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    United States Patent ‘US00696470482 ty (a0) Patent No. US 6,964,704 B2 Cox et al. 45) Date of Patent Nov. 15, 2005 (51) CALCIUM SULPHATE-BASED 4A73610 A W197 Hater ta COMPOSITION AND METHODS OF tama a ‘Wise o Maing Sane Smad A MSR Ruan ASO A 21905 Cohen (95). inventors: Danny W. Cox, College Park, GA 501549 At §1991_Koudowa (US); Robert B. Bruce, Burlingion eoieatati meee) cauanl (CA) $93,093 A 3/1992. Koslowski Sooo? A ls Clement (73) Assignee: G.B, Technologes, LLC, Futburn, GA een Sc ws) Shaan « oth ta Sa7850 A Koo ta (1). Notice: Subject to any disclaimer the term of this Soa A Kivetal alent extended or adjusted under 35/8401 & Tangle a USC. 154) by Od ss65 8 Piece ea 4b) by O days, 200210164281 AL 11/2002. Sethuraman et al. (@1)_Appl No. 10/800,780 FOREIGN PATENT DOCUMENTS (22) Files: Mar. 15, 2008 be rows + aot 0) Prior Publication Data + cited by examiner [Us 20182986 AL Sep, 2, 2004 Primary Examiner—Pasl Mascon (4) Aitorney, Agen, or” Firm Thomas, Kayden, Related U.S. Application Data Horsiemeyer & Riley, LLP (60). Provsionapliction No 856,07, fed on Mat 2, Bas 6 ABSTRACT 6D CO4B 11/00 Disclosed is an improved alpha calcium sulfate he () US.Cl 106/77: 423555 dae Methods of producing an improved powdered calcium (58) Field of Search: 106/772; 423/555 _ sulfate hemihydrate (CaSO,-!SH,O) [alpha-type] compound tre disclosed at Teast one method including forming eatcium (0) References Cited Sullate diate (CaSO, 21,0) into a baguette ude high Presse, calining the briquette to transform the calcium De eeeed eran ‘sulfate dihydrate to calcium sulfate bemihydrate [alpha 190,051 A —X19R9 Randa ‘ypel dying the calcium sulfate hemi [lphs-ype] Zawsais A Ribas Haden row tit briqucte, and optionally grinding the Drguste. Ao die 25408 A ADS Daley ea 23122 lowed are methods of producing. an improved gypsum 2387330 A tive Woes 26353 aster including producing te disclosed pow eed elo BTS A MITTA Chnkon 24129 folate emia [aiphstype] and mixing the powdered Sooeg3 A 91975. Georee "Giga calcium sulfate bemiydrate [alpha-type) with water diocese A sone Rouge sss Gini A 11978 Rewer at Tosi09 40 Claims, 37 Drawing Sheets 410 Rate of Calcination; Effect of Pressure, KMp3 5% HO @ 270°C 30 min ‘hamid 38 me U.S. Patent Nov. 15, 2005 Sheet 1 of 37 US 6,964,704 B2 rere are PRIOR ART U.S. Patent Nov. 15, 2005 Sheet 2 of 37 US 6,964,704 B2 er PRIOR ART U.S. Patent Nov. 15, 2005 Sheet 3 of 37 US 6,964,704 B2 US 6,964,704 B2 Sheet 4 of 37 Nov. 15, 2005 U.S. Patent OL (%) suaju0g s9yeM 2024 8 Z 9 gs v pow {921 0 yous sonenbg aunssaud yBiy 1e 29}em Dappe 10 80) 21Q'8S0d ‘uoisayoo ype} sayanduq ‘9624 00) sonenbuq sonanbug 9801006 sapanbuq ‘21 po0B pede yeaug pue sped euysew Sunjonbua yorewoy (9 yous sayanbug uuonewno) Bun reuajew jo sso) 9612} :Kuapmod pue 4 00) sayanbuq ‘Sumanbug Ya12WOH, apewayds sayjanbl1g 30 Ai/END y “O14 ooL 002 ove (ed) uoneuuos ayanbug Jo ainssaig US 6,964,704 B2 Sheet 5 of 37 Nov. 15, 2005 U.S. Patent [rey Boa) aR J00L2 O kane CHE OSa76| [Ee (un) outs, 0b ooe oz oo yenbuia 0042 @ eaniooz zis 95014! y90/g SNSJaA aYaNbig ‘uo!JEU!D]eD Jo aJeY S “O14 sz ————-———-} 0s SL oo SyeIPAYIWOH % US 6,964,704 B2 Sheet 6 of 37 Nov. 15, 2005 U.S. Patent (uw) oui oor ose —o0e—SSz—OZ_—Si<—iSL:SC Ct 8 o (LuV YOlad) Budweg uoye907 YUM 4.01% © 49019 dW € O7H WE NSAT JO UOHeUID}eD Jo a}ey 9 “O14 se os SL aVEIPAYIWOH % U.S. Patent Nov. 15, 2005 Sheet 7 of 37 US 6,964,704 B2 FIG. 7A U.S. Patent Nov. 15, 2005 Sheet 8 of 37 US 6,964,704 B2 U.S. Patent Nov. 15, 2005 Sheet 9 of 37 US 6,964,704 B2 U.S. Patent Nov. 15, 2005 US 6,964,704 B2 US 6,964,704 B2 Sheet 11 of 37 Nov. 15, 2005 U.S. Patent [ enepoine =| | angjooyne yeux ord —— uoyeulsje9 qe SNsJeA [e141 30 ost ozt (uy) ow, 08 09 of 0 ‘eunyesodwia| eaejooyiny 8 ‘Did os oor ost 00z + 0Sz 008 (4,) eameandwa, US 6,964,704 B2 Sheet 12 of 37 Nov. 15, 2005 U.S. Patent (uy) owt O0r O0€ 00z ool 0 — — — 0 sz . [5sa75] Led | os — 7 = —} se o 8 4 3 . oe6oo a = oo A.0LZ © PdW00Z OTH%S EdAL wnsdAH ‘uopeujsjed JO ayy 6 “Old aqespAYWOH % US 6,964,704 B2 Sheet 13 of 37 Nov. 15, 2005 U.S. Patent ose 00 ost (eaw) eunssaig oor 0s 9,022 © 07H %S Edy ‘OuNSsarg Jo J9aYq ‘UOHEUIZIED Jo Bey OL “Old un og sz os SL oor ul Of 38 ayesPAYIWaH % US 6,964,704 B2 Sheet 14 of 37 Nov. 15, 2005 U.S. Patent smog se wnnoea ws 0} mou ane aonpa1 01 24% pod ojdures dor 01 poppe ananbug 18q aan —— 10 aoe |+—— ww papaou4t a ee —~ 9 — Busnoy sod DIa198 ysour QOL aa® punoss oa ~ 34199 ononbug ee tonpoud 30) wanae,, saquieye Apu’ snjeseddy Burpung ju soueH LL “O14 US 6,964,704 B2 Sheet 15 of 37 Nov. 15, 2005 U.S. Patent uinsdfg jo aA Ed 002 ezis ewes — BdIN 002 OZH %S ed 002 ed 002, edW OOL OZH %S d104 sadalq yoy —unsdABoydsoud ©=OZH%S9SA1 OZH%S9IW OZH %S Edy | : er ssp se es (Bo011u) pueweg sem gop - — 0s o9 Uw OS} 4,022 winsdAy jo adA] ‘puewag 19}eM ZL O14 US 6,964,704 B2 Sheet 16 of 37 Nov. 15, 2005 U.S. Patent (eaw) aanssaig osz o0z ost 001 os uw OL OSAT = = UW OF OST1-- > - ul OL Edm — um og edi —e—} (6001 w) pueweg sarey do02Z 07H %S O4nssaid JO s}oayy :puewag J3}eM EL “Old U.S. Patent Nov. 15, 2005 Sheet 17 of 37 US 6,964,704 B2 FIG. 144 U.S. Patent Nov. 15, 2005 Sheet 18 of 37 US 6,964,704 B2 FIG. 14B U.S. Patent Noy. 15, 2005 Sheet 19 of 37 US 6,964,704 B2 FIG. 14C U.S. Patent Noy. 15, 2005 Sheet 20 of 37 US 6,964,704 B2 FIG. 14D U.S. Patent Nov. 15, 2005 US 6,964,704 B2 FIG. 14E U.S. Patent Noy. 15, 2005 Sheet 22 of 37 US 6,964,704 B2 FIG. 14F U.S. Patent Nov. 15, 2005 Sheet 23 of 37 US 6,964,704 B2 FIG, 14G U.S. Patent Nov. 15, 2005 Sheet 24 of 37 US 6,964,704 B2 U.S. Patent Noy. 15, 2005 Sheet 25 of 37 US 6,964,704 B2 FIG. 141 Wy ; US 6,964,704 B2 Sheet 26 of 37 Nov. 15, 2005 U.S. Patent egNooz 9S079 edNO0! Edy © oF OH% UIW 0S} 4,022 O7H JO S}9ey4y ‘pueWag 419}e/4 SI * Old se 2 (80017) pueweg sare os US 6,964,704 B2 Sheet 27 of 37 g Zz U.S. Patent ulw OSL 4022 SOAnPPY ost 144 % I aleujoong ayeurrong ayeurong PN M%LO — FOSTH'A%L FOSTH'MWLO EN AME EN 'WH%L'0 Seppe ou ae ee ov or ey 8” Ed 002 OZH %E ECINM SOARIPPY JO 539943 :puewiag J9}eM 9} “Did se g ¢ (600171u) pueweg sae los U.S. Patent Calcined 150 min @ 270°C FIG. 17 Briquette Void Percentage: Nov. 15, 2005 iume % H2O ‘Volume % of Air | [avon Sheet 28 of 37 oes oF SRSA ASS SaE SASS waz EES] er ves % BUINJOA, US 6,964,704 B2 PAW 0 OH %40 990s oquNIG, E97 FETE edi 0 02H %0 1eishv0 ayuajas ESESRTEE| edW vt OZH %I dIOd SEE EEE] PdWW 001 OZH %1 dIGS 7 ov REDE PAW 002 OZH Sb 104 PdWW #1 OZH %€ dIGS Pal GOL OZH %€ JIGS Pai 002 OZH %E JIGS ed ¥) OZH %1 981 "AW 001 OZH %t 9807 Pd 002 OZH 91 9807 PAWN»! OZH %E OSAT PAW O0b OZH %€ 9807 PaWW 002 OZH %€ 9SC7 Pan 9b OZH %b COW PAWN 001 OZH Mot EW 2a 002 O2H Yo CoN PAWN #1 OH %E COW Pa 001 O7H %e EW PAW 002 OH %e CoN U.S. Patent ‘ined Uncalci FIG. 18 Briquette Void Percentage: Nov. 15, 2005 Volume % H2O ELVolume % of Air | Sheet 29 of 37 40.0 wee! % OUIN}OA US 6,964,704 B2 Bd 0 OZH %0 490s oquTIG, dW 0 O2H %40 IeIsh9 ayuaIes Pa bt OZH 51 GIO PAW OOL OZH %! IGS PAWN 002 OZH %t Idd PAW vt OH 6E CIOS Pav oot OZH %E AIS ea 002 OH %E JIGS Pal PL OZH%L OSA ER] ed O01 OZH %t 9SAT PAW 002 OZH %1 OST PAW 91 OZH %E OSAT PAI O04 OZH %E OST eaW 002 OZH %E 9SA1 PaWN 7} OZH 961 ESI PAW OOb OZH %L ed Bea 002 O2H %I ed PAWN 1 OZH %E ESN PAW OOF OZH %E Ed PAW 002 OZH %E EdWD US 6,964,704 B2 Sheet 30 of 37 Nov. 15, 2005 U.S. Patent (uy) oun, Buitag 0009 00S 000¢ 00g 0002 0001 Av6E ] |PdW L°8LL OZH %Z OL» BEEP} — 0 — 40P01 BAHN 8S) OZH %2 SLND Br'S) —e— 0 AoP6} SNSIOA 4,0) ‘senanbiug e61e7 Jo sayey Bulg GL “Old BIN|SIOW 2213 % US 6,964,704 B2 Sheet 31 of 37 Nov. 15, 2005 U.S. Patent oost coset 0004 paup uam TeyON I) | Jepmod 0} paysnio-eid enanbuq -e — | ananbuq peup—»— edIN 2S} OZH %S SLW By9'eL ‘spoyaw Burysni9/Burkug Bulfuen ym 4,p61 3 Sayey Bulkug 0z ‘O14 oz aIMSIOW 9213 % US 6,964,704 B2 Sheet 32 of 37 Nov. 15, 2005 U.S. Patent OzH %1bo paseidoy pues % zr o 8 9 + 0 0st © a ogp welt TT ae | eae | -- ———} oooz — ——+ oszz . eoez i ose sy Aj4 yum pues Buloejdey 40 ujBuasys aaissasdwiod uo 39ay49 12 “O14 (tsd) Buang onissaduiog, US 6,964,704 B2 Sheet 33 of 37 Nov. 15, 2005 U.S. Patent aieydg 41 suosotw uy sejewelq oned w/a plosdiia vo % BUINIOA, 9 ox « (Z) awWNjOA Jo % SNssaA (A) (w/a) Plosdi1a snsseA (x) (2129s °'607) asayds 41 sajoWeIQ eda Med V2z ‘Old US 6,964,704 B2 Sheet 34 of 37 Nov. 15, 2005 U.S. Patent esaydg 4! suosonw Uy Jejoweyg zo eo OEY Wa Plosdiia vo [ % OwN|on 9 OLX © (Z) awNJOA Jo % SNSJVA (A) (w/a) prosdij1a snsiaa (x) (9129s °'H07) esayds yy JayaweIG S07 Mey gzz “‘DId auaudg 41 suosoiw ut sayouerg US 6,964,704 B2 t 35 of 37 Sh % aunjon, so atx Nov. 15, 2005 (Z) ewiNjoA JO % SNsJ9aA (A) (v/a) prosdi1z snsuaa (x) (2/298 ©1607) osayds 4! JayoWeIG Bd IN OOL O7H %F EdINM PUNCID pue pould|eg vez “DI4 U.S. Patent US 6,964,704 B2 g Zz U.S. Patent auayds J! suoso} uy sayoweLg oney wa plosdii3 _b0 co so cor > % aWN}on, 9 ox (z) awnjoa yo % snsi0eA (A) (w/a) plosdil1g snsiaa (x) (2729s 94605) asayds 41 sayawelq 2dIN O0L 07H %S Ed PUNoJD pue peulsjed gez ‘Old US 6,964,704 B2 Pa Zz U.S. Patent auaydg 41 suosoiw ut JyawelG 20g CnPN Wa PlosdiIa v0 so See Sean % aUNIon on (z) awuinjo, yo % SNs4aA (A) (w/a) prosdifig snsuea (x) (2129s 91607) asoydg 41 sajeweIQ ed 00L 07H %§ OSG punosg pue paugje9 O¢z ‘O14 US 6,964,704 B2 1 ‘CALCIUM SULPHATE-BASED COMPOSITION AND METHODS OF MAKING SAME, CLAIM OF PRIORITY This application is related and claims priovity 19 US. provisional patent application entitled “Gypsum-Based CCompesition and Methods of Making Same” filed on Mar. 20, 2003 and accorded Ser. No. 60/456,207, which is ‘entirely incorporated herein by reference BACKGROUND 1, Field of the Invention ‘The present disclosure is generally elated to gypsum= based and calcium sulphate-based compositions and meth- ‘ods of making the same and, more particularly, is related to ‘construction-grade gypsum-lype compositions and methods ‘of making the same. 2. Description of Related Art Gypsum and calcium sulphate-based compositions and ‘compounds are use in a variety of industries, particularly in the construction industy. For example, eypsum plaster is ‘widely uscd in construction products such as sellevelers, ‘such as in poured floor technology aod repair mortars. Using heat to drive water from gypsum, or calcium sulfate diy- date (CaS0,2H0), to form calcium sulfate hemibydeate (C380 ,°5H.0) generally produces gypsum plaster used in these products, The gypsim plaster is also refered to as plascr of Pais or stucco ‘There ae a number of processes used to perform the ‘dehydration, or calcination, process, Calcination may be performed by, for example, fash drying st high temperature, ‘cooking in large Kettles, heating in furnaces or rotary kilns, using team, or cooking in aqueous suspensions "These many different techniques can result in plasters ‘with a wide range of composition and properties, but gen- ally two types are formed: alpha-hemihydeste type and hetachemihydrate type. These Wo types ate distinguished from one another by the amount of waler that is necessary to make a pourable Slury with the finely ground powdered hhemibydrate, with alphi-hemibydrate requiring less than about 50 mL. per 100 g of plaster, and beta-heminydrate requiring substantially above this amount, normally more than 70 mL per 100 g of hemihydrate plaice, This amount ‘of Water is Known as the Water demand. A process is known for making alplia calcium sulfate hemibydrate suitable for construction material ftom & ‘moist finely divided gypsum obtained by desullurization of flue gas from a power plant fred by broxen coal oF lignite, ‘especially from 4 gypsim obisined by fue gas desutfuriza: tion fom a wet fie gas desulfurization unit (called desulfo- xypsum or DSG), This process proceeds by eerystallizatio transformation ofthe calcium sulfate dihydrate contained in the DSG in the presence of saturated steam. Different processes are known for transforming calm ‘sulfate dihydrate into alpha caleium sulfate hemibydrate. One such process for making the alpha-hemihydrate from natural aypsum is described in Ullmans Encyclopedia of Indusirial Chemistry, 12, 301 (1976). I this process, ‘cium sulfate dihydrate pieees, namely oatually-oceurting ‘eypsum pieces are fed to an autoclave andl are converted to alpha-hemiydrate pieces inthe autoclave in the presence of Saturated steam ata temperature of 266° Fo 275° F. This alpha-hemihydrate product is dried above the temperature that heminyelrate will convert hack to calcium sulfate diy- drate (~113* F) and is ground up for further use % o 2 ‘More specifically, the eypsum removed from a natural deposit is broken up into a grain size of 150 to 300 ‘millimeters (mm), is filled into baskets, and & fed to an Suloclave in the baskets. The autoclave is dincely o¢ ind ‘rectly heated with steam from 266° Fto 275" F. The heating js controlled so that a pressure of 4to 5 bar (04 10 05 MPa) builds up in about four hours aocoring to siturated steam curve. Transformation of the calcium sulfate dihydrate to alpha-hemiydrate by this process usually takes at last six hours. The autoclave is then emptied "The alphi-hemiydrate gypsum is introduced into a dry ing chamber in the baskets and died under standard pressure at about 221” F. and subsequently finely ground. In the surface repions ofthe pivoes of material, well-defined alpha- hemibydrate crystals grow in a more or less needlelike shape: FIG. I shows a scanning electron microscope (SEM) ricrograph of an example of the ncedlelike crystals of alpha-hemihydrate obtained by this process ‘Additives for control of the pH-value and for changing the cenystal pattern ean be metered into the autoclave and a radictaiphs-hemiylrate with various properties isobtain- able. To this known process, however, the expensive puefi tation steps are troublesome. In tis proces, distinc slpha- hhemiydrate crystals arise more by chance, and contol of the process in regard to crystal pattern and surface fine structure of the crystals formed is not provided Inattemping fo solve this problem, one process described in, for example, U.S. Pat. No. 5,015,449 issued 10 ‘Koslowski, forms moist fine grained gypsum (caleium sul- fate dinydrate) into a molded body ata pressure between O.L to 14 Nimm* (MP2). Koslovsk states that when forming 2 ‘molded body by pressing the caleium sulfate dihydrate at pressures greater than 16 Nim", “one of eourse ablains ‘molded oF formed bodies but they are aot auloclavable ‘without forming fractures or cracks an ae destroyed daring autoclaving.” Koslowski at column 7, lines 41-45, The molded gypsum body of the’ process disclosed in Koslovski has total volume of 15 to 60% by volume pore volume, with more than 5% by volume of the pare volume containing ic. When the starting material is Wet, the remain- ing balance of the pores is filed with water. The molded body is then fed into an autoclave. The exystl growth and crystal pattern of the alphashemihydkate is regulated by control of a process temperature in the range between 230° F- and 356° F- and by pressure ofthe process atmosphere in the autoclave. The molded body is removed from the auto- clave and delivered for use after the recrystallization trans- Tormation. Prismatic columnar alpha calcium sulfate hemibydrate crystals are produced from this process, « SEM microgeapl ‘of which is shown in FIG. 2, The calcination time for the process for producing these crystals is approximately four to Seven hours per batch. This long cycle time makes this process difficult and expensive from a production elieency sanpoint, ‘hus, heretofore unaddressed need exists inthe industry to address the aforementioned deficiencies and inadequs- SUMMARY, Embodiments of the present disclosure provide calcium sulfate bemiltydrate [alpha-type] (‘alpha-bemihydrate”) ‘with improved crystal morphology, methods of making alpha-hemihydate, and products made with the disclesed alpha-hemihydate Briefly deseribed, one embodiment of such a method of producing the alpha-hemibydrate with improved crystal US 6,964,704 B2 7 ‘moxphology includes forming caeium sulfate dihydrate into a briquette under high pressure, calcining the briquette to transform the caleium sulfate dibydrate 10 alpha- hhemibydrate, drying the briquctt, and optionally grinding the briquette, Ia one embodiment of the disclosed alpha- hhemibydrate, the alpha-hemihydeate crystals are grown together to form clusers of the erystals, with substantially reduced pore volume between the agglomerated clusters, as ‘compared 10 the pore volume of slphachemiydrate made from briquettes formed under pressutes les han of equal to 14 megapascal (MP2). One embodiment of a product made with the disclosed alpha-hemibydrate includes « mixture of| the disclosed alpha-hemibydrate and water, [BRIEF DESCRIPTION OF THE DRAWINGS ‘Many aspects of the disclosure ean be better understood ‘with relerence tothe following drawings. The components in the drawings are not necessarily to scale. Moreover like reference numerals designate correspondig parts through- ‘out the several views. FIG. 1 is a scanning electron microscope (SEM) miero- graph depicting erysials of prior art calium sulfate hemi- hydrate alpha-type] (alpha-temihydlrate") formed from calcination of calcium sullatedibydrae rock. FIG. 2 i¢ SEM mieograph depicting erstals of prior a alpha-hemiydrate formed from calcination of moked cal- ‘cium sulfate dikydrate FIG, 3 is a SEM micrograph depicting crystals of the “disclosed improved alpha-hemihydate FIG. 4 is a representation of the water content and pressure ranges that yield the disclosed briquettes, and the ‘quality of briquettes produced FIG. $ is a graphical eprescatation of the rate of calei= nations of exemplary briquetes versus a block, FIG, 6 is a graphical presentation showing the rate of ‘conversion of gypsum to hemihyeate throughout the inte rior of a calcined block as performed using the prior at process, demonstrating the relatively long calcination time needed Tor the prio art process, FIGS. 7A-7D ace microscope pictures showing crystal ‘growth over increasing calcination time for Kerr McGee eyrsum, FIG, 8 is a graphical representation of autoclave temperatuse, comparing 8 pilot trial vermis lab calcination, FIG. 9 is a graphical eprescatation of the rate of ealei= nation of two different synthetic gypsum sources that have heen briqucted and calcined using an embodiment of the disclosed process. FIG. 10 isa graphical presentation of the effect of the process variable of pressure on the rate of calcination of ypsum fo hemibydrate using an embodiment of the dis- _losed process. FIG. 11 is schematic detailing the layout of lab seale ‘custom grinding equipment FIG, 12 is graphical representation of the water demand ‘of exemplary hemibytrate materials prepare by an embod rent of the disclosed process from various sources of sypsum. FIG. 13 is «graphical representation of the water demand ‘of various hemibydrate materials that were prepared from ‘emboviiment ofthe disclosed process, wih increasing pres> ‘sure used in making briquetes, FIG, 4A-141 are microscope photographs illustrating the ‘rysial structures of exemplary hemibydrate products. Note % o 4 FIG, 14E was taken at a different magnification, and FIG. AL is the scale FIG. 15 isa graphical representation ofthe water demand of exemplary hemibydrate materials prepared from an tembodiment ofthe disclosed process with increasing Wat content in making briquettes. FIG, 16 is graphical representation of the water demand ‘of exemplary hemiaydrate materials that were prepared from an embodiment of the disclosed) process with exemplary Additives to the gypsum used in making briquettes or added to the briquettes directly. FIG. 17 is a bar chart illustrating the void content of the ‘exemplary calcined briquettes prepared using an embod meat of the disclosed process. FIG. 18 is a bar char illustrating the void eontent of the ‘exemplary uncalcined briquettes prepared using an embod meat of the disclosed proves. FIG. 19 is graphical representation of impact of drying temperature on the deying rate of exemplary calcined but wet large briquettes mide by embodiments of disclosed processes FIG. 20 isa graphical representation of impact of dying! crashing on the drying rate at 194” F.of exemplary ealined but wet large briquettes made by embodiments of disclosed processes. FIG. 21 is graphical illustration of the dependence of the compressive stecngt of an exemplary product made fr alpha-hemiydrate onthe percentage of sand replaced by fly ‘sh. FIGS, 22A and 2B are computer-eenerated graphical illustrations of panicle size and shape distribution data of ‘exemplary raw material gypsum, FIGS, 23A-28C are computer-gencrated graphical illus: trations of partiele size and shape distribution data of the gypsum of FIG. 9 afler being subjected wo embodiments of isclased processes. DETAILED DESCRIPTION As identitie inthe foregoing, gypsum plaster, or calcium sulfate hemibydrate (CaSO,:5H.0) [alpha-hemihyérate] (hereinafter “alpha-temiydrate") and methods for produc: jing it have lengthy calcination times, and are therefore expensive, and not always sufficient to produce a consist alphe-hemihydate. In stempting t0 solve some of these problems, other methods for producing the alpha- Fhemiydrate have been developed that involve expensive additives andior prooestes which are complicated to install fand operate often resulting in lengthy calcination times ‘while ill not producing an alpha-hemiyate with optinal cenystal sinicture. Therefore, noded isan alpha-hemibydeate that is quick and easy to produce with an optimal crystal structure for producing strong. gypsum plaster proces, Disclosed isan improved alpha-hemibydrate product that is more ideally formed to produce a high siragth, low wat demand plaster upon subsequent gsinding and’ drying. Io fdition, the pracess by Which this improved. alph hemibydrate is manufactured is easier and mote ficient than oer known methoxs af procicing alpha-hemiydrate Referring now to FIG. 3, shown is a scanning electron microscope (SEM) micrograph of exystals of the disclosed improved alphachemibydrate. Wi known that idividyal censtals of the alpha-heminytirate have an average particle diameter of approximately 20 microns (um) (FIG. 2). Asean be seen from the scale of the micrograph in FIG. 3, the average particle dismeter of the clusters or agglomerates of US 6,964,704 B2 5 the improved alpha-hemibydate crystals is about 100 yn ‘As can be seen in comparison with the alpha-heminydrate ‘eysials of FIGS. Land 2, the improved alphachemiydrate cchisters of FIG. 3 hive a smaller pore volume, with the disclosed alphachemitytate crystal clusters being larger find more blocky thin the acelelike and columnar erysals ‘OF FIGS. I and 2. This “blockicr”exysal structure leads (0 improved propertics inthe material, such as reduced water ‘demand. Blockier erysals lead 10 a mow efficient packing ‘volume, which reduces the amouat of water used t0 create the desied slurry. In adition to shape characteristics, pare ticle size is also a coatributr to water demand properties. A broad particle size distribution of spherical or blocky exys- tals allows maximum packing efficiency and lowest water ‘demand, ‘An exemplary embodiment of a method for making the alpha-bemibydrate includes forming calcium sulfate dihy- ‘rate (CaSO,-2H,0) (hereinafter “dinydrate") into a be ‘quelle under high pressure, caleining the briquette to trans form the calcium sulfate dihydrate to alpha calcium sulfate 2 hhemibydrate, drying the briquette, and grinding the bri- ‘quette. The dihydrate used to form the briquettes includes natural gypsum fom mines and quarties around the world, a8 well as byproduct gypsum from a variety of chemical processes. Some examples of these chemical processes Include the desulfurization of flue gases, the production of titanium dioxide, the production of” phosphate-based fertilizers, the neviralization of waste sulfuric acid steams from chemical processes, or the production of organic acids and their salts, such as citric aid, citrate, cte. Recycled jxypsum from gypsum products would also be suitable for this process. Specific eximples of dihydrate material include but aze not Kimited to, Lambton desulfogypsum (LD Ker-McGee gypsum (KMG), natural gypsum from neat Drumbo, Ontario, Canada, natural gypsum liom near Fort Doge, fows, USA (“Fort Dodge Land Plaster”, or FDLP) and recycled gypsum board cor. CContcary 10 what has been taught in the prior art, the inventors have unexpectedly determined that forming a dihydrate briquette under high pressures yields a briquette that is not cracked or destroyed during the calcination process. It may be noted that for some combinations of pressure of formation and free water content, some minor ‘racking may be observed, bt this eacking dacs not destray the briquette nor prevent it from being usable. For each investigated material, an optimized combination of high pressure of formation and five water content fo produce 3a tuncracked briquette was achievable. In one example, the briquette may be formed under a pressure greater than approximately 14 megapaseals (MPa) wp to a pressure at ‘which the briquetting machine cannot practically work, ‘currently about 320 MPa, For example, when compressing iydrate with relatively litle or no added water, at ‘extremely high pressure, eg, about 320 MPa, the briguet- ting machine begins to sereech at such a high decibel level that an operator, even with the use of ear protection, cannot tolerate it For diaylate to which water has been added, at high pressures, e., about 320 MPa, the briquettes begio to stick or adhere othe machine parts, Thus, tbe upper Timit of pressure under which te briquettes may be formed i irgely 4 Tunction of the operating limits ofthe briqutting machine In theory, future advancements in briquetting technology to allow even greater pressure may be even more ideal than the ‘cureal investigated pressure limits In another example, the briquettes may be formed under ‘pressure of about 50 to 30 MPa, In another example, it has ben determined that the briquettes formed under a pressure % o 6 ‘of 100 10 200 MPa exhibit beneficial properties. FIG, 4 shows «schematic detailing a region of pressure and mois- ‘ure within which briquetes ean be formed. These process variables contribute diteetly to the ability 1o adequately ‘weate and handle the unealeined eypsum product, herein referred to asthe "quality" of briquettes formed, This quality oflriquetes is alse a funetion of the gypsum source material sed, ‘There are several factors that can affect the ease with whieh the briquettes can be made, a8 well as the overall strength of the briquettes. The strength of the briquettes impacts their ability to be transported, conveyed, etc. with- ‘out damage. The prior act deseribes « process. whereby ‘gypsum is Formed into blocks of size about 10 em by 20/em by 20 em, made at a pressure of under 14 MPs. The briquettes used in the process disclosed herein may range in size, for example, from about 0.125 (“smallee” type) to 125 (Clatgee” type) euic inches. Ia another example, the brie (quettes are about 1 to 27 cubic inches. It has been deter ‘mined that in another example, briquettes of about 1 0 8 cubic inches exhibit beneficial properties. For example, the briquette may be approximately two square inches by one inch thick. The term “briquette” as used herein means a ‘compacted shaped mass of dihydrate material formed under pressure. The brick-shaped mass ean be, for example, Pillowsike (as in shape of charcoal briquettes used for ebarcoal barbecue grils), puetc-like, table-ike,eylindical, fat plates, ee ‘he dihydrate briquettes formed under the disclosed high pressures Iypically lave physically bound water in a range from about 15 t0 21% by weight, This is for 75 to 100% pure gypsum. Preferred is 85-100% pure eypsum or 17 0 21% physially bound water, and most preferred is 93 t0 100% pure gypsum or 19.5 to 21% physically bound water. In addition to, and diferent fom, physically bound water, the briquettes may also inclide free water added to the briquette to facilitate processing (€. 10 lubricate the br- {quelte during pressing or formation ofthe briquette and thus increase the compressibility of the dihydrate material). Adktionaly ree water added t the briquette may aid inthe reerysallization process by assisting in the beat transfer andor reerystallization during calcination of the briquette With a special feeding, mechanism and production seale briquetting equipment, itis possible to make briquettes with ‘bo moisture, or inthe moistire range of just greater than OF up 12% by weight In one example the free waters about 10 5% by weight ofthe briquet. It as been determined that a free water content of about 2 to 3% by weight yields beneticial results during the disclosed methods for produe- ing te disclosed hemi rat, "The disclosed dihydrate briquettes were calcined at a femperature in the range of about 248 to 284° F. The ihydrate briquettes formed under a high pressure as ‘eseribed above caleie at much faster cates than has tad tionally been accomplished with gypsum. For example, a8 ean be seen from FIG. 5, when using KMG, the disclosed nethod substantially completes the transformation of the dihydrate to the alphs-hemiby date during ealeinaton in ess than approximately 1 hour, wheteas the larger blocks a8 pet the prior art are only about 40% complete in about a 3-hour time frame. FIG, 6 further iMlustrtes that if the gypsum blocks as serie in the prior art are examined afer 3 hours, rather than the normal caleination time of 6 hours, the dehydration fon the edges of the block are substantially complete, ein the conversion of gypsum to hemibydrate. However, 2 US 6,964,704 B2 1 ‘sample taken from the face to a depth of 1 inch is not fully calcined, and 4 sample taken Irom the interior of the block ‘as aly calcined. Note that “substantially complete” a8, used herein means that approximately 93% ofthe briquette 's transformed to alph-hemibyclrate, with about 3 10 4% remaining asthe dihydrate. The remaining 3 104% can be, for example, various mineral impurities, Percent composition of dibydate, hemihydrate, free water, and other material may be determined through a ypsim phase analysis procedure as follows, Weigh an ‘empty container and record ilntiier found on container ‘Add about 4 to 6 grams of simple to the container (previously fine ground with mortar and pestle). Record the Weight of the sample and container and leave in ait (preferably 60-80% relative humidity) overnight. Dry the ‘ample for sbout 2 hours at about 113° F. and weigh, CCareflly add about 20 mil. of distilled water, making sure 10 ‘wet all the powder. Let stand on counter covered for about 2 hours. Putin an oven overnight at about 113 ‘weight Heat the sample for about 2 hours a Place sample on cooling tray and cower, Weigh agtin as soon as cool enough to handle. Calculate % water, © anhydrite Al), % dihydrate, % heminydeate, and % weight other ‘Microscopic examination of the briguctes can follow the

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