CN102502545A - Method for preparing sodium hypophosphite - Google Patents
Method for preparing sodium hypophosphite Download PDFInfo
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- CN102502545A CN102502545A CN2011103777827A CN201110377782A CN102502545A CN 102502545 A CN102502545 A CN 102502545A CN 2011103777827 A CN2011103777827 A CN 2011103777827A CN 201110377782 A CN201110377782 A CN 201110377782A CN 102502545 A CN102502545 A CN 102502545A
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- sodium hypophosphite
- sodium
- phosphite
- hypophosphite
- product
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- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 229910001379 sodium hypophosphite Inorganic materials 0.000 title claims abstract description 102
- 238000000034 method Methods 0.000 title claims abstract description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 40
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 36
- 239000011574 phosphorus Substances 0.000 claims abstract description 36
- 238000005273 aeration Methods 0.000 claims abstract description 25
- 238000001953 recrystallisation Methods 0.000 claims abstract description 24
- 238000002425 crystallisation Methods 0.000 claims abstract description 15
- 230000008025 crystallization Effects 0.000 claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 238000001704 evaporation Methods 0.000 claims abstract description 5
- 230000008020 evaporation Effects 0.000 claims abstract description 5
- NCPXQVVMIXIKTN-UHFFFAOYSA-N trisodium;phosphite Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])[O-] NCPXQVVMIXIKTN-UHFFFAOYSA-N 0.000 claims description 64
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- 238000006243 chemical reaction Methods 0.000 claims description 31
- 239000003513 alkali Substances 0.000 claims description 26
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 26
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 26
- 239000000920 calcium hydroxide Substances 0.000 claims description 26
- 239000007787 solid Substances 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 235000019441 ethanol Nutrition 0.000 claims description 18
- 238000002360 preparation method Methods 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 10
- 230000001476 alcoholic effect Effects 0.000 claims description 10
- 239000011790 ferrous sulphate Substances 0.000 claims description 10
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- 235000011194 food seasoning agent Nutrition 0.000 claims description 10
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 10
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 230000003534 oscillatory effect Effects 0.000 claims description 9
- 230000001105 regulatory effect Effects 0.000 claims description 9
- 238000005189 flocculation Methods 0.000 claims description 6
- 230000016615 flocculation Effects 0.000 claims description 6
- -1 aluminium chlorohydroxide Chemical group 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 2
- 239000012535 impurity Substances 0.000 abstract description 41
- 229910052785 arsenic Inorganic materials 0.000 abstract description 27
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 abstract description 26
- 229910052731 fluorine Inorganic materials 0.000 abstract description 23
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 22
- 239000011737 fluorine Substances 0.000 abstract description 22
- 230000008901 benefit Effects 0.000 abstract description 8
- 239000011259 mixed solution Substances 0.000 abstract description 6
- 229910000162 sodium phosphate Inorganic materials 0.000 abstract 2
- 239000001488 sodium phosphate Substances 0.000 abstract 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 abstract 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 abstract 1
- 150000003839 salts Chemical class 0.000 abstract 1
- 239000010802 sludge Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 58
- 239000000243 solution Substances 0.000 description 13
- 238000004821 distillation Methods 0.000 description 7
- 239000012141 concentrate Substances 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- VUEDNLCYHKSELL-UHFFFAOYSA-N arsonium Chemical compound [AsH4+] VUEDNLCYHKSELL-UHFFFAOYSA-N 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000002910 solid waste Substances 0.000 description 3
- OBSZRRSYVTXPNB-UHFFFAOYSA-N tetraphosphorus Chemical compound P12P3P1P32 OBSZRRSYVTXPNB-UHFFFAOYSA-N 0.000 description 3
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 2
- AQLMHYSWFMLWBS-UHFFFAOYSA-N arsenite(1-) Chemical compound O[As](O)[O-] AQLMHYSWFMLWBS-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 2
- 229910001634 calcium fluoride Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000001627 detrimental effect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- RMBBSOLAGVEUSI-UHFFFAOYSA-H Calcium arsenate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-][As]([O-])([O-])=O.[O-][As]([O-])([O-])=O RMBBSOLAGVEUSI-UHFFFAOYSA-H 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 229910001378 barium hypophosphite Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- BMWMWYBEJWFCJI-UHFFFAOYSA-K iron(3+);trioxido(oxo)-$l^{5}-arsane Chemical compound [Fe+3].[O-][As]([O-])([O-])=O BMWMWYBEJWFCJI-UHFFFAOYSA-K 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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Abstract
The invention discloses a method for preparing sodium hypophosphite. Aeration and a lime-ferric salt method are adopted for removing arsenic and fluorine impurities, and a mixed solution of the sodium hypophosphite and sodium phosphate is obtained; and evaporation concentration, crystallization and ethanol distillation-recrystallization methods are used for obtaining high-purity industrial level sodium hypophosphite and sodium phosphate products. According to the method, the comprehensive utilization rate of effective elements of phosphorus in phosphorous sludge is improved, wherein extracting agents of ethanol can be recovered and utilized, resources are saved, and simultaneously, the environment pollution is avoided; and in addition, the method has the advantages that the operation is simple, the equipment requirement is not high, the investment cost is low, and obvious environment benefits and economic benefits are realized.
Description
Technical field
The present invention relates to a kind of is the method that raw material is produced the purification sodium hypophosphite with mud phosphorus, belongs to the field of reclamation of solid wastes and sodium hypophosphite industry.
Background technology
Mud phosphorus is the solid waste that producing yellow Phosphorus by electric oven produces, and is the mixture of a kind of dust, phosphorus, water, and its phosphorus content generally is about 5%～50% because made from extra care degree difference difference to some extent, in addition, also contains other impurity such as SiO
2, CaO, C, Fe
2O
3, As, F, A1
2O
3Deng, belong to Hazardous wastes.Is that raw material is produced the treatment process that sodium hypophosphite is a kind of cleaning, economy according to bibliographical information with mud phosphorus.Sodium hypophosphite is a kind of important industrial reduction agent, is widely used in aspects such as electroless plating, the production of nickel metal hydride battery negative electrode, foodstuff production, organic synthesis, oil field petroleum emulsification auxiliary agent production, medicine.Therefore, utilizing phosphorus in the mud phosphorus to make the sodium hypophosphite product not only can harmless treatment yellow phosphorus industry solid waste, and phosphorus wherein is converted into the high product of economic worth, has favorable economic benefit and environmental benefit.
But owing to also contain detrimental impurity such as arsenic, fluorine in the mud phosphorus, when utilizing mud phosphorus to produce sodium hypophosphite, detrimental impurity also enters into the sodium hypophosphite product along with phosphorus together; In addition, also there is the side reaction product sodium phosphite in the product.These impurity and sodium phosphite all will influence the grade of product sodium hypophosphite, therefore, obtain high-quality technical grade sodium hypophosphite product, just must remove impurity, the separating by-products sodium phosphite.
Contain cl ions, sulfate ion and heavy metal ion lead, arsenic etc. in the technical grade sodium hypophosphite product.At present sodium hypophosphite is purified preliminary achievement in research has been arranged; Mainly contain: (1) is raw material with the technical grade sodium hypophosphite; Adopt the sedimentary method of Silver monochloride, permanent white and heavy metal sulfide to remove contained cl ions, sulfate radical and heavy metal ion such as iron, lead (patent publication No. CN1762796A) in the sodium hypophosphite raw material respectively; Though this method can effectively be removed above-mentioned ion; But the removal of not mentioned arsonium ion, fluorion and sodium phosphite, this method is not suitable for the system that mud phosphorus is produced the product sodium hypophosphite.(2) patent 101332981A (publication number) discloses a kind of barium hypophosphite that adopts and has removed the sulfate radical in the solution; Then through process steps such as concentrated, cooling, crystallization and centrifugal packings; The method of refined product sodium hypophosphite; But when adopting this method, the by product sodium phosphite is failed effective recycling.
Summary of the invention
The present invention has aimed to provide a kind of preparation method of sodium hypophosphite; For effectively removing with mud phosphorus is that raw material is produced arsonium ion, the fluorion in the sodium hypophosphite product; Simultaneously sodium phosphite and sodium hypophosphite are effectively separated obtaining two kinds of products, reach the purpose of the comprehensive utilization ratio of further raising phosphorus.
The present invention realizes through following technical scheme:
1, Impurity removal: under nitrogen protection, mud phosphorus, water and alkali mixing are reacted, make the thick product of sodium hypophosphite after the reaction; Get the thick product solution of sodium hypophosphite and carry out first aeration and make trivalent arsenic be oxidized to pentavalent arsenic, add calcium hydroxide and ferrous sulfate then after, aeration, oscillatory reaction once more; After reacting completely; Add flocculation agent again, leave standstill filtration, obtain sodium hypophosphite and sodium phosphite and mix filtrating; Fluorine and calcium hydroxide reaction generate the Calcium Fluoride (Fluorspan) deposition and are able to removal in the reaction; Oxidation of divalent becomes ferric iron during aeration; Ferric iron and arsenic reaction generate ferric arsenate, the iron arsenite deposition is able to remove; Remaining calcium hydroxide and arsenic generate Tricalcium arsenate and calcium arsenite deposition, simultaneously because the ironic hydroxide hydrate has adsorptivity removes after with impurity absorption co-precipitation such as Calcium Fluoride (Fluorspan), arsenides.
2, separate sodium phosphite: get sodium hypophosphite and sodium phosphite and mix filtrating evaporation concentration, crystallization; In ethanol and sodium hypophosphite and sodium phosphite mixeding liquid volume ratio is the ratio interpolation ethanolic soln of 1 ~ 1.4:1; The pH value is regulated in the dissolving back; Carry out crystallization, filtration, obtain the sodium phosphite solid, the seasoning at normal temperatures of sodium phosphite solid promptly gets the sodium phosphite product;
3, extract sodium hypophosphite: will be dissolved in the alcoholic acid sodium hypophosphite solution distills-recrystallization separation sodium hypophosphite, solid seasoning at normal temperatures can obtain the sodium hypophosphite product after the crystallization, and the ethanol that distills returns recycle.
Be under the nitrogen protection of 10～30mL/min at flow velocity described in the present invention, mud phosphorus, water and alkali are carried out hybrid reaction at 80～90 ℃, wherein mud phosphorus: water: the mol ratio of alkali is 1:100～130:2.8～5.4; Make the thick product of sodium hypophosphite behind reaction 5.5～6.5h, get the thick product solution of 100ml sodium hypophosphite and carry out first aeration, aeration time is 5～6h; Add 1.2～1.6g calcium hydroxide and 0.4～0.6g ferrous sulfate then, regulating pH is 8.2～12.6, and aeration time is 11～12h once more; Behind oscillatory reaction 40～45min, add flocculation agent, leave standstill 50～60min; Filter, obtain sodium hypophosphite and sodium phosphite and mix filtrating.
Alkali described in the present invention is sodium hydroxide and the calcium hydroxide mixture formed of 4～6:1 in molar ratio.
Flocculation agent described in the present invention is aluminium chlorohydroxide (PAC) or SEPIGEL 305 (PAM), and the SEPIGEL 305 addition is 0.1～0.2mg/100ml, and the aluminium chlorohydroxide addition is 1～2mg/100ml.
Get the 50mL sodium hypophosphite described in the present invention and the sodium phosphite mixed solution carries out evaporation concentration at 95～105 ℃; Carry out crystallization at 64～66 ℃, in crystalline product, add ethanolic soln 50～70mL, in 40～45 ℃ of dissolvings down of temperature; Regulating pH is 7.6～7.85; Under 70～75 ℃ of conditions, carry out ethyl alcohol recrystallization at last, filter, obtain the sodium phosphite solid.
Distillation-the recrystallization that is dissolved in alcoholic acid sodium hypophosphite filtrating described in the present invention is to carry out under 70～75 ℃ of conditions in temperature, and recrystallization solvent is an ethanol.
The concentration of alcohol solvent described in the present invention is 90～93%.
The present invention adopts aeration and lime-iron salt method to remove wherein arsenic, fluorine impurity; Sodium phosphite for wherein then utilizes the method for ethanol distillation-recrystallization to separate, and obtains reductibility sodium phosphite product preferably simultaneously.Recycle for distillation method recrystallization solvent ethanol, avoided pollution, practiced thrift resource.
Major advantage of the present invention and effect:
The present invention utilizes the solid waste-mud phosphorus in the yellow phosphorus industry production process to produce the sodium hypophosphite product; Not only can effectively remove impurity such as arsonium ion in the product sodium hypophosphite, fluorion; Obtain the purified product sodium hypophosphite, can also obtain the sub product sodium phosphite, improve the comprehensive utilization ratio of mud phosphorus; Extraction agent ethanol obtains recycle, has practiced thrift resource; Can also avoid mud phosphorus to store up the environmental pollution that causes in a large number, have tangible environmental benefit and economic benefit, and present method is simple to operate, not high to equipment requirements, cost of investment is low.
Description of drawings
Fig. 1 is a removal of impurities schematic flow sheet in the inventive method.
Fig. 2 is a separation process synoptic diagram in the inventive method.
Embodiment
Below in conjunction with accompanying drawing and embodiment the present invention is described further, but protection scope of the present invention is not limited to said content.
Embodiment 1: the preparation method of this sodium hypophosphite, and concrete steps are following:
At flow velocity is under the nitrogen protection of 20mL/min, mud phosphorus, water and alkali is carried out hybrid reaction at 85 ℃, wherein mud phosphorus: water: the mass ratio of alkali is 1:110:3.6; Wherein alkali is that (sodium hydroxide: calcium hydroxide=5:1), the thick product of sodium hypophosphite that contains arsenic 1.57%, fluorine 0.11%, sodium phosphite 45.48%, sodium hypophosphite 52.47%, other foreign matter content 0.1% that makes behind the reaction 6h is got the thick product solution of 100ml sodium hypophosphite for sodium hydroxide and calcium hydroxide; First aeration time is 6h, add calcium hydroxide 1.6g, ferrous sulfate 0.6g, adjustment pH then is 8.6, once more behind the aeration 12h, and oscillatory reaction 40min; Add 0.15mg PAM non-ionic type, time of repose is 60min, filtering and impurity removing; Get 95 ℃ of distillations of 50ml mixing solutions after the removal of impurities and concentrate, under 65 ℃ of conditions, carry out crystallization, in crystalline product, add the alcohol solvent of 50ml 92%; 45 ℃ of dissolvings; Regulate pH=7.65,, filter at 70 ℃ of following recrystallizations; Obtain the sodium phosphite solid, the seasoning at normal temperatures of sodium phosphite solid promptly gets the sodium phosphite product; Be dissolved in alcoholic acid sodium hypophosphite filtrating; Under the condition of 72 ℃ of temperature, distill-recrystallization; After passing through removal of impurities and separating, the sodium hypophosphite product purity 98.98% that obtains, wherein sodium phosphite content 0.92%, arsenic content 0.0003%, fluorine 0.00001%, other impurity are less than 0.1%; The sodium phosphite product purity reaches 99.21%, and wherein sodium hypophosphite content 0.65%, arsenic content 0.0002%, fluorine 0.00002%, other impurity are less than 0.14%.
Embodiment 2: the preparation method of this sodium hypophosphite, and concrete steps are following:
At flow velocity is under the nitrogen protection of 20mL/min, mud phosphorus, water and alkali is carried out hybrid reaction at 80 ℃, wherein mud phosphorus: water: the mass ratio of alkali is 1:110:3.6; Wherein alkali be sodium hydroxide and calcium hydroxide (sodium hydroxide: calcium hydroxide=4:1), make the thick product of sodium hypophosphite that contains arsenic 1.55%, fluorine 0.13%, sodium phosphite 48.18%, sodium hypophosphite 50.04%, other foreign matter content 0.1% behind the reaction 5.5h, get the thick product solution of 100ml sodium hypophosphite; First aeration time is 5h, add calcium hydroxide 1.4g, ferrous sulfate 0.5g, adjustment pH then is 9.0, and aeration 11h, duration of oscillation reaction 43min add the 0.2mg anionic PAM once more; Time of repose is 55min, and filtering and impurity removing is got 100 ℃ of distillations of 50ml mixing solutions and concentrated after the removal of impurities; 64 ℃ of following crystallizations; In crystalline product, add 60ml 90% alcohol solvent, 42 ℃ of dissolvings, regulator solution pH=7.60; At 73 ℃ of following recrystallizations; Filter, obtain the sodium phosphite solid, the seasoning at normal temperatures of sodium phosphite solid promptly gets the sodium phosphite product; Being dissolved in alcoholic acid sodium hypophosphite filtrating distills under 70 ℃ condition-recrystallization; After passing through removal of impurities and separating; The sodium hypophosphite product purity 98.95% that obtains, wherein sodium phosphite content 0.97%, arsenic content 0.0002%, fluorine 0.00003%, other impurity are less than 0.08%; The sodium phosphite product purity reaches 99.32%, and wherein sodium hypophosphite content 0.55%, arsenic content 0.0001%, fluorine 0.00001%, other impurity are less than 0.13%.
Embodiment 3: the preparation method of this sodium hypophosphite, and concrete steps are following:
At flow velocity is under the nitrogen protection of 30mL/min, mud phosphorus, water and alkali is carried out hybrid reaction at 90 ℃, wherein mud phosphorus: water: the mass ratio of alkali is 1:130:5.4; Wherein alkali be sodium hydroxide and calcium hydroxide (sodium hydroxide: calcium hydroxide=6:1), make the thick product of sodium hypophosphite that contains arsenic 1.57%, fluorine 0.11%, sodium phosphite 45.48%, sodium hypophosphite 52.47%, other foreign matter content 0.1% behind the reaction 6.5h, get the thick product solution of 100ml sodium hypophosphite; First aeration time is 5.5h, add calcium hydroxide 1.2g, ferrous sulfate 0.4g, adjustment pH then is 12.6, once more behind the aeration 11.5h, and oscillatory reaction 45min; Add 0.1mg non-ionic type PAM, time of repose is 50min, filtering and impurity removing; Get 105 ℃ of distillations of 50ml mixed solution after the removal of impurities and concentrate,, in crystalline product, add the alcohol solvent of 70ml 93% 66 ℃ of following crystallizations; 40 ℃ of dissolvings; Regulate pH=7.85,, filter at 75 ℃ of following recrystallizations; Obtain the sodium phosphite solid, the seasoning at normal temperatures of sodium phosphite solid promptly gets the sodium phosphite product; Be dissolved in alcoholic acid sodium hypophosphite filtrating; Under the condition of 75 ℃ of temperature, distill-recrystallization; After passing through removal of impurities and separating, the sodium hypophosphite product purity 98.96% that obtains, wherein sodium phosphite content 0.94%, arsenic content 0.0002%, fluorine 0.00002%, other impurity are less than 0.1%; The sodium phosphite product purity reaches 99.35%, and wherein sodium hypophosphite content 0.61%, arsenic content 0.0002%, fluorine 0.00002%, other impurity are less than 0.12%.
Embodiment 4: the preparation method of this sodium hypophosphite, and concrete steps are following:
At flow velocity is under the nitrogen protection of 10mL/min, mud phosphorus, water and alkali is carried out hybrid reaction at 85 ℃, wherein mud phosphorus: water: the mass ratio of alkali is 1:100:2.8; Wherein alkali be sodium hydroxide and calcium hydroxide (sodium hydroxide: calcium hydroxide=5:1), make the thick product of sodium hypophosphite that contains arsenic 1.56%, fluorine 0.12%, sodium phosphite 45.68%, sodium hypophosphite 52.54%, other foreign matter content 0.1% behind the reaction 6h, get the thick product solution of 100ml sodium hypophosphite; First aeration time is 6h, add calcium hydroxide 1.5g, ferrous sulfate 0.5g, adjustment pH then is 10, once more behind the aeration 12h, and oscillatory reaction 45min; Add 1mg PAC, time of repose is 60min, filtering and impurity removing; Get 100 ℃ of distillations of 50ml mixed solution after the removal of impurities and concentrate,, in crystalline product, add the alcohol solvent of 50ml 93% 66 ℃ of following crystallizations; 40 ℃ of dissolvings are regulated pH=7.7, at 75 ℃ of following recrystallizations; Filter, obtain the sodium phosphite solid, the seasoning at normal temperatures of sodium phosphite solid promptly gets the sodium phosphite product; Be dissolved in alcoholic acid sodium hypophosphite filtrating; Under the condition of 75 ℃ of temperature, distill-recrystallization; After passing through removal of impurities and separating, the sodium hypophosphite product purity 98.97% that obtains, wherein sodium phosphite content 0.93%, arsenic content 0.0002%, fluorine 0.00002%, other impurity are less than 0.1%; The sodium phosphite product purity reaches 99.31%, and wherein sodium hypophosphite content 0.59%, arsenic content 0.0002%, fluorine 0.00001%, other impurity are less than 0.12%.
Embodiment 5: the preparation method of this sodium hypophosphite, and concrete steps are following:
At flow velocity is under the nitrogen protection of 20mL/min, mud phosphorus, water and alkali is carried out hybrid reaction at 90 ℃, wherein mud phosphorus: water: the mass ratio of alkali is 1:120:4.0; Wherein alkali be sodium hydroxide and calcium hydroxide (sodium hydroxide: calcium hydroxide=4:1), make the thick product of sodium hypophosphite that contains arsenic 1.45%, fluorine 0.13%, sodium phosphite 46.18%, sodium hypophosphite 52.14%, other foreign matter content 0.1% behind the reaction 5.5h, get the thick product solution of 100ml sodium hypophosphite; First aeration time is 6h, add calcium hydroxide 1.3g, ferrous sulfate 0.4g, adjustment pH then is 10, once more behind the aeration 11h, and oscillatory reaction 42min; Add 2mg PAC, time of repose is 55min, filtering and impurity removing; Get 95 ℃ of distillations of 50ml mixed solution after the removal of impurities and concentrate,, in crystalline product, add the alcohol solvent of 60ml 90% 65 ℃ of following crystallizations; 41 ℃ of dissolvings are regulated pH=7.8, at 70 ℃ of following recrystallizations; Filter, obtain the sodium phosphite solid, the seasoning at normal temperatures of sodium phosphite solid promptly gets the sodium phosphite product; Be dissolved in alcoholic acid sodium hypophosphite filtrating; Under the condition of 75 ℃ of temperature, distill-recrystallization; After passing through removal of impurities and separating, the sodium hypophosphite product purity 98.94% that obtains, wherein sodium phosphite content 0.94%, arsenic content 0.0001%, fluorine 0.00002%, other impurity are less than 0.1%; The sodium phosphite product purity reaches 99.33%, and wherein sodium hypophosphite content 0.58%, arsenic content 0.0001%, fluorine 0.00002%, other impurity are less than 0.12%.
Embodiment 6: the preparation method of this sodium hypophosphite, and concrete steps are following:
At flow velocity is under the nitrogen protection of 25mL/min, mud phosphorus, water and alkali is carried out hybrid reaction at 80 ℃, wherein mud phosphorus: water: the mass ratio of alkali is 1:115:4.0; Wherein alkali be sodium hydroxide and calcium hydroxide (sodium hydroxide: calcium hydroxide=4:1), make the thick product of sodium hypophosphite that contains arsenic 1.57%, fluorine 0.13%, sodium phosphite 44.48%, sodium hypophosphite 52.65%, other foreign matter content 0.1% behind the reaction 6h, get the thick product solution of 100ml sodium hypophosphite; First aeration time is 5.5h, add calcium hydroxide 1.3g, ferrous sulfate 0.5g, adjustment pH then is 11.5, once more behind the aeration 11h, and oscillatory reaction 44min; Add 1.5mg PAC, time of repose is 55min, filtering and impurity removing; Get 100 ℃ of distillations of 50ml mixed solution after the removal of impurities and concentrate,, in crystalline product, add the alcohol solvent of 65ml 92% 65 ℃ of following crystallizations; 42 ℃ of dissolvings are regulated pH=7.75, at 75 ℃ of following recrystallizations; Filter, obtain the sodium phosphite solid, the seasoning at normal temperatures of sodium phosphite solid promptly gets the sodium phosphite product; Be dissolved in alcoholic acid sodium hypophosphite filtrating; Under the condition of 70 ℃ of temperature, distill-recrystallization; After passing through removal of impurities and separating, the sodium hypophosphite product purity 98.99% that obtains, wherein sodium phosphite content 0.91%, arsenic content 0.0002%, fluorine 0.00002%, other impurity are less than 0.1%; The sodium phosphite product purity reaches 99.32%, and wherein sodium hypophosphite content 0.62%, arsenic content 0.0002%, fluorine 0.00002%, other impurity are less than 0.11%.
Claims (7)
1. the preparation method of a sodium hypophosphite is characterized in that carrying out as follows:
(1) under nitrogen protection, mud phosphorus, water and alkali mixing are reacted, make the thick product of sodium hypophosphite after the reaction; Get the thick product solution of sodium hypophosphite and carry out first aeration, add calcium hydroxide and ferrous sulfate then after, aeration once more; Oscillatory reaction; Add flocculation agent after reacting completely again, leave standstill filtration, obtain sodium hypophosphite and sodium phosphite and mix filtrating;
(2) get sodium hypophosphite and sodium phosphite and mix filtrating evaporation concentration, crystallization; Add ethanolic soln in ethanol and sodium hypophosphite and sodium phosphite mixeding liquid volume than the ratio of 1～1.4:1; The pH value is regulated in the dissolving back; Carry out recrystallization, filtration, obtain the sodium phosphite solid, the seasoning at normal temperatures of sodium phosphite solid promptly gets the sodium phosphite product;
(3) be dissolved in alcoholic acid sodium hypophosphite filtrating, adopt distillation-recrystallization method to separate sodium hypophosphite, solid seasoning at normal temperatures can obtain the sodium hypophosphite product after the crystallization.
2. sodium hypophosphite preparation method according to claim 1 is characterized in that: be under the nitrogen protection of 10～30mL/min at flow velocity, mud phosphorus, water and alkali are carried out hybrid reaction at 80～90 ℃; Mud phosphorus wherein: water: the mol ratio of alkali is 1:100～130:2.8～5.4, makes the thick product of sodium hypophosphite behind reaction 5.5～6.5h, gets the thick product solution of 100mL sodium hypophosphite and carries out first aeration; Aeration time is 5～6h, adds 1.2～1.6g calcium hydroxide and 0.4～0.6g ferrous sulfate then, and regulating pH is 8.6～12.6; Aeration 11～12h once more; Behind oscillatory reaction 40～45min, add flocculation agent, leave standstill 50～60min; Filter, obtain sodium hypophosphite and sodium phosphite and mix filtrating.
3. sodium hypophosphite preparation method according to claim 1 and 2 is characterized in that: alkali is sodium hydroxide and the calcium hydroxide mixture formed of 4～6:1 in molar ratio.
4. sodium hypophosphite preparation method according to claim 1 and 2 is characterized in that: flocculation agent is aluminium chlorohydroxide or SEPIGEL 305, and the SEPIGEL 305 addition is 0.1～0.2mg/100ml, and the aluminium chlorohydroxide addition is 1～2mg/100ml.
5. according to the sodium hypophosphite preparation method described in the claim 1, it is characterized in that: get 50mL sodium hypophosphite and sodium phosphite mixing filtrating and carry out evaporation concentration, carry out crystallization at 64～66 ℃ at 95～105 ℃; In crystalline product, add ethanolic soln 50～70mL; In 40～45 ℃ of dissolvings down of temperature, regulating pH is 7.6～7.85, under 70～75 ℃ of conditions, carries out ethyl alcohol recrystallization at last; Filter, obtain the sodium phosphite solid.
6. sodium hypophosphite preparation method according to claim 1 is characterized in that: the distillation-recrystallization that is dissolved in alcoholic acid sodium hypophosphite filtrating is to carry out under 70～75 ℃ of conditions in temperature, and recrystallization solvent is an ethanol.
7. according to the sodium hypophosphite preparation method described in claim 5 or 6, it is characterized in that: alcohol solvent concentration is 90～93%.
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| CN110451469A (en) * | 2019-08-21 | 2019-11-15 | 武汉工程大学 | A kind of processing method of Sodium hypophosphite production residue |
| CN113636573A (en) * | 2021-09-08 | 2021-11-12 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for producing qualified primary brine by deeply refining chlor-alkali based on NaCl brine recovered from fused salt chlorination residues |
| CN117771905A (en) * | 2024-02-28 | 2024-03-29 | 常熟新特化工有限公司 | Preparation method and equipment of high-purity sodium hypophosphite |
| CN117771905B (en) * | 2024-02-28 | 2024-05-17 | 常熟新特化工有限公司 | Preparation method and equipment of high-purity sodium hypophosphite |
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