CN1261328A - Soluble acid polyphosphaies and device for their production - Google Patents

Soluble acid polyphosphaies and device for their production Download PDF

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CN1261328A
CN1261328A CN98806585A CN98806585A CN1261328A CN 1261328 A CN1261328 A CN 1261328A CN 98806585 A CN98806585 A CN 98806585A CN 98806585 A CN98806585 A CN 98806585A CN 1261328 A CN1261328 A CN 1261328A
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polyphosphate
melt
phosphate
content
test
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CN1161273C (en
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T·克莱恩
T·斯塔费尔
A·莫瑞尔
F·瓦尔
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BK Giulini GmbH
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    • 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

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  • 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

The invention relates to a method for producing soluble acid polyphosphates with an Na/P ratio of 0.3 to 0.6, a P2O5 content of over 77 %wt., a Na2O content of under 20 % and a residual water content of 3-10 %. The invention is characterized in that an aqueous phosphate solution is dried in order to form chain-like polyphosphates with an average chain length of 10 to 30, and then fused for 30-180 minutes at temperatures of 400-600 DEG C. The fusion is cooled, forming a vitreous product. During fusion, steam pressure of 0.1 to 0.5 bar is maintained in the atmosphere in contact with the fusion. The invention also relates to the polyphosphates produced by this method and to their use.

Description

Soluble acid polyphosphate and preparation method thereof and equipment
The present invention relates to easily soluble, have a high P 2O 5The acid polyphosphate and its preparation method of content, the present invention also describes a kind of suitable equipment that can operate continuously in addition,
For acid polyphosphate, the professional is interpreted as it is those sodium/phosphorus mol ratio＜1, particularly＜0.9 (is equivalent to Na 2O content＜30 weight %) also comprise those of 2 to 10 weight % water and under solid state usually.Water-content is the existence of depending on free phosphoric acid-oh group basically.In addition, to can be used for characterizing with chain and ring texture be the phosphoric acid salt of feature to the polymerization degree.Because high free hydroxyl group group content, phosphate solution has very strong acidity.This acidic-group has further polymerizing power losing in principle under the situation of water, at this also through PO 4Tetrahedron carries out crosslinked, and forms 3 D cross-linked, anhydrous structure basically.This has low Na 2The structure of O and water-content is called as ultra-phosphates.Essential characteristic is that the dissolution rate in the water significantly reduces, because dissolving is only undertaken by being hydrolyzed into than junior unit.
Occurring condition crosslinked and that therefore form ultra-phosphates under than the situation of＜0.9 sodium polyphosphate at Na/P is a) high temperature of fusion and b) low water vapor pressure (referring to A.Winkler and the inorganic general chemistry magazine of E.Thilo (Z.anorg.allg.Chemie) 298 the 302nd to 315 pages (1959)).
In addition, Westman etc. the 1764th to 1775 page, nineteen fifty-nine, have described the composition of the acid phosphatase soda glass of measuring according to chemical analysis and the relation between the preparation condition in " Canadian Journal of Chemistry " the 27th phase.
In addition, find that when acid polyphosphate melt was slowly annealed, the specific composition of acid polyphosphate was converted into crystallized product.So dry under 400 ℃ the temperature with fusing and after about 300 ℃ of slow down annealing, NaH (PO 3) 2The aqueous solution become crystalline solid, think that thus this solid is the ring-type trimetaphosphate.This product is dissolved in the water very lentamente.Its composition is equivalent to Na under 300 ℃ 2H (PO 3) 3Mixture be converted into the fibrous crystals that is insoluble in water, it comprises long-chain polyphosphate (referring to Griffith, ACS1956, the 5892nd page) according to X-ray spectrum.
Another crystallized form is structure Na 3H (PO 3) 4, it is by heating down and annealing acquisition in 12 hours under 350 ℃ at 600 ℃.Same this product water fast (Griffith, ACS1956,3867-3870 page or leaf and US-P2,774,672).
In DE 4128124 C2, described as additive and be used to prepare the acid polyphosphate of cheese as fused salt.This polyphosphate can be under 400 to 500 ℃, under 20 minutes to 2 hours the residence time, directly prepare by the monosodium phosphate with proper mixture ratio and phosphoric acid or sodium hydroxide solution and phosphoric acid by fusing, wherein the composition of final product by temperature of fusion, the residence time and Na/P than determining.Preparation condition for routine sees also above-mentioned US-P2,774,672.This polyphosphate should have stable and storge quality.P 2O 5Content be 73 to 77 weight %, Na 2The content of O is 20 to 25 weight %, and surplus water content is 2 to 3 weight %.Therefore the Na/P ratio is 0.6 to 0.8.About 90 minutes of the solubleness meter of this product, this uses for the expection as fused salt and stablizer, and is especially oversize concerning cheese industry.Owing to necessary process period, wish that dissolution time is lower than 30 minutes, preferably is lower than 20 minutes.
For as the phosphatic application of food, especially for the preparation of fused cheese, such polyphosphate must have a series of following performances:
A) it must be solid, easy processed powders,
B) this powder has high solubleness, and the time that particularly is dissolved in fully in the water is lower than 30 minutes, preferably is lower than 20 minutes,
C) have and alkaline-earth metal particularly calcium and the good coordination ability of magnesium,
Have good surge capability when d) particularly in the acid range of for example salad dressing and mayonnaise, using,
E) have antiseptic power (with number of bacteria minimizing/volume and quantitaes) between the shelf lives at ready-made cheese,
F) to other additive, particularly vitamin C shows stabilization.
According to DE4128124 C2, use Na/P than the slightly acidic polyphosphate that is 0.8 to 0.6 for this purpose up to now, yet it does not show gratifying solvability.The content of inferring ultra-phosphates for quick dissolving based on statement up to now is too high.
Therefore, task of the present invention be find polyphosphate that solid-state, solvable and tart has a low levels crosslinking structure (ultra-phosphates) with and preparation method thereof.
Now, be surprisingly found out that, under suitable condition, can with Na/P than be 0.3-0.6 the strongly-acid polyphosphate (solution of 1% concentration, its pH＜2! ) change into have about 10 to 30, best 20 to 30 PO 3Unitary medium longer chain forms, it only has the disclosed crosslinked action of document on a small scale, and does not have (the Na of document description 2H 2PO 3) 4Ring or metaphosphate structure.
The chain of this moderate-length has very high dissolution rate astoundingly, wherein under favourable situation, reaches about 10 minutes for the dissolution time of 10 weight %.Most of acidic-group is blocked by chain-like structure, so that the acidity of these polymkeric substance is significantly less than the phosphorus acid content of analysis is pairing.Yet, the hydrolysis lentamente of this compound, and just can produce strong shock absorption in this point.On the other hand, polymer architecture can with divalent ion, particularly magnesium ion and calcium ion coordination, therefore and stop it to be settled out as difficultly-soluble phosphates.In addition, prove that this polyphosphate is extraordinary stablizer.Antibacterium, particularly the fungi aspect shows slight function of killing microorganism equally.
With previous wherein must to measure the method for polyphosphate chain length by the end group volumetry opposite difficultly, by means of the advanced person's 31The P-NMR method can be measured the chain length and the degree of crosslinking of polyphosphate very simply, in the method, polyphosphate is dissolved in the heavy water, and during the dissolution process or just after dissolution process, promptly the obvious hydrolysis of beginning and make the result insincere before, make the resonance signal of record different phosphate acid group.The end phosphate radical has resonance effect under-6 to-12ppm, the resonant frequency of the phosphate radical at chain middle part is-18 to-24ppm, ring-type phosphoric acid salt-23 (trimetaphosphates) or-21ppm (tetrametaphosphate) has resonance effect.According to acidity, under the situation of 0 ± 2ppm, find the signal of free orthophosphoric acid salt.
The water content of product (determining that in this case great majority are combination water) is measured by the ignition loss assay method under 600 to 800 ℃ usually, wherein when measuring, for fear of the P of acid polyphosphate 2O 5Loss all adds zinc oxide in each case.
That adopts the LTP5 type turbidity photometer of Dr.Lange company and Heidolph company is furnished with the Glaswerke of being used for Wertheim Nr.3, and RZR-2000 (being furnished with velocity gauge) the type agitator of the KPG paddle agitator of No. 855 50ml flasks is measured dissolution rate.
In order to carry out this test, in each case, in photometric measure sample pond, add 45 ml waters to 5 gram polyphosphate, under 500 rev/mins rotating speed, stir.Afterwards, remove agitator in predetermined Measuring Time (5,10,15,20,30,40,50 and 60 minutes), measure turbidity, wherein this process should be fast as much as possible, so that avoid calcium phosphate precipitation as much as possible.
According to following standard, the turbidity of measuring with the TE/F visual assessment:
1-2 TE/F=is transparent
2-10 TE/F=is opaque
10-15 TE/F=is muddy slightly
15-20 TE/F=muddiness
＞20 TE/F=are very muddy
Be prepared as follows product of the present invention: the dry aqueous solution of being made by phosphoric acid and sodium phosphate or sodium hydroxide solution (sodium/phosphorus is than=0.3 to 0.6) is about 20% until water content, by in suitable process furnace, in 60 to 120 minutes, slowly heat this mixture to 400 and melt to 600 ℃.By in continuation method, feeding the air of corresponding profit temperature, perhaps for example in retort furnace water-content by making the desire evaporation and stove volume adapt to regulate and cling to 0.1-0.5 as the water vapor pressure above the melt of another parameter.
In anhydrous atmosphere, after of short duration cooling stages, melt is cooled to room temperature, and is ground to fineness of powder.Na/P can not be ground or at room temperature do not rehardened than the product that is lower than 0.3 again.
Infer by test subsequently, under the residence time of 400 to 550 ℃ of temperature of fusion and 60 to 120 minutes, obtain mean chain length and be 10 to 30, dissolution rate is up to 20 minutes required chain product.Temperature surpasses 550 ℃ and reaction times when surpassing 180 minutes, and chain length is increased to and surpasses 30, so dissolution rate and ring-type phosphate content obviously improve, and such product not too is fit to purpose of the present invention.Regulating chain by the water vapor pressure to 0.2 of regulating the melt top best to 0.3 crust grows in the scope of about 20-25.
Embodiment 1
The assaying reaction temperature
In can being heated to 400 to 800 ℃ retort furnace (Heraeus Typ MR 70E), put in the platinum ware by 131.6 gram NaH 2PO 4(1.1 moles), 114.4 gram H 3PO 4Solution that (0.96 mole of industrial 82.2% concentration ≈) and 39.5 gram water (2.2 moles) are formed and slowly heating are to avoid the solution splash.During test-results is listed in the table below.
Table 1
Lot number Parameter Analyze
Time [minute] Temperature [℃] P 2O 5??[％] Ignition loss [%] pH ??NMR ??n Water-absorbent Fusing point [℃] Dissolution rate 20 minutes [TE/F]
After 5 hours [%] After 24 hours [%]
Test 1 ??60 ??400 ??74,89 ??9,7 ??1,9 ????3,2 ????3,38 ????9,22
Test 2 ??120 ??400 ??73,82 ??9,8 ??1,9 ????5,0 ????3,76 ??105-115 ????0,7
Test 3 ??120 ??500 ??78,00 ??4,7 ??1,9 ????29,0 ????1,90 ????7,81 ??175-185 ????1,0
Test 4 ??120 ??600 ??79,80 ??4,0 ??1,8 ????42,0 ????1,51 ????5,77 ?190-200 ????4,8
Table 2
Lot number Parameter IC-analyzes
Time [minute] Temperature [℃]
?P1 ?[％] ??P2 ??[％] P3 [％] P4 [％] ?P5-P10 ?[％] P11-P50 [％] ＞P50 [％] cycl.P [％]
Test 2 ??120 ??400 ??4,6 ??9,9 ??6,7 ??9,0 ??28,0 ??14,8 ??0,9
Test 3 ??120 ??500 ??1,0 ??0,6 ??0,2 ??0,8 ??8,2 ??42,1 ????21,4 ??3,7
Test 4 ??120 ??600 ??1,4 ??0,3 ??0,2 ??1,3 ??12,4 ??47,2 ????10,4 ??5,6
Table 3
Sequence number Reaction parameter P2O5 Ignition loss NMR Mark
Temperature ℃ Time minute Theoretical % Actual % Theoretical % Actual measurement % Chain length n ??P1
500 ℃ of temperature of fusion
Test 5 ????500 ??30 ??74,86 ??75,29 ??8,03 ??5,2 ?5,0
Test 6 ????500 ??60 ??77,84 ??78,28 ??4,37 ??16,6 ?2,1
Test 7 ????500 ??120 ??79,05 ??79,54 ??2,87 ??4,70 ??24,5 ?1,3
Test 8 ????500 ??180 ??79,48 ??79,69 ??2,35 ??30,0 ?0,7
600 ℃ of temperature of fusion
Test 9 ????600 ??60 ??79,02 ??80,12 ??2,6 ??30,6 ?0,7
Test 10 ????600 ??120 ??79,93 ??79,80 ??1,8 ??4,0 ??42,0 ?0,6
700 ℃ of temperature of fusion
Test 11 ????700 ??30 ??78,85 ??79,09 ??2,8 ??21,0 ?1,3
Test 12 ????700 ??60 ??79,51 ??80,12 ??2,0 ??31,6 ?1,3
800 ℃ of temperature of fusion
Test 13 ????800 ??15 ??78,93 ??79,11 ??3,4 ??27,2 ?1,1
Test 14 ????800 ??30 ??78,93 ??80,35 ??1,9 ??30,9 ?0,5
Test 15 ????800 ??60 ??80,84 ??80,99 ??1,0 ??23,1 ?1,3
Table 4
Title Dry g Fusing Ignition loss P 2O 5 Mean chain length
Amount g before Amount g afterwards Loss % Temperature C Time minute ??H 2O ??C ??WDD 1??mbar ??％ Theoretical % Actual measurement The NMR-data
Test
16 ??278,31 ??221,36 ??20,46 ??500 ??120 Do not have ??0 ??2,85 ??80,60 ??80,7 ??31,7
Test 17 ??278,31 ??221,36 ??20,46 ??500 ??120 ??50 ??120 ??3,47 ??80,6 ??25,7
Test 18 ??278,31 ??221,36 ??20,46 ??500 ??120 ??80 ??470 ??3?63 ??80,1 ??23,3
The 1=water vapor pressure
Table 1 shows that under 400 to 500 ℃ temperature of fusion, after 20 minutes, solubleness is very satisfactory.Water-absorbent is also with desired equally increase.Under identical water vapor pressure, along with temperature raises, ignition loss reduces, and is as shown in table 2 like this, and average condensation degree and ring-type phosphate content raise, and consequence is the corresponding reduction of solubleness.Mark P1 to P50 represents the analysis to measure content of respective chain length in the table 2.
Table 3 shows, under 500 ℃ and very long residence time or under higher temperature and short residence time, mean chain length obviously increases, this reduces by ignition loss equally and shows.Correspondingly strong crosslinked product no longer can fully dissolve, so that can not use in the present invention.
Embodiment 2
In another test, change weighing and make Na 2O/P 2O 5Mol ratio be 0.5, being equivalent to total molecular formula is NaHP 2O 6* H 2O.Table 4 shows that aspect composition, this product is compared with embodiment 1 does not have significant difference.Only because acidity improves, and water-absorbent strengthens, and obviously owing to crosslinked increasing, some reduction of solubleness.
Embodiment 3
Preparation continuously in tube furnace
The industrial H that in the quartz reactor of being furnished with agitator and refrigerating unit, adds 13.8 kilogram 85% 3PO 4Solution, and the under agitation so slow sodium hydroxide solution that adds 5.9 kilogram 49.2% are so that temperature remains on below the boiling point.Obtain 19 kilograms of Na 2O/P 2O 5Than be 0.533 and density be 1.61 phosphate solution.
In membrane type dosing pump (its pistons work volume and pulse-repetition frequency can be regulated) is packed above-mentioned phosphate solution into the smelting furnace of accompanying drawing 1 continuously.Just as seen, in tube furnace 1 (total length that uses Gero company under practical situation is that 750 centimetres and heating region are 500 centimetres F 500 type tube furnaces), length is that 880 centimetres and diameter are that 55 centimetres silica tube 3 is as reactor.In silica tube, be inserted with the melting channel that mills out by the graphite pole of slight inclination, the area of this groove is 256 square centimeters, volume is 1024 cubic centimetres, if desired, can make volume reduce to 256 cubic centimetres (except that graphite by embedding webge groove, can also use silicon carbide as starting material, the phosphoric acid salt melt corrodes other stupalith sometimes).Under the delivery rate of 300 Grams Per Hours, add phosphate solution through pipeline 4, because melting channel 2 tilts, the melt of making flows out through pipeline 5 continuously at the melting channel end, and is condensed into glassy through refrigerative roll 6.The phosphate glass that obtains uses scraper to smash under the situation of getting rid of moisture, and in container 8 after the relay storage, grind into powder.The inlet zone 1a of silica tube is preheated to 100 ℃, and real conversion zone 1b is adjusted to 650 to 675 ℃, obtains 515 to 560 ℃ of melt temperatures thus.In order to regulate water vapor pressure, flow velocity is that 10 liters/minute nitrogen gas stream is crossed this device through pipeline 9 Continuous Flow, and this nitrogen gas stream is crossed 60 ℃ of hot water by percolation in washer 10, and to regulate water vapor pressure be 150 millibars.The results are shown in the following table 5 of this test.Its result shows, reaching under 530 ℃ the temperature of fusion, reached the optimal dissolution degree, and it is 20 to 30 that corresponding chain is about.
Table 5
Title Reaction parameter Analytical results
Temperature The amount of counting g/h ??P 2O 5??％ Solvability %ig minute Ignition loss % Chain length n ?pH ?1％ig The water vapor pressure millibar
Stove The fusing ℃
Regulate ℃ Inner ℃
Test 1 ????650 ????660 ????515 ????3000 ????77,89 ????10 1) ????5,17 ????24 ????1,89 ????150
Test 2 ????650 ????665 ????515 ????3100 ????78,50 ????15 1) ????4,94 ????27 ????1,79
Test 3 ????655 ????663 ????520 ????3100 ????78,71 ????15 1) ????4,80 ????31 ????1,86
Test 4 ????660 ????677 ????533 ????3100 ????78,93 ????15 1) ????4,49 ????33 ????1,88
Test 5 ????675 ????702 ????556 ????3100 ????78,6 ????30 1) ????4,45 ????38 ????1,85
1)All all are opaque to slight haze

Claims (9)

1, a kind of method for preparing soluble acid polyphosphate, the Na/P ratio of this polyphosphate is 0.3 to 0.6, P 2O 5Content surpasses 77 weight %, Na 2O content is lower than 20%, residual moisture content is 3 to 10%, it is characterized in that, in order to form mean chain length is 10 to 30 chain polyphosphate, the dry phosphatic aqueous solution, fusing is 30 to 180 minutes under 400 to 600 ℃ temperature, and cools off this melt and form glassy product, and wherein the water vapor pressure of the atmosphere that keeps in touch with melt between melting period maintains 0.1 to 0.5 crust.
2, the method for claim 1 is characterized in that, Na/P than＞0.5 and＜0.6.
3, the method for each of claim 1 to 2 is characterized in that, phosphate solution mixes acquisition by water-bearing phosphate with sodium phosphate or sodium hydroxide solution.
4, the method for each of claim 1 to 3, it is characterized in that, this method is carried out in tube furnace continuously, wherein makes phosphate solution in the melting channel by this tube furnace, and regulates water vapor pressure by the rare gas element that feeding comprises respective amount water vapour.
5, the method for each of claim 1 to 4 is characterized in that, temperature of fusion is 450 to 550 ℃, and the length of phosphoric acid salt chain is 20 to 30 PO 3The unit.
6, the polyphosphate of the method for each of claim 1 to 5 preparation.
7, the application of the polyphosphate of claim 6, it is used as fused salt and stablizer in the fused cheese.
8, be used for the equipment of continuous preparation according to the acid polyphosphate of claim 1 to 6, it comprises
A) tube furnace (1)
B) this tube furnace has the furnace lining of being made by silica tube (3),
C) slight inclination is installed and is convenient to the melting channel of melt flow (2) in silica tube, this groove have phosphatic feeding line (4) and polyphosphate melt discharging pipeline (5) and
D) is furnished with the pipeline (9) of supplying with water vapour.
9, the equipment of claim 8 is characterized in that, has the cooling roll (6) that is used for effusive polyphosphate melt, and smashes the phosphate glass of formation and be transported in the storage vessel (8) through scraper (7).
CNB988065851A 1997-06-26 1998-06-23 Soluble acid polyphosphaies and device for their production Expired - Fee Related CN1161273C (en)

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DE19727144A DE19727144A1 (en) 1997-06-26 1997-06-26 Soluble, acidic polyphosphates and process and device for their production
DE19727144.8 1997-06-26

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CN1161273C CN1161273C (en) 2004-08-11

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Cited By (2)

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Publication number Priority date Publication date Assignee Title
CN111547695A (en) * 2020-05-19 2020-08-18 云南莱德福科技有限公司 Polyphosphate with net-shaped branch structure and preparation method thereof
CN116812892A (en) * 2023-07-10 2023-09-29 四川金地亚美科技有限公司 Preparation method of acid sodium hexametaphosphate

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DE10163954C5 (en) * 2001-12-22 2016-12-22 Bk Giulini Gmbh Use of a phosphate mixture for the production of concentrated solutions and brine sheets for the food industry
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

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SU814855A1 (en) * 1979-06-19 1981-03-23 Белорусский Технологический Институтим. C.M.Кирова Method of producing sodium polyphosphate
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DE4128124C2 (en) * 1991-08-24 1993-12-02 Benckiser Knapsack Ladenburg Use of sodium polyphosphates for the production of cheese

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111547695A (en) * 2020-05-19 2020-08-18 云南莱德福科技有限公司 Polyphosphate with net-shaped branch structure and preparation method thereof
CN116812892A (en) * 2023-07-10 2023-09-29 四川金地亚美科技有限公司 Preparation method of acid sodium hexametaphosphate

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