EP0991589A1 - Polyphosphates acides solubles et dispositif utilise pour leur fabrication - Google Patents

Polyphosphates acides solubles et dispositif utilise pour leur fabrication

Info

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
Application number
EP98938627A
Other languages
German (de)
English (en)
Inventor
Thomas Klein
Thomas Staffel
Alexander Maurer
Friedrich Wahl
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BK Giulini Chemie GmbH
Original Assignee
BK Giulini Chemie GmbH
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by BK Giulini Chemie GmbH filed Critical BK Giulini Chemie GmbH
Publication of EP0991589A1 publication Critical patent/EP0991589A1/fr
Ceased legal-status Critical Current

Links

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 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)

Abstract

L'invention concerne un procédé de fabrication de polyphosphates acides solubles de rapport Na/P de 0,3 à 0,6, ayant une teneur en P2O5 supérieure à 77 % en poids, une teneur en Na2O inférieure à 20 % et une teneur en eau résiduelle de 3 à 10 %, caractérisé en ce qu'on sèche une solution aqueuse de phosphate en vue de former des polyphosphates en chaînes, de longueur de chaînes moyenne comprise entre 10 et 30, on effectue la fusion à des températures de 400 à 600 DEG C pendant 30 à 180 minutes et on refroidit le composé fondu, ce qui donne lieu à la formation d'un produit vitreux, et en ce qu'on maintient, pendant la fusion, une pression de vapeur d'eau dans l'atmosphère en contact avec le composé fondu, comprise entre 0,1 et 0,5 bar. L'invention concerne également les polyphosphates fabriqués suivant ce procédé, ainsi que leur utilisation.
EP98938627A 1997-06-26 1998-06-23 Polyphosphates acides solubles et dispositif utilise pour leur fabrication Ceased EP0991589A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19727144A DE19727144A1 (de) 1997-06-26 1997-06-26 Lösliche, saure Polyphosphate und Verfahren und Vorrichtung zu ihrer Herstellung
DE19727144 1997-06-26
PCT/EP1998/003823 WO1999000324A1 (fr) 1997-06-26 1998-06-23 Polyphosphates acides solubles et dispositif utilise pour leur fabrication

Publications (1)

Publication Number Publication Date
EP0991589A1 true EP0991589A1 (fr) 2000-04-12

Family

ID=7833709

Family Applications (1)

Application Number Title Priority Date Filing Date
EP98938627A Ceased EP0991589A1 (fr) 1997-06-26 1998-06-23 Polyphosphates acides solubles et dispositif utilise pour leur fabrication

Country Status (13)

Country Link
EP (1) EP0991589A1 (fr)
JP (1) JP2002507957A (fr)
KR (1) KR100522290B1 (fr)
CN (1) CN1161273C (fr)
AU (1) AU734894B2 (fr)
BR (1) BR9811271A (fr)
CA (1) CA2295687C (fr)
CZ (1) CZ300062B6 (fr)
DE (1) DE19727144A1 (fr)
HU (1) HUP0003050A3 (fr)
PL (1) PL192090B1 (fr)
SK (1) SK286395B6 (fr)
WO (1) WO1999000324A1 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
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
US20130216669A1 (en) * 2012-02-07 2013-08-22 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
CN116812892A (zh) * 2023-07-10 2023-09-29 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)

* Cited by examiner, † Cited by third party
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
NL7310452A (fr) * 1972-07-31 1974-02-04
GB1547993A (en) * 1976-04-14 1979-07-04 Albright & Wilson Manufacture of condensed phosphates
DD125401A1 (fr) * 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 (fr) * 1982-11-04 1984-05-16 Calgon Corporation Phosphate cristallin et vitreux et procédé pour sa préparation
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

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9900324A1 *

Also Published As

Publication number Publication date
AU8728198A (en) 1999-01-19
CA2295687C (fr) 2003-11-18
SK286395B6 (sk) 2008-09-05
CZ300062B6 (cs) 2009-01-21
PL192090B1 (pl) 2006-08-31
JP2002507957A (ja) 2002-03-12
KR100522290B1 (ko) 2005-10-19
SK176899A3 (en) 2000-07-11
CN1161273C (zh) 2004-08-11
DE19727144A1 (de) 1999-01-07
HUP0003050A2 (hu) 2001-02-28
CZ451099A3 (cs) 2000-06-14
CA2295687A1 (fr) 1999-01-07
WO1999000324A1 (fr) 1999-01-07
CN1261328A (zh) 2000-07-26
KR20010014220A (ko) 2001-02-26
AU734894B2 (en) 2001-06-28
PL337655A1 (en) 2000-08-28
BR9811271A (pt) 2000-07-18
HUP0003050A3 (en) 2003-02-28

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