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    US8071067B2

    Uploaded by

    Amin Zamani

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    © All Rights Reserved
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    (2) 6a 03) en @ 6s) oy (32) 658) (6) 'US008071067B2 United States Patent (10) Patent No. US 8,071,067 B2 Eskilsson et al. 4s) Date of Patent: Dec. 6, 2011 PROC TABLE FERRIC 6.902700 12* 62005 Limetal aris ous soovocttost AI? 11200) Temasho 2349 Spouvotions Ale ‘13uD8 tek eal Soon Inventors: Keister Eskilsson, Landskron (SE) eff Campbell, Lakeland, FL. (US): Stig FOREIGN PATENT DOCUMENTS. Gunaarstonficinghorg (SE) Jan BE se Ti Paslice, Det Mi (US) Be OS as Lt ae Sooras © "eto Asiance:Kemira Water Soations ne 7 eR AL 993 Takelan, PLUS) 7 cues areas oti ’ B Seroer A> Patent i excnded or antl under 35. FR 2oHeio AL USC. 154) by 361 da, S47 Appl. No 121471,868 Filed: May 26, 2009 Prioe Publication Data US 2010030125541 Dee. 2,2010 Incl. cuiG 4910 (2006.01) Cl... 423/493; 423/481; 425/488; 425/D1G. 1 Field of Classification Search 425/481, 435/488, 493, DIG. 1 ‘See application file for complete search history References Cited US. PATENT DOCUMENTS 2096885 A 101987 Lad Senses A "Sons MaComik ta dimenas & Uioee Lander Siisam A Glo Clursta SQuoI A oer Labererat SSoozes A dood San Dist tal Sionoot A 105 Creat Sine A Sloee Claret 8 0 6 5 i“ 28 Zi gu 210 2° Se Z7 56 zs a 3 2 1 a 10111213 14 15 16 (Continved) (OTHER PUBLICATIONS Inverasional Search Repost; Date of Mailing: Avg. 26, 2010 for International Applicaton No, PCTUS2O10 035931, 6 page, (Continsed) Primary Examiner —Ngoc-Yen Ngoyen (74) Attorney, Agent, or Frm Thomas, Kayden, Horstemeyer & Risley, LLP on ABSTRACT Processes for forming ferric corde soutions that are stable atrelatively low temperatnes and stitable for transportation ‘without precipitation ae provided, The stable ferric ehlorie ‘olutons bave a ir content of bout 16 to about 23 weight percent and « hydrochloric acd content of about 11 to wbout 17 weight percent, whervia the Terie chloride soluion is sable solution andor reversibly freezes at =10° C, Also dis ‘lose are processes lor reconstituting the sable feriechlo- rides solutions to provide a fina iron content of 10 10 14 ‘weight percent and lower the concentration of hydrochloric ‘acid contained therein, 21 Claims, 1 Drawing Sheet O00 2-PHASE LINE 17 18 19 20 21 22 23 24 Fe WEIGHT(PERCENT) US 8,071,067 B2 Page 2 FOREIGN PATENT DOCUMENTS sv L2s70s7 AL 911986 ® casos + 34078 3 Touts A 11589 OTHER PUBLICATIONS i onoassiy © 1961 i Gras a + vot ‘Waten Opinion; Dat fwiing: Aug. 2, 2005 fr i omansisid * "$3000 ication No, PCTUS2O100359316 ko ‘nies 3206 a ns sv 1081808 AL 11983 * ited by examiner U.S. Patent Dee. 6, 2011 US 8,071,067 B2 18 0 16 15 ; 5 213 Zr NH eu 4 = 10 = 9 & 8 eT se zs 4 sat O00 2-PHASE LINE 1 0 oo 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 Fe WEIGHT(PERCENT) Fig. 1 18 7 . 16 . os es ++ & gl sss £13 * + Sle * Fu . ° 210 oe 9 oe tf © 2-PHASE PRECIPITATION e 4 FREEZING REVERSIBLE 77] m_STABLE>30 DAYS 6 15 16 17 18 19 2 2 2 2 Fe WEIGHT (PERCENT) Fig. 2 US 8,071,067 B2 1 PROCESSES FOR MAKING STABLE FERRIC ‘CHLORIDE SOLUTIONS, BACKGROUND ‘The present disclosure genemlly relates to ferie chloride solutions, and more particularly, to processes for making stable ferric chloride solutions stable for transport thers, ‘wherein the iron content in these soltionsisabout 160 bout 23 weight percent and docs nol precipitate al temperatures treater than =10° C “Aqueous solutions of ferric chloride (PeCl,)are commonly used as floceulating agents for treatment of water, for hydro- en sulfide contol, struvite contro), sludge conditioning, ‘colorremoval, phosphateremoval, heavy meta moval, line softening applications, and the like. For water treatment applications, the trivalent iton functions exceptionally well qorboth potable and wastewater clarification, Solutions cone taining ferric chloride can be prepared ina variety of ways. For example, ferric chloride solutions ean be produced by ‘oxidation of ferrous ebloride using oxygen (0) or chlorine (Cl); by dissolution of ferric oxide with hydrochloric sei nd the lke. These ir solitons ae typically suppl with ‘an iron concentration about 10 to about 14 weight percent bhcanse at iron concentrations greater than 159% by Weight, precipitation can result especially when the ferrie chloride Solution is subjected to relatively low temperatures of about OC. or less ‘Moreover, because many of the processes for mamafsetur- ing ferric ehioride use hydrochloric acd as a reagent in the reaction, precipitation can result at even lower iron concen- trations depending on the concentration of hydrochlorie acid inthe final feric chloride solution. For example, the reaction ‘of frre oxide with hydrochloric aeidto form ferric chloride ‘ean equated as follows: 1,0 ,selC1-2FeCi 1,0 The hydrochloric acid and ferrie oxide reaet to form ree tion products including ferric chloride, water, and residuals including unreacted hydrochloric acid and unreacted ferric ‘oxide. The amount of unreacted hydrochloric acid in the product is typically onthe order ofa few weight percent at Ios. Asshown in priorart FIG. 1, the phase behaviorat 0° C. ‘ofa ferric chloride, hydrochloric acid, and water system is, ‘uch that the maximum iron content in solution decreases as «function of increasing hydrochloric acid up to an excess of about 15 weight percent hydrochloric acid In view of economies of seale, it would be desirable to ‘maximize the amount of tvalent iron content available in lerric chloride solutions and provide high ion coatent ferric ‘chloride stutions that are stable during transportation from ‘one location to another location, especially if subjected t0 relatively low temperatures. Aeconlingly, it would be desi able and a significant commercial advantage to define a pro- ‘cess and solution composition that provides a stable ferric ‘chloride solution with increased iron content, BRIEF SUMMARY Disclosed herein are processes lor stabilizing a ferric chlo Fide solution and processes for reconstituting the stable feric chloride solutions. In one embodiment, a process for stabi Tizinga ferric ehlorie solution comprises evaporating water froma erie chloride solution to inetease an ion content and decreases hydrochloric acid concentration; nd exposing the {ere chloride solution to gaseous hydrochloric acid in an noun effective to decrease the iva conten and increase the 0 o hydrochloric acid concentration, wherein the final iron con ‘ents 16 to 23 weight percent and the free hydrochloric acid concentration is 11 0 17 weight percent, and wherein the {ert chloride solution isa stable solution and/or reversibly Treezes at -10° C. In another embodiment, the process for forming a sable ferric chloride solution comprises mixing sn iron material ‘with liquid hydrochloric acid and gaseous hydroclorie acid to forma fericchloride solution with an ton content of about 16toabout 23 weight percent anda hydrochloric eid eonte ‘of about 11 to about 17 weight percent, wherein the ferie chloride solution isa stable solution andr reversibly freezes at temperatures greater than 10°C. A process for reconstituing an aqueous Ferrie chloride solution having an ron content of about 16 to abot 23 weight percent andthe hydrochloric acideoncentrationof about 11% about 17 weight percent comprises diluting the aqueous feric chloride solution to reduee the iron content; mixing the dilute ‘aqueous ferric chloride solution with ferrous ion containing pickling liquor, and oxidizing o form a ferric chloride solu- tion having less than 2 percent by weight hydochlori acid ‘concentration and about 1D to about 14 weight percent feric ‘In another embodiment, the process for reconstituting an ‘aqucous Ferric chloride solution having an iron coatent of bout 16,0 about 23 weight percent and the hydrochloric acid ‘eancentraion oF about 11 to about 17 weight peoest,com- prises diting the frei chloride solution; and adding an ion contzining material to the ferric chloride solution in an amount eifetive to decrease the hydrochloric acid concen- tration to less than 2 percent by weight ofthe leric chloride solution and inerease the Ferric ion content about 10 10 fout 14 Weight percent ‘In yet another embodiment, the process for reconstituting ‘an ageous frre chloride solution having an iron content oF bout 16t0 about 23 weight percent and the hydrochloric acid ‘concentration of about 11 1 about 17 weight percent com- prises evaporating HCI from the feric chioride solution to concomitantly reduce the HCI concentration to less than $ ‘weight percent and increase the iton content in the feric chloride solution; and diluting the ferric chloride solution to ‘ecease the iron content to about 10 to about 14 weight percent and the hydrochloric acid to less than 2 weight per Instill another embodiment, proces for fomning a stable {erie chloride rolution comprises mixing an iron material with ferrous andlor feric chloride solution and gaseous hydrochloric acid to form a ferous andlor ferric chloride solution with an iron content of about 16 to about 28 weight percent ands hydrochloric acl content of about 11 to about 17 weight percent, whercin the ferric chloride sotution is 2 stable solution andlor reversibly freezes at temperatures steater than =10° C. The disclosure may be understood more readily by eler- cence tothe following detailed description ofthe Various fea- tures ofthe disclosure aid the examples included therein BRIBE DESCRIPTION OF THE DRAWINGS. Referring now to the figures wherein the like elements are numbered alike FIG. 1 graphically illystates phase behavior of a ferric chloride, hydrochloric acid and water system at -0° C: FIG. 2 graphically illustrates various experimental ferric chloride solutions that exhibited stability, reversible frecring, and 2-phase precipita US 8,071,067 B2 3 DETAILED DESCRIPTION Disclosed herein ae processes for forming frre chloride solutions baving an iron content of about 16 to about 23 ‘weight percent that do not precipitate at temperatures greater than =10° C. The ferric chloride solutions are stable and well suited for transportation between locations. IG. 1 graphically illustrates a phase diagram of a ferric chloride, iydrochlori acid (also referred to herein as ICT), tnd water system at °C. As show, the stability line at O° C shows that as the amount of hydrochlorie acid is increased rom zero upto about 16 weight percent, he solubility of oa Jin the frre chloride solution asa fanetion of weight percent is deereased, Inother words, the solubility ion ia the feric chloride solution decreased from about 15 weight percent ron fo about I weight percent ion upon inereasing hydro- ’hlorie seid concentration up to about 16 weight percent. AL hydrochloric acid concentrations greater than 16 weight per ‘ent, the ferie chloride solutions were stable fr ion concen- teaons greater than 15 weight percent, The phase ithustrates that ferric chloride solutions stable at 0° C. are provided at hydrochloric acid concentrations of about 11 10 bout 17 weight percent, wherein the iron contcat is at about 16 w about 23 weight percent ‘While not wanting tobe bound by theory, itis boioved that «simile phase behavior will exist t = 10°C. Referring now ‘FIG. 2, there is graphically shown precipitation behavior at 10°C. for various ferie chloride solutions, which is consis- tent with the phase behavior observed at O° C. in FIG. 1. FIG. 2 illustrates actual data points for various feric chioride solutions that exhibited solution stability for greater than 30 days, reversible freeing, and precipitation at=10° C, Similar to that observed in 1G. 1, less LICL By weight percent was needed to provide solution stability or reversible freezing as the iron weight percent content was increased fom 15 weight percent to 21 weigh percent Ttshould also be noted that there are regions of hydrochlo- ric acid concentrations shown in FIG. 2 where the feric chloride solution reversibly freezes at 10° C., which can be ‘sed to expand the range of available ion content and hydro- ‘chlorie acid concentrations fr transportation in tanks oF ‘way cars such that free chloride salt precipitation is avoided. temperatures of about 10° C. or greater. Clearly, the samples in the phase region that leads (© reversibly frozen Tere chloride solutions have diferent kinetic properties ‘depending on the concentration of FCT inthe ferric chloride solution “The present diselosure details methods that provide stable {erie chloride solutions and/or solutions that are reversibly frozen at 10" C- having the ion concentration at about 160 bout 23 weight percent wih hydrochloric acid of about 1 40 about 17 weight pereent, thereby providing high trivalent iro ‘content frre ebloide solutions that ae stable during trans portation at relatively low temperatures, These stable soht- tions ean then be reconstituted onsite Tn one embodiment, the process generally inchides evapo- rating water froma fei chloride solution to inerease the ion ‘content toa desired amount, greater than the above noted target amounts and then exposing the ferric chloride solution tw gaseous hydrochloric acid in an amount effective ‘decrease the iron eontent tothe target amount and inerease the free hydrochloric acid concentration, wherein the fina iron ‘content is about 16 to aout 23 weight percent and the free hydrochlorie acid concentration is about 11 t0 about 17 ‘weight percent. Evaporation increases the iron content and ‘concomitantly removes portion of the hydrochloric cid and ‘ater, Optionally, the Ferre chloride solution is first provided 0 o 4 by oxidizing aferous chloride solution sucha ferrous chlo- side containing pickling liquor. The iron content and the free hydrochloric acid concentration age selected so ato provide 4 ferric chloride solution that is a stable solution andlor reversibly freezes at ~10° C. In this manner, the ferie chla- ‘ide solution with the desired iron content and hyerochlaric acid concentration can be safely transported from one loca tion to another location withost precipitation at relatively low temperatures Tnanother embodiment, solid iron containing materials are first mixed with liguid HCl and then gaseous HCL is addled 10 increase dissolution ofthe solid iron containing materials to provide an iron contentofabout 16:0 about 23 weight percent ‘nd a free hydrochloric acid concentration is about L110 bout 17 weight percent. The solid iron containing materials vay be Terie andioe Ferrous miaterials. Dissolution of the sold iron material, similar to HCI) absoepton, is exotber- ‘nic. Suitable solid iron materials include, without limitation, iron, serap iron, ron ore et hemuite, magnetite, imonite, ‘nd the ike), all industrial formed iron oxides, and the ike Optionally, instead ofa solid ion containing material, pick- Jing iquors canbe usd that contain high amounts of ion, and the ike. Again, the pickling liquors may include ferrous salts ferric salls,or mixtures thereof The pickling iquor may be concentrated such as by distillation fo inerease the iron con- tent if desired, In anther embodiment, solid ferrous containing materials ‘are mixed with Tiquid FICTand gaseous HCI, The ferous ions fare subsequently oxidized to Terie ions s0 98 to provide @ ‘Sable fer chloride safution having anion content of abut 16 to about 23 weight percent and a free hydrochloric aid ‘concentration is about I tosbout 17 weight pereent. In some tembodiniens, oxidation may occur prior ta contact with the gaseous HCl Tayet another embodiment, solid iron containing materials ‘are mixed with ferous andor feric cilorie solution and ‘gaseous hydrochloric acid to form a ferrous and/or ferie lorie solution with an iron content of about 16 0 about 23 ‘weight percent and a hydrochlarie acid content of about 11 to about 17 weight percent, wherein the ferric chloride solution js stable solution andioe reversibly freezes st temperatures steater than ~10 C. The ferous ions contained therein can be ‘oxidized prior io or subsequent to mixing with the iron cone ‘aining material and yaseous hydrochloric acid Tnsill another embodiment, a femous ebloride hydrate of the formula FeCl, XH,0 (eg. dihydrate, tetrahydrate, and the like) is precipitated from the ferous chloride picking Jiquor and subsoquently isolated. Water o¢ HCI or picking liquids then added o the Fermous chloride dihydrate to form 4 solution to which gaseous HCl is then introduced. The ‘acidified ferrous chloride solution is then oxidized to form a ‘table erie chloride solution having an iron content of abut 16 w about 23 weight percent und a free hydrochloric aid ccncentration of about 11 to about 17 weight percent. Option- ally, oxidation ofthe ferous ions inthe solution can occur prior o contact with the gaseous FICL It should be noted that in any ofthese embodiments, the starting solution can contain 2 mixture of ferous and feric ions, if desired. I ferrous (Fe™) ions are present the process ‘may further include oxidation with oxygen (or ater oxidants suel as, for example, Cl,, NaCIOy. ai and the Tike) 10 ‘nerease the oxidation stat of the Fe to Fe", With respect ‘o oxidation with oxygen, hecause the stabilized fei chlo- ride solutions contain high ratios of HCI, itis belived that lower oxidation temperatures can be employed. The high acid concentrations appear to facilitate oxidation, For example, ‘ypically a temperature ofabout 70° C-80° C. anda pressure US 8,071,067 B2 5 ‘of 6 bars are needed to start oxidation with O,, which isthe Increased 120°C. tocomplete oxidation However, withthe high acid content present in the solution, oxidation has been ‘observed to start tt about 20° C, with a pressure ws low as 3 bars and was finished t about 80°C. It should be ote that the dissoltion ofthe solid iron material (or acidification of| the picking liquor andthe absorption of HCl gas ean bedone in one step, i desired, With reward to magnetite soid iron ‘material, dissolntion can result in feerous chloride precipi tation, which can be removed by fitation and processed as noted above to form stable feeric chloride solutions ‘The generation of the gaseous FICI for inclusion in the {eric chloride solutions is aot intended to be limited to any Particular process. For example, the HCI gas (g) ean be gen- erated by the combustion of chlorine and hydrogen on demand. Advantageously, combustion generates. eneray, Which may alo be ulized. Allematvely. itis possible to

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