US20160324893A1 - Calcium polyphosphate salts, methods of making and use in beverage compositions - Google Patents
Calcium polyphosphate salts, methods of making and use in beverage compositions Download PDFInfo
- Publication number
- US20160324893A1 US20160324893A1 US15/066,652 US201615066652A US2016324893A1 US 20160324893 A1 US20160324893 A1 US 20160324893A1 US 201615066652 A US201615066652 A US 201615066652A US 2016324893 A1 US2016324893 A1 US 2016324893A1
- Authority
- US
- United States
- Prior art keywords
- calcium
- polyphosphate
- sodium
- acid
- salt
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 235000013361 beverage Nutrition 0.000 title claims abstract description 67
- 239000000203 mixture Substances 0.000 title claims abstract description 67
- 150000003839 salts Chemical class 0.000 title claims abstract description 44
- 239000004132 Calcium polyphosphate Substances 0.000 title claims description 52
- 235000019827 calcium polyphosphate Nutrition 0.000 title claims description 52
- 238000000034 method Methods 0.000 title claims description 46
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 84
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 83
- 239000011575 calcium Substances 0.000 claims abstract description 83
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims abstract description 60
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims abstract description 51
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims abstract description 49
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims abstract description 25
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 25
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 159000000007 calcium salts Chemical class 0.000 claims abstract description 10
- 235000019828 potassium polyphosphate Nutrition 0.000 claims abstract description 10
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 claims abstract description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 96
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 75
- 239000000243 solution Substances 0.000 claims description 65
- 229920000388 Polyphosphate Polymers 0.000 claims description 60
- 239000001205 polyphosphate Substances 0.000 claims description 60
- 235000011176 polyphosphates Nutrition 0.000 claims description 60
- 238000002156 mixing Methods 0.000 claims description 41
- 239000000796 flavoring agent Substances 0.000 claims description 35
- 235000019634 flavors Nutrition 0.000 claims description 34
- 235000015165 citric acid Nutrition 0.000 claims description 32
- 239000011734 sodium Substances 0.000 claims description 21
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 20
- 229910052708 sodium Inorganic materials 0.000 claims description 20
- 239000007764 o/w emulsion Substances 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 16
- 235000003599 food sweetener Nutrition 0.000 claims description 16
- 239000003765 sweetening agent Substances 0.000 claims description 16
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 14
- 235000011116 calcium hydroxide Nutrition 0.000 claims description 14
- 239000003086 colorant Substances 0.000 claims description 14
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 13
- 239000001506 calcium phosphate Substances 0.000 claims description 13
- 235000011010 calcium phosphates Nutrition 0.000 claims description 13
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 12
- ROPDWRCJTIRLTR-UHFFFAOYSA-L calcium metaphosphate Chemical compound [Ca+2].[O-]P(=O)=O.[O-]P(=O)=O ROPDWRCJTIRLTR-UHFFFAOYSA-L 0.000 claims description 11
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 11
- 235000010755 mineral Nutrition 0.000 claims description 11
- 239000011707 mineral Substances 0.000 claims description 11
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 10
- 238000011065 in-situ storage Methods 0.000 claims description 9
- 239000011541 reaction mixture Substances 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 8
- 239000000292 calcium oxide Substances 0.000 claims description 8
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 8
- 239000000828 canola oil Substances 0.000 claims description 8
- 235000019519 canola oil Nutrition 0.000 claims description 8
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 7
- 239000001736 Calcium glycerylphosphate Substances 0.000 claims description 7
- 229920002472 Starch Polymers 0.000 claims description 7
- 239000003929 acidic solution Substances 0.000 claims description 7
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 7
- 239000001110 calcium chloride Substances 0.000 claims description 7
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 7
- 235000011148 calcium chloride Nutrition 0.000 claims description 7
- 229940095618 calcium glycerophosphate Drugs 0.000 claims description 7
- UHHRFSOMMCWGSO-UHFFFAOYSA-L calcium glycerophosphate Chemical compound [Ca+2].OCC(CO)OP([O-])([O-])=O UHHRFSOMMCWGSO-UHFFFAOYSA-L 0.000 claims description 7
- 235000019299 calcium glycerylphosphate Nutrition 0.000 claims description 7
- 239000008107 starch Substances 0.000 claims description 7
- 235000019698 starch Nutrition 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- IXHOXXFTTQTNQS-UHFFFAOYSA-N [Ca].[Na].[K] Chemical compound [Ca].[Na].[K] IXHOXXFTTQTNQS-UHFFFAOYSA-N 0.000 claims description 6
- JUNWLZAGQLJVLR-UHFFFAOYSA-J calcium diphosphate Chemical compound [Ca+2].[Ca+2].[O-]P([O-])(=O)OP([O-])([O-])=O JUNWLZAGQLJVLR-UHFFFAOYSA-J 0.000 claims description 6
- 229940043256 calcium pyrophosphate Drugs 0.000 claims description 6
- 235000019821 dicalcium diphosphate Nutrition 0.000 claims description 6
- 229910001415 sodium ion Inorganic materials 0.000 claims description 6
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 5
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 claims description 5
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 5
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 5
- 235000011054 acetic acid Nutrition 0.000 claims description 5
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 5
- -1 color Substances 0.000 claims description 5
- 239000000174 gluconic acid Substances 0.000 claims description 5
- 235000012208 gluconic acid Nutrition 0.000 claims description 5
- 239000004310 lactic acid Substances 0.000 claims description 5
- 235000014655 lactic acid Nutrition 0.000 claims description 5
- 239000001630 malic acid Substances 0.000 claims description 5
- 235000011090 malic acid Nutrition 0.000 claims description 5
- 235000011007 phosphoric acid Nutrition 0.000 claims description 5
- OQZCJRJRGMMSGK-UHFFFAOYSA-M potassium metaphosphate Chemical compound [K+].[O-]P(=O)=O OQZCJRJRGMMSGK-UHFFFAOYSA-M 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 239000011975 tartaric acid Substances 0.000 claims description 5
- 235000002906 tartaric acid Nutrition 0.000 claims description 5
- 239000012736 aqueous medium Substances 0.000 claims description 4
- 235000013305 food Nutrition 0.000 claims description 4
- 229940099402 potassium metaphosphate Drugs 0.000 claims description 4
- 235000019830 sodium polyphosphate Nutrition 0.000 claims description 4
- KIBXMJQKVVOEFO-UHFFFAOYSA-K 15551-60-7 Chemical compound [Na+].[Ca+2].[O-]P(=O)=O.[O-]P(=O)=O.[O-]P(=O)=O KIBXMJQKVVOEFO-UHFFFAOYSA-K 0.000 claims description 3
- 239000004136 Calcium sodium polyphosphate Substances 0.000 claims description 3
- 235000019348 calcium sodium polyphosphate Nutrition 0.000 claims description 3
- 235000011167 hydrochloric acid Nutrition 0.000 claims description 3
- 239000003921 oil Substances 0.000 claims description 3
- 235000019198 oils Nutrition 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 3
- 239000003995 emulsifying agent Substances 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims 1
- 230000002335 preservative effect Effects 0.000 abstract description 23
- 239000003755 preservative agent Substances 0.000 abstract description 21
- 239000000463 material Substances 0.000 abstract description 20
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 abstract description 14
- 229940005740 hexametaphosphate Drugs 0.000 abstract description 12
- KRSIWAJXDVVKLZ-UHFFFAOYSA-H tricalcium;2,4,6,8,10,12-hexaoxido-1,3,5,7,9,11-hexaoxa-2$l^{5},4$l^{5},6$l^{5},8$l^{5},10$l^{5},12$l^{5}-hexaphosphacyclododecane 2,4,6,8,10,12-hexaoxide Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P1(=O)OP([O-])(=O)OP([O-])(=O)OP([O-])(=O)OP([O-])(=O)OP([O-])(=O)O1 KRSIWAJXDVVKLZ-UHFFFAOYSA-H 0.000 abstract description 6
- 235000019981 calcium hexametaphosphate Nutrition 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000003352 sequestering agent Substances 0.000 abstract 6
- 150000001875 compounds Chemical class 0.000 abstract 1
- 239000011159 matrix material Substances 0.000 abstract 1
- 229960005069 calcium Drugs 0.000 description 73
- 235000002639 sodium chloride Nutrition 0.000 description 31
- 239000000047 product Substances 0.000 description 28
- 239000002245 particle Substances 0.000 description 27
- 230000008569 process Effects 0.000 description 15
- 239000000839 emulsion Substances 0.000 description 13
- 239000011521 glass Substances 0.000 description 12
- 239000007787 solid Substances 0.000 description 11
- 229960001714 calcium phosphate Drugs 0.000 description 10
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 9
- 239000011591 potassium Substances 0.000 description 9
- 230000000873 masking effect Effects 0.000 description 8
- 229910052700 potassium Inorganic materials 0.000 description 8
- 235000012255 calcium oxide Nutrition 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 229960003563 calcium carbonate Drugs 0.000 description 5
- 235000010216 calcium carbonate Nutrition 0.000 description 5
- 229960002713 calcium chloride Drugs 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 229910001414 potassium ion Inorganic materials 0.000 description 5
- 241000196324 Embryophyta Species 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000002738 chelating agent Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 125000005341 metaphosphate group Chemical group 0.000 description 4
- 239000001509 sodium citrate Substances 0.000 description 4
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 4
- 235000011083 sodium citrates Nutrition 0.000 description 4
- FNAQSUUGMSOBHW-UHFFFAOYSA-H calcium citrate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O FNAQSUUGMSOBHW-UHFFFAOYSA-H 0.000 description 3
- 239000001354 calcium citrate Substances 0.000 description 3
- 229960004256 calcium citrate Drugs 0.000 description 3
- 230000002496 gastric effect Effects 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 150000001455 metallic ions Chemical class 0.000 description 3
- 244000005700 microbiome Species 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 235000013337 tricalcium citrate Nutrition 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QYSXJUFSXHHAJI-XFEUOLMDSA-N Vitamin D3 Natural products C1(/[C@@H]2CC[C@@H]([C@]2(CCC1)C)[C@H](C)CCCC(C)C)=C/C=C1\C[C@@H](O)CCC1=C QYSXJUFSXHHAJI-XFEUOLMDSA-N 0.000 description 2
- 229940095643 calcium hydroxide Drugs 0.000 description 2
- 229940087373 calcium oxide Drugs 0.000 description 2
- 238000010494 dissociation reaction Methods 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000002255 enzymatic effect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000000813 microbial effect Effects 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000011343 solid material Substances 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 230000009469 supplementation Effects 0.000 description 2
- 235000019640 taste Nutrition 0.000 description 2
- IIZPXYDJLKNOIY-JXPKJXOSSA-N 1-palmitoyl-2-arachidonoyl-sn-glycero-3-phosphocholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCC\C=C/C\C=C/C\C=C/C\C=C/CCCCC IIZPXYDJLKNOIY-JXPKJXOSSA-N 0.000 description 1
- MOMKYJPSVWEWPM-UHFFFAOYSA-N 4-(chloromethyl)-2-(4-methylphenyl)-1,3-thiazole Chemical compound C1=CC(C)=CC=C1C1=NC(CCl)=CS1 MOMKYJPSVWEWPM-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 230000005526 G1 to G0 transition Effects 0.000 description 1
- 229920000881 Modified starch Polymers 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 229930003316 Vitamin D Natural products 0.000 description 1
- VEUACKUBDLVUAC-UHFFFAOYSA-N [Na].[Ca] Chemical compound [Na].[Ca] VEUACKUBDLVUAC-UHFFFAOYSA-N 0.000 description 1
- YGJZDMFVIMWCHL-UHFFFAOYSA-N [Na].[Mg].[K] Chemical compound [Na].[Mg].[K] YGJZDMFVIMWCHL-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- 239000004227 calcium gluconate Substances 0.000 description 1
- 235000013927 calcium gluconate Nutrition 0.000 description 1
- 229960004494 calcium gluconate Drugs 0.000 description 1
- MKJXYGKVIBWPFZ-UHFFFAOYSA-L calcium lactate Chemical compound [Ca+2].CC(O)C([O-])=O.CC(O)C([O-])=O MKJXYGKVIBWPFZ-UHFFFAOYSA-L 0.000 description 1
- 239000001527 calcium lactate Substances 0.000 description 1
- 235000011086 calcium lactate Nutrition 0.000 description 1
- 229960002401 calcium lactate Drugs 0.000 description 1
- 239000001362 calcium malate Substances 0.000 description 1
- OLOZVPHKXALCRI-UHFFFAOYSA-L calcium malate Chemical compound [Ca+2].[O-]C(=O)C(O)CC([O-])=O OLOZVPHKXALCRI-UHFFFAOYSA-L 0.000 description 1
- 229940016114 calcium malate Drugs 0.000 description 1
- 235000011038 calcium malates Nutrition 0.000 description 1
- 229940069978 calcium supplement Drugs 0.000 description 1
- 239000001427 calcium tartrate Substances 0.000 description 1
- GUPPESBEIQALOS-UHFFFAOYSA-L calcium tartrate Chemical compound [Ca+2].[O-]C(=O)C(O)C(O)C([O-])=O GUPPESBEIQALOS-UHFFFAOYSA-L 0.000 description 1
- 235000011035 calcium tartrate Nutrition 0.000 description 1
- NEEHYRZPVYRGPP-UHFFFAOYSA-L calcium;2,3,4,5,6-pentahydroxyhexanoate Chemical compound [Ca+2].OCC(O)C(O)C(O)C(O)C([O-])=O.OCC(O)C(O)C(O)C(O)C([O-])=O NEEHYRZPVYRGPP-UHFFFAOYSA-L 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000001332 colony forming effect Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 235000015872 dietary supplement Nutrition 0.000 description 1
- WPUMTJGUQUYPIV-JIZZDEOASA-L disodium (S)-malate Chemical compound [Na+].[Na+].[O-]C(=O)[C@@H](O)CC([O-])=O WPUMTJGUQUYPIV-JIZZDEOASA-L 0.000 description 1
- 230000035622 drinking Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 235000020509 fortified beverage Nutrition 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000000787 lecithin Substances 0.000 description 1
- 235000010445 lecithin Nutrition 0.000 description 1
- 229940067606 lecithin Drugs 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 150000003904 phospholipids Chemical class 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000035479 physiological effects, processes and functions Effects 0.000 description 1
- 229940068065 phytosterols Drugs 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 235000019265 sodium DL-malate Nutrition 0.000 description 1
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229960004249 sodium acetate Drugs 0.000 description 1
- 235000019829 sodium calcium polyphosphate Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000001394 sodium malate Substances 0.000 description 1
- 235000019983 sodium metaphosphate Nutrition 0.000 description 1
- 239000001433 sodium tartrate Substances 0.000 description 1
- 229960002167 sodium tartrate Drugs 0.000 description 1
- 235000011004 sodium tartrates Nutrition 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 235000019166 vitamin D Nutrition 0.000 description 1
- 239000011710 vitamin D Substances 0.000 description 1
- 150000003710 vitamin D derivatives Chemical class 0.000 description 1
- 235000005282 vitamin D3 Nutrition 0.000 description 1
- 239000011647 vitamin D3 Substances 0.000 description 1
- QYSXJUFSXHHAJI-YRZJJWOYSA-N vitamin D3 Chemical compound C1(/[C@@H]2CC[C@@H]([C@]2(CCC1)C)[C@H](C)CCCC(C)C)=C\C=C1\C[C@@H](O)CCC1=C QYSXJUFSXHHAJI-YRZJJWOYSA-N 0.000 description 1
- 229940046008 vitamin d Drugs 0.000 description 1
- 229940021056 vitamin d3 Drugs 0.000 description 1
- 150000003722 vitamin derivatives Chemical class 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K33/00—Medicinal preparations containing inorganic active ingredients
- A61K33/42—Phosphorus; Compounds thereof
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L2/00—Non-alcoholic beverages; Dry compositions or concentrates therefor; Their preparation
- A23L2/42—Preservation of non-alcoholic beverages
- A23L2/44—Preservation of non-alcoholic beverages by adding preservatives
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L2/00—Non-alcoholic beverages; Dry compositions or concentrates therefor; Their preparation
- A23L2/52—Adding ingredients
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L33/00—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof
- A23L33/10—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof using additives
- A23L33/16—Inorganic salts, minerals or trace elements
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/32—Phosphates of magnesium, calcium, strontium, or barium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/38—Condensed phosphates
- C01B25/40—Polyphosphates
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23V—INDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
- A23V2002/00—Food compositions, function of food ingredients or processes for food or foodstuffs
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/38—Condensed phosphates
- C01B25/385—Condensed phosphates of alkaline-earth metals or magnesium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/38—Condensed phosphates
- C01B25/44—Metaphosphates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
Definitions
- the present invention relates to the formulation of mineral fortified beverage products containing sodium hexametaphosphate as a preservative.
- SHMP sodium hexametaphosphate
- a beverage product is to be fortified with vitamin D3
- federal regulations require that the beverage also be fortified with calcium.
- Calcium can deactivate the SHMP preservative, thereby significantly decreasing the shelf-life of the product.
- the beverage must be formulated such that the calcium does not deactivate the SHMP or otherwise impede its function, the calcium must also be bio-available, not produce unacceptable tastes or colors, must not settle out of the product, must be able to be processed on a large scale, and not add significant cost to the beverage product.
- the goal in formulating beverages is to develop a form of calcium which is an effective dietary supplement (i.e., bio-available), but which does not deactivate the SHMP preservative, and which is safe, cost-effective and easy to use in a beverage product.
- the calcium material utilized in the beverage cannot impart off-flavors or bad mouthfeel to the product and must be easy to incorporate within the product. That is what the present invention accomplishes.
- SHMP is a powerful chelating agent. It functions as a preservative by extraction of divalent metallic ions (e.g., calcium, iron, magnesium) from microbial enzymatic systems. The extracted metals are no longer available to the microbes and so the microbes enter a stationary phase and, finally, a death phase.
- divalent metallic ions e.g., calcium, iron, magnesium
- the present invention provides a calcium polyphosphate product (e.g., calcium hexametaphosphate) which can be used to provide a bio-available source of calcium to a beverage product without deactivating the SHMP preservative in that beverage product.
- a calcium polyphosphate product e.g., calcium hexametaphosphate
- the present application also describes the formation of calcium hexametaphosphate particles, particularly coated particles, and also describes methods of making the calcium polyphosphate-calcium hexametaphosphate material.
- the present invention teaches how to formulate the calcium polyphosphate so as to minimize any off-tastes.
- a calcium polyphosphate salt can be produced and maintained in equilibrium with SHMP in such a manner so as to not affect the preservative action of SHMP.
- the average polyphosphate chain length of SHMP is 19-25, which makes it a very strong chelating agent. It has been found that by producing a calcium polyphosphate salt with a phosphorus chain length of 11-15, the salt not only remains in equilibrium with SHMP, but releases its calcium cations at gastric pH making the calcium bio-available.
- the ratio of calcium to lower chain polyphosphate is critical as well.
- the optimum molar ratio of calcium polyphosphate is about 4:1. Lowering the level causes overuse of polyphosphate whereas exceeding a ratio of about 4:1 causes the formation of a sticky amorphous glass structure which physically separates from the aqueous base during preparation. This amorphous glass solid is unstable in that form and will not mix homogenously with aqueous beverages.
- the present application therefore describes a calcium polyphosphate salt, such as a calcium hexametaphosphate salt, in soluble form, which has a calcium/polyphosphate molar ratio of from about 2.5:1 to about 4.5:1, and wherein the polyphosphate has a phosphorus chain length of from about 9 to about 16, for example, from about 11 to about 15.
- the present application also describes a method of making a calcium polyphosphate salt, in particulate form, comprising the steps of:
- the present application also describes two methods for the preparation of the calcium polyphosphate salt; this can be done in situ thereby allowing the completed reaction mixture to be made directly into a beverage product.
- the first such method which directly reacts calcium with the polyphosphate includes the following steps:
- a metallic polyphosphate such as a sodium, potassium polyphosphate
- the solubility of the calcium source will typically be low in near neutral pH aqueous medium and so will slowly react with the polyphosphate, for example, having a 10-15 minute reaction time.
- That completed reaction mixture can then be used to formulate a beverage in situ by the addition of water, sodium hexametaphosphate, flavor, color and sweetener (and, if desired, other conventional beverage components).
- the second such method for preparing the calcium polyphosphate salt comprises the steps of:
- step (c) with agitation, adding the calcium and surrogate solution (step (a)) to the polyphosphate solution (step (b)), thereby forming the calcium polyphosphate salt.
- reaction mixture can be used to formulate a beverage in situ by addition of water, sodium hexametaphosphate, flavor, color and sweetener (and, if desired, other conventional beverage components).
- the calcium polyphosphate particles as described in paragraph [0011] herein are insoluble in a beverage product of typical pH, such as between pH 2.8 and 7.6.
- the formation of the particles lends itself to a purification step that allows the removal of byproducts that may impact flavor (i.e., potassium ions).
- This higher calcium loaded polyphosphate material does not affect the preservative action of SHMP and releases its calcium cations at gastric pH, making the calcium bioavailable.
- an oil-in-water (O/W) emulsion such as those used to provide beverage opacity or disperse flavors, can mask the unpleasant flavor that may come from displaced ions (e.g., potassium) that are present as a result of the making of the calcium polyphosphate.
- displaced ions e.g., potassium
- sodium ions must also be present with the emulsion to optimally mask the unpleasant flavor that may come from displaced ions (e.g., potassium) that are present as a result of the making of the calcium polyphosphate.
- the present invention thus provides a calcium polyphosphate product (e.g., calcium metaphosphate or calcium polyphosphate) which:
- (a) is soluble and does not deactivate a chelating preservative, such as SHMP, and can be used to provide a bio-available source of calcium to a beverage product;
- (b) is in particulate form, free from extraneous matter that may impact flavor (e.g., potassium ions), does not deactivate a chelating preservative, such as SHMP, and can be used to provide a bio-available source of calcium to a beverage product;
- flavor e.g., potassium ions
- SHMP chelating preservative
- (c) can be used in combination with an oil-in-water emulsion that masks the unpleasant flavor that may be associated with potassium ions that are present as a result of the making of the calcium polyphosphate;
- (d) utilizes sodium ions in addition to the oil-in-water emulsion that masks the unpleasant flavor that may be associated with potassium ions that are present as a result of the making of the calcium polyphosphate.
- the present invention relates to calcium polyphosphate materials (such as calcium hexametaphosphate), containing relatively short polyphosphate chain lengths and utilizing specific calcium:phosphate molar ratios. These materials can be used to provide calcium supplementation to beverages, particularly beverages which use a chelating preservative (such as SHMP) without deactivating that preservative. The methods of making these materials are also disclosed in this application.
- a chelating preservative such as SHMP
- a calcium polyphosphate salt can be produced and maintained in equilibrium with SHMP in a beverage product in such a manner as to not affect the preservative activity of the SHMP in that beverage.
- the average polyphosphate chain length of SHMP is from 19 to 25. This makes for a very strong chelating agent (which accounts for SHMP's excellent preservative characteristics). It has now been found that by producing a calcium, polyphosphate salt with a relatively short phosphorus chain length of from about 9 to about 16, such as from about 11 to about 15, the calcium polyphosphate not only remains in equilibrium with SHMP (i.e., does not ruin SHMP's preservative properties) but also releases its calcium cation at gastric pH making the calcium bio-available.
- the ratio of calcium to lower chain polyphosphate in the composition is important.
- the molar ratio of calcium to polyphosphate in the material is from about 2.5:1 to about 4.5:1, such as about 4:1. Lowering the ratio causes the overuse of polyphosphate, whereas significantly exceeding the ratio causes the formation of a sticky, amorphous, glass structure which physically separates from the aqueous base during preparation.
- This amorphous glass solid is unusable in that form to be a calcium supplement in a beverage, and will not itself mix homogeneously with aqueous beverages. However, it has been found that this amorphous glass solid can be dehydrated, ground or physically processed by a jet mill or similar methods to produce small particles. These particles can then be added back to the SHMP-containing beverage with great success.
- the amorphous glass solid can be decanted and dehydrated by filtering, evaporation, solvent extraction, microwave heating or other similar means, for example, such that it has a water content of no greater than about 0.1%, preferably no greater than about 0.05%.
- the particles formed by grinding this solid typically have an average particle size of no greater than about 0.5 ⁇ m, such as from about 0.1 ⁇ m to about 0.3 ⁇ m. This small particle size is primarily important to avoid product grittiness or otherwise inappropriate mouthfeel for the consumer.
- calcium phosphate amorphous glass solid at a molar ratio of from about 5:1 to about 9:1, such as about 5.5:1, calcium:short chain polyphosphate, a high calcium loaded salt, suitable for use after dehydration and particle processing is produced.
- An added benefit of this approach is that any metallic ions (sodium, potassium, etc.) originating from the starting shorter chain polyphosphate are essentially removed during the isolation of the amorphous glass solid.
- shorter chain polyphosphate materials ideally has a phosphorus chain length of from about 9 to about 16, such as from about 11 to about 15, but longer chain lengths, for example 19-25, can be used particularly in conjunction with shorter chain length polyphosphates. They can, for example, be selected from the group consisting of metal salts of polyphosphates and metaphosphates, such as sodium metaphosphate, sodium calcium metaphosphate, sodium calcium polyphosphates, or sodium potassium metaphosphate, as well as other salts of metaphosphates or polyphosphates either of mono, binary, tertiary salts (e.g., a sodium potassium magnesium polyphosphate) encompassing all ratios of salt, for example, a sodium potassium polyphosphate with a sodium: potassium molar ratio of from about 1:9 to about 9:1.
- metal salts of polyphosphates and metaphosphates such as sodium metaphosphate, sodium calcium metaphosphate, sodium calcium polyphosphates, or sodium potassium metaphosphate, as well as other salts of metaphosphates or polyphosphates either
- the calcium polyphosphate salts defined herein can be synthesized in several ways.
- the first is to directly react the metallic short chain polyphosphate with a calcium source (for example, calcium hydroxide) in an aqueous neutral medium. Since the solubility of calcium hydroxide is very low in an aqueous medium, the calcium hydroxide solely reacts over the course of from about 5 to about 20 minutes, such as from about 10 to about 15 minutes, as calcium is transferred from the calcium hydroxide to the polyphosphate.
- a small amount of organic or mineral acid, such as citric acid is added toward the end of this process to complete the dissociation of calcium from its hydroxide moiety and complete the transfer of calcium to the polyphosphate substrate.
- a metallic polyphosphate having a phosphorus chain length of from about 9 to about to about 16 with a calcium source selected from calcium hydroxide, calcium oxide, calcium phosphate, calcium chloride, calcium carbonate, calcium glycerophosphate, calcium pyrophosphate, calcium metaphosphate, or any calcium salt ionizable at aqueous, acidic solution, and mixtures thereof, in an aqueous medium, having a pH of from about 6 to about 7.5, the molar ratio of calcium to polyphosphate source being from about 2.5:1 to about 4.5:1;
- an organic acid is utilized as a surrogate carrier of the calcium. This is accomplished by first preparing an aqueous solution of the acid (for example, citric acid). To this aqueous solution the correct amount of calcium salt (e.g., calcium hydroxide) is added. The amount of calcium salt used is based on the desired ratio of calcium to metaphosphate or polyphosphate. Because the solution is acidic (pH of from about 1.5 to about 2.5), calcium hydroxide immediately dissociates allowing the calcium to react with the acid forming a salt (e.g., calcium citrate). Separately, the polyphosphate is solubilized in water.
- the acid for example, citric acid
- calcium salt e.g., calcium hydroxide
- This polyphosphate is reacted with the calcium salt (i.e., the surrogate carrier solution) (e.g., calcium citrate, calcium malate, calcium tartrate, calcium phosphate, calcium lactate, calcium acetate, calcium chloride, calcium carbonate, calcium gluconate, and mixtures thereof) by mixing of the calcium salt solution into the polyphosphate solution.
- the calcium is then quickly chelated or transferred from the calcium salt to the polyphosphate resulting in the formation of calcium polyphosphate.
- an aqueous solution of an organic or mineral acid such as citric acid, malic acid, tartaric acid, phosphoric acid, carbonic acid, lactic acid, gluconic acid, acetic acid, hydrochloric acid, and mixtures thereof
- a calcium source selected from calcium hydroxide, calcium oxide, calcium phosphate, calcium chloride, calcium carbonate, calcium glycerophosphate, calcium pyrophosphate, calcium metaphosphate, or any calcium source ionizable at aqueous, acidic solution, and mixtures thereof, to achieve a calcium to polyphosphate molar ratio of from about 2.5:1 to about 4.5:1 when mixed with the polyphosphate solution, said solution having a pH of from about 1.5 to about 3.5, such as from about 1.5 to about 2.5;
- the metallic polyphosphate utilized in this reaction can, for example, be a sodium or a sodium/potassium polyphosphate.
- the Na/K mixture can preferably include from about 50% to about 75% potassium.
- the calcium polyphosphate formed by the reaction include calcium metaphosphate, calcium sodium metaphosphate, calcium sodium potassium metaphosphate, calcium sodium polyphosphate, and calcium sodium potassium polyphosphate.
- the above reaction can be optimized to form a material which includes a relatively high loading of calcium so that fewer particles can be used in the beverage product to attain the desired level of calcium in that product; this will minimize aesthetic concerns in the final beverage product.
- the calcium polyphosphate particles can be separated out and incorporated into a separate beverage making process.
- the beverage can actually be formed in situ in the reaction mixture used to prepare the calcium polyphosphate material.
- water, preservative such as sodium hexametaphosphate
- flavor materials, colorants, and sweeteners are added to the reaction mixture. All of these materials are well-known to those skilled in the beverage art and they are used at their conventional levels for their conventional purposes.
- the finished beverage compositions typically contain from about 100 mg to about 300 mg of calcium per serving, and from about 0.1 wt % to about 0.18 wt % of the SHMP preservative.
- the calcium source utilized in these reactions is selected to be compatible with a beverage product.
- calcium hydroxide or calcium oxide can be used because water is then formed in the reaction.
- Calcium phosphate can be used, but care must be taken to be sure that the phosphorus RDI is not exceeded in the final product.
- the reaction needs to drive calcium to the sodium/potassium polyphosphate where it is bound, and not to the acid in the form of calcium citrate because in that instance it would still be available to deactivate the SHMP preservative.
- Examples of calcium sources which can be used in the present reactions include calcium hydroxide, calcium oxide, calcium phosphate, calcium chloride, calcium carbonate, calcium glycerophosphate, calcium phyrophosphate, calcium metaphosphate, or any calcium source ionizable at aqueous, acidic solution, and mixtures thereof.
- the acid selected for use in the reactions defined herein must be edible and have a pKa at low pH so that the acid stays protonated, thereby assuring that the calcium will not bind to it (this is because the calcium acid salt will not prevent the calcium from deactivating the SI-IMP preservative).
- useful acids in the reactions herein include citric acid, malic acid, tartaric acid, phosphoric acid, carbonic acid, lactic acid, gluconic acid, acetic acid, hydrochloric acid, and mixtures thereof.
- the reactions defined herein typically take place at a temperature within the range of from about 10 to about 30 degrees C.
- the amorphous glass solid material is formed, it is allowed to settle and the liquid is decanted off or filtered, and then the remaining amorphous solid material is dried using conventional means, such as a static dryer, solvent extraction, microwave heating or other similar means.
- This dry material is then ground into calcium polyphosphate particles using conventional means, such as a jet mill, to a particle size which is less than about 0.5 ⁇ m, such as from about 0.1 to about 0.3 ⁇ m.
- the particles can be added to the beverage product as is or can be coated (such as with a hydrogenated phospholipid material, for example, lecithin).
- the particles comprise from about 10 to about 90 weight percent of the calcium polyphosphate material, and from about 90 to about 10 weight percent of the coating material.
- the coating itself can be carried out using any known coating process, such as using a process by which the coating is sprayed onto the calcium polyphosphate particles and allowed to dry; or by incorporating the particles in a melt of phytosterols and other plant lipids and then spray chilling (prilling) the melt to allow a core of calcium polyphosphate and a coating of phytosterol.
- the present application also describes a method of utilizing an oil-in-water (O/W) emulsion, such as those used to provide beverage opacity or disperse flavors, to mask the unpleasant flavor that may come from displaced ions (i.e., potassium) that are present as a result of the making of the soluble calcium phosphate.
- O/W oil-in-water
- composition of the O/W emulsion is from about 10% to about 20%, such as about 14%, oil such as food approved oils (e.g., canola oil) used for such purposes; from about 5% to about 10%, preferably about 7%, emulsifier such as modified food starch; from about 68% to about 83%, preferably about 77%, water; and may include necessary preservatives, colors, and flavors to meet desired beverage organoleptics.
- the droplet size of the discontinuous phase of the O/W emulsion is less than about 1 ⁇ m, such as less than about 0.5 ⁇ m; it is preferred that 90% or greater of the droplets are at 0.1 ⁇ m; which can be achieved through typical emulsification methods such as high shear mixing or high pressure homogenization. Droplet size can be measured, for example, using a Horiba, Laser Diffraction Particle Size Analyzer.
- the present invention describes utilizing sodium ions in addition to the O/W emulsion to further mask any unpleasant flavor that may come from displaced ions (i.e., potassium) that are present as a result of the making of the soluble calcium phosphate.
- the sodium concentration is from about 100 ppm to about 500 ppm, such as about 250 ppm, not to exceed about 400 mg per 8 oz serving of the finished beverage;
- the sodium source is selected from sodium ions present in softened process water, and inorganic or organic salts approved for food use (such as sodium chloride, sodium citrate, sodium malate, sodium tartrate, sodium acetate, encompassing all food approved sodium-containing additives or mixtures thereof).
- SHMP sodium potassium hexametaphosphate
- SHMP sodium potassium hexametaphosphate
- SHMP sodium hexametaphosphate
- SHMP sodium potassium hexametaphosphate
- SHMP sodium hexametaphosphate
- the calcium polyphosphate particles can now be utilized in an SHMP-containing beverage where the salt. remains insoluble without deactivating SHMP.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Nutrition Science (AREA)
- Polymers & Plastics (AREA)
- Food Science & Technology (AREA)
- Engineering & Computer Science (AREA)
- Animal Behavior & Ethology (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- General Health & Medical Sciences (AREA)
- Epidemiology (AREA)
- Pharmacology & Pharmacy (AREA)
- Medicinal Chemistry (AREA)
- Mycology (AREA)
- Non-Alcoholic Beverages (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
Description
- The present application is based on and claims priority from U.S. Provisional Patent Application Ser. No. 62/157,680, Sarama and Arcuino, filed May 6, 2015, incorporated herein by reference.
- The present invention relates to the formulation of mineral fortified beverage products containing sodium hexametaphosphate as a preservative.
- Beverage products frequently utilize sodium hexametaphosphate (SHMP) as a preservative. It is important to have an effective preservative in beverage products since such products tend to require a relatively long shelf life from manufacture to retail outlet to drinking by the consumer. SHMP, although often referred to as a hexametaphosphate, technically is a polyphosphate and a powerful chelating agent. The SHMP functions as a preservative by extracting divalent metallic ions from microbial enzymatic systems. This prevents calcium, iron and magnesium utilization by microorganisms; this interrupts their physiology, resulting in the organisms' death.
- While it is desirable to provide vitamin or mineral fortification in some beverage products, particularly beverage products aimed at children, such supplementation can present formulation difficulties in beverages with chelating preservatives. For example, if a beverage product is to be fortified with vitamin D3, federal regulations require that the beverage also be fortified with calcium. Calcium, however, can deactivate the SHMP preservative, thereby significantly decreasing the shelf-life of the product. Thus, the beverage must be formulated such that the calcium does not deactivate the SHMP or otherwise impede its function, the calcium must also be bio-available, not produce unacceptable tastes or colors, must not settle out of the product, must be able to be processed on a large scale, and not add significant cost to the beverage product. Thus, the goal in formulating beverages, and particularly the goal in the present invention, is to develop a form of calcium which is an effective dietary supplement (i.e., bio-available), but which does not deactivate the SHMP preservative, and which is safe, cost-effective and easy to use in a beverage product. In addition, the calcium material utilized in the beverage cannot impart off-flavors or bad mouthfeel to the product and must be easy to incorporate within the product. That is what the present invention accomplishes.
- Specifically, SHMP is a powerful chelating agent. It functions as a preservative by extraction of divalent metallic ions (e.g., calcium, iron, magnesium) from microbial enzymatic systems. The extracted metals are no longer available to the microbes and so the microbes enter a stationary phase and, finally, a death phase.
- It has been estimated to require 0.24 g of a polyphosphate (e.g., SHMP) to kill 1×103 CFU's (colony-forming units) of microorganisms. The level of calcium contained in 1×103 CFU's of microorganisms is estimated to be approximately 2.6×10−8 g. The addition of 100 mg of calcium to a beverage containing SHMP will inactivate the SHMP and support the growth of 3.85×109 CFU's.
- The question arises as to how best to add calcium to a beverage containing SHMP as required by 21 CFR 172.380, in order to supplement with Vitamin D. In addition, the calcium must not deactivate the SHMP or impede its function, the calcium must be bio-available, produce no unacceptable taste or color, must not precipitate out and be able to be processed on a large scale.
- The present invention provides a calcium polyphosphate product (e.g., calcium hexametaphosphate) which can be used to provide a bio-available source of calcium to a beverage product without deactivating the SHMP preservative in that beverage product. The present application also describes the formation of calcium hexametaphosphate particles, particularly coated particles, and also describes methods of making the calcium polyphosphate-calcium hexametaphosphate material. Finally, the present invention teaches how to formulate the calcium polyphosphate so as to minimize any off-tastes.
- It has been discovered that a calcium polyphosphate salt can be produced and maintained in equilibrium with SHMP in such a manner so as to not affect the preservative action of SHMP. The average polyphosphate chain length of SHMP is 19-25, which makes it a very strong chelating agent. It has been found that by producing a calcium polyphosphate salt with a phosphorus chain length of 11-15, the salt not only remains in equilibrium with SHMP, but releases its calcium cations at gastric pH making the calcium bio-available.
- The ratio of calcium to lower chain polyphosphate is critical as well. The optimum molar ratio of calcium polyphosphate is about 4:1. Lowering the level causes overuse of polyphosphate whereas exceeding a ratio of about 4:1 causes the formation of a sticky amorphous glass structure which physically separates from the aqueous base during preparation. This amorphous glass solid is unstable in that form and will not mix homogenously with aqueous beverages.
- The present application therefore describes a calcium polyphosphate salt, such as a calcium hexametaphosphate salt, in soluble form, which has a calcium/polyphosphate molar ratio of from about 2.5:1 to about 4.5:1, and wherein the polyphosphate has a phosphorus chain length of from about 9 to about 16, for example, from about 11 to about 15.
- The present application also describes a method of making a calcium polyphosphate salt, in particulate form, comprising the steps of:
- (a) preparing a calcium phosphate salt having a phosphorus chain length of from about 9 to about 16, and a calcium:polyphosphate molar ratio of from about 5:1 to about 9:1 (especially about 5.5:1), in the form of an amorphous glass solid;
- (b) dehydrating the amorphous glass solid to form a solid having a water content no greater than about 0.1%; and
- (c) processing the solid (such as by grinding) to form particles having an average particle size no greater than about 0.5 μm.
- The present application also describes two methods for the preparation of the calcium polyphosphate salt; this can be done in situ thereby allowing the completed reaction mixture to be made directly into a beverage product. The first such method which directly reacts calcium with the polyphosphate includes the following steps:
- (a) directly reacting a metallic polyphosphate (such as a sodium, potassium polyphosphate) having a phosphorus chain length of from about 9 to about 16 (such as from about 11 to about 15), with a calcium source selected from calcium hydroxide, calcium oxide, calcium phosphate, calcium carbonate, calcium glycerophosphate, calcium pyrophosphate, calcium metaphosphate or any other calcium source ionizable at aqueous, acidic solution, and mixtures thereof, in an aqueous near neutral (pH=about 6 to about 7.5) medium, the molar ratio of polyphosphate to calcium source being from about 2.5:1 to about 4.5:1; and
- (b) adding a minor portion, for example about 25% of the total added, the total being from about 0.18 wt % to about 0.725 wt %, of an organic or mineral acid toward the end of this reaction to complete the dissociation of the calcium from its counter moiety and complete the transfer of calcium to the polyphosphate substrate thereby forming the soluble calcium phosphate salt.
- The solubility of the calcium source will typically be low in near neutral pH aqueous medium and so will slowly react with the polyphosphate, for example, having a 10-15 minute reaction time.
- That completed reaction mixture can then be used to formulate a beverage in situ by the addition of water, sodium hexametaphosphate, flavor, color and sweetener (and, if desired, other conventional beverage components).
- The second such method for preparing the calcium polyphosphate salt comprises the steps of:
- (a) preparing an aqueous solution of an organic mineral acid (such as citric acid), together with from about 1.3 parts to about 10 parts of a calcium source selected from calcium hydroxide, calcium oxide, calcium phosphate, calcium chloride, calcium glycerophosphate, calcium pyrophosphate, calcium metaphosphate, or any calcium source ionizable at aqueous, acidic solution, and mixtures thereof, to one part polyphosphate, said solution having a pH of from about 1.5 to about 3.5, with the amount of calcium used based on a calcium polyphosphate molar ratio from about 2.5:1 to about 4.5:1;
- (b) forming a separate aqueous solution of a metallic (such as a sodium or sodium/potassium) polyphosphate having a chain length of from about 9 to about 16 (such as from about 11 to about 15), at such a concentration as to form a calcium polyphosphate soluble salt with a molar ratio from about 2.5:1 to about 4.5:1; and
- (c) with agitation, adding the calcium and surrogate solution (step (a)) to the polyphosphate solution (step (b)), thereby forming the calcium polyphosphate salt.
- This completed reaction mixture can be used to formulate a beverage in situ by addition of water, sodium hexametaphosphate, flavor, color and sweetener (and, if desired, other conventional beverage components).
- The calcium polyphosphate particles as described in paragraph [0011] herein are insoluble in a beverage product of typical pH, such as between pH 2.8 and 7.6. The formation of the particles lends itself to a purification step that allows the removal of byproducts that may impact flavor (i.e., potassium ions). This higher calcium loaded polyphosphate material does not affect the preservative action of SHMP and releases its calcium cations at gastric pH, making the calcium bioavailable.
- It has also been discovered that an oil-in-water (O/W) emulsion, such as those used to provide beverage opacity or disperse flavors, can mask the unpleasant flavor that may come from displaced ions (e.g., potassium) that are present as a result of the making of the calcium polyphosphate.
- Further, it has been found that, in addition to the flavor masking of the O/W emulsion, sodium ions must also be present with the emulsion to optimally mask the unpleasant flavor that may come from displaced ions (e.g., potassium) that are present as a result of the making of the calcium polyphosphate.
- The present invention thus provides a calcium polyphosphate product (e.g., calcium metaphosphate or calcium polyphosphate) which:
- (a) is soluble and does not deactivate a chelating preservative, such as SHMP, and can be used to provide a bio-available source of calcium to a beverage product;
- (b) is in particulate form, free from extraneous matter that may impact flavor (e.g., potassium ions), does not deactivate a chelating preservative, such as SHMP, and can be used to provide a bio-available source of calcium to a beverage product;
- (c) can be used in combination with an oil-in-water emulsion that masks the unpleasant flavor that may be associated with potassium ions that are present as a result of the making of the calcium polyphosphate; and
- (d) utilizes sodium ions in addition to the oil-in-water emulsion that masks the unpleasant flavor that may be associated with potassium ions that are present as a result of the making of the calcium polyphosphate.
- All references herein to polyphosphates are interchangeable with the terms hexametaphosphates and metaphosphates, including reference to their cyclic or linear forms, and can refer to any member of their metallic salts. All percentages and ratios stated herein are “by weight”, unless otherwise specified. Further, all patents, patent applications and other publications cited in this application are incorporated by reference herein.
- The present invention relates to calcium polyphosphate materials (such as calcium hexametaphosphate), containing relatively short polyphosphate chain lengths and utilizing specific calcium:phosphate molar ratios. These materials can be used to provide calcium supplementation to beverages, particularly beverages which use a chelating preservative (such as SHMP) without deactivating that preservative. The methods of making these materials are also disclosed in this application.
- It has been discovered that a calcium polyphosphate salt can be produced and maintained in equilibrium with SHMP in a beverage product in such a manner as to not affect the preservative activity of the SHMP in that beverage. The average polyphosphate chain length of SHMP is from 19 to 25. This makes for a very strong chelating agent (which accounts for SHMP's excellent preservative characteristics). It has now been found that by producing a calcium, polyphosphate salt with a relatively short phosphorus chain length of from about 9 to about 16, such as from about 11 to about 15, the calcium polyphosphate not only remains in equilibrium with SHMP (i.e., does not ruin SHMP's preservative properties) but also releases its calcium cation at gastric pH making the calcium bio-available.
- The ratio of calcium to lower chain polyphosphate in the composition is important. The molar ratio of calcium to polyphosphate in the material is from about 2.5:1 to about 4.5:1, such as about 4:1. Lowering the ratio causes the overuse of polyphosphate, whereas significantly exceeding the ratio causes the formation of a sticky, amorphous, glass structure which physically separates from the aqueous base during preparation.
- This amorphous glass solid is unusable in that form to be a calcium supplement in a beverage, and will not itself mix homogeneously with aqueous beverages. However, it has been found that this amorphous glass solid can be dehydrated, ground or physically processed by a jet mill or similar methods to produce small particles. These particles can then be added back to the SHMP-containing beverage with great success. The amorphous glass solid can be decanted and dehydrated by filtering, evaporation, solvent extraction, microwave heating or other similar means, for example, such that it has a water content of no greater than about 0.1%, preferably no greater than about 0.05%. The particles formed by grinding this solid typically have an average particle size of no greater than about 0.5 μm, such as from about 0.1 μm to about 0.3 μm. This small particle size is primarily important to avoid product grittiness or otherwise inappropriate mouthfeel for the consumer. By producing calcium phosphate amorphous glass solid at a molar ratio of from about 5:1 to about 9:1, such as about 5.5:1, calcium:short chain polyphosphate, a high calcium loaded salt, suitable for use after dehydration and particle processing is produced. An added benefit of this approach is that any metallic ions (sodium, potassium, etc.) originating from the starting shorter chain polyphosphate are essentially removed during the isolation of the amorphous glass solid.
- The selection of shorter chain polyphosphate materials ideally has a phosphorus chain length of from about 9 to about 16, such as from about 11 to about 15, but longer chain lengths, for example 19-25, can be used particularly in conjunction with shorter chain length polyphosphates. They can, for example, be selected from the group consisting of metal salts of polyphosphates and metaphosphates, such as sodium metaphosphate, sodium calcium metaphosphate, sodium calcium polyphosphates, or sodium potassium metaphosphate, as well as other salts of metaphosphates or polyphosphates either of mono, binary, tertiary salts (e.g., a sodium potassium magnesium polyphosphate) encompassing all ratios of salt, for example, a sodium potassium polyphosphate with a sodium: potassium molar ratio of from about 1:9 to about 9:1.
- The calcium polyphosphate salts defined herein can be synthesized in several ways. The first is to directly react the metallic short chain polyphosphate with a calcium source (for example, calcium hydroxide) in an aqueous neutral medium. Since the solubility of calcium hydroxide is very low in an aqueous medium, the calcium hydroxide solely reacts over the course of from about 5 to about 20 minutes, such as from about 10 to about 15 minutes, as calcium is transferred from the calcium hydroxide to the polyphosphate. A small amount of organic or mineral acid, such as citric acid, is added toward the end of this process to complete the dissociation of calcium from its hydroxide moiety and complete the transfer of calcium to the polyphosphate substrate.
- Specifically, in this first method of making the calcium polyphosphate salt, where there is a direct reaction of the calcium with the polyphosphate, the following steps are utilized:
- (a) reacting a metallic polyphosphate having a phosphorus chain length of from about 9 to about to about 16, with a calcium source selected from calcium hydroxide, calcium oxide, calcium phosphate, calcium chloride, calcium carbonate, calcium glycerophosphate, calcium pyrophosphate, calcium metaphosphate, or any calcium salt ionizable at aqueous, acidic solution, and mixtures thereof, in an aqueous medium, having a pH of from about 6 to about 7.5, the molar ratio of calcium to polyphosphate source being from about 2.5:1 to about 4.5:1;
- (b) adding to the reaction mixture from about 0.18 wt % to about 0.725 wt % of an organic or mineral acid (such as citric acid, malic acid, tartaric acid, phosphoric acid, carbonic acid, lactic acid, gluconic acid, acetic acid, and mixtures thereof), thereby forming the calcium phosphate salt.
- In a second method of preparing the soluble calcium polyphosphate salt described herein, an organic acid is utilized as a surrogate carrier of the calcium. This is accomplished by first preparing an aqueous solution of the acid (for example, citric acid). To this aqueous solution the correct amount of calcium salt (e.g., calcium hydroxide) is added. The amount of calcium salt used is based on the desired ratio of calcium to metaphosphate or polyphosphate. Because the solution is acidic (pH of from about 1.5 to about 2.5), calcium hydroxide immediately dissociates allowing the calcium to react with the acid forming a salt (e.g., calcium citrate). Separately, the polyphosphate is solubilized in water. This polyphosphate is reacted with the calcium salt (i.e., the surrogate carrier solution) (e.g., calcium citrate, calcium malate, calcium tartrate, calcium phosphate, calcium lactate, calcium acetate, calcium chloride, calcium carbonate, calcium gluconate, and mixtures thereof) by mixing of the calcium salt solution into the polyphosphate solution. The calcium is then quickly chelated or transferred from the calcium salt to the polyphosphate resulting in the formation of calcium polyphosphate.
- More specifically, in the second method of preparing the calcium polyphosphate salt, where there is a surrogate carrier of the calcium, the following steps are utilized:
- (a) preparing an aqueous solution of an organic or mineral acid (such as citric acid, malic acid, tartaric acid, phosphoric acid, carbonic acid, lactic acid, gluconic acid, acetic acid, hydrochloric acid, and mixtures thereof) together with a calcium source selected from calcium hydroxide, calcium oxide, calcium phosphate, calcium chloride, calcium carbonate, calcium glycerophosphate, calcium pyrophosphate, calcium metaphosphate, or any calcium source ionizable at aqueous, acidic solution, and mixtures thereof, to achieve a calcium to polyphosphate molar ratio of from about 2.5:1 to about 4.5:1 when mixed with the polyphosphate solution, said solution having a pH of from about 1.5 to about 3.5, such as from about 1.5 to about 2.5;
- (b) forming a separate aqueous solution of from about 3 wt % to about 5 wt % of metallic polyphosphate having a phosphate chain length of from about 9 to about 16, such as from about 11 to about 15; and
- (c) mixing the calcium salt solution into the polyphosphate solution thereby forming the calcium polyphosphate salt.
- The metallic polyphosphate utilized in this reaction can, for example, be a sodium or a sodium/potassium polyphosphate. For health reasons, it is desirable to keep sodium levels relatively low; thus, the Na/K mixture can preferably include from about 50% to about 75% potassium. Examples of the calcium polyphosphate formed by the reaction include calcium metaphosphate, calcium sodium metaphosphate, calcium sodium potassium metaphosphate, calcium sodium polyphosphate, and calcium sodium potassium polyphosphate. The above reaction can be optimized to form a material which includes a relatively high loading of calcium so that fewer particles can be used in the beverage product to attain the desired level of calcium in that product; this will minimize aesthetic concerns in the final beverage product.
- Once the reaction is completed, the calcium polyphosphate particles can be separated out and incorporated into a separate beverage making process. In the alternative, the beverage can actually be formed in situ in the reaction mixture used to prepare the calcium polyphosphate material. In order to achieve that in situ beverage formulation, water, preservative (such as sodium hexametaphosphate), flavor materials, colorants, and sweeteners (as well as other formulation materials well-known in the beverage art) are added to the reaction mixture. All of these materials are well-known to those skilled in the beverage art and they are used at their conventional levels for their conventional purposes. The finished beverage compositions typically contain from about 100 mg to about 300 mg of calcium per serving, and from about 0.1 wt % to about 0.18 wt % of the SHMP preservative.
- The calcium source utilized in these reactions is selected to be compatible with a beverage product. As an example, calcium hydroxide or calcium oxide can be used because water is then formed in the reaction. Calcium phosphate can be used, but care must be taken to be sure that the phosphorus RDI is not exceeded in the final product. The reaction needs to drive calcium to the sodium/potassium polyphosphate where it is bound, and not to the acid in the form of calcium citrate because in that instance it would still be available to deactivate the SHMP preservative. Examples of calcium sources which can be used in the present reactions include calcium hydroxide, calcium oxide, calcium phosphate, calcium chloride, calcium carbonate, calcium glycerophosphate, calcium phyrophosphate, calcium metaphosphate, or any calcium source ionizable at aqueous, acidic solution, and mixtures thereof.
- The acid selected for use in the reactions defined herein must be edible and have a pKa at low pH so that the acid stays protonated, thereby assuring that the calcium will not bind to it (this is because the calcium acid salt will not prevent the calcium from deactivating the SI-IMP preservative). Examples of useful acids in the reactions herein include citric acid, malic acid, tartaric acid, phosphoric acid, carbonic acid, lactic acid, gluconic acid, acetic acid, hydrochloric acid, and mixtures thereof.
- The reactions defined herein typically take place at a temperature within the range of from about 10 to about 30 degrees C.
- In making the particles of the calcium polyphosphate material (i.e., having a high calcium:polyphosphate molar ratio), see paragraph [0011] herein, the amorphous glass solid material is formed, it is allowed to settle and the liquid is decanted off or filtered, and then the remaining amorphous solid material is dried using conventional means, such as a static dryer, solvent extraction, microwave heating or other similar means. This dry material is then ground into calcium polyphosphate particles using conventional means, such as a jet mill, to a particle size which is less than about 0.5 μm, such as from about 0.1 to about 0.3 μm. The particles can be added to the beverage product as is or can be coated (such as with a hydrogenated phospholipid material, for example, lecithin). When used, the particles comprise from about 10 to about 90 weight percent of the calcium polyphosphate material, and from about 90 to about 10 weight percent of the coating material. The coating itself can be carried out using any known coating process, such as using a process by which the coating is sprayed onto the calcium polyphosphate particles and allowed to dry; or by incorporating the particles in a melt of phytosterols and other plant lipids and then spray chilling (prilling) the melt to allow a core of calcium polyphosphate and a coating of phytosterol.
- The present application also describes a method of utilizing an oil-in-water (O/W) emulsion, such as those used to provide beverage opacity or disperse flavors, to mask the unpleasant flavor that may come from displaced ions (i.e., potassium) that are present as a result of the making of the soluble calcium phosphate.
- Three critical elements support the use of the O/W emulsion as masking agent:
- (a) The soluble calcium polyphosphate salt must make contact with the O/W emulsion separately prior to addition of other beverage components; and maximum contact is ensured with the mixture thoroughly agitated, such as with high shear mixing, for a period of contact time of about five minutes or more.
- (b) The composition of the O/W emulsion is from about 10% to about 20%, such as about 14%, oil such as food approved oils (e.g., canola oil) used for such purposes; from about 5% to about 10%, preferably about 7%, emulsifier such as modified food starch; from about 68% to about 83%, preferably about 77%, water; and may include necessary preservatives, colors, and flavors to meet desired beverage organoleptics.
- (c) The droplet size of the discontinuous phase of the O/W emulsion is less than about 1 μm, such as less than about 0.5 μm; it is preferred that 90% or greater of the droplets are at 0.1 μm; which can be achieved through typical emulsification methods such as high shear mixing or high pressure homogenization. Droplet size can be measured, for example, using a Horiba, Laser Diffraction Particle Size Analyzer.
- In addition, the present invention describes utilizing sodium ions in addition to the O/W emulsion to further mask any unpleasant flavor that may come from displaced ions (i.e., potassium) that are present as a result of the making of the soluble calcium phosphate. In formulating such beverages, the sodium concentration is from about 100 ppm to about 500 ppm, such as about 250 ppm, not to exceed about 400 mg per 8 oz serving of the finished beverage; the sodium source is selected from sodium ions present in softened process water, and inorganic or organic salts approved for food use (such as sodium chloride, sodium citrate, sodium malate, sodium tartrate, sodium acetate, encompassing all food approved sodium-containing additives or mixtures thereof).
- The following examples are intended to illustrate the present invention and are not intended to be in any way limiting thereof.
- 1. In an appropriate vessel, add 1094 g distilled H2O (ca. 25% of total water).
- 2. While high shear mixing the water, add 21.592 g sodium potassium hexametaphosphate (SHMP) to dissolve.
- 3. While high shear mixing the solution from (2), add 3.831 g Ca(OH)2.
- 4. Mix for 10-15 minutes.
- 5. While high shear mixing the solution from (4), add 8.51 g citric acid (ca. 23% of total citric acid).
- 6. Mix for 5 minutes.
- 7. In another vessel, add 3280.74 g distilled water (ca. 75% of total water).
- 8. While high shear mixing the water, add 4.92 g sodium hexametaphosphate (SHMP) to dissolve.
- 9. While high shear mixing the solution from (8), add 28.71 g citric acid (ca. 78% of total citric acid).
- 10. To the solution from (9), add flavors, colors and sweeteners and mix well.
- 11. To achieve the finished beverage, to the solution from (10) add the solution from (6) and mix well.
- 1. In an appropriate vessel, add 1094 g distilled H2O (ca. 25% of total water).
- 2. While high shear mixing the water, add 21.592 g sodium potassium hexametaphosphate (SHMP) to dissolve.
- 3. In another vessel, add 1094 g distilled H2O (ca. 25% of total water).
- 4. While high shear mixing the solution from (3), add 3.831 g Ca(OH)2.
- 5. While high shear mixing the solution from (4), add 37.22 g citric acid to dissolve.
- 6. In another vessel, add 2186.74 g distilled H2O (ca. 50% of total water).
- 7. While high shear mixing the water, add 4.92 g sodium hexametaphosphate (SHMP) to dissolve.
- 8. To the solution from (7) add flavors, colors and sweeteners and mix well.
- 9. Mix the solution from (5) into the solution from (2).
- 10. Mix the solution from (9) into the solution from (8) to achieve the finished beverage.
- 1. Add 80% of the batch's process water to the blend tank and start agitator and recirculation pump.
- 2. Add the Ca(OH)2 to the tank and agitate to disperse.
- 3. Add the sodium potassium hexametaphosphate (SHMP) to the above solution as it is being agitated and continue agitating from 5 minutes up to 12 minutes.
- 4. To the tank add a portion of the citric acid that equals 21.48% of the total citric acid being added to the batch.
- 5. Mix for 2-5 minutes, then circulate through the recirculation loop to remove any unreacted calcium.
- 6. While agitating the above solution, add sodium hexametaphosphate (SHMP) to dissolve.
- 7. Add flavors, colors and sweeteners and agitate to mix ingredients well.
- 8. Add the remaining citric acid.
- 9. Add the remaining process water and agitate well until homogenous.
- 1. In an appropriate vessel, add 1094 g distilled H2O (ca. 25% of total water).
- 2. While high shear mixing the water, add 21.592 g sodium potassium hexametaphosphate (SHMP) to dissolve.
- 3. While high shear mixing the solution from (2), add 3.831 g Ca(OH)2.
- 4. Mix for 10-15 minutes.
- 5. While high shear mixing the solution from (4), add 8.51 g citric acid (ca. 23% of total citric acid).
- 6. Mix for 5 minutes.
- 7. While high shear mixing the solution from (6) add 25.53 g of oil-in-water emulsion (the o/w emulsion as described herein containing starch, water and canola oil).
- 8. High shear mix for 10-15 minutes.
- 9. In another vessel, add 3280.74 g distilled water (ca. 75% of total water).
- 10. While high shear mixing the water, add 4.92 g sodium hexametaphosphate (SHMP) to dissolve.
- 11. While high shear mixing the solution from (10), add 28.71 g citric acid (ca. 78% of total citric acid).
- 12. To the solution from (11), add flavors, colors, and sweeteners and mix well.
- 13. To achieve the finished beverage, to the solution from (12) add the solution from (8) and mix well.
- 1. In an appropriate vessel add 1094 g distilled H2O (ca. 25% of total water).
- 2. While high shear mixing the water, add 21.592 g sodium potassium hexametaphosphate (SHMP) to dissolve.
- 3. In another vessel add 1094 g distilled H2O (ca. 25% of total water).
- 4. While high shear mixing the solution from (3), add 3.81 g Ca(OH)2.
- 5. While high shear mixing the solution from (4), add 37.22 g citric acid to dissolve.
- 6. In another vessel, add 2186.74 g distilled H2O (ca. 50% of total water).
- 7. While high shear mixing the water, add 4.92 g sodium hexametaphosphate (SHMP) to dissolve.
- 8. To the solution from (7) add flavors, colors and sweeteners and mix well.
- 9. Mix the solution from (5) into the solution from (2).
- 10. While high shear mixing the solution from (9) add 25.53 g of oil-in-water emulsion (the o/w emulsion as described herein containing starch, water and canola oil).
- 11. High shear mix for 10-15 minutes.
- 12. Mix the solution from (11) into the solution from (8) to achieve the finished beverage.
- 1. Add 80% of the batch's process water to the blend tank and start agitator and recirculation pump.
- 2. Add the Ca(OH)2 to the tank and disperse.
- 3. Add the sodium potassium hexametaphosphate (SHMP) to the above solution as it is being agitated and continue agitating from 5 minutes up to 12 minutes.
- 4. To the tank add a portion of the citric acid that equals 21.48% of the total citric acid being added to the batch.
- 5. Mix for 2-5 minutes, then circulate through the recirculation loop to remove any unreacted calcium.
- 6. While high shear mixing the solution from (5) add the oil-in-water emulsion (the o/w emulsion as described herein containing starch, water and canola oil).
- 7. High shear mix for 10-15 minutes.
- 8. While agitating the above solution, add sodium hexametaphosphate (SHMP) to dissolve.
- 9. Add flavors, colors and sweeteners and agitate to mix ingredients well.
- 10. Add the remaining citric acid.
- 11. Add the remaining process water and agitate well until homogenous.
- 1. To the process water add sodium citrate to dissolve and bring the water sodium level to 255 ppm, resulting in modified process water (MPW).
- 2. In an appropriate vessel, add 1094 g MPW (ca. 25% of total water).
- 3. While high shear mixing the water, add 21.592 g sodium potassium hexametaphosphate (SHMP) to dissolve.
- 4. While high shear mixing the solution from (3), add 3.831 g Ca(OH)2.
- 5. Mix for 10-15 minutes.
- 6. While high shear mixing the solution from (5), add 8.51 g citric acid (ca. 23% of total citric acid).
- 7. Mix for 5 minutes.
- 8. While high shear mixing the solution from (7) add 25.53 g of oil-in-water emulsion (the o/w emulsion as described herein containing starch, water and canola oil).
- 9. High shear mix for 10-15 minutes.
- 10. In another vessel, add 3280.74 g MPW (ca. 75% of total water).
- 11. While high shear mixing the water, add 4.92 g sodium hexametaphosphate (SHMP) to dissolve.
- 12. While high shear mixing the solution from (11), add 28.71 g citric acid (ca. 78% of total citric acid).
- 13. To the solution from (12), add flavors, colors, and sweeteners and mix well.
- 14. To achieve the finished beverage, to the solution from (13) add the solution from (9) and mix well.
- 1. To the process water add sodium citrate to dissolve to bring the water sodium level to 255 ppm, resulting in modified process water (MPW).
- 2. In an appropriate vessel add 1094 g MPW (ca. 25% of total water).
- 3. While high shear mixing the water, add 21.592 g sodium potassium hexametaphosphate (SHMP) to dissolve.
- 4. In another vessel add 1094 g MPW (ca. 25% of total water).
- 5. While high shear mixing the solution from (4), add 3.81 g Ca(OH)2.
- 6. While high shear mixing the solution from (5), add 37.22 g citric acid to dissolve.
- 7. In another vessel, add 2186.74 g MPW (ca. 50% of total water).
- 8. While high shear mixing the water, add 4.92 g sodium hexametaphosphate (SHMP) to dissolve.
- 9. To the solution from (8) add flavors, colors and sweeteners and mix well.
- 10. Mix the solution from (6) into the solution from (3).
- 11. While high shear mixing the solution from (10) add 25.53 g of oil-in-water emulsion (the o/w emulsion as described herein containing starch, water and canola oil).
- 12. High shear mix for 10-15 minutes.
- 13. Mix the solution from (12) into the solution from (9) to achieve the finished beverage.
- 1. Modify the process water to achieve 255 ppm sodium by adding sodium citrate to dissolve.
- 2. Add 80% of the batch's process water to the blend tank and start agitator and recirculation pump.
- 3. Add the Ca(OH)2 to the tank and disperse.
- 4. Add the sodium potassium hexametaphosphate (SHMP) to the above solution as it is being agitated and continue agitating from 5 minutes up to 12 minutes.
- 5. To the tank add a portion of the citric acid that equals 21.48% of the total citric acid being added to the batch.
- 6. Mix for 2-5 minutes, then circulate through the recirculation loop to remove any unreacted calcium.
- 7. While high shear mixing the solution from (6) add the oil-in-water emulsion (the o/w emulsion as described herein containing starch, water and canola oil).
- 8. High shear mix for 10-15 minutes.
- 9. While agitating the above solution, add sodium hexametaphosphate (SHMP) to dissolve.
- 10. Add flavors, colors and sweeteners and agitate to mix ingredients well.
- 11. Add the remaining citric acid.
- 12. Add the remaining process water and agitate well until homogenous.
- 1. In an appropriate vessel, add 1094 g distilled H2O (ca. 25% of total water).
- 2. While high shear mixing the water, add 21.59 g sodium potassium hexametaphosphate (SHMP) to dissolve.
- 3. While high shear mixing the solution from (2), add 5.268 g Ca(OH)2.
- 4. Mix for 5-10 minutes or until mixture begins to clear.
- 5. Stop agitating.
- 6. Decant aqueous supernatant containing potassium and sodium ions.
- 7. Collect amorphous glass precipitate and place into a drying vessel.
- 8. Dry at 50-58 degrees C. until moisture content is less than 0.1% as measured by Karl Fisher.
- 9. Pulverize the dried salt and follow with high intensity grinding to achieve appropriate size and distribution as measured by using a Horiba PSA.
- 10. If particles exceed 0.5 μm, prepare an aqueous slurry using the particles and high shear grind until desired particle size and distribution are achieved.
- 11. After drying and grinding, the calcium polyphosphate particles can now be utilized in an SHMP-containing beverage where the salt. remains insoluble without deactivating SHMP.
Claims (22)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US15/066,652 US20160324893A1 (en) | 2015-05-06 | 2016-03-10 | Calcium polyphosphate salts, methods of making and use in beverage compositions |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US201562157680P | 2015-05-06 | 2015-05-06 | |
US15/066,652 US20160324893A1 (en) | 2015-05-06 | 2016-03-10 | Calcium polyphosphate salts, methods of making and use in beverage compositions |
Publications (1)
Publication Number | Publication Date |
---|---|
US20160324893A1 true US20160324893A1 (en) | 2016-11-10 |
Family
ID=55646884
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US15/066,652 Abandoned US20160324893A1 (en) | 2015-05-06 | 2016-03-10 | Calcium polyphosphate salts, methods of making and use in beverage compositions |
US15/066,678 Active 2036-09-27 US10005670B2 (en) | 2015-05-06 | 2016-03-10 | Calcium polyphosphate salt particles and method of making |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US15/066,678 Active 2036-09-27 US10005670B2 (en) | 2015-05-06 | 2016-03-10 | Calcium polyphosphate salt particles and method of making |
Country Status (4)
Country | Link |
---|---|
US (2) | US20160324893A1 (en) |
BR (2) | BR112017023878B1 (en) |
MX (2) | MX2017014242A (en) |
WO (2) | WO2016178747A1 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10005670B2 (en) | 2015-05-06 | 2018-06-26 | Sunny Delight Beverages Co. | Calcium polyphosphate salt particles and method of making |
CN109399598A (en) * | 2018-12-28 | 2019-03-01 | 湖北泰盛化工有限公司 | A kind of method that the purification of crude product sodium pyrophosphate produces sodium pyrophosphate and sodium chloride |
CN111634897A (en) * | 2020-05-27 | 2020-09-08 | 天宝动物营养科技股份有限公司 | Nano-grade calcium hydroxy phosphate/calcium hydrogen phosphate and preparation method thereof |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111405928B (en) * | 2017-11-30 | 2023-06-20 | 高露洁-棕榄公司 | Oral care compositions |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4696826A (en) * | 1986-05-16 | 1987-09-29 | General Foods Corporation | Process for manufacture of emulsions containing soy protein |
US4906482A (en) * | 1986-03-19 | 1990-03-06 | Zemel Michael B | Method of making calcium fortified soy milk and the calcium fortified soy milk |
WO2014160920A1 (en) * | 2013-03-29 | 2014-10-02 | Cargill, Incorporated | Process for the production of stable emulsions |
Family Cites Families (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2852341A (en) * | 1954-08-20 | 1958-09-16 | Victor Chemical Works | Calcium polyphosphate and method of producing the same |
US4010241A (en) * | 1974-08-27 | 1977-03-01 | Alfred Lvovich Mosse | Process for the production of hydrogen fluoride, phosphoric anhydride, calcium polyphosphates and nitric acid |
US4360625A (en) * | 1979-12-14 | 1982-11-23 | Monsanto Company | Acicular, crystalline calcium metaphosphate |
US5431940A (en) * | 1994-02-24 | 1995-07-11 | The Procter & Gamble Company | Preparation of noncarbonated beverage products with improved microbial stability |
US6261619B1 (en) * | 1994-02-24 | 2001-07-17 | The Procter & Gamble Co. | Noncarbonated beverage products with improved microbial stability and processes for preparing |
US6294214B1 (en) * | 1994-02-24 | 2001-09-25 | The Procter & Gamble Co. | Noncarbonated beverage products with improved microbial stability and processes for preparing |
US6268003B1 (en) * | 1994-02-24 | 2001-07-31 | The Procter & Gamble Company | Noncarbonated beverage products with improved microbial stability and processes for preparing |
BR9604884A (en) * | 1995-02-28 | 1998-05-19 | Procter & Gamble | Preparation of non-carbonated beverage products with superior microbial stability |
US6326040B1 (en) | 1999-03-08 | 2001-12-04 | The Procter & Gamble Co. | Beverage products having superior vitamin stability |
US7094282B2 (en) | 2000-07-13 | 2006-08-22 | Calcitec, Inc. | Calcium phosphate cement, use and preparation thereof |
GB0007421D0 (en) | 2000-03-27 | 2000-05-17 | Smithkline Beecham Plc | Novel use |
US7494614B2 (en) * | 2002-07-12 | 2009-02-24 | Pilliar Robert M | Method of manufacture of porous inorganic structures |
US8067321B2 (en) * | 2008-05-21 | 2011-11-29 | Icl Performance Products, Lp | Sodium-potassium hexametaphosphate and potassium metaphosphate with a low insolubles content |
US8999031B2 (en) * | 2010-08-10 | 2015-04-07 | Agtec Innovations, Inc. | Polyphosphate fertilizer combinations |
ES2399000B1 (en) * | 2012-12-12 | 2014-01-28 | Biotechnology Institute I Mas D S.L. | Method to produce a porous structure of calcium polysphosphate |
US20140199439A1 (en) | 2013-01-14 | 2014-07-17 | Sunny Delight Beverages Company | Coated calcium particulates for use in beverage products |
GB2532283A (en) | 2014-11-17 | 2016-05-18 | Ernst Ludwig Georg Muller Werner | Morphogenetically active calcium polyphosphate nanoparticles |
US20160324893A1 (en) | 2015-05-06 | 2016-11-10 | Sunny Delight Beverages Co. | Calcium polyphosphate salts, methods of making and use in beverage compositions |
-
2016
- 2016-03-10 US US15/066,652 patent/US20160324893A1/en not_active Abandoned
- 2016-03-10 US US15/066,678 patent/US10005670B2/en active Active
- 2016-03-15 BR BR112017023878-0A patent/BR112017023878B1/en active IP Right Grant
- 2016-03-15 WO PCT/US2016/022451 patent/WO2016178747A1/en active Application Filing
- 2016-03-15 MX MX2017014242A patent/MX2017014242A/en unknown
- 2016-03-15 WO PCT/US2016/022460 patent/WO2016178748A1/en active Application Filing
- 2016-03-15 MX MX2017014243A patent/MX2017014243A/en unknown
- 2016-03-15 BR BR112017023880A patent/BR112017023880A2/en not_active Application Discontinuation
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4906482A (en) * | 1986-03-19 | 1990-03-06 | Zemel Michael B | Method of making calcium fortified soy milk and the calcium fortified soy milk |
US4696826A (en) * | 1986-05-16 | 1987-09-29 | General Foods Corporation | Process for manufacture of emulsions containing soy protein |
WO2014160920A1 (en) * | 2013-03-29 | 2014-10-02 | Cargill, Incorporated | Process for the production of stable emulsions |
Non-Patent Citations (3)
Title |
---|
CRC Handbook of Food Additives, Second edition. Vol 1. Edited by Thomas Furia. 1972. CRC Press, Boca Raton Florida. pages 628-629. * |
Exerpt from Wikipedia entry for soy milk. From: Wikipedia entry for Soy Milk, downloaded December 21, 2016 from https://en.wikipedia.org/wiki/Soy_milk * |
Wilson, Pamela. The Good on Cooking Oils. Downloaded December 26, 2016, from http://www.abc.net.au/health/thepulse/stories/2012/04/24/3471676.htm. * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10005670B2 (en) | 2015-05-06 | 2018-06-26 | Sunny Delight Beverages Co. | Calcium polyphosphate salt particles and method of making |
CN109399598A (en) * | 2018-12-28 | 2019-03-01 | 湖北泰盛化工有限公司 | A kind of method that the purification of crude product sodium pyrophosphate produces sodium pyrophosphate and sodium chloride |
CN111634897A (en) * | 2020-05-27 | 2020-09-08 | 天宝动物营养科技股份有限公司 | Nano-grade calcium hydroxy phosphate/calcium hydrogen phosphate and preparation method thereof |
Also Published As
Publication number | Publication date |
---|---|
BR112017023880A2 (en) | 2018-07-24 |
WO2016178748A1 (en) | 2016-11-10 |
US10005670B2 (en) | 2018-06-26 |
MX2017014243A (en) | 2018-06-28 |
US20160325997A1 (en) | 2016-11-10 |
BR112017023878B1 (en) | 2022-03-29 |
WO2016178747A1 (en) | 2016-11-10 |
MX2017014242A (en) | 2018-06-28 |
BR112017023878A2 (en) | 2018-07-24 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP1743530B1 (en) | Iron fortified food product and additive | |
US10005670B2 (en) | Calcium polyphosphate salt particles and method of making | |
KR100381632B1 (en) | Calcium fortified beverages and preparation methods thereof | |
US20200339922A1 (en) | Preparation of a powdered vinegar | |
US20090238947A1 (en) | Calcium Fortified Food Product and Additive | |
CN102228249A (en) | Method for manufacturing wheat germ oil microcapsule | |
US8501255B2 (en) | Particulate composition comprising calcium lactate and calcium citrate microparticles | |
JP4700497B2 (en) | Method for preventing or fading green color of chlorophyll-containing food by mineral-containing lactic acid bacteria and restoring green color of bleached chlorophyll-containing food | |
CN102892308A (en) | Encapsulated salts and use in high acid beverages | |
DE60002678T2 (en) | SYSTEM FOR ENRICHING WITH IRON | |
WO2007107501A1 (en) | Double-fortified salt and preparation process therefor | |
EP2988614B1 (en) | Lutein composition suitable for infant food formulations | |
CN108013319A (en) | Antioxidation activity lotion and preparation method thereof | |
JP4042977B2 (en) | Method for producing food additive composition | |
US3600197A (en) | Flavor enhancing compositions for foods and beverages | |
KR100974852B1 (en) | Inorganicparticlecontaining additive composition, process for producing the same, and food composition containing the additive composition | |
KR100839211B1 (en) | Composite of iron content and their manufacturing method | |
KR20070019132A (en) | Calcium slurry composition for food additives and preparation method thereof | |
JPH11132A (en) | Chlorophyll preparation and its production | |
US20040259937A1 (en) | Hydroxycitric acid complex metal salts, composition, and methods | |
EP0838161A2 (en) | Flavor-stabilized beet colorant composition | |
EP1792543A1 (en) | Magnesium fortified food product and additive | |
JP2001186863A (en) | Food additive slurry composition, powder composition and food composition containing these compositions | |
JPH0380054A (en) | Calcium enriching agent | |
WO2022048873A1 (en) | Iron-fortified food concentrate |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: SUNNY DELIGHT BEVERAGES CO., OHIO Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:SARAMA, ROBERT;ARCUINO, GREGORY;REEL/FRAME:041486/0280 Effective date: 20150826 |
|
AS | Assignment |
Owner name: TCW ASSET MANAGEMENT COMPANY LLC, AS COLLATERAL AG Free format text: ASSIGNMENT FOR SECURITY -- PATENTS;ASSIGNORS:SUNNY DELIGHT BEVERAGES CO.;SD IP HOLDINGS COMPANY;REEL/FRAME:042384/0430 Effective date: 20170501 |
|
STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |
|
AS | Assignment |
Owner name: SUNNY DELIGHT BEVERAGES CO., OHIO Free format text: RELEASE OF SECURITY INTEREST UNDER REEL/FRAME NO. 42384/430;ASSIGNOR:TCW ASSET MANAGEMENT COMPANY LLC;REEL/FRAME:053663/0844 Effective date: 20200828 Owner name: SD IP HOLDINGS COMPANY, OHIO Free format text: RELEASE OF SECURITY INTEREST UNDER REEL/FRAME NO. 42384/430;ASSIGNOR:TCW ASSET MANAGEMENT COMPANY LLC;REEL/FRAME:053663/0844 Effective date: 20200828 |