EP0991589A1 - Lösliche, saure polyphosphate und verfahren und vorrichtung zu ihrer herstellung - Google Patents
Lösliche, saure polyphosphate und verfahren und vorrichtung zu ihrer herstellungInfo
- Publication number
- EP0991589A1 EP0991589A1 EP98938627A EP98938627A EP0991589A1 EP 0991589 A1 EP0991589 A1 EP 0991589A1 EP 98938627 A EP98938627 A EP 98938627A EP 98938627 A EP98938627 A EP 98938627A EP 0991589 A1 EP0991589 A1 EP 0991589A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- polyphosphates
- melt
- phosphate
- melting
- content
- 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.)
- Ceased
Links
- 229920000388 Polyphosphate Polymers 0.000 title claims abstract description 29
- 239000001205 polyphosphate Substances 0.000 title claims abstract description 29
- 235000011176 polyphosphates Nutrition 0.000 title claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 7
- 239000002253 acid Substances 0.000 title abstract 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 10
- 239000010452 phosphate Substances 0.000 claims abstract description 10
- 239000011734 sodium Substances 0.000 claims description 19
- 230000002378 acidificating effect Effects 0.000 claims description 17
- 235000021317 phosphate Nutrition 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 16
- 238000002844 melting Methods 0.000 claims description 15
- 230000008018 melting Effects 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 11
- 239000000155 melt Substances 0.000 claims description 9
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 6
- 239000010453 quartz Substances 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 claims description 4
- 239000001488 sodium phosphate Substances 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000010924 continuous production Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 3
- 239000003381 stabilizer Substances 0.000 claims description 3
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 239000005365 phosphate glass Substances 0.000 claims description 2
- 235000014059 processed cheese Nutrition 0.000 claims description 2
- 238000003860 storage Methods 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims 1
- 230000004927 fusion Effects 0.000 abstract 3
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 abstract 1
- 239000000047 product Substances 0.000 description 12
- 238000004090 dissolution Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 235000013351 cheese Nutrition 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N Heavy water Chemical compound [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- 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 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000003139 buffering effect Effects 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- AZSFNUJOCKMOGB-UHFFFAOYSA-K cyclotriphosphate(3-) Chemical compound [O-]P1(=O)OP([O-])(=O)OP([O-])(=O)O1 AZSFNUJOCKMOGB-UHFFFAOYSA-K 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000011022 opal Substances 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 235000011008 sodium phosphates Nutrition 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 238000005496 tempering Methods 0.000 description 2
- GIXFALHDORQSOQ-UHFFFAOYSA-J 2,4,6,8-tetraoxido-1,3,5,7,2$l^{5},4$l^{5},6$l^{5},8$l^{5}-tetraoxatetraphosphocane 2,4,6,8-tetraoxide Chemical compound [O-]P1(=O)OP([O-])(=O)OP([O-])(=O)OP([O-])(=O)O1 GIXFALHDORQSOQ-UHFFFAOYSA-J 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 101000578195 Lens culinaris Non-specific lipid-transfer protein 5 Proteins 0.000 description 1
- HCBIBCJNVBAKAB-UHFFFAOYSA-N Procaine hydrochloride Chemical compound Cl.CCN(CC)CCOC(=O)C1=CC=C(N)C=C1 HCBIBCJNVBAKAB-UHFFFAOYSA-N 0.000 description 1
- 229930003268 Vitamin C Natural products 0.000 description 1
- 238000002083 X-ray spectrum Methods 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 244000052616 bacterial pathogen Species 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- -1 cyclic phosphates Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 235000010746 mayonnaise Nutrition 0.000 description 1
- 230000003641 microbiacidal effect Effects 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 235000014438 salad dressings Nutrition 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 235000019830 sodium polyphosphate Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 235000019154 vitamin C Nutrition 0.000 description 1
- 239000011718 vitamin C Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/38—Condensed phosphates
- C01B25/40—Polyphosphates
- C01B25/41—Polyphosphates of alkali metals
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23C—DAIRY PRODUCTS, e.g. MILK, BUTTER OR CHEESE; MILK OR CHEESE SUBSTITUTES; MAKING OR TREATMENT THEREOF
- A23C19/00—Cheese; Cheese preparations; Making thereof
- A23C19/06—Treating cheese curd after whey separation; Products obtained thereby
- A23C19/068—Particular types of cheese
- A23C19/08—Process cheese preparations; Making thereof, e.g. melting, emulsifying, sterilizing
- A23C19/082—Adding substances to the curd before or during melting; Melting salts
Definitions
- the present invention relates to readily soluble, acidic polyphosphates with a high P 2 O 5 content and processes for their preparation and furthermore describes a suitable device which permits continuous operation.
- Acidic polyphosphates are understood by those skilled in the art to be those which have a sodium / phosphorus molar ratio of ⁇ 1, in particular ⁇ 0.9, corresponding to an Na 2 O content of ⁇ 30% by weight, and in the solid state usually 2- Contain 10% by weight of water.
- the water content is essentially based on the presence of free phosphoric acid hydroxyl groups.
- the degree of polymerization also serves to characterize these phosphates, which are characterized by chain and ring-shaped structures. Due to the high content of free hydroxyl groups, the solutions of these phosphates are very acidic.
- Another crystalline form corresponds to the formula Na 3 H (P0 3 ) 4 , which can be obtained in 12 hours by heating to 600 ° C. and tempering at 350 ° C. This product is also insoluble in water (Griffith.ACS 1956, pp. 3867-3870 and US-P 2,774,672).
- DE 4128124 C2 describes acidic polyphosphates as an additive or as a molten salt for the preparation of cheese. These polyphosphates are produced from monosodium phosphate and phosphoric acid or sodium hydroxide solution and phosphoric acid in suitable mixing ratios directly by melting at 400 ° C to 500 ° C, with residence times of 20 min to 2 hours, the composition of the end product being determined by melting temperature, residence time and Na / P- Ratio is determined. For the general manufacturing conditions, reference is made to the above US Pat. No. 2,774,672. These polyphosphates are said to have stabilizing and preserving properties.
- the P 2 O 5 content is between 73 and 77% by weight, the Na 2 O content is between 20 and 25% and the residual water content is 2 to 3% by weight.
- the Na / P ratio is therefore between 0.6 and 0.8.
- the solubility of such products is about 90 minutes, which is necessary for the intended use as a molten salt and stabilizing agent. tel in the cheese industry is too slow. Because of the necessary processing times, dissolving times of less than 30 minutes, preferably less than 20 minutes, would be desirable.
- polyphosphates For use as food phosphates, including for processed cheese production, such polyphosphates must have a number of properties and functions:
- a) there must be solid, easy-to-handle powders which b) have a high solubility, in particular a time to dissolution in water of less than 30, preferably less than 20 minutes, c) a good complexing ability for alkaline earth metals, in particular calcium and magnesium, d ) a good buffering effect in the acidic range, especially for use in salad dressings and mayonnaises, for example, e) a preserving effect (expressed in the reduction in the number of germs per volume and amount) even during the storage time of the finished cheese, f) a stabilizing effect compared to other additives, in particular Show vitamin C.
- These medium-length chains surprisingly have a very high dissolution rate, with dissolution times for 10% by weight of about 10 minutes being achieved in favorable cases.
- a large part of the acidic groups is blocked by the chain-like structure, so that these polymers are significantly less acidic than the analytical content of phosphoric acid.
- the compounds are able to hydrolyze slowly and to this extent exert a strong buffering effect.
- the polymeric structure is capable of complexing divalent ions, especially magnesium and calcium ions, and thus preventing their precipitation as poorly soluble phosphates.
- these polyphosphates have proven to be surprisingly good stabilizers. They also show a slightly microbiocidal effect on bacteria and especially fungi
- chain lengths and the degree of crosslinking of polyphosphates can be determined very easily with modern 31 P-NMR methods by dissolving the polyphosphate in deuterium oxide and during or briefly after the dissolution process, ie before a noticeable hydrolysis begins and the result is falsified, picks up the resonance signals of the different phosphate groups.
- Terminal phosphate groups have a resonance at -6 to -12 ppm
- medium-sized phosphate groups in the chain have a resonance frequency of -18 to -24 ppm
- cyclic phosphates have a resonance at -23 (trimetaphosphate) or -21 ppm (Tetrametaphosphate).
- the signal of the free orthophosphates is found under these circumstances at 0 ⁇ 2 ppm, depending on the acidity.
- the water content of the products which in this case determines predominantly bound water, is usually determined by determining the loss on ignition at 600 to 800 ° C., zinc oxide being added to the determinations in order to avoid P 2 O 5 losses in the case of acidic polyphosphates.
- the measured turbidity in TE / F is assessed visually according to the following scheme:
- the products according to the invention are prepared by predrying an aqueous solution of phosphoric acid and sodium phosphate or sodium hydroxide solution in a sodium / phosphorus ratio of 0.3 to 0.6 to a water content of approximately 20% and melting by slowly heating this mixture in a suitable oven at temperatures of 400 to 600 °, for a period of 60 to 120 minutes.
- a suitable oven at temperatures of 400 to 600 °, for a period of 60 to 120 minutes.
- the water vapor pressure above the melt is set to 0.1-0.5 bar as a further parameter.
- the melt After a short cooling phase, the melt is cooled to room temperature in an anhydrous atmosphere and ground to fineness of powder. Products with a Na / P ratio of less than 0.3 can no longer be ground or solidify at room temperature.
- Table 3 shows that with a very long residence time at temperatures of 500 ° or with shorter residence times at even higher temperatures, the average chain length increases significantly, which is also shown by the decrease in the loss on ignition. The corresponding, more crosslinked products are no longer sufficiently soluble to be used according to the invention.
- the aforementioned phosphate solution is continuously introduced into a melting furnace according to FIG. 1 via a diaphragm metering pump, whose stroke volume and cycle frequency can be adjusted.
- a tube furnace 1 in the current case a type F 500 from Gero, with a total length of 750 cm and a heating zone of 500 cm was used
- a quartz tube 3 with a length of 880 cm and a diameter of 55 cm.
- a slightly inclined melting tank 2 which is milled out of a graphite rod, which has an area of 256 cm 2 and a volume of 1024 cm 3 , which can be reduced to 256 cm 3 by inserting an insert wedge if necessary
- silicon carbide can also be used as the material; other ceramic materials are partially attacked by the phosphate melts.
- the Phosphate solution is fed in at a metering rate of 300 g / h via line 4, the melt produced runs continuously via line 5 due to the inclination at the end of the melting tank 2 and is solidified in a glass-like manner via a cooled roller 6.
- the phosphate glass obtained is broken with the exclusion of atmospheric moisture with a scraper 7 and ground to powder after being stored temporarily in container 8.
- the inlet zone of the quartz tube 1a is preheated to 100 °, the actual reaction zone 1b is set to 650 to 675 °, resulting in melt temperatures of 515 to 560 °.
- the apparatus is continuously flowed through with a 10 l / min nitrogen stream via line 9, which is set to 150 mbar water vapor pressure by passing through 60 ° warm water in the scrubber 10.
- Table 5 It is shown that optimal solubilities corresponding to chain lengths of approximately 20 to 30 can be achieved at melt temperatures of up to 530 °.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Food Science & Technology (AREA)
- Polymers & Plastics (AREA)
- Glass Compositions (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Dairy Products (AREA)
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19727144 | 1997-06-26 | ||
| DE19727144A DE19727144A1 (de) | 1997-06-26 | 1997-06-26 | Lösliche, saure Polyphosphate und Verfahren und Vorrichtung zu ihrer Herstellung |
| PCT/EP1998/003823 WO1999000324A1 (de) | 1997-06-26 | 1998-06-23 | Lösliche, saure polyphosphate und verfahren und vorrichtung zu ihrer herstellung |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP0991589A1 true EP0991589A1 (de) | 2000-04-12 |
Family
ID=7833709
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP98938627A Ceased EP0991589A1 (de) | 1997-06-26 | 1998-06-23 | Lösliche, saure polyphosphate und verfahren und vorrichtung zu ihrer herstellung |
Country Status (13)
| Country | Link |
|---|---|
| EP (1) | EP0991589A1 (cs) |
| JP (1) | JP2002507957A (cs) |
| KR (1) | KR100522290B1 (cs) |
| CN (1) | CN1161273C (cs) |
| AU (1) | AU734894B2 (cs) |
| BR (1) | BR9811271A (cs) |
| CA (1) | CA2295687C (cs) |
| CZ (1) | CZ300062B6 (cs) |
| DE (1) | DE19727144A1 (cs) |
| HU (1) | HUP0003050A3 (cs) |
| PL (1) | PL192090B1 (cs) |
| SK (1) | SK286395B6 (cs) |
| WO (1) | WO1999000324A1 (cs) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10163954C5 (de) * | 2001-12-22 | 2016-12-22 | Bk Giulini Gmbh | Verwendung einer Phosphatmischung zur Herstellung von konzentrierten Lösungen und Salzlaken für die Nahrungsmittelindustrie |
| US20040002444A1 (en) * | 2002-04-08 | 2004-01-01 | Toshikazu Shiba | Polyphosphate-water soluble collagen complexes and process for preparation thereof |
| WO2013119672A2 (en) * | 2012-02-07 | 2013-08-15 | Icl Performance Products Lp | Use of acidic polyphosphates in beverage products |
| CN111547695B (zh) * | 2020-05-19 | 2021-09-10 | 云南莱德福科技有限公司 | 一种网状分支结构的多聚磷酸盐及其制备方法 |
| CN116812892B (zh) * | 2023-07-10 | 2024-07-16 | 四川金地亚美科技有限公司 | 一种酸式六偏磷酸钠的制备方法 |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2021012A (en) * | 1932-10-27 | 1935-11-12 | Swann Res Inc | Process for production of acid alkali-metal pyrophosphates |
| US2774672A (en) * | 1955-03-18 | 1956-12-18 | Monsanto Chemicals | Metaphosphate composition |
| IL42828A (en) * | 1972-07-31 | 1976-12-31 | Rhone Progil | Process and apparatus for the manufacture of alkali metal polyphosphates |
| GB1547993A (en) * | 1976-04-14 | 1979-07-04 | Albright & Wilson | Manufacture of condensed phosphates |
| DD125401A1 (cs) * | 1976-04-30 | 1977-04-20 | ||
| SU814855A1 (ru) * | 1979-06-19 | 1981-03-23 | Белорусский Технологический Институтим. C.M.Кирова | Способ получени полифосфатаНАТРи |
| SU994403A1 (ru) * | 1980-04-09 | 1983-02-07 | Институт химических наук АН КазССР | Способ получени триполифосфата натри |
| DE3033065C2 (de) * | 1980-09-03 | 1984-05-24 | Giulini Chemie Gmbh, 6700 Ludwigshafen | Verfahren zur Herstellung eines schnellöslichen Alkalipolyphosphatglases |
| EP0108685A2 (en) * | 1982-11-04 | 1984-05-16 | Calgon Corporation | A glassy crystalline phosphate product and a process for the production thereof |
| CS270316B1 (cs) * | 1988-03-11 | 1990-06-13 | Kucera Miloslav | Způsob výroby tripolyfosfátu sodného |
| FR2634191B1 (fr) * | 1988-07-13 | 1991-12-27 | Rhone Poulenc Chimie | Procede de preparation de phosphates par fusion |
| SU1692936A1 (ru) * | 1988-09-13 | 1991-11-23 | Белорусский технологический институт им.С.М.Кирова | Способ получени полифосфата натри |
| DE4128124C2 (de) * | 1991-08-24 | 1993-12-02 | Benckiser Knapsack Ladenburg | Verwendung von Natriumpolyphosphaten zur Herstellung von Käse |
-
1997
- 1997-06-26 DE DE19727144A patent/DE19727144A1/de not_active Ceased
-
1998
- 1998-06-23 BR BR9811271-6A patent/BR9811271A/pt not_active IP Right Cessation
- 1998-06-23 AU AU87281/98A patent/AU734894B2/en not_active Ceased
- 1998-06-23 CN CNB988065851A patent/CN1161273C/zh not_active Expired - Fee Related
- 1998-06-23 CA CA002295687A patent/CA2295687C/en not_active Expired - Fee Related
- 1998-06-23 PL PL337655A patent/PL192090B1/pl unknown
- 1998-06-23 EP EP98938627A patent/EP0991589A1/de not_active Ceased
- 1998-06-23 JP JP50526999A patent/JP2002507957A/ja not_active Ceased
- 1998-06-23 HU HU0003050A patent/HUP0003050A3/hu unknown
- 1998-06-23 SK SK1768-99A patent/SK286395B6/sk not_active IP Right Cessation
- 1998-06-23 CZ CZ0451099A patent/CZ300062B6/cs not_active IP Right Cessation
- 1998-06-23 WO PCT/EP1998/003823 patent/WO1999000324A1/de not_active Ceased
- 1998-06-23 KR KR10-1999-7012306A patent/KR100522290B1/ko not_active Expired - Fee Related
Non-Patent Citations (1)
| Title |
|---|
| See references of WO9900324A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CZ451099A3 (cs) | 2000-06-14 |
| PL192090B1 (pl) | 2006-08-31 |
| JP2002507957A (ja) | 2002-03-12 |
| DE19727144A1 (de) | 1999-01-07 |
| PL337655A1 (en) | 2000-08-28 |
| CN1261328A (zh) | 2000-07-26 |
| CZ300062B6 (cs) | 2009-01-21 |
| CA2295687A1 (en) | 1999-01-07 |
| CA2295687C (en) | 2003-11-18 |
| HUP0003050A2 (hu) | 2001-02-28 |
| BR9811271A (pt) | 2000-07-18 |
| SK176899A3 (en) | 2000-07-11 |
| KR20010014220A (ko) | 2001-02-26 |
| KR100522290B1 (ko) | 2005-10-19 |
| WO1999000324A1 (de) | 1999-01-07 |
| AU8728198A (en) | 1999-01-19 |
| AU734894B2 (en) | 2001-06-28 |
| HUP0003050A3 (en) | 2003-02-28 |
| SK286395B6 (sk) | 2008-09-05 |
| CN1161273C (zh) | 2004-08-11 |
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