CN1046119C - Polyphosphate compound salt series - Google Patents
Polyphosphate compound salt series Download PDFInfo
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- CN1046119C CN1046119C CN93109096A CN93109096A CN1046119C CN 1046119 C CN1046119 C CN 1046119C CN 93109096 A CN93109096 A CN 93109096A CN 93109096 A CN93109096 A CN 93109096A CN 1046119 C CN1046119 C CN 1046119C
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- phosphate
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Abstract
The present invention relates to a series of polyphosphate complex salts. A quantity of phosphates, polyphosphates and organic acid salts, all of which belong to a monoclinic system structure, are utilized, and the ionicity of bonds of the phosphates, the ionicity of bonds of the polyphosphates and the ionicity of bonds of the organic acid salts are similar so that the phosphates, the polyphosphates and the organic acid salts are combined into the complex salts by 'salt bridges' or 'hydrogen bonds'. The biological performance, the physical performance and the chemical performance of the polyphosphate complex salts are obviously superior to those of a single kind in the components or those of a mixture of the components. The series of polyphosphate complex salts can be widely used for foods, such as fruit juice, carbonated beverages, sour milk beverages, milk products, bread, pastries, other rice products, other paste products, fish, meat, fish products, meat products, canned foods, pickles, flavorings, etc., medicines and fodder. The polyphosphate complex salts are used as additive agents for bacterium resistance, mildew prevention, oxidation resistance, quality improvement, pH buffering and intensifying, etc.
Description
The present invention relates to a series of polyphosphate compound salt additives, in food, medicine and feed, be used as antibiotic, mildew-resistant, anti-oxidant, quality-improving, pH buffering, dispersion, enhancer additives.
At present existing many organic acids and salt thereof are as foodstuff additive, report phosphoric acid salt is also early arranged owing to complex ability and pH shock absorption to metal ion, have and improve the effect of using sanitas and antioxidant in the food always, also developed a lot by the composite additive of above-mentioned substance.But present product and use-pattern all are one matter or mixture or mixing use, and lay particular emphasis on function in a certain respect more, and range of application has certain limitation.The moisture absorption is clamminess easily on the other hand, even agglomerating, and situation is particularly serious when having sorbate, poly-phosphate etc. to exist.Some organic acid also is difficult for dissolving, need be converted into an alkali metal salt etc.The present invention seeks to invention polyphosphate compound salt and manufacture method thereof to overcome above-mentioned shortcoming, development function is complete, applied range, additive easy to use.
It is oblique system that the present invention utilizes organic acid salt that food uses and phosphoric acid salt, the poly-phosphate overwhelming majority, and chemical bond is ionic close again, dexterously phosphoric acid salt, poly-phosphate and the organic acid salt of existing dispersion or partially mixed use, preferred group is synthesized double salt, thereby develops all remarkable enhanced polyphosphate compound salt of a series of biologies, physics, chemical property.The invention is characterized in that said polyphosphate compound salt is a monoclinic structure, and by acid phosphate and or poly-phosphate and organic acid salt form.
Known the first dissociation constant K between phosphoric acid as the organic acid dissociation constant K of foodstuff additive
1With the second dissociation constant K
2Between, the present invention has utilized this character, uses in the alkaline phosphate (for example Sodium phosphate dibasic) and organic acid; Utilize above-mentioned organic acid salt and the phosphoric acid salt (for example SODIUM PHOSPHATE, MONOBASIC) that generates simultaneously again, the chemical bond of the organic acid salt that perhaps adds and the phosphoric acid salt of acid or poly-phosphate is ionic close, crystalline structure belongs to oblique system, and the form that can make them pass through " salt bridge " or " hydrogen bond " forms double salt; Utilized again to belong to together between the monoclinic phosphoric acid salt, between phosphoric acid salt and the poly-phosphate, the ability that forms double salt has been arranged again, obtained a series of polyphosphate compound salts.
Polyphosphate compound salt series of the present invention, mol ratio is an acid phosphate in its theoretical composition: poly-phosphate: organic acid salt is 0～3: 0～2: 1, acid phosphate and poly-phosphate can not be 0 simultaneously, the experiment composition only is similar to this theory and forms.
Above-mentioned said acid phosphate, for example SODIUM PHOSPHATE, MONOBASIC, Sodium phosphate dibasic, said poly-phosphate comprise poly-orthophosphoric acid salt, polymetaphosphate and the pyrophosphate salt for example normal salt of tri-polyphosphate, hexametaphosphate, tetra-sodium and acid salt etc.Said organic acid salt comprises sorbate, benzoate, propionic salt, lactic acid salt, fumarate, ascorbate salt, tartrate, acetate, stearate etc.
Above-mentioned said acid phosphate, poly-phosphate and organic acid salt all comprise its sodium salt, sylvite, calcium salt etc., can be one or more materials wherein.
The manufacture method of polyphosphate compound salt series of the present invention is to choose above-mentioned one or more acid phosphate or poly-phosphate (wherein at least a moisture or add water) with ratio at first on demand, make it to be in and be dissolved in its crystal water or be dissolved in the state that adds water, add in proportion while stirring above-mentioned organic acid and or organic acid salt, also add poly-phosphate when needing, fully stir the back and place for some time, about 1～2h or longer does not have strict restriction, and purpose is to make it abundant diffusion.Then mixture is carried out compoundly 40～110 ℃ of heating, at room temperature pulverize, pack.Combined temp is different and different with needs compound material with used raw material.For same situation, compound degree depends on combined temp, and is generally comparatively suitable at 60～90 ℃.
Proportioning raw materials is to calculate according to reacting the theoretical molecular composition that need obtain product in the double salt manufacture method of the present invention.Raw materials used weight percent is that acid phosphate accounts for 0～90% in the raw material gross weight, and poly-phosphate accounts for 0～90%, and organic acid or its salt account for 10～70%, with to want compound double salt function different, and very big-difference is arranged with raw materials used.
The particle diameter of raw material is preferably in below the 1mm.The powder particle diameter of double salt is looked purposes and is different, generally between 1mm to 0.1mm.
Because the factor of chemical reaction influence is a lot, situation of the present invention is particularly special, so the molecular formula of actual product can only the approximation theory molecular formula.During polyphosphate compound salt of the present invention was formed, the mol ratio of phosphoric acid salt, poly-phosphate and organic acid salt allowed the little scope that departs from, and does not influence its performance.Can also contain crystal water in the double salt, depend on the temperature of compound tense.
The present invention arbitrarily is combined into a series of double salt to phosphoric acid salt, poly-phosphate and organic acid salt according to above-mentioned principle and method, both can concentrate one to various functions, can be of wide application according to unique certain the aspect function of different needs again.And can directly make the organic acid that is insoluble in water participate in generating double salt, and not only soluble in water but also non-hygroscopic deliquescence, the physicals when it is solid-state significantly is better than mixture.Its biology, chemical property then significantly strengthen when water-soluble.The function of several double salt of the present invention sees embodiment for details.Now by experiment biology, chemical property and the single-component additive of the polyphosphate compound salt of embodiment one, three compared.
(1) anti-microbial property: for aspergillus niger, bread mould, yeast saccharomyces cerevisiae, streptococcus aureus, 1g polyphosphate compound salt (contain Sorbic Acid or Sodium Benzoate is about 28%) is equivalent to 600～800mg Sorbic Acid or Sodium Benzoate.Polyphosphate compound salt also has anti-microbial property clearly for flavus, aspergillus versicolor, Mucor, withered mould, shadow yeast, intestinal bacteria in addition; (2) complexation of metal ions ability, 1g polyphosphate compound salt (containing Sodium hexametaphosphate 99 24% approximately) is to Ca
++, Hg
++Complex ability be equivalent to the 1.7gEOIA disodium, 1.5g Sodium hexametaphosphate 99 or tripoly phosphate sodium STPP; (3) antioxygenation; The oxygenizement of vitamins C and pigment and trace metal ion Cu
++, Fe
++, Zn
++Catalysis substantial connection is arranged, the 1g polyphosphate compound salt is equivalent to 1.5～2.0 Sodium hexametaphosphate 99s to these complexing of metal ion effects, and (the 1g polyphosphate compound salt is to Cu
++, Fe
++, Zn
++Complex ability respectively greater than 10.5mg, 6.0mg, 2.0mg).In addition, the 1g polyphosphate compound salt is equivalent to 3～27mg vitamins C to the antioxygenation of oxygenant; (4) quality-improving effect: polyphosphate compound salt of the present invention does not singly have anti-microbial effect, and has a pH regulator effect, prevent that meat from producing lactic acid, and can open protein molecular structure, water is combined in above the protein negatively charged ion and has retentiveness, thereby can keep the color of meat, improvement to organize, prevent that soluble protein runs off, and play freshening effect.
The a series of polyphosphate compound salts of the present invention can separately or be mixed for beverages such as fruit juice, carbonic acid, milk-acid bacteria, milk-product, bread, cake, biscuit and other rice product, fish, meat and goods thereof, can, salted vegetables, food and medicine and feeds such as seasonings are as antibiotic, mildew-resistant, anti-oxidant, quality-improving, pH buffering, dispersion, enhancer additives.
Embodiment one;
After 60g crystallization Sodium phosphate dibasic and 30g crystallization SODIUM PHOSPHATE, MONOBASIC are heated to and are dissolved in crystal water, be cooled to about 40 ℃, add 23g Sorbic Acid and the 20g vitreous state Sodium hexametaphosphate 99 of particle diameter while stirring less than 1mm, stir, allow it fully spread and a part neutralization reaction, to be cooledly after room temperature, be warmed up to 75 ℃ again, and stir frequently until block scatter and disappear reactant powdered till.Cool to room temperature also is ground into the polyphosphate compound salt of particle diameter less than 1mm.Its theoretical molecular formula NaPO
32NaH
2PO
4C
6H
7O
2Na.
Embodiment two:
Get three groups of each 100ml just squeeze out, without the orange juice of sterilization and disinfection, wherein one group of not doping, two groups of polyphosphate compound salts that add 100mg Sorbic Acid and 100mg embodiment one respectively in addition.After the 3d, white mould appears in not additivated orange juice, occurs yellow mouldly behind the 5d again, and its pH value drops to 2.7 from 3.5～3.7, and it is rotten to turn sour.And two groups of orange juices of interpolation additive still do not have considerable change behind the 20d.PH drops to that 3.0 left and right sides smells are pure and fresh not to have mould to occur behind the 30d.60d aftertaste souring (pH ≈ 2.8), color does not have considerable change.And in marmalade, add the polyphosphate compound salt of 0.2% embodiment one, does not still have behind the 180d and find the spoiled phenomenon that goes bad.
Embodiment three;
36g crystallization SODIUM PHOSPHATE, MONOBASIC and 30g crystallization Sodium phosphate dibasic are cooled to 43 ℃ after being heated to and being dissolved in crystal water, add the 33g Sodium Benzoate of particle diameter less than 1mm while stirring
*With 24g vitreous state Sodium hexametaphosphate 99, stir relief its fully spread, concurrent first portion complex reaction is warming up to 80～85 ℃ again and makes it fully compound after the room temperature to be cooled, until block is separated into powder.Cool to room temperature is ground into the particle diameter (polyphosphate compound salt of 1mm.Its theoretical molecular formula Na
2HPO
4NaPO
3NaH
2PO
4C
7H
6O
2Na.
*Can use the mixture of 20g Sodium Benzoate and 12g Sorbic Acid.
Embodiment four:
Get three groups of each 100ml just squeeze out, without the orange juice of sterilization and disinfection, wherein one group of not doping, two groups of polyphosphate compound salts that add 100mg Sodium Benzoate and 100mg embodiment three respectively in addition, its result is identical with embodiment two.
Embodiment five:
To salt down good black salted turnip, sauerkraut is cut into small pieces and immerses in the 0.2% embodiment tri-polyphosphate complex salt solution, takes out to put in the food bag and seals, and packs into the black salted turnip, the sauerkraut that did not soak complex salt solution and does the contrast experiment in the food bag.The black salted turnip, the sauerkraut that soaked double salt behind the 30d do not have the spoiled phenomenon of blackening, and contrast beginning variable color.Behind the 90d the former still color, smell and taste are complete, and the latter 40d variable color is smelly.
The salted vegetables of complex salt solution and variable color is not spoiled, variable color is spoiled again three groups of each 15g of contrast salted vegetables were soaked in taking-up, and chopping is immersed in the 100ml deionized water, gets 2ml solution after the 15b and is NO
2 -Test, NO in spoiled group of black salted turnip of variable color as a result
2 -Content high this 100 * 10
-6, NO in the not spoiled group black salted turnip of variable color
2 -Content is greater than 0.5 * 10
-6, and soaked the black salted turnip NO of double salt
2 -Content is less than 0.1 * 10
-6The mensuration of resampling behind the 24h, the result repeats.
Embodiment six:
60g crystallization Sodium phosphate dibasic is heated to and is dissolved in crystal water postcooling to 42 ℃, adds 25g Sorbic Acid and the 40g vitreous state Sodium hexametaphosphate 99 of particle diameter less than 1mm while stirring, and stirring allows it fully spread.Treat that being warmed up to 75 ℃ after cold every room temperature carries out complex reaction, stir and smash certainly shape thing, compound finishing when powdering does not lump.Cool to room temperature is ground into the polyphosphate compound salt of particle diameter less than 1mm, and its theoretical molecular formula is 2NaPO
3NaH
2PO
4C
6H
7O
2Na.Add 30 * 10 with 0.2% this double salt
-6NaNO
2Solution-treated meat product (sausage, bacon) time, singly can resist Clostridium botulinum and keep scarlet color, and NO
2 -Content is 2 * 10
-6Below, singly use NaNO
2And NaNO
3Dye and during anti-Clostridium botulinum NO
2 -Content is 20 * 10
-6More than.
Embodiment seven:
The double salt of getting 2g embodiment six adds the double salt of 2g embodiment three, adds 0.2g xitix, 3ml glycerine and 5ml ginger juice again, and water is towards rare 100ml that arrives, fresh pork soaks 5min therein, take out to hang and do, be placed under 35 ℃ of environment and do fresh-keeping test, with the pork contrast of not soaking fresh-keeping liquid.The result shows that the pork 8h that did not soak fresh-keeping liquid begins to occur peculiar smell, and stink appears in 10h, and soaked look in the pork 22h of fresh-keeping liquid, flavor does not change, and 23h begins to occur peculiar smell, 24h begins to occur stink.
Embodiment eight:
65g contains crystal water monocalcium phosphate and 45g calcium propionate (it is following that particle diameter is 1mm), and uniform mixing adds less water and makes it become to stick with paste and receive, be warmed up to 85 ℃ compound.Compound finishing in the time being broken into powder.The theoretical molecular formula Ca of gained polyphosphate compound salt (H
2PO
4) Ca (C
3H
5O
2)
2
Embodiment nine:
For the polyphosphate compound salt of comparing embodiment eight effect, be easy to chopping tomato mouldy, fermentation and do experiment as substratum with nutritious as the bread mould inhibitor.In three groups of 60～80g tomatos, add the polyphosphate compound salt of 0.25% calcium propionate, 0.25% embodiment eight respectively and do not add any additives.2.5d doping afterwards white mould occurs for one group, occurs black mould and a large amount of Mucor behind the 5d.And begin fermentation after adding one group of 3d of calcium propionate, and do not find mould behind the 9d as yet, abnormal conditions do not appear and add one group of 5d of double salt, begin fermentation behind the 5d, 10d does not see mould.This shows that the both can only mould fungus inhibition and can not suppress fermentation, can be used as bread additive.For this reason, in dough, add polyphosphate compound salt and the yeast of 0.25% calcium propionate and an amount of yeast, 0.25% embodiment eight respectively and singly add yeast, found that the three can ferment, 2.5d after singly add yeast and a mould occurs for, all begin to occur mould (experiment condition is 30 ± 2 ℃ of temperature, and humidity is more than 90%) and add the calcium propionate group behind the 4d and add the double salt group.In two groups of adding additive, the one group of bread made that adds double salt is more loose.Prove that this double salt is better than the calcium propionate of existing use as bread, cake mould inhibitor effect.In addition, because its Ca: P is the preferable ratio of calcium and phosphorus of human body than near 1.4, help the absorption of calcium.And calculate by 0.25% addition, the content of Ca meets one day amount of replenishing the calcium of United Nations's health organization new regulation up to 450mg in the 1Kg bread.This double salt also can be used as feedstuff mildew and phosphorus calcium additive.
Embodiment ten:
Get 65g calcium lactate and 40g secondary calcium phosphate (granularity is all below 1mm), add and ask on a small quantity and uniform mixing post-heating to 80 ℃, stir frequently, promptly obtaining theoretical molecular formula is CaHPO
4H
2OCa (C
3H
5O
3)
2Polyphosphate compound salt.Be ground into the following granularity of particle diameter 0.1mm, promptly can be used as the calsium supplement of biscuit, milk-product, also can be used as the Creta Preparata of bread, cake and other meter, flour products, and, more help the absorption of calcium than calcium lactate because best ratio of calcium and phosphorus (1.7) is arranged.
Claims (9)
1, polyphosphate compound salt is characterized in that it being the compound of monoclinic structure, is by heating, by acid phosphate and or poly-phosphate and the compound double salt of forming of organic acid salt.
2, polyphosphate compound salt according to claim 1, it is characterized in that mol ratio is an acid phosphate in its composition: poly-phosphate: organic acid salt is 0～3: 0～2: 1, acid phosphate and poly-phosphate can not be 0 simultaneously, said acid phosphate is one or more in the acid phosphate, said poly-phosphate is poly-orthophosphoric acid salt, polymetaphosphate, the normal salt of tetra-sodium and in the acid salt one or more, said organic acid salt is a sorbate, benzoate, propionic salt, lactic acid salt, fumarate, ascorbate salt, tartrate, acetate, in the stearate one or more.
3, according to the described polyphosphate compound salt of claim 1, it is characterized in that mol ratio is an acid phosphate in its composition: poly-phosphate: organic acid salt is 2: 1: 1, described acid phosphate is SODIUM PHOSPHATE, MONOBASIC or dipotassium hydrogen phosphate, described poly-phosphate is a Sodium hexametaphosphate 99, and described organic acid salt is potassium sorbate or sodium sorbate.
4, polyphosphate compound salt according to claim 1, it is characterized in that mol ratio is an acid phosphate in its composition: poly-phosphate: organic acid salt is 2: 1: 1, described acid phosphate is SODIUM PHOSPHATE, MONOBASIC or potassium primary phosphate and Sodium phosphate dibasic or dipotassium hydrogen phosphate, described poly-phosphate is a Sodium hexametaphosphate 99, and described organic acid salt is potassium benzoate or Sodium Benzoate.
5, polyphosphate compound salt according to claim 1, it is characterized in that mol ratio is an acid phosphate in its composition: poly-phosphate: organic acid salt is 1: 2: 1, described acid phosphate is SODIUM PHOSPHATE, MONOBASIC or potassium primary phosphate, described poly-phosphate is a Sodium hexametaphosphate 99, and described organic acid salt is sodium sorbate and or sodium ascorbate.
6, polyphosphate compound salt according to claim 1, it is characterized in that mol ratio is an acid phosphate in its composition: poly-phosphate: organic acid salt is 1: 0: 1, and described acid phosphate is a monocalcium phosphate, and described organic acid salt is a calcium propionate.
7, polyphosphate compound salt according to claim 1, it is characterized in that mol ratio is an acid phosphate in its composition: poly-phosphate: organic acid salt is 1: 0: 1, and described acid phosphate is a secondary calcium phosphate, and described organic acid salt is a calcium lactate.
8, make the method for polyphosphate compound salt, it is characterized in that making be dissolved in its crystal water be dissolved in the acid phosphate that adds under the water state or poly-phosphate and organic acid and or organic acid salt, also add poly-phosphate when needing, uniform mixing, treat after the fully diffusion, its mixture is compound 40～110 ℃ of heating.
9, polyphosphate compound salt according to claim 1 is characterized in that it can also contain crystal water in forming.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN93109096A CN1046119C (en) | 1993-07-22 | 1993-07-22 | Polyphosphate compound salt series |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN93109096A CN1046119C (en) | 1993-07-22 | 1993-07-22 | Polyphosphate compound salt series |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1097576A CN1097576A (en) | 1995-01-25 |
| CN1046119C true CN1046119C (en) | 1999-11-03 |
Family
ID=4987452
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN93109096A Expired - Fee Related CN1046119C (en) | 1993-07-22 | 1993-07-22 | Polyphosphate compound salt series |
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| Country | Link |
|---|---|
| CN (1) | CN1046119C (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1074659C (en) * | 1995-11-06 | 2001-11-14 | 张毅 | Technique for processing natural nutritious flavouring salt |
| WO2001006862A1 (en) * | 1999-07-22 | 2001-02-01 | Astaris Llc | Antimicrobial polyphosphates in food processing |
| CN100407949C (en) * | 2001-02-19 | 2008-08-06 | 好侍食品株式会社 | Method for processed food preparation and retort food |
| AR057882A1 (en) | 2005-11-09 | 2007-12-26 | Novartis Ag | DOUBLE ACTION COMPOUNDS OF ANGIOTENSIN RECEPTOR BLOCKERS AND NEUTRAL ENDOPEPTIDASE INHIBITORS |
| CN101999595B (en) * | 2010-11-11 | 2012-11-07 | 东莞市圣心食品有限公司 | Glutinous rice product and preparation method thereof |
| CN105495283B (en) * | 2015-12-01 | 2019-02-05 | 天津科技大学 | A kind of wet Flour product modifying agent of life and application |
| CN106418432A (en) * | 2016-09-29 | 2017-02-22 | 益盐堂（应城）健康盐制盐有限公司 | Novel edible salt |
| CN106900835A (en) * | 2017-02-28 | 2017-06-30 | 浙江海洋大学 | A kind of freezing shrimp meat protective agent and plating water glaze method |
| CN109134240B (en) * | 2018-08-29 | 2021-06-08 | 长沙兴嘉生物工程股份有限公司 | Calcium fumarate phosphate and preparation method and application thereof |
| CN110893169B (en) * | 2019-12-23 | 2023-05-02 | 广州微肽生物科技有限公司 | Whitening moisturizing mask and preparation method thereof |
| CN115159488B (en) * | 2022-07-22 | 2023-06-30 | 承德莹科精细化工股份有限公司 | Preparation method of high water-solubility glassy sodium metaphosphate |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5716682A (en) * | 1980-07-03 | 1982-01-28 | Kibun Kk | Food preservative |
| US4670277A (en) * | 1986-01-16 | 1987-06-02 | Stauffer Chemical Company | Increased shelf-life for refrigerated fish |
-
1993
- 1993-07-22 CN CN93109096A patent/CN1046119C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5716682A (en) * | 1980-07-03 | 1982-01-28 | Kibun Kk | Food preservative |
| US4670277A (en) * | 1986-01-16 | 1987-06-02 | Stauffer Chemical Company | Increased shelf-life for refrigerated fish |
Non-Patent Citations (1)
| Title |
|---|
| 《化工辞典》第三版 1992.7.1 化学工业出版社 * |
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| CN1097576A (en) | 1995-01-25 |
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