2) United States Patent Heidel et al (54) RECOVERING A CAUSTIC SOLUTION VIA CALCIUM CARBONATE CRYSTAL AGGREGATES (71) Applicant: Carbon Engineering Ltd., ca (72) Inventors: Kenton Robert Heidel, Calgary (CA) David William Keith, Canmore (CA) Jane Anne Ritchie, Calgary (CA): Nicholas Vollendorf, New Berlin, WL (US); Bre Ressler, Brooktiold, WI ws) (73) Assignee: Carbon Engineering Ltd., Squamish, (A) (©) Notice: Subject wo any diseluimer the term of this patent is extended or adjusted under 35 USC. 154) by 0 days. This patent is subject to a terminal dis- claim, Appl. Nos 17236478 Filed: Apr. 21, 2021 Prior Publication Data 202110284845. A1 Sep. 16, 2021 Related U.S. Application Data (60) Continuation of application No, 167704,088, filed on Dee. 5, 2019, now Pat, No, 11,014,823, which is a (Continved) (1) Inc. Cor 118 (2006.01) BoID 900 (2008.01) pic 1100 (2006.01) (2 COLE 11/182 2013.01); BOLD 970036 (201301): COP 11181 (2013.01) (Continued) 'USO11667538B: (10) Patent No.: (4s) Date of Patent: US 11,667,538 B2 *Jun. 6, 2023 (58) Fleld of Classification Search CPC. COIF 11/182; COP 11/181; COIF 11/183: RIC 11/0078; COLP 2004/61; COLP 2008/62: BOLD 9/0036; ROID 2009/0086, ‘See application file for complete search history 60) References Cited US. PATENT DOCUMET oes 2 S198) inch (Continaed) POREIGN PATENT DOCUMENTS ow 111999 &N T2001 (Continved) (OTHER PUBLICATIONS Anwar ea, "Mode of Action and Design Rules for Additives That Modulate Crystal Nucleation” Angew Chern. 2009, vo. 121, pp. 1608 (Continved) Robert M Kunemund Fish & Ris Primary Examiner: (74) Attornes, Agent, or Firm on ABSTRACT Techniques for growing crystalline calcium earbonste solids stich thatthe crystalline ealeium carbone solids include @ Volume of 0.0005 mm to $ mu’, inelude a slaker to react ‘Quicklime (CaO) and low carbonate content Hid to yield slurry of primarily slaked Time (Ca(OH),): 2 Muidized-bed reactive erysalizer that encloses solid bed mass and includes an input for a slurry of primarily slaked lime, an input for an alkaline soltion and carbonate, and aa outpt forerysalline calcium earbonate solids that include particles ‘and an alkaline carbonate solution; a dewatering epparats that includes an input coupled to the erystallizer and an ‘output to discharge plurality of separate streams that each include portion of the erystalline calcium carbonate solids ‘nd alkaline carbonate solution; and a seed transfer appara (Continved) 101 02US 11,667,538 B2 Page 2 tus to deliver sed material into the crystallizes to maintaia JP 2o1osos613, 22010 ‘consistent mass of seed materia B zouotett 1204 3 DuUNisieN) 92011 Wo worsonsst i999 28 Claims, 6 Drawing Sheets WO — WO200800919 42008 WO — Wo2o10289 32010 Wo Wo20l4I6I738 10014 Related U.S. Application Data ‘continuation of application No, 15/370,620, filed on Dee. 6, 2016, now Pat. No. 10,519,081. which is a division of application No. 14/281 19, 2014, now Pat. No. 9,637.33 (52) Us.c. 66) US. PATENT DOCUMENTS. 6961869 BL Soo7st9 Be 3728-028 BI 45905 BE Sieata03 Ba 9137s Bo 9978100 BE 1oi388361 B2 To'sigioat Ba T0144 Bo 200Si07L17 AL 20080283956 AL so100034724 AL aoinon64t0o aowwoa0»? ao1D0003135 201300173303 ao120r30807| dowgox7 1379 Al doisoos03s Al aoison29369 Al 20170081207 Al 20200100059 AL filed on May COLE 11/183 2013.01); DIC HANTS (201301); BOLD 2009/0086 2013.01}; COIP 2004/61 (2013.01); COLP 200462 (2013.01): y References Cited ‘72004 $3006 52014 Sania S207 32018 S208 709 Bans Sana, anos 02008 22010 32010 e010 52011 tani2 702 92012 Gi Sania 22015 Hoi 32017 4020 Vinanen Konno Heel Henly Heel Soca Heda Soca Heidel Heide “Talahashi of Rost Keith eta. Keith etal. Cckaer et Lackner el ello? Giton ce Heide Heel a Heel 2P 40/40 (2015.11) baie 1vo0rs cour 1viss aie 10078 FOREIGN PATENT DOCUMENTS ox rosso40 oO betrse @ cosas P ses ae S5176198 ® S59213617 ie Seani06t6 ® HOso4s71 ae Hoss1390 ny 10292083 ® 2001199720 ® 3002093537 ae 2008292320, . 200s 79788 a 0052es68% ny dooroni394 ® So0m0014 7002 76 31999 12002 i976 L198 11987 11996 41998 111998 "2001 10.2002 1.2008 2005 10.2008 "22007 1am) (OTHER PUBLICATIONS [Biocehi tal, “Process design and energy requirements fr the spre of carbon dioxide from ain” Chemical Engincering and Processing. vol 45, No. 12, Dee. 1 2008, pp. 1047-1058 Caneel. "Measurement ofthe Vapor Pressure of Supecooled Water Using faa Spactoscopy.” Atmos. Oceans Technol vol 25,2008, pp. 172441729. {Chinese Notice onthe First fice Action, Chinese Application No, 2014800275110, dated Sep. 12,2016, 13 pages ‘Chinese Notice onthe Fir Ofice Action, Chinese Application No, 00393427, de Now. 14,2017, 14 page CCosiodes, "Reactive crystallization of nickel hyrosy-arbonate in ‘uidized bed reactor Fines production andeolump desig." Cheri cal Engineering Seiene, tol 61, 2006, pp 1377-1388 International Search Report and Write Opinion for Intemational aplication No. PCTUS2UIG23368, dated Oct 13, 2014, It pages Tnerationa Search Report and Writen Opinion for intemal aplicaion No, PCTUS2018030095, dated Aug. 13, 2018. 13 pases Japanese Notice on the First Ofice Acton, Japanese Application No. 20U6-S01218, data Feb. 19,2018, 6 pages ma, et al. "Caustic Sod Proton fom Green Lior Using the Green Liquor Spliting (LS) System.” retrieved fiom Inet ‘Mar 1.2013 hp. wwtapons Doncads unsota UNTITLED: ICho453pasp, ila inst” Sol gid separation ning yom luna the Environment, 25h Annual Hieromstallergea! Mest Ing an, 1999 retrieved online: tp! www enionmentalespert ‘com FlesteSCS¥ 4st anileaSCSS20%6SC pages? pak pases Pulping and Bloaching. PSE 47, Lecture 6, Kraft Plping Chem cals, PowerPoint tied fom Internet, Mar. 13,2013, hips ‘rw google cr uePsa-tdbetjhqnaese-ss0urce-webst ‘Sved-0CCAQHA Aur tpg AV 02 wo Sef. ashing. ‘luti2F classes pso.476%2Powerpoiat s2FPowerpoint Rena’ Srp 2047o-6e2520ktf%42$ pulping? 20cheicale pp ‘ei 9UL_UbfeNtdapqwit3-YGIBARsE- APOJCNFSIS7F ares MKEANGH 48m byAB2STAD A AWMcad-ra, 17 pases, Redy et al, "Calite Ciysal Growth Inhibition by Phosphonstes,” Desalination, vol. 12, 1973, pp. 61-73 Reddy eal, "Calcite Crystal Growth Rate tnkibition By Aquatic unic Subsiances." Advances in Crystal Growth Inhibition Teck- nologies, 2000 pp. 107-121, {aie al Elects of magnetic ld the enystalization of CaCos ‘sing permanent magnets, Chemical Engineering Sience 53, 2008, pp. 3606-3612. ‘ai etal, "Crystal Growth Kinesis of Cakitein a Dense Fiza ‘Bail Crstalize.” AICHE doural, Aug. 1998, vo. 48, No.8, pp. aos-t6ta ‘eistbch eal, “Tailor Mad” Additives and Imparites,Crysa- lation Techpology Handbook, A. Mersmana, Second Edition ‘Marcel Deer, oe, 2001, pp. S636, ‘Wrenosk, "Cytalizaton of rosin” Alla S. Myerson, Han book of Industrial Cystalizaton, Second Bion, Butervork ‘einemaaa, 2002, chapter 12, pp. 267-285, * cited by examinerU.S. Patent Jun. 6, 2023 Sheet 1 of 6 US 11,667,538 B2 00 106. +#——---— 110 11109 H109 hort} 109 104 ———> 107 108 H 109 +1109 H 109 105 «+ | 109 1 109 ._| | 102 FIG. 1U.S. Patent Jun. 6, 2023 Sheet 2 of 6 US 11,667,538 B2 200 206 + 110 H 209 H 209 Lenten 4 209 : : 207 4209 209 1209 208 205 1209 i {209 203 201 202 FIG. 2U.S. Patent Jun. 6, 2023 Sheet 3 of 6 US 11,667,538 B2 300~ 306 <—______ 308 Yd 304———+} 305+ 301 31173 302 FIG. 3US 11,667,538 B2 Sheet 4 of 6 Tun. 6, 2023 U.S. Patent v-Old cOLL zen ZL othe —2 oz \oaerridaad PULL bolt very] Che 9011 ZLLE guip | SSEEE BOLL Sith NoorUS 11,667,538 B2 Sheet 5 of 6 Tun. 6, 2023 U.S. Patent vOLL $"Sld VStL SOLL £011 zp Ls 4 osty OPL ie v Of He OZ He v OLL v f \ zelb LLL boll zsh ZELL IX zort bybl Tt y OzhUS 11,667,538 B2 Sheet 6 of 6 Tun. 6, 2023 U.S. Patent 9°Old ISLE ZbLb hs £OLL 2 : Ts ori v O€L He v OZ v OL LL v roll =F wa zeLL LZLL LELL LOLL i K, ZLLL ZOLL LLL Lape ‘ip y cen |0'sH \ oostUS 11,667,538 B2 1 RECOVERING A CAUSTIC SOLUTION VIA ‘CALCIUM CARBONATE CRYSTAL, "AGGREGATES, CROSS-REFERENCE TO RELATED s APPLICATION This application i» continuation application of and claims priority under 35 USC. § 12010 US. application Ser. No. 16/704,088, fled on Dec. 5, 2019 now U.S. Pat. No. 11,014,823, which is continuation application of and ‘laims priority to U.S. application Ser. No. 15/370,620, fled ‘on Dos. 6, 2016, now USS Pat. No. 10,519,041, which is 9 divisional of, and claims priority to, US. patent application Ser. No. 14/281,430, entitled “Recovering a Caustic tion Via Calcium Carbonate Crystal Aggregates,” fled May 19, 2014, now US. Pat. No. 9,687,393, the entire ‘contents of which are incorporated by reference herein. TECHNICAL FIELD. “The disclosure is related to @ method of recovering 8 ‘caustic solution from a carbonate solution, BACKGROUND “The industrial Kraft process takes wood and convert it Jno wood pulp for many uses. In. general, the process jnvolves cooking the wood chips in chemicals, mainly ‘comprising a mix of sodium hydroxide and sodium sulfide, ‘the resuiting liquid is commonly called black liquor, with varying chemical composition depending upon the type of woed. The black liquor is converted back jinto shite liquor ins process commonly known as ‘caustic secovery process, or chemical recovery process "The first step inthe conventional caustic roovery process js concentration of black liquor from the pulping process. ‘Concentrated black liquor is sent to a recovery boiler to (1) recover the key chemical compounds, such as sium ear bonate, sulfides et; (2) combust the organics material in the black liquor, and (3) to recover energy which may be used throughout the pulp and paper mill oF exported out of the plant. The smelt from the recovery boiler is generally mixed With a solution commonly known 2s weak liquor from the ‘caustic recovery process, the resulting mixture ofthe weak Tigo and the boiler smelt is commonly refered to as green Tiguor and generally contains sodium carbonate, sodium hydroxide, sodium hydrosulide and may contain other ‘compounds such as sodium sulfite, sodium thiosulfate and ‘other process or non-process impurities, ‘The green liquor and ealeium oxide, CaO, solids (@om= ‘monly known as quicklime or burt ime) from the dawn- stream calciner ace fed ato a strted tank reactor, generally known as slaker or Time-saker. Two reaetions, reaction (1) and reaction (2), take place in the slaker. First CaO reacts with water in the green Tiquor to form calcium hydroxide (Ca(OH), commonly known s slaked lime, hydrated lime, builders Time, pickling ime, or Chun) vi reaction (1). Huq *CHO) a As soon as any caleium hydroxide Ca(OH), i formed it 0 o orm sold calcium carbonate (CaCO,) through ueleation, via reaetion (2). CHO) eN CO og) CACO, ¥2NAOHT) ® 2 Reaction (1) and Reaetion (2) are generally known a the slaking reaction and the cavsticization reaction, respec- tively; and both reactions occur simultaneously anytime ‘water containing earbonste is mixed with quieklime. “The bulk of the causticizaion reaction takes place ia the slaker. Generally, the contents fom the slaker are fed into a series of stirred tanks, typically referred to as eaustcizers, ‘where the reactions are allowed to proceed to near comple ‘ion, The resulting solution js refered to as uncarified white liquor and contains, among other chemicals, suspended CaCO, particles, called Hime mud which are azound 15 ya in diameter ‘Thereafter, generally the lime mud is frst removed from the white liquor via clarifying tanks or pressurized filters Typical filtration equipment for this step inchudes pressur- ied tubular filters or pressurized dise filters. The resulting clarified white liqoor is retumed to the pulping process 10 ‘cook more wood chips, and the lime mul s set for further ‘washing and filtration before being calcined. Calcination is the term for converting the lime mud (CaCO,) into quiek- lime (CaO) cac0j0) =O.) o ‘The resulting off-gas is typically cleaned and discharged {o atmosphere while the produced CaO is sent back to the slaker for reaction with the green liquor “The lime mud in the conventional eastie recovery’ peo= cess fouls both the ealciner and any downstream gas pro- ‘cessing equipment. Rotary kil have been shown to tolerate the fouling caused by the lime mud and operate continuously requiring only minor shutdowns for cleaning and mainte- nance. As a result the rotary kiln isthe most common type of caleiner applied today 10 ealeine lime mud and the hot off gases from the kiln are commonly used 1 dey incoming Time mud as they will foul any other type of equipment. The rotary kiln isa large, expensive, difficult to operate piece of ‘equipment and the olfgases are vented to the atmosphere still containing a large quantity of hih grade heat resulting ‘nan overall them efficiency of around 408%, Many ofthe challenges in the calcination section of the conventional ‘caustic recovery process ae a direct result of the fine particle size of Hime mud and its tendency to foul high temperature solids processing equipment. SUMMARY In a general implementation, a method for prowing erys- {alline caleium carbonate solids in the pesence ofan alka- Tine carbonate solution in a Muidizd-hed reactive erystal- lizer such that each of at least a portion of the crystalline calcium carbonate solids reach a volume of 0.0005 ram’ to ‘S'mm* includes: reacting, in a slaking process, quicklime (CaO) aad a Tow carbonate coateat uid to yield a slury of primarily slaked lime (Ca(OH); introducing the shamy of Frimuarily slaked Time and an alkaline solution including between 0.IM to 4.0M hydroxide and between 0.IM 0 41M carhonate into a fuidized-hed reativeerystalizer that ‘includes a sold ed mass; reacting the Ca(OH) shury and the alkaline carbonate solution to deposit a portion of the precipitated calcium carbonate (CaCOs) onto the existing ‘bed of solids that (1) causes the solids to grow in volume, 2) decreases a concentation of dissolved carbonate, and G) ‘increases 4 concentration of dissolved hydroxide; and dis charging a portion of the crystalline calcium carbonate solids and the alkaline carbonate solution, the slid includ- ing particles that each ince a volume within the range from about 0.0005 inn? to about SmUS 11,667,538 B2 3 Afirst aspect combinable wit the general implementato further includes introducing seed material 10 maintain & ‘consiant mass of seed material within the Muidized-bed reactive crystallize In a second aspect combinable with aay of the previous aspects, the Ca(OH) slurry conteat includes a range of percent by weight of solid Ca(OH), between: 2 wt % t0 40 WE 9%; 20-1 % to 40 wt %; 28 wt % t0 40 wt M30 wt % to 38 wt % or 30 Wh % 10 35 WH %, A third aspect combinable with any of the previous aspeets further includes controlling an environment of the slaking process to yield Ca(OH), particles that are each sized between 0.1 19 100 micrometers, between 0.1 to 50 micrometers, tween 0.1 to 20 micrometers, beeen 0.1 10 10 micrometers, or between 0.1 to $ micrometers. Ina fourth aspect combinable with any of the previous aspects, the low carbonate content uid includes water, and ‘an amount of carbonate in the water includes less than about (0.1 moles of earbonate for every 1 mole of CaO delivered to the slaking process. In a fillh aspect combinable with any of the previous aspects, introducing the slury of primarily slaked lime includes injecting the slury into a recirculation stream influent upstream of the Muidized-bed reactive erystllizer In a sixth aspect combinable with any of the previous aspects, introducing the alkaline solution includes injecting the alkaline solution ito the reireultion stream influent upstream of the Muidized-hod reactive crystallize. In. seventh aspect combinable with any of the previous pees, introducing the Ca(OH), slury includes feeding the sly into one or more planes that are omhogonal to Mid flow along a height ofthe Muidized-bed reactive crystallize, and at one or more points within each plane. In an cighth aspect combinable with any of the previous aspects, introducing the Ca(OH), slurry inchudes using an ‘educior to dilute the sinrry with ud and facilitate transport ‘of slurry into the fuidized-bed reactive erystallizer with at Jeast one injection port or atleast one lace Muidly coupled lo the fidized-bed reactive erytallizer A ninth aspect combinable with any of the previous aspects further includes introducing an ative. ‘A tenth aspect combinable with any of the previous ‘aspects further ineludes lowering a viscosity ofthe Ca(OH), slay based on introducing the additive, ‘An eleventh aspect combinable with any of the previous aspects further includes reducing an amount of time t0 ‘complete the slaking process bused on introducing. the additive In a bwellh aspoct combinable with any of the previous sxpecis, each Ca(OH), particle in the shury includes Volume within the range from between 5310-10 mim and 510-4 mm3, between 510-10 mm3 and 6.5x10-5 mm3, beeen 510-10 mm3 and 410-6 mms, between 5x10-10 rmim3 and 510-7 mms, or between 510-10 mm’ and 6.5x10-8 mm3, based on introducing the additive Ina thirteenth aspect combinable with any of he previous aspects, the aditive includes sn inorganic or organic adi In a fourteenth aspect combinable with aay of the previ ‘ous aspects, the additive inchides a natural or synthetic ‘adkitive ‘A fiftonth aspect combinable with any of the previous aspects further includes controlling a dissolution rate of (Ca(OH), in the fuidized-bed reactive crystallizr based on. Introducing the ative 0 o 4 able with any ofthe previous live includes nitrletrieetic acid, pheno, serose, NHACI, or H-EDTA, “A seventecnth aspect combinable wth any ofthe previous aspects further includes accelerating a growth rate of the calcium carbonate crystals formed om the slid bed mass ‘within the fuidized-bed reactive erystallizer, a a particular calcium saturation level, based on introducing he additive, ‘Aneighteenth aspect combinable with any ofthe previous aspects further includes controlling one oF more pliysical properties of the calcium earbonate erystals formed within the fuidized-bed reactive erystllizer based on introducing the additive ‘Annineteenth aspect combinable with any ofthe previous aspects further inchides decreasing. porosity ofthe ealeinm carbonate crystals based on introducing the additive. ‘Arwentcth aspect combinable with any of the previous aspects further incldes increasing a hardness o a resistance to erushing of the calcium carbonate crystals based on introducing the additive, ‘A twenty-first aspect combinable with any of the previous aspects fither includes reducing a presence of low melting. salts associated withthe calcium carhonate crystals based on introdicing the additive, the low melting salis located on a surface ofthe ealium carbonate erystsl azarevates, within ‘lattice ofthe ealeium carbonate erystals, oF within pores of the calcium carbonate crystal aggregates. ‘A wenty-second aspect combinable with any of the previous aspects further inclides redicing a spontaneous fucleation of new calcium carbonate crystals based on introcicing the additive, In a twenty-third aspect combinable with any of the previous aspects, the height ofthe soi hed mass is between 15 feet aad 50 feet, between 30 feet and 50 feet, or between 30 feet and 40 fet A twenty-fourth aspect combinable with any of the pre- vious aspects further inekades controlling a level of total suspended solids within the fuidized-bed reactive erystal- Iizer to between 0 ppm and 10.000 ppm, between $0 pps and 5,000 ppm, or between 100 ppm and 1500 ppm. Tn a twenty-fith aspect combinable with any of the previous aspects, coniolling a level of total suspended Solids within the Duidized-bed reactive crystallizer inclides at Teast one off using a solis-liguid separation process: ‘controling calcium loading rut; oe conmoling atleast one equipment configuration characteristic, In a twenty-sixth aspect combinable with any of the previous aspects, the equipment configuration characteristic Jnclides at least one of a solid mass bed height, or a chemical injection delivery device In.a twenty-seveath aspect combinable with any of the previous aspects, the solids-liquid separation - process Jncludes atleast one of iirution, larfcaion, or eenteli- ation ‘A wenty-eighth aspect combinable with any of the pre= vious aspects further includes minimizing a time spent outside ofthe solid bed mass of any fluid including undis solved Ca(OH), which is withdraw from and intended! to be returned to the Thidized-bed reactive crystallizes Ina twenty-ninth aspoct combinable with any of the previous aspects, a volume of each discharged crystalline calcium carbonate solid is between 0.068 mum to 4.2 mm", between 0.22 mm* to 1.77 mm, or between 0:32 mm" t0 102 mm In a thinieth aspect combinable with any ofthe previous aspects, a volume of each discharged crystalline calcinm ‘arbonste solid is between 0.0005 mm t6 004 numUS 11,667,538 B2 5 A thinty-fist aspect combinable with any of the previous aspects further includes separting & portion of the dise fang estan cau earborte sols that re below ‘volume; and returning the separated portion tothe fiz bed eactveerystalzr fo contin tO ‘A thty-sccond aspect combinable with any of the pr vious aspects further includes removing, from the alkaline ‘carbonate solution, an amount of carbonate between 10 mole % 10 100 mole %, between 15 mole % to 30 mole %, between 15 mole % to 40 mole %, oF between 20 mole % 1 30 mole % that is delivered to the Nuidized-bed reactive cenystllizer a part of te inlueat alkaline solution stream. ‘In a thiny-third aspect combinable with any of the pre- vious aspects, the removed carbonate includes a solid cal- ium carbonate. In a thirty-fourth aspect combinable with any of the previous aspects, removing, from the alkaline carbonate ‘olution, an amount of carbonate includes leaving an amount ‘of hydroxide from the void Ca(OH)? influent slurry steam dissolved in the alkaline carbonate solution as an aqueous > hydroxide In a thiny-fith aspect combinable with any ofthe previ- ‘ous aspects, the sced material possesses similar crystalline structure to that of the erytaline calcium carbonate soi and the crystalline structe is similar to at least one silica, aragonite, ealite, or vaterite In a thiny-sxth aspect combinable with any of the pre= vious aspecis, a volume of each seed in the seed material is sclctel such that the seed material makes up between 0.5 wt 5% to 20 wt %, borwoen 1 wt % to 10 wi Mo, between 2 Wt 9610 7 wt%, or between 2 wt Yt0 5 wt Yoo the discharged ‘enstlline calcium carhonate solids. "A thity-seventh aspect combinable with any of the pro= vious aspects further inludes processing at least a portion of the crystalline calcium carbonate solids to produce a seed material; and growing new caleium carbonate crystal agare- ‘gates on the seed! material ‘A thinty-eighth aspect combinable with any ofthe previ= ‘ous aspects further incldes controlling material introduced Jno the fhidized-hod reactive erystallizer to control an ‘impurity concentration level within the crystalline calcium ‘carbonate solids below a maximum seceptable impurity ‘concentration level In a thiny-ninth aspect combinable with any of the previous aspects, an impurity of the crystalline caleium ‘carbonate solids includes one oF more of phosphates, cal ‘cium carbonate, magnesium ions, Group TL A ions, ston- ‘ium, radium, ion ions, phosphonates, o zine In a fonieth aspect combinable with any of the previous ‘aspects, reacting, ina sloking process, quieklime (CaO) and alow carbonate content fhuid to yield a slury of primarily slaked lime (Ca(OH),) includes tescting, ina slaking pro- ‘ess for pursicular time and at a paricular temperature at fre based at least in par on a desired rate of conversion of calcium oxide to calcium hydroxide Tina forty-first aspect combinable with any ofthe previous aspeos, the particular time includes between I minute and 120 minutes In a forty-sevond aspect combinable with any of the previous aspects, inttoducing the slurry of primarily slaked Time includes injecting, with one or more lanees, the slurry directly into the solid bod mass, ‘In. forty-thied aspect combinable with any of the provi= ‘ous aspects, the one of more lances inclies « plurality of Tances positioned to inject the slurry at injecting sites through a horizontal cross section ofan are of the solid bed 6 In a forty-four aspect combinable with any of the previous aspects, intexlocing an ative includes introdue- fing an ative into the staking process or the Ca(OH)2 slurry transfer system. ‘A forty-fh aspect combinable with any of the previous aspects further includes increasing a transfer rate of the slury w the Muidized-bed reactive erystallizer based on introducing the additive. ‘Another general implementation ineludes a system for rowing crystalline caleium carbonate solids in the presence of an alkaline carbonate solution such that each of atleast portion ofthe crystalline calcium carbonate solids include a volume of 0.0008 mm’ to $ mum’. inching a shaker eon- figured 1 react guicklime (CaO) and a low carbonate content fuid to yield a slurry of primarily staked time (C(O) fuidized-bed reactive erysalizer that encloses solid hed mass and includes an input for a slurry of primarily slaked Time, an inpot for an alkaline solution including between 0.1M 10 40M hydroxide and between O.1M 10 4.1M carbonate, and an output for erystaline caleium carbonate solids that include particles each with a Volume between 0.0008 mm? and about $ mam and an alkaline carbonate solution: « dewatering. apparatus that includes an input coupled to the output of the thidized-hed reactive ergstallizer and an output configured to discharge a plrality of separate streams that exch include portion of {he erystlline calcium earbonate solids and alkaline car ‘bona soution; anda seed transfer apparatus configured to Gelver Sood material into the fudizes-bed reaetve erytal- lizer to maintain a consistent mass of seed material within the fuidized-hed reactive erystalizer. na first aspect combinable withthe general implemen- tation, the seed transfer apparatus is further configured to return a portion of the crystalline caleum earbonate solids tbat inelnde a volume less than about 03 mm from the watering apparatus, together wit the seed materi othe Iiized-bed reactive erystalizer In a sccond aspect combinable with any of the previous aspects, the seed transfer apparatus is farther configured t0 return portion ofthe crystallin ealeum earbonste solids that inclnde a volume less than about 03 mm from the dewatering apparatus, 1 the uidized-bed reactive crystal lize in separate batches from the seed material, In a third aspect combinable with any of the previous aspects, the fhuiized-hed reactive erytallizer inehudes a spouted bed In a fourth aspect combinable with any of the previous aspects, the Midized-bed reactive erystalizer”furher includes a cone shaped entry section In a fifth aspect combinable with any of the previous aspects, the input for @sluny of primarily slsked ime includes an injection port fidly voupled to a receculation stream influent upsteim ofthe Huidizeded reactive erys- taller Tn a sixh aspect combinable with any of the previous aspects, the input for the alkaline solution includes an injection port tuidly coupled to the recirculation stream afluent upsteam of the Huidized-bed reactive erystallize. Ina seventh aspect combinable with any ofthe previous aspects, the input for a sluny of primarily saked ime inches a plurality of injetion prs positioned to introduce te slurry into one or more plans that are orthogonal oid flow along the height of the Muidizd-bed reactive eryta- Tizer and at one or more points within each plane. “An cighth aspect combinable with any of the previous aspects further includes an input for an additiveUS 11,667,538 B2 1 In a ninth aspect combinable with any of the previous aspects, the height of the soi bed mass is between 1S feet ‘andl 50 eet, between 30 fet and 0 feet, or between 30 feet and 40 fect. ‘A tenth aspect combinable with any of the previons aspects frther inclides a solids-iquid separator to control a level of total suspended solids within the tuidized-bed reactive erystallizr. Tnan eleventh aspect combinable with any of the previous aspects, the solidsligud separator includes at least one of a fer, a clarification system, or a centrifuge. ‘A wwelh aspect combinable with any of the previous ‘aspects farther inelndes a controller configured to contol 3 calcium loading rate to control a level of total suspended solids within the uidized-bod reactive erystallzer ‘A thirteenth aspect combinable with any of the previous aspects futher includes a separator uidly coupled to an ‘output of the dewatering appamitus to separate a portion of the discharged crystalline calcium carbonate soli that are below a desired volume, the separator including an output ‘Tuidly coupled tothe fuidized bed reactive erytallizer to return the separated portion to the Muidized bed reactive censtllizer Ina fourteenth aspect combinable with any of the previ- ‘ous aspects, the Muidized bed reactive erystallizer is further ‘configured to process at least a portion of the erystaline calcium carbonate solids to produce a seed material, and row new caleium carbonate crystal aggregates on the seed materia. ‘Ina fiReenth aspect combinable with any ofthe previons aspects, the input for the stury of primarily slaked lime includes an edvetor configured to dilute the slury with id and facilitate transport of slurry into the Buidized-bed reac- Live erystallizer; and at least one injection port or at least one lance fuidly coupled to the Hudized-bed reactive exystal lize. ‘Various implementations of the systems and processes for recavering a caustic solution fom & carbonate solution may jnchide one oF more of the following features, For example, the disclosed systems and processes may uilizea fuidized- bod reactive erystallizer miher than a standard erystallizer vessel. As another example, systems and processes may {ealure the production of calcium carbonate crystal agere- ates with average volumes equivalent to spheres. with ‘diameters between 0.1 mm to 2 mim, As another example, systems and processes may feature calcium carbonate erys- tal aggregates having the size, morphology. and physical properties so that any moisture they retin upon removal from a solution is primarily surface moisture and easily displaced or removed. As another example, systems and processes may features a low carbonate conversion rte tolerance for TSS in influent streams, high solution pH and slow dissolution of Ca(OH), slurry.'As a futher example systems and processes may run at higher efflaent TSS levels than are normally expected to produce poor reactor perfor- mance in lower pH (e., pH 7-10) systems, because itis ‘ypically expected that a higher TSS in the effluent is associated with @ redvetion in the percent of calcium retained on the pellets inside the bed mass. Further, the disclosed systems and processes may achieve economically Viable retention rates at caleium leading Fates compatable 10 ‘water treatment indistries, In some example implementa tions, the diselosed systems and! processes may operate With high pH (for example, pH>14) where most of the CO. is present as carbonate (CO,), and very litle as bicarbonate (HCO,). Further, the systems and processes may utilize a spouted bed of cone fuidized-bed reactor design for aa 0 o 8 elegant and less expensive solution that is etter suited for iret feed of a concentrated lime slurry when compared to systems designed to deal with chemical addition in appli- cations where the chemical dissolution rates are much faster fand where relative calcium carbonate supersaturation is more likely to occur "These general and specific aspects may be implemented using a device, system, process, or any combinations of devices, systems, or processes. For example, asystem of one ‘oF more computers can be configured to perform particular actions by virtue of having software, fimaware, hardware, or combination of them installed on the system that in ‘operation causes or cause the system to perf the actions. ‘One oF more computer programs can be configured 10 perform panicular actions hy vietue of including insteetions ‘hat, when executed by data processing apparatus, cause the apparatus to perform the action. BRIEF DESCRIPTION OF DRAWINGS FIG. 1 illustrates an example implementation of afd ined-bed reactive erysalization process unit that may be used as part of a larger process for growing calcium car Donate crystal aggregates while reducing the dissolved car- Donate content and inereasing the dissolved hydroxide eon- teat of the eluent lguid strea FIG. 2 illustrates a second example implementation of 3 ‘Muidized-bed reactive erystallization process unit that may be used a8 part of a larger process for growing caleinm carbonate crystal aggregates while reducing the dissolved carbonate content and increasing the dissolved hydroxide content ofthe eflvent liquid stream: FIG. 3 illustrates @ third example implementation of a Iuidized-bed reactive erystllization process unit that may be used as part of a larger process for growing caleinm carbonate crystal aggregates While reducing the dissolved carbonate content and increasing the dissolved hydroxide ‘sontent of the ellen Fguid stream FIG. 4 illustrates an example process for growing calcium carbonate crystal aggregates while reducing the dissolved carbonate content and increasing the dissolved hydroxide content ofthe eflvent liquid steam; FIG. § illstrtes an example process for growing and processing calcium earbonate crystal aggregates to convert Clarified green liquor from a pulp plant to clarified white Tiquor, and FIG. 6 illustrates an exsmple process for growing calcium carbonate crystal apgregates while reducing the dissolved carbonate content and increasing the dissolved hydroxide content of the eflluent Tiguid in an aircapture plant, in association with an airfired or oxygen-fiod caleiner, and CO, capture, and gas absorber, DETAILED DESCRIPTION ‘The systems and processes deseribed in the preset di closure, in some implementations, segregates the reactions (1) and (2) mentioned above ino diferent units within the processes instead of allowing these reaetions to oeeur within common environment andior unit. The systems and pro- ‘esses described in the prevent disclosure also use a different process and apparatus, Within which reaction (2) takes place, as compared to convention systems and processes, This apparatus, 2 Muidized-bod reactive enystalizer(pellotreac- ‘or), enabies the production of large, low porosity pellets that fare easier to handle and dewater than the above mentioned Time mud,US 11,667,538 B2 9 This pellet reactor technology is curently used in appl ceations within the water sollening amd water treatment industries under significantly dilferent conditions, environ- rents, chemistry and equipment configurations, and for talizer provides a relatively lamer surface area for the calcium earbonate to precipitate onto, thus reducing the mount of spontaneous ndceation relative toa system which ‘does not have a bed of solid material. This environment promotes growth of individual pellets having a major axis Fength of up to approximately 2 mm instead of the mich smaller particles soon in standard crystallizes (major axis lengths of the individual particles produced in standard cegstllizers are in the $ to. 100 micron range). Example implementations of systems andlor processes described herein feature operation at higher eluent TSS. levels, which are expecied to produce poor eactor perfor mance in ower pH (eg. pH 7-10) systems, This is because itis typically expected that a higher TSS inthe efluent s an indication that the calcium is nncleating and forming fines rather than precipitating onthe bed mass and essing erystal growth, therefore retaining the calcium as part of the bed ‘mast within the Muidized-bed reactive erystallizer. In ‘example implementations of systems andor processes 0 o 18 described herein, the system can be operated at muck higher e_lllcat TSS, for example, between S00 ppm and 2000 ppm. rather than below 100 ppm as commonly seen in water softening and water treatment applications. For example, the systems.and processes deseriba heroin may not follow the ‘expected rection in performance associated with high TSS content in the infuent and instead may’ operate with higher TSS levels while achieving economically viable retention ‘aes af calcium Joading rates comparable to water treatment industries. For example, inital tests ofthe described systems ‘and processes were aun at much lower loading rates of about 2 hy-Ca/m Trin onder to minimize eluent TSS to approxi- ‘mately 200 ppm in order, fo instance, to maintain the high retention levels of about 84% to 93% seen in these initial tests. However, tests showed unexpected resulls in that calcium retention above 85% at efflent TSS levels of 1400) ‘ppm and a ealeium loading rate of 15 kg-Calm/hr were achieved. ‘These results were unexpected but show th, ‘while having potentially high TSS, example implementa. tions of systems andlor processes deseribed herein ean still ‘work at economically viable Toading rats. Example implementations of systems andor processes describe herein operate with high pll (for example, plI>14) ‘where most of the CO, is present as carbonate (CO;), and very little as bicarbonate (HCO). Other applications of ‘Muidized-bed reactive crystallizers, such as seen in water {reatment, operate at lower pH of approximately 8 10, and as such are dependent on the amount of bicarbonate and carbonate in the water, due 0 the nature ofthe bicarb-carb ‘equilibrium reaction, This effets the relative calcium car Donate supersaturation within the vessel in a very different ‘manner than when the pl is higher, for example above 12, asin example implementations of systems and/or processes ‘eseribed herein, Ths, the kinetics are different operat the higher pl] ofthe curent application, and the goversing resistances within the process are also different Tn some aspocts depicted by FIG. 2, the systoms andor processes enable the use of a simple reactor design, for xample,a spouted or cone Muidized-hed reactor. The slow issoltion rate of Ca(OH), in example implementations of systems andlor processes described herein allow for the Ca(OH), slurry to be added upstream of te solid bed mass, {or example mixed into the influent solutions (eg. recireu- Jation andor alkaline solution) upstream ofthe fidized bed sateral, The spouted bed or cone Muidized-bed revctor design may be simpler, less expensive, and better suited for ‘iret feed of a concentrated lime slury when compared to systems designed to deal with chemical addition in app tations where the chemical dissolution rates are much faster and where felative calcium carbonate supersaturation is more likely to occu In some aspects, the use of influent solution tat is low in impurities eomsisting of, for example phosphates, phospho- nates, Group IA ions, polyacrylic acid, ion, and magne- sium. s prefered, as these impurities can inhibit he calcinm ‘arbonate growth rte or become included within the crystal structure, changing the erystal structure and properties. In some implementations, Group ILA ions may ineude ions of elements Be, Mg, Ca, Se, Ba, and Ra on the periodic table of elements. Those elements are aso often called alkaline- ‘earth metals, These metals tend to lose two electeons to Form M+ ions, such as Cast, Best, Mgs¢, ete. The amount of Group TIA ions brought into the process may be controled, since these metal ions have the ability to compete with the intended Ca,+ ions in the crystallization lattice causing changes to the pellet properties. These ions ean also react to orm salt compounds ad, if incorporated into the pellet,US 11,667,538 B2 19 may change the pellets physical andior reactive properties, for example making the pellet softer and more prone to attrition, Other ions or additives could be selected which ‘when included in the erystallatice via the method above, ‘will result in an increase in harness of the macroscopic ‘etal, making it less prone to attrition. ‘Bivalent itoa ean atach itselt into the calcium carbonate cenystl structure, and duet its size difference from eau ‘carbonate, it can cause disruptions tothe erystal stricture, placing strain on the crystal structure tht leads to bigher Fiskof attrition and fines, Phosphates can also at inasimilar fashion, whereby they attach t the erystal and prevent further Ia addition, some phosphonate compounds Such as HEDP have boen shown to inhibit caleium carbonate posh (ex, used in the cooling towerichiller industry to prevent scaling). "Additives (and for that matter impurities) may alter erys- tal nucleation and growth, Whether a given additive allots ‘enstal_nuceation (eg, rather than crystal growth) ean be ‘determined by measuring the wid of the metastable zone, ‘which is widened by macleaton inhibitors. There may be several generic features of how additives and impurities can allect crystal nucleation. For example, to efictively inhibit ‘eystal nucleation (eg, ines formation) the additive should Jnteract strongly with the solute (in this ease calcium car bonate solid) and also have a structure that can disrupt the Periodicity associated with the emerging erystal nucleus ‘These characteristics may ensure that tbe additive ends up ‘within the aggregating crystals and that the erystals must ‘de slurry with the green liquor stream 1211 discharged from the pulp plant unit 1210, The calcium hydroxide raets with the dissolved carbonate coateat of steam 1211 in a co ‘wold manner via reaetion (2). This reaction is carried out jn a Muidized bed reactive crystallizer which has been ‘optimized to operate ina high pl environment. The ealeiam hydroxide slurry of stream 1111 is metered into this device 1p conto the rte at which caleium carbonate is formed and the device is arranged such that reaction (2) oceurs in close proximity to growing calcium carbonate crystal aaregates As a result of contclling the rate of reaction (2) and the ‘environment as reaction (2) occurs, caleium carbonate erys- tal aggregates with average volumes equivalent to spheres swith diameters betscen 0.1 mm and 2 mm are prodced The Tiguid from this equipment has had a portion of the ‘carhonate precipitated ont (redacing the dissalved carbonate concentration) and addtional hydroxide dissolved in (in- creasing the dissolved hydroxide concentration), and the resulting liquid with ts modified composition is discharged back to the Pulp Plant unit 1210 as the product clarified ‘white liquor steam 1221 while the solid eleium carbonate cesta aggregates which have grown to the desired size are removed from the fuidized bed reactive erystalizer as @ mixture of solution ad calcium earbonate crystal agaregates and sent onward to the next processing step as stream 1121. ‘Due to the size, morphology, and physical propertis of the calcium carbonate erystal aguregatesin steam 1121 they ‘ean be almost completely sepamted from the solution ia stream 1121, such that the accompanying. solution after Separation isles than 159% ofthe total Weight of the ealeinm ‘carbonate erystal aggregates, in unit 1130 using industrial Separation equipment such as screens or spiral classifies The undiluted hydroxide solution is sent back to the Pulp Plant (unit 1120) as steam 1231 and has similar properties to clarified white liquor in the pulping process. The eaeinm ‘carbonate erysial aggregates are then Washed with stream 1103 shich consists of clean water and removes « majority ‘of any residual solution on the ealeium carbonate crystal fggregate surface. The spent caustic wash water (seam 1232) is also sent bock to the Pulp plant (unit 1210), to be used fo dissolve the lack liquor and form green liquor. The solution and water removed in this processing step could instad be recycled back to the Duidized bed reactive crys talizer unit 1120, The calcium carbonate crystal agaregates ‘which have now been washed and separated from the hydroxide solution are sent as steam 1132 to a system such as acaleiner which is designed to conver them from CaCO. to CaO Which can be reused in the slaker unit 1110. The pellets produced! by this process have physical properties ‘and characteristics, such as size, low porosity, low alkali 0 o ory content, which are preferable to lime mud and enable the use ‘of more ellicent andor low cost calcination equipment. FIG, 6illustates an example process 1500 for growing ‘and. processing caleium carbonate crystal aggregates by reacting the incoming Ca(OH), slury and the alkaline carbonate solution via the causticzaton reaction (feaction {@) above) to deposit portion ofthe precipitated caleinm carbonate (CaCO,) onto the existing bed of solids eausing the solids t grow in volume as well as reducing the dissolved carbonate content and increasing the hydroxide content of the figuid stream as applied in the process of ‘apluring CO, from atmospheric ait. Process 1500, as ilu trated, inlndes a gas absorber or airabsorber or ar-contac~ tor 1510 in material communication with the Muidized bed reactive crystallize 1120 and the separation and washing station 1130. Further, process 1800 includes, in the illus ‘tated implementation, the unit 1110 (e., slaker, the dryer 1140, and calciner 1150. Inthe illustrated process 1500, the gas absorber unit 1810 hsorbs « fraction of CO, from atmospheric sir using « ‘combination of CO,-Kean solution stream 1421 from the ‘uidized bed reative erystallizer 1120 and dilute CO,-lean stream L491 fom separation and washing unit 130. After the absorption of CO,, the as absorber returns te resulting COpetich steam 141 to unit 120. Therefore in one aspect, at Teast CO,-lean solution may be provided to the gas absorber, and the process in-tum receives the CO, rich solution Irom the gas absorber In the illustrated process 1800, in association with a caleiner, CO, capture, and a gas absorber is illustrated. In some aspect, the slaking unit 1110 as employed in this embodiment operates in the same or similar manner, using the same or similar input material streams and outputting the sane or similar materials a shown i FIG. 4 and desribed inthe fist embodiment. Once the ealeium hydroxide slurry (stream 1111) is pro- duced itis transfered to unit 1120 which grows ealeiam carbonate aggregates by reacting the calcium hydroxide shy with the CO.-rich stream L411 discharged from the ar ‘oF gas absorber unit 1510, The calcium hydroxide reaets ‘with a portion of the dissolved carbonate content of stream 411 ina controlled manner via tesction (2). This reaction is carried out in a fluidized bed reactive erytallizer which ‘has been optimized t operate in high pH environment. The calcium hydroxide slur of steam 111 is metered ino this ‘vice to conteol the Fate at which ealeium carbonate is ‘ormed andthe device is arranged such tht the reaction to orm the calcium carbonate occurs in close proximity 10 arwsing calcium carbonate crystal agarepates ‘As a result of controlling the rate of reaction (2) and the cnviroameat as reaction (2) occurs calcium earbonate crystal aggregates with average volumes equivalent to spheres with ‘Gamers between 0.1 mm to 2mm are produced. The iguid from this equipment has had a portion of the carbonate precipitated out (reducing the dissolved carbonate concen- tration) and additional hydroxide dissolved in (increasing the dissolved hydroxide concentration), and the resulting Jiquid with its modified composition is discharged back to the air or gas absorber unit 1810 as the CO.-lean see 1421 while the solid calcium carbonate erystal aggregates ‘which have grown (othe desired size are removed trom the Auidized bed reactive erystallizer as & mixture of solution and calcium carbonate crystal agaregates andl sent onward 10 the next processing step as stream 1121 ue to the size, morphology, and physical properties of the calcium carbonate crystal aggregates in stream II2L they can be almost completely separated from the solution