CN102173387A - Solid stable chlorite of phosphate buffer system and preparation method thereof - Google Patents

Solid stable chlorite of phosphate buffer system and preparation method thereof Download PDF

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Publication number
CN102173387A
CN102173387A CN 201110041778 CN201110041778A CN102173387A CN 102173387 A CN102173387 A CN 102173387A CN 201110041778 CN201110041778 CN 201110041778 CN 201110041778 A CN201110041778 A CN 201110041778A CN 102173387 A CN102173387 A CN 102173387A
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China
Prior art keywords
chlorite
crystal water
phosphate
pickering
weakly alkaline
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CN 201110041778
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Chinese (zh)
Inventor
徐福乐
翁莹冰
林秀
张美娟
翁仁发
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CHAODA MODERN AGRICULTURE DEVELOPMENT Co Ltd FUZHOU
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CHAODA MODERN AGRICULTURE DEVELOPMENT Co Ltd FUZHOU
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Priority to CN 201110041778 priority Critical patent/CN102173387A/en
Publication of CN102173387A publication Critical patent/CN102173387A/en
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Abstract

The invention relates to a solid stable chlorite of a phosphate buffer system and a preparation method thereof. The solid stable chlorite provided by the invention is characterized in that the solid stable chlorite comprises a weakly-alkaline phosphate and a chlorite, the phosphate is weakly-alkaline crystal water-containing disodium hydrogen phosphate with a pH value of 9.0 to 9.4 or weakly-alkaline crystal water-containing dipotassium hydrogen phosphate with a pH value of 8.9 to 9.3. In the preparation method provided by the invention, a solid stable chlorite is prepared from a weakly-alkaline phosphate and a chlorite by mixing, co-dissolution and re-crystallization. Specifically, the method comprises the following steps: firstly dissolving a crystal water-containing divalent salt of phosphoric acid in autologous crystal water at a temperature not less than 40 DEG C to form a supersaturated phosphate solution; and then mixing and co-dissolving the supersaturated phosphate solution with sodium chlorite crystals or potassium chlorite crystals at a phosphate-to-chlorite ratio of 1:(1-9), followed by re-crystallization, to obtain the solid stable chlorite.

Description

A kind of Pickering chlorite and manufacture method thereof of phosphate buffer
Technical field
The present invention relates to a kind of chloritic manufacture method of Pickering of phosphate buffer, relate to particularly that the phosphoric acid hydrogen disalt that a kind of usefulness contains crystal water mixes with chlorite, technology molten, recrystallization is made solid-state stable chloritic method altogether.
Background technology
The dioxide peroxide industry has been internationally recognized green sunrise industry, and the dioxide peroxide product also is universally acknowledged latest generation safety, efficient, wide spectrum, disinfection sanitizer, reodorant, mould inhibitor, food preservative and association with pulp bleaching agent fast.Be used widely at aspects such as sterilization and disinfection, anti-corrosive fresh-keeping, deodorizing, industrial bleaching and environmental pollution improvements, the Application Areas of dioxide peroxide has been penetrated into the every aspect of industrial production, agriculture production and people's daily life, is showing boundless prospect.Chlorite is the donor that generates dioxide peroxide, is the main raw material of preparation dioxide peroxide, utilizes the acidifying chlorite can obtain the dioxide peroxide that purity is good, yield is high, by product is few easily.
That the acidifying Textone is directly fresh-keeping as food sterilization abroad, and obtain good effect, FDA (Food and Drug Adminstration) (FDA) approved as the secondary foodstuff additive, is used for the anti-microbial agents of finwhale and Crustacean with the acidifying Textone.
But, the Textone less stable, particularly chlorite has deliquescence, and chlorite crystal behind the deliquescence and chlorite solution soluble in water are unstable to light, heat, acid under normal temperature condition, easily decompose.This makes chloritic application be subjected to certain restriction, the chlorite of necessary research and development stability, particularly can keep when being in a liquid state also keeping stable to light, heat, stable chlorite, the acidifying chlorite that after its acidifying, generates, the dioxide peroxide of acid when chlorite is soluble in water, this stable chlorite composition can be expanded chloritic Application Areas greatly.
The stability sodium chlorite solution is a kind of with Textone and buffering solution and the formulated by a certain percentage stabilising system of other compositions.The stability sodium chlorite solution can increase substantially its stability to light, heat, acid, prepare dioxide peroxide by stable sodium chlorite solution's acidifying, also simplified the program of dioxide peroxide preparation greatly, make the operation of on-site preparation dioxide peroxide become easier, make the practicality of dioxide peroxide preparation become stronger, security is higher, also has more promotional value.But stable sodium chlorite solution store, extremely inconvenient in the transportation, and limited its applying aborning.
At home to the existing more report of stable sodium chlorite solution's research, as Guizhou University's master thesis " research of stable sodium chlorite solution's research and biological antibiotic effect thereof ", " applied research of stable sodium chlorite solution on food fresh keeping ".Reported stable chlorite solution's technology of preparing and the application on food fresh keeping thereof, what relate to is stable chloritic solution.
State such as the U.S., Switzerland has also applied for a collection of patent of invention of using stable chlorite treatment disease that relates in China;
Switzerland OXO Chemie AG application, application number is the patent of invention of 98811885.8 " using chemically stable chlorite solution to be used to suppress the immunoreactive purposes of antigen-specific ";
Switzerland OXO Chemie AG application, application number is the patent of invention of 00814063.4 " chemically-stabilized chlorite solutions that is used for the treatment of cancer and other diseases ";
US P﹠G Company application, application number is the patent of invention of 02817903.x " stable comprise chloritic oral care composition ";
The California, USA College application, application number is the patent of invention of 200580003723.6 " chlorite treatment neurodegenerative disease ".
Above-mentioned patent of invention discloses the application of stable chlorite solution in the treatment disease, and what relate to is stable chloritic solution.
The stable chloritic report that academic paper that summary has extremely been published at present at home and patent documentation all only relate to liquid, do not see the report that relates to solid stability Textone or potassium chlorite, do not find chlorite is mixed, is dissolved in altogether with the phosphoric acid salt that contains crystal water among the phosphate crystal water yet, make the chloritic report of Pickering of phosphate buffer again with the method for recrystallization.
Summary of the invention
One of purpose of the present invention provides a kind of Pickering chlorite of phosphate buffer.
Two of purpose of the present invention provides that the phosphoric acid hydrogen disalt that a kind of usefulness contains crystal water mixes with chlorite, molten, recrystallization technology is made the chloritic method of Pickering altogether.
The object of the present invention is achieved like this: a kind of Pickering chlorite of phosphate buffer is characterized in that being made up of weakly alkaline phosphoric acid salt and chlorite; Described phosphoric acid salt is that the pH value is that 9.0~9.4 weakly alkaline Sodium phosphate dibasic that contains crystal water or pH value are 8.9~9.3 the weakly alkaline dipotassium hydrogen phosphate that contains crystal water; Described chlorite is a Textone, or potassium chlorite; The chloritic manufacture method of a kind of Pickering of phosphate buffer is characterized in that adopting weakly alkaline phosphoric acid salt to mix with chlorite, altogether molten, recrystallization makes the Pickering chlorite; Its concrete steps are that the phosphoric acid hydrogen disalt that will contain crystal water earlier is dissolved in self crystal water and forms the supersaturation phosphate solution under 〉=40 ℃ of temperature, again with Textone crystal or potassium chlorite crystal by phosphoric acid salt: chlorite=1: 1~9 ratio prescriptions mix with it, common molten, recrystallization makes the Pickering chlorite; The described phosphoric acid hydrogen disalt that contains crystal water is the Sodium phosphate dibasic that contains 12 crystal water, or contains the dipotassium hydrogen phosphate of 3 crystal water, contains the Sodium phosphate dibasic (Na of 12 crystal water 2HPO12H 2O) in the time of 34.6 ℃~35.1 ℃, be dissolved in self crystal water, form pH and be 9.0~9.4 weakly alkaline supersaturation disodium phosphate soln, contain the dipotassium hydrogen phosphate (K of 3 crystal water 2HPO3H 2O) in the time of 〉=40 ℃, be dissolved in self crystal water, formation pH is 8.9~9.3 weakly alkaline supersaturation dipotassium hydrogen phosphate solution, weakly alkaline Sodium phosphate dibasic and weakly alkaline dipotassium hydrogen phosphate all are chloritic stablizer and pH system buffer, also are the molten carrier and the chlorine dioxide slow-release carriers deposited of the dioxide peroxide that generates after the stable chlorite acidifying; Described method is applied to the dipotassium hydrogen phosphate that the agricultural field can preferably contain 3 crystal water and makes the Pickering chlorite with preferred potassium chlorite compatibility; Be applied to the Sodium phosphate dibasic that other field can preferably contain 12 crystal water and make the Pickering chlorite with preferred Textone compatibility.
Embodiment
The invention will be further described for following examples, but be not limitation of the present invention.
The Pickering chlorite of phosphate buffer of the present invention, it is characterized in that adopting the chlorite xln to mix, be dissolved in altogether in the phosphate crystal water, make the Pickering chlorite of the crystalline state of phosphate buffer again with recrystallization technology with phosphoric acid hydrogen two salt crystals that contain crystal water.
Described chlorite is Textone or potassium chlorite, and Textone, potassium chlorite are the oxygenatedchemicals of chlorine soluble in water, and the stable chlorite of phosphate buffer of the present invention is the dioxide peroxide donor as preparation dioxide peroxide preparation.
The dioxide peroxide preparation that the solid chlorite of phosphate buffer of the present invention is made, if be applied to agricultural, field of forestry, preferred potassium chlorite is applied to the preferred inexpensive Textone in other field as the dioxide peroxide donor as the dioxide peroxide donor.
The described phosphoric acid hydrogen disalt that contains crystal water is the Sodium phosphate dibasic that contains crystal water, or contains the dipotassium hydrogen phosphate of crystal water.It is characterized in that containing the Sodium phosphate dibasic (Na of 12 crystal water 2HPO12H 2O) in the time of 34.6 ℃~35.1 ℃, be dissolved in self crystal water, form pH and be 9.0~9.4 weakly alkaline supersaturation disodium phosphate soln.Dipotassium hydrogen phosphate (the K that contains 3 crystal water 2HPO3H 2O) in the time of 〉=40 ℃, be dissolved in self crystal water, formation pH is 8.9~9.3 weakly alkaline supersaturation dipotassium hydrogen phosphate solution, weakly alkaline Sodium phosphate dibasic and weakly alkaline dipotassium hydrogen phosphate all are chloritic stablizer and pH system buffer, also are the molten carrier and the chlorine dioxide slow-release carriers deposited of the dioxide peroxide that generates after the stable chlorite acidifying.
The dioxide peroxide preparation that the solid chlorite of phosphate buffer of the present invention is made, if be applied to agricultural and field of forestry, outside the preferred potassium chlorite of dioxide peroxide donor, water-bearing phosphate salt should preferred 3 crystal water dipotassium hydrogen phosphate, be applied to other field can preferred 12 crystal water Sodium phosphate dibasic.
Described phosphoric acid hydrogen disalt and the chloritic formula rate that contains crystal water is 1: 1~9, and obtained Pickering chlorite contains chlorite can reach 50%~90%.The stability chlorite solution generally contains chlorite 10%~15%, and moisture and other compositions are up to 85%~90%.And the obtained Pickering chlorite of the present invention contains chlorite up to 50%~90%, be higher than the contained chlorite of stable chlorous acid solution far away, and solid stability chlorite stability is better, security is higher, avoided the storage water a large amount of in storage and the transportation, therefore can save a large amount of storages and transportation cost with transportation.
Described employing chlorite and phosphoric acid hydrogen two salt crystals that contain crystal water, under suitable temperature condition, mix, be dissolved in the crystal water of phosphoric acid hydrogen disalt altogether, form oversaturated chlorite-phosphoric acid hydrogen two mixed salt solutions, recrystallization makes the Pickering chlorite of the crystalline state of phosphate buffer under≤30 ℃ temperature then, and chlorite is mixed, is wrapped among the weakly alkaline phosphate buffer.
The solid chlorite of phosphate buffer of the present invention, its principal character is that to be to utilize the phosphoric acid hydrogen disalt that contains crystal water be that pH is about 9.0 weakly alkaline pH system buffer, its xln is under suitable temperature condition, in the meeting self-dissolving crystal water, form oversaturated weakly alkaline phosphate solution, after temperature descends, the physical phenomenon separated out of recrystallization again.As the Sodium phosphate dibasic of 12 water 34.6 ℃~35.1 ℃ the time from being dissolved in the crystal water, oneself is dissolved in the crystal water 3 water dipotassium hydrogen phosphates in the time of 39.0 ℃~40.0 ℃, recrystallization is separated out again in the time of≤30 ℃.
Utilize simultaneously chlorite to have the characteristics of very strong solubleness again in water, 5 ℃ the time, its solubleness is 34% as Textone, and in the time of 30 ℃, its solubleness is 46%, and in the time of 60 ℃, its solubleness is 55%.Therefore adopt the chlorite xln is mixed, is dissolved in altogether in the phosphate crystal water with phosphoric acid hydrogen two salt crystals that contain crystal water, make the Pickering chlorite of weakly alkaline phosphate buffer again with recrystallization technology.
Embodiment one
12 water phosphoric acid hydrogen two of the Textone xln of weight ratio 90% and weight ratio 10% are received the xln proportioning, earlier 12 water Sodium phosphate dibasics are placed the stainless steel jacketed kettle, the water bath method rises to about 40 ℃ the temperature in the stainless steel jacketed kettle, 12 water Sodium phosphate dibasics are dissolved in the crystal water of self, the Textone xln that adds proportioning weight then, and constantly mix, the part Textone also is dissolved in the weakly alkaline Sodium phosphate dibasic supersaturated solution, also fully mixes with weakly alkaline Sodium phosphate dibasic with undissolved Textone.At its xln surface parcel weakly alkaline phosphoric acid salt of one deck or be mixed among the weakly alkaline Sodium phosphate dibasic, promptly make the Pickering Textone of weakly alkaline phosphate buffer.
Embodiment two
With the potassium chlorite xln of weight ratio 60% and 3 water dipotassium hydrogen phosphate xln proportionings of weight ratio 40%, earlier 3 water dipotassium hydrogen phosphates are placed the stainless steel jacketed kettle, the water bath method rises to about 45 ℃ the temperature in the stainless steel jacketed kettle, 3 water dipotassium hydrogen phosphates are dissolved in the crystal water of self, the potassium chlorite xln that adds proportioning weight then, and constantly mix, the part potassium chlorite also is dissolved in the weakly alkaline dipotassium hydrogen phosphate supersaturated solution, also fully mixes with weakly alkaline dipotassium hydrogen phosphate with undissolved potassium chlorite.At its xln surface parcel weakly alkaline phosphoric acid salt of one deck or be mixed among the weakly alkaline dipotassium hydrogen phosphate, promptly make the Pickering potassium chlorite of weakly alkaline phosphate buffer.
Can be according to the prescription of chlorite with phosphoric acid hydrogen disalt Different Weight ratio, the manufacture method of pressing the foregoing description one, embodiment two can make the Pickering chlorite that contains chlorite 50%~90%.
The present invention adopts the common recrystallization technology of twin crystal to make the chloritic method of Pickering, and whole process flow is being carried out below 50 ℃, is a kind of environmental-protecting process that does not have waste gas, no waste liquid, no waste residue, also is the novel process of a kind of less energy-consumption, low-carbon (LC) simultaneously.
The Pickering chlorite of phosphate buffer of the present invention can be developed to the dioxide peroxide preparation of various uses, is applied to fields such as sterilization and disinfection, anti-corrosive fresh-keeping, deodorizing, industrial bleaching and environmental pollution improvement.
With the Pickering chlorite of phosphate buffer, when being developed to the dioxide peroxide preparation of phosphate buffer, can develop phosphoric acid potash fertilizer and soil disinfectant especially with sterilization and disinfestation function.
If with the phosphoric acid salt of foodstuff additive as the chloritic buffer reagent of Pickering to the food safety height, so the dioxide peroxide preparation of phosphate buffer can be developed to fruits and vegetables coating antistaling agent, fruits and vegetables dipping fresh-keeping liquid and raw materials of food processing sterilization and disinfection pretreating agent etc.

Claims (5)

1. the Pickering chlorite of a phosphate buffer is characterized in that being made up of weakly alkaline phosphoric acid salt and chlorite; Described phosphoric acid salt is that the pH value is that 9.0~9.4 weakly alkaline Sodium phosphate dibasic that contains crystal water or pH value are 8.9~9.3 the weakly alkaline dipotassium hydrogen phosphate that contains crystal water.
2. the Pickering chlorite of a kind of phosphate buffer according to claim 1 is characterized in that described chlorite is a Textone, or potassium chlorite.
3. the chloritic manufacture method of the Pickering of a phosphate buffer is characterized in that adopting weakly alkaline phosphoric acid salt to mix with chlorite, molten, recrystallization makes the Pickering chlorite altogether; Its concrete steps are that the phosphoric acid hydrogen disalt that will contain crystal water earlier is dissolved in self crystal water and forms the supersaturation phosphate solution under 〉=40 ℃ of temperature, again with Textone crystal or potassium chlorite crystal by phosphoric acid salt: chlorite=1: 1~9 ratio prescriptions mix with it, common molten, recrystallization makes the Pickering chlorite.
4. the chloritic manufacture method of the Pickering of a kind of phosphate buffer according to claim 3, it is characterized in that the described phosphoric acid hydrogen disalt that contains crystal water is the Sodium phosphate dibasic that contains 12 crystal water, or contain the dipotassium hydrogen phosphate of 3 crystal water, contain the Sodium phosphate dibasic (Na of 12 crystal water 2HPO12H 2O) in the time of 34.6 ℃~35.1 ℃, be dissolved in self crystal water, form pH and be 9.0~9.4 weakly alkaline supersaturation disodium phosphate soln, contain the dipotassium hydrogen phosphate (K of 3 crystal water 2HPO3H 2O) in the time of 〉=40 ℃, be dissolved in self crystal water, formation pH is 8.9~9.3 weakly alkaline supersaturation dipotassium hydrogen phosphate solution, weakly alkaline Sodium phosphate dibasic and weakly alkaline dipotassium hydrogen phosphate all are chloritic stablizer and pH system buffer, also are the molten carrier and the chlorine dioxide slow-release carriers deposited of the dioxide peroxide that generates after the stable chlorite acidifying.
5. the chloritic manufacture method of the Pickering of a kind of phosphate buffer according to claim 3 is characterized in that described method is applied to the dipotassium hydrogen phosphate that the agricultural field can preferably contain 3 crystal water and makes the Pickering chlorite with preferred potassium chlorite compatibility; Be applied to the Sodium phosphate dibasic that other field can preferably contain 12 crystal water and make the Pickering chlorite with preferred Textone compatibility.
CN 201110041778 2011-02-18 2011-02-18 Solid stable chlorite of phosphate buffer system and preparation method thereof Pending CN102173387A (en)

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4104190A (en) * 1976-03-23 1978-08-01 Minnesota Mining And Manufacturing Company Generation of chlorine dioxide for disinfection and sterilization

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4104190A (en) * 1976-03-23 1978-08-01 Minnesota Mining And Manufacturing Company Generation of chlorine dioxide for disinfection and sterilization

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