US20080182001A1 - Sodium Diformate Production and Use - Google Patents
Sodium Diformate Production and Use Download PDFInfo
- Publication number
- US20080182001A1 US20080182001A1 US11/911,292 US91129206A US2008182001A1 US 20080182001 A1 US20080182001 A1 US 20080182001A1 US 91129206 A US91129206 A US 91129206A US 2008182001 A1 US2008182001 A1 US 2008182001A1
- Authority
- US
- United States
- Prior art keywords
- weight
- sodium diformate
- formic acid
- sodium
- drying
- 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
- MRXCOLWWZJKPPA-UHFFFAOYSA-L disodium diformate Chemical compound [Na+].[Na+].[O-]C=O.[O-]C=O MRXCOLWWZJKPPA-UHFFFAOYSA-L 0.000 title claims abstract description 90
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 21
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 167
- 235000019253 formic acid Nutrition 0.000 claims abstract description 87
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims abstract description 80
- 239000007787 solid Substances 0.000 claims abstract description 27
- 241001465754 Metazoa Species 0.000 claims abstract description 26
- 238000001035 drying Methods 0.000 claims description 51
- 238000000034 method Methods 0.000 claims description 32
- 239000000203 mixture Substances 0.000 claims description 31
- 239000004280 Sodium formate Substances 0.000 claims description 27
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims description 27
- 235000019254 sodium formate Nutrition 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 238000002425 crystallisation Methods 0.000 claims description 20
- 230000008025 crystallization Effects 0.000 claims description 20
- 239000012452 mother liquor Substances 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 15
- 239000007790 solid phase Substances 0.000 claims description 15
- 239000007789 gas Substances 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 12
- 239000011734 sodium Substances 0.000 claims description 11
- 239000008240 homogeneous mixture Substances 0.000 claims description 10
- 239000000654 additive Substances 0.000 claims description 9
- 229910001414 potassium ion Inorganic materials 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 7
- 239000012159 carrier gas Substances 0.000 claims description 6
- 230000000996 additive effect Effects 0.000 claims description 5
- 238000000113 differential scanning calorimetry Methods 0.000 claims description 3
- 239000012071 phase Substances 0.000 claims description 3
- 230000007704 transition Effects 0.000 claims description 2
- 239000003674 animal food additive Substances 0.000 abstract description 11
- 239000002535 acidifier Substances 0.000 abstract description 5
- 239000003755 preservative agent Substances 0.000 abstract description 4
- 239000003337 fertilizer Substances 0.000 abstract description 3
- 239000002269 analeptic agent Substances 0.000 abstract 1
- 239000012752 auxiliary agent Substances 0.000 abstract 1
- 235000013305 food Nutrition 0.000 abstract 1
- 239000000047 product Substances 0.000 description 38
- 239000000243 solution Substances 0.000 description 29
- 239000013078 crystal Substances 0.000 description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 238000003756 stirring Methods 0.000 description 11
- SOBHUZYZLFQYFK-UHFFFAOYSA-K trisodium;hydroxy-[[phosphonatomethyl(phosphonomethyl)amino]methyl]phosphinate Chemical compound [Na+].[Na+].[Na+].OP(O)(=O)CN(CP(O)([O-])=O)CP([O-])([O-])=O SOBHUZYZLFQYFK-UHFFFAOYSA-K 0.000 description 11
- -1 formate anions Chemical class 0.000 description 8
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- 150000001875 compounds Chemical class 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
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- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000000576 coating method Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- BCEOEOBICHVYDJ-UHFFFAOYSA-M sodium;formic acid;formate Chemical compound [Na+].OC=O.[O-]C=O BCEOEOBICHVYDJ-UHFFFAOYSA-M 0.000 description 5
- 239000011782 vitamin Substances 0.000 description 5
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- 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 description 4
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- BINNZIDCJWQYOH-UHFFFAOYSA-M potassium;formic acid;formate Chemical compound [K+].OC=O.[O-]C=O BINNZIDCJWQYOH-UHFFFAOYSA-M 0.000 description 4
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- 239000000126 substance Substances 0.000 description 3
- YDVCSVVUQFMIBY-UHFFFAOYSA-J tetrasodium tetraformate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C=O.[O-]C=O.[O-]C=O.[O-]C=O YDVCSVVUQFMIBY-UHFFFAOYSA-J 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
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- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical class [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 2
- 230000001882 diuretic effect Effects 0.000 description 2
- 238000010981 drying operation Methods 0.000 description 2
- 238000000855 fermentation Methods 0.000 description 2
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- XVVLAOSRANDVDB-UHFFFAOYSA-N formic acid Chemical class OC=O.OC=O XVVLAOSRANDVDB-UHFFFAOYSA-N 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N n-hexadecanoic acid Natural products CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 235000015097 nutrients Nutrition 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- WFIZEGIEIOHZCP-UHFFFAOYSA-M potassium formate Chemical compound [K+].[O-]C=O WFIZEGIEIOHZCP-UHFFFAOYSA-M 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
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- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 235000012424 soybean oil Nutrition 0.000 description 2
- 239000003549 soybean oil Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- 235000013619 trace mineral Nutrition 0.000 description 2
- 239000011573 trace mineral Substances 0.000 description 2
- 150000003722 vitamin derivatives Chemical class 0.000 description 2
- 230000010641 Acidifying Activity Effects 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- 240000002791 Brassica napus Species 0.000 description 1
- 235000004977 Brassica sinapistrum Nutrition 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 235000019750 Crude protein Nutrition 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- 241000287828 Gallus gallus Species 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
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- 240000005979 Hordeum vulgare Species 0.000 description 1
- 235000007340 Hordeum vulgare Nutrition 0.000 description 1
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- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 description 1
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- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 description 1
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- 108010064851 Plant Proteins Proteins 0.000 description 1
- 241000209504 Poaceae Species 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- 240000004808 Saccharomyces cerevisiae Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
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- 235000021355 Stearic acid Nutrition 0.000 description 1
- 241000271567 Struthioniformes Species 0.000 description 1
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- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
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- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical class [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 description 1
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- BSXZJWHTFAEYDT-UHFFFAOYSA-N diazanium diformate Chemical compound [NH4+].[NH4+].[O-]C=O.[O-]C=O BSXZJWHTFAEYDT-UHFFFAOYSA-N 0.000 description 1
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- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
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- 238000002156 mixing Methods 0.000 description 1
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- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
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- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
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- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 description 1
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
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- C07C53/00—Saturated compounds having only one carboxyl group bound to an acyclic carbon atom or hydrogen
- C07C53/02—Formic acid
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- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
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- A23K20/105—Aliphatic or alicyclic compounds
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- A23K20/00—Accessory food factors for animal feeding-stuffs
- A23K20/20—Inorganic substances, e.g. oligoelements
- A23K20/22—Compounds of alkali metals
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- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
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- A23K30/00—Processes specially adapted for preservation of materials in order to produce animal feeding-stuffs
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K30/00—Processes specially adapted for preservation of materials in order to produce animal feeding-stuffs
- A23K30/10—Processes specially adapted for preservation of materials in order to produce animal feeding-stuffs of green fodder
- A23K30/15—Processes specially adapted for preservation of materials in order to produce animal feeding-stuffs of green fodder using chemicals or microorganisms for ensilaging
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
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- A23K50/00—Feeding-stuffs specially adapted for particular animals
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K50/00—Feeding-stuffs specially adapted for particular animals
- A23K50/30—Feeding-stuffs specially adapted for particular animals for swines
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K50/00—Feeding-stuffs specially adapted for particular animals
- A23K50/70—Feeding-stuffs specially adapted for particular animals for birds
- A23K50/75—Feeding-stuffs specially adapted for particular animals for birds for poultry
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05F—ORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C, e.g. FERTILISERS FROM WASTE OR REFUSE
- C05F11/00—Other organic fertilisers
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/02—Preparation of carboxylic acids or their salts, halides or anhydrides from salts of carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
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- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/582—Recycling of unreacted starting or intermediate materials
Definitions
- the present invention relates to a method for producing sodium diformate in solid form having a high formic acid content, use thereof in animal feeds, as acidifier, preservative, silage aid, fertilizer and growth and performance promoter, and also to animal feed additives comprising the inventive sodium diformate.
- Formic acid formates have antimicrobial activity and are used, for example, for preserving and acidifying plant and animal materials, for instance grasses, agricultural products or meat, for treating biowastes, or as an additive for animal nutrition.
- a content of formate anions as high as possible as one of the active constituents is desirable for the use of hydrogenformates. From the economic aspect, it is advantageous in particular if this increased content of formate anions is accompanied by a formic acid fraction as high as possible, since this simultaneously offers the acidifying activity.
- the use of formic acid sodium formate is particularly expedient, since, in this case, compared with trisodium hydrogentetraformate, and also compared with formic acid potassium formate, in each case a higher theoretical content, both in formate ions and in formic acid is present. Although both values are somewhat more expedient in the case of ammonium diformate, this is, however, a very unstable compound.
- Formic acid formates in solid form and their production have long been known as such, e.g. from Gmelins Handbuch der anorganischen Chemie [Gmelin's handbook of inorganic chemistry], 8th edition, number 21, pages 816 to 819, Verlag Chemie GmbH, Berlin 1928 and also number 22, pages 919 to 921, Verlag Chemie GmbH, Berlin 1937.
- the formic acid formates potassium diformate and sodium diformate are said to be obtainable in principle by dissolving potassium formate or sodium formate in formic acid and subsequently cooling.
- the more stable crystal form trisodium hydrogenformate exits.
- reference is made to the fact that especially sodium diformate is accessible only with difficulty in crystalline dry form and, furthermore, is relatively unstable. The statements in Gmelin's handbook only permit the conclusion that the products described there were not pure sodium diformate.
- EP 0 824 511 B1 describes a method for producing products which comprise disalts of formic acid.
- certain alkali metal or ammonium formates, hydroxides, (bi)carbonates or ammonia are mixed at 40° C. to 100° C. with formic acid which has a content of at least 50%.
- the mixture is subsequently cooled and the disalts are obtained by filtration.
- formic acid potassium formate and also of mixtures of formic acid sodium formate with trisodium hydrogentetraformate are presented by way of example, the production of solid pure sodium diformate, in contrast, is not taught.
- the temperatures and concentration limits specified for the method for the (aqueous) potassium and sodium formate solutions to be used in the method only permit the production of potassium diformate, since (aqueous) solutions of sodium formate cannot be produced in the concentrations specified, owing to the lower solubility limit compared with potassium formate. Therefore, although potassium diformate is obtained, sodium diformate is present solely in a mixture with trisodium hydrogentetraformate.
- German patent DE 42 40 17 (of Jan. 14, 1926) teaches the production of formic acid sodium formates having various acid contents by introducing sodium formate into aqueous formic acid. The resultant crystals are obtained by cooling the solution to ambient temperature. Depending on the water content of the formic acid, in addition to trisodium hydrogenformate and mixtures of trisodium hydrogenformate with sodium diformate, sodium diformate is also said to be accessible. The latter is said to be obtained by the method of DE 424017 when the formic acid used has a content of more than 50%, e.g. 80%, as in example 2. The inventors' own experiments, however, found that, under the conditions specified in DE 424017, sodium diformate cannot be obtained in pure, crystalline form. Rather, in this procedure a mixture with trisodium hydrogenformate is obtained, the formic acid content of which is markedly below the expected theoretical value for pure sodium diformate of 40.36% by weight, based on the total dry weight.
- Adequate stability of formic acid sodium formate in solid form is of particular importance not only with respect to handling and storage life, but also with respect to production. In particular, release to any great extent of the formic acid present in the formic acid sodium formate is undesirable owing to its corrosive activity.
- sodium diformate offers the advantage that the trace element sodium need not be added separately in the form of NaCl, as is otherwise customary, but already represents a sodium source as such.
- the content of sodium ions is limited.
- a low or limited content of cations, e.g. including potassium ions, is desirable inasmuch as the latter, in particular in the case of monogastric animals and especially in the case of poultry can lead to an increased liquid intake (increased drinking) and thus to dilution of the excreta of the animals, that is to say can develop diuretic activity.
- the object underlying the present invention was to provide a method for producing sodium diformate in solid form and of high purity, i.e. especially having a high formic acid content.
- the inventive method should, in particular, enable the production of a sodium diformate in comparatively stable and dry form and thus open up a route to its industrial production.
- This object has surprisingly been achieved by crystallizing out the target compound from a mixture of sodium formate with a more than one and a half times molar excess of concentrated or aqueous formic acid while maintaining a molar ratio of formic acid to water of at least 1.1:1.
- the present invention therefore firstly relates to a method for producing sodium diformate in solid form having a formic acid content of at least 35% by weight, based on the total weight of sodium diformate, which comprises producing, at elevated temperature, from sodium formate and aqueous or concentrated formic acid having a formic acid content of at least 74% by weight, a homogeneous mixture which has a molar ratio of HCOOH to Na[HCOO] of greater than 1.5:1 and a molar ratio of formic acid to water of at least 1.1:1, cooling the mixture and separating off the solid phase from the mother liquor.
- the method according to the invention makes possible for the first time the production of a sodium diformate in solid dry form having a formic acid content of at least 35% by weight, frequently at least 36% by weight, in particular at least 37% by weight, especially at least 38% by weight, very especially at least 39% by weight, and still more especially at least 40% by weight, in each case based on the total weight of the sodium diformate.
- a sodium diformate of this type is therefore a further subject matter of the invention.
- a homogeneous mixture in the meaning of the present invention is taken to mean a clear aqueous solution of formic acid in which all of the sodium formate present in the solution is in dissolved form. If appropriate this inventively produced homogeneous mixture comprises sodium diformate crystals for the purpose of seeding the crystallization, as described hereinafter in detail.
- the term “homogeneous mixture” used here comprises not only the aqueous solution comprising formic acid and dissolved sodium formate, but also the sodium diformate crystals which are added if appropriate.
- the starting materials sodium formate and formic acid used in the present invention are commercially available and can be used as such without pretreatment.
- the sodium formate present as solid at room temperature can be used, e.g., as technical-grade sodium formate.
- Sodium formate occurring in the production of polyols as waste product is also suitable for use in the present invention.
- use is made of a sodium formate whose Na[HCOO] content is at least 97% by weight, based on the total weight of the sodium formate source used.
- use is made of a sodium formate which comprises less than 0.1% by weight, and in particular less than 0.05% by weight, potassium ions, in each case based on the total weight of the sodium formate source used.
- the sodium formate intended for the reaction with formic acid e.g. by reacting sodium hydroxide, carbonate or hydrogencarbonate with formic acid in concentrated aqueous solution, by reacting carbon monoxide with liquid sodium hydroxide, or by reacting methyl formate with sodium hydroxide.
- a procedure can be followed, e.g., such that solid NaOH or a concentrated aqueous solution thereof, if appropriate with cooling and/or stirring, is dissolved in concentrated formic acid.
- the ratios of the starting materials can advantageously be directly chosen such that the components formic acid, sodium formate and water in the resultant mixture are already in the abovementioned molar ratios which are required.
- an aqueous formic acid solution having a formic acid content of at least 74% by weight or a concentrated formic acid.
- the concentrated formic acid is taken to mean by those skilled in the art a formic acid solution having a formic acid content of 94% by weight or more, i.e. having a residual water content of less than 6% by weight, in each case based on the total weight of formic acid solution.
- aqueous formic acid a solution of formic acid in water having a formic acid content of less than 94% by weight, based on the total weight of the aqueous formic acid solution.
- the aqueous formic acid solution used preferably has a concentration of at least 75% by weight, preferably at least 80% by weight, and particularly preferably at least 90% by weight. Very particularly preferably, use is made of concentrated formic acid having a formic acid content of at least 94% by weight.
- the concentration of the formic acid or solution will preferably not exceed 99% by weight, and is particularly preferably in the range from 80 to 99% by weight, and especially in the range from 94 to 98% by weight.
- the molar ratio used of HCOOH:Na[HCOO] will lie in the range from 1.6:1 to 3:1, and in particular in the range from 1.8:1 to 2.5:1.
- the molar ratio of HCOOH:H 2 O in the homogeneous mixture is at least 1.5:1, and particularly preferably at least 1.8:1; very particularly preferably, it is in the range 1.5:1 to 10:1, and in particular in the range from 1.8:1 to 6.1:1.
- the sequence in which the starting materials are used is of subsidiary importance.
- the mixture proceeds in such a manner that a homogeneous liquid mixture of the starting materials is obtained in the molar ratio which is to be kept.
- the homogeneous mixture is produced at elevated temperature. This is generally taken to mean temperatures of at least 30° C., in particular at least 40° C., and especially at least 50° C.
- Said homogeneous mixture can be produced using conventional procedures known to those skilled in the art, e.g. by mixing, stirring and/or dissolving, using elevated temperature, or by a combined use of these methods.
- an aqueous or concentrated, preferably concentrated, solution of formic acid is initially charged.
- the sodium formate in solid form or in the form of an aqueous solution or suspension.
- the addition can proceed in portions, e.g. in 2, 3, 4 or more individual portions which are added to the mixture at a predetermined time interval from one another, or continuously, i.e. at constant, decreasing, or increasing, rate.
- a temperature increase occurs, so that if appropriate additional heating is not necessary.
- the temperature of the mixture is set, e.g.
- the crystallization proceeds from an aqueous solution.
- This solution as set forth below, can be admixed, or become admixed, with seed crystals as soon as before the start of crystallization.
- the solution or suspension is advantageously agitated, e.g. stirred.
- the agitation is continued until termination of the addition, at least until a homogeneous mixture is obtained, generally until the end or termination of the crystallization.
- the starting materials can be mixed in all reactors, kettles, flasks, containers and other apparatuses, in particular in stirred tanks having internal heat exchange surfaces, customarily used for producing a homogeneous liquid mixture.
- reactors kettles, flasks, containers and other apparatuses, in particular in stirred tanks having internal heat exchange surfaces, customarily used for producing a homogeneous liquid mixture.
- stirred tanks having internal heat exchange surfaces, customarily used for producing a homogeneous liquid mixture.
- the mixture preferably with continued stirring, is brought to crystallization.
- This can be achieved, e.g., by partial evaporation or cooling, preferably by cooling.
- the crystallization is caused, or initiated or accelerated by a controlled evaporation of the liquid phase, preferably under vacuum, it will generally be ensured that the molar ratios of the components in the homogeneous mixture are within the above specified ranges at the start of, and during, the crystallization. If appropriate, in this case, however, the ratio of HCOOH to H 2 O can shift toward higher molar ratios than in the starting solution in the course of crystallization.
- the crystallization is effected by cooling, this is preferably performed slowly, advantageously over a time period of one to a plurality of hours, e.g. up to 24, or up to 12 h, in particular from 1 to 15 h, especially from 2 to 10 h, more especially from 3 to 10 h and very especially from 4 to 8 h.
- the sodium diformate crystallizes out. It has proved to be advantageous if the cooling proceeds at a cooling rate in the range of about 1 to about 30 K/h, and in particular of about 2 to about 20 K/h, e.g. about 5 to 15 K/h.
- the reaction mixture within the said period to a temperature of below 30° C., e.g. about 25, 20, 15 or 10° C. or below, in particular below 20° C., e.g. about 18° C. or below, or 16° C. or below.
- the temperature will not fall below 0° C., in particular 5° C., especially 10° C., and very especially 15° C.
- crystals of sodium diformate e.g. crystals produced in advance by the inventive method
- seeding Such crystals can be added in dry or moist form, suspended in a liquid phase, e.g. aqueous or formic acid phase, or a combination of these forms.
- the addition generally proceeds above a temperature which leads to a crystal formation, but below a temperature at which a homogeneous solution is present.
- the temperature of the reaction mixture therefore generally not exceeds 65° C. during the addition of crystals, and will preferably be in the range from 25 to 50° C.
- the crystallization operation can then proceed as described above, at a cooling rate in the range from about 0.5 to about 20 K/h, e.g. about 1 to 15 K/h, in particular about 2 to 15 K/h, and especially about 5 to 10 K/h.
- the crystallization temperature is in the abovementioned ranges.
- the resultant solid product is separated off from the mother liquor.
- the solid phase can be separated off from the mother liquor by methods which are customary for this and are known to those skilled in the art, e.g. filtration or centrifugation, preferably by centrifugation, in particular by using pusher-type or peeler centrifuges.
- the mother liquor is frequently removed to the extent that the solid phase which is separated off has a water content in the range from 2 to 0.2% by weight, in particular in the range from 1.5 to 0.4% by weight, and especially in the range from 1 to 0.5% by weight, in each case based on the total weight of the solid phase which is separated off.
- the mother liquor is frequently removed to the extent that the solid phase which is separated off has a formic acid content in the range from 40.5 to 43.5% by weight, in particular in the range from 41 to 43% by weight, especially in the range from 41 to 42.5% by weight, and very especially in the range from 41 to 42.2% by weight, in each case based on the total weight of the solid phase which is separated off.
- the moist product thus obtained is subsequently dried by drying methods, e.g. under vacuum and/or moderate heating.
- Dryers and drying methods which are usable for this are known per se to those skilled in the art and are described, e.g. in K. Kröll, Trockner und Trocknungsvon [Dryers and drying methods], 2nd edition, Springer Verlag, Berlin 1978.
- K. Kröll, Trockner und Trocknungsvon Dryers and drying methods
- the relatively high volatility of the formic acid present in the product and also the limited temperature stability of the product must be taken into account. It is therefore generally necessary to control the drying conditions within relatively narrow parameter ranges, as set forth in detail hereinafter.
- the moist product or the dry material can be admixed or mixed with desiccants known to those skilled in the art.
- desiccants such as silicic acid, e.g. the Sipernat brands from Degussa, inorganic alkali metal salts and alkaline earth metal salts, e.g. Mg, Ca, Zn, Na, K sulfates, carbonates, silicates or phosphates; in addition inorganic buffers such as alkali metal hydrogenphosphates, in particular sodium and potassium hydrogenphosphates, e.g. K 2 HPO 4 , KH 2 PO 4 and Na 2 HPO 4 .
- desiccants such as silicic acid, e.g. the Sipernat brands from Degussa
- inorganic alkali metal salts and alkaline earth metal salts e.g. Mg, Ca, Zn, Na, K sulfates, carbonates, silicates or phosphates
- the product is advantageously agitated in the dryer.
- This can proceed, in particular, via mechanical elements, e.g. mixer blades, or via a gas stream, e.g. a customary fluidized bed.
- Particularly suitable drying apparatuses or dryers are, e.g., contact dryers, fluidized-bed dryers and jet dryers, if appropriate spray dryers can be used.
- Those which are especially suitable are blade dryers, and in the case of drying under reduced pressure, especially vacuum blade dryers, or convective dryers equipped with mixer blades, e.g. from Forberg.
- the solid phase which is separated off from the mother liquor will be dried at a product temperature of no more than 60° C., in particular no more than 55° C., and especially no more than 50° C.
- the solid phase which is separated off from the mother liquor will be dried at a pressure of at most 10 5 Pa.
- this is preferably at most 10 4 Pa, and particularly preferably at most 6 ⁇ 10 3 Pa, e.g. in the range from 1 ⁇ 10 3 Pa to 6 ⁇ 10 3 Pa.
- Particularly advantageous results are achieved by vacuum drying at a pressure of less than 4 ⁇ 10 3 Pa, e.g. in the range from 1 ⁇ 10 3 Pa to 3.5 ⁇ 10 3 Pa.
- drying proceeds by means of contact drying at a wall temperature of at most 100° C., particularly preferably at most 80° C., and very particularly preferably at most 65° C.
- the vapors can be removed by a stripping gas stream, e.g. air or nitrogen.
- a stripping gas stream e.g. air or nitrogen.
- the contact drying is carried out at a pressure in the range from 2 ⁇ 10 3 Pa to about atmospheric pressure, e.g. in the range from 2 ⁇ 10 3 Pa to 1 ⁇ 10 4 Pa.
- drying proceeds by means of convective drying at a carrier gas inlet temperature in the range from 20 to 120° C., more preferably in the range from 50 to 100° C., particularly preferably in the range from 60 to 90° C.
- a suitable carrier gas is, e.g. air or nitrogen.
- the carrier gas stream can be conducted in a known manner linearly or in a circle through the drying apparatus. If appropriate, the carrier gas is subjected before the drying operation to conditioning (predrying); obviously, such an operation can also be connected downstream of the drying operation, so that the gas dried in such a manner, e.g. by means of condensation or adsorption, can be reused as carrier gas for the product drying. Customarily, an amount of gas is allowed to flow through the drying apparatus per hour such that this approximately corresponds to 100 times to 10 000 times the volume of the respective drying apparatus.
- the water content remaining in the product after drying is generally no more than 0.5% by weight, and is customarily in the range from about 0.5 to 0.01% by weight, preferably at most 0.3% by weight, more preferably at most 0.2% by weight, particularly preferably at most 0.15% by weight, and very particularly preferably at most 0.1% by weight, based on the total weight, determined by oxidimetric titration according to Karl Fischer (e.g. described in Wiland, Wasserbetician Anlagen Maschinen-Fischer-Titration [Water determination by Karl-Fischer titration], Darmstadt, GIT, 1985).
- the inventive method can be carried out continuously, batchwise or semibatchwise.
- the sodium diformate is obtained in solid dry form as described, with the mother liquor completely or in part advantageously being able to be reused for producing the starting mixture, or for adjusting the molar concentration ratios in the starting material stream.
- the mother liquor after separating off the crystals, can be neutralized, e.g. using sodium hydroxide solution, essentially a sodium formate solution resulting which if appropriate can be evaporated or again brought to crystallization.
- the sodium diformate in solid dry form is obtained by the inventive method in high purity and therefore has a high formic acid content, generally at least 35% by weight, frequently at least 36% by weight, in particular at least 37% by weight, especially at least 38% by weight, very especially at least 39% by weight, and still more especially at least 40% by weight, in each case based on the total weight of the sodium diformate.
- the formic acid content in the inventive sodium diformate will be no more than 41% by weight, and in particular no more than 40.5% by weight, in each case based on the total weight.
- the content is in the range from 38 to 41% by weight, more especially in the range from 39 to 41% by weight, and very especially in the range from 39 to 40.5% by weight, or in the range from 40 to 41% by weight, in each case based on the total weight of the sodium diformate obtainable.
- total weight of sodium diformate is used synonymously with the expression total dry weight.
- the total dry weight is to be taken to mean the weight of sodium diformate which is given by drying the product below its decomposition temperature, e.g. by drying over a period of 1 h at a temperature of 35° C. and at a pressure of 50 mbar.
- the formic acid content in the dry product can be determined in a conventional manner, e.g. by titration of the formic acid with a base.
- a high content of formate anions is likewise present in the dry product.
- the inventively produced sodium diformate is typically obtained in crystalline form. It is assumed that it essentially or completely corresponds to the formula Na[HCOO].HCOOH, but which is not to be taken to mean a limit of the invention. At about 65° C., a phase transition point may be observed by means of DSC (differential scanning calorimetry).
- the inventively obtained crystalline modification of sodium diformate may be identified, for example, via x-ray wide angle scattering. Unwanted modifications, e.g. trisodium hydrogentetraformate, can likewise be detected qualitatively by the same method.
- the x-ray powder diffractogram of the inventive sodium diformate exhibits all diffraction reflections characteristic of the specific crystal structure.
- a decrease in the intensity of the diffraction reflections can occur in the x-ray powder diffractogram, which can be to such an extent that individual lesser-intensity diffraction reflections are no longer detectable in the x-ray powder diffractogram.
- Individual lesser-intensity diffraction reflections can therefore be absent or the intensity ratio can be modified in the x-ray powder diffractogram.
- inventive sodium diformate in addition to the respectively stated characteristic diffraction reflections, can have further diffraction reflections.
- mixtures of the inventive sodium diformate with other crystalline compounds generally have additional diffraction reflections.
- the sodium diformate produced according to the invention is generally obtained in a purity such that the molar ratio of the components sodium formate and formic acid is customarily in the range from 0.9:1 to 1.1:1; in particular in the range from 0.95:1 to 1.05:1, and especially corresponds to about 1:1.
- the fraction of sodium diformate in the solid product obtained is customarily at least 97% by weight, in particular at least 98% by weight, and especially at least 99% by weight, in each case based on the total weight of solid product.
- the product may comprise, owing to residual moisture or crystallized residual moisture, generally up to 1.5% by weight of formic acid, up to 1.5% by weight of sodium formate and/or up to 0.5% by weight of water, in each case based on the total weight of the product.
- the sodium diformate produced according to the invention is distinguished by a relatively low hygroscopicity, in particular compared with trisodium hydrogentetraformate. Furthermore, the sodium diformate obtained according to the invention is sufficiently stable to ensure problem-free handling and (further) processing.
- the potassium ion content of the inventive sodium diformate is generally at most 1000 ppm, and in particular at most 500 ppm, in each case based on the total weight.
- the chloride content in the inventive sodium diformate is generally less than 1500 ppm, and in particular less than 1000 ppm, in each case based on the total weight.
- the inventive method for producing solid, dry sodium diformate in crystalline, pure and stable form makes it possible for the first time to apply the production conditions to an industrial scale.
- the inventively produced sodium diformate can be further processed, in particular powders of defined particle sizes can be produced, the particles produced can be coated with coating materials and/or mixtures with other additives can be produced.
- coating materials oils such as soybean oil, fats and fatty acids such as palmitic or stearic acid or polymer coatings, e.g. of polyalkylenes and derivatives thereof may be mentioned.
- Customary additives are, in particular, anticaking aids and desiccants such as those mentioned above, e.g. silicic acid etc. Customary methods for coating and also the additives coming into consideration are thoroughly known to those skilled in the art in the respective sector, see, e.g., DE 102 31 891 A1.
- the resultant solid product can be comminuted before and/or after the drying step, e.g. by means of mortars, cutters, punch presses and roller mills, agglomerated, e.g. by means of mixers, and/or compacted, e.g. by means of presses and compacters.
- the apparatuses used for such a comminution are known to those skilled in the art.
- the inventive sodium diformate is present in solid form as crystal powder or as granules or compactate.
- the powders, granules or compactates have a mean particle size in the range from 1 ⁇ m to 10 000 ⁇ m, in particular from 10 ⁇ m to 5000 ⁇ m, and especially from 100 ⁇ m to 2500 ⁇ m.
- inventive sodium diformate in solid form and preparations comprising this are suitable for use in feeds for animals (animal feeds), in particular as additive to animal feed in the form of feed additives and especially as additive to premixes for animal feeds.
- Premixes are mixtures which generally comprise minerals, vitamins, amino acids, trace elements and also, if appropriate, enzymes.
- Animal feeds and feed additives which comprise the inventive sodium diformate are particularly suitable for monogastric animals such as hogs, especially piglets, breeding sows and fattening hogs, and also poultry, especially broilers, laying hens, turkeys, ducks, geese, quails, pheasants and ostriches.
- the content of the inventively prepared sodium diformate in the feed or feed additive can vary greatly.
- the content furthermore depends on the type of the formulation, e.g. on the addition of aids such as desiccants, on a possible coating and on the residual moisture content.
- the content of inventive sodium diformate in the feed additive is, e.g., in the range from 0.1 to 99.5% by weight, in particular from 0.5 to 75% by weight, and especially from 1 to 50% by weight, based on the total dry weight of feed additive.
- the inventive sodium diformate is also suitable for use in a premix and can in this case be used, e.g. admixed, in the customary amounts.
- inventive sodium diformate for the abovementioned purpose thus provides an acidic sodium and formate source, without the fraction of potassium ions being necessarily increased.
- a further subject of the invention is therefore a solid feed additive which comprises the inventive sodium diformate in solid form and is essentially free from potassium ions.
- essentially free from potassium ions means that the content of potassium ions is at most 1000 ppm, and in particular at most 500 ppm, in each case based on the weight of the feed additive.
- Animal feeds are composed in such a way that the corresponding nutrient requirement for each animal species is optimally covered.
- plant feed components such as corn, wheat or barley meal, whole soybean meal, soybean extraction meal, linseed extraction meal, rapeseed extraction meal, green meal or pea meal are selected as crude protein sources.
- soybean oil or other animal or vegetable fats are added. Since the plant protein sources comprise some essential amino acids only in an insufficient amount, feeds are frequently enriched with amino acids. These are primarily lysine and methionine.
- minerals and vitamins are added.
- the type and amount of added minerals and vitamins depends on the animal species and is known to those skilled in the art (see, for example, Jeroch et al.,110 land Anlagenr Nutztiere [Nutrition of agricultural farm animals], Ulmer. UTB).
- To cover the nutrient and energy requirement use can be made of complete feeds which comprise all nutrients in a ratio to one another covering requirements. It can form the sole feed of the animals.
- a supplementary feed can be added to a grain feed of cereals.
- the supplementary feed can comprise protein-, mineral- and vitamin-rich feed mixtures which supplement the feed.
- the inventive sodium diformate is particularly suitable as what is termed an acidifier.
- Acidifiers are taken to mean those substances which lower the pH.
- the expression comprises not only those substances which lower the pH in the substrate (e.g. animal feed) but also those which lower the pH in the gastrointestinal tract of the animal.
- inventive sodium diformate is suitable, in particular, as a composition having performance- and/or growth-promoting effect.
- the solid sodium diformate is used as such a performance- and/or growth-promoting composition for monogastric animals, in particular for hogs and/or poultry.
- inventive sodium diformate is suitable, in addition, as preservative, in particular as preservative for green feeds and/or animal feeds.
- inventive sodium diformate is suitable, in addition, as aid for pharmaceutical preparations, e.g. as disintegrant.
- the inventive sodium diformate can advantageously be used in the production of silage. It accelerates lactic acid fermentation or prevents secondary fermentation and inhibits the development of harmful yeasts. In this case it also acts in the manner described above for use as an acidifier, in a regulatory manner on the pH.
- the invention therefore further relates to the use of the inventive sodium diformate as silage additive (silage aid).
- the present invention further relates to the use of the inventive sodium diformate as fertilizer.
- FIG. 1 shows a light micrograph of sodium diformate crystals obtained according to the invention.
- the size ratios and also an essentially generally hexagonal base shape may easily be recognized.
- FIG. 2 shows, for comparison, a light micrograph of crystallized sodium tetraformate.
- Significant differences from the sodium diformate crystals may be seen; in particular, the sodium tetraformate is distinguished by a pronounced needle-shaped crystal growth which does not have a correspondence in sodium diformate.
- the sodium tetraformate needles only achieve in the longitudinal direction the dimensions of the sodium diformate crystals of a few hundred up to over 2000 ⁇ m, whereas the needles having a diameter of significantly less than 50 ⁇ m do not approximately reach the dimensions of the sodium diformate crystals.
- Examples 1 and 2 were carried out in a 1 l stirred vessel which was equipped with heating and cooling apparatus and also an outlet.
- aqueous formic acid solution 650 g were initially charged and heated to 55° C. with stirring. The stirring was continued for the entire experimental period. 350 g of solid sodium formate (purity >97%) were dissolved in the formic acid solution, a clear solution being obtained. Subsequently, the solution was slowly cooled. After about 4 hours, a temperature of about 12° C. was reached, at which a sudden precipitation was observed. The suspension was heated to about 35° C. until only slight turbidity was still observed. The suspension was then cooled to 20° C. over a period of about 6 h and drained from the stirred vessel. The mother liquor was separated off from the crystals by means of a vacuum filter.
- the yield of moist sodium diformate was about 125 g. After drying in the vacuum drying cabinet at a temperature of 35° C., the remaining water content in the product was determined at approximately 0.1% by weight, based on the total dry weight of about 122 g. The formic acid content in the dry product was 40.3% by weight, based on the total dry weight.
- aqueous formic acid solution 650 g of an 80% strength by weight aqueous formic acid solution were initially charged and heated to 55° C. with stirring. Under continued stirring, 430 g of solid sodium formate (purity >97%) were dissolved in the formic acid solution, a clear solution being obtained. Subsequently, the solution was slowly cooled. After about 5 hours, a temperature of about 24° C. was reached, at which a sudden precipitation was observed. The suspension was heated to about 35° C. with stirring, until only a slight turbidity was still observed. The suspension was then cooled to 15° C. over a period of about 6 h with stirring, and drained from the stirred vessel. The mother liquor was separated off from the crystals by means of a vacuum filter.
- the yield of moist sodium diformate was about 280 g. After drying in the vacuum drying cabinet at a temperature of 35° C., the remaining water content in the product was determined as approximately 0.15% by weight, based on the total dry weight of 270 g. The formic acid content in the dry product was 40.1% by weight, based on the total dry weight.
- Examples 4 to 16 were carried out in a similar manner to example 3. In each case a speed of rotation of 10 rpm was employed, in examples 14 and 16 a speed of rotation of 20 rpm. The amount of nitrogen stripping gas stream was in each case 5 l/h, except in example 15, 10 l/h. Further parameter values set as exceptions are indicated in each case in table 2 below. Table 2 also summarizes the results achieved in drying.
- Examples 18 to 21 were carried out in a similar manner to example 17. In each case a speed of rotation of 80 rpm was employed. The gas stream rate of nitrogen (example 18) or air (examples 19 to 21) was in each case 5 m 3 (S.T.P.)/h, and drying was carried out in each case at atmospheric pressure. Further parameter values set as exceptions are indicated in each case in table 3 below. Table 3 also summarizes the results achieved in drying.
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DE102005017089.7 | 2005-04-13 | ||
DE102005017089A DE102005017089A1 (de) | 2005-04-13 | 2005-04-13 | Herstellung und Verwendung von Natriumdiformiat |
EP06003445 | 2006-02-20 | ||
EP06003445.1 | 2006-02-20 | ||
PCT/EP2006/003398 WO2006108652A1 (de) | 2005-04-13 | 2006-04-12 | Herstellung und verwendung von natriumdiformiat |
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US13/566,376 Continuation US8497394B2 (en) | 2005-04-13 | 2012-08-03 | Sodium diformate production and use |
US13/566,376 Division US8497394B2 (en) | 2005-04-13 | 2012-08-03 | Sodium diformate production and use |
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US11/911,292 Abandoned US20080182001A1 (en) | 2005-04-13 | 2006-04-12 | Sodium Diformate Production and Use |
US13/566,376 Expired - Fee Related US8497394B2 (en) | 2005-04-13 | 2012-08-03 | Sodium diformate production and use |
US13/922,418 Expired - Fee Related US8993802B2 (en) | 2005-04-13 | 2013-06-20 | Sodium diformate production and use |
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US13/922,418 Expired - Fee Related US8993802B2 (en) | 2005-04-13 | 2013-06-20 | Sodium diformate production and use |
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DE102005020890A1 (de) * | 2005-05-04 | 2006-11-09 | Basf Ag | Herstellung von Natriumformiat |
DE102005062931A1 (de) * | 2005-12-29 | 2007-07-05 | Basf Ag | Herstellung von Natriumdiformiat |
FI121541B (fi) | 2008-04-21 | 2010-12-31 | Kemira Oyj | Menetelmä muurahaishapon talteenottamiseksi |
CN104876815B (zh) * | 2014-02-28 | 2017-04-05 | 中国科学院过程工程研究所 | 一种二甲酸钠的制备方法 |
DE102016203477A1 (de) | 2016-03-03 | 2017-09-07 | Addcon Europe Gmbh | Herstellung und Verwendung von Alkalimetalldiformiaten mit mittelkettigen Fettsäurederivaten |
CN113754529B (zh) * | 2021-08-31 | 2024-05-10 | 潍坊加易加生物科技有限公司 | 一种利用有机羧酸钾制备二甲酸钾、二甲酸钠的方法 |
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US5935625A (en) * | 1995-05-12 | 1999-08-10 | Norsk Hydro Asa | Animal feed additives and feedstuff containing said additives |
US6906222B2 (en) * | 2001-11-09 | 2005-06-14 | Basf Aktiengesellschaft | Preparation for production of formic acid formates |
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DE424017C (de) * | 1922-09-05 | 1926-01-14 | Egon Eloed Dr | Verfahren zur Herstellung saurer Natriumformiate |
NO300038B1 (no) | 1995-05-12 | 1997-03-24 | Norsk Hydro As | Fremgangsmåte for fremstilling av produkter inneholdende dobbelsalter av maursyre |
DE19609636C1 (de) * | 1996-03-12 | 1997-08-14 | Siemens Ag | Chipkarte und Verfahren zur Herstellung einer Chipkarte |
NO304093B1 (no) * | 1996-11-01 | 1998-10-26 | Norsk Hydro As | FremgangsmÕte for fremstilling av fiskef¶r samt fiskef¶r |
DE10231891A1 (de) | 2002-07-12 | 2004-01-22 | Basf Ag | Zubereitungen, enthaltend Diformiate |
DE10237379A1 (de) * | 2002-08-12 | 2004-02-19 | Basf Ag | Verfahren und Vorrichtung zur Herstellung von ameisensauren Formiaten und deren Verwendung |
DE10237380A1 (de) * | 2002-08-12 | 2004-02-19 | Basf Ag | Verfahren und Vorrichtung zur Herstellung von ameisensauren Formlaten und deren Verwendung |
DE10261577A1 (de) | 2002-12-23 | 2004-07-01 | Basf Ag | Verwendung von Hydroformiat(en) |
TW200523246A (en) * | 2003-11-06 | 2005-07-16 | Basf Ag | Preparation of acid formates |
DE102005020890A1 (de) * | 2005-05-04 | 2006-11-09 | Basf Ag | Herstellung von Natriumformiat |
DE102005062931A1 (de) * | 2005-12-29 | 2007-07-05 | Basf Ag | Herstellung von Natriumdiformiat |
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- 2006-04-12 EP EP06724298.2A patent/EP1904431B1/de not_active Not-in-force
- 2006-04-12 JP JP2008505816A patent/JP5582699B2/ja not_active Expired - Fee Related
- 2006-04-12 US US11/911,292 patent/US20080182001A1/en not_active Abandoned
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- 2006-04-12 CA CA2604070A patent/CA2604070C/en not_active Expired - Fee Related
- 2006-04-12 WO PCT/EP2006/003398 patent/WO2006108652A1/de not_active Application Discontinuation
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Publication number | Priority date | Publication date | Assignee | Title |
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US5935625A (en) * | 1995-05-12 | 1999-08-10 | Norsk Hydro Asa | Animal feed additives and feedstuff containing said additives |
US6906222B2 (en) * | 2001-11-09 | 2005-06-14 | Basf Aktiengesellschaft | Preparation for production of formic acid formates |
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EP1904431A1 (de) | 2008-04-02 |
CN101160279B (zh) | 2013-03-20 |
MY158458A (en) | 2016-10-14 |
TW200643006A (en) | 2006-12-16 |
AR053581A1 (es) | 2007-05-09 |
US20130281738A1 (en) | 2013-10-24 |
US8993802B2 (en) | 2015-03-31 |
US8497394B2 (en) | 2013-07-30 |
NO340043B1 (no) | 2017-03-06 |
EP1904431B1 (de) | 2015-07-08 |
DK1904431T3 (en) | 2015-10-05 |
JP5582699B2 (ja) | 2014-09-03 |
JP2008535881A (ja) | 2008-09-04 |
WO2006108652A1 (de) | 2006-10-19 |
CN101160279A (zh) | 2008-04-09 |
ES2546646T3 (es) | 2015-09-25 |
CA2604070C (en) | 2013-06-11 |
US20120296118A1 (en) | 2012-11-22 |
CA2604070A1 (en) | 2006-10-19 |
TWI418537B (zh) | 2013-12-11 |
NO20074865L (no) | 2007-11-09 |
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