CN104692347A - Synthesis method of carbonate hydroxyapatite with reducing function - Google Patents
Synthesis method of carbonate hydroxyapatite with reducing function Download PDFInfo
- Publication number
- CN104692347A CN104692347A CN201510046029.8A CN201510046029A CN104692347A CN 104692347 A CN104692347 A CN 104692347A CN 201510046029 A CN201510046029 A CN 201510046029A CN 104692347 A CN104692347 A CN 104692347A
- Authority
- CN
- China
- Prior art keywords
- calcium
- carbonate
- hydroxyapatite
- phosphorus
- source
- 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.)
- Pending
Links
Landscapes
- Coloring Foods And Improving Nutritive Qualities (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention relates to a synthesis method of carbonate hydroxyapatite with a reducing function. With biological calcium carbonate in biological mineral as a calcium source and a phosphorus-containing material with a phosphorous acid group as a phosphorous source, the synthesis method comprises the following two steps: synthesizing composite calcium hydrophosphate-calcium phosphite by a wet grinding method: proportioning a pretreated biological mineral calcium source and a phosphorus-containing material with a phosphorous acid group according to a calcium-phosphorus molar ratio of 1:1, and performing a grinding reaction in a wet condition to generate the composite calcium hydrophosphate-calcium phosphite; and (II) synthesizing the carbonate hydroxyapatite with a reducing function by a mechanochemical method: proportioning the composite calcium hydrophosphate-calcium phosphite synthesized in the synthesis step (I) and the pretreated biological mineral calcium source according to a calcium-phosphorus molar ratio of 5:3; and converting to generate the carbonate hydroxyapatite with a reducing function under a high-speed grinding condition by a mechanochemical method. The carbonate hydroxyapatite with a reducing function, synthesized by the method provided by the invention, can be used as a heavy metal-polluted soil remediation agent and a water purifying agent.
Description
Technical field
The invention belongs to the manufacturing technology of hydroxyapatite, be specifically related to a kind of synthetic method with the carbonate hydroxyapatite of reductibility function.
Background technology
It is healthy that China's heavy metal pollution of soil situation has had a strong impact on farmland quality, food safety and even human body.According to incomplete investigation, the contaminated cultivated area of China has reached 2,000 ten thousand hm
2, produce about 1,200 ten thousand jin, the grain by heavy metal contamination every year, the financial loss caused is more than 2,500,000,000 dollars.
Tealeaves is the important cash crop of China, and scholarly forecast 21 century beverage will be the tea drink epoch.But tealeaves heavy metal pollution problem also happens occasionally, the metal such as copper (Cu), plumbous (Pb), cadmium (Cd), chromium (Cr), arsenic (As), mercury (Hg) all likely forms pollution to tealeaves.It is reported, extra-strong tea, green tea, Leaf of Assam Tea etc. that some places of nearest south China produce are detected rare earth element and exceed standard and reach 8 times.
Above-mentioned situation shows, administers heavy-metal contaminated soil extremely urgent.The current reparation for heavy-metal contaminated soil mainly comprises the restorative procedure of physics, chemistry and biological three major types, and often kind of restorative procedure has relative merits.Wherein chemical repair method because of its have that the feature such as to be easy to implement is employed more.
Chemical repair method is mainly chemistry and washes pouring, chemical passivation and redox etc., wherein chemical passivation method because of the advantages such as tool is cheap, effective be one of method generally used both at home and abroad.
Conventional chemical inactivators mainly contains clay pit, phosphoric acid salt material, phosphate fertilizer class material, silicon element class material, wherein phosphorated material because of its non-toxic and safe, can not secondary pollution be caused, again can to soil supplement that phosphoric is employed the most extensive.
Inorganic phosphor-contained material have adsorb with heavy metal ion, coordination, the series reaction such as precipitation, change the occurrence patterns of heavy metal, significantly reduce its biological effectiveness and transport property.Therefore utilize the phosphorated materials such as phosphoric acid, soluble phosphate, insoluble phosphorus acid calcium salt, heavy metal contaminated soil fixation in situ is administered, and is a noticeable branch field during Heavy-metal Polluted Environment is repaired.
Patent of invention " a kind of method of restoring heavy metal pollution of vegetable field soil with in-situ passivation " (number of patent application: 200910070713.4) disclose the heavy metal passivation restoring material with sepiolite and monocalcium phosphate composition.
Patent of invention " utilizing the method for nm amorphous calcium phosphate fixation in situ soil heavy metal ion " (number of patent application: 201010523379.6) disclose and directly apply nm amorphous calcium phosphate in-situ immobilization in the soil of heavy metal contamination.
Patent of invention " a kind of preparation method reducing the organic/inorganic composite passivant of farming land heavy metal in soil Cd activity " (number of patent application: the organic/inorganic composite passivant 201410097940.7) disclosing the heavy metal in soil Cd activity be made up of rape stalk, peat, wilkinite, phosphoric acid salt (potassium primary phosphate).
Patent of invention " technology of the various heavy such as a kind of dystopy passivation Cadmium in Soil, lead, chromium " (number of patent application: 201410097947.9) disclose by bio-matrix (organic matter+humic acids), active sludge is planted in corruption, phosphoric acid salt (potassium primary phosphate) forms cadmium, lead, chromium heavy metal deactivator.
But, phosphoric acid, soluble phosphate material easily run off, also body eutrophication can be caused, and the fixed efficiency of insoluble phosphorus acid calcium salt to heavy metal in soil ion is on the low side, amount of application must be strengthened, rehabilitation cost can be caused again too high, especially its Cost Problems of mass control heavy metal pollution of soil is given prominence to, limit the application in fixed and repaired heavy metal pollution of soil in position.
Hydroxyapatite (Ca
10(PO
4)
6(OH)
2, HAP), there is because of the crystalline structure of its uniqueness good biocompatibility, biological activity and ion exchangeable.Because hydroxyapatite has very strong surface adsorption property, by surface adsorption and ion-exchange, by heavy metal ion adsorbed, be fixed on hydroxyapatite surface.Meanwhile, hydroxyapatite also has good Harmony, can not cause secondary pollution, is a kind of generally acknowledged novel environmental functional material.
Patent of invention " a kind of preparation method of efficient heavy ion adsorbent carbonate hydroxyapatite " (number of patent application: the preparation method 200610031700.2) disclosing good, the with low cost new and effective heavy metal ion adsorbed carbonate hydroxyapatite of a kind of absorptive character.
Patent of invention " the nano material renovation agent of restoration of soil polluted by heavy metal and restorative procedure thereof " (number of patent application: 201310141962.4) disclose by particle diameter 27nm, purity be 98% nanometer hydroxyapatite (nHA), particle diameter be the heavy-metal contaminated soil nano material renovation agent that 10nm presents spherical nano zero valence iron (nZVI) particle and oleic acid composition.
Patent of invention " for administering Multifunctional combined cooker agent and the Cadmium Pollution in Soils restorative procedure of cadmium pollution soil " (number of patent application: the method 201310574410.2) disclosing the Cadmium Pollution in Soils passivator be made up of red mud, hydroxyapatite, wilkinite, zeolite or rhombspar and Cadmium Pollution in Soils reparation.
Patent of invention " compound heavy metal contaminated soil conditioner and application and application process " thereof (number of patent application: 201410077079.2) disclose the compound heavy metal contaminated soil conditioner be made up of plant ash, fused(calcium magnesium)phosphate, unslaked lime, zeolite, hydroxyapatite, fertilizer etc.
Research shows, the hydroxyapatite synthesized by the calcium source containing carbonate, is a kind of hydroxyapatite containing structural carbonate, is referred to as carbonate hydroxyapatite.Owing to being rich in CO
3 2-, its degree of crystallinity is poor, and particle diameter is little, and specific surface area and surfactivity greatly, have the absorption property of better biocompatibility and heavy metal ion.
Research also shows, containing the hydroxyapatite of structural carbonate to heavy metals removal better effects if such as Pb, Cd, Hg, and its reaction product stability is high.
In shell, eggshell, cuttlebone, coral, biological calcium carbonate purity is very high, is a kind of calcium source containing carbonate of high-quality.With the calcium carbonate in shell, eggshell, cuttlebone, coral for calcium source, take phosphoric acid salt as phosphorus source, adopting the hydroxyapatite of hydrothermal conversion method synthesis, is a kind of carbonate hydroxyapatite being rich in structural carbonate.
Patent of invention " preparation method of hydroxyapatite " (number of patent application: 200410067736.7) disclosing with shell powder is raw material, with the aqueous solution of hydrophosphate, in encloses container, at 90 ~ 105 DEG C, reacting by heating 6 ~ 48 hours obtained hydroxyapatites.
Patent of invention " a kind of method of synthesizing hydroxylapatite " (number of patent application: 200810073647.1) disclose with oyster chalk layer as raw material, hydrothermal synthesis reaction 24h ~ 96h is carried out with ammonium dibasic phosphate aqueous solution, obtained hydroxyapatite under the condition of normal pressure, heating in water bath 60 ~ 95 DEG C.
Patent of invention " a kind of preparation method of slice-shaped B type carbonate phosphorite " (number of patent application: 201010287689.2) disclose biological mineral matters such as calcium carbonate or shell calciferous, coral, fish-bone, Os Sepiaes, be placed in phosphate buffer solution, through microwave treatment, be rapidly converted into Type B carbonate Apatite materials.
Patent of invention " a kind of preparation method of hydroxyapatite nano sheet " (number of patent application: 201410262587.3) disclose and adopt oyster shell whiting or Ovum crusta Gallus domesticus to be calcium source, take ammonium phosphate as phosphorus source, take water as solvent, the obtained hydroxyapatite nano sheet of reaction under 30 ~ 70 DEG C of conditions.
Foregoing invention patented technology is all calcium source with biological calcium carbonate, take phosphoric acid salt as phosphorus source, adopts hydrothermal conversion reaction technology, or adopts microwave radiation hydrothermal conversion reaction technology, and the feature of these technology is: calcium source is utilization of waste material, turn waste into wealth, wide material sources.Another feature of these technology is that technique is simple and easy to control, low production cost.
Also there are some defects in foregoing invention technology:
First hydroxyapatite only has absorption, fixes the single effect of heavy metal ion, does not have the effect of heavy metal ionic redox.
Secondly, biological calcium carbonate particle and phosphoric acid salt are when in water matchmaker Jie, hydrothermal conversion is reacted, there will be calcium carbonate granule top layer and generate hydroxyapatite, but its granule interior remains calcium carbonate, the conversion reaction speed of its internal layer is very slow, short then a few hours, long then tens of hours, the internal layer calcium carbonate be wrapped by even cannot be made to transform and to generate hydroxyapatite.And a large amount of water of hydrothermal conversion reaction needed is mediated, and solids ratio is in a liquid very little, and therefore output is on the low side, is not suitable for suitability for industrialized production.
Through retrieving the patent documentation relating to hydroxyapatite and academic paper published, do not find to relate to the relevant report of the hydroxyapatite with reductibility function.
Do not find that both there is chemical passivation function, there is again the heavy-metal contaminated soil renovation agent of redox function and the relevant report of Water body cleansing agent yet.
Summary of the invention
An object of the present invention is to provide a kind of carbonate hydroxyapatite with reductibility function.
Another object of the present invention is to provide a kind of synthetic method with the carbonate hydroxyapatite of reductibility function.
The described carbonate hydroxyapatite with reductibility function, being a kind of carbonate hydroxyapatite of the phosphorous acid containing reductibility function, is a kind of heavy-metal contaminated soil renovation agent and heavy metal-polluted water scavenging agent of having chemical passivation and redox dual-use function concurrently.
The described synthetic method with the carbonate hydroxyapatite of reductibility function, for calcium source with the biological calcium carbonate in biomineral, with the phosphorated material containing phosphorous acid for phosphorus source, two step synthesis techniques are adopted to obtain the carbonate hydroxyapatite with reductibility function.
Arizona bacilli, at nontoxic, the efficient reductibility rust proof paint of the U.S., Japan and other countries widespread use, has good sticking power, weathering resistance and rust-proof effect.
Containing phosphorous acid in carbonate hydroxyapatite of the present invention, and be present in hydroxyapatite with Arizona bacilli morphologization compound, there is good stability, remain efficient, lasting reductibility function.
China is that shellfish food first big producing country and first consumes big country in the world, and be also that egg food first big producing country and first consumes big country in the world, shell, the eggshell of the annual enormous quantity produced have become great source of pollution.Meanwhile, China is again the very serious country of heavy-metal contaminated soil and heavy metal-polluted water.
The present invention utilizes the exploitations of discarded shell, eggshell to have the carbonate hydroxyapatite of reductibility function, utilization of waste material, turns waste into wealth, and its technique is simple, with low cost, practical, biological safety is good, can not cause secondary pollution.
Phosphate anion in the carbonate hydroxyapatite with reductibility function of the present invention and orthophosphite ions are all in slowly-releasing state, therefore, have the phosphate fertilizer that the phosphate radical in the carbonate hydroxyapatite of reductibility function, orthophosphite are again long-acting types.
Phosphite is a kind of mineral compound of non-agricultural chemicals, it is a kind of known Fungicidal active substance, have directly with indirectly dual effect of preventing and curing diseases, direct disease-proof functions mainly induces the disease-resistant function of crop self, and has the growth suppressing knot nematodes concurrently.Carbonate hydroxyapatite phosphorous acid radical ion of the present invention has stronger suppression and killing action to the germ in soil, virus, also has stronger restraining effect to the root-knot nematode egg in soil.The carbonate hydroxyapatite with reductibility function of the present invention, for preventing and treating Heavy Metal Pollution In Cultivated Land, not only has the effect of restoration of soil polluted by heavy metal, also has effect of improvement soil and the insect pest of control soil-borne disease concurrently.
In order to realize above-mentioned object, the present invention adopts following technical scheme:
Having the synthetic method of the carbonate hydroxyapatite of reductibility function, is with the biological calcium carbonate in biomineral for calcium source, with the phosphorated material containing phosphorous acid for phosphorus source, adopts following two step synthesis techniques:
It is by pretreated biomineral calcium source and the phosphorated material containing phosphorous acid that synthesis step one adopts hygrometric state polishing to synthesize secondary calcium phosphate-calcium phosphite composite salt, by calcium: the mol ratio proportioning of phosphorus=1:1, under hygrometric state condition, generate secondary calcium phosphate-calcium phosphite composite salt through griding reaction;
Synthesis step two adopts mechanochemical reaction to synthesize the carbonate hydroxyapatite with reductibility function, the secondary calcium phosphate that step one is synthesized-calcium phosphite composite salt again with pretreated biomineral calcium source, by calcium: the mol ratio proportioning of phosphorus=5:3, application machine chemical method, transforms the carbonate hydroxyapatite generated containing reductibility function under speed lapping condition;
Its concrete synthesis step is as follows:
(1) synthesis has pre-treatment and the preparation of the carbonate hydroxyapatite raw material of reductibility function:
The pre-treatment in a, calcium source:
Shell, corallite, cuttlebone and eggshell all have the biomineral of network-like vesicular structure, it is the biological calcium carbonate that a kind of purity is very high, it is the high-quality calcium source of synthesis carbonate hydroxyapatite, through cleaning, go-on-go remove impurity, oven dry and through pulverize make 80 ~ 100 object biological calcium carbonate powders, namely can be used as synthesis carbonate hydroxyapatite calcium source;
B, preparation containing the phosphorus source composition of phosphorous acid:
Phosphorus source composition containing phosphorous acid be by phosphoric acid, hydrophosphate and phosphorous acid, phosphorous acid hydrogen salt by phosphate radical: the weight ratio mixed preparing of orthophosphite=1.0:0.1 ~ 0.6 forms, and is the combination phosphorus source that the phosphorated material compound of a kind of phosphorated material by phosphate radical and orthophosphite forms;
(2) synthesis step one adopts hygrometric state polishing to synthesize secondary calcium phosphate-calcium phosphite composite salt:
The formula rate of a, synthesis secondary calcium phosphate-calcium phosphite composite salt: with the phosphorus in the combination phosphorus source of the calcium in above-mentioned pretreated biological calcium carbonate and above-mentioned preparation, by calcium: the mol ratio proportioning of phosphorus=1:1;
B, first above-mentioned pretreated biological calcium carbonate powder is mixed with the suspension of 30% ~ 40%, be placed in the acid tolerance response tank being designed with grinding facility and be connected, again the combination phosphorus source of above-mentioned preparation is added water and be mixed with the acidic aqueous solution of 50% concentration, be placed in the high-order acid storage tank being designed with flow velocity control switch, open the agitator dripping acid solution switch and retort, the acid phosphorus source aqueous solution is added drop-wise in the biological calcium carbonate powder suspension constantly stirred, biological calcium carbonate and the acid phosphorus source aqueous solution in biological calcium carbonate powder are produced react, after the acid phosphorus source aqueous solution dropwises, mixed slurry is transported in grinding plant from retort and grinds 30min ~ 60min, calcium source is fully reacted in process of lapping, secondary calcium phosphate-calcium phosphite composite salt the whizzer generated is separated the removing aqueous solution from suspension, without the need to drying directly as the intermediate of synthesis containing the carbonate hydroxyapatite of phosphorous acid,
(3) synthesis step two adopts mechanochemical reaction to synthesize the carbonate hydroxyapatite containing reductibility function:
A, by the hygrometric state of above-mentioned preparation secondary calcium phosphate-calcium phosphite composite salt again with above-mentioned pretreated biological calcium carbonate powder, by calcium: the mol ratio proportioning of phosphorus=5:3;
B, the clean water of 3 ~ 5 times of its gross weight is added in the material of above-mentioned formula, load together in vibration mill, application machine chemical synthesis, 30 ~ 60min is ground in the vibration mill of 800 ~ 1000r/min, make the biological calcium carbonate in biomineral and secondary calcium phosphate-calcium phosphite composite salt, in water medium, in speed lapping, produce conversion reaction generate the hydroxyapatite containing phosphorous acid, the carbonate hydroxyapatite suspension containing phosphorous acid generated, after solution is anhydrated in centrifugation, the carbonate hydroxyapatite containing phosphorous acid of hygrometric state is dried about 80 DEG C temperature, the obtained carbonate hydroxyapatite containing reductibility function.
Described biomineral calcium source is pretreated, there is the powder of the shell of network-like vesicular structure, corallite, cuttlebone and eggshell, they are all the calcium sources of high-quality, chalk layer wherein in shell has more flourishing network-like vesicular structure, aperture is 2 ~ 10um, the biological calcium carbonate of network-like vesicular structure transforms Formed hydroxyapatite and still retains its network-like vesicular structure, is the first-selected calcium source of synthesis carbonate hydroxyapatite.
The described phosphorus source composition containing phosphorous acid is phosphorus source, it is the phosphorated material of phosphorated material by phosphate radical and orthophosphite, by phosphate radical: the weight ratio composite combined of orthophosphite=1.0:0.1 ~ 0.6 forms, wherein the phosphorated material of phosphate radical is one kind or two or more in phosphoric acid, hydrophosphate, and the phosphorated material of orthophosphite is one kind or two or more in phosphorous acid, phosphorous acid hydrogen salt.
The present invention compared with prior art, has following three advantages:
1, the present invention introduces phosphorous acid in hydroxyapatite, hydroxyapatite is made to have reductibility function, hydroxyapatite is become have heavy-metal contaminated soil renovation agent and the heavy metal-polluted water scavenging agent of chemical passivation and redox dual-use function, and have effect of soil improvement and the insect pest of control soil-borne disease concurrently;
2, the present invention is using discarded shell, eggshell as the calcium source of synthesizing carbonate hydroxyapatite, change refuse is resource, low production cost, be conducive to having carbonate hydroxyapatite large scale application in improvement heavy-metal contaminated soil and heavy metal-polluted water of reductibility function, be particularly suitable in big area, use in the agricultural land soil of slight pollution;
3, the present invention adopts mechanochemical reaction synthesis technique, in grinding fast, biological calcium carbonate produces conversion reaction with the phosphorated material containing phosphorous acid, generate the carbonate hydroxyapatite with reductibility function, this technique is simple, generated time is short, is suitable for large-scale industrial production.
specific embodiment:
Below in conjunction with embodiment, the invention will be further described, and protection scope of the present invention is not only confined to following examples.
embodiment 1
(1) synthesis has pre-treatment and the preparation of the carbonate hydroxyapatite raw material of reductibility function:
The pre-treatment in a, calcium source:
Shell is the biological calcium carbonate that a kind of purity is very high, it is the high-quality calcium source of synthesis carbonate hydroxyapatite, through cleaning, go-on-go remove impurity, oven dry and through pulverize make 80 ~ 100 object biological calcium carbonate powders, namely the calcium source that can be used as synthesis carbonate hydroxyapatite is (different owing to often criticizing source, biomineral calcium source, the content of its calcium there are differences, often criticize pretreated biomineral calcium source, need calcium contents after measured, to ensure the accuracy of calcium phosphorus mol ratio proportioning);
B, preparation containing the phosphorus source composition of phosphorous acid:
Phosphorus source composition containing phosphorous acid be by phosphoric acid, hydrophosphate and phosphorous acid, phosphorous acid hydrogen salt by phosphate radical: the weight ratio mixed preparing of orthophosphite=1:0.1 forms, that a kind of combination phosphorus source be made up of the phosphorated material of phosphate radical and the phosphorated material compound of orthophosphite is (because the phosphorated material containing phosphorous acid often criticizing preparation is originated different, the content of its phosphorus there are differences, often criticize the phosphorated material composition containing phosphorous acid of preparation, need phosphorus content after measured, to ensure the accuracy of calcium phosphorus mol ratio proportioning);
(2) synthesis step one adopts hygrometric state polishing to synthesize secondary calcium phosphate-calcium phosphite composite salt:
The formula rate of a, synthesis secondary calcium phosphate-calcium phosphite composite salt: with the phosphorus in the combination phosphorus source of the calcium in above-mentioned pretreated biological calcium carbonate and above-mentioned preparation, by calcium: the mol ratio proportioning of phosphorus=1:1;
B, first above-mentioned pretreated biological calcium carbonate powder is mixed with the suspension of 30% ~ 40%, be placed in the acid tolerance response tank being designed with grinding facility and be connected, again the combination phosphorus source of above-mentioned preparation is added water and be mixed with the acidic aqueous solution of 50% concentration, be placed in the high-order acid storage tank being designed with flow velocity control switch, open the agitator dripping acid solution switch and retort, the acid phosphorus source aqueous solution is added drop-wise in the biological calcium carbonate powder suspension constantly stirred, biological calcium carbonate and the acid phosphorus source aqueous solution in biological calcium carbonate powder are produced react, after the acid phosphorus source aqueous solution dropwises, mixed slurry is transported in grinding plant from retort and grinds 30min ~ 60min, calcium source is fully reacted in process of lapping, secondary calcium phosphate-calcium phosphite composite salt the whizzer generated is separated the removing aqueous solution from suspension, the intermediate of the carbonate hydroxyapatite of phosphorous acid is directly contained as synthesis (because the secondary calcium phosphate-calcium phosphite composite salt transformation efficiency often criticizing synthesis is different without the need to drying, moisture content is different, its calcium phosphorus content there are differences, often criticize the secondary calcium phosphate-calcium phosphite composite salt of synthesis, need calcium phosphorus content after measured, to ensure the accuracy of calcium phosphorus mol ratio proportioning),
(3) synthesis step two adopts mechanochemical reaction to synthesize the carbonate hydroxyapatite containing reductibility function:
A, by the hygrometric state of above-mentioned preparation secondary calcium phosphate-calcium phosphite composite salt again with above-mentioned pretreated biological calcium carbonate powder, by calcium: the mol ratio proportioning of phosphorus=5:3;
B, the clean water of 3 ~ 5 times of its gross weight is added in the material of above-mentioned formula, load together in vibration mill, application machine chemical synthesis, 30 ~ 60min is ground in the vibration mill of 800 ~ 1000r/min, make the biological calcium carbonate in biomineral and secondary calcium phosphate-calcium phosphite composite salt, in water medium, in speed lapping, produce conversion reaction generate the hydroxyapatite containing phosphorous acid, the carbonate hydroxyapatite suspension containing phosphorous acid generated, after solution is anhydrated in centrifugation, the carbonate hydroxyapatite containing phosphorous acid of hygrometric state is dried about 80 DEG C temperature, the obtained carbonate hydroxyapatite containing reductibility function.
embodiment 2
(1) synthesis has pre-treatment and the preparation of the carbonate hydroxyapatite raw material of reductibility function:
The pre-treatment in a, calcium source:
Shell is the biological calcium carbonate that a kind of purity is very high, it is the high-quality calcium source of synthesis carbonate hydroxyapatite, through cleaning, go-on-go remove impurity, oven dry and through pulverize make 80 ~ 100 object biological calcium carbonate powders, namely the calcium source that can be used as synthesis carbonate hydroxyapatite is (different owing to often criticizing source, biomineral calcium source, the content of its calcium there are differences, often criticize pretreated biomineral calcium source, need calcium contents after measured, to ensure the accuracy of calcium phosphorus mol ratio proportioning);
B, preparation containing the phosphorus source composition of phosphorous acid:
Phosphorus source composition containing phosphorous acid be by phosphoric acid, hydrophosphate and phosphorous acid, phosphorous acid hydrogen salt by phosphate radical: the weight ratio mixed preparing of orthophosphite=1.0:0.3 forms, that a kind of combination phosphorus source be made up of the phosphorated material of phosphate radical and the phosphorated material compound of orthophosphite is (because the phosphorated material containing phosphorous acid often criticizing preparation is originated different, the content of its phosphorus there are differences, often criticize the phosphorated material composition containing phosphorous acid of preparation, need phosphorus content after measured, to ensure the accuracy of calcium phosphorus mol ratio proportioning);
(2) synthesis step one adopts hygrometric state polishing to synthesize secondary calcium phosphate-calcium phosphite composite salt:
The formula rate of a, synthesis secondary calcium phosphate-calcium phosphite composite salt: with the phosphorus in the combination phosphorus source of the calcium in above-mentioned pretreated biological calcium carbonate and above-mentioned preparation, by calcium: the mol ratio proportioning of phosphorus=1:1;
B, first above-mentioned pretreated biological calcium carbonate powder is mixed with the suspension of 30% ~ 40%, be placed in the acid tolerance response tank being designed with grinding facility and be connected, again the combination phosphorus source of above-mentioned preparation is added water and be mixed with the acidic aqueous solution of 50% concentration, be placed in the high-order acid storage tank being designed with flow velocity control switch, open the agitator dripping acid solution switch and retort, the acid phosphorus source aqueous solution is added drop-wise in the biological calcium carbonate powder suspension constantly stirred, biological calcium carbonate and the acid phosphorus source aqueous solution in biological calcium carbonate powder are produced react, after the acid phosphorus source aqueous solution dropwises, mixed slurry is transported in grinding plant from retort and grinds 30min ~ 60min, calcium source is fully reacted in process of lapping, secondary calcium phosphate-calcium phosphite composite salt the whizzer generated is separated the removing aqueous solution from suspension, the intermediate of the carbonate hydroxyapatite of phosphorous acid is directly contained as synthesis (because the secondary calcium phosphate-calcium phosphite composite salt transformation efficiency often criticizing synthesis is different without the need to drying, moisture content is different, its calcium phosphorus content there are differences, often criticize the secondary calcium phosphate-calcium phosphite composite salt of synthesis, need calcium phosphorus content after measured, to ensure the accuracy of calcium phosphorus mol ratio proportioning),
(3) synthesis step two adopts mechanochemical reaction to synthesize the carbonate hydroxyapatite containing reductibility function:
A, by the hygrometric state of above-mentioned preparation secondary calcium phosphate-calcium phosphite composite salt again with above-mentioned pretreated biological calcium carbonate powder, by calcium: the mol ratio proportioning of phosphorus=5:3;
B, the clean water of 3 ~ 5 times of its gross weight is added in the material of above-mentioned formula, load together in vibration mill, application machine chemical synthesis, 30 ~ 60min is ground in the vibration mill of 800 ~ 1000r/min, make the biological calcium carbonate in biomineral and secondary calcium phosphate-calcium phosphite composite salt, in water medium, in speed lapping, produce conversion reaction generate the hydroxyapatite containing phosphorous acid, the carbonate hydroxyapatite suspension containing phosphorous acid generated, after solution is anhydrated in centrifugation, the carbonate hydroxyapatite containing phosphorous acid of hygrometric state is dried about 80 DEG C temperature, the obtained carbonate hydroxyapatite containing reductibility function.
embodiment 3
(1) synthesis has pre-treatment and the preparation of the carbonate hydroxyapatite raw material of reductibility function:
The pre-treatment in a, calcium source:
Shell is the biological calcium carbonate that a kind of purity is very high, it is the high-quality calcium source of synthesis carbonate hydroxyapatite, through cleaning, go-on-go remove impurity, oven dry and through pulverize make 80 ~ 100 object biological calcium carbonate powders, namely the calcium source that can be used as synthesis carbonate hydroxyapatite is (different owing to often criticizing source, biomineral calcium source, the content of its calcium there are differences, often criticize pretreated biomineral calcium source, need calcium contents after measured, to ensure the accuracy of calcium phosphorus mol ratio proportioning);
B, preparation containing the phosphorus source composition of phosphorous acid:
Phosphorus source composition containing phosphorous acid be by phosphoric acid, hydrophosphate and phosphorous acid, phosphorous acid hydrogen salt by phosphate radical: the weight ratio mixed preparing of orthophosphite=1.0:0.5 forms, that a kind of combination phosphorus source be made up of the phosphorated material of phosphate radical and the phosphorated material compound of orthophosphite is (because the phosphorated material containing phosphorous acid often criticizing preparation is originated different, the content of its phosphorus there are differences, often criticize the phosphorated material composition containing phosphorous acid of preparation, need phosphorus content after measured, to ensure the accuracy of calcium phosphorus mol ratio proportioning);
(2) synthesis step one adopts hygrometric state polishing to synthesize secondary calcium phosphate-calcium phosphite composite salt:
The formula rate of a, synthesis secondary calcium phosphate-calcium phosphite composite salt: with the phosphorus in the combination phosphorus source of the calcium in above-mentioned pretreated biological calcium carbonate and above-mentioned preparation, by calcium: the mol ratio proportioning of phosphorus=1:1;
B, first above-mentioned pretreated biological calcium carbonate powder is mixed with the suspension of 30% ~ 40%, be placed in the acid tolerance response tank being designed with grinding facility and be connected, again the combination phosphorus source of above-mentioned preparation is added water and be mixed with the acidic aqueous solution of 50% concentration, be placed in the high-order acid storage tank being designed with flow velocity control switch, open the agitator dripping acid solution switch and retort, the acid phosphorus source aqueous solution is added drop-wise in the biological calcium carbonate powder suspension constantly stirred, biological calcium carbonate and the acid phosphorus source aqueous solution in biological calcium carbonate powder are produced react, after the acid phosphorus source aqueous solution dropwises, mixed slurry is transported in grinding plant from retort and grinds 30min ~ 60min, calcium source is fully reacted in process of lapping, secondary calcium phosphate-calcium phosphite composite salt the whizzer generated is separated the removing aqueous solution from suspension, the intermediate of the carbonate hydroxyapatite of phosphorous acid is directly contained as synthesis (because the secondary calcium phosphate-calcium phosphite composite salt transformation efficiency often criticizing synthesis is different without the need to drying, moisture content is different, its calcium phosphorus content there are differences, often criticize the secondary calcium phosphate-calcium phosphite composite salt of synthesis, need calcium phosphorus content after measured, to ensure the accuracy of calcium phosphorus mol ratio proportioning),
(3) synthesis step two adopts mechanochemical reaction to synthesize the carbonate hydroxyapatite containing reductibility function:
A, by the hygrometric state of above-mentioned preparation secondary calcium phosphate-calcium phosphite composite salt again with above-mentioned pretreated biological calcium carbonate powder, by calcium: the mol ratio proportioning of phosphorus=5:3;
B, the clean water of 3 ~ 5 times of its gross weight is added in the material of above-mentioned formula, load together in vibration mill, application machine chemical synthesis, 30 ~ 60min is ground in the vibration mill of 800 ~ 1000r/min, make the biological calcium carbonate in biomineral and secondary calcium phosphate-calcium phosphite composite salt, in water medium, in speed lapping, produce conversion reaction generate the hydroxyapatite containing phosphorous acid, the carbonate hydroxyapatite suspension containing phosphorous acid generated, after solution is anhydrated in centrifugation, the carbonate hydroxyapatite containing phosphorous acid of hygrometric state is dried about 80 DEG C temperature, the obtained carbonate hydroxyapatite containing reductibility function.
embodiment 4
(1) synthesis has pre-treatment and the preparation of the carbonate hydroxyapatite raw material of reductibility function:
The pre-treatment in a, calcium source:
Eggshell is the biological calcium carbonate that a kind of purity is very high, it is the high-quality calcium source of synthesis carbonate hydroxyapatite, through cleaning, go-on-go remove impurity, oven dry and through pulverize make 80 ~ 100 object biological calcium carbonate powders, namely the calcium source that can be used as synthesis carbonate hydroxyapatite is (different owing to often criticizing source, biomineral calcium source, the content of its calcium there are differences, often criticize pretreated biomineral calcium source, need calcium contents after measured, to ensure the accuracy of calcium phosphorus mol ratio proportioning);
B, preparation containing the phosphorus source composition of phosphorous acid:
Phosphorus source composition containing phosphorous acid be by phosphoric acid, hydrophosphate and phosphorous acid, phosphorous acid hydrogen salt by phosphate radical: the weight ratio mixed preparing of orthophosphite=1.0:0.2 forms, that a kind of combination phosphorus source be made up of the phosphorated material of phosphate radical and the phosphorated material compound of orthophosphite is (because the phosphorated material containing phosphorous acid often criticizing preparation is originated different, the content of its phosphorus there are differences, often criticize the phosphorated material composition containing phosphorous acid of preparation, need phosphorus content after measured, to ensure the accuracy of calcium phosphorus mol ratio proportioning);
(2) synthesis step one adopts hygrometric state polishing to synthesize secondary calcium phosphate-calcium phosphite composite salt:
The formula rate of a, synthesis secondary calcium phosphate-calcium phosphite composite salt: with the phosphorus in the combination phosphorus source of the calcium in above-mentioned pretreated biological calcium carbonate and above-mentioned preparation, by calcium: the mol ratio proportioning of phosphorus=1:1;
B, first above-mentioned pretreated biological calcium carbonate powder is mixed with the suspension of 30% ~ 40%, be placed in the acid tolerance response tank being designed with grinding facility and be connected, again the combination phosphorus source of above-mentioned preparation is added water and be mixed with the acidic aqueous solution of 50% concentration, be placed in the high-order acid storage tank being designed with flow velocity control switch, open the agitator dripping acid solution switch and retort, the acid phosphorus source aqueous solution is added drop-wise in the biological calcium carbonate powder suspension constantly stirred, biological calcium carbonate and the acid phosphorus source aqueous solution in biological calcium carbonate powder are produced react, after the acid phosphorus source aqueous solution dropwises, mixed slurry is transported in grinding plant from retort and grinds 30min ~ 60min, calcium source is fully reacted in process of lapping, secondary calcium phosphate-calcium phosphite composite salt the whizzer generated is separated the removing aqueous solution from suspension, the intermediate of the carbonate hydroxyapatite of phosphorous acid is directly contained as synthesis (because the secondary calcium phosphate-calcium phosphite composite salt transformation efficiency often criticizing synthesis is different without the need to drying, moisture content is different, its calcium phosphorus content there are differences, often criticize the secondary calcium phosphate-calcium phosphite composite salt of synthesis, need calcium phosphorus content after measured, to ensure the accuracy of calcium phosphorus mol ratio proportioning),
(3) synthesis step two adopts mechanochemical reaction to synthesize the carbonate hydroxyapatite containing reductibility function:
A, by the hygrometric state of above-mentioned preparation secondary calcium phosphate-calcium phosphite composite salt again with above-mentioned pretreated biological calcium carbonate powder, by calcium: the mol ratio proportioning of phosphorus=5:3;
B, the clean water of 3 ~ 5 times of its gross weight is added in the material of above-mentioned formula, load together in vibration mill, application machine chemical synthesis, 30 ~ 60min is ground in the vibration mill of 800 ~ 1000r/min, make the biological calcium carbonate in biomineral and secondary calcium phosphate-calcium phosphite composite salt, in water medium, in speed lapping, produce conversion reaction generate the hydroxyapatite containing phosphorous acid, the carbonate hydroxyapatite suspension containing phosphorous acid generated, after solution is anhydrated in centrifugation, the carbonate hydroxyapatite containing phosphorous acid of hygrometric state is dried about 80 DEG C temperature, the obtained carbonate hydroxyapatite containing reductibility function.
embodiment 5
(1) synthesis has pre-treatment and the preparation of the carbonate hydroxyapatite raw material of reductibility function:
The pre-treatment in a, calcium source:
Eggshell is the biological calcium carbonate that a kind of purity is very high, it is the high-quality calcium source of synthesis carbonate hydroxyapatite, through cleaning, go-on-go remove impurity, oven dry and through pulverize make 80 ~ 100 object biological calcium carbonate powders, namely the calcium source that can be used as synthesis carbonate hydroxyapatite is (different owing to often criticizing source, biomineral calcium source, the content of its calcium there are differences, often criticize pretreated biomineral calcium source, need calcium contents after measured, to ensure the accuracy of calcium phosphorus mol ratio proportioning);
B, preparation containing the phosphorus source composition of phosphorous acid:
Phosphorus source composition containing phosphorous acid be by phosphoric acid, hydrophosphate and phosphorous acid, phosphorous acid hydrogen salt by phosphate radical: the weight ratio mixed preparing of orthophosphite=1.0:0.4 forms, that a kind of combination phosphorus source be made up of the phosphorated material of phosphate radical and the phosphorated material compound of orthophosphite is (because the phosphorated material containing phosphorous acid often criticizing preparation is originated different, the content of its phosphorus there are differences, often criticize the phosphorated material composition containing phosphorous acid of preparation, need phosphorus content after measured, to ensure the accuracy of calcium phosphorus mol ratio proportioning);
(2) synthesis step one adopts hygrometric state polishing to synthesize secondary calcium phosphate-calcium phosphite composite salt:
The formula rate of a, synthesis secondary calcium phosphate-calcium phosphite composite salt: with the phosphorus in the combination phosphorus source of the calcium in above-mentioned pretreated biological calcium carbonate and above-mentioned preparation, by calcium: the mol ratio proportioning of phosphorus=1:1;
B, first above-mentioned pretreated biological calcium carbonate powder is mixed with the suspension of 30% ~ 40%, be placed in the acid tolerance response tank being designed with grinding facility and be connected, again the combination phosphorus source of above-mentioned preparation is added water and be mixed with the acidic aqueous solution of 50% concentration, be placed in the high-order acid storage tank being designed with flow velocity control switch, open the agitator dripping acid solution switch and retort, the acid phosphorus source aqueous solution is added drop-wise in the biological calcium carbonate powder suspension constantly stirred, biological calcium carbonate and the acid phosphorus source aqueous solution in biological calcium carbonate powder are produced react, after the acid phosphorus source aqueous solution dropwises, mixed slurry is transported in grinding plant from retort and grinds 30min ~ 60min, calcium source is fully reacted in process of lapping, secondary calcium phosphate-calcium phosphite composite salt the whizzer generated is separated the removing aqueous solution from suspension, the intermediate of the carbonate hydroxyapatite of phosphorous acid is directly contained as synthesis (because the secondary calcium phosphate-calcium phosphite composite salt transformation efficiency often criticizing synthesis is different without the need to drying, moisture content is different, its calcium phosphorus content there are differences, often criticize the secondary calcium phosphate-calcium phosphite composite salt of synthesis, need calcium phosphorus content after measured, to ensure the accuracy of calcium phosphorus mol ratio proportioning),
(3) synthesis step two adopts mechanochemical reaction to synthesize the carbonate hydroxyapatite containing reductibility function:
A, by the hygrometric state of above-mentioned preparation secondary calcium phosphate-calcium phosphite composite salt again with above-mentioned pretreated biological calcium carbonate powder, by calcium: the mol ratio proportioning of phosphorus=5:3;
B, the clean water of 3 ~ 5 times of its gross weight is added in the material of above-mentioned formula, load together in vibration mill, application machine chemical synthesis, 30 ~ 60min is ground in the vibration mill of 800 ~ 1000r/min, make the biological calcium carbonate in biomineral and secondary calcium phosphate-calcium phosphite composite salt, in water medium, in speed lapping, produce conversion reaction generate the hydroxyapatite containing phosphorous acid, the carbonate hydroxyapatite suspension containing phosphorous acid generated, after solution is anhydrated in centrifugation, the carbonate hydroxyapatite containing phosphorous acid of hygrometric state is dried about 80 DEG C temperature, the obtained carbonate hydroxyapatite containing reductibility function.
embodiment 6
(1) synthesis has pre-treatment and the preparation of the carbonate hydroxyapatite raw material of reductibility function:
The pre-treatment in a, calcium source:
Eggshell is the biological calcium carbonate that a kind of purity is very high, it is the high-quality calcium source of synthesis carbonate hydroxyapatite, through cleaning, go-on-go remove impurity, oven dry and through pulverize make 80 ~ 100 object biological calcium carbonate powders, namely the calcium source that can be used as synthesis carbonate hydroxyapatite is (different owing to often criticizing source, biomineral calcium source, the content of its calcium there are differences, often criticize pretreated biomineral calcium source, need calcium contents after measured, to ensure the accuracy of calcium phosphorus mol ratio proportioning);
B, preparation containing the phosphorus source composition of phosphorous acid:
Phosphorus source composition containing phosphorous acid be by phosphoric acid, hydrophosphate and phosphorous acid, phosphorous acid hydrogen salt by phosphate radical: the weight ratio mixed preparing of orthophosphite=1.0:0.6 forms, that a kind of combination phosphorus source be made up of the phosphorated material of phosphate radical and the phosphorated material compound of orthophosphite is (because the phosphorated material containing phosphorous acid often criticizing preparation is originated different, the content of its phosphorus there are differences, often criticize the phosphorated material composition containing phosphorous acid of preparation, need phosphorus content after measured, to ensure the accuracy of calcium phosphorus mol ratio proportioning);
(2) synthesis step one adopts hygrometric state polishing to synthesize secondary calcium phosphate-calcium phosphite composite salt:
The formula rate of a, synthesis secondary calcium phosphate-calcium phosphite composite salt: with the phosphorus in the combination phosphorus source of the calcium in above-mentioned pretreated biological calcium carbonate and above-mentioned preparation, by calcium: the mol ratio proportioning of phosphorus=1:1;
B, first above-mentioned pretreated biological calcium carbonate powder is mixed with the suspension of 30% ~ 40%, be placed in the acid tolerance response tank being designed with grinding facility and be connected, again the combination phosphorus source of above-mentioned preparation is added water and be mixed with the acidic aqueous solution of 50% concentration, be placed in the high-order acid storage tank being designed with flow velocity control switch, open the agitator dripping acid solution switch and retort, the acid phosphorus source aqueous solution is added drop-wise in the biological calcium carbonate powder suspension constantly stirred, biological calcium carbonate and the acid phosphorus source aqueous solution in biological calcium carbonate powder are produced react, after the acid phosphorus source aqueous solution dropwises, mixed slurry is transported in grinding plant from retort and grinds 30min ~ 60min, calcium source is fully reacted in process of lapping, secondary calcium phosphate-calcium phosphite composite salt the whizzer generated is separated the removing aqueous solution from suspension, the intermediate of the carbonate hydroxyapatite of phosphorous acid is directly contained as synthesis (because the secondary calcium phosphate-calcium phosphite composite salt transformation efficiency often criticizing synthesis is different without the need to drying, moisture content is different, its calcium phosphorus content there are differences, often criticize the secondary calcium phosphate-calcium phosphite composite salt of synthesis, need calcium phosphorus content after measured, to ensure the accuracy of calcium phosphorus mol ratio proportioning),
(3) synthesis step two adopts mechanochemical reaction to synthesize the carbonate hydroxyapatite containing reductibility function:
A, by the hygrometric state of above-mentioned preparation secondary calcium phosphate-calcium phosphite composite salt again with above-mentioned pretreated biological calcium carbonate powder, by calcium: the mol ratio proportioning of phosphorus=5:3;
B, the clean water of 3 ~ 5 times of its gross weight is added in the material of above-mentioned formula, load together in vibration mill, application machine chemical synthesis, 30 ~ 60min is ground in the vibration mill of 800 ~ 1000r/min, make the biological calcium carbonate in biomineral and secondary calcium phosphate-calcium phosphite composite salt, in water medium, in speed lapping, produce conversion reaction generate the hydroxyapatite containing phosphorous acid, the carbonate hydroxyapatite suspension containing phosphorous acid generated, after solution is anhydrated in centrifugation, the carbonate hydroxyapatite containing phosphorous acid of hygrometric state is dried about 80 DEG C temperature, the obtained carbonate hydroxyapatite containing reductibility function.
It is more than the preferred embodiment of the present invention, its display and describe ultimate principle of the present invention and principal character and effect of the present invention and advantage, be be described in detail a kind of synthetic method with the carbonate hydroxyapatite of reductibility function provided by the invention, unspecified technical characteristic is known technology.Apply specific case herein to set forth principle of the present invention and embodiment, the explanation of this embodiment just understands method of the present invention and core concept thereof for helping.Should be understood that; for the technician of the industry; should understand; the present invention is not restricted to the described embodiments; what describe in above-described embodiment and specification sheets just illustrates principle of the present invention; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications; these changes and improvements all fall in the claimed scope of the invention; all similar changes done according to above-mentioned design; ought to belong to of the present invention and contain content, the scope of protection of present invention is defined by appending claims and equivalent thereof.
Claims (3)
1. one kind has the synthetic method of the carbonate hydroxyapatite of reductibility function, it is characterized in that: having the phosphorous acid containing reductibility function in the carbonate hydroxyapatite of reductibility function, is a kind of heavy-metal contaminated soil renovation agent and heavy metal-polluted water scavenging agent of having chemical passivation and redox dual-use function concurrently; Having the synthetic method of the carbonate hydroxyapatite of reductibility function, is with the biological calcium carbonate in biomineral for calcium source, with the phosphorated material containing phosphorous acid for phosphorus source, adopts following two step synthesis techniques:
It is by pretreated biomineral calcium source and the phosphorated material containing phosphorous acid that synthesis step one adopts hygrometric state polishing to synthesize secondary calcium phosphate-calcium phosphite composite salt, by calcium: the mol ratio proportioning of phosphorus=1:1, under hygrometric state condition, generate secondary calcium phosphate-calcium phosphite composite salt through griding reaction;
Synthesis step two adopt mechanochemical reaction synthesize the carbonate hydroxyapatite with reductibility function be secondary calcium phosphate-calcium phosphite composite salt that above-mentioned synthesis step one is synthesized again with pretreated biomineral calcium source, by calcium: the mol ratio proportioning of phosphorus=5:3, application machine chemical method, transforms the carbonate hydroxyapatite generated containing reductibility function under speed lapping condition;
Its concrete synthesis step is as follows:
(1) synthesis has pre-treatment and the preparation of the carbonate hydroxyapatite raw material of reductibility function:
The pre-treatment in a, calcium source:
Shell, corallite, cuttlebone and eggshell all have the biomineral of network-like vesicular structure, it is the biological calcium carbonate that a kind of purity is very high, it is the high-quality calcium source of synthesis carbonate hydroxyapatite, through cleaning, go-on-go remove impurity, oven dry and through pulverize make 80 ~ 100 object biological calcium carbonate powders, namely can be used as synthesis carbonate hydroxyapatite calcium source;
B, preparation containing the phosphorus source composition of phosphorous acid:
Phosphorus source composition containing phosphorous acid be by phosphoric acid, hydrophosphate and phosphorous acid, phosphorous acid hydrogen salt by phosphate radical: the weight ratio mixed preparing of orthophosphite=1.0:0.1 ~ 0.6 forms, and is the combination phosphorus source that the phosphorated material compound of a kind of phosphorated material by phosphate radical and orthophosphite forms;
(2) synthesis step one adopts hygrometric state polishing to synthesize secondary calcium phosphate-calcium phosphite composite salt:
The formula rate of a, synthesis secondary calcium phosphate-calcium phosphite composite salt: with the phosphorus in the combination phosphorus source of the calcium in above-mentioned pretreated biological calcium carbonate and above-mentioned preparation, by calcium: the mol ratio proportioning of phosphorus=1:1;
B, first above-mentioned pretreated biological calcium carbonate powder is mixed with the suspension of 30% ~ 40%, be placed in the acid tolerance response tank being designed with grinding facility and be connected, again the combination phosphorus source of above-mentioned preparation is added water and be mixed with the acidic aqueous solution of 50% concentration, be placed in the high-order acid storage tank being designed with flow velocity control switch, open the agitator dripping acid solution switch and retort, the acid phosphorus source aqueous solution is added drop-wise in the biological calcium carbonate powder suspension constantly stirred, biological calcium carbonate and the acid phosphorus source aqueous solution in biological calcium carbonate powder are produced react, after the acid phosphorus source aqueous solution dropwises, mixed slurry is transported in grinding plant from retort and grinds 30min ~ 60min, calcium source is fully reacted in process of lapping, secondary calcium phosphate-calcium phosphite composite salt the whizzer generated is separated the removing aqueous solution from suspension, without the need to drying directly as the intermediate of synthesis containing the carbonate hydroxyapatite of phosphorous acid,
(3) synthesis step two adopts mechanochemical reaction to synthesize the carbonate hydroxyapatite containing reductibility function:
A, by the hygrometric state of above-mentioned preparation secondary calcium phosphate-calcium phosphite composite salt again with above-mentioned pretreated biological calcium carbonate powder, by calcium: the mol ratio proportioning of phosphorus=5:3;
B, the clean water of 3 ~ 5 times of its gross weight is added in the material of above-mentioned formula, load together in vibration mill, application machine chemical synthesis, 30 ~ 60min is ground in the vibration mill of 800 ~ 1000r/min, make the biological calcium carbonate in biomineral and secondary calcium phosphate-calcium phosphite composite salt, in water medium, in speed lapping, produce conversion reaction generate the hydroxyapatite containing phosphorous acid, the carbonate hydroxyapatite suspension containing phosphorous acid generated, after solution is anhydrated in centrifugation, the carbonate hydroxyapatite containing phosphorous acid of hygrometric state is dried about 80 DEG C temperature, the obtained carbonate hydroxyapatite containing reductibility function.
2. a kind of synthetic method with the carbonate hydroxyapatite of reductibility function according to claim 1, it is characterized in that: described biomineral calcium source is pretreated, there is the powder of the shell of network-like vesicular structure, corallite, cuttlebone and eggshell, they are all the calcium sources of high-quality, chalk layer wherein in shell has more flourishing network-like vesicular structure, aperture is 2 ~ 10um, the biological calcium carbonate of network-like vesicular structure transforms Formed hydroxyapatite and still retains its network-like vesicular structure, is the first-selected calcium source of synthesis carbonate hydroxyapatite.
3. a kind of synthetic method with the carbonate hydroxyapatite of reductibility function according to claim 1, it is characterized in that: the described phosphorus source composition containing phosphorous acid is phosphorus source, it is the phosphorated material of phosphorated material by phosphate radical and orthophosphite, by phosphate radical: the weight ratio composite combined of orthophosphite=1.0:0.1 ~ 0.6 forms, wherein the phosphorated material of phosphate radical is one kind or two or more in phosphoric acid, hydrophosphate, and the phosphorated material of orthophosphite is one kind or two or more in phosphorous acid, phosphorous acid hydrogen salt.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510046029.8A CN104692347A (en) | 2015-01-30 | 2015-01-30 | Synthesis method of carbonate hydroxyapatite with reducing function |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510046029.8A CN104692347A (en) | 2015-01-30 | 2015-01-30 | Synthesis method of carbonate hydroxyapatite with reducing function |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104692347A true CN104692347A (en) | 2015-06-10 |
Family
ID=53339967
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510046029.8A Pending CN104692347A (en) | 2015-01-30 | 2015-01-30 | Synthesis method of carbonate hydroxyapatite with reducing function |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104692347A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105502323A (en) * | 2015-12-17 | 2016-04-20 | 中国科学院合肥物质科学研究院 | Micro-nano structure hydroxyapatite and preparing method and application thereof |
| CN106082155A (en) * | 2016-06-07 | 2016-11-09 | 广西壮族自治区药用植物园 | Utilize the method that fishbone prepares hydroxyapatite |
| CN108483417A (en) * | 2018-05-07 | 2018-09-04 | 南昌大学 | A kind of preparation method of carbonate hydroxyapatite |
| CN110511073A (en) * | 2019-09-11 | 2019-11-29 | 东北农业大学 | A kind of method of indissoluble phosphor effectuation |
| CN110918633A (en) * | 2019-12-03 | 2020-03-27 | 沈阳大学 | Method for repairing metal cadmium contaminated soil by using nano hydroxyapatite-rape |
| CN112980448A (en) * | 2021-02-03 | 2021-06-18 | 湖北省农业科学院植保土肥研究所 | Rice field soil conditioner and preparation method and application thereof |
| CN118023270A (en) * | 2024-01-26 | 2024-05-14 | 浙江大学台州研究院 | Method for strengthening mineralization of heavy metal in fly ash and synergistic carbon fixation and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07206412A (en) * | 1994-01-18 | 1995-08-08 | Taihei Kagaku Sangyo Kk | Production of hydroxyapatite |
| CN101254910A (en) * | 2008-04-14 | 2008-09-03 | 北京化工大学 | Method for preparing calcium phosphate composite powder |
| CN101306806A (en) * | 2008-06-30 | 2008-11-19 | 广西大学 | Process for synthesizing hydroxylapatite |
| CN101920947A (en) * | 2010-09-20 | 2010-12-22 | 上海师范大学 | Preparation method of slice-shaped B type carbonate phosphorite |
| CN102701172A (en) * | 2012-06-21 | 2012-10-03 | 昆明理工大学 | Method for preparing hydroxyapatite nanocrystals or microcrystals by using plant as template |
-
2015
- 2015-01-30 CN CN201510046029.8A patent/CN104692347A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07206412A (en) * | 1994-01-18 | 1995-08-08 | Taihei Kagaku Sangyo Kk | Production of hydroxyapatite |
| CN101254910A (en) * | 2008-04-14 | 2008-09-03 | 北京化工大学 | Method for preparing calcium phosphate composite powder |
| CN101306806A (en) * | 2008-06-30 | 2008-11-19 | 广西大学 | Process for synthesizing hydroxylapatite |
| CN101920947A (en) * | 2010-09-20 | 2010-12-22 | 上海师范大学 | Preparation method of slice-shaped B type carbonate phosphorite |
| CN102701172A (en) * | 2012-06-21 | 2012-10-03 | 昆明理工大学 | Method for preparing hydroxyapatite nanocrystals or microcrystals by using plant as template |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105502323A (en) * | 2015-12-17 | 2016-04-20 | 中国科学院合肥物质科学研究院 | Micro-nano structure hydroxyapatite and preparing method and application thereof |
| CN106082155A (en) * | 2016-06-07 | 2016-11-09 | 广西壮族自治区药用植物园 | Utilize the method that fishbone prepares hydroxyapatite |
| CN106082155B (en) * | 2016-06-07 | 2018-04-06 | 广西壮族自治区药用植物园 | The method that hydroxyapatite is prepared using fish-bone |
| CN108483417A (en) * | 2018-05-07 | 2018-09-04 | 南昌大学 | A kind of preparation method of carbonate hydroxyapatite |
| CN110511073A (en) * | 2019-09-11 | 2019-11-29 | 东北农业大学 | A kind of method of indissoluble phosphor effectuation |
| CN110511073B (en) * | 2019-09-11 | 2021-11-30 | 东北农业大学 | Method for effectively dissolving insoluble phosphorus |
| CN110918633A (en) * | 2019-12-03 | 2020-03-27 | 沈阳大学 | Method for repairing metal cadmium contaminated soil by using nano hydroxyapatite-rape |
| CN112980448A (en) * | 2021-02-03 | 2021-06-18 | 湖北省农业科学院植保土肥研究所 | Rice field soil conditioner and preparation method and application thereof |
| CN112980448B (en) * | 2021-02-03 | 2022-02-11 | 湖北省农业科学院植保土肥研究所 | Rice field soil conditioner and preparation method and application thereof |
| CN118023270A (en) * | 2024-01-26 | 2024-05-14 | 浙江大学台州研究院 | Method for strengthening mineralization of heavy metal in fly ash and synergistic carbon fixation and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104692347A (en) | Synthesis method of carbonate hydroxyapatite with reducing function | |
| CN105802637B (en) | A kind of soil heavy metal passivant and preparation method and the passivating method to Cadmium in Soil | |
| CN105713619B (en) | Method for preparing iron silicon sulfur multi-element composite biochar soil heavy metal conditioner | |
| RU2233293C1 (en) | Humine-mineral reagent and method for its preparing, method for sanitation of polluted soil, method for detoxification of output waste and processing mineral resources and recultivation of mountain rock damp and tail-storing, method for treatment of sewage waters and method for utilization of deposits | |
| Usman et al. | Remediation of a soil contaminated with heavy metals by immobilizing compounds | |
| CN105567249B (en) | Agricultural land soil cadmium pollution chemical remediation agent | |
| CN106147778A (en) | Passivator, preparation method and applications for repairing heavy metal in soil combined pollution | |
| CN103951530A (en) | Peptide calcium salt in-situ passivation agent for treating heavy metal contaminated soil, and preparation method and application thereof | |
| CN105419805A (en) | Preparing method for complex function repairing agent for treatment of heavy metal contaminated soil | |
| CN107350281A (en) | One kind is applied to northern farmland soil of sewage irrigation area passivator and its application process | |
| CN103834411A (en) | Preparation method of organic/inorganic composite passivator for reducing activity of heavy metal Cd in farmland soil | |
| KR20190018184A (en) | Particle type soil conditioner and fertilizer composition using bio-char, and preparation method of the same | |
| CN105419807A (en) | Curing agent for heavy metal and organic matter combined polluted soil, and preparation and application methods for curing agent | |
| CN101003452A (en) | Regulation and control agent in use for treating soil polluted by heavy metals | |
| Hossain et al. | Lead immobilization in soil using new hydroxyapatite-like compounds derived from oyster shell and its uptake by plant | |
| CN111171830A (en) | Passivator for soil heavy metal pollution treatment and preparation method thereof | |
| Li et al. | Effects of amendments on the bioavailability, transformation and accumulation of heavy metals by pakchoi cabbage in a multi-element contaminated soil | |
| CN103788955B (en) | For the treatment of the cadmium fixing agent of contaminated soil and the treatment process of this soil | |
| CN104946262A (en) | Acidic farmland soil heavy metal cadmium pollution in situ passivation conditioner and preparation method thereof | |
| CN113290043A (en) | Mine ecological greening matrix material and preparation method and application thereof | |
| CN110776222A (en) | Preparation and application of sediment nitrogen and phosphorus fixing and repairing agent | |
| CN103011973A (en) | Manufacture method of synergic type nitrogen-phosphorus-potassium mixed fertilizer with slow release and loss control effect | |
| CN111100648A (en) | Heavy metal composite stabilizer and preparation method and application thereof | |
| Carricondo Anton et al. | Alternative use of rice straw ash as natural fertilizer to reduce phosphorous pollution in protected wetland ecosystems | |
| CN114907860A (en) | Soil treatment agent and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| AD01 | Patent right deemed abandoned | ||
| AD01 | Patent right deemed abandoned |
Effective date of abandoning: 20170801 |