CN1153137A - Production method of toothpaste grade calcium hydrophosphate - Google Patents
Production method of toothpaste grade calcium hydrophosphate Download PDFInfo
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- CN1153137A CN1153137A CN 96116483 CN96116483A CN1153137A CN 1153137 A CN1153137 A CN 1153137A CN 96116483 CN96116483 CN 96116483 CN 96116483 A CN96116483 A CN 96116483A CN 1153137 A CN1153137 A CN 1153137A
- Authority
- CN
- China
- Prior art keywords
- phosphoric acid
- solution
- calcium hydrophosphate
- wet process
- defluorinate
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- Granted
Links
- 239000011575 calcium Substances 0.000 title claims abstract description 64
- 229910052791 calcium Inorganic materials 0.000 title claims abstract description 55
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 229940034610 toothpaste Drugs 0.000 title claims abstract description 39
- 239000000606 toothpaste Substances 0.000 title claims abstract description 39
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 23
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 168
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 83
- 238000000034 method Methods 0.000 claims abstract description 75
- 230000008569 process Effects 0.000 claims abstract description 47
- 239000000047 product Substances 0.000 claims abstract description 28
- 238000006115 defluorination reaction Methods 0.000 claims abstract description 20
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims abstract description 11
- 235000011941 Tilia x europaea Nutrition 0.000 claims abstract description 11
- 239000004571 lime Substances 0.000 claims abstract description 11
- 238000012545 processing Methods 0.000 claims abstract description 11
- 239000012535 impurity Substances 0.000 claims abstract description 9
- 239000002002 slurry Substances 0.000 claims abstract description 9
- 230000003472 neutralizing effect Effects 0.000 claims abstract 5
- 239000000243 solution Substances 0.000 claims description 44
- 238000006386 neutralization reaction Methods 0.000 claims description 24
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 16
- 239000011737 fluorine Substances 0.000 claims description 14
- 229910052731 fluorine Inorganic materials 0.000 claims description 14
- 239000001103 potassium chloride Substances 0.000 claims description 14
- 235000011164 potassium chloride Nutrition 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 14
- 239000006227 byproduct Substances 0.000 claims description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 claims description 10
- 150000002500 ions Chemical class 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 230000001376 precipitating effect Effects 0.000 claims description 9
- 239000000920 calcium hydroxide Substances 0.000 claims description 7
- 235000011116 calcium hydroxide Nutrition 0.000 claims description 7
- 239000000706 filtrate Substances 0.000 claims description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 210000000481 breast Anatomy 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 239000011574 phosphorus Substances 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 235000019353 potassium silicate Nutrition 0.000 claims description 6
- 229910021536 Zeolite Inorganic materials 0.000 claims description 5
- 239000004411 aluminium Substances 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 5
- 239000010457 zeolite Substances 0.000 claims description 5
- 238000000975 co-precipitation Methods 0.000 claims description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 4
- 238000010521 absorption reaction Methods 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 3
- 238000005352 clarification Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000009775 high-speed stirring Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 208000006558 Dental Calculus Diseases 0.000 claims description 2
- 239000004111 Potassium silicate Substances 0.000 claims description 2
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 230000004913 activation Effects 0.000 claims description 2
- 238000004061 bleaching Methods 0.000 claims description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 2
- 235000015320 potassium carbonate Nutrition 0.000 claims description 2
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 claims description 2
- 229910052913 potassium silicate Inorganic materials 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 8
- -1 activated silica compound Chemical class 0.000 claims 2
- 230000003311 flocculating effect Effects 0.000 claims 2
- 239000006104 solid solution Substances 0.000 claims 2
- 230000000536 complexating effect Effects 0.000 claims 1
- 150000002222 fluorine compounds Chemical class 0.000 claims 1
- 238000001035 drying Methods 0.000 abstract description 6
- 239000008267 milk Substances 0.000 abstract description 4
- 210000004080 milk Anatomy 0.000 abstract description 4
- 235000013336 milk Nutrition 0.000 abstract description 4
- 239000002244 precipitate Substances 0.000 abstract description 4
- 238000004042 decolorization Methods 0.000 abstract 1
- 150000003016 phosphoric acids Chemical class 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 description 7
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 6
- 238000012805 post-processing Methods 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 210000000988 bone and bone Anatomy 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000005189 flocculation Methods 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- RBLGLDWTCZMLRW-UHFFFAOYSA-K dicalcium;phosphate;dihydrate Chemical compound O.O.[Ca+2].[Ca+2].[O-]P([O-])([O-])=O RBLGLDWTCZMLRW-UHFFFAOYSA-K 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 230000016615 flocculation Effects 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000012860 organic pigment Substances 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 229910021332 silicide Inorganic materials 0.000 description 2
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910004261 CaF 2 Inorganic materials 0.000 description 1
- 229910021532 Calcite Inorganic materials 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 230000008979 phosphorus utilization Effects 0.000 description 1
- 238000011020 pilot scale process Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Cosmetics (AREA)
Abstract
The invention discloses a production method of toothpaste grade calcium hydrophosphate, which mainly comprises the following steps: (1) defluorination of wet-process phosphoric acid, P in treated phosphoric acid2O5the/F is more than or equal to 300; (2) adding lime milk into defluorinated phosphoric acid to neutralize and remove impurities until the pH value of the solution is 3.0-3.5, and clarifying and separating to obtain a clear liquid and a thick slurry; (3) further neutralizing the thick slurry with lime until the pH value is 5.5-7.0, centrifuging and drying to obtain feed-grade calcium hydrophosphate; (4) subjecting the clear liquid to fine defluorination and decolorization to obtain clear and transparent' Ca (H)2PO4)2-H3PO4-H2O' solution; (5) and (3) using the refined lime milk to neutralize the solution to obtain a calcium hydrophosphate precipitate, and then processing the calcium hydrophosphate precipitate through a conventional post-treatment process to obtain a toothpaste grade calcium hydrophosphate product.
Description
The present invention relates to a kind of is the method for raw material production toothpaste grade calcium hydrophosphate with the phosphoric acid by wet process.
As everyone knows, secondary calcium phosphate is a kind of fine toothpaste friction agent, and existing manufacturing technique mainly contains following several.
1. bone black method: paying product bone slag with refining glue is raw material, obtains the clear liquid part with hcl as extraction agent, again with soda ash neutralize the secondary calcium phosphate slip, through rinsing, separation, drying, grind toothpaste level product.This method is more because of organic impurity in the bone black, and when the charing of bone slag was incomplete, quality product, especially color and luster were difficult to reach requirement.This technology more complicated in addition, long reaction time, yield poorly, equipment corrosion and problem of environmental pollution be comparatively serious, and the trend that is eliminated is arranged.
2. double decomposition: thermal phosphoric acid and soda ash reaction, make qualified sodium radio-phosphate,P-32 solution, again with the calcium chloride reaction, the dicalcium phosphate dihydrate slip, through rinsing, separate dry, grind toothpaste level product.The shortcoming of this method: raw material availability is low, the production cost height, and corrosion is also more serious with problem of environmental pollution.
3. direct neutralisation: with the thermal phosphoric acid is raw material, after pre-treatment such as dilution, decolouring directly and calcite in powder or purified milk of lime carry out neutralization reaction, slip through adding conventional postprocessing working procedures such as stablizer, rinsing, separation, drying, pulverizing, obtains toothpaste level product again.It is comparatively economic at present production method that this method is compared with above-mentioned two kinds of methods, but the influence that constantly appreciated by the raw material thermal phosphoric acid, production cost is also improving constantly, use this method manufacturing enterprise to be absorbed in crag-fast predicament, influenced secondary calcium phosphate type toothpaste the popularizing of China, for this reason, branch of industry wishes that the scientific worker looks for Xi Jing in addition, provide a kind of cheap and easy to get, and the novel method of practicable production toothpaste grade calcium hydrophosphate.
Purpose of the present invention is to satisfy the above-mentioned requirements of branch of industry, overcomes the above-mentioned shortcoming of prior art, and providing a kind of is raw material with the phosphoric acid by wet process, by comprehensive utilization or deep development, reaches the method for producing toothpaste grade calcium hydrophosphate economically.
The present invention's design is such:
The contriver is on the basis of being engaged in the phosphide research work for a long time, imagination utilizes phosphoric acid by wet process cheap and easy to get to produce toothpaste grade calcium hydrophosphate, and when obtaining toothpaste grade calcium hydrophosphate, obtain by product-calcium hydrophosphate fodder, promptly, make method of the present invention have the wide industrial development prospect by obtaining the production cost that by product reduces toothpaste grade calcium hydrophosphate in the process of purification of wet process phosphoric acid.
The present invention is achieved by the following technical solution:
When being raw material with the phosphoric acid by wet process, its key problem in technology is to solve the defluorinate and the deep purifying problem of phosphoric acid by wet process, thereby obtains purified Ca (H
2PO
4)
2-H
3PO
4-H
2O solution just can be produced the toothpaste grade calcium hydrophosphate product according to prior art with above-mentioned purified solution afterwards easily.
Defluorinate and deep purifying problem with regard to relevant phosphoric acid by wet process is described below respectively below:
The defluorinate of A, phosphoric acid by wet process is handled:
Want to produce qualified toothpaste grade calcium hydrophosphate product by phosphoric acid by wet process, wherein defluorinate is a primary big technical barrier that solves.Because the source difference of phosphoric acid by wet process, thereby the existence form of fluorine and feature have very big difference, and the contriver is according to own three kinds of defluorination technologies of practice proposition for this reason.
1. the F in phosphoric acid by wet process is all with H
2SiF
6When form exists,, make fluorion in the solution with K as long as add sylvite (as defluorinating agent)
2SiF
6Form precipitation remove, can satisfy P in the phosphoric acid
2O
5/ F 〉=300 (wt/wt) requirement down together.The add-on of said sylvite is 120～150% (weight ratios, as follows) of theoretical amount, and said sylvite is Repone K, salt of wormwood, vitriolate of tartar or their mixture.
2. the F in phosphoric acid by wet process is with H
2SiF
6When existing with two kinds of forms of HF, then must add active silicide and sylvite (as defluorinating agent) simultaneously, (1) the described method that is similar to obtains good defluorination effect, can satisfy P in the phosphoric acid
2O
5The requirement of/F 〉=300.Wherein said active silicide is active SiO
2, water glass, potassium silicate or their mixture.
3. point out F in passing when phosphoric acid by wet process, except existing, when also having other form, can adopt disclosed method in another patent application of applicant with above-mentioned form, be the combined method that sylvite once removes fluoro-fluorochemical activation-activated silica secondary defluorination, can satisfy P in the phosphoric acid equally
2O
5The requirement of/F 〉=300 (because this method also has himself, thereby having patent application open in addition, here) so narration is omitted.
The neutralization reaction purifying treatment of B, phosphoric acid solution
In order to remove other foreign ions in the phosphoric acid, before smart defluorinate, adopt milk of lime to regulate PH to 3.0～3.5 of phosphoric acid defluorination solution (or claiming the neutralization reaction removal of impurities to handle), under this PH condition, on the one hand in the phosphoric acid metal ion such as residual Fe, Al and nonmetallic ion with phosphatic form precipitating, and with portion C aH-PO
42H
2O co-precipitation mode is removed (throw out by further handling, obtains the by product of calcium hydrophosphate fodder later on) together, and on the other hand, fluorine residual in the phosphoric acid is further with CaF
2Form removed by precipitating, and make the purification degree of depth of phosphoric acid reach P
2O
5/ F 〉=3000.If branch of industry is when only needing to produce ordinary toothpaste calcium hydrophosphate product (only require in the secondary calcium phosphate F content≤0.015% o'clock), the phosphoric acid after the neutralization reaction purifying treatment has met the specification of quality of this product to fluorine content, so no longer carry out smart defluorinate processing.
The further smart defluorinate of C, phosphoric acid by wet process is handled
The phosphoric acid of handling by above-mentioned preliminary defluorinate (abbreviation phosphoric acid defluorination) when branch of industry needs production high-quality type toothpaste grade calcium hydrophosphate product, promptly requires fluorion≤0.005% o'clock in the secondary calcium phosphate, also needs further smart defluorinate to handle.The contriver has proposed and will pass through activated alumina (Al through the phosphoric acid solution of neutralization reaction purifying treatment through experimental study
2O
3) or natural zeolite carry out the deep purifying defluorinate, can be with phosphoric acid purification to P
2O
5The requirement of producing high-quality type toothpaste grade calcium hydrophosphate is satisfied in/F 〉=10000.Smart defluorinating agent: the consumption of activated alumina or natural zeolite adds by every cubic metre of phosphoric acid solution 8～12kg.In general the first two step defluorinate is handled well as phosphoric acid solution, and then smart defluorinating agent consumption is just few.
The adsorption bleaching of D, phosphoric acid solution is handled
Owing to have organic pigment impurity inevitably in the phosphoric acid by wet process, the phosphoric acid solution after neutralization reaction purifying treatment or the smart defluorinate also must be handled by the charcoal absorption decolouring, guarantees to obtain the pure white toothpaste grade calcium hydrophosphate product of fine like this.The consumption of gac is 4～6kg/m
3Solution (phosphoric acid solution of processing).
In a word, phosphoric acid by wet process is handled by above-mentioned defluorinate and deep purifying and can be obtained purified Ca (H
2PO
4)
2-H
3PO
4-H
2O solution.Then this solution is carried out neutralization reaction with the purified lime milk solution again, can obtain the said fine toothpaste grade calcium hydrophosphate of the present invention product.Above-mentioned said phosphoric acid by wet process should be got P
2O
5The phosphoric acid by wet process of content 〉=17% (wt).
Comprehensive the above as seen: the present invention compared with prior art has following advantage:
1. with the phosphoric acid by wet process be raw material, not only cheap and easy to get, and because the method that adopts purification of raw materials to combine with by product feed calcium hydrophosphate production technique, thus solved the deep purifying problem of raw material phosphoric acid more economically.
2. because the deep purifying of raw material phosphoric acid, thereby can obtain the pure white toothpaste grade calcium hydrophosphate product of fine.
3. though according to technical scheme of the present invention, during production high-quality toothpaste grade calcium hydrophosphate product, total phosphorus utilization in the phosphoric acid by wet process only is 30～50% (all the other phosphorus enter in the by product feed calcium hydrophosphate), but because calcium hydrophosphate fodder is a very large product, according to technical scheme of the present invention, can build up the above device of ten tons easily, thereby the output of toothpaste grade calcium hydrophosphate product can not be restricted, on the contrary, because phosphoric acid by wet process has obtained rational comprehensive utilization, increased the added value of phosphoric acid by wet process deep processing, the operational path that the present invention is opened up enters industrialization soon.
Further illustrate content of the present invention below in conjunction with accompanying drawing.
Accompanying drawing is the process flow diagram of production high-quality toothpaste grade calcium hydrophosphate and by-product calcium hydrophosphate fodder.
Wherein:
The major product technical process mainly comprises following operation:
1---the defluorination reaction device;
2---the neutralization reaction groove;
3---settler;
4---smart defluorination reaction device;
5---decolorizer;
6---main neutralization reactor;
7---the aftertreatment technology device;
The byproduct technical process outside above-mentioned 1,2,3 total operations, also comprises following master operation:
8---neutralization reactor;
9---centrifugation apparatus;
10---the dry setting.
According to the technological process that accompanying drawing is showed that content description of the present invention is as follows:
1. earlier wet method phosphoric acid is placed defluorination reaction device 1, according to the source of raw material and the difference of component (by assay determination), add different defluorinating agent (as adding sylvite or sylvite+active silicon etc.) and generate K2SiF
6Flocculation sediment (can by removing by filter the fluorine ion more than 97%) makes the P in the solution2O
5/F≥300。
Its sylvite adding amount is 120～150% of theoretical amount.
2. then with the wet method phosphoric acid after the defluorinate, in delivering to and in the reactive tank 2, be 8～12%wt with containing CaO The milk of lime reaction that neutralizes, end to the PH=3.0 of solution～3.5, under this PH condition, on the one hand The reaction of part phosphoric acid in the solution and calcium generates phosphoric acid hydrogen calcium precipitate, remains in simultaneously the gold such as iron in the phosphoric acid, aluminium Belong to the impurity ion, and the nonmetallic inclusion ion, with the form flocculation precipitating of phosphate, and with phosphoric acid hydrogen calcium altogether The precipitation and be removed; On the other hand in the phosphoric acid residual fluorine further with CaF2Form removed by precipitating, make phosphoric acid purification to P2O
5/F≥3000。
3. the above-mentioned solution that contains solid sediment is imported in the clarifier 3, through 4～10hr clarified separation.
4. the clarified solution from clarifier 3 tops imports in the smart defluorination reaction device 4, in smart defluorination reaction device, According to producing the different quality requirements of product, can add different smart defluorinating agent. Used smart defluorinating agent is active Aluminium oxide or natural zeolite. In smart defluorination reaction device, by filtering behind stirring and adsorbing 3～5hr, obtain to contain P2O
5The filtrate of/F 〉=10000.
5. above-mentioned filtrate is delivered in the decolorizer 5, added active carbon and stir decolouring 1.5～3.0hr, organic pigment absorption residual in the filtrate can be removed, can obtain after filtration the colourless " Ca (H of clear2PO
4)
2-H
3PO
4-H
2O " solution.
6. above-mentioned solution is delivered in the primary stainless steel and groove 6 in, slow plain silk fabrics adds the refined lime breast under high-speed stirred Leading neutralization and reacting PH=5.5 to thing system～6.5, and 40～50 ℃ of the temperature of control reactant system, warp Test show add the ash time suitable 〉=50 minutes, after reaction finished, thing system imported in the conventional post processing process unit 7. Said smart ash breast is for containing the solution of CaO amount 6～12% (wt).
7. (the post processing process unit all is the routine of producing toothpaste grade calcium hydrophosphate in the post processing process unit Technology, it mainly comprises and under agitation adds stabilizing agent, rinsing, centrifugal dehydration, air-flow drying, pulverizing, screening etc. Step), obtain the toothpaste grade calcium hydrophosphate product.
8. the production technology of accessory substance-calcium hydrophosphate fodder:
Thick slurry by clarifier 3 bottoms emit imports in the neutralization reactor 8, under agitation adds then lime The PH=6.0 of Ruzhong and instrumentality system～7.0 make the whole form phosphoric acid of the phosphoric acid hydrogen calcium precipitate in the thing system, again After processing, the devices such as centrifugal, drying make the calcium hydrophosphate fodder product. Point out in passing by-product the production of material worker Skill provides support for the reasonability of technology of the present invention, but it is not core of the present invention, because any phosphorus of being engaged in The worker of compound exploitation can consider to fully utilize problem like this.
Further illustrate content of the present invention below in conjunction with embodiment.In order to compose a piece of writing conveniently; said embodiment is representative with pilot scale amplifieroperation example only; we think the engineering technical personnel that letter is relevant, can according to the present invention conceive can according to one return three ground realize of the present invention, so embodiment itself does not limit protection scope of the present invention.
Produce ordinary toothpaste calcium hydrophosphate product:
1. get industrial phosphoric acid by wet process 1m
3(wherein contain: P
2O
5250g/L, F17.2g/L, Al
2O
30.8g/L, Fe
2O
31.8g/L) place the defluorination reaction device, add defluorinating agent KCl 30kg, (water glass contains SiO to water glass
228%wt) 5kg, in 30 ℃ of following stirring reaction 2hr, contained F has more than 97% with K in the phosphoric acid by wet process
2SiF
6The form precipitation is separated out, and removes by filter throw out, and contained fluorine concentration has dropped to 0.51g/L in the gained clear liquid (being phosphoric acid defluorination), at this moment P
2O
5The ratio of/F has reached 490.
2. above-mentioned phosphoric acid defluorination is pumped in the neutralization reaction groove, add then and contain the milk of lime that CaO is 100g/L (is 10%wt near containing CaO), end until neutralization reaction terminal point PH=3.1～3.3, under this PH condition, on the one hand metal ion such as contained iron, aluminium and nonmetallic ion and are followed the co-precipitation of part secondary calcium phosphate and are removed all with phosphatic form flocculation precipitating in the phosphoric acid defluorination; Residual fluorine in the phosphoric acid defluorination is further with CaF on the other hand
2Form is removed by precipitating.
3. 2. the solid system that contains of gained pumps in the settler, and (generally should clarify 6～8hr), top obtained clear liquid 1.2m more than clarification separated 4hr
3(wherein contain P
2O
585g/L, F 0.027g/L, P
2O
5/ F=3148), the bottom obtains thick slurry 0.85m
3, directly pump to neutralization reactor, the by-product calcium hydrophosphate fodder.
4. incite somebody to action the 3. upper clear supernate 1.2m of gained
3Pump in the decolorizer, add the 5kg gac then, stir decolouring 1.5hr, filter and obtain 1.2m
3The decolouring clear liquid of clear, i.e. " Ca (H
2PO
4)
2-H
3PO
4-H
2O " solution.
5. 4. resulting decolouring clear liquid pump is become owner of in the neutralization reactor, then the purified lime milk solution (is contained CaO 80g/L, near concentration 8%wt) under high-speed stirring, add in the decolouring clear liquid, the speed that adds maintains between 45～50 ℃ with the temperature of reaction of control system, end until reaction end PH=5.8～6.2 of system, stabilized again processing, and after common process such as rinsing, centrifugal, dry, pulverizing operate, obtain 220kg ordinary toothpaste calcium hydrophosphate product, wherein contain P
2O
541.5%wt, F 0.013%wt, Ca23.4%wt, whiteness is 95.3%, all the other indexs all meet ZBG 12023-90 standard-required; Point out that in passing the raffinate of rinsing and centrifugal gained is because of all containing P
2O
5So, answer pump to neutralization reactor, the by-product calcium hydrophosphate fodder.
6. in neutralization reactor (auxiliary process of the present invention) adds from the thick slurry 0.85m of bottom 3.
3, and the raffinate of the centrifugal gained of rinsing, after post-processing operation such as centrifugal, drying, obtains 405kg calcium hydrophosphate fodder byproduct and (wherein contains P again to PH=6.5～6.8 with the milk of lime neutralization reaction
2O
539%wt, F0.165%wt).
In the present embodiment, contained P in the toothpaste level phosphorus level hydrogen calcium product
2O
5Account for total P in the phosphoric acid by wet process
2O
5Ratio be 36.5% or to be called for short yield be 36.5%, calcium hydrophosphate fodder byproduct yield is 63.2%.
Production high-quality toothpaste grade calcium hydrophosphate product:
1. press earlier 1.～3. identical method operation among the embodiment 1, obtain upper clear supernate 1.2m
3(wherein contain P
2O
585g/L, F 0.027g/L, P
2O
5=3148wt/wt).
2. above-mentioned clear liquid is pumped in the smart defluorination reaction device, add the 10kg zeolite adsorbents then, under 30 ℃, whip attachment 2hr filters and obtains filtrate, wherein contains: P
2O
583g/L, F 0.005g/L, P
2O
5/ F=16600.
3. above-mentioned filtrate is pumped in the decolorizer, and press method operation 4. identical among the embodiment 1, obtain 1.2m
3The decolouring clear liquid of clear promptly obtains purified " Ca (H
2PO
4)
2-H
3PO
4-H
2O " solution.
4. above-mentioned decolouring clear liquid pump is become owner of in the neutralization reactor, and press method operation 5. identical among the embodiment 1, obtain 215kg fine toothpaste grade calcium hydrophosphate product, wherein contain P
2O
541.3%wt, F0.003%wt, Ca23.5%wt, whiteness is 95.6%, all the other indexs all meet the ZBG12023-90 standard-required.
Claims (5)
1. the production method of a toothpaste grade calcium hydrophosphate when it is characterized in that being the raw material production toothpaste grade calcium hydrophosphate with the phosphoric acid by wet process, mainly comprises following processing step:
(1) at first phosphoric acid by wet process is carried out defluorinate and handle, make the P in the phosphoric acid solution after the processing with defluorinating agent
2O
5/ F 〉=300 (weight ratio);
(2) be phosphoric acid solution after the defluorinate of 8～12% (wt) milk of lime neutralizing treatment with containing CaO, end until PH=3.0～3.5, under this PH condition, on the one hand in the phosphoric acid solution metallic impurity ions such as contained iron, aluminium and nonmetallic impurity ion all with the phosphatic form precipitating of flocculating, and be removed by the co-precipitation of part secondary calcium phosphate, residual fluorine is sanitised to P in the phosphoric acid solution on the other hand
2O
5The degree of depth of/F 〉=3000;
(3) solid solution that contains with above-mentioned (2) pumps in the settler, and clarification separates 4～10hr, obtains the thick slurry in upper clear supernate and bottom (thick slurry is for reclaiming the by-product calcium hydrophosphate fodder) respectively;
(4) will clarify separating obtained upper clear supernate and handle, filter " Ca (the H that the back obtains clear with activated carbon decolorizing
2PO
4)
2-H
3PO
4-H
2O " solution;
(5) above-mentioned solution pump is become owner of in the neutralizing well, under high-speed stirring, slowly add the refined lime breast and carry out main neutralization reaction, obtain fine secondary calcium phosphate precipitation, said refined lime breast is the solution of CaO content 6～12% (wt), after reaction finishes this system is pumped in the conventional after-treatment device, can obtain pure white toothpaste grade calcium hydrophosphate product by aftertreatment.
2. the production method of a toothpaste grade calcium hydrophosphate when it is characterized in that being the raw material production toothpaste grade calcium hydrophosphate with the phosphoric acid by wet process, mainly comprises following processing step:
(1) at first phosphoric acid by wet process is carried out defluorinate and handle, make the P in the phosphoric acid solution after the processing with defluorinating agent
2O
5/ F 〉=300 (weight ratio);
(2) be phosphoric acid solution after the defluorinate of 8～12% (wt) milk of lime neutralizing treatment with containing CaO, end until PH=3.0～3.5, under this PH condition, on the one hand in the phosphoric acid solution metallic impurity ions such as contained iron, aluminium and nonmetallic impurity ion all with the phosphatic form precipitating of flocculating, and be removed by the co-precipitation of part secondary calcium phosphate, residual fluorine is sanitised to P in the phosphoric acid solution on the other hand
2O
5The degree of depth of/F 〉=3000;
(3) solid solution that contains with above-mentioned (2) pumps in the settler, and clarification separates 4～10hr, obtains the thick slurry in upper clear supernate and bottom (thick slurry is for reclaiming the by-product calcium hydrophosphate fodder) respectively;
(4) (3) described upper clear supernate is carried out smart defluorinate with smart defluorinating agent and handle, the small amount of fluorine that remains in the clear liquid is further removed by smart defluorinating agent absorption, said smart defluorinating agent is activated alumina or natural zeolite, and its consumption is 8～12g/m
3Clear liquid, in smart defluorinate device, whip attachment 3～5hr obtains to contain P after filtration
2O
5The filtrate of/F 〉=10000;
(5) filtrate that gained is handled in (4) described smart defluorinate is handled with activated carbon decolorizing, filters " Ca (the H that the back obtains clear
2PO
4)
2-H
3PO
4-H
2O " solution;
(6) above-mentioned solution pump is become owner of in the neutralizing well, under high-speed stirring, slowly add the refined lime breast and carry out neutralization reaction, obtain fine secondary calcium phosphate precipitation, said refined lime breast is the solution of CaO content 6～12% (wt), after reaction finishes, this system is pumped in the conventional after-treatment device, can obtain pure white toothpaste grade calcium hydrophosphate product by aftertreatment.
3. method as claimed in claim 1 or 2 is characterized in that said defluorinate handles, and because of the source difference of phosphoric acid by wet process, the existence form difference of fluorine wherein has following three kinds of methods:
(1) in adopting the phosphoric acid by wet process make by the high-quality phosphorus ore and ore, there is the SiO of q.s
2The time, the fluorine in the phosphoric acid by wet process is only with H
2SiF
6Shape exists, and only need add the sylvite defluorinating agent this moment, makes fluorine with K
2SiF
6The form precipitating is removed, and the add-on of sylvite is 120～150% (wt) of theoretical amount, and said sylvite can be Repone K, vitriolate of tartar, salt of wormwood or their mixture.
(2) outside adopting the phosphoric acid by wet process that makes by the high-quality phosphorus ore, but the active SiO in the ore
2When not enough, the fluorine in the phosphoric acid by wet process is with H2
SIF
6Exist with two kinds of forms of HF, need assist adding activated silica compound to carry out defluorinate simultaneously and handle this moment except adding defluorinating agent sylvite, and said activated silica compound is a water glass, potassium silicate, active SiO
2A kind of in the powder;
During phosphoric acid by wet process that (3) low-grade phosphorus ore makes in adopting, because the existence form of fluorine is comparatively complicated in the phosphoric acid by wet process, except there being H
2SiF
6Outside HF, the water-soluble fluorine compound that also has foreign ion complexings such as a class and iron, aluminium, this class fluorochemical is comparatively stable, needs activated processing, and the combined method that must adopt this moment sylvite once to remove fluoro-fluorochemical activation-activated silica secondary defluorination comes defluorinate to handle.
4. method as claimed in claim 1 or 2, activated carbon dosage is 4～6kg/m when it is characterized in that said activated carbon decolorizing is handled
3Solution, and adsorption bleaching 1.5～3.0hr under agitation filter the " Ca (H that the back obtains clear
2PO
4)
2-H
3PO
4-H
2O " solution.
5. method as claimed in claim 1 or 2 is characterized in that said main neutralization reaction, and the temperature during its reaction is controlled at 40～50 ℃, and the reaction end pH value is controlled at 5.5～6.5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96116483A CN1044460C (en) | 1996-08-23 | 1996-08-23 | Production method of toothpaste grade calcium hydrophosphate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96116483A CN1044460C (en) | 1996-08-23 | 1996-08-23 | Production method of toothpaste grade calcium hydrophosphate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1153137A true CN1153137A (en) | 1997-07-02 |
| CN1044460C CN1044460C (en) | 1999-08-04 |
Family
ID=5123584
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96116483A Expired - Fee Related CN1044460C (en) | 1996-08-23 | 1996-08-23 | Production method of toothpaste grade calcium hydrophosphate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1044460C (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103738933A (en) * | 2013-12-13 | 2014-04-23 | 江苏晓春新材料有限公司 | Method for recovering high purity calcium hydrogen phosphate in sulfur acid-containing waste phosphoric acid |
| CN104628206A (en) * | 2015-02-11 | 2015-05-20 | 北京赛科康仑环保科技有限公司 | Recycling technique of lithium iron phosphate production wastewater |
| CN104628207A (en) * | 2015-02-11 | 2015-05-20 | 北京赛科康仑环保科技有限公司 | Resourceful treatment method and system of lithium battery cathode material production wastewater |
| CN106853962A (en) * | 2016-12-18 | 2017-06-16 | 贵州越都化工有限公司 | A kind of feed-level calcium biphosphate and preparation method thereof |
| CN110078039A (en) * | 2019-06-04 | 2019-08-02 | 瓮福（集团）有限责任公司 | A kind of low-concentration phosphorus-containing wastewater step produces the method and device of calcium hydrophosphate fodder |
| CN112408350A (en) * | 2020-11-03 | 2021-02-26 | 中国五环工程有限公司 | Process for producing feed-grade calcium hydrophosphate from phosphorus-containing wastewater |
| CN115282063A (en) * | 2022-09-02 | 2022-11-04 | 米乐医疗科技有限公司 | Tooth desensitizer |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3427125A (en) * | 1966-04-06 | 1969-02-11 | Central Glass Co Ltd | Process for preparing highly pure calcium hydrogen phosphate dihydrate |
| DE3347476A1 (en) * | 1982-12-29 | 1984-07-05 | Lion Corp., Tokio / Tokyo | DENTAL CARE AND SUITABLE ABRASIVE |
| RU1792914C (en) * | 1990-02-19 | 1993-02-07 | Предприятие П/Я Р-6295 | Method of calcium phosphate production |
| DE4305276A1 (en) * | 1993-02-20 | 1994-08-25 | Hoechst Ag | Process for the preparation of a dicalcium phosphate dihydrate suitable for use in toothpastes |
-
1996
- 1996-08-23 CN CN96116483A patent/CN1044460C/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103738933A (en) * | 2013-12-13 | 2014-04-23 | 江苏晓春新材料有限公司 | Method for recovering high purity calcium hydrogen phosphate in sulfur acid-containing waste phosphoric acid |
| CN104628206A (en) * | 2015-02-11 | 2015-05-20 | 北京赛科康仑环保科技有限公司 | Recycling technique of lithium iron phosphate production wastewater |
| CN104628207A (en) * | 2015-02-11 | 2015-05-20 | 北京赛科康仑环保科技有限公司 | Resourceful treatment method and system of lithium battery cathode material production wastewater |
| CN106853962A (en) * | 2016-12-18 | 2017-06-16 | 贵州越都化工有限公司 | A kind of feed-level calcium biphosphate and preparation method thereof |
| CN110078039A (en) * | 2019-06-04 | 2019-08-02 | 瓮福（集团）有限责任公司 | A kind of low-concentration phosphorus-containing wastewater step produces the method and device of calcium hydrophosphate fodder |
| CN110078039B (en) * | 2019-06-04 | 2023-09-22 | 瓮福（集团）有限责任公司 | Method and device for preparing feed-grade calcium hydrophosphate in low-concentration phosphorus-containing wastewater step manner |
| CN112408350A (en) * | 2020-11-03 | 2021-02-26 | 中国五环工程有限公司 | Process for producing feed-grade calcium hydrophosphate from phosphorus-containing wastewater |
| CN112408350B (en) * | 2020-11-03 | 2023-04-07 | 中国五环工程有限公司 | Process for producing feed-grade calcium hydrophosphate from phosphorus-containing wastewater |
| CN115282063A (en) * | 2022-09-02 | 2022-11-04 | 米乐医疗科技有限公司 | Tooth desensitizer |
| CN115282063B (en) * | 2022-09-02 | 2023-11-24 | 米乐医疗科技有限公司 | Tooth desensitizer |
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|---|---|
| CN1044460C (en) | 1999-08-04 |
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Free format text: CORRECT: PATENTEE; FROM: LOMON MINERALS AND FEEDS(GROUP) CO., LTD,MIANZHU, SICHUAN TO: SICHUAN LOMON GROUP CO., LTD. |
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Address after: Sichuan city in Mianzhu province of South Road Patentee after: Longmang Group Co., Ltd., Sichuan Prov Address before: Sichuan province Mianzhu County South high respect Temple Patentee before: Longmang Mineral Material Fodder Group Co., Ltd., Mianzhu County, Sichuan Prov. |
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Granted publication date: 19990804 |