for every Find of regional protection available): ARIPO (BW, Gil, (72) Inventors; and GM, KE, LR, LS, MW, MZ, NA, RW, SD, SL, SZ, TZ, (75) InventorsApplicants. (or US only): MORSING, Per UG, ZM, ZW), Eiasiaa (AM, AZ, BY. KG, KZ, RU, TS, [DKIDK|; Presteager 10, DK-2950 Vedbak (DK). ‘TM), European (AL, AT, BE, BG, CH, CY, CZ, DE, DK, CHRISTENSEN, Kurt, Agerbaek [DK/DK]; Nondvangs- EE, BS, FI, FR, GB, GR, HR, HU, IE, 1S, IT, LT, LU, LV, parken 4, DK-3460 Birkerud (DK), LOJ, Lusi, Hindiyartl MC, MK, MT, NL, NO, PL, PT, RO, RS, SE, SL, SK, SM, [IDIDK|; Borgendiget 110, DK-2730 Heriev (DK), {Continued on newt pag (64) Title: HIGH FLOW CAPACITY CONDENSER TUBE FOR SULPHURIC ACID CONDENSATION. (57) Abstrnet: A condenser for condensing vapours of sulphuric acid contained 1¢{n process gas comprising a tube of an acid resistant material, configured for * having a process gas inlet proximate to one end, a process gas oulet proximate to the other end and an seid outlet proximate to the bottom end, said tubes com figured for extending through a cooling zone and said cooling zane configured for having a cooling medium infet and a cooling medium outlet, for a gaseous cooling medium being passed counter-curtenly to the process gus, characterized in tha the tube has a length of 7$:m to 12 m. I ~ RAAT avaval = = x S 5 a Ss ° = CONN ae PPP DAT f FigWO 2012/171824 A1 MII INN NI A A ‘TR), OAPI (BF, BI, CF, CG, ML, MR, NE, SN, TD, TG) before the expiration of the time limit for amending the claims and to be republished in the event of receipt of Published: ‘amendments (Rate 48.205) C1, CM, GA, GN,GQ, GW, __ with international search report (Art. 21(3))10 15 20 25 30 WO 2012/171824 PCT/EP2012/060514 Title: High Flow Capacity Condenser Tube for Sulphuric Acid Condensation The present invention relates to a condenser for sulphuric acid having an increased gas flow capacity. This is especially useful in connection with purification of sulphur containing flue gasses and off-gasses, where sulphur is present as sulphur trioxide and is removed as sulphuric acid, which is formed by condensation of the sul- phur trioxide / water containing gas. This process is called Wet gas Sulphuric Acid process, WSA. The WSA process has proven its value in industries like oil refining, metallurgy, petrochemicals production, coking, coal gasification, non-ferrous roasters and smelters, power plants and production of viscose fibers. It is known to remove sulphur from flue gas or off-gas by oxidising sulphur compounds to sulphur trioxide, and then cool the sulphur trioxide in the presence of the water in the gas to form sulphuric acid followed by condensation and concentration of the formed sulphuric acid. Oleum may be produced from a gas with a deficit of water compared to sulphur trioxide (less than one mole of water per mole of sulphur trioxide) or by subsequently absorbing sulphur tri- oxide in the produced sulphuric acid. In patent US 5,198,206 a desulphurisation process with ad- dition of particles to the process gas is disclosed and in US 5,108,731 a demister for use in condensation tubes for condensation of sulphuric acid mist is disclosed. In the10 15 20 25 30 WO 2012/171824 PCT/EP2012/060514 experimental data presented, the tubes are up to 6 m long and configured for evaluating the effect of the length of the cooling zone at 4.05 m, 4.45 m, 4.95 m and 5.4 m. With the length of the cooling zone being 5.4 m, it was found possible to obtain a satisfactory level of H,S0, after the tube in the range below 10 ppm. Furthermore, the use of a demister was found to effectively remove acid mist from the flow outlet. In the process according to the prior art, the capacity of a condenser was considered a function of the number of tubes provided in the condenser. With twice the number of tubes, the flow area will be doubled, and thus the associ- ated flow capacity will be doubled. Providing a WSA plant with extra tubes is naturally costly and space consuming too, and therefore there is a need to identify means of providing increased capacity with little or no increase in the space required. The limiting factor for the glass tube condenser capacity is the heat exchange capacity - i.e. how much gas that ef- fectively may be cooled in the condenser. In the prior art the tube length has been evaluated according to whether the removal of sulphur trioxide and sulphuric acid was suffi- cient. The tube length can be used also to increase the flow capa- city of a tube, since an increase in tube length will also increase the tube surface area, and thus the heat transfer area. The same heat transfer contact time can therefore be obtained with a higher flow rate, and therefore an in-10 15 20 25 30 WO 2012/171824 PCT/EP2012/060514 creased process gas capacity per tube proportional to the tube length was expected. However, with increasing length of the glass tube challenges relating to production and handling of the glass tubes are also increased, and there- fore glass tubes for sulphuric acid condensers have only been produced in 6 m and 7 m lengths corresponding to an active cooling zone of 5.45 m or 6.45 m. An analysis of the available means for increasing the gas flow capacity, while ensuring sufficient heat exchange with the gas has now surprisingly revealed that the effect of increasing the length of condenser glass tubes upon the heat exchange is significantly stronger than would be ex- pected from the increased tube surface area alone. An in- creased area allows for an increased flow rate inside the tube, and calls for an increased flow rate on the outside of the tube to provide sufficient cooling air. The combined effect of these factors is surprisingly that with an in- crease in tube length of e.g. 18% from 7 m to 8.25 m and a corresponding 19% increase in active cooling zone from 6.45 m to 7.7m, the thermal gas flow capacity is increased by 32-58%, which is far more than the expected proportional increase. The effect of this super-proportional effect of increased length is that the number of tubes for a WSA plant, e.g. for HyS removal from viscose production may be decreased without negative effects on the desulphurisation. This al- lows a reduction of the footprint of the condenser and may be related to a lower production cost too.10 15 20 25 30 WO 2012/171824 PCT/EP2012/060514 As used herein gas flow capacity of a condenser tube shall be understood as the mass flow rate of process gas in a tube, which allows sufficient cooling of the process gas. As used herein, process gas is to be understood as a gas comprising sulphur trioxide and water. As used herein, cooling medium is to be understood as a me- dium used for heat transfer without significant chemical reaction such as air. A cooling medium may in a different position in the process also be involved in chemical reac- tions. As used herein cooling zone shall be understood as a sec- tion of tube which is configured for having its outer sur- face contacted with a cooling medium during operation. As used herein concentrations of sulphur trioxide in gas form are stated as mol under the assumption that all hexavalent sulphur is present as sulphur trioxide, and therefore it includes sulphur trioxide as well as sulphur trioxide hydrated to gaseous sulphuric acid. The present invention provides a condenser for condensing vapours of sulphuric acid contained in a process gas com- prising a tube of an acid resistant material configured for having a process gas inlet proximate to one end, a process gas outlet proximate to the other end and an acid outlet proximate to the bottom end, said tubes configured for ex- tending through a cooling zone and said cooling zone con- figured for having a cooling medium inlet and a cooling me- dium outlet, for a gaseous cooling medium being passed10 15 20 25 30 WO 2012/171824 PCT/EP2012/060514 counter-currently to the process gas, characterized in that the tube has a length of 7.5 m to 12 m, a tube of an acid resistant material, configured for having a process gas inlet proximate to one end, a process gas outlet proximate to the other end and an acid outlet proximate to the bottom end, said tubes configured for extending through a cooling zone and said cooling zone configured for having a cooling medium inlet and a cooling medium outlet for a gaseous cooling medium being passed counter-currently to the proc- ess gas, characterized in that the tube has a length of 7.5 m to 12 m, preferably 8 m to 11 m and even more preferably having a length of @ m to 9m, with the associated benefit of an increased heat exchange with increasing length, ena~ bling an increased gas flow, while avoiding handling chal- lenges of excessive lengths. In an embodiment of the present disclosure further compris- ing a high velocity aerosol filter mounted in substantially tight connection with the condenser tube in the end of the cooling zone proximate to the process gas outlet, said fil- ter comprising fibres or filaments with a diameter of 0.05 to 0.5 mm, the fibres or filaments so being present in an amount, @ layer thickness and @ configuration such as to ensure that the pressure drop through the filter at a gas velocity of 1-7 m/sec will be between 2 and 20 mbar with the associated benefit that acid mist is condensed as drop- lets by contact with the aerosol filter. In a further embodiment, the present disclosure further comprises a turbulence generation means inside the tube, such as a spiral, glass indents or glass protrusions with10 15 20 25 30 WO 2012/171824 PCT/EP2012/060514 the associated benefit that increased turbulence increases the heat transfer at the inner tube surface. In a further embodiment the present disclosure is further configured for having a re-heating zone proximate to the process gas outlet with the associated benefit of providing a process gas downstream the condenser, having a tempera- ture above the sulphuric acid dew point, and thus substan- tially without presence of corrosive liquid sulphuric acid. In a further embodiment, the present disclosure is further configured for the condensed sulphuric acid flowing counter-currently to the process gas in the condenser by configuring the process gas inlet to be proximate to the bottom end of the tube with the associated benefit of a high sulphuric acid concentration, due to the counter- current flow. In a further embodiment, the present disclosure is config- ured for the condensed sulphuric acid flowing co-currently with the process gas in the condenser by configuring the process gas inlet to be proximate to the top end of the tube with the associated benefit of reducing the risk of flooding in the condenser tube and in the demister. In a further embodiment of the present disclosure, the con- denser comprises multiple condenser tubes having a distance between tubes of at least 1/3 of the tube diameter with the associated benefit of a lower pressure drop on the cooling medium side of the condenser.10 15 20 25 30 WO 2012/171824 PCT/EP2012/060514 In a further embodiment, the present disclosure relates to a process with two sulphuric acid condensers in series with an intermediate sulphur dioxide oxidation step with the as- sociated benefit of treating process gases with an extra high concentration of sulphur trioxide or with an extra low sulphur dioxide emission. In a further embodiment the present disclosure relates to a process with two sulphuric acid condensers in series with the first condenser operating with a deficit of water com- pared to the sulphur trioxide (less than one mole of water per mole of sulphur trioxide) and the second downstream condenser operating with a surplus of water compared to sulphur trioxide (more than one mole of water per mole of sulphur trioxide) with the associated benefit that oleum can be produced in the first upstream condenser. In an embodiment, the diameter of the condenser tube may range from 20 to 70 mm, preferably between 25 and 60 mm and even more preferably between 30 and 50 mm. With narrow tubes the benefit is related to increased heat exchange surface per cross sectional area, whereas wider tubes pro- vide lower pressure drops. In an embodiment, the process gas contains less than 2.0 % sulphur trioxide, and preferably less than 1.0 % sulphur trioxide with the associated benefit of an even increased super proportional effect of tube length with low concen- trations of sulphur trioxide. Figure 1 shows a condenser according to the present disclo- sure.10 15 20 25 30 WO 2012/171824 PCT/EP2012/060514 The present disclosure relates to a condenser 2, in which a process gas 20 flows inside tubes 4 and a cooling medium 22 flows outside the tubes 4. The inside of the condenser tubes 4 can be equipped with a spiral 8 or other turbu- lence-enhancing element. The tubes 4 can be made from glass, such as borosilicate glass, and are connected to the process gas inlet of the condenser by means of a bottom plate 10 having substantially airtight contact with the outside of the tubes 4 and their position is stabilised by baffle plates 12 across the condenser on the cooling medium side. At the process gas outlet 16 from the condenser, the tubes 4 are fixed and sealed against a top plate 14. The cooling medium 22, which typically can be air, will thus flow substantially in cross flow across the tubes 4. The cooling medium can be at a slightly higher pressure than the process gas to avoid leaks of corrosive process gas to the cooling medium side. At the end of the tubes an op- tional aerosol filter 30 may also be present. According to the prior art, the typical length of the cool- ing section of the tubes has been 4 to 6.5 m with the cor- responding length of the tubes being 5 to 7 m. According to the present disclosure, the tubes are 7.5 mor longer. When the length of the condenser tubes is increased, it becomes possible to increase the flow rate inside the tube, while having the same contact time between the process gas and the tube wall. With an increased gas flow rate in the tubes, it is possible to reduce the number of tubes for the same volumetric flow. With the present disclosure, we have further found that the effect of the increased volumetric flow inside the tubes is an increased heat transfer from10 15 20 25 30 WO 2012/171824 PCT/EP2012/060514 the process gas to the tube wall thus contributing to a su- per-proportional effect of the increased tube length. To be able to cool the process gas, it is also required that an increased flow of cooling medium is provided. The increased flow rate of cooling medium also increases the heat trans- fers on the outside of the tubes and thus contributes fur- ther to the super-proportional effect with respect to the tube length, while maintaining the ratio between the mass flows of process gas and cooling medium, Therefore, with increased tube length a surprising super-proportional in- crease of the heat transfer due to an increased flow rate of process gas and cooling medium is observed. With increasing $0; content, the contribution te the heat transfer from heat of condensation is increased. Therefore, the relative effect of increased flow rate is lower for high SO; levels. On the other hand for tubes with process gas flowing vertically upwards and with low SO; levels, the flooding in the demister or in the tubes becomes limiting, i.e. the process gas drives the condensed sulphuric acid towards the gas outlet of the condenser and the flow rate may no longer be increased. However, in processes where flooding becomes a limiting factor, it may be chosen to op- erate the condenser such that the process gas flows down- wards. This overcomes problems with flooding, but can re- sult in a lower concentration of sulphuric acid. Alterna- tively, with an upward gas flow the flooding limit in the demister may be increased by increasing the demister diame- ter or by using a more open demister material with a higher void fraction. It is also preferred to balance the flow rate, the tube diameter of the demister section and the void fraction of the demister such that the linear flow10 15 20 25 30 WO 2012/171824 PCT/EP2012/060514 10 rate is in the range 1-7 m/sec, and the associated demister pressure drop is less than 20 mbar. An upper limit of the increased flow rate inside the tubes exists due to potential flooding in the condenser tube i.e. the effect that with an increasing flow rate of gas, the condensed sulphuric acid may be drawn upwards and out of the glass tubes by the gas flow. The flooding limit inside the tubes may be increased by increasing the tube diameter or altering the shape or size of any turbulence generation means installed inside the tubes. Since the flow rate of the cooling medium is increased, the pressure drop over the condenser on the cooling medium side will also increase. To reduce or avoid this pressure drop, the distance between condenser tubes, may be increased. In a further embodiment, an optional demister may be posi- tioned at the exit of the cooling section of the condenser tube to prevent acid mist from leaving the condenser. This demister may preferably be positioned in a zone of the con- denser tube having a larger diameter to provide a demister zone with minimal pressure drop, which otherwise may be an increasing problem with increased gas flow rate. A further embodiment involves a condenser in which the process gas is re-heated in the last part of the condenser, such that corrosive liquid sulphuric acid not captured in the condenser is evaporated, and the risk of corrosion is reduced in the downstream equipment.10 15 20 25 30 WO 2012/171824 PCT/EP2012/060514 qi EXAMPLES In a validation of the performance of the disclosure, the heat transfer of different tube condensers has been evalu- ated for different gas composition. A zone for fastening the tubes in the condenser is necessary such that for a 6 m tube the effective cooling length is reduced by about 0.55 m to 5.45 m, a 7m tube has an effective cooling zone length of 6.45 m and an 8.25 m tube has an effective cooling zone length 7.7 m etc. Investigations of the heat exchange per- formance were made for 7 effective cooling zone lengths in the range 5.45 m to 11.45 m. The heat exchange was evaluated for compositions with 12% Or, 2% COz, 7-10% H20, 1.0%-5.5% SO: and Nz as balance. For all tube lengths for each $0; concentration, the flow was adjusted to obtain the same cooling medium outlet tempera- ture. The cooling medium outlet temperature varied slightly between the three investigated $0; concentrations. From Table 1 it is clearly seen that with increased tube length the flow may be increased to a higher extent than that expected from an assumption of proportionality. With increasing flow rate there will also be an increase in the pressure drop over the condenser both on the process gas side and on the cooling medium side. On the cooling me~ dium side the pressure drop is 16-200 mbar and it is as- sumed that a pressure drop below 100 mbar is acceptable, but for higher pressure drops there may be a need for coun- teracting the pressure drop by increasing the pitch, ee the distance between tubes in the condenser.WO 2012/171824 PCT/EP2012/060514 12 On the process gas side the pressure drop in the tube ranges from 5 to 200 mbar. Here the pressure drop may be problematic already from values around 60 mbar, and there- fore the tube diameter may have to be increased already with flows around 30 Nm’/h per tube. For tubes equipped with a demister, an additional pressure drop ranging from 4 to 347 mbar over the demister is ob- served. Again, this is mainly an issue of operational cost and to some extent, it may be ignored, but it may be bene ficial to counteract this increased pressure drop. This may be done by increasing the tube area in the section of the demister or by providing a more open demister material with a higher void fraction. Table 1 50; con- P#FESTIVE Gag Expected ‘ap de- tp to- bp coo- carne Sty gee Za arabe SE a alg ale Soren mer aber bar 1.008 5.45 10.78 205, a “ 16 re a ne a es) fore ote os tar 20s 22 1.08 2s 3 Loot t0as 6.20 20s iy Looe ances nes 208 D 2e0 7st TT 5 7 pw sss ak 208 3 pss 7.70 oes abt 2 ais as a 4 86 psn 94s st oe 2.50% 10.45 20.59 203 38 129 7 zisos nas mass 08a aio 5.508 5.45 208 “ o 7 5.508 6.45 12.07 ee “ ue aL cso) ones ase 8g 5.508 45 18.57 14.62 ee . 2 oe 55 5.508 9.45 22.55 16.35 oon 2 ue “ a sisoh toa 7.09 aon 208 6 8 on 5.508 11.45 19.81 208 7 ’ 210 15 20 25 30 WO 2012/171824 PCT/EP2012/060514 13 CLAIMS 1. A condenser for condensing vapours of sulphuric acid contained in a process gas comprising a tube of an acid re- sistant material, configured for having a process gas inlet proximate to one end, a process gas outlet proximate to the other end and an acid outlet proximate to the bottom end, said tubes configured for extending through a cooling zone, and said cooling zone configured for having a cooling me- dium inlet and a cooling medium outlet for a gaseous cool- ing medium being passed counter-currently to the process gas, characterized in that the tube has a length of 7.5 m to 12 m, preferably 8 m to 11 m and even more preferably having a length of 8 m to 9m. 2. A condenser according to claim 1 further comprising a high velocity aerosol filter mounted in substantially tight connection with the tube in the end of the cooling zone proximate to the process gas outlet, said filter comprising fibres or filaments with a diameter of 0.05 to 0.5 mm, the fibres or filaments so being present in an amount, a layer thickness and a configuration such as to ensure that the pressure drop through the filter at a gas velocity of 1-7 m/sec will be between 2 and 20 mbar. 3. A condenser according to claim 1 or 2 further compris- ing turbulence generation means inside the tube. 4. A condenser according to claim 1, 2 or 3 further con- figured for having a re-heating zone proximate to the proc- ess gas outlet.10 15 20 25 30 WO 2012/171824 PCT/EP2012/060514 14 5. A condenser according to claim 1, 2, 3 or 4 further configured for the condensed sulphuric acid flowing counter-currently with the process gas in the condenser, by configuring the process gas inlet proximate to be at the bottom end of the tube. 6. A condenser according to claim 1, 2, 3 or 4 further configured for the condensed sulphuric acid flowing co- currently with the process gas in the condenser, by config- uring the process gas inlet proximate to be at the top end of the tube. 7. A condenser according to any claim above having a con- denser tube diameter between 20 and 70 mm, preferably be- tween 25 and 60 mm and even more preferably between 30 and 50 mm. 8. A condenser according to any claim above comprising multiple condenser tubes having a distance between tubes of at least 1/3 of the tube diameter. 9. A condenser according to any claim of 1 to 7 condens- ing sulphuric acid from a process gas containing less than 2.0 % sulphur trioxide, and preferably less than 1.0 % sul- phur trioxide. 10. A plant for production of oleum comprising two sul- phuric acid condensers in series with the first condenser configured for operating with less than one mole of water per mole of sulphur trioxide and the second downstream con- denser configured for operating with more than one mole of water per mole of sulphur trioxide.41 CLL LL Ls AISA SF, FIG.1INTERNATIONAL SEARCH REPORT International application No PCT/EP2012/060514 te B61b8/60 "ESB 17/80 ADD. Acsordng o International Patent Ossafeaon IPO) er tbethnatonal elation and IPC Timm socurertatonserahad (ousafcaTon system flawedby Saretonion TOR) BO1D CO1B BOlJ F28B ‘locos da base coneued dura The Plaratonal searah (name dala base and, where pratoaile, sarah Wve used) EPO-Internal, WPI Data (DOCUMENTS CONSIDERED TO BE RELEVANT e907 ‘Caton of dosuret wih ndbaton, where appropri, of he relevant passeges Relevantto claim x WO 2009/094103 Al (DOW TECHNOLOGY 1 A page 5, paragraph 4 - page 8 pages 15, 16; example 1 figure 1A INVESTMENTS LLC [US]; RHODES CLYDE L [US]; SZUL JOHN F) 30 July 2009 (2009-07-30) 2-10 x Us 2010/068127 Al (SCHOUBYE PETER [DK]) 19 18 March 2010 (2010-03-18) A paragraphs [0041], [0046] page 5; table 1 1-9 x US 5 277 247 A (CAMERON GORDON M [CA]) 1-9 11 January 1994 (1994-01-11) colum 6, lines 13-34 column 7, lines 21-31 figures 1,3 colum 2, line 54 - colum 4, line 13 X] Further documents are ated inthe contruation of Box Di] span ne ~Spesalcaegorce of oted doauments ‘obo of pari mavanee sari: ppestion optet but planes ono ater he tran Sted enaotah te puctaton dae arater thon or ter Special reason (as soeathed) "0" document refering oan orl dsosure, use, exhbtion or other “F eeement pba pote tara fing dt but terthen st and notin cons with he appeaton ut etd To undertand ‘he panels or theory unserying be vention, ‘onadered hovel oeannot be conaderedto ive an vente SMtpwhon the document taken lone “Y dosumentf partulrrelevanos; he claimed invention sant be ‘anaderadfofalvean invents slep when the socuvert Somos wih one or mote cine uh documents, sun combination Sting dvious o's person sted nthe a ‘Date a th aul completion ofthe htemalonl seach 29 October 2012 Date ofmaing othe Wamaonal seach report 09/11/2012 ‘Namo and maling adres ofthe ISAT Tel 31-70 340-2000, Fax (a7 03016 Thahoraed fier Baumlin, Sébastien Fam POTENT fase hen ONO page 1 of 2INTERNATIONAL SEARCH REPORT International application No PCT/EP2012/060514 ‘iCantination), DOCUMENTS CONSIDERED TO BE RELEVANT Ccateg007 ‘Ctaton of dosument with inceaton where appropri, of he relevant passages Relevanto aime, x US 2004/141909 Al (CHRISTENSEN KURT AGERBAK [DK] ET AL CHRISTENSEN KURT AGERBAEK [DK] ET) 22 July 2004 (2004-07-22) paragraphs [0016], [0017] figure 1 US 5 108 731 A (SCHOUBYE PETER [DK]) 28 April 1992 (1992-04-28) cited in the application column 5, lines 17-33 colum 5, line 65 - colum 7, line 24 figures 2-4 table 1 GB 2 117 368 A (TOPSOE HALDOR AS) 12 October 1983 (1983-10-12) page 2, line 34 - page 3, line 14 page 4; example 1 Figures 1,3 US2007/110663 Al (CHRISTENSEN KURT A [DK] CHRISTENSEN KURT AGERBAEK [DK]) 17 May 2007 (2007-05-17) paragraphs [0054], [0055] figure 2 WO 2010/069461 A1 (TOPSOE HALDOR AS [DK]; SCHOUBYE PETER [DK]; THELLEFSEN MORTEN {DK]) 24 June 2019 (2010-06-24) page 1, lines 4-15 page 3, line 7 - page 4, line 11 page 5, lines 13-24 page 9, lines 17-22 figure'1 GB 142 522 A (PAUL AUDIANNE) 7 May 1920 (1920-05-07) the whole document 1-9 1-9 1-9 1-9 1-9 1-9 Fam PETER nn ein a page 2 of 2INTERNATIONAL SEARCH REPORT International application No mation on patent family members PCT/EP2012/060514 Patent cooument Prbleaton Patent family Publeaton cited sarah report cate members) cate WO 2009094103 Al 30-07-2009 CA 2712985 Al 30-07-2009 CN 101925387 A 22-12-2010 EP 2247355 Al 10-11-2019 TW 200940151 A 01-10-2009 Us 2012088940 Al 12-04-2012 WO 2009094103 Al 30-07-2009 US 2010068127 Al 18-03-2010 2009213076 01-04-2010 BR 10903398 A2 13-03-2012 cA 2678416 Al 12-03-2010 CN 101683973 A 31-03-2010 ep 2163515. A2 17-03-2010 PE 05772010 Al 19-09-2010 RU 2009134062 A 20-03-2011 Us 2010068127 Al 18-03-2010 ZA 200906261 A 29-09-2010 US 5277247 A —-*11-01-1994 AU “4130293 A 20-01-1994 CA 2094783 Al 30-12-1993 us 5277247 A 11-01-1994 ZA 9304376 A 01-02-1994 US 2004141999 Al 22-07-2004 AT 396146 15-06-2008 cA 2453811 Al 18-07-2004 CN 1519194 A 11-08-2004 EP 1443022 Az 04-08-2004 ES 2305395 13 01-11-2008 UP 2004224689 A 12-08-2004 kR 20040067891 A 30-07-2004 NX pag4000477 A 23-07-2004 RU 2350551 C2 27-03-2009 TW 1259167 B 01-08-2006 US 2004141909 Al 22-07-2004 US 5108731 A 28-04-1992 AU 621908 B2 26-03-1992 AU 3779889 A 05-01-1990 BR 8907463 A 21-05-1991 cA 1338816 C 31-12-1996 CN 1038796 A 17-01-1990 cs 8903346 Az 13-08-1991 oD 283791 AS 24-10-1990 DE 68912776 D1 10-03-1994 DE 68912776 T2 18-08-1994 ok 168702 B1 24-05-1994 EP 0417200 AL 20-03-1991 ES. 2012727 AG 01-04-1990 HU 208290 B 28-09-1993 IE 62709 B1 22-02-1995 oP 2758470 B2 28-05-1998 JP HO3504714 A 17-10-1991 NO 905183 A 29-11-1990 PL 163844 B1 31-05-1994 sk 281808 B6 06-08-2001 TR 26606 A 04-05-1994 US 5108731 A 28-04-1992 WO 8912024 Al 14-12-1989 GB 2117368 A 12-10-1983 CA 1205614 10-06-1986 Fam PETER ae ay ano) RPT) page 1 of 2INTERNATIONAL SEARCH REPORT mation on patent family members International application No US 2007110663 WO 2010069461 GB 142522 A AL Al 17-05-2007 24-06-2010 CN us WO 07-05-1920 8301537 A 102257346 PCT/EP2012/060514 Patent cooument Prbleaton Patent family Publeaton cited sarah report cate members) cate DE 331079 Al 29-09-1983 ok 136182 A 26-09-1983 FR 2523948 Al 30-09-1983 6B 2117368 A 12-10-1983 JP 59018103 A 30-01-1984 26-09-1983 23-11-2011 2011247793 AL 13-10-2011 2010069461 AL 24-06-2010 Fam PETER ae ay ano) RPT) page 2 of 2