Purification of crude polyalkylene oxide polymers with acid functionalized silicas and metal silicates
10808076 ยท 2020-10-20
Assignee
Inventors
Cpc classification
B01J20/28004
PERFORMING OPERATIONS; TRANSPORTING
B01D15/00
PERFORMING OPERATIONS; TRANSPORTING
B01J20/04
PERFORMING OPERATIONS; TRANSPORTING
B01J20/28069
PERFORMING OPERATIONS; TRANSPORTING
B01J20/3085
PERFORMING OPERATIONS; TRANSPORTING
B01J20/28011
PERFORMING OPERATIONS; TRANSPORTING
B01J20/28057
PERFORMING OPERATIONS; TRANSPORTING
B01J20/28061
PERFORMING OPERATIONS; TRANSPORTING
B01J20/28064
PERFORMING OPERATIONS; TRANSPORTING
International classification
C08G65/30
CHEMISTRY; METALLURGY
B01J20/30
PERFORMING OPERATIONS; TRANSPORTING
B01J20/28
PERFORMING OPERATIONS; TRANSPORTING
Abstract
A method of purifying a crude polyalkylene oxide polymer that contains a catalyst, such as potassium hydroxide. The method comprises contacting the crude polyalkylene oxide polymer with a composition comprising an acid functionalized silicate, such as an acid functionalized magnesium silicate adsorbent containing at least one acid in an amount effective to remove the catalyst from the polyalkylene oxide polymer. Such a method provides for an improved removal of the catalyst from the polyalkylene oxide polymer.
Claims
1. A method of purifying a crude polyalkylene oxide polymer, said crude polyalkylene oxide polymer containing a catalyst, said method comprising: contacting said crude polyalkylene oxide polymer with a composition comprising an acid functionalized silicate adsorbent containing at least one acid, wherein said acid functionalized silicate adsorbent is acid functionalized by contacting a silicate adsorbent with at least one polyprotic acid, wherein said crude polyalkylene oxide polymer is contacted with said composition in an amount effective to remove said catalyst from said crude polyalkylene oxide polymer.
2. The method of claim 1 wherein said acid functionalized silicate is an acid functionalized metal silicate.
3. The method of claim 2 wherein said acid functionalized metal silicate is an acid functionalized magnesium silicate.
4. The method of claim 1 wherein said at least one polyprotic acid is selected from the group consisting of H.sub.2SO.sub.4, H.sub.2SO.sub.3, H.sub.2S.sub.2O.sub.3, H.sub.3 PO.sub.4, H.sub.4P.sub.2O.sub.7, H.sub.2PO.sub.2, H.sub.3PO.sub.3, H.sub.2CO.sub.3, and mixtures thereof.
5. The method of claim 4 wherein said at least one polyprotic acid is sulfuric acid.
6. The method of claim 4 wherein said at least one polyprotic acid is phosphoric acid.
7. The method of claim 3 wherein said at least one acid is present in said acid functionalized magnesium silicate in an amount of from about 0.2 wt. % to about 40 wt. %.
8. The method of claim 7 wherein said at least one acid is present in said acid functionalized magnesium silicate in an amount of from about 0.2 wt. % to about 25 wt. %.
9. The method of claim 8 wherein said at least one acid is present in said acid functionalized magnesium silicate in an amount of from about 1 wt. % to about 15 wt. %.
10. The method of claim 3 wherein said acid functionalized magnesium silicate has a molar ratio of MgO to SiO.sub.2 of from about 1:1.0 to about 1:4.0.
11. The method of claim 10 wherein said acid functionalized magnesium silicate has a molar ratio of MgO to SiO.sub.2 of from about 1:1.4 to about 1:4.0.
12. The method of claim 11 wherein said acid functionalized magnesium silicate has a molar ratio of MgO to SiO.sub.2 of from about 1:2.5 to about 1:3.6.
13. The method of claim 3 wherein said acid functionalized magnesium silicate has a pH in a 5% slurry of from about 3.0 to about 10.8.
14. The method of claim 13 wherein said acid functionalized magnesium silicate has a pH in a 5% slurry of from about 7.5 to about 10.5.
15. The method of claim 5 wherein said sulfuric acid functionalized magnesium silicate has a pH in a 5% slurry of from about 8.0 to about 10.5.
16. The method of claim 15 wherein said sulfuric acid functionalized magnesium silicate has a pH in a 5% slurry of from about 8.0 to about 9.7, and a molar ratio of MgO to SiO.sub.2 of from about 2.5 to about 2.8.
17. The method of claim 15 wherein said sulfuric acid functionalized magnesium silicate has a pH in a 5% slurry of from about 8.0 to about 10.5, and a molar ratio of MgO to SiO.sub.2 of from about 3.2 to about 3.6.
18. The method of claim 3 wherein said acid functionalized magnesium silicate has a has a conductance in a 1.0% slurry of from about 0.2 mS/cm to about 5.0 mS/cm.
19. The method of claim 5 wherein said sulfuric acid functionalized magnesium silicate has a conductance in a 1.0% slurry of from about 0.2 mS/cm to about 2.6 mS/cm.
20. The method of claim 6 wherein said phosphoric acid functionalized magnesium silicate has a conductance in a 1.0% slurry of from about 0.2 mS/cm to about 1.5 mS/cm.
21. The method of claim 3 wherein said acid functionalized magnesium silicate has a loss on ignition of from about 10.0% to about 15.0%.
22. The method of claim 3 wherein said acid functionalized magnesium silicate has a surface area of at least 30 square meters per gram.
23. The method of claim 22 wherein said acid functionalized magnesium silicate has a surface area of at least 50 square meters per gram.
24. The method of claim 23 wherein said acid functionalized magnesium silicate has a surface area of from about 50 square meters per gram to about 700 square meters per gram.
25. The method of claim 3 wherein said acid functionalized magnesium silicate has a total pore volume of at least 0.1 ml per gram.
26. The method of claim 25 wherein said acid functionalized magnesium silicate has a total pore volume of from about 0.1 ml per gram to about 1.2 ml per gram.
27. The method of claim 3 wherein said acid functionalized magnesium silicate has a mean particle size of from about 10 microns to about 1,000 microns.
28. The method of claim 27 wherein said acid functionalized magnesium silicate has a mean particle size of from about 10 microns to about 500 microns.
29. The method of claim 28 wherein said acid functionalized magnesium silicate has a mean particle size of from about 10 microns to about 250 microns.
30. The method of claim 29 wherein said acid functionalized magnesium silicate has a mean particle size of from about 10 microns to about 175 microns.
31. The method of claim 30 wherein said acid functionalized magnesium silicate has a mean particle size of from about 10 microns to about 125 microns.
32. The method of claim 31 wherein said acid functionalized magnesium silicate has a mean particle size of from about 30 microns to about 100 microns.
33. The method of claim 3 wherein said acid functionalized magnesium silicate has a bulk density of from about 0.2 g/cc to about 0.8 g/cc.
34. The method of claim 3 wherein said crude polyalkylene oxide polymer is contacted with said acid functionalized magnesium silicate in an amount of from about 0.1 wt. % to about 3.0 wt. %, based on the weight of said crude polyalkylene oxide polymer.
35. The method of claim 34 wherein said crude polyalkylene oxide polymer is contacted with said acid functionalized magnesium silicate in an amount of from about 0.5 wt. % to about 3.0 wt. %, based on the weight of said crude polyalkylene oxide polymer.
36. The method of claim 3 wherein said catalyst is an alkali catalyst.
37. The method of claim 36 wherein said alkali catalyst is potassium hydroxide.
38. The method of claim 3, and further comprising: contacting said crude polyalkylene oxide polymer with a liquid comprising water subsequent to contacting said crude polyalkylene oxide polymer with said acid functionalized magnesium silicate.
39. The method of claim 38 wherein said crude polyalkylene oxide polymer is contacted with said liquid comprising water in an amount of from about 0.5 wt. % to about 4.0 wt. %, based on the weight of said crude polyalkylene oxide polymer.
40. The method of claim 38 wherein said liquid comprising water further comprises at least one alcohol.
41. The method of claim 40 wherein said at least one alcohol is selected from the group consisting of methanol, ethanol, propanol, isopropanol, and mixtures thereof.
42. The method of claim 3, and further comprising: contacting said crude polyalkylene oxide polymer with at least one alcohol subsequent to contacting said crude polyalkylene oxide polymer with said acid functionalized magnesium silicate.
43. The method of claim 42 wherein said at least one alcohol is selected from the group consisting of methanol, ethanol, propanol, isopropanol, and mixtures thereof.
44. The method of claim 42 wherein said crude polyalkylene oxide polymer is contacted with said at least one alcohol in an amount of from about 0.5 wt. % to about 4.0 wt. %, based on the weight of said crude polyalkylene oxide polymer.
45. The method of claim 1 wherein said crude polyalkylene oxide polymer is a polyether monol.
46. The method of claim 1 wherein said crude polyalkylene oxide polymer is a polyether polyol.
47. The method of claim 2 wherein said acid functionalized metal silicate is acid functionalized calcium silicate.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
(1) The invention now will be described with respect to the drawings, wherein:
(2)
(3)
(4)
(5)
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(8)
EXAMPLES
(9) The invention now will be described with respect to the following examples. It is to be understood, however, that the scope of the present invention is not intended to be limited thereby.
Example 1
(10) Magnesium Silicate Production
(11) Synthetic magnesium silicate was produced by a precipitation reaction between concentrated sodium silicate, magnesium sulfate (10% wt.) and water in a continuous process. The three reagents were dosed in a large reactor where the following precipitation reaction takes place. In the reaction equation below, x=2.5, and m=0.78.
Na.sub.2Ox*SiO.sub.2+MgSO.sub.4+H.sub.2O.fwdarw.MgOx*SiO.sub.2.mH.sub.2O+Na.sub.2SO.sub.4
(12) It was found that when a molar excess of magnesium sulfate was kept between 5 and 30% of the stoichiometric amount, the precipitation reaction was completed much faster and the final product has less sodium impurities. The reaction temperature usually was kept between 20 and 60 C., pH was 8.5, and the solids content was varied from 5 to 20% wt., depending upon water addition. After the precipitation reaction, the magnesium silicate slurry was washed with water, and concentrated by filtration.
(13) Preparation of Magnesium Silicate Samples with Activated Magnesium Containing Groups
(14) A magnesium silicate concentrated slurry was used for acid functionalization of magnesium containing groups. A magnesium silicate slurry was prepared by a precipitation reaction and had a mole ratio equal to 2.5 (MR=SiO.sub.2/MgO). The slurry was water washed. The initial pH of the concentrated slurry was 9.9 and the conductance was equal to 3.2 mS/cm.
(15) 200 g of concentrated slurry were added to a stainless vessel and heated at 45 C. under sufficient agitation. A concentrated H.sub.2SO.sub.4 solution (from 1 to 15% wt. based on the weight of dry sample) then was added directly to the slurry and agitated for 15 min. The acid treated slurry was dried at 105 C. in an oven overnight. Then the dried material was milled and found to have particle sizes from 53 to 212 urn. The magnesium silicate samples modified with sulfuric acid were designated the with letter S #, where # is the sample example. An unmodified sample (S0) was prepared the same way, except without any acid addition. The sulfuric acid contents in the modified samples were measured according to the gravimetric method and conductance method (express method), preliminary calibrated with a known amount of sulfate in magnesium silicate.
(16) Data on the pH of 5% powder suspension, conductivity, and % LOI (loss of ignition) are shown in Table 1. A higher percentage of acid addition correlates to a higher conductance in a 1.0% adsorbent slurry in deionized (DI) water. Conductance data demonstrated that all sulfuric acid was functionalized on magnesium silicate and a minimal loss was observed after drying. A higher percentage of acid addition correlates to a lower pH of the adsorbent. Synthetic magnesium silicate, due to the presence of magnesil basic groups, has a buffering capacity for acids and the pH is lowered when the amount of acid dose is increased.
(17) TABLE-US-00002 TABLE 1 Chemical properties of oven dried samples modified with sulfuric acid % Acid Conductance, LOI, Sample addition pH mS/cm % S0 0 9.7 0.32 13.8 S1 1.1 9.14 0.34 10.7 S2 2.2 8.68 0.53 10.5 S3 3.0 8.51 0.64 10.9 S4 5.0 8.39 0.88 11.0 S5 6.6 8.26 1.33 12.3 S6 9.8 8.15 1.94 13.2 S7 15.6 8.03 2.63 13.0
(18) The porous structures of the samples of magnesium silicate modified with sulfuric acid were analyzed by a standard nitrogen adsorption method at 193 C. using an ASAP 2020 instrument (Micromeritics, Inc). Surface area was determinated by BET method (A.sub.BET). Total Pore Volume (V.sub.tot) was calculated from the last point of adsorption isotherm at P/Po=0.99. Average Pore Diameter was calculated by the formula
D.sub.pore=4V.sub.tot/A.sub.BET.
(19) The parameters of the porous structures of oven dried samples of magnesium silicate modified with sulfuric acid are shown in Table 2. Acid functionalization of magnesium silicate resulted in a significant increase in the surface area at low acid dose, while at high acid doses this effect was not significant. Total pore volume was reduced gradually after acid treatment. All these changes resulted in the formation of new small pores, which is reflected in an average pore diameter reduction.
(20) TABLE-US-00003 TABLE 2 Parameters of porous structure of oven dried samples modified with sulfuric acid BET Surface Total Pore Average Pore Area, Volume, diameter, Sample m.sup.2/g cc/g S0 265 0.506 76 S3 507 0.495 39 S4 453 0.501 44 S5 469 0.457 39 S6 391 0.403 41 S7 300 0.365 49
Example 2
(21) KOH Adsorption Test
(22) The potassium hydroxide (KOH) adsorption capacities of the adsorbents prepared in Example 1 were determined in a special test utilizing a low molecular weight polyether polyol (dipropylene glycolDPG) containing 3000 ppm (3.0 mg KOH/g polyol) of potassium hydroxide as catalyst. A 3-neck flask was fitted with an agitator and thermometer. 200 grams of DPG containing 3000 ppm KOH were added to the 3-neck flask. The DPG solution was heated to 95 degrees Celsius under the required agitation. In order to avoid polyol oxidative degradation, a nitrogen blanket was used by purging nitrogen over polyol treatment. The polyol solution was heated to 95 degrees Celsius and then 2 grams of adsorbent (dose % equal to 1% wt.) were added. The adsorbent/polyol mixture was heated and agitated for 40 minutes and then filtered immediately under 25 inches of vacuum into a 5 centimeter diameter Buchner funnel using a Whatman #1 filter paper. The filtrate was analyzed for residual KOH by titration with 0.02 N HCl and/or by atomic absorption (AA) method.
(23) Residual KOH concentration (C.sub.res) was calculated from the titration data by the formula:
C.sub.res(mg/gpolyol)=Vtitr.NHCl56.1/Wt. filtrate,
Where Vtitr. is the volume of used titrant (mL of HCl), N is the normality of the titrant (0.02N) and Wt. filtrateis the weight of filtrated polyol sample (g).
Adsorptivity or KOH adsorption capacity of adsorbent was calculated from:
Adsorptivity (mg KOH/g ads)=200(C.sub.inC.sub.res)/Wt..sub.ads,
Where C.sub.in and C.sub.res are the initial and residual concentrations of KOH in polyol, Wt..sub.ads is the adsorbent weight, g.
Adsorbent dose % is equal to
Dose %=Wt..sub.ads/Wt..sub.polyol100.
Distribution Constant (K.sub.D) was calculated by:
K.sub.D=Adsorptivity/C.sub.res
(24) KOH Adsorptivity is the parameter of the adsorbent KOH adsorption capacity, the higher the adsorptivity the better the adsorbent, which means that less adsorbent is required to achieve the same residual KOH concentration. Distribution Constant shows the ratio of KOH present in the adsorbent phase to KOH present in the polyol phase, the higher the K.sub.D, the more effective the adsorbent.
(25) In a modified customer application, 4 grams of deionized (DI) water (water dose=2%) were added to the polyol before adsorbent dosing. Then treatment was continued according to the procedure described above.
(26) Data for the residual KOH concentration, KOH adsorption, and Distribution Constant for low molecular weight polyol experiments conducted in dry test (without water addition) and in the modified test with 2% water addition are shown in Table 3 and
(27) TABLE-US-00004 TABLE 3 KOH adsorption parameters for sulfuric acid modified samples. Initial KOH = 3000 50 ppm Dry test (Without water addition) 2% water addition Residual KOH Distribution Residual KOH Distribution KOH, adsorption, Constant, KOH, adsorption, Constant, Sample ppm mg/g Kd ppm mg/g Kd S0 1169 189 162 907 210 232 S1 1188 193 162 819 224 274 S2 1193 193 162 813 225 277 S3 1007 205 204 582 247 424 S4 1030 202 196 491 256 522 S5 1180 177 150 550 242 440 S6 940 202 215 360 261 725 S7 1080 188 174 340 263 774
(28) The residual KOH concentrations in the dry test were much higher than in the test with 2% water addition. From
(29) KOH adsorption is increased for magnesium silicate adsorbents functionalized with sulfuric acid up to 15% by weight,
Example 3
(30) Plant Test
(31) Synthetic magnesium silicate was produced by a precipitation reaction between concentrated sodium silicate, 10% wt. magnesium sulfate, and water in a continuous process. The three reagents were dosed in a large reactor where the precipitation reaction took place. The reaction temperature was kept at 45 C., and the pH was 8.5. The slurry was water washed to have a conductance of 3.5 mS/cm and was concentrated. The concentrated slurry then was transferred to the next reactor, where concentrated sulfuric acid was added, and the reaction mixture was agitated intensively to avoid dead zone formation. This slurry was sent to a spray drying machine where it was dried.
(32) The chemical properties of spray dried magnesium silicate samples (S8) and (S9), modified respectively with 3.8% and 5.3% sulfuric acid (Plant test) are shown in Table 4 in comparison with the standard unmodified sample (S0). Mean value particle size (MV) measured by laser diffraction method for the plant sample was around 93 microns. Porosity data for the plant test sample are shown in Table 5.
(33) TABLE-US-00005 TABLE 4 Chemical properties of spray dried magnesium silicate modified with sulfuric acid (Plant test) Bulk % Acid Conductance, LOI, density Sample addition pH mS/cm % g/cc S0 0 9.7 0.32 13.8 0.43 S8 (Plant test) 3.8 8.75 0.76 12.9 0.41 S9 (Plant test) 5.3 8.70 1.0 13.0 0.42
(34) TABLE-US-00006 TABLE 5 Parameters of porous structure of spray dried magnesium silicate samples modified with sulfuric acid BET Surface Total Pore Average Pore Area, Volume, diameter, Sample m.sup.2/g cc/g S0 265 0.506 76 S8 (Plant test) 389 0.528 54 S9 (Plant test) 343 0.490 57
(35) The plant samples were tested for KOH adsorptivity according to Example 2. For comparison, two commercially available magnesium silicate samples that were not acid functionalized and are used in the polyol industry for potassium removal were tested under the same conditions. These samples were designated as samples A and B. Data for the unmodified sample (S0) also are included. The data are shown in Table 6 below.
(36) TABLE-US-00007 TABLE 6 KOH adsorption parameters for sulfuric acid modified plant samples. Initial KOH = 3000 50 ppm Dry test (Without water addition) 2% water addition KOH Distri- Re- KOH Distri- Residual adsorp- bution sidual adsorp- bution KOH, tion, Constant, KOH, tion, Constant, Sample ppm mg/g Kd ppm mg/g Kd S0 1169 189 162 907 210 232 S8 749 213 284 505 238 471 S9 710 230 324 420 258 614 A 800 215 269 680 227 334 B 970 198 204 790 216 273
(37) The acid functionalized magnesium silicate plant samples with 3.8% and 5.3% sulfuric acid performed better than the unmodified sample and the two commercial products A and B in the dry test, as well as in the test with 2% water addition.
Example 4
(38) Preparation of Magnesium Silicate Adsorbents Modified with Phosphoric Acid
(39) A magnesium silicate concentrated slurry with a solid content of 25% was used for phosphoric acid modification. Magnesium silicate in slurry was prepared by a precipitation reaction and had a mole ratio equal to 2.5 (MR=SiO.sub.2/MgO). The slurry was water washed. The initial pH of the concentrated slurry was 9.9 and the conductance was 3.2 mS/cm.
(40) 200 g of concentrated slurry were introduced into a stainless vessel and heated at 45 C. under sufficient agitation. 85% H.sub.3PO.sub.4 (from 1 to 5% wt. based on the weight of dry sample) then was added directly to slurry and agitated for 15 min. The acid treated slurry was dried at 105 C. in an oven overnight. Then the dried material was milled and found to have a particle size from 53 to 212 urn. Magnesium silicate samples modified with phosphoric acid were designated with the letter P #, where # is the sample example. The unmodified sample (P0) was prepared the same way only without any acid addition. Data on the pH of 5% powder suspension and conductivity are shown in Table 7.
(41) TABLE-US-00008 TABLE 7 Chemical properties of oven dried samples modified with phosphoric acid % Acid Conductance, LOI, Sample addition pH mS/cm % P0 0 9.7 0.32 13.8 P1 1.4 9.52 0.28 11.3 P2 2.1 9.45 0.29 10.9 P3 2.5 9.47 0.33 11.5 P4 3.0 9.39 0.34 11.8 P5 5.1 9.27 0.35 11.7
(42) Data with respect to BET surface area, total pore volume, and average pore diameter are shown in Table 8 below.
(43) TABLE-US-00009 TABLE 8 Parameters of porous structure of oven dried samples modified with phosphoric acid BET Surface Total Pore Average Pore Area, Volume, diameter, Sample m.sup.2/g cc/g A P0 265 0.506 76 P2 480 0.50 39 P4 469 0.47 40 P5 479 0.494 41
(44) Data on the residual KOH concentration, KOH adsorption and Distribution Constant for low molecular weight polyol experiments conducted in dry test (without water addition) and in modified test with 2% water addition are shown in Table 9
(45) TABLE-US-00010 TABLE 9 KOH adsorption parameters for phosphoric acid modified samples. Initial KOH = 3000 50 ppm Dry test (Without water addition) 2% water addition KOH Distri- KOH Distri- Residual adsorp- bution Residual adsorp- bution Sam- KOH, tion, Constant, KOH, tion, Constant, ple ppm mg/g Kd ppm mg/g Kd P0 1130 192 170 907 210 232 P1 1320 180 136 819 224 274 P2 1370 175 128 761 230 302 P3 1407 171 122 773 231 299 P4 1144 191 167 616 244 395 P5 1060 199 188 723 233 322
(46) The phosphoric acid functionalization of synthetic magnesium silicate improves KOH adsorption significantly and achieves lower residual KOH concentration after treatment of low molecular weight polyols. Atomic adsorption data confirmed that there was no neutralization reaction with phosphoric acid and KOH observed in polyol volume, and, correspondingly, there was no observed crystallization of potassium monophosphate in the reactor volume. The acid modified magnesium silicate separated from the polyol by filtration easily.
Example 5
(47) KOH Removal Efficiency Test
(48) This KOH removal efficiency test was conducted in an apparatus as described in Example 2. The sulfuric acid functionalized magnesium silicate sample S8, containing 3.8 wt. % sulfuric acid as described in Example 3, was used in this test. A commercial crude polypropylene glycol, having a molecular weight of 3,000 and a hydroxyl number of 56, containing 2,300 ppm of KOH catalyst also was used in this test. 200 grams of the polyol was heated to 120 C. under agitation. In order to avoid oxidative degradation of the polyol, a nitrogen blanket was used by purging nitrogen over the polyol during the treatment. After the polyol was heated, 1.5 grams (0.75 wt %) of sample S8 was added to the polyol, followed by addition of 4 grams (2 wt. %) of deionized water. The mixture of polyol, sample S8, and water was heated and agitated for 120 minutes, and then filtered immediately under 25 inches of vacuum into a 5 cm diameter Buchner funnel using a Whatman #1 filter paper. The filtrate was analyzed for residual KOH using the atomic absorption (AA) method.
(49) The above experiment was repeated using 1 wt. % and 1.5 wt. % sample S8 adsorbent. The results are shown in Table 10 below.
(50) TABLE-US-00011 TABLE 10 Results of KOH removal efficiency test on the acid functionalized magnesium silicate sample S8. Initial KOH = 2300 ppm. Adsorbent Residual KOH Dose, KOH, adsorption, % ppm mg/g 0.75 84 309 1.0 6 240 1.5 <0.1 160
Example 6
(51) In this example, further comparative data are presented with respect to Sample S0 and Sample S9.
(52) Adsorptivity Test
(53) The potassium hydroxide (KOH) adsorption capacities of the magnesium silicate adsorbents were determined as described in Example 2.
(54) Isotherm of Adsorption
(55) One of the best ways to determine the feasibility of using an adsorbent for a particular application is to determine the adsorption isotherm for the system. In the case of KOH adsorption from polyols, an isotherm is a plot of the amount of KOH adsorbed per unit of adsorbent weight versus the concentration of KOH remaining in polyol (the residual). To collect data for a KOH adsorption isotherm, a set of experiments were conducted according to the description above. The adsorptivity test utilized DPG as the model polyol and adsorbent samples with different weights (usually 0.5; 1.0; 1.5; 2.0; 3.0 and 5.0 grams) were used. The treatment time was 40 minutes at 95 C.
(56) Commercial crude polyols were treated using the same procedure. The type of adsorbent, adsorbent dose %, treatment temperature, and time were varied depending on the objective of the experiment. The initial and residual potassium concentrations in polyol were measured by a titration method using iso-propyl alcohol/DI water solution and by an atomic absorption, or AA method using AAnalyst 200 (PerkinElmer). For AA analysis polyol samples were diluted with isopropyl alcohol (IPA). The pH values of the polyols were determined as the pH of a 5% wt. solution of polyol in 65/30 IPA/water solution. Water content values in the polyols were analyzed by a Karl Fisher (KF) method using DL31 Titrator (Mettler Toledo).
(57) Adsorbent Selection at High and Low Catalyst Concentrations
(58) The isotherm of adsorption is the fundamental characteristic of adsorbent and solution systems, and represents thermodynamic equilibrium between adsorbent (magnesium silicate) and adsorbate (KOH) in solvent (polyol). The isotherms presented are a plot of adsorption in mg of KOH adsorbed per gram of adsorbent plotted on the Y axis as a function of the residual KOH concentration in the DPG on the X-axis. The isotherms of KOH adsorption from DPG on unmodified Sample S0 and Sample S9, modified with 5.3% sulfuric acid, show (
(59) KOH adsorptivity on the acid-functionalized Sample S9 is higher than the adsorptivity on the unmodified Sample S0 in the entire range of KOH concentrations. For example, adsorptivity at equilibrium concentration of C.sub.1 (1.5 mg KOH/g polyol) for adsorbent Sample S9 (A.sub.2) is higher than adsorptivity (A.sub.1) for Sample S0 which is an industry leader. Therefore, Sample S9 is a more preferred adsorbent from the point of adsorption capacity. The presentations of isotherms on a logarithmic concentration scale (
(60) Low residual potassium content in a polyol is achievable with magnesium silicate adsorbents through optimization of processing parameters. Adsorbent type and adsorbent dose are two of the most important factors influencing the residual potassium content for specific polyols. Results of purification of a commercial crude polyol (MW=3000 and hydroxyl number, OH #=56) initially containing 1700 ppm of potassium are presented in
(61) Water Addition
(62) It is known that the addition of water to the polyol-adsorbent suspension prior to heating and filtration promotes and accelerates removal of the catalyst from the crude polyether polyols. (U.S. Pat. Nos. 4,029,879; 4,482,750; and 5,105,019). Alkali metal catalysts, for example, potassium hydroxide, are bound to the polyol molecule after completion of the polymerization reaction. Purification of polyols with higher molecular weights requires higher doses of adsorbent and long treatment times due to the slow diffusion of high molecular weight crude polyols to the adsorbent active sites. (De Lucas, et al., Chem. Eng. J., Vol. 66, pg. 137 (1997).).
(63) Water addition enhances potassium transfer from the polyol phase to the water phase. Then potassium is adsorbed easily by magnesium silicate from the water phase:
(64) ##STR00015##
(65) Water also activates sites on the surface of the adsorbent in the process of polyol purification. A water dose of 0.5% and greater in some polyols can increase the performance of magnesium silicate significantly. Dipropylene glycol containing 3000 ppm of KOH was treated with a 1% dose of the unmodified Sample S0 and the modified Sample S9 adsorbents at different water addition percentages (Water dose) at 95 C. in laboratory conditions. Results collected in
Example 7
(66) Twelve acid functionalized magnesium silicate samples, designated S10 through S21, to which sulfuric acid was added in amounts of from 7.8 wt. % to 62 wt. %, were prepared according to Example 1. Data on the amount of % acid addition, pH of 5% powder suspension, and conductivity are shown in Table 11 below.
(67) TABLE-US-00012 TABLE 11 Chemical properties of Samples S10 through S21. % Acid Conductance, Sample addition pH mS/cm S10 13 8.09 2.27 S11 7.8 8.28 1.21 S12 15 8.36 2.0 S13 20 8.29 2.43 S14 27 8.17 2.9 S15 30 8.15 3.03 S16 33 8.15 2.99 S17 40 7.98 3.06 S18 42 7.86 3.53 S19 45 2.78 3.3 S20 50 2.07 4.94 S21 62 1.75 6.54
(68) The above results show that acid addition in amounts of 45 wt. % or more results in a significant drop in the pH. This is because the acid present in Samples S19 through S21 is in excess above the stoichiometric amount. This results in conversion of a portion of the magnesium silicate to silica gel (SiO.sub.2) and magnesium sulfate (Mg SO.sub.4).
(69) The conductivity data shown in this example, as well as in Example 1, show that the conductivity is dependent linearly on the percentage of acid addition in amounts up to 15 wt. %. In amounts of from 20 wt. % to 40 wt. %, the dependence of conductivity on the percentage of acid addition shown is a tendency toward saturation, and then the conductivity is increased sharply at acid addition above 45 wt. %.
(70) Samples S10 through S21 were tested for surface area and pore volume as described in Example 1. As shown in Table 2 of Example 1, the BET surface area of Samples S3, S4, and S5, treated with low acid addition (i.e., below 7%) was increased as compared to the unmodified Sample S0. At higher percentages of acid addition, up to 40 wt. %, there was a significant decrease in the BET surface area and total pore volume of the adsorbent. Sample S17 had a surface area of 30 m.sup.2/g and a total pore volume of 0.14 cc/g, while Sample S4 had a BET surface area of 453 in.sup.2/g and a total pore volume of 0.501 cc/g.
(71) The surface areas and porosities of the adsorbents are increased again at percentages of acid addition of 45 wt. % or more. This may correspond to the loss of chemical stability of the magnesium silicate and the formation of silica gel.
Example 8
(72) The KOH adsorption capacity of Samples S10 through S21 was determined in accordance with the procedure described in Example 2, except that after heating and agitation of the adsorbent/polyol mixture, the mixture was filtered immediately under 30 psi of nitrogen pressure using a Gelman filter with Whatman #1 filter paper. In addition, 2% deionized water was added to the polyol after the adsorbent dosing, also as described in Example 2. The KOH adsorption results are shown in Table 12 below.
(73) TABLE-US-00013 TABLE 12 KOH adsorption for Samples S10 through S21. KOH % Acid adsorption, Sample addition mg/g S10 13 260 S11 7.8 258 S12 15 262 S13 20 249 S14 27 253 S15 30 251 S16 33 247 S17 40 241 S18 42 225 S19 45 227 S20 50 241 S21 62 259
(74) As shown in Table 3 in Example 2 and in Table 12, the KOH adsorption is increased from 210 mg/g for untreated Sample S0 to 263 mg/g for Sample S7, treated with 15.6 wt. % acid addition. The highest KOH adsorptivity is observed for samples with an acid addition of from about 8 wt. % to about 15 wt. %. At higher percentages of acid addition, the KOH adsorption is decreased gradually, and reached a minimum at 42 wt. % acid addition (Sample S18). After this point, the KOH adsorption is increased again up to 62 wt. % acid addition (Sample S21), but this sample did not filter well, and the filtration time (Data not shown.) increased 10 times in comparison with the other samples.
(75) The disclosures of all patents and publications, including published patent applications, are incorporated herein by reference to the same extent as if each patent and publication were incorporated individually by reference.
(76) It is to be understood, however, that the scope of the present invention is not to be limited to the specific embodiments described above. The invention may be practiced other than as particularly described and still be within the scope of the accompanying claims.