US00797.6804B2

(12) United States Patent (10) Patent No.: US 7,976,804 B2 Jantsch et al. (45) Date of Patent: Jul. 12, 2011

(54) METHOD FOR THE DECOMPOSITION OF 4,157.316 A 6/1979 Thompson et al. NO IN THE OSTWALD PROCESS 4,172,047 A * 10/1979 Gandhi et al...... 502,332 2 4,183,829 A * 1/1980 Adachi et al...... 502/.328 4,233,189 A * 1 1/1980 Gandhi et al...... SO2,325 (75) Inventors: Uwe Jantsch, Freigericht (DE): 4,316,822 A * 2/1982 Fujitani et al...... 502,304 Jonathan Lund, Kelkheim (DE); Marek 4,367,162 A * 1/1983 Fujitani et al. . ... SO2,178 Gorywoda, Hof (DE); Marcus Kraus, 4,440,874. A * 4/1984 Thompson . ... SO2/327 Bruchköbel (DE) 4,476,246 A * 10, 1984 Kim et al...... 502,304 4,536,482 A 8, 1985 Carcia 4.675,308 A * 6/1987 Wan et al...... 502,304 (73) Assignee: W.C. Heraeus GmbH, Hanau (DE) 4,678,770 A * 7/1987 Wan et al...... 502,304 4,795,733. A 1/1989 De Thomas (*) Notice: Subject to any disclaimer, the term of this 4,868,149 A 9, 1989 Bricker patent is extended or adjusted under 35 4,904,633. A * 2/1990 Ohata et al...... 502,304 U.S.C. 154(b) by 0 days. 4,910, 180 A * 3/1990 Berndt et al...... 502,304 5,102,851 A 4, 1992 Eri et al. 5,108,978 A * 4/1992 Durand et al...... 502,304 (21) Appl. No.: 12/351,257 5,116,800 A * 5/1992 Williamson et al...... 502,303 5,177,041 A 1/1993 Horiuchi et al. (22) Filed: Jan. 9, 2009 5.439,865 A 8, 1995 Abe et al. 5,459,119 A 10, 1995 Abe et al. (65) Prior Publication Data 5,478,549 A 12/1995 Koch 5,591,771 A 1/1997 Markonius US 2009/O13OO1 O A1 May 21, 2009 5,597,772 A * 1/1997 McCabe et al...... 502,332 5,612,009 A 3, 1997 Fetzer et al. Related U.S. Application Data 5,753,580 A 5/1998 Hayashi et al. 5,814,576 A 9, 1998 Yamamoto (62) Division of application No. 11/053,708, filed on Feb. 5,849,660 A 12/1998 Takemoto et al. 8, 2005, now abandoned 5,856.263 A * 1/1999 Bhasin et al...... 502/.333 s s 5,894,068 A * 4/1999 Kharas et al...... 5O2/327 O O 5,958,826 A 9, 1999 Kurokawa et al. (30) Foreign Application Priority Data 6,060,420 A 5/2000 Munakata et al. 6,080,375 A 6/2000 Mussmann et al. Mar. 11, 2004 (DE) ...... 10 2004 O12333 6,087.295 A * 7/2000 Kharas et al...... 502,300 May 13, 2004 (DE) ...... 10 2004 O24 O26 6,147,027 A * 1 1/2000 Miyake et al. . ... SO2,325 6,165,429 A * 12/2000 Ikeda et al...... 423,213.5 (51) Int. Cl. 6,187,7096.165.623 AB1* 12/20002200 FifeMcCabe et al. 5O2/52 BOLD50/00 (2006.01) 6,321.804 B1* 4/2001 Yamada et al. ... 502,326 BOID 33/34 (2006.01) 6,261,989 B1* 7/2001 Tanaka et al...... 502/217 BOLD 53/56 (2006.01) 6,294,140 B1* 9/2001 Mussmann et al...... 423,213.5 BOLD 53/86 (2006.01) (Continued) BOI. 8/00 (2006.01) BOI. 23/00 (2006.01) FOREIGN PATENT DOCUMENTS BOI 2L/00 (2006.01) DE 35 43 640 6, 1987 BOI 20/00 (2006.01) Continued COIB 2L/00 (2006.01) (Continued) (52) U.S. Cl...... 423/239.1; 422/177; 422/180; OTHER PUBLICATIONS 502/261; 502/302:502/303: 502/304: 502/326; 502/327: 502/332: 502/333; 502/339; 502/349; Applied Catalysis B: Environmental 44 (2003) pp. 117-151. 502/350, 502/355; 502/415: 502/439 (58) Field of Classification Search ...... 423/239.1; Primary Examiner — Cam N. Nguyen 502/261, 302,303,304,326, 327, 332, 333, (74) Attorney, Agent, or Firm — Norris McLaughlin & 502/339, 349,350,355, 415, 439; 422/177, Marcus PA 422/180 See application file for complete search history. (57) ABSTRACT (56) References Cited A CatalVStcatalyst forOr the ddeCOmoS1t1On position ofO NO underunderth the COnd1t1OnSditi of the Ostwald process, comprising a carrier and a coating U.S. PATENT DOCUMENTS made of rhodium, rhodium/palladium or rhodium oxide 3,840,471 A 10, 1974 Acres applied thereto, ensures to yield NO with a particularly low

3,914,376 A * 10/1975 Barker ...... 423,213.5 content of laughing gas as the first process product. 3,951,860 A * 4, 1976 Acres et al...... 5O2/2O7 4,117,082 A * 9/1978 Matsuyama ...... 423,247 7 Claims, No Drawings US 7,976,804 B2 Page 2

U.S. PATENT DOCUMENTS 2003,0162656 A1 8, 2003 Wu et al. 2003. O181324 A1 9, 2003 Hotta et al. 3.3 R 1939, E. 2004/0023796 A1 2/2004 Nirisen et al. 6375,704 B1 4/2002 Habecker et al. 2004.0102315 A1 5, 2004 Bailie et al. 6,376.433 B2 4, 2002 Yagi et al. 2004/0228785 A1* 11/2004 Ducloset al...... 423,239.1 6,379,640 B1 4/2002 Ver Nooy 2004/0235651 A1 11/2004 Uenishi et al. 6,395.675 B1 5/2002 Suga et al. 2005, 0096.215 A1 5/2005 Espinoza et al. 6,413.483 B1* 7/2002 Brisley et al...... 423,239.1 2005/0255993 A1 11/2005 Tanaka et al. 6,537,511 B1* 3/2003 Chattha et al...... 423,213.5 2006/0008401 A1 1/2006 Hotta et al...... 423,239.1 6,610,628 B2 8/2003 Nordquist et al. 6,623,716 B2 * 9/2003 Suga et al...... 423,239.1 FOREIGN PATENT DOCUMENTS 6,649,134 B2 * 1 1/2003 Gorywoda et al...... 423,239.1 6,692,712 B1 2, 2004 Andersen RE s 3. 3. E. 6,702,960 B1 3/2004 Schaddenhorst et al. DE 19543 102 11, 1996 6,723,295 B1 * 4/2004 Baier et al...... 423,239.1 DE 198 19882 10, 1999 6,743,404 B1 6/2004 Schumacher et al. DE 100 16276 10, 2001 6,761,755 B2 7/2004 Jantsch et al. DE 10 2004 O24 026 9, 2005 6,764,665 B2 7/2004 Deeba et al. EP O946 290 10, 2001 6,797,668 B2 * 9/2004 Yoshikawa ...... 502,304 EP 1 O76 634 6, 2002 6,827,917 B1 12/2004 Ward et al. JP 55-031463 3, 1980 6,858,193 B2 * 2/2005 Ruwisch et al...... 423,213.5 JP 06-142509 5, 1994 6,864,214 B2 * 3/2005 Uenishi et al...... 502,304 JP 06-142517 5, 1994 6,875,408 B1 4/2005 Yamamoto et al. JP 06-182203 T 1994 6,887,443 B2 * 5/2005 Suga et al...... 423,239.1 JP 2002-253967 9, 2002 6,946,107 B2 * 9/2005 Carlborg et al...... 423,239.1 WO WO99,64139 12/1999 6,967,186 B2 11/2005 Takaya et al. WO WOOOf 51715 9, 2000 7,011,801 B2 * 3/2006 Van Den Brink et al. . 423/239.2 WO WO 2004/OO3949 1, 2004 7,041.263 B2 * 5/2006 Sung ...... 423,239.1 WO WO2004OO3949 1, 2004 2002/0172642 A1 11/2002 Dindi et al. WO WO 2004/0967O2 11, 2004 2003.01.03886 A1 6, 2003 Dou 2003/0124046 A1 7/2003 Gorywoda et al. * cited by examiner US 7,976,804 B2 1. 2 METHOD FOR THE DECOMPOSITION OF ment also mentions Ru and Iras catalysts. These metals, in NO IN THE OSTWALD PROCESS turn, do not have any effect in the Ostwald process. JP 6142517 A1 describes catalysts with alpha-Al-O as This application is a division of application Ser. No. carrier material, which comprise Rh or Ru and at least one of 11/053,708 filed Feb. 8, 2005, now abandoned. 5 the oxides of Ti, Zror Nb. The fact that Ru is not suited for the The subject of the invention is a catalyst for the decompo Ostwald process applies here as well. Furthermore, titanium sition of NO that results as a by product from the catalytic and niobium oxides are not suitable either. oxidation of ammonia according to the Ostwald process. According to JP 2002253967 A1, Ru or Pd on SiO, or Al-O are also used to destroy laughing gas that is excessive BACKGROUND OF THE INVENTION 10 as anesthetic gas. Appropriate reactors are steel pipes which are packed with Al2O grains that are coated with noble metal The catalytic oxidation of ammonia for the production of and are operated at 150 to 550° C. (JP 55031463 A1). Here as nitric acid is known (as Ostwald process). The oxidation of well, the requirements are different in that both Ru and Pd do ammonia for large-size production of NO as the first product not have any effect in the Ostwald process and SiO, is chemi 15 cally unstable under the conditions of the Ostwald process.JP of the process is achieved on, for example, PtRh or PtRhPd 06182203 relates to fluoride-containing carriers for noble alloy catalysts at a high temperature (usually 800 to 950° C.). metal catalysts. Said alloy catalysts are piled up in the reactor in several layers According to DE 4020914A1, ammonia undergoes com one upon the other, usually in the form of knitted or woven bustion almost without any formation of laughing gas if it is gauzes. Typically, PtRh or PtRhPd wire which is, for brought into contact with Pt, Pd, Rh or Ir, in combination with example, 76 um in diameter is used for producing said gauzes. at least one of the oxides of Mo, V. The process described is