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    Paten Poly Aluminium Chlorida

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    Paten Poly Aluminium Chlorida

    Copyright:

    © All Rights Reserved
    Download as PDF or read online from Scribd
    Flag for inappropriate content
    13 views16 pages

    Paten PAC

    Uploaded by

    rizkamaya28_rm
    Paten Poly Aluminium Chlorida

    Copyright:

    © All Rights Reserved
    Download as PDF or read online from Scribd
    Flag for inappropriate content
    of 16
    ‘US 20071 cu») United States 2) Patent Application Publication co) Pub. No.: US 2007/0187256 A1 oy 76) en @ (60 Pratt et al. POLYALUMINUM CHLORIDE AND ALUMINUM CHLOROHYDRATE, PROCESSES AND COMPOSITION: HIGH-BASICITY AND ULTRA HIGH-BASICITY PRODUCTS. Inventors: Willam E, Pratt, Morehead City, NC (US); Joseph J. Stevens, West Point, MS (US) Comesponilence Address: DORSEY & WHITNEY LLP INTELLECTUAL PROPERTY DEPARTMENT SUITE. 1500 50 SOUTH SIXTH STREET MINNEAPOLIS, MN 55402-1498 (US) Appl. Nos 111619,483 Filed: Jan. 3, 2007 Related U.S. Application Data Provisional application No. 601756 848, filed! on Jan. 6.2006, Provisional application No, 60/829,804, filed fon Ost. 17, 2006. S7256A1 (43) Pub. Date: Aug. 16, 2007 Publication Classification ca) 5B 0 (2006.01) (2) 2051508 6 ABSTRACT The invention relates generally to proceses for the prodic- tion of high-basiity and ultrhigh basicity polyalaminam chlorides incloding aluminum chioraydrate. The processes can produce products of a wide range of basiciies and are particularly useful in producing high basicity products. The pracess can produce & wide range of solution coneentations ‘nd are particularly useful in producing high solution eon- centrations. The processes described generate high purity praducts, which are fre af by-product sl(s). The processes Seseribed herein ean also be wilized to produce enhanced ‘licaey polyaluminum chlorides includ aluminum chlo- rohydrate. When compared to conventional processes for ‘manufacturing. these Compounds the processes, disclosed herein are unique insofar asthe disclose! processes do not rehire aluminum metal asa stating material. The products ‘of the processes are suitable in applications ineluding water purification, catalysts, and antiperspirats. In addition, the Invention is directed to the products prepared by the pro- cesses described herein, anode a | 7 cathode ik fe] K] ME pe DATE pep Oo k il | i Solutions 4 Receiving Solutions Electrodialysis Stack Showing the Removal of Electrolyte, MX from Depleting Solution ‘and the Concentration of MX in the Re iving Solution Patent Application Publication Aug. 16,2007 Sheet 1 of 5 US 2007/0187256 AI anode a | a re | ie gg lode - aa] Depleting Solutions Receiving Solutions Figure 1. Electrodialysis Stack Showing the Removal of Electrolyte, MX rom Depleting Solution and the Concentration of MX in the Receiving Solution Patent Application Publication Aug. 16,2007 Sheet 2 of 5 US 2007/0187256 AI Current Density for PAC Eleetrodialysis @ Various Temperatures ‘EURGC-20, (560 em2 by 20 membrane pairs). CMX, ASM Charge passed (mote e) Figure 2. Patent Application Publication Aug. 16,2007. Sheet 3 of 5 40% PAC Enriching Stream ~ | Depleting Stream 40% PAC US 2007/0187256 AI Production | Make-up Aiuminum Es | Tribydrate & HCL Enriching Stream 40% PAC. Figure 3 Process Patent Application Publication Aug. 16,2007 Sheet 4 of 5 US 2007/0187256 AI Low- Ultra High- Basicity Basicity PAC PAC t High- Step 1 Basicity Step 3 PAC > Electrodialysis Electrodialysis Step 2 Heat Treat Figure 4. Patent Application Publication Aug. 16,2007 Sheet 5 of 5 US 2007/0187256 AI mooz> on chy on PAC FIGURE 5. Schematic Representation of Bipolar Membranes to Increase the Basicity of Polyvalent Metal Hydroxychlorides Bipolar Cell Configuration Employed for Production of ACH at 40°C fs Ones Fale Se Sg) 21° IE|o Og Se PES 3 oe 7 ae FIGURE 6. Cell Configuration of Bipolar Electrodialysis Stack US 2007/0187256 Al POLYALUMINUM CHLORIDE AND ALUMINUM ‘CHLOROHYDRATE, PROCESSES AND COMPOSITIONS: HIGH-BASICITY AND ULTRA, HIGH-BASICITY PRODUCTS. CROSS REFERENCE TO RELATED 'APPLICATIONS| [0001] This pplication claims benetit under 35 US.C. § 119(@) 10 US. Ser, No, 601756,848, entitled “Process for Increasing the Basicity of Polymetal Halides led Jan. 6 2006 (attomey docket number 186931/US) by William FE Pratt and Joseph J. Stevens [0002] This application also claims benefit under 35 USC. § 119{6) to US. Ser. No. 60'829,804, emilled “Poly- ‘sluminum chloride al Aluminum Chloroby date, Processes ‘nd Compositions: High-Basicity and Ultra High Basicity Prodiets™(attomey docket number 186931/18/2), filed Oct. 17, 2006 by William F. Prat and Joseph J. Stevens, the ‘contents this provisional application of which are incorpo> rated herein by reference in their entirety FIELD OF THE INVENTION [0003] This invention relates to process to produce high basicity polyaluminum chloride and sluminam chlorohy- “rate By electrodialysis, BACKGI {OUND OF THE INVENTION {0004} Polysiuminum chloride (PAC) isthe name given to the family of compounds defined by the Formul [0005] Where O12.5%) Vina variety of treatment, paper making. ant The processes taught by the perspirants and catalyst present invention produce unigue products with regard to molecular species distribution and said products per- orm uniguely in product applications [0048] The present invention embraces processes for increasing the hascity of aluminum compounds. The pro- cesses are unique when compared to existing commercial processes for making the products because the use of expensive aluminum metal is avoided and wasteful neutral ization with alkalis is avoided. The processes ean produce products of a wide range of basieities and are particularly ‘selUl ia producing high-basiity products and ultra high- basicity products. The process can produce a wide range of solution concentrations. The processes described generate high pority products. The products of the present invention are compounds of Formula MalOH.X o [0045] - wherein “a” i the valence ofthe metal ion; [0046] x is an anion; [0047] O ‘cesses of the present invention are markedly improve by ‘operating at increased temperature. FIG. 2 compares the ‘current dessity at SO" C, $5° C, and 60? C. asa function of basicity for the electrodialysis processes of the present jvention. The information depicted in this diagram shows that current density is reiuce asthe basicity is increased but that the reduction ia curent ensity is mitigated by increas- ing temperate. This reduetion in current density. at eased basicity was confimied by operating the electro alysis processes ofthe present invention at various tempera tures, Operation at 58°C. t 63° C. permitted. current densities of 50 to 40 mamplem’ tobe realized over the range ‘of basicites from 402% to 70%; in contradistinetion opera= tion at ambient temperature resulted in current densities of 42 to 18 mamplem over the same range of basiciies, AUSS° (C.the current density at 83% basicity was 30 mamplem?; while operation at ambient temperature resulted in a current density of 2-4 mamplcm? at 8¥% basicity. Without being bound by theory, these observations suggests that polyal- ‘minum chlorides participate in a procest that cases mem- brane fouling as the basicity increases and that this Fouling process is mitigated asthe temperature is increase. [0067] ‘The observations cited above demonstrate thatthe ‘current deasity for the electrodialysis processes of the present invention inereases as the temperature of operation Increases. The temperature of operation for electrodialysis is limited by various characteristics elated tothe materials of ‘constriction ofthe eleciradialysis stack. Although, ion per- meable hydrocarbon membranes rate to 80° C. af operation are available, operation above 40°C. is uncommon. Stack dlstortion, spacer manufacturing technology and. spacer Jnegrty’ re the primary factors Hting higher temperstare ‘operation. Stack eomponents that permit the present inven- tion to operate at temperatures tp to 65° C, were utilized in the present work. Operation at temperatures higher than 65° C, while not practical with components currently available ‘would be beneficial tothe process ofthe present invention, [0068] Membrane fouling, the deposition of materials (exe, solids and or gels) that inhibit ion permeable me Aug. 16, 2007 borane performance, leads to membrane degradation and should be minimized ia order to maintain high curent densities for extended periods of time, Macromolecules with ionizable functionalities promote membrane fouling since their charge causes them 10 migrate to the ion permeable membrane surface but thie size prevents passage through ssid membrane, Polyaluminum chloride solutions form mae- romolecules and this stibute adversely influences the per formance of electrodialysis. The propensity of PAC sol tions to form macromolecules increases as the basicity increases and or as the concentration of the PAC solution increases. At bascities of greater than about S0% and oF concentrations above about | molar (measured on an al ‘minum basis) membrane fouling ean adversely impact the racesses ofthe present invention I was surprisingly’ found that the fouling can be minimized by either using freshly prepared starting materials and or heat treating the eaction solutions prior or during the electrodialysis process. twas surprisingly discovered, that feed stocks forthe electrod- alysis processes ofthe present invention perform best if they are loss than 30 days old, preferably less than 20 days old, ‘and most preferably used within 10 days from the ime they fare manisfactired. The heat treating process of the present invention is conveniently performed by heating the feed solitons toa temperature af 70°C. to boiling for a period ff 15 min to 24 hours, The heat treating procedure of the present invention is conveniently caried out by heating the eed solutions toa temperature of 99°C. fora period of one hour. When low-basiity PAC is subjected to the heat ‘eeating process there isa change inthe molecular speciation as determined by size exchason high pressure chromatog- phy (HPLC). HPLC indicates that the heat treatment process induces an increase in lower molecular weight species. [0069] The production of ulrahigh-basicity PAC is eon- veniently carried ott in either a one stop of a three stop procedure. Inthe three step procedure (shown ia FIG. 4) the eps are comprised of electrodialysis of low-basicity PAC (ea. 40% PAC) tw some intermediate basicity, ike 65% basicity PAC to 75% ascity PAC, heat treating the product of step 1, followed by electrodialysis of the heat treated product from step 1 ino the final proict. was surprisingly ound that heat eating 65% to 75% PAC causes the molecular species distribution to fivor high molecular ‘weight species. In this case, the heat treating process lowers the viscosity of the intermediate PAC (ie, 65% to 75% PAC). Lower viscosity is beneficial since, electrodialysis processes are intolerant of viscosities above ~20 eps. The {ree step procedure is particularly useful when ules igh- basicity PAC with Al,0, concentrations greater than 14-17% ALLO, is desire. [0070] Successful application of electrodialysis also requires that the ion permeable membranes have a high degree of selectivity with respect 1o ion transport. Curent efficiency is measie of the seletvity of ion tansport. The current eficency isthe ratio of current used by the desired process (removal of hydrogen ion and mono-valent snion (ea, ehloride) ion in the present invention) to the (otal current consumed by fon transport. Low curenteficiencies indicate the presence of nonselective ion transpor. High ccurtent efficiencies are important tothe economics of elee- tmodialysis since the eurea eflcieney impacts the size ofthe clectodialyss cll, the electrical power consid and prod vet purty US 2007/0187256 Al [0071] While back migration of anions across eation per- rmeable membranes is uncommon, back migration of hydro- jon across anion permeable membranes is common in dic media, The processes ofthe present invention operate under acidic conditions (pH<35) and back migration of H* ‘ross union membrane must be minimized in order to maintain high current ficiency, In addition, the processes ‘of the present invention require that hydrogen ion (present in ‘concentrations of -10-! molar to~10"* molar in the deplet- ing solution be transfered across the cation permeable ‘membranes in preference to AI (present in concentrations ‘of greater than 1 molar when measured on an aluiau basis). Non-sclective cation transport can lead to reduced ‘current elliciency and contamination of the receiving und oF the depleting solution [0072] Itas surprisingly discovered that highly selective fon transport (ie, minimum back migration of H* across sion permeable membrane and minimum contamination of the depleting solution) and high current efficiencies (greater than $5%-90%) result from appropriate selection of the receiving solution emplayed, When polyaluminum chloride with basicity greater than $%, preferably basicity greater than ~10% is used a the receiving solution, the hydrochloric id removed from the depleting soliton reacts with the PAC jn the receiving solution. ‘Thus, utilizing PAC as the receiving solution maintains the hydrochloric acid concen- teaton in the receiving solution at low levels, back migration ‘of hydrogen jon is markedly reduced and high current ‘elliciencios are realize [0073] _Incomparison, when PAC is replaced by lumina chloride as the receiving solution, the soltion becomes rich in hydrochloric acid and the current ellcieney drops to impractical levels (<65%), The use of ealeium chloride with ‘calcium hydroxide asthe receiving solution was also exam- ined, The calcium chloride-hydroxide receiving soliton ave current efficiencies of about 60% to 80%. [0074] The overall process forthe all aluminum system (je, when MeAl) is characterized by the reaction sequence below Dept Sli: (OFesCh + HO PE AWOH ach + HCL Resi Solin: AOH,0 + ECL — ANOHegoha + 0 [0075] wherein x varies from shout 2 to about 6, y varies from about Ito about 5, and whereby the hydrochloric acid present ia the PAC soliton of the depleting compartments js transferred across the ion permeable membranes 10 the receiving solution. The hydroehlorie aeid so translered fsctoss jon permeable membranes reacts with the PAC present inthe receiving solution. The overall process causes the PAC in the depleting solution to become more basic (dae to the current driven removal of hydrochloric acid) and the PAC in the receiving solution to become less basic. The PAC Aug. 16, 2007 of the receiving solution is wtlized in the manufacturing process at depicted in FIG, 3 wherein said PAC is removed rom the electrodialysis process and its basicity is inereased by reaction with aluminum wiydrate (Al,0, 31,0). Thus the overall process js highly efficent with respect t ray materials because the hydrochloric acid removed from the depleting solution is used to manufacture addtional PAC (Gee FIG. 3) [0076] ‘The basicities of the PAC solutions in the eaetions hove and in FIG. 3 are used for illustrative purposes and ‘other combinations of practical basiciies will be readily ‘ppareat to those skilled in the art [0077] | Most electrodialysis processes are based on the use ‘fmonolayer membranes made from fonctionalized organic voieties like divinyTbenzene and styrene, These membranes are commonly refered to as hydrocarbon membranes in ‘order 10 dillereniate them fom membranes made Irom Tunctionalized polytetaluoroethylenes (PTFE). The hydro- carbon membranes are inexpensive when compared 10 their PTFE counterparts and their use i preferred in mild app cations (i. near neural pH, ambient temperature, and the hsence of redox processes). Hydrocarbon membranes are available as both anion penmeable membranes and estion permeable membranes: while PTFE membranes ae prima- Fly available s cation permeable membranes Interestingly. these two types of membres have distinelly different physical structures and modes of operation, While the hhydrocarhon membranes are considers to function as con tinvous gels, the PTFE membranes are thought to be con posed ofa rigid hydrophobic backbone structure filled with hydrophilic channels where ion transport takes place. While physical evidence supports the idea that hydrocarbon and PEFE membranes operate through different mechanisms, both function to provide highly elective ton transport, The processes of the present invention ean be practiced with either hydrocarbon membranes or PTFE membranes. [0078] _In select applications electrodialysis processes ut lize bilayer membranes commonly koown as bipolar mem- branes, Bipolar membranes are formed by combining. an ‘anion permeable membranes and cation permeable mem- branes. Bipolar membranes are used in electrodialysis pro- cesses to split water In this manner, hydrogen ions migrate throvgh the cation jon penueable membrane toward the cathode and hydroxyl ions migrate through anion permeable ‘membrane toward the anode. Bipolar membranes can be Utilized inthe process ofthe present invention as showa ia FIG. §. [0079] The processes ofthe present invention are operated ineithera batch, semi-continssus mode (commonly refered to as the “shallow dump" process) or a continuous mode (commonly referred to as the “feed and bleed” process). Shallow dimp refers to @ made of eperation wherchy ater the electrodialysis process is taken to completion, the deplet- ing and receiving solutions are partially drained from their respoetive recycle loops. The recyele loops are then reper ished with fresh staring solutions and the electrodialysis process is resumed, Feed and bleed refers 19 a mode of ‘operation whereby the electrodialysis prooess is maintained ina stendy state finshed product is continaowsly bled from the rcyele loop and eontinvously replenished with starting ‘material. All three mades of operation accommodate the ‘opportunity to practice an operation known as CIP (leaning US 2007/0187256 Al in place) whereby the electrodialysis process is discontin ued, receiving solutions and depleting solutions are removed from the electrodialysis stack and membranes are washed with a cleaaing solution, Although aay number of cleaning solutions may be utilized, the processes of the present fnvention are particularly responsive to acidic cleaning solutions; preferably hydrochloric acid cleaning solutions. [0080] Thus, ithas been found that many of the disad tages associated with the currently known processes for manufacturing high-basicity PAC and ulinv-high basicity PAC are overcome and the objects of this invention are realized by utilizing electrodialysis to increase the basicity ‘of aluminum salts Although the present invention ean be ‘sed fo produce aluminum compounds witha wide range of basiites of particular relevance is the ability to produce high-basicty and wlt-high basiity products [0081] provides [0082] paragraph 1. a method to increase the hydride ‘content of compounds comprising the formula (1 [0083] wherein M isa metal that undergoes the reaction: Inthe following paragraphs, the present invention MyXen(Corpaund) + 140 MOH Xen (D+ 1K [0084] wherein “a isthe valence of the metal ion: [0085] X is an anion: [0086] o

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