WO2005066075A1 - Process for production of glycine enriched sodium chloride crystals with improved flow - Google Patents
Process for production of glycine enriched sodium chloride crystals with improved flow Download PDFInfo
- Publication number
- WO2005066075A1 WO2005066075A1 PCT/IB2003/006237 IB0306237W WO2005066075A1 WO 2005066075 A1 WO2005066075 A1 WO 2005066075A1 IB 0306237 W IB0306237 W IB 0306237W WO 2005066075 A1 WO2005066075 A1 WO 2005066075A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- glycine
- brine
- salt
- crystals
- saturated brine
- Prior art date
Links
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 title claims abstract description 237
- 239000004471 Glycine Substances 0.000 title claims abstract description 119
- 239000013078 crystal Substances 0.000 title claims abstract description 72
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 title claims abstract description 62
- 238000000034 method Methods 0.000 title claims abstract description 49
- 239000011780 sodium chloride Substances 0.000 title claims abstract description 44
- 230000008569 process Effects 0.000 title claims abstract description 43
- 238000004519 manufacturing process Methods 0.000 title description 15
- 235000002639 sodium chloride Nutrition 0.000 claims abstract description 121
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims abstract description 98
- 239000012267 brine Substances 0.000 claims abstract description 57
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 claims abstract description 28
- 238000001704 evaporation Methods 0.000 claims abstract description 28
- 238000005406 washing Methods 0.000 claims abstract description 28
- 230000008020 evaporation Effects 0.000 claims abstract description 23
- 239000012452 mother liquor Substances 0.000 claims abstract description 16
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 7
- 150000003839 salts Chemical class 0.000 claims description 75
- 239000000796 flavoring agent Substances 0.000 claims description 6
- 235000019634 flavors Nutrition 0.000 claims description 6
- 239000011785 micronutrient Substances 0.000 claims description 6
- 235000013369 micronutrients Nutrition 0.000 claims description 6
- 239000002689 soil Substances 0.000 claims description 6
- 230000002335 preservative effect Effects 0.000 claims description 5
- 239000003755 preservative agent Substances 0.000 claims description 4
- 239000004033 plastic Substances 0.000 claims description 3
- 230000002939 deleterious effect Effects 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000002425 crystallisation Methods 0.000 description 12
- 239000003607 modifier Substances 0.000 description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- 230000008025 crystallization Effects 0.000 description 9
- 239000000654 additive Substances 0.000 description 7
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 235000011121 sodium hydroxide Nutrition 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 235000005911 diet Nutrition 0.000 description 3
- 230000000378 dietary effect Effects 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 235000012041 food component Nutrition 0.000 description 3
- 230000000717 retained effect Effects 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- UCMIRNVEIXFBKS-UHFFFAOYSA-N beta-alanine Chemical compound NCCC(O)=O UCMIRNVEIXFBKS-UHFFFAOYSA-N 0.000 description 2
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 2
- 125000003630 glycyl group Chemical group [H]N([H])C([H])([H])C(*)=O 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000000051 modifying effect Effects 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 231100000683 possible toxicity Toxicity 0.000 description 2
- 239000000276 potassium ferrocyanide Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- XOGGUFAVLNCTRS-UHFFFAOYSA-N tetrapotassium;iron(2+);hexacyanide Chemical compound [K+].[K+].[K+].[K+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] XOGGUFAVLNCTRS-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000238557 Decapoda Species 0.000 description 1
- 206010013911 Dysgeusia Diseases 0.000 description 1
- 241000237536 Mytilus edulis Species 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- WTNGOZWAAYJNNH-UHFFFAOYSA-N azane;n,n-diacetylacetamide Chemical compound N.CC(=O)N(C(C)=O)C(C)=O WTNGOZWAAYJNNH-UHFFFAOYSA-N 0.000 description 1
- 229940000635 beta-alanine Drugs 0.000 description 1
- 229960003237 betaine Drugs 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 235000013365 dairy product Nutrition 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 235000003599 food sweetener Nutrition 0.000 description 1
- 230000036449 good health Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 235000010746 mayonnaise Nutrition 0.000 description 1
- 239000008268 mayonnaise Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 235000020638 mussel Nutrition 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011236 particulate material Substances 0.000 description 1
- 235000021110 pickles Nutrition 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 description 1
- 229940081974 saccharin Drugs 0.000 description 1
- 235000019204 saccharin Nutrition 0.000 description 1
- 239000000901 saccharin and its Na,K and Ca salt Substances 0.000 description 1
- 235000014214 soft drink Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 235000019614 sour taste Nutrition 0.000 description 1
- 239000003765 sweetening agent Substances 0.000 description 1
- 235000019640 taste Nutrition 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D3/00—Halides of sodium, potassium or alkali metals in general
- C01D3/04—Chlorides
- C01D3/06—Preparation by working up brines; seawater or spent lyes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D3/00—Halides of sodium, potassium or alkali metals in general
- C01D3/26—Preventing the absorption of moisture or caking of the crystals
Definitions
- the present invention relates to a simple, economical, and efficient cyclic process for producing rhombic dodecahedron shaped glycine enriched, free flowing common salt from brine.
- Common salt apart from being an essential dietary component, is a basic raw material for the manufacture of a wide variety of industrial chemicals viz. sodium carbonate (soda ash), sodium hydroxide (caustic soda), and chlorine.
- salt is used in textile, dairy, dyeing, food, fertilizer, paper and pharmaceutical industries.
- Caking of water-soluble inorganic salt such as common salt is a common storage problem. Caldng is believed to occur in such salt because of the formation of solid inter-crystalline bridges that cement crystals together. Evaporation of minute amount of water on the surface of the .crystals causes the formation of inter-crystalline bridges and consequently caldng over the period of storage time.
- caking reduces free-flow properties of common salt that has got direct negative influence in its use as dietary component and increases storage problem.
- shape of the crystalline particles has got direct influence on the free-flow property of the substance.
- Larger inter-crystalline surface area contacts, as it is in cubic form, has negative influence on the free-flow properties.
- the inter-crystalline surface contact area is greatly reduced in case of spherical or near spherical crystallites and thereby increasing its free-flow property.
- R. Kern, 1953, Compt. Rend., 23b, 830 it is shown that supersaturation has definite effect on the modification of crystal habit of common salt.
- citric acid has good health care property
- the disadvantage of this method is the requirement of pH adjustment and the fact that only octahedral crystals — which are less spherical in nature compared to dodecahedral crystals of the present invention — are obtained.
- Glycine, pyridine, betaine, and ⁇ -alanine in aq. NaCl solutions modify the crystal habit of growing NaCl; the first causes the formation of rhombic dodecahedra, the others give octahedra.
- the main drawback of the prior art is that, even though rhombic dodecahedra are obtained with Glycine, the initial concentration of Glycine required is as high as 10% in saturated brine. Moreover, in the course of the crystallization process, the Glycine concentration continues to increase and a sizable amount of Glycine can co-precipitate along with salt after the saturation limit of Glycine is attained. This would make the process uneconomical and render the salt unacceptable. The prior art neither points out this weakness nor states any solution. Theoretical considerations (A. Julg and B. Deprick, J. Cryst. Growth., 1993, 62, 587; B. Deprick-Cote, J. Langlet, J. Caillet, J. Berges, E.
- Glycine According to Ullmann's Encyclopedia (2002), Glycine is reported to have a refreshing, sweetish flavor, and occurs abundantly in mussels and prawns. It is considered to be an important flavor component of these products. When used as an additive for vinegar, pickles, and mayonnaise, it attenuates the sour taste and lends a note of sweetness to their aroma. In other prior art [Pillsbury Comp., US 3510310, 1970 and C. Colburn, Am. Soft Drink J. 126 (1971)] Glycine is reported to be used to mask the aftertaste of the sweetener saccharin. Glycine is also reported to exhibits a special preservative effect [A. G. Castellani, Appl. Microbiol. 1 (1953) 195.
- the main object of the present invention is to develop a simple, economical, and efficient cyclic process for producing rhombic dodecahedron shaped glycine enriched, free flowing common salt from brine.
- Yet another object of the present invention is to develop process wherein the brine can be taken from all possible sources.
- Glycine can be largely removed from the salt by washing with saturated brine.
- Still another object of the present invention is to overcome the difficulty in the use of
- Glycine as crystal habit modifier of salt as revealed in the prior art and to provide a practical process to generate near spherical (rhombic dodecahedron) crystallites of NaCl using Glycine as habit modifier.
- Another objective is to show that Glycine can be dissolved up to the required quantity in both artificial and natural brines to effect the desired habit modification during solar salt production.
- Another objective is to show that the crystal habit modification is best effected when the temperature of brine during evaporation is less than 40 °C maldng it ideally suited for solar salt production.
- Yet another objective is to devise a simple means of removing excess quantities of Glycine that simultaneously crystallize with salt during the evaporation process. Another objective is to show that the habit modification property of Glycine is retained in real brine systems that contain other dissolved salts.
- Another objective is to use saturated brine for washing the habit modified salt crystals in order to dissolve the Glycine in the saturated brine without loss of salt.
- Another objective is to adjust the quantity of saturated brine taken for washing of the habit modified salt as described in 5 above in a manner so as to obtain saturated brine with required concentration of Glycine for direct re-use.
- Another objective is to show that during washing of habit-modified salt with saturated brine as described in 5 above there is no alteration in the crystal morphology of the salt. Another objective is to show that the salt obtained has superior flow characteristics when compared with the salt produced under similar conditions without the use of Glycine. Yet another objective is to provide between 0.5-1.0% Glycine in the habit modified salt for memeposes where Glycine is reported to have a beneficial effect as micronutrient, flavorant or preservative. Another objective is to produce habit modified salt from the the Glycine-containing saturated brine obtained after washing of the habit modified salt.
- the present invention relates to a simple, economical, and efficient cyclic process for producing rhombic dodecahedron shaped glycine enriched, free flowing common salt from brine, said process comprising steps of adding glycine of concentration ranging between 10 to 25% to the saturated brine, evaporating the saturated brine containing glycine to obtain crystals having high content of glycine, with mother liquor, washing the crystals with saturated brine to obtain rhombic dodecahedron shaped glycine enriched common salt having glycine content ranging between 0.5 to 1.0% and a washed brine, combining the mother liquor and the washed brine to obtain resulting brine, subjecting the resultant brine to solar evaporation, and repeating the steps of (iii) to (v) to obtain rhombic dodecahedron
- the present invention relates to a simple, economical, and efficient cyclic process for producing rhombic dodecahedron shaped glycine enriched, free flowing common salt from brine, said process comprising steps of adding glycine of concentration ranging between 10 to 25% to the saturated brine, evaporating the saturated brine containing glycine to obtain crystals having high content of glycine, with mother liquor, washing the crystals with saturated brine to obtain rhombic dodecahedron shaped glycine enriched common salt having glycine content ranging between 0.5 to 1.0% and a washed brine, combining the mother liquor and the washed brine to obtain resulting brine, subjecting the resultant brine to solar evaporation, and repeating the steps of (iii) to (v) to obtain rhombic dodecahedron shaped glycine enriched common salt from brine with glycine concentration ranging between 0.5 to 1.0%.
- a simple, economical, and efficient cyclic process for producing rhombic dodecahedron shaped glycine enriched, free flowing common salt from brine comprising steps of: • adding glycine of concentration ranging between 10 to 25% to the saturated brine, • evaporating the saturated brine containing glycine to obtain crystals having high content of glycine, with mother liquor, • washing the crystals with saturated brine to obtain rhombic dodecahedron shaped glycine enriched common salt having glycine content ranging between 0.5 to 1.0% and a washed brine, • combining the mother liquor and the washed brine to obtain resulting brine, • subjecting the resultant brine to solar evaporation, and • repeating the steps of (iii) to (v) to obtain rhombic dodecahedron shaped glycine enriched common salt from brine with glycine concentration ranging between 0.5 to 1.0%.
- the brine is selected from a group comprising synthetic brines, natural brines including sea-, sub-soil and lake brines.
- evaporation is conducted in the temperature range of 20-40 °C and more preferably solar evaporation under ambient condition.
- Glycine in saturated brine is maintained in the range 22-25 % (w/v).
- co-crystallised Glycine can be largely removed from the salt by washing with saturated brine.
- the volume of saturated brine taken for washing is such that the Glycine content of the brine becomes 22-25% after washing.
- the washings can be directly subjected to solar evaporation to once again produce habit modified salt or combined with the mother liquor remaining after salt preparation and then subjected to solar evaporation.
- washing of the salt with saturated brine has no deleterious effect on the morphology of the habit modified salt.
- the habit-modified salt has improved flow characteristics because of its near spherical shape.
- the habit modified salt has lesser tendency to stick to the surface of plastic.
- the glycine utilization efficacy is ranging between 95 to 100%.
- the glycine in the salt can serve as flavorant, preservative and micronutrient as reported in the prior art on the properties of Glycine.
- a method for producing Glycine-fortified common salt wherein the Glycine serves the additional function of being a habit modifier to produce near spherical crystals with improved flow characteristics is reported.
- the Glycine is recycled in the method of the invention for practicality.
- the invention is applicable to salt production from both synthetic and natural brines and especially suitable for solar salt production.
- the present invention relates to a method for recycling Glycine in the process for generating near spherical crystals of NaCl enriched with Glycine micronutrient.
- the present process deals with the recrystallization of commercially available common salt crystals under ambient conditions in presence of Glycine (crystal habit modifier) to produce rhombic dodecahedron crystals with superior free-flow property instead of the normal cubic form.
- Glycine crystal habit modifier
- the Glycine habit modifier is continuously recycled while retaining 0.5-1.0 % (w/w) of Glycine in the salt to serve as micronutrient.
- the process can be applied to pure brine solutions or is even amenable to natural brine systems such as sea brine and sub-soil brine.
- the present invention seeks to obviate the apparent difficulties in utilising the crystal habit modifying characteristics of glycine, namely, the requirement for high concentrations of glycine for effective habit modification and the problem of high amounts of Glycine in the crystallized salt which was not reported in the prior art but became evident in the course of the present invention.
- the process as reported in the prior art is practically unviable both in terms of high usage level of Glycine and also in terms of too high a level of Glycine in habit modified salt which can affect the taste and suitability of the salt.
- the main inventive steps of the present invention are: the realisation that substantial quantities of Glycine are lost in the salt during the evaporation process, (ii) the realisation that Glycine can be washed off from crystal habit modified salt using saturated brine without any loss of salt and retaining the desired morphology of the salt crystal, (iii) the further realisation that the brine obtained after washing the salt contains Glycine in the desired amount and can therefore be solar evaporated to directly obtain habit modified salt without the need for any additional Glycine.
- a further inventive step is the generation of twin benefits from the use of Glycine as additive in brine, namely the crystal habit modifying property that imparts free flow characteristics due to the near-spherical shape of the salt and its potential use as a flavorant, preservative and micronutrient in the salt.
- the brine used for production of habit modified salt can either be synthetic brine obtained by dissolving salt or brine of natural origin such as sea-, sub-soil and lake brines.
- Glycine is added into saturated brine to a concentration of 22-25 % (w/v) to ensure dodecahedron form of salt crystals from inception of crystallisation.
- the temperature of brine is maintained at less than 4O°C and evaporation was conducted under ambient conditions.
- the volume of saturated brine taken was in the range of 100-500 ml and the brine was evaporated to 10-20% of the original volume.
- the mother liquor is decanted and the crystallised salt is washed with fresh saturated brine not containing Glycine.
- the volume of saturated brine taken for washing is such that the Glycine content in the washing is restored to the original 22-25% (w/v) after addition of the mother liquor from salt crystallisation into the washing.
- the salt retains its habit modified form after washing with fresh saturated brine.
- the habit modified salt is distinctly more free flowing in nature than salt produced without Glycine during the crystallisation process under otherwise identical conditions.
- the Glycine residue in salt is in the range of 0.5-1.0 % w/w.
- the Glycine utilisation efficiency is between 95-100 %.
- Saturated brine was prepared as in 1 above. 10 g of commercially available Glycine was added into 100 ml of brine and stirred at room temperature. The resulting solution containing 10 % (w/v) Glycine in saturated brine was evaporated under otherwise identical condition as in 1 above and the crystals were isolated by filtration and dried in a fluidized bed type of drier. The crystals obtained were largely of cubic and octadecahedron forms.
- Example 3 The experiment of Example 2 was repeated with 15% initial Glycine concentration instead of 10%.
- the crystals of NaCl were mainly of octadecahedron shape. Some Glycine crystals were also observed.
- Example 2 The experiment of Example 2 was repeated with 25% initial Glycine concentration instead of 10%.
- the crystals of NaCl were mainly of rhombic dodecahedron shape. Significant amount of Glycine crystals were also found to be co-crystallized with NaCl.
- the flow properties of the salt crystals were compared qualitatively with that of the salt of Example
- Example 6 The experiment of Example 4 was repeated except that evaporation was carried out at 50 0C instead of under ambient condition.
- the resulting salt crystals were found to be of cubic form and of similar shape as that described in Example 1. Glycine crystals were also present in the salt.
- Example 6
- Example 4 The crystals obtained in Example 4 were washed with 90 ml of saturated brine prepared as in Example 1 above. After washing, the resulting crystals were isolated and dried as described in Example 1. Observation of such crystals revealed that the crystals of salt retained the rhombic dodecahedron morphology but most of the Glycine crystals had disappeared. IR analysis of the salt using a quantitative calibration technique indicated that its Glycine content to be 0.83 % (w/w).
- Example 7 The mother liquor obtained in Example 4 was combined with the washings of Example 6 and left for evaporation under ambient condition. Crystals were then harvested and dried. The salt crystals were found to be rhombic dodecahedron in shape and contained significant quantities of Glycine crystals in a manner identical to the salt described in Example 4. This process of recycling the mother liquor and washings was repeated seven times and each time the salt crystals were found to be rhombic dodecahedron in shape, with 0.5-1.0 Glycine content.
- Example 8
- Example 4 The experiment of Example 4 was repeated with 500 mL of sub-soil brine instead of pure brine.
- the specific gravity of the brine was 1.208 kg/L.
- the brine was evaporated up to a specific gravity of 1.239 kg/L.
- the resulting crystals of salt were of rhombic dodecahedron shape with significant quantities of co-crystallised Glycine crystals.
- the salt was washed with fresh 1.208 kg/L sub-soil brine and the crystal morphology was found to be retained while the Glycine crystals were found to have largely disappeared.
- the main advantages of the present invention are: A process for generating Glycine-enriched salt with improved flow characteristics " due to the near spherical nature of the crystals. 2. Use of permissible additive as crystal habit modifier 3. Versatility of the process in as much as impurities in natural brine have no adverse effect on the crystal habit modification that leads to improved flow characteristics.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Seasonings (AREA)
- Coloring Foods And Improving Nutritive Qualities (AREA)
- Food Preservation Except Freezing, Refrigeration, And Drying (AREA)
Abstract
Description
Claims
Priority Applications (10)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/IB2003/006237 WO2005066075A1 (en) | 2003-12-24 | 2003-12-24 | Process for production of glycine enriched sodium chloride crystals with improved flow |
JP2005513078A JP4805677B2 (en) | 2003-12-24 | 2003-12-24 | Process for the production of glycine-concentrated sodium chloride crystals with improved flowability |
GB0612958A GB2440138B (en) | 2003-12-24 | 2003-12-24 | Process for production of glycine enriched NaCl crystals with improved flow |
DE10394353.6T DE10394353B4 (en) | 2003-12-24 | 2003-12-24 | Process for the preparation of glycine-enriched sodium chloride crystals with improved flow |
CN2003801109228A CN1972869B (en) | 2003-12-24 | 2003-12-24 | Process for production of glycine enriched sodium chloride crystals with improved flow |
MXPA06007390A MXPA06007390A (en) | 2003-12-24 | 2003-12-24 | Process for production of glycine enriched sodium chloride crystals with improved flow. |
AU2003288642A AU2003288642B2 (en) | 2003-12-24 | Process for the production of glycine enriched sodium chloride crystals with improved flow | |
CA2551051A CA2551051C (en) | 2003-12-24 | 2003-12-24 | Process for production of glycine enriched nacl crystals with improved flow |
BRPI0318682-2B1A BR0318682B1 (en) | 2003-12-24 | 2003-12-24 | process for producing improved flow glycine enriched naci crystals. |
IL176542A IL176542A (en) | 2003-12-24 | 2006-06-25 | Process for production of glycine enriched sodium chloride crystals with improved flow |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/IB2003/006237 WO2005066075A1 (en) | 2003-12-24 | 2003-12-24 | Process for production of glycine enriched sodium chloride crystals with improved flow |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2005066075A1 true WO2005066075A1 (en) | 2005-07-21 |
Family
ID=34746632
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/IB2003/006237 WO2005066075A1 (en) | 2003-12-24 | 2003-12-24 | Process for production of glycine enriched sodium chloride crystals with improved flow |
Country Status (9)
Country | Link |
---|---|
JP (1) | JP4805677B2 (en) |
CN (1) | CN1972869B (en) |
BR (1) | BR0318682B1 (en) |
CA (1) | CA2551051C (en) |
DE (1) | DE10394353B4 (en) |
GB (1) | GB2440138B (en) |
IL (1) | IL176542A (en) |
MX (1) | MXPA06007390A (en) |
WO (1) | WO2005066075A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2009087645A1 (en) * | 2008-01-07 | 2009-07-16 | Council Of Scientific & Industrial Research | Free flowing 100 - 500 mm size spherical crystals of common salt and process for preparation thereof |
US8323360B2 (en) | 2008-06-30 | 2012-12-04 | 3M Innovative Properties Company | Method of crystallization |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB0807919D0 (en) | 2008-05-01 | 2008-06-04 | Moorlodge Biotech Ventures Ltd | |
US9808030B2 (en) | 2011-02-11 | 2017-11-07 | Grain Processing Corporation | Salt composition |
CN103373735A (en) * | 2012-04-27 | 2013-10-30 | 北京美华盛工程技术有限公司 | Method for producing food-grade sodium chloride and potassium chloride salt with anti-blocking property |
BR112015025834B1 (en) * | 2013-04-10 | 2021-12-21 | Smart Salt Inc | HOMOGENEOUS CO-CRYSTALLIZED SALT PRODUCT, ITS USES AND ITS PREPARATION METHOD |
US10881123B2 (en) * | 2017-10-27 | 2021-01-05 | Frito-Lay North America, Inc. | Crystal morphology for sodium reduction |
CN111302362B (en) * | 2020-04-03 | 2021-05-07 | 天津科技大学 | Large-particle spherical salt and preparation method thereof |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3856922A (en) * | 1973-11-06 | 1974-12-24 | R Bragdon | Process for preparing substantially non-caking sodium chloride |
JP2001061417A (en) * | 1999-08-25 | 2001-03-13 | Sanei Gen Ffi Inc | Powdery substance-containing composition |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH1142064A (en) * | 1997-07-28 | 1999-02-16 | Akou Kasei Kk | Common salt composition having high mineral content |
FI110474B (en) * | 1999-01-27 | 2003-02-14 | Modulpo Salts Oy | Nutritional physiological salt product, its use and process for its preparation |
KR100427012B1 (en) * | 2000-01-12 | 2004-04-30 | 오성은 | a manufacturing process of a pure salt |
AU2001269122B2 (en) * | 2000-08-14 | 2004-06-10 | Unilever Plc | Granulation process |
JP4246407B2 (en) * | 2001-04-27 | 2009-04-02 | キッセイ薬品工業株式会社 | Liquid seasoning |
-
2003
- 2003-12-24 WO PCT/IB2003/006237 patent/WO2005066075A1/en active Application Filing
- 2003-12-24 CA CA2551051A patent/CA2551051C/en not_active Expired - Fee Related
- 2003-12-24 GB GB0612958A patent/GB2440138B/en not_active Expired - Fee Related
- 2003-12-24 JP JP2005513078A patent/JP4805677B2/en not_active Expired - Fee Related
- 2003-12-24 MX MXPA06007390A patent/MXPA06007390A/en active IP Right Grant
- 2003-12-24 BR BRPI0318682-2B1A patent/BR0318682B1/en active IP Right Grant
- 2003-12-24 DE DE10394353.6T patent/DE10394353B4/en not_active Expired - Fee Related
- 2003-12-24 CN CN2003801109228A patent/CN1972869B/en not_active Expired - Fee Related
-
2006
- 2006-06-25 IL IL176542A patent/IL176542A/en not_active IP Right Cessation
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3856922A (en) * | 1973-11-06 | 1974-12-24 | R Bragdon | Process for preparing substantially non-caking sodium chloride |
JP2001061417A (en) * | 1999-08-25 | 2001-03-13 | Sanei Gen Ffi Inc | Powdery substance-containing composition |
Non-Patent Citations (1)
Title |
---|
PATENT ABSTRACTS OF JAPAN vol. 2000, no. 20 10 July 2001 (2001-07-10) * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2009087645A1 (en) * | 2008-01-07 | 2009-07-16 | Council Of Scientific & Industrial Research | Free flowing 100 - 500 mm size spherical crystals of common salt and process for preparation thereof |
US8770500B2 (en) | 2008-01-07 | 2014-07-08 | Council Of Scientific & Industrial Research | Free flowing 100-500 micrometer size spherical crystals of common salt and process for preparation thereof |
US8323360B2 (en) | 2008-06-30 | 2012-12-04 | 3M Innovative Properties Company | Method of crystallization |
Also Published As
Publication number | Publication date |
---|---|
CA2551051C (en) | 2011-08-02 |
DE10394353B4 (en) | 2014-09-11 |
CN1972869A (en) | 2007-05-30 |
DE10394353T5 (en) | 2006-11-23 |
JP4805677B2 (en) | 2011-11-02 |
JP2007527834A (en) | 2007-10-04 |
AU2003288642A1 (en) | 2005-08-12 |
IL176542A (en) | 2010-12-30 |
CN1972869B (en) | 2011-03-30 |
IL176542A0 (en) | 2006-10-05 |
BR0318682B1 (en) | 2013-07-16 |
CA2551051A1 (en) | 2005-07-21 |
BR0318682A (en) | 2006-12-12 |
GB0612958D0 (en) | 2006-08-30 |
GB2440138A (en) | 2008-01-23 |
GB2440138B (en) | 2009-04-08 |
MXPA06007390A (en) | 2007-03-23 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CA2551051C (en) | Process for production of glycine enriched nacl crystals with improved flow | |
US7220435B2 (en) | Process for the production of glycine enriched NaCI crystals with improved flow | |
US2306646A (en) | Preparation of monosodium glutamate | |
Sarig et al. | Crystal habit modifiers: I. The relationship between the structure of the additive and the crystal lattice | |
AU2003288642B2 (en) | Process for the production of glycine enriched sodium chloride crystals with improved flow | |
WO2005062720A2 (en) | PROCESS FOR PRODUCTION OF GLYCINE ENRICHED NaCl CRYSTALS WITH IMPROVED FLOW | |
RU2235065C2 (en) | Method for producing potassium sulfate from potash and sodium sulfate | |
US6800263B1 (en) | Non-caking sodium chloride crystals, a process to make them, and their use in an electrolysis process | |
US3975499A (en) | Sodium carbonate monohydrate crystallization | |
US3772202A (en) | Moist road salt composition and process for making the same | |
Ballabh et al. | A practical approach to produce near-spherical common salt crystals with better flow characteristics | |
CN101289165B (en) | Method for preparing sodium chloride crystal without agglomeration | |
DE69216902T2 (en) | Process for the crystallization of aspartame | |
US3591391A (en) | Compound seasoning | |
MXPA04001598A (en) | Co-retarding agents for preparing purified brine. | |
Davidson et al. | Salt crystals-science behind the magic | |
HU227772B1 (en) | Process to make high-purity wet salt, wet salt so obtainable, and the use thereof in an electrolysis process | |
US1321282A (en) | George b | |
US2021093A (en) | Process for producing coarse crystalline ammonium sulphate and product thereof | |
CA2426356C (en) | Retarding agents for preparing purified brine | |
CA1064676A (en) | Process for modifying the appearance of crystalline sodium chloride | |
US3497314A (en) | Recovery of potassium from sea water | |
US1156388A (en) | Process of obtaining potassium chlorid. | |
RU2040517C1 (en) | Method for production of chlorine-free nitrogen - potassium - - magnesium fertilizer | |
SU829567A1 (en) | Method of producing potassium sulfate |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 200380110922.8 Country of ref document: CN |
|
WWE | Wipo information: entry into national phase |
Ref document number: 384/DELNP/2004 Country of ref document: IN |
|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): BW GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
DFPE | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101) | ||
WWE | Wipo information: entry into national phase |
Ref document number: 2551051 Country of ref document: CA Ref document number: 2003288642 Country of ref document: AU Ref document number: 2005513078 Country of ref document: JP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 176542 Country of ref document: IL |
|
WWE | Wipo information: entry into national phase |
Ref document number: PA/a/2006/007390 Country of ref document: MX Ref document number: 103943536 Country of ref document: DE |
|
ENP | Entry into the national phase |
Ref document number: 0612958 Country of ref document: GB Kind code of ref document: A Free format text: PCT FILING DATE = 20031224 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 0612958.9 Country of ref document: GB |
|
ENP | Entry into the national phase |
Ref document number: PI0318682 Country of ref document: BR |
|
122 | Ep: pct application non-entry in european phase |