US 2005O230659A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2005/0230659 A1 Hampden-Smith et al. (43) Pub. Date: Oct. 20, 2005 (54) PARTICULATE ABSORBENT MATERIALS Related U.S. Application Data AND METHODS FOR MAKING SAME (63) Continuation-in-part of application No. 10/723,424, (76) Inventors: Mark J. Hampden-Smith, filed on Nov. 26, 2003. Albuquerque, NM (US); Paolina Atanassova, Albuquerque, NM (US); (60) Provisional application No. 60/525,462, filed on Nov. Jian-Ping Shen, Albuquerque, NM 26, 2003. Provisional application No. 60/525,467, (US); James Brewster, Rio Rancho, filed on Nov. 26, 2003. NM (US); Paul Napolitano, Publication Classification Albuquerque, NM (US); Agathagelos Kyrlidis, Malden, MA (US) (51) Int. Cl." ....................................................... C09K 3/00 (52) U.S. Cl. .............................................................. 252/189 Correspondence Address: (57) ABSTRACT MARSH, FISCHMANN & BREYFOGLE LLP Solid absorbent materials that are useful for absorption of 3151 SOUTH WAUGHN WAY chemical Species from a fluid, Such as a gas Stream or a SUTE 411 liquid Stream. The absorbent materials are formed by Spray AURORA, CO 80014 (US) processing and posses a well-defined chemical composition and microstructure. The absorbent materials can have a high absorption capacity for a chemical Species Such as H2S, (21) Appl. No.: 10/996,672 CO, NO, and H and have a high recylability, such that the chemical Species can be absorbed and desorbed over a large (22) Filed: Nov. 24, 2004 number of cycles. Increasing Temperature and Time old Liquid Phase Solid State Ca(NO), -- Pore formers Patent Application Publication Oct. 20, 2005 Sheet 1 of 57 US 2005/0230659 A1 Qu?LpueQunqeJ?duºLºu?seQJOUI V o SIQUILIOJQJOGI Patent Application Publication Oct. 20, 2005 Sheet 2 of 57 US 2005/0230659 A1 CSa 8-- O9->5 O SD CDE St.A. ga H 2. D". tC CMO C s ?e Z Z. CD O 2. GN w as a a Ye 9 2. L. -Q g b) CS -> s S 9. -Q 1a sM 5 CS 3.s s 4,cy S2Cys S. i O O Patent Application Publication Oct. 20, 2005 Sheet 3 of 57 US 2005/0230659 A1 Patent Application Publication Oct. 20, 2005 Sheet 4 of 57 US 2005/0230659 A1 Increasing Temperature and Time T last Liquid Phase Solid State syegy Zn(NO) +" CO NH NO ZnCO, ZnCO, +2NH NO NO + H.O Fig. 4 Patent Application Publication Oct. 20, 2005 Sheet 5 of 57 US 2005/0230659 A1 Post Processing Temperature and Time 300 C, 3h Ai. u/ E.(? Y2f ZnCO . ZnCO (25g zno, co, Zinc oxide 500 C, 3h precursors Fig. 5 Patent Application Publication Oct. 20, 2005 Sheet 6 of 57 US 2005/0230659 A1 Gas stream Contaminated Activated Absorbent Unreacted Uncontaminated Gas stream gas stream Contaminated ES Uncontaminated Gas Stream Contaminated gas stream Gas stream Gas stream containing Contaminated H2O Patent Application Publication Oct. 20, 2005 Sheet 7 of 57 US 2005/0230659 A1 Inter-aggregate Supported porosity absorbent intra-aggregateporosity , Y Low-density intermediate Absorbent Reacted absorbent particle particle particle Patent Application Publication Oct. 20, 2005 Sheet 8 of 57 US 2005/0230659 A1 Patent Application Publication Oct. 20, 2005 Sheet 9 of 57 US 2005/0230659 A1 O O O O D O O O O O O O O s CY) CN ve (ur) eZIS eloue Patent Application Publication Oct. 20, 2005 Sheet 10 of 57 US 2005/0230659 A1 O O CY) CN frzu eele esoeuns Patent Application Publication Oct. 20, 2005 Sheet 11 of 57 US 2005/0230659 A1 ve CO CO r CN O O O O f5/guo eunom euo Patent Application Publication Oct. 20, 2005 Sheet 12 of 57 US 2005/0230659 A1 z-Z (0.000dd) 29-Z (0.000dd) 69–Z (0.00€dd) ºff-Z (0.000dd) 8-Z (0.00€dd) Fig. 14 Patent Application Publication Oct. 20, 2005 Sheet 13 of 57 US 2005/0230659 A1 TOET..)- §!!!!!!!!!!!· ||___. Avg. Pore dia (nm) BET Surface Area (m 2 g) Pore volume (x100 cm/g) ||(O,000dd)yy-Z Ü?l(0.000da)+z (O,009dd)yL-Z Fig. 15 Patent Application Publication Oct. 20, 2005 Sheet 14 of 57 US 2005/0230659 A1 Patent Application Publication Oct. 20, 2005 Sheet 15 of 57 US 2005/0230659 A1 in 4.3m 2o.dkvision sun Fig. 17 Patent Application Publication Oct. 20, 2005 Sheet 16 of 57 US 2005/0230659 A1 SE 7-Oct-O2 Patent Application Publication Oct. 20, 2005 Sheet 17 of 57 US 2005/0230659 A1 CNCN LOO LO DC10 d50 CD Od90 ...……) LOCD f*º******** 0| } 9f7-Z (O,000ddºO?iv%9) Fig. 19 US 2005/0230659 A1 BET Surface Area (m?g) Pore volume (x100 cm/g) Fig. 20 Patent Application Publication Oct. 20, 2005 Sheet 19 of 57 US 2005/0230659 A1 Avg. Pore dia. (nm) (uuu)e?peuod 9 21 Patent Application Publication Oct. 20, 2005 Sheet 20 of 57 US 2005/0230659 A1 (un)3ZIS310??ued ZZ-Z OIS%9) ) Fig. 22 Patent Application Publication Oct. 20, 2005 Sheet 21 of 57 US 2005/0230659 A1 BET Surface Area (m?g) Avg. Pore dia (nm) Pore volume (x100 cm/g) 6 &N N -<g O5 n SS is s to Fig. 23 Patent Application Publication Oct. 20, 2005 Sheet 22 of 57 US 2005/0230659 A1 Carbonation: 600C Decarbonation: 750°C 45.0 40.0 35.0 -0- CaO1 30.0 (Prior Art) 25.O 2O.O 15.0 1 O.O 5.O 0.0 O 5OOO 1OOOO 15OOO 2OOOO Time (sec) Fig. 24 Patent Application Publication Oct. 20, 2005 Sheet 23 of 57 US 2005/0230659 A1 Á??oede.OZOO (e|duues600??OO6) [-]91,aloko ?,?8||313Ko T??ozepoko zze?oÁo Fig. 25 Patent Application Publication Oct. 20, 2005 Sheet 24 of 57 US 2005/0230659 A1 60 CaO1 (27 cycles) CaO1 (Prior Art) Avg. pore dia (nm) BET(m/g) Pore volume (x100 cc/g) CaO1 (Prior Art) CaO1 (27 cycles) Fig. 27 Patent Application Publication Oct. 20, 2005 Sheet 25 of 57 US 2005/0230659 A1 Z-Vy G-W S&SRSSSSSSSSSSSSSSSSSS&Ss 7-W is:sixxxxxx-xxxxxxxxxxxx& xxxx 9-V (JW Joud) OleO (WJOJ) ZOeo (iv Joud) OleO C. C C C C C C C C. O O O O O O O O O e o N s v r N V (%iou) uoroeuy uoloee Oeo Patent Application Publication Oct. 20, 2005 Sheet 26 of 57 US 2005/0230659 A1 i 90.0 E 80.0 s 70.0 - -- CaO 1 is 60.0 -e-A-16 50.0 -- A-14 30.0 s - A-13 5 20.0 R 10.0 c5 O.O Y’azurs O 5OOO 1OOOO 15OOO 200OO Time (sec) Fig. 29 Patent Application Publication Oct. 20, 2005 Sheet 28 of 57 US 2005/0230659 A1 & C f GNS g (%IOu) uooey uoloee Oeo Patent Application Publication Oct. 20, 2005 Sheet 29 of 57 US 2005/0230659 A1 WD 4.3m 200kv 350kis loun Patent Application Publication Oct. 20, 2005 Sheet 30 of 57 US 2005/0230659 A1 SE O2-Oct.-02 is a 3 is WD 4.4 min 20. OkW X5.93 all Our (b) Fig. 34 Patent Application Publication Oct. 20, 2005 Sheet 31 of 57 US 2005/0230659 A1 Patent Application Publication Oct. 20, 2005 Sheet 32 of 57 US 2005/0230659 A1 25 c\;–— esuooloº F ig. 36 Patent Application Publication Oct. 20, 2005 Sheet 34 of 57 US 2005/0230659 A1 -A-A-20 -x-A-23 -e-A-24 -0-A-7 -- A-26 -x- A-25 120.0 2 100.0 8. O 80.0 S 60.0 5 7. s 40.0 y S; Ot 2O.O s O O.O i an O 5000 10000 15000 2OOOO Time(sec) Fig. 38 Patent Application Publication Oct. 20, 2005 Sheet 35 of 57 US 2005/0230659 A1 CaO-TiO2 (4:1 molar ratio) Carbonation 600C Decarbonation 800C C .9 5 CS t C .9 5 c CD O CVS O O.O sease O 5OOO 10000 15000 2OOOO Time(sec) Fig. 39 Patent Application Publication Oct. 20, 2005 Sheet 36 of 57 US 2005/0230659 A1 CN O s O r 9. C 9 e O (fff) uequoSce?zO3 "Aloedeo Patent Application Publication Oct. 20, 2005 Sheet 37 of 57 US 2005/0230659 A1 O O O O CN O O O D V s O O 55 v.N 53 : - O. Y 9E L O O O LO O C C C C C C C. O O. O. O. O. O. O. CN O OO CO. Y. CN ve ve (%lou) uopoeuy, uoloee Oeo Patent Application Publication Oct. 20, 2005 Sheet 38 of 57 US 2005/0230659 A1 (SeoAo all) Z-W - | G is (£OCIW9%g "WW Ol:06) up ZZ-W sis al em m (SeoAo () O-W (W/W 0:06) O-W (SeoAo () 9-W (eOzIV%g "WW 09/09) 9-W (SeoMoC) |-W (M/W 09/09) A-W (un) eZS eloued Patent Application Publication Oct. 20, 2005 Sheet 39 of 57 US 2005/0230659 A1 (Seowo all) ZZ-V (OIW9%g "WW 0:06) ZZ-W (SeoAoz) Oz-Vy (WWOL:06) Oz-W (SeoAO all) 8-W (OIW%g"WW Og:Og 8-W (SeoMo () W (WMOG/OG) 1-W Patent Application Publication Oct. 20, 2005 Sheet 40 of 57 US 2005/0230659 A1 '; ...,’ & ... w is is:: A. & - - - ..... : :----'s 1s--a- - - S8 8. es ::::::3333333333333 i C e C C C C C C Patent Application Publication Oct. 20, 2005 Sheet 41 of 57 US 2005/0230659 A1 | ?| | 0'09 0'09 0'07 Juaq-Iosqe foo/ZO) “A oedeo ZOO Patent Application Publication Oct.