Resin beads and use in processing of aqueous solutions

Abstract

A method of processing an aqueous solution, wherein the aqueous solution comprises one or more dissolved sugar, one or more dissolved sugar alcohol, or a mixture thereof, wherein the method comprises bringing the aqueous solution into contact with a collection of resin beads, wherein the resin beads comprise functional groups of structure (S1).

Claims

1. A method of processing an aqueous solution, wherein the aqueous solution comprises one or more dissolved sugar, one or more dissolved sugar alcohol, or a mixture thereof, wherein the method comprises bringing the aqueous solution into contact with a collection of resin beads, wherein the resin beads comprise functional groups of structure (S1) ##STR00024## wherein —X— is a bivalent linking group, wherein —Y is a monovalent group having structure (S2) ##STR00025## wherein the circular structure in structure (S2) has four or more atoms.

2. The method of claim 1, wherein the aqueous solution has pH less than 6.

3. The method of claim 1, wherein the dissolved sugar is present in an amount, by weight based on the weight of the aqueous solution, of 5% to 60%.

4. The method of claim 1, wherein the collection of resin beads has harmonic mean diameter of 200 μm or higher.

5. The method of claim 1, wherein the collection of resin beads has uniformity coefficient of 1.02 or greater.

Description

EXAMPLE 1: PREPARATION OF RESIN BEADS

(1) Resin beads DOWEX™ BSR-1 were used. These beads are macroporous, contain styrene/divinylbenzene copolymer, and contain pendant groups of the structure (S18):

(2) ##STR00020##

(3) where the symbol

(4) ##STR00021##

(5) represents the polymer backbone. The two carbon atoms at the far right hand side of (S18) and their attached hydroxyl groups are in a cis-diol configuration. To make the resin beads of the present invention, 1.5 L of DOWEX™ BSR-1 beads was mixed with 2 L of a 2.0 N solution of H.sub.3BO.sub.3 in deionized water. The mixture was stirred for 2 hours at room temperature (approximately 23° C.). Then excess liquid was decanted, and the resin was rinsed with deionized water until the pH of the rinse water was approximately 7. It is contemplated that the pendant groups shown above were all converted to the following structure (S19):

(6) ##STR00022##

(7) The collection of resin beads produced in Example 1 had harmonic mean diameter of 611 μm and had uniformity coefficient of 1.39.

EXAMPLE 2: PULSE TESTS ON VARIOUS SOLUTES

(8) Pulse tests were performed on the following solutes:

(9) TABLE-US-00001 TABLE 1 List of Solutes Label Solute A Inositol B Xylitol C D-Mannose D Glucose E Maltitol F L-Arabinose G Maltose H Sucrose I Meso-Erythritol J D-Galactose K D-Raffinose (Pentahydrate) L Stachyose M D-Mannitol N D-Lactose (Monohydrate) O D-Xylose P Sorbitol Q Fructose S Potassium Chloride T Trehalose U Isomaltulose

(10) Pulse tests were performed as follows. A solution of a single solute was prepared at 20% by weight solute in water. A column was used that was 91 cm tall and 2.7 cm diameter. Volume of resin packed in the column was 526 mL. 26.3 mL of the solution was placed on top of the resin in the column. Elution was performed with water at 2.0 column volumes per hour (17.47 mL/min) at 60° C. “Comparative” (“Com”) tests were performed using DOWEX® BSR-1 resin, and “Example” (“Ex”) tests were performed using resin made by the method of Example 1.

(11) For each pulse test, a retention time and a width was determined. Then, for a given resin type and a given pair of solutes, a resolution was determined using resolution calculation as defined by Fornstedt et al., as described above. The resolution values were as follows:

(12) TABLE-US-00002 TABLE 2A Resolution Values for Solute Pairs A A B B C C D D Com Ex Com Ex Com Ex Com Ex B 0.032 0.260 C 0.040 0.064 0.009 0.200 D 0.008 0.023 0.023 0.274 0.032 0.085 E 0.044 0.061 0.074 0.187 0.081 0.002 0.051 0.081 F 0.063 0.098 0.031 0.170 0.022 0.034 0.054 0.118 G 0.035 0.027 0.065 0.277 0.073 0.089 0.042 0.004 H 0.043 0.025 0.074 0.268 0.081 0.085 0.051 0.003 I 0.058 0.087 0.026 0.174 0.017 0.025 0.050 0.107 J 0.027 0.068 0.004 0.184 0.012 0.008 0.019 0.088 K 0.077 0.065 0.107 0.283 0.114 0.118 0.084 0.044 L 0.149 0.087 0.181 0.345 0.188 0.151 0.157 0.060

(13) As an illustration of how data are presented in the table above, the following is noted. For solutes J and B, resolution in the comparative resin was 0.004, while resolution in the Example resin was 0.184.

(14) TABLE-US-00003 TABLE 2B Resolution Values for Solute Pairs E E F F G G H H Com Ex Com Ex Com Ex Com Ex F 0.104 0.030 G 0.008 0.084 0.095 0.122 H 0.001 0.081 0.104 0.117 0.008 0.001 I 0.100 0.022 0.005 0.008 0.091 0.111 0.100 0.107 J 0.069 0.006 0.034 0.024 0.060 0.092 0.069 0.088 K 0.033 0.113 0.136 0.148 0.041 0.040 0.034 0.040 L 0.098 0.142 0.214 0.188 0.107 0.055 0.100 0.055

(15) TABLE-US-00004 TABLE 2C Resolution Values for Solute Pairs I I J J K K Com Ex Com Ex Com Ex J 0.029 0.016 K 0.133 0.137 0.101 0.120 L 0.211 0.174 0.173 0.152 0.061 0.006

(16) TABLE-US-00005 TABLE 2D Resolution Values for Solute Pairs E E F F G G H H Com Ex Com Ex Com Ex Com Ex F 0.104 0.030 G 0.008 0.084 0.095 0.122 H 0.001 0.081 0.104 0.117 0.008 0.001 I 0.100 0.022 0.005 0.008 0.091 0.111 0.100 0.107 J 0.069 0.006 0.034 0.024 0.060 0.092 0.069 0.088 K 0.033 0.113 0.136 0.148 0.041 0.040 0.034 0.040 L 0.098 0.142 0.214 0.188 0.107 0.055 0.100 0.055

(17) TABLE-US-00006 TABLE 2E Resolution Values for Solute Pairs A A B B C C D D Com Ex Com Ex Com Ex Com Ex M 0.021 0.224 0.010 0.025 0.018 0.167 0.013 0.239 N 0.051 0.040 0.081 0.293 0.089 0.103 0.059 0.016 O 0.080 0.189 0.049 0.060 0.040 0.131 0.071 0.205 P 0.016 0.334 0.015 0.096 0.023 0.280 0.008 0.345 Q 0.040 0.285 0.009 0.026 0.000 0.225 0.032 0.298 S 0.015 0.133 0.022 0.160 0.031 0.062 0.006 0.154 T 0.035 0.032 0.065 0.284 0.073 0.094 0.043 0.008 U 0.046 0.352 0.076 0.146 0.083 0.307 0.053 0.361

(18) TABLE-US-00007 TABLE 2F Resolution Values for Solute Pairs E E F F G G H H Com Ex Com Ex Com Ex Com Ex M 0.063 0.156 0.040 0.138 0.055 0.242 0.063 0.235 N 0.008 0.097 0.111 0.137 0.016 0.012 0.009 0.013 O 0.119 0.122 0.019 0.102 0.111 0.208 0.120 0.201 P 0.058 0.264 0.045 0.255 0.049 0.347 0.058 0.338 Q 0.081 0.211 0.021 0.197 0.072 0.301 0.081 0.292 S 0.065 0.056 0.058 0.026 0.055 0.158 0.065 0.151 T 0.008 0.089 0.095 0.128 0.000 0.004 0.007 0.005 U 0.002 0.292 0.106 0.285 0.010 0.363 0.002 0.355

(19) TABLE-US-00008 TABLE 2G Resolution Values for Solute Pairs I I J J K K L L Com Ex Com Ex Com Ex Com Ex M 0.035 0.142 0.006 0.153 0.096 0.252 0.168 0.306 N 0.107 0.125 0.076 0.106 0.025 0.030 0.089 0.044 O 0.024 0.107 0.051 0.118 0.151 0.221 0.228 0.271 P 0.041 0.256 0.011 0.263 0.091 0.346 0.162 0.410 Q 0.016 0.199 0.012 0.209 0.112 0.304 0.185 0.369 S 0.052 0.034 0.017 0.050 0.104 0.181 0.192 0.232 T 0.091 0.116 0.060 0.097 0.041 0.037 0.106 0.052 U 0.102 0.286 0.071 0.361 0.032 0.361 0.097 0.417

(20) TABLE-US-00009 TABLE 2H Resolution Values for Solute Pairs M M N N O O P P Com Ex Com Ex Com Ex Com Ex N 0.071 0.257 O 0.057 0.034 0.127 0.223 P 0.005 0.116 0.066 0.363 0.063 0.149 Q 0.018 0.050 0.088 0.317 0.039 0.086 0.023 0.071 S 0.010 0.126 0.074 0.175 0.078 0.087 0.004 0.251 T 0.055 0.248 0.016 0.008 0.111 0.214 0.050 0.354 U 0.065 0.163 0.006 0.377 0.122 0.191 0.060 0.058

(21) TABLE-US-00010 TABLE 2I Resolution Values for Solute Pairs Q Q S S T T Com Ex Com Ex Com Ex S 0.031 0.189 T 0.072 0.308 0.055 0.165 U 0.083 0.124 0.068 0.284 0.010 3.465

(22) Use of the Example resin brings about a general improvement in the resolution values. For example, for a specific pair of solutes, one can consider the quotient of the resolution values RQ=(resolution using Ex resin)/(resolution using Comresin).

(23) One aspect of the general improvement becomes apparent if the results are ignored for pairs where the resolution is low for both the Com resin and the Ex resin. For example, in one analysis, the data are ignored if, for a specific pair of solutes, the resolution using Com resin and the resolution using Ex resin are both below 0.16. In this analysis, both resins are poor at resolution for that specific pair of solutes, and so it is irrelevant which one is better. In the remaining data (that is, when all the solute pairs are considered in which one resolution or the other, or both, is 0.16 or above, the quotient RQ varies from 0.81 (solute pair CL) to 659 (solute pair CQ). Thus, whenever at least one resin has a resolution of 0.16 or higher, either the resins are similar or else the Example resin is better, possibly far better.

(24) In another analysis, pairs are considered in which results are ignored for solute pairs in which the resolution using the Comparative resin and the resolution using the Example resin are both below 0.22. Then the quotient RQ varies from 1.19 (solute pair LO) to 659 (solute pair CQ). Thus, in any solute pair in which at least one resin shows relatively good resolution (that is, 0.22 or above), the Example resin is always better. A few representative RQ values from this data set are shown below:

(25) TABLE-US-00011 Solute Pair: AM AP BC BD BJ CP CQ DM DP RQ: 10 21 23 12 52 12 659 18 43

(26) TABLE-US-00012 Solute Pair: EU HU IQ JP JQ KU NU PS TU RQ: 179 143 12 24 17 11 62 70 361

EXAMPLE 3: SEPARATION OF MIXED-SUGAR SOLUTION

(27) The following Comparative Resins were tested:

(28) CR-2=Macroporous resin similar to the resin of Example 1, having the same harmonic mean diameter (611 μm) and the same uniformity coefficient (1.39). However, the pendant groups, instead of (S19), were (S20):

(29) ##STR00023##

(30) CR-3=Macroporous resin similar to CR-2, but harmonic mean diameter of 640 μm and uniformity coefficient of less than 1.1.

(31) CR-4=Resin similar to CR-2, but was a gel resin, had harmonic mean diameter of 320 μm and had uniformity coefficient of less than 1.1.

(32) CR-5=DOWEX™ BSR-1. This resin is similar to Example 1 except for having pendant groups (S18) instead of pendant groups (S19).

(33) An aqueous sugar solution was prepared that contained 42% by weight fructose, that also contained glucose, and that had 50.05% dissolved solids by weight. Sugar concentration was 50 Brix.

(34) Resin was placed in a column as in Example 2. A sample of the aqueous sugar solution was placed onto the top of the column. The volume of aqueous sugar solution was 11.2% of the column volume. The column was then eluted with water at 1.2 bed volume per hour at 60° C. The column had 25 mm diameter and 1219 mm length. Total bed volume was 525 mL. Individual fractions of eluate were collected with an autosampler. Each fraction was analyzed for the presence and type of sugar using high performance liquid chromatography (HPLC) using AMINEX™ HPX-87C column (Bio-Rad Laboratories, Inc.) at 85° C., 0.6 mL/min, 20 μL injection volume. The concentration results for glucose and fructose from the fractions were plotted against the elution volume (bed volumes) and the resolution calculated using the methods described above. As in Example 2, a resolution value for glucose and fructose was obtained. The experiment was performed four times, using four different resins, with results as follows:

(35) TABLE-US-00013 Resin Size.sup.(1) UC.sup.(2) Pendant Type.sup.(3) Resolution Example 1 611 μm 1.39 S19 M 0.37 CR-2 611 μm 1.39 S20 M 0.16 CR-3 640 μm <1.1 S20 M 0.19 CR-4 320 μm <1.1 S20 gel 0.32 CR-5 611 μm 1.39 S18 M 0.01 .sup.(1)Harmonic Mean Diameter .sup.(2)Uniformity Coefficient .sup.(3)M = macroporous

(36) The table shows that, when using sulfonate pendant groups (i.e., S20), the only resin having resolution value above 0.3 was CR-4, which had both small diameter and uniform distribution. The Example 1 resin (using the Boron-containing pendant group S19) achieved the best resolution value even though it has relatively large size and relatively large uniformity coefficient. Also, comparison of Example 1 with CR-5 shows that the presence of the boron-containing group greatly improves the resolution.