(12) INTERNATIONAL APPLICATION PUBLISHED UNDEI (19) World Intellectual Property Organization International Bureau (43) International Publication Date 19 May 2008 (19.05.2008) PCT ‘THE PATENT COOPERATION TREATY (PCT) (10) International Publication Number WO 2005/044742 Al (61) International Patent Clasifeath COI 17100, C12 300 CORK 3/34, 21) Internation: PCT/NL2004/000791, (2) International Filing Dai 11 November 2004 (11.11.2008) (25) Filing Language: English (26) Publication Language: English G0) Priority Data: OBOTSSS1.3 LI November 2003 (11.2003) (71) Applicant (or all designated States except US BLY. [NLINL] T-de Boerstraat 24, NL-8561 EI (72) Inventors; and (75) Inventors/Applicants (fr US only): HUISMAN, Jacob, [Leendert [NLINL; Pijkruidhof 9, NL-8446 BV Heeren veen (NL). BUISMAN, Cees, Jan, Nieo [NLINL: Stin senviei I, NL-8571 RH Harich (NL), 4) ay ss) ) Agents: VAN WESTENBRUGGE, Andrles tl; Ned. erlandsch Octroibureau, Scheveningsewes 82, PO. Box 29720, NL-2502 LS The Hague (NL), ) Designated States (unless otherwise indicated, for every ind of national protection available): NB, AG, AL, AM, AT, AU, AZ, BA, BB, BG, BR, BW, BY, BZ, CA, CH, CN, C0, CR, CU, CZ, DE, DK, DM, DZ, EC, EE, BG, BS, GB, GD, GE, GH, GM, HR, HU, ID, IL, IN, IS, IP, KE, KG, KP, KR, KZ, LC, LK,LR, 18, LT, LU, LV, MA, MD, MG, MK, MN, MW, MX, MZ, NA, NI, NO, NZ, OM, PH, PL, PI, RO,RU, SC, SD, SE,8G, SK, SL S¥,1J, TM. TTN.TR, TT, TZ, UA, UG, US, UZ, VC, VN, YU,ZA,ZM, mW. Designated States (unless otherwise indicated, for every kind of regional protection available): ARIPO (BW, GH, GM, KE, LS, MW, MZ, NA, SD, SL, SZ, TZ, UG, ZM. 2), Burasan (AM, AZ, BY. KG, KZ, MD, RU, TI, TM), European (AT, BE, BG, CH, CY, CZ, DE, DK, EE, ES, I FR, GB, GR, HU, IE, IS, T, LU, MC, NL, PL, PI, RO, SE, SISK, TR), OAPI(BF, BJ,CF.CG, Cl, CM, GA,GN, GQ. GW, ML, MR, NE, SN, TD, TG {Continued on next pagel © 2005/044742 A1 IIIT ($4) Title: PROCESS FOR THE BIOLOGICAL TREATMENT OF SULPHUR SALTS. _ Recycle _ Blood sur |-+! sattor L Go2_|Onstaliser| ‘Sule conning ‘ation orgs —+) oniding Hedico2 Torreuse aticos | NaHCO 602 dr other als Dyer (for prtcontol) Aroroe ‘Nutents Dry waco sure 1 (87) Abstract: The invention provides a process for the treatment of sulphur-containing sats by converting, ee in the case of| treatment of sulphate, the sulphur-containing salto a sulphide salt solution, and biologically oxidising the sulphide salt to clement sulphur and alkali using an alkali metal canon concentration between 2 and 8 M and preferably at pH of between 9 and 12. The clerental sulphur is separated off andthe alkalis neutralised with an acid form of a buffering compound, especially carbon dioxide, resulting in slid alkali metal (bicarbonate which ean be recovered,WO 2005/044742 Al For two-letter codes and other abbreviations, refer ta the "Guid- ‘ance Notes on Codes and Abbreviations” appearing at the begin ning of each regular issue of the PCT Gazette. Published: = with imemational search eport = before the expiration of the time limit for amending the claims and to be republished in the event of receipt of ‘amendments10 18 20 25 30 WO 20051044742 PCT/NL.2004/000791 PROCESS FOR THE BIOLOGICAL TREATMENT OF SULPHUR SALTS Field of the invention The invention relates to the treatment of sulphur-containing salts using biological oxidation with the possibility of recovering dissolved salts Background Liquid and dissolved forms of sulphur salt are released in many different processes. An example of a dissolved oxidised sulphur salt is sodium sulphate. This is commonly formed when sulphuric acid is neutralised with caustic soda. Under many circumstances, such highly concentrated salt streams cannot be released into the environment. Consequently, at the expense of huge energy consumption, water is evaporated to obtain a solid salt. Another common way to treat such a stream is by adding a calcium salt, resulting in the formation of gypsum (CaSOs.2H,0). ‘An example of material that contains reduced sulphur is the slag that is formed by certain smelting processes. Such slag contains among others sodium sulphide. This slag is unstable against leaching when land filled. Another example of a stream with reduced sulphur is spent caustic (hydrogen sulphide dissolved in sodium hydroxide-solution), A process for eliminating sulphur dioxide or hydrogen sulphide from gases through absorption of these sulphur compounds in an alkaline washing liquid containing (bicarbonate, optionally reducing sulphite and sulphate to sulphide and biologically oxidising the sulphide salts to elemental sulphur is described in WO 92/10270. The biological oxidation is carried out after adjusting the concentration of buffer to 20-2000 meq/l (in case of sodium carbonate: 1-70 g/l = 0.02-1.3 M Na) and at a pH of 6-9. The resulting desulphurised liquid containing carbonate and bicarbonate is returned to the gas washing step. WO 97/43033 discloses the use of particular alkaliphilic bacteria in oxidising sulphide to clemental sulphur at a pH of 9-11, using lye or soda where necessary for pH adjustment. Description of the invention Jt has been found that sulphur-containing salts, such as sodium sulphate and sodium sulphide waste and slags, can be treated efficiently to produce elemental sulphur and sodium carbonate and bicarbonate, each of which can be useful materials. Thus, the invention pertains to a process of desalination and desulphurisation and recovery of sodium (or other) salts and sulphur. The process converts alkali metal salts of oxidised and reduced sulphur (¢.g. sodium sulphate, sodium sulphite, sodium sulphide ete.) toWO 20051044742 PCTINL2004/000791 10 1s 20 25 30 35 elemental sulphur and dissolved carbonate, followed by the recovery of the carbonate as the solid alkali metal carbonate salt. An important step in this process is the biological partial oxidation of the sulphide to elemental sulphur according to the following equation: Nat +HS'+%O) > Na“+S°+OH (1) where sodium (Na’) can also be another alkali metal such as potassium or lithium, or alkaline earth metal, or a mixture of sodium with such other metal(s). The conversion can be carried out at a total cation concentration up to 8 M, preferably in the range of 2 to 4M. In case of sodium, a particularly useful concentration is between 2 and 6.4 M. Metal cation concentrations can be measured by standard methods, including e.g Inductive Coupled Plasma, after suitable dilution where necessary The conversion can be carried out in the range from pH 7 to pH 13, though the preferred pH is from pH 9 to pH 12, especially about 10.5. The reaction is carried in a bioreactor, and, in principle, the reaction can occur between 0 and 100°C, though preferably at 25 — 35°C. The pH can be adjusted using the redox potential of the medium as described in WO098/04503; thus the redox potential can be adjusted between —300 and —350 mV using a platinum-coated electrode and an Ag/AgCl reference electrode. ‘The bacteria required for the biological oxidation of sulphide should be resistant to and active under the alkaline pH and the high salt concentrations, Suitable bacteria are halo- alkaliphilic sulphide-oxidising bacteria, Several of such bacteria are known and have been obtained from soda lakes. They include the genera Thi(o)alkalivibrio, Thialkali- microbium, Thi(o)alkalispira and Thioalkalicoccus. Examples are Thialkalivibrio versutus (DSM 13738) (AL2), Tv. nitratis (DSM 13741), Tv. denitrificans\(DSM_ 13742), Ty. paradoxus (DSM 13531), Ty. thiocyanoxidans (DSM 13532), Tv. jannaschii (DSM 14478), Thialkalimicrobium aerophilum (DSM 13739) (AL3), Tm. sibiricum (DSM 13740), Tm. cyelicum (DSM 14477) and Thialkalispira microaerophila (DSM 14786). Moderately haloalkaliphilic sulphur-oxidising bacteria and their use in oxidation of sulphide have also been described in WO97/43033. The alkalinity that is formed during this conversion can be neutralised by an acid, in particular carbon dioxide (CO;), in order to keep the pH in the reactor constant. When pH control with carbon dioxide is applied, the overall conversion can be written as follows (neglecting the formation of biomass): Na‘ + HS" +% 02 + CO)» Na*+S°+HCOs (2) Bicarbonate (HCOs) is in equilibrium with carbonate (C03): Na’ +HCOs <=> Na’ +H"+C0;*10 1s 20 25 30 35 WO 20051044742 PCTINL2004/000791 ‘The actual concentration of both species depends on the pH. ‘The elemental sulphur (S*) is separated from the liquid as a solid, It may be disposed or used for the production of sulphuric acid. The liquid resulting after separation of elemental sulphur is loaded with a bicarbonate/carbonate solution, and is then led to a device that recovers the bicarbonate/carbonate as a solid, especially as sodium carbonate and/or bicarbonate, Several methods for recovering carbonate and bicarbonate salts ate possible, including the following: 1) Water is evaporated and a mixture of sodium carbonate and sodium bicarbonate is recovered. This is the least preferred method of the four, as it requires a lot of energy. 2) The pH of the liquid is lowered, preferably with carbon dioxide (CO.). The pH drop and the presence of additional dissolved CO» results in an increase of the dissolved bicarbonate: 3 Na’ + HCOs + COs” + CO>(g) + Ha <==> 3 Na* +3 HCOs {As the solubility of sodium bicarbonate, certainly per sodium ion, is much lower than the solubility of sodium carbonate, it is possible in this way to supersaturate the solution with sodium bicarbonate, resulting in the crystallisation of this compound. This can be done by decreasing the pH to between 5.5 and 11, preferably to between 6 and 9, especially about pH 7. The solid sodium bicarbonate can be separated from the liquid and dried, If required, the sodium bicarbonate can be converted to sodium carbonate by heating the solid until water vapour and carbon dioxide are released. These compounds can be recycled back to the process, as a liquid and/or as a gas. 3) By lowering the temperature, a supersaturation of sodium carbonate can be obtained. This is possible because the solubility of sodium carbonate has a much more pronounced temperature dependency than the solubility of sodium bicarbonate. For example, the solubility of sodium bicarbonate drops from about 1.1 to about 0.8 M upon cooling from 30° to 10°C, while the solubility of sodium carbonate drops from about 1.35 to about 0.45 M upon the same cooling. This method is especially favourable when the conversion of reaction (2) has occurred at the upper range of the indicated pH range (pH 6 to 13). The temperature can be lowered from the temperature at which reaction (2) has occurred down to close to the freezing point of water, e.g. to between 0 and 10°C, 4) By raising the pH to between about 11 and 13, together with lowering the temperature to about 10°C (e.g. between 5 and 15°C). In this way, sodium carbonate is obtained above its solubility limit, and thus precipitates. This method has the advantage of saving a calcination step when producing solid sodium carbonate,10 1s 20 25 30 35 WO 2005044742 PCTINL2004/000791 ‘The methods above can also be combined for an optimum result, ic. the temperature is lowered, some water is evaporated and the pH is lowered. The liquid remaining after the crystallisation of solid sodium carbonate or bicarbonate (supernatant) can be used for dissolution of material containing solid sodium sulphide or for dilution or pH adjustment of the influent sulphur containing stream. Although sodium is the preferred cation to be removed and recovered, the process can also be applied to other metals such as potassium; in this case, higher concentrations and/or lower temperatures are applied in the salt recovery steps as described above, because of the higher solubility of potassium (bicarbonate; e.g. a factor of 1.5 or 2 on concentrations, or a temperature decrease of 10°C, or a pH adjustment. Although in most applications it is preferred to separately recover elemental sulphur and sodium (bicarbonate, it is also possible to combine the precipitation of elemental sulphur and (bicarbonate, e.g. in small-size desulphurisation plants. This can be done by adding carbon dioxide before the separation of sulphur, e.g. immediately after the bioreactor, or, preferably while biologically oxidising the sulphide, ic. in the bioreactor. This allows the process to be carried out in a simplified manner, applying conditions in the bioreactor, especially a pH between about 7 and 9 eg. resulting from adding CO2 {nto the bioreactor, that result in simultaneous formation of elemental sulphur and crystallisation of bicarbonate. The sulphur and bicarbonate can then be separated off in a single step. This embodiment is particularly advantageous in special industrial plants producing spent caustic or similar unwanted by-product streams, such as refineries at remote loc: otherwise problematic. rions, where water supply and liquid waste disposal are expensive or ‘A central step in the process of the invention is the provision of a solution containing sulphide ions, in particular a solution of sodium (hydrogen) sulphide. Depending on the origin of the sulphide, this sulphide-containing solution is produced by different pre- treatments, First, if the sulphide originates as a solution, no further pre-treatment will be necessary other than proper dilution or concentration or adjustment of pH or temperature, If the sulphide is produced as a solid or semi-solid, the (semi)solids are mixed with the supernatant from the carbonate recovering step, make-up water and pH control agents, resulting in a sulphide-containing solution. In case of gaseous sulphide, ie. hydrogen sulphide and/or carbonyl sulphide, the gas is scrubbed with an aqueous liquid at the appropriate pH, for example as described in WO 92/10270, resulting in a sulphide solution.WO 2005044742 PCTINL2004/000791 10 15 20 25 30 35 In a special embodiment, the sulphur-containing salts are oxidised sulphur salts, especially sulphite or sulphate or thiosulphate, which, prior to the treatment as described above, are reduced to sulphide according to the following equation: 2Na" + SO) + 8H" +8¢> 2Na” +S* +4 HO The eight electrons (¢-) are supplied by hydrogen or another electron donor like ethanol. In the case of hydrogen, the electrons are formed as follows’ 4ih> SH'+8e Both reactions are preferably carried out using bacteria. The conversion can be carried out at a total cation concentration up to 8 M, preferably in the range of 2 to 4 M. The conversion can be carried out in the range from pH 1 to pH 13, though the preferred pH is from 5 to 9, especially from 6 to 8. The preferred temperature is in the range of 20 — 35°C, Here again, the starting salts may be provided as a solution, only requiring adjustment of concentration, temperature and /or pH, or as solids, requiring appropriate mixing and dissolution, or as a gas, in particular sulphur dioxide, requiring scrubbing with an aqueous liquid e.g. as described in WO 92/10270. Bacteria capable of reducing sulphate and other oxidised sulphur species to sulphide include Desulforomonas sp. (mesophilic), Desulfotomaculum KT7 (thermophilic), the species Desulforolobus ambivalens, Acidianus infernus, Acidianus brierley, Stygiolobus azoricus (mesophilic), Thermoproteus neutrophilus, Thermoproteus tenax, Thermo- discus. maritimus (thermophilic), Pyrobaculum islandicum, Pyrodictium occultum, Pyrodictium brockii (hyperthermophilic), and other species of the genera Desulfovibrio, Desulfotomaculum, Desulfomonas, Desulfobulbus, Desulfobacter, Desulfococcus, Desulfonema, Desulfosarcina, Desulfobacterium and Desulforomas (mesophilic), and species of sulphur-reducing methanogenic bacteria such as from the genera Methano- coccus and Methanobacterium. It is prefered however, that the sulphate-teducing bacteria tolerating high salt concentrations. These include species of the genera Desulfovibrio, Desulfonatronovibrio and Desulfohalobium e.g. Desulfonatronovibrio hydrogenovorans (DSM. 9292), Desulfovibrio halophilus (DSM. 5663), Desulfovibrio salexigens (DSM 2638) en Desulfohalobium retbaense (DSM 5692). Electron donors to be used in the biological sulphate reduction can be hydrogen, carbon monoxide, alcohols, fatty acids and other readily degradable organic matter, as known in the art The sulphate reduction prior to the sulphide oxidation can e.g. be applied in case of concentrated sodium sulphate solutions issuing from reversed osmosis plants used for desulphurising sulphate-containing water. The reversed osmosis yields highly purified water, but it also produces a concentrated sulphate effluent, This effluent can be10 15 20 25 30 35 WO 2005044742 PCTINL2004/000791 advantageously treated using the process of the invention, and is then be disposed of or retumed to the reversed osmosis Description of the figures Figure 1 shows the flow sheet for the conversion of a dissolved alkali sulphide. The stream originally containing sulphide passes through a sulphide-oxidising bioreactor for oxidising the sulphide to sulphur, a sulphur settler for separating off elemental sulphur, a bicarbonate crystalliser and a bicarbonate dryer. The resulting carbonated water can be reused in the bioreactor. Figure 2 shows a similar flow sheet for solid material containing dissolvable sulphide salts. The installation of figure 1 is then preceded upstream by a solids dissolving unit and a separator for removing non-dissolved material. ‘The recycle in both flow sheets is optional. The bleed is required to let out surplus water and to bleed of accumulating salts. The location that is shown is an example. The bleed can be located anywhere in the liquid loop. Figure 3 shows a flow sheet for the conversion of sulphate salts, comprising biological reduction as a prior step compared to the flow sheets of figures 1 and 2 carried out in an anaerobic sulphate-reducing bioreactor Example: Soda slag from a company that recycles car batteries by pyrometallurgical means was, dissolved in water. The solution was clarified from particles by settling. It contained about 75 g/l of sodium (3 M) and 45 g/l of dissolved sulphide. It was fed together with a nutrient solution containing among other a nitrogen and a phosphorous source to a continuously operating 5 litre bioreactor at a temperature of 30°C containing Thifo)- alkalivibrio strains comprising strain DSM 13738. A gas recycle over the bioreactor ensured mixing, Oxygen was added to the gas recycle in order to maintain the redox potential in solution to a value between -100 and -450 mV, preferably -360 to -430 mV ‘measured with a platinum electrode against an Ag/AgCl! reference electrode, The pH ‘was measured with a glass electrode. It was controlled at a value between 9 and 12, in particular at about 10.5 through the injection of CO» gas in the gas reeycle. Thi(o)alkali- vibrio bacteria converted the dissolved sulphide to elemental sulphur. Effluent from the bioreactor was led through a settler where the sulphur was separated from the liquid. ‘The effluent of the settler was treated batch-wise with COp gas and the treated effluent ‘was cooled to ambient temperature to precipitate the major part (>60%) of the original sodium as crystalline NaHCO; as described above leaving approx 1 M of sodium in solution.WO 2005/044742 PCT/NL.2004/000791 Claims 1. A process for the treatment of sulphur-containing salts by converting, where necessary, the sulphur-containing salt to a metal sulphide salt solution, biologically oxidising ‘the sulphide salt to elemental sulphur and alkali and neutralising the alkali and separating the elemental sulphur, characterised by carrying out the biological oxidation at a metal cation concentration between 2 and 8 M and at a pH of between 7 and 13 and by neutralising the alkali wit acid form of a buffering compound. 2. Aprocess according to claim 1, in which the acid form of the buffering compound is carbon dioxide. 3. Aprocess according to claim 1 or 2, in which an alkaline form of the buffering compound is recovered from the solution in solid form. 4, Aprocess according to claim 3, in which solid carbonate and/or bicarbonate is recovered by adding further carbon dioxide and/or lowering the temperature of the solution 5. A process according to claim 4, in which further carbon dioxide is added until a pH of between 5.5 and 8.5 is reached. 6. A process according to any one of claims 1-5, in which the biological oxidation is carried out at a pH between 9 and 12. 7. Approcess according to any one of the preceding claims, in which the biological oxidation is carried out at a pH between 9.5 and 11, and/or a temperature between 25 and 35°C, and/or a metal cation concentration between 2 and 4 M. 8. A process according to any one of the preceding claims, in which the biological oxidation is carried out using haloalkaliphilic bacteria, especially of the genera Thialkalivibrio and/or Thialkalimicrobiuam. 9, A process according to any one of the preceding claims, in which the sulphur- containing salt comprises sulphate and/or thiosulphate and/or sulphite and said sulphate or sulphite or thiosulphate is converted to a sulphide salt solution by biological reduction. 10. A process according to claim 9, in which the biological reduction is performed using bacteria of the genera Desulfovibrio, Desulfonatronovibrio and/or Desulfohalobium. 11, A process according to claim 9 or 10, in which the biological reduction is carried out at a pH between 5 and 9, and/or a temperature between 20 and 35°C, and/or a cation concentration between 2 and 4 M.WO 2005044742 PCTINL2004/000791 12. 13, A process according to any one of claims 1-10, where the metal cation comprises sodium, A process according to any one of the preceding claims, in which carbon dioxide is added while biologically oxidising the sulphide salt, and solid carbonate and/or bicarbonate are separated with the elemental sulphur.PCT/NL.2004/000791 WO 2005/044742 3 oo | aning eoozeN hig squalgny ZO 40417 (souoo-}4d 404 ) wohg |, pyge 48490 10 ZOD €OOHEN | : £00HEN ls sn 0} 209/0ZH 4ojoea/01q Busipxo + seB10 ‘epying. uognjos Buyuquos epyng Jasqpeystig| €9 Jeyjes anyins peed ‘10h0% L 64PCT/NL.2004/000791 WO 2005/044742 Bupeyemep 0} Spilos- | anyns, s0ozeN Aig sjueLjnN Z0 10.1 (touoa-Hd 404 ) Jekig pyoe 104j0 10 ZOD EOOHEN | E09HEN ‘sna 10} zOO/OZH sq880019 Buysipixo \(soquo9-H1d 40} ) 9pyins z09 uognjossip ZOO spijog =—Bers pyjos 4osmeysAg 49/198, r) uoyesredes anyins Spjos Sz seqein dn-oyeW peeig epohoay zZ 4PCT/NL2004/000791 WO 2005/044742 oO | anyng e0ozen Aig squeujny — 4ou0p ‘s]ueLAnN L woqo913 z0 40.41y (ronuos-Hd 404 ) Jetua pape 104700 200 | EOOHEN £0OHEN ‘sna Jo} 200/02H 4oj8e1019 Joyoe9101q uognjos BUISIPKO J~— uogrjos —) 5u0NPeL }=—— Bujunuco puns | Guunuco epying | 24S apyjns 40 e7eying sesestio| 89 [jones anying peed 210hoey € 614INTERNATIONAL SEARCH REPORT Inter al Appaton No Pci, NL 2004/000791 OCU Aa CeTbi7/00 —cizp3/00 ozone rersonal alent lestcabon (PC) orto bth nation! sition an PO '. FIELDS SEARCHED Taney decantation Soaehed (Sapalzaon ja otowed by easton DOB) IPC 7 CO2F CO1B C1ZP TSS SET ON a TT CSET To a Ha al HOG) SOSA AS TED We FIGS ST ‘eon da bas neue during aaa oar (ato Gala aso and, Whore PAO Sai ToT wa) EPO-Internal _ DOCUMENTS CONSIDERED TO BE RELEVANT ‘Galego | Ctaien ot doctmert, wih eaten, where appropiate rsvan passages oteanto an No. Wo 92/10270 A (PACQUES BV) 1 25 dune 1992 (1992-06~25) 9. cited in the application ‘the whole document | | | | | WO 96/30110 A (BUISMAN CEES JAN NICO 1-13 3PACQUES BV (NL)) | 3 October 1996 (1996-10-03) | the whole document | Wo 94/29227 A (BUISNAN CEES JAN NICO 113 | ;PACQUES BY (NL)) | 22 December 1994 (1994-12-22) | the whole docunent i} | | X] Furtercooimens are tstoain ho conuaon of tox. Di] Patt tana emir a stdin anno. * Speia egpies of ed documents Paty cama pbahed ae the intraoral ng ae ‘rpterty de ard cn ect wake apleaen Bet “a ae ue tse einen Seeianantasia okay areas scoctontene amet ine aoecasiiaen aceon ene | |. | am eee animacion aga aarti meron oer + ceuetnmamrter gz eee Sac nceeresata tera ai crt Sec, Se ae eee wenvaemanunte sans ~ cemaneeere mone reuse, extibon or ‘eoument combined wit one or mar *0” documenta oan orl doa ‘marmot Imani such combination beng obvcus Toa parson Sled *P* documant published proto tha nematic ing de ba iehear : Loe ‘lerthan tbe pry date camo 18 cecaent member ofthe sare pata tami ‘Die ote chal competion ofthe ieratonal search ‘ata of mang he erainal search opt 1 March 2005 17/03/2005 ‘Ware and mating adress ofthe SA ‘hare oes Eyopean Paton ice, PB. 818 Patan 2 HEE Ocoee sa 200, T9651 ep Fac oi) 0-016 Vogt, T Sen FOTRENO Gea Garon BO page 1 of 2INTERNATIONAL SEARCH REPORT Tntga onal Appleton No PCi,'NL2004/000791 ‘{Cortinaton) DOCUMENTS CONSIDERED TO BE RELEVANT Cog ‘lato cima wh al, whos sppopale, oe aN sea Rae Soa Y WO 97/43033_A (BUISMAN CEES JAN NICO ;0ANSSEN JOZEF HENDRIK (NL); ROBERTSON LESLE) 20 November 1997 (1997-11-20) cited in the application the whole document WO 99/06328 A (JOHNSON TERENCE LESLIE 3CSIR (ZA); GERBER ANDRIES (ZA); MAREE JOHA) 11 February 1999 (1999-02-11) the whole document Fan POTTonate sateen eat page 2 of 2INTERNATIONAL SEARCH REPORT Patent document ciladin sare port wo 9210270 A Wo 9630110 A wo 9429227 A 22-12-1994 ints ona Appicalon No pee eee erate Pc. PNL2004/000791 Publeaton Paton family Prubleaon ne members) eat 25-06-1992 NL 9002661 A (01-07-1992 aT 113497 T 15-11-1994 AU 648129 B2 14-04-1994 AU 9067291 A 08-07-1992 BG 61069 B1 31-10-1996 BG 97844 A 27-05-1994 BR 9107117 A 22-02-1994 CA 2096660 AL 05-06-1992 CZ 9301058 A3 19-01-1994 DE 69104997 D1 08-12-1994 DE 69104997 12 23-03-1995 DK 561889 13 05-12-1994 fe 2976 Bi 15-04-1997 EP 0561889 AL 29-09-1993 ES 2062883 73 16-12-1994 FI 932534 A 09-07-1993 HU 64875 A2 28-03-1994 JP 7075685 B 16-08-1995 oP 8807235 T 21-10-1993 KR 9610378 BI 31-07-1996 wo 9210270 AL 25-06-1992 No 931943 A,B, 28-05-1993 PL 168365 B1 29-02-1996 RU 2089267 C1 10-09-1997 US 5354545 A 11-10-1994 03-10-1996 NL 9500577 A 01-11-1996 AU 691097 B2 07-05-1998 AU 4958096 A 16-10-1996 CA 2216461 AL 03-10-1996 CZ 9702982 A3 15-04-1998 DE 69603838 D1 23-09-1999 DE 69603838 72 20-01-2000 EP 0814894 AL 07-01-1998 Wo 9630110 AL 03-10-1996 No 974378 A 20-11-1997 Nz 303302 A 28-01-2000 PL 322381 Al 19-01-1998 RU 2164167 C2 20-03-2001 Us 5976868 A 02-11-1999 9301000 A 02-01-1995 aT 148082 T 15-02-1997 AU 673753 B2 21-11-1996 AU 6937994 A 03-01-1995 BG 61602 BL 30-01-1998 Be 100205 A 29-11-1996 BR 9406771 A 27-02-1996 CA 2164090 AL 22-12-1994 CN 1125432 Ac 26-06-1996 CZ 9503249 a3 17-04-1996 DE 69401586 D1 06-03-1997 DE 69401586 T2 22-05-1997 ok 702663 13 30-06-1997 EP 0702663 AL 27-03-1996 Es 2096474 73 01-03-1997 FL 955915 A 08-12-1995 HU 77974 Ae 28-01-1999 so page 1 of 2INTERNATIONAL SEARCH REPORT formation en patont ary members Tec onal Appilaton No Pc. FnL2004/000791 Patent document cota in search reper: wo 9429227 WO 9743033 A wo 9906328 A Publeation cae 20-11-1997 7A 2693272 B2 8506271 T 9429227 AL 954862 A 311869 AL 2109692 CL 5637220 A 713082 B2 2714197 A 9708944 A 2253936 AL 1218421 A.C 69706179 D1 69706179 T2 914192 13 9800391 A. 0914192 AL 2161461 13 9743033 AL 985151 A 329723 Al 2162729 C2 6156205 A 8636198 A 9906328 AL 6306302 B1 9806902 A Patontiamily Publication member(s) ‘aie 24-12-1997 09-07-1996 22-12-1994 08-12-1995 18-03-1996 27-04-1998 10-06-1997 25-11-1999 05-12-1997 03-08-1999 20-11-1997 02-06-1999 20-09-2001 02-05-2002 08-10-2001 15-06-1999 12-05-1999 01-12-2001 20-11-1997 06-01-1999 12-04-1999 10-02-2001 05-12-2000 22-02-1999 11-02-1999 23-10-2001 01-02-1999 Fem PSTAGNATO ony ae eH page 2 of 2