(12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT) (19) World Intellectual Property Organization International Bureau (10) International Publication Number (43) International Publication Date WO 2014/011496 Al 16 January 2014 (16.01.2014) P O P C T

(51) International Patent Classification: AO, AT, AU, AZ, BA, BB, BG, BH, BN, BR, BW, BY, C13B 20/00 (201 1.01) BZ, CA, CH, CL, CN, CO, CR, CU, CZ, DE, DK, DM, DO, DZ, EC, EE, EG, ES, FI, GB, GD, GE, GH, GM, GT, (21) International Application Number: HN, HR, HU, ID, IL, IN, IS, JP, KE, KG, KN, KP, KR, PCT/US20 13/0494 19 KZ, LA, LC, LK, LR, LS, LT, LU, LY, MA, MD, ME, (22) International Filing Date: MG, MK, MN, MW, MX, MY, MZ, NA, NG, NI, NO, NZ, 5 July 20 13 (05.07.2013) OM, PA, PE, PG, PH, PL, PT, QA, RO, RS, RU, RW, SC, SD, SE, SG, SK, SL, SM, ST, SV, SY, TH, TJ, TM, TN, (25) Filing Language: English TR, TT, TZ, UA, UG, US, UZ, VC, VN, ZA, ZM, ZW. (26) Publication Language: English (84) Designated States (unless otherwise indicated, for every (30) Priority Data: kind of regional protection available): ARIPO (BW, GH, 61/690,955 9 July 2012 (09.07.2012) US GM, KE, LR, LS, MW, MZ, NA, RW, SD, SL, SZ, TZ, 61/743,886 13 September 2012 (13.09.2012) US UG, ZM, ZW), Eurasian (AM, AZ, BY, KG, KZ, RU, TJ, TM), European (AL, AT, BE, BG, CH, CY, CZ, DE, DK, (72) Inventor; and EE, ES, FI, FR, GB, GR, HR, HU, IE, IS, IT, LT, LU, LV, (71) Applicant : BUSHONG, James [US/US]; 23 1 Katheryn MC, MK, MT, NL, NO, PL, PT, RO, RS, SE, SI, SK, SM, Lane, Collegeville, Pennsylvania 19426 (US). TR), OAPI (BF, BJ, CF, CG, CI, CM, GA, GN, GQ, GW, KM, ML, MR, NE, SN, TD, TG). (74) Agent: JAMES M SMEDLEY LLC; 776 Mountain Blvd. STE 105, Watchung, New Jersey 07069 (US). Published: (81) Designated States (unless otherwise indicated, for every — with international search report (Art. 21(3)) kind of national protection available): AE, AG, AL, AM,

(54) Title: MATERIALS AND METHODS FOR IMPROVED CLARIFICATION PROCESSES (57) Abstract: The present invention offers improved clarification materials and process methods for sugar purification processes. Polyacrylate is utilized to flocculate the carbonate particles formed in the carbonatation clarification process to improve the © filterability of the . The present invention provides even more substantial improvements in the filterability of the calcium carbonate floes with the addition of either a polymer color precipitant and/or a sequestrant added to the sugar liquor either o before, during, or after the carbonatation process but before the filtration of the carbonated liquor, with the addition of the polyac - rylate added after the last stage of carbonatation saturation but before the first filtration of the carbonated liquor. The invention also provides for polyacrylate that can be dosed directly to the sugar liquor as a solid particulate, enabling greater convenience and reliab - o ility of dosing as well as providing a time-release flocculation functionality to enable other purification chemicals to react prior to being incorporated into the polyacrylate induced floes. Materials and Methods for Improved Sugar Clarification Processes

Field of the Invention

[0001] The present invention relates generally to materials and process methods for improved clarification processes for sugar processing and purification.

Cross Reference to Related Applications

[0002] This application claims the benefit of provisional application serial no. 61/690,955 filed July 9, 2012 by the inventor herein and entitled Improved Carbonatation Clarification in Sugar Processing, and provisional application serial no. 61/743,886 filed September 13, 2012 by the inventor herein and entitled Materials and Methods for Improved Sugar Clarification Processes-

Related Art

[0003] The carbonatation clarification process has been an industry standard in sugar processing for many years. hydrate () is added to the sugar liquor or juice, followed by contact with to form calcium carbonate precipitate. The calcium carbonate precipitate forms a floe wherein impurities such as color are removed from the sugar liquor or juice. Many references exist related to the basics of the process, as well as the two main goals of the process, viz. to remove impurities from the raw sugar liquors (in sugar refineries) or raw sugar juice (in sugar mills) while producing a calcium carbonate floe that filters well enough to enable sufficient sugar liquor or juice throughput to achieve the desired amount of final sugar products per day. One well- known problem with carbonatation, is that for a variety of reasons the calcium carbonate floe might not filter well enough to enable sufficient sugar throughput to achieve the desired amount of final sugar products per day, or the process brix (sugar solids per volume of sugar liquor or juice) must be lowered to achieve the desired amount of final sugar products per day. Lowering the process brix increases the amount of water to evaporate upon boiling the sugar liquor or juice into crystal sugar, and thus increases the energy consumed per ton of crystal sugar produced. Additionally, even if the calcium carbonate floe filters well enough to achieve the current desired production rate, it may not allow for future sugar throughput increases in the case of e.g. the desire to increase the sugar production rate to fulfill increased demand for sugar. [0004] The traditional sugar refinery carbonatation process utilizes lime hydrate dosages of about 0.5% to about 0.9% (based on CaO content in the lime hydrate per weight of dissolved sugar solids in the sugar liquor); for a typical purity lime hydrate this is about

0.7 to 1.3 % lime hydrate basis per weight of dissolved sugar solids in the sugar liquor or juice). In addition to high daily consumption of lime hydrate (7 to 13 tons/day and 210 to 390 tons/month of lime hydrate consumption for a modest size sugar refinery of 1000 tons sugar/day) and associated cost and logistics, the high dosages of lime hydrate require more carbon dioxide and increased power to drive the carbon dioxide compressors, and can lead to the undesirable effect of an increase in certain type of colorants at the high liquor or juice pH associated with high lime hydrate concentrations in the sugar liquor or juice. [0005] Polymer color precipitants have also been utilized in carbonatation processes in sugar processing to increase the color removal of the carbonatation process. Typical polymer color precipitants include dimethyldialkylammonium chloride or dimethylamine- epichlorohydrin cationic polymer surfactants. Dimethyl di-tallow ammonium chloride and diallyldimethyl ammonium chloride can also be utilized as the polymer color precipitants. Literature as well as empirical data obtained has demonstrated that some of these polymer color precipitants can reduce the carbonated liquor filterability, thus causing a disadvantage to their use.

Summary of the Invention

[0006] The present invention relates generally to materials and process methods for improved clarification processes for sugar processing and purification. For example, the present invention provides an improved carbonatation process for sugar purification and materials used therein, via enabling the production of an improved filtering calcium carbonate floe. The present invention produces the improved filtering calcium carbonate floe via treating of the carbonated liquor with polyacrylate as an anionic flocculant. The polyacrylate utilized for the present invention is added after the last stage of carbonatation saturation, but before the first filtration of the carbonated liquor. The polyacrylate can impart a favorable flocculation to the calcium carbonate particles formed in the carbonatation process to improve the filterability of the calcium carbonate. The present invention provides even more substantial improvements in the filterability of the calcium carbonate floes with the addition of either a polymer color precipitant and/or a sequestrant added to the sugar liquor or juice either before, during, or after the carbonatation process but before the filtration of the carbonated liquor, with the addition of the polyacrylate added after the last stage of carbonatation saturation but before the first filtration of the carbonated liquor. 07] The present invention also provides an improved method and materials used therein for utilizing polymer color precipitants in the carbonatation clarification process without a detrimental effect on the sugar liquor or juice filterability. The addition of the polymer color precipitant can enable a substantial increase in color removal and other impurity removal. The problem that has been found is that a sugar liquor that has been treated with polymer color precipitant either before, during, or after the carbonatation process but before the filtration of the carbonated liquor of the conventional carbonatation process, can have decreased filterability of the calcium carbonate and decreased sugar liquor or juice filterability compared to the conventional carbonatation process (without any polymer color precipitant added). In the present invention it has been found that addition of polyacrylate, with the molecular weight and dosage ranges claimed, to a sugar liquor that has been treated with polymer color precipitant either before, during, or after the carbonatation process but before the filtration of the carbonated liquor, can result in at least as good of calcium carbonate and sugar liquor or juice filterability as the conventional carbonatation process (without polymer color precipitant added). In fact it has been found that the addition of polyacrylate, within certain ranges of molecular weight and dosages claimed, when added to a sugar liquor that has been treated with polymer color precipitant either before, during, or after the carbonatation process but before the filtration of the carbonated liquor, can substantially improve the calcium carbonate and sugar liquor filterability compared to the conventional carbonatation process (without polymer color precipitant added). Thus the addition of the polyacrylate according to the present invention can enable all of the benefits for using polymer color precipitants, but without the typical disadvantage of reduced sugar liquor filterability that polymer color precipitants can impart to the carbonated liquor of the conventional carbonatation process. [0008] Another feature of the present invention is to utilize a sequestrant to treat a sugar liquor or juice before, during, or after the carbonatation process but before the carbonated liquor filtration process, that is also treated with polyacrylate after the carbonatation saturation process but before the filtration of carbonated liquor process, to achieve an improved filterability carbonated liquor. A polymer color precipitant added either before, during, or after the carbonatation process but before the carbonated liquor filtration process, can also be utilized with the sequestrant in this improved filterability carbonated liquor process. [0009] The present invention also provides the ability to operate an effective carbonatation process for sugar liquors or juices at substantially reduced lime dosages to the sugar liquor or juice. Through experimentation, it was found that a sugar liquor that was treated with either or both of a polymer color precipitant and/or a sequestrant either before, during, or after the carbonatation process but before the filtration of carbonated liquor process, that is also treated with polyacrylate after the carbonatation saturation process but before the filtration of carbonated liquor process, can enable a lime reduction up to 90% compared to lime dosages utilized in conventional carbonatation processes. The liquor filterability was observed to be the same or better than the conventional carbonatation process. [0010] A further novel feature of this invention is that the unique calcium carbonate floes formed in a sugar liquor that is treated with either or both of a polymer color precipitant and/or a sequestrant either before, during, or after the carbonatation process but before the filtration of carbonated liquor process, that is also treated with polyacrylate after the carbonatation saturation process but before the filtration of carbonated liquor process, can settle rapidly from the sugar liquor or juice solution, providing a 2-phase system characterized by a solid phase calcium carbonate floe that settles rapidly from solution, leaving a clear supernatant sugar liquor or juice liquid above the solid calcium carbonate settled floes; thus the present invention is also observed to result in a superior decantation separation process compared to the conventional calcium carbonate floe formed in the conventional carbonatation process method utilized in sugar processing. [0011] Another novel feature of the present invention is to offer a polyacrylate anionic flocculant that can be added directly to the sugar liquor or juice as a solid particulate. Within certain molecular weight ranges claimed in the present invention, the solid particulate polyacrylate can be added directly to the carbonated liquor after the carbonatation saturators but before the first filtration stage. The molecular weight of the polyacrylate for the present invention is about 3,000 to about 1,000,000; this is much lower than the polyacrylamide anionic flocculants that have heretofore been utilized and recommended in sugar clarification processes that typically are between 12,000,000 to 28,000,000 molecular weight. The typical high molecular weight of polyacrylamide flocculants used in sugar clarification require first preparing very dilute solutions (around 0.20% weight or less of polyacrylamide flocculant in water) so that the high molecular weight polyacrylamide can dissolve into the sugar solution. Even at 0.20% or less of the high molecular weight polyacrylamide flocculant solutions, care must be taken to insure a

homogenous solution; this is difficult owing to the high viscosity even at 0.20%> solution concentration. If the high molecular weight polyacrylamide solution in water is not a homogenous solution, globs of polyacrylamide can be formed that can substantially reduce the flocculation effectiveness of the polyacrylamide. It is believed that the use of solid particulate polyacrylate added directly to the sugar liquor or juice is therefore a novel, and simpler, approach to improving sugar clarification processes. [0012] Another principle of the present invention is to utilize solid particulate polyacrylate added directly to a sugar liquor or juice, wherein the molecular weight of the solid particulate polyacrylate is selected to provide a time-release dissolution in the sugar liquor or juice. It has been observed that when polyacrylate of certain molecular weight ranges of the present invention are utilized, that the polyacrylate can take several minutes to fully dissolve into the sugar solution; the time -release dissolution enables other chemical additives, such as polymer color precipitants, to be added to the sugar liquor or juice at essentially the same time and essentially the same location in the sugar production process as the solid particulate polyacrylate. The polymer color precipitants are cationic in charge; thus the polymer color precipitant can achieve most of its primary function of decolorizing the sugar liquor or juice in the time that it takes the solid particulate polyacrylate to fully dissolve in the sugar liquor or juice, prior to the cationic polymer color precipitant being incorporated into a larger floe formed by the anionic polyacrylate. If a conventional polyacrylamide anionic flocculant is dissolved into dilute solution of e.g. 0.20% or less in water, and dosed into the sugar liquor at essentially the same time and essentially the same location as a cationic polymer color precipitant, the anionic flocculant typically will immediately react with some of the cationic charge of the polymer color precipitant and thus neutralize some of the cationic polymer color precipitants ability to remove color from the sugar liquor. 13] The present invention therefore provides new process and cost advantages to the sugar processor. Namely, these new process and cost advantages include the ability to produce the desired sugar production when previously they could not due to poorly filtering calcium carbonate precipitate floes, or to operate at higher process brix (higher viscosity) and still achieve the desired production rate at lower energy costs, or to achieve increased production via increased volumetric flow rate and/or increased process brix. Another advantage of the present process is that it enables the benefits of utilizing polymer color precipitants to remove more color and other impurities in the clarification process while eliminating the potential problem of reduced liquor filterability that can occur when utilizing polymer color precipitants with the conventional carbonatation process. Other advantages include the possibility to operate the carbonatation process at lower temperature and/or lower pH than traditional methods, to save energy per ton of sugar produced as well as to decrease the amount of undesirable color that can form in the carbonatation process at high temperature and high pH. Another advantage of the improved process is that it can enable the production of a highly filterable calcium carbonate floe at much lower lime dosages than the conventional carbonatation process, saving lime costs and logistics, enabling a lower carbonatation process pH, reduced carbon dioxide requirements, reduced carbon dioxide compressor power, and the possibility to essentially complete the carbonatation process in a single-stage saturation instead of the typical 2 saturation stages in series, thereby decreasing residence time and operational complexity of the carbonatation process. Another advantage of the present invention is that the uniquely formed calcium carbonate floe can settle from the sugar liquor or juice very rapidly, achieving a 2-phase system characterized by a solid phase calcium carbonate floe that settles from solution, leaving a clear supernatant sugar liquor or juice liquid above the solid calcium carbonate settled flocs; thus the present invention is also observed to result in a superior decantation separation process compared to the conventional calcium carbonate floe formed in the conventional carbonatation process method utilized in sugar processing. Another advantage of the present invention is to offer a polyacrylate anionic flocculant that can be added as a particulate solid directly to the sugar liquor or juice process, and therefore does not require the preparation of a dilute polymeric anionic flocculant in water solution as is the case of the polyacrylamide anionic flocculants currently used in sugar processing. Another advantage of utilizing the polyacrylate of the present invention dosed as a particulate solid to the sugar liquor or juice, is that typically it takes several minutes for the polyacrylate to completely dissolve in the sugar liquor or juice; the polyacrylate flocculant is thus observed to offer a "time release" advantage to enables other purification chemical process reactions such as cationic polymer color precipitants to take place prior to being completely incorporated into the polyacrylate anionic floe. 14] As used throughout this document, the term "sugar solids" refers to the amount of sugar solids as measured by brix (refractometer). The term "carbonated liquor" refers to sugar liquor after the sugar liquor has reacted with carbon dioxide gas in the final carbonatation saturators. The term "sugar liquor" or "liquor" as used herein refers to any sugar solution from about 5 to about 72 brix sugar concentration. The term "carbonated liquor" can refer to any sugar solution from about 5 brix to about 72 brix that has undergone the carbonatation clarification process, and refers specifically to the liquor after the final carbonatation saturator but before the filtration process where the calcium carbonate precipitate is removed from the sugar liquor. The term "carbonatation saturator" refers to the reaction vessels wherein carbon dioxide gas is bubbled into the sugar liquor or juice to react with the lime that has previously been added to the sugar liquor or juice. The term "final carbonatation saturator" refers to the last reaction vessels wherein carbon dioxide is bubbled into the sugar liquor or juice to react with the lime; typically in sugar refining there are 2 carbonatation saturation stages in series; in this typical situation, the 2nd stage saturator is the "final carbonatation saturator." [0015] Further novel features and other advantages of the present invention will become apparent from the following detailed description, discussion and the appended claims.

Detailed Description

[0016] Although specific embodiments of the present invention will now be described, it should be understood that such embodiments are by way of example only and merely illustrative of but a small number of the many possible specific embodiments which can represent applications of the principles of the present invention. Changes and modifications by persons skilled in the art to which the present invention pertains are within the spirit, scope and contemplation of the present invention as further defined in the appended claims. All references cited herein are incorporated by reference as if each had been individually incorporated. [0017] One example of the present invention is to provide an improved carbonatation clarification process for sugar purification and materials used therein, via enabling the production of an improved filtering calcium carbonate floe. One method of the present invention produces the improved filtering calcium carbonate floe via treating of the carbonated liquor with a polyacrylate as an anionic flocculant. The polyacrylate utilized for the present invention is added after the last stage of carbonatation saturation, but before the first filtration of the carbonated liquor process. The polyacrylate can impart a favorable flocculation to the calcium carbonate particles formed in the carbonatation process to improve the filterability of the calcium carbonate. The dosage of polyacrylate can be from about 1 to about 150 parts per million (ppm basis as weight of polyacrylate per weight of sugar solids in the liquor for about 50 brix or higher liquor typical of sugar refineries, and ppm basis as weight of polyacrylate per weight of juice for about 30 brix or lower sugar juice processes typical of sugar mill processes), or from about 3 to about 125 ppm, or from about 3 to about 100 ppm, or from about 3 to about 75 ppm, or from about 3 to about 25 ppm. The molecular weight of the polyacrylate can be from about 1,000 to about 1,000,000, or from about 3,000 to about 500,000, or from about 10,000 to about 500,000, or from about 20,000 to about 500,000. This molecular weight range is far different from the polyacrylamide anionic flocculants currently used in sugar processing applications, wherein the molecular weight is typically 1 million up to about 28 million. The polyacrylate possesses the advantage of much easier dissolution in sugar liquors and juices. The polyacrylate does not even need to be pre-prepared in highly dilute water solutions that the polyacrylamides require (manufacturers of polyacrylamides for sugar processing recommend preparing 0.05 - 0.20% polyacrylamide solutions in water prior to dosing). Even at these very dilute concentrations, polyacrylamides can be very difficult to dissolve into water solution due to their high molecular weight and high viscosity; improperly dissolved polyacrylamides may not achieve the desired flocculation. In contrast, the polyacrylate flocculant of the present invention can be added as a particulate solid directly to the sugar liquor or juice, without having to first dissolve the polyacrylate in water. The solid particulate polyacrylate of the present invention is observed to dissolve in the sugar liquor or juice, enabling it to disperse in the sugar liquor or juice and perform its function as an anionic flocculant to improve the filterability of the calcium carbonate floe. Another interesting characteristic of the polyacrylate is that it can serve as a "time release" anionic flocculant when it is added as a solid particulate to the sugar liquor or juice; empirical observations have indicated that it can take about 1 to about 7 minutes for the polyacrylate in some of the molecular weight ranges of the present invention to completely dissolve in the sugar liquor or juice. This can enable other chemical additives, such as polymer color precipitants, to achieve more of their desired functionality in solution before being incorporated into the maximum amount of floes formed by the polyacrylate when it finally completely dissolves in the sugar liquor or juice. The polyacrylate of the present invention can therefore have advantages for any sugar liquor or juice clarification process, not just the carbonatation clarification process. Sodium polyacrylate is preferred due to commercial availability, however any polyacrylate of suitable purity within the molecular weight and dosage ranges indicated can be utilized. 18] Another method of the present invention produces the improved filtering calcium carbonate floe via treating of the carbonated liquor or juice with polyacrylate as an anionic flocculant to a sugar liquor or juice that is also treated with polymer color precipitant either before, during, or after the carbonatation process but before the filtration of the carbonated liquor. The dosage locations, ranges, and properties and advantages of the polyacrylate utilized for this method are the same as described above. The addition of the polymer color precipitant can enable a substantial increase in color removal and other impurity removal. The cationic nature of polymer color precipitant can also impart a strong positive charge to the calcium carbonate formed in the carbonatation process; the positively charged surface of the calcium carbonate is then much more amenable to bridge flocculation by the anionic polyacrylate flocculant, compared to calcium carbonate only (without cationic polymer color precipitant added). The preferred polymer color precipitants are of the quaternary ammonium compound variety, characterized by a positive charge on a central pentavalent nitrogen atom. Especially preferred are the compounds dimethyldialkylammonium chloride or dimethylamine-epichlorohydrin cationic polymer surfactants. Dimethyl di-tallow ammonium chloride and diallyldimethyl ammonium chloride can also be utilized as the polymer color precipitants. The dosage of polymer color precipitant can range from about 5 to 1000 ppm (ppm based on the as-is weight of polymer color precipitant including any water content, per weight of dissolved sugar solids in the sugar liquor or juice), or from about 5 to about 500 ppm, or from about 5 to 350 ppm, or from about 5 to about 250ppm. These dosage ranges are based on the "as commercially available" weight of polymer color precipitant, in the typical 20% to 50% by weight polymer commercially available state, with the balance of the content being typically water or an alcohol solvent. For example, the range of about 25 to about 250 ppm is defined as the "as is" weight of these polymer color precipitants (including polymer and water); the actual polymer content dosage would then be 20%> to 50%> of the 25 to 250 ppm "as is" dosage, depending on whether the polymer was purchased as e.g. 20% or 50% (or any % in between) polymer content. Thus the addition of the polyacrylate according to the present invention can enable all of the benefits for using polymer color precipitants, but without the typical disadvantage of reduced sugar liquor filterability that polymer color precipitants can impart to the carbonated liquor of the conventional carbonatation process. 19] Another method of the present invention produces the improved filtering calcium carbonate floe via treating of the carbonated liquor or juice with polyacrylate as an anionic flocculant to a sugar liquor or juice that is also treated with a sequestrant either before, during, or after the carbonatation process but before the filtration of the carbonated liquor. The dosage locations, ranges, and properties and advantages of the polyacrylate utilized for this method are the same as described above. The addition of the sequestrant provides characteristics to the calcium carbonate precipitate formed in the carbonatation process that make the calcium carbonate precipitate more amenable to form larger floes with the polyacrylate anionic flocculant compared to the calcium carbonate formed in the conventional carbonatation process (without the addition of a sequestrant). Although it is conceived that any sequestrant of suitable purity can be utilized in the method of the present invention, it has been found that certain sequestrants produce superior results. The preferred sequestrants found for the methods of the present invention are polyphosphates.

Any water-soluble polyphosphate of the formula M(n+2) P 0 (3n+1) or (MP0 3) wherein M is hydrogen, ammonium or alkali metal and n is an integer of 2 or greater, can be used. Polyphosphate in which an alkaline earth metal or zinc is the cation may also be used. Particularly suitable polyphosphates include the alkali metal polyphosphates and metaphosphates wherein n is from 2 to 25. Preferred are alkali metal pyrophosphate, tripolyphosphate and especially sodium hexametaphosphate. The dosage of polyphosphate can range from about 5 to 500 parts per million (ppm based on weight polyphosphate per weight of dissolved sugar solids in the sugar liquor or juice), or from about 5 to 300 ppm, or from about 10 to about 200 ppm, or from about 10 to about 100 ppm. Other sequestrants may also be utilized in the present invention in these dosage ranges; examples include sodium gluconate, potassium gluconate, and sodium salts of EDTA. 20] Another method of the present invention produces the improved filtering calcium carbonate floe via treating of the carbonated liquor or juice with polyacrylate as an anionic flocculant to a sugar liquor or juice that has been treated with both a polymer color precipitant and a sequestrant either before, during, or after the carbonatation process but before the filtration of the carbonated liquor. The dosage locations, ranges, and properties and advantages of the polyacrylate utilized for this method are the same as described above. The polymer color precipitant and sequestrant can be dosed at the same location such as adding both prior to the carbonatation process, or they can be dosed at different locations such as dosing the sequestrant prior to the carbonatation process, and the polymer color precipitant after the carbonatation process. The dosage ranges, properties, chemical selection, and advantages for the polymer color precipitant and the sequestrant are the same as described above. [0021] Generally speaking, when improved color removal or improved liquor filterability is required, additional lime dosage is utilized in the conventional carbonatation process. With the methods of the present invention, the improved liquor filterability with the polyacrylate anionic flocculant addition can enable the desired filterability without increasing the lime dosage. With other methods of the present invention, the improved liquor filterability with the polyacrylate anionic flocculant with the polymer color precipitant can enable the desired filterability and color removal without increasing the lime dosage. In fact, the lime dosage with the methods of the present invention can actually be considerably less than the lime dosages of the conventional carbonatation process, while offering improved liquor or juice filterability and the same or improved color removal compared to the conventional carbonatation process. [0022] The methods of the present invention are also observed to result in an improved 2- phase separation process, wherein the calcium carbonate floes obtained are larger and much more clearly distinct as a separate solid phase from the sugar liquor or juice liquids compared to the calcium carbonate floe of the conventional carbonatation process, enabling the possibility for an improved decantation separation process compared to the calcium carbonate floe obtained from the conventional carbonatation process. The improved 2-phase separation process is especially apparent with the addition of either or both of the polymer color precipitant and/or sequestrant into the sugar liquor or juice either before, during, or after the carbonatation process but before the filtration of the carbonated liquor , with the polyacrylate anionic flocculant added to the carbonated liquor or juice. [0023] In the present invention, the improved filterability calcium carbonate floes are then filtered or settled (decanted) from the sugar liquor or juice, substantially removing a variety of impurities there from. Noting that the primary function of the carbonatation process is to remove color impurities from the sugar liquor while providing a calcium carbonate precipitate as the filtration aid to the sugar liquor or juice, the methods of the present invention are observed to enable an improved carbonatation process. Claims

I Claim:

1. A carbonatation process for sugar purification wherein polyacrylate is dosed to the carbonated sugar liquor after the final carbonatation saturator but before the first filtration of the carbonated liquor.

2. The method of Claim 1 wherein the polyacrylate is sodium polyacrylate.

3. The method of Claim 1 wherein the polyacrylate has a molecular weight ranging from 1,000 to 1,000,000.

4. The method of Claim 1 wherein the dosage of polyacrylate is from 1 to 150 parts per million based on the weight of polyacrylate per weight of sugar solids in the sugar liquor.

5. The method of Claim 1 wherein the polyacrylate is dosed as a solid particulate directly to the carbonated sugar liquor.

6. A carbonatation process for sugar purification wherein polyacrylate is dosed to the carbonated sugar liquor after the final carbonatation saturator but before the first filtration of the carbonated liquor, and the sugar liquor has been treated with a polymer color precipitant added to the sugar liquor in at least one location selected from the list of before, during, and after the carbonatation process but before the first filtration of the carbonated liquor .

7. The method of Claim 6 wherein the polyacrylate is sodium polyacrylate.

8. The method of Claim 6 wherein the polyacrylate has a molecular weight ranging from 1,000 to 1,000,000.

9. The method of Claim 6 wherein the dosage of polyacrylate is from 1 to 150 parts per million based on the weight of polyacrylate per weight of sugar solids in the sugar liquor. 10. The method of Claim 6 wherein the polyacrylate is dosed as a solid particulate directly to the carbonated sugar liquor.

11. The method of Claim 6 wherein the polymer color precipitant is selected from the list dimethyldialkylammonium chloride, dimethylamine-epichlorohydrin, dimethyl di-tallow ammonium chloride, and diallyldimethyl ammonium chloride.

12. A carbonatation process for sugar purification wherein polyacrylate is dosed to the carbonated sugar liquor after the final carbonatation saturator but before the first filtration of the carbonated liquor, and the sugar liquor has been treated with a sequestrant added to the sugar liquor in at least one location selected from the list of before, during, and after the carbonatation process but before the first filtration of the carbonated liquor .

13. The method of Claim 1 wherein the polyacrylate is sodium polyacrylate.

14. The method of Claim 12 wherein the polyacrylate has a molecular weight ranging from 1,000 to 1,000,000.

15. The method of Claim 12 wherein the dosage of polyacrylate is from 1 to 150 parts per million based on the weight of polyacrylate per weight of sugar solids in the sugar liquor.

16. The method of Claim 12 wherein the polyacrylate is dosed as a solid particulate directly to the carbonated sugar liquor.

17. The method of Claim 12 wherein the sequestrant is selected from the list of any water- soluble polyphosphate of the formula M(n+2) P 0 (3n+1) and (MP0 3) wherein M can be hydrogen, ammonium, alkali metal, alkaline earth metal, and zinc, and n is an integer of at least 2.

18. The method of Claim 12 wherein the sequestrant is selected from the list of sodium polymetaphosphate, sodium pyrophosphate, sodium tripolyphosphate, sodium hexametaphosphate, sodium gluconate, potassium gluconate, and sodium salts of EDTA. 19. The method of Claim 1 wherein the sequestrant dosage is from 5 to 500 parts per million based on the weight of sequestrant per weight of sugar solids in the sugar liquor.

20. The method of Claim 6 wherein the sugar liquor is also treated with a sequestrant added to the sugar liquor in at least one location selected from the list of before, during, and after the carbonatation process but before the first filtration of the carbonated liquor .

21. The method of Claim 20 wherein the sequestrant is selected from the list of any water-

ΐ soluble polyphosphate of the formula M(n+2) P 0 (3 + ) and (MP0 ) wherein M can be hydrogen, ammonium, alkali metal, alkaline earth metal, and zinc, and n is an integer of at least 2.

22. The method of Claim 20 wherein the sequestrant is selected from the list of sodium polymetaphosphate, sodium pyrophosphate, sodium tripolyphosphate, sodium hexametaphosphate, sodium gluconate, potassium gluconate, and sodium salts of EDTA. International application No. INTERNATIONAL SEARCH REPORT PCT/US 2013/049419

A. CLASSIFICATION OF SUBJECT MATTER C13B 20/00 (2011. 01)

According to International Patent Classification (IPC) or to both national classification and IPC B. FIELDS SEARCHED Minimum documentation searched (classification system followed by classification symbols)

C13B 20/00

Documentation searched other than minimum documentation to the extent that such documents are included in the fields searched

Electronic data base consulted during the international search (name of data base and, where practicable, search terms used)

PatSearch (RUPTO internal), Esp@cenet, RUPTO, USPTO

C. DOCUMENTS CONSIDERED TO BE RELEVANT Category* Citation of document, with indication, where appropriate, of the relevant passages Relevant to claim No.

Y SU 1147770 A (MOSKOVSKIY TEKHNOLOGICHESKIY INSTITUT 1-22 PISCHEVOY PROMYSHLENNOSTI) 30.03. 1985, claims

Y CN 102392081 A (GUANGXI LIGHT IND SCI & TECHNOLOGY INST) 1-22 28.03.2012, abstract

Y W O 201 1/060169 A l (CARBO-UA LIMITED et al.) 19.05.201 1, paragraphs [0017], 6- 1, 20-22 [0019]

Y US 6146465 A (BETZDEARBORN INC.) 14.1 1.2000, claims 1, 3 12-22

Further documents are listed in the continuation of Box C . See patent family annex,

* Special categories of cited documents: "T" later document published after the international filing date or priority date and not in conflict with the application but cited to understand "A" document defining the general state of the art which is not considered the principle or theory underlying the invention to be of particular relevance "X" document of particular relevance; the claimed invention cannot be "E" earlier document but published on or after the international filing date considered novel or cannot be considered to involve an inventive "L" document which may throw doubts on priority claim(s) or which is step when the document is taken alone cited to establish the publication date of another citation or other "Y" document of particular relevance; the claimed invention cannot be special reason (as specified) considered to involve an inventive step when the document is "O" document referring to an oral disclosure, use, exhibition or other combined with one or more other such documents, such combination means being obvious to a person skilled in the art "P" document published prior to the international filing date but later than "&" document member of the same patent family the priority date claimed

Date of the actual completion of the international search Date of mailing of the international search report

18 September 2013 (18.09.2013) 02 October 2013 (02.10.2013)

Name and mailing address of the ISA/ FEPS Authorized officer Russia, 3995 , Moscow, G-59, GSP-5, Berezhkovskaya nab., 0- 1 T . Schitova

Facsimile No. + 7 (499) 243-33-37 Telephone No. (495)53 1-64-81 Form PCT/ISA/210 (second sheet) (July 2009)