CN110015688B - Preparation method for reducing particle size of sodium pyroantimonate - Google Patents
Preparation method for reducing particle size of sodium pyroantimonate Download PDFInfo
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- CN110015688B CN110015688B CN201810020736.3A CN201810020736A CN110015688B CN 110015688 B CN110015688 B CN 110015688B CN 201810020736 A CN201810020736 A CN 201810020736A CN 110015688 B CN110015688 B CN 110015688B
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- CIWAOCMKRKRDME-UHFFFAOYSA-N tetrasodium dioxido-oxo-stibonatooxy-lambda5-stibane Chemical compound [Na+].[Na+].[Na+].[Na+].[O-][Sb]([O-])(=O)O[Sb]([O-])([O-])=O CIWAOCMKRKRDME-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000002245 particle Substances 0.000 title abstract description 43
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 105
- 238000006243 chemical reaction Methods 0.000 claims abstract description 46
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 37
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000004094 surface-active agent Substances 0.000 claims abstract description 23
- 238000001556 precipitation Methods 0.000 claims abstract description 18
- 238000005406 washing Methods 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims abstract description 14
- 238000000926 separation method Methods 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims description 16
- 239000007853 buffer solution Substances 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 10
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- 239000003063 flame retardant Substances 0.000 claims description 9
- 239000011521 glass Substances 0.000 claims description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 7
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 6
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 6
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 claims description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 235000002906 tartaric acid Nutrition 0.000 claims description 3
- 239000011975 tartaric acid Substances 0.000 claims description 3
- 238000010951 particle size reduction Methods 0.000 claims 4
- 230000008569 process Effects 0.000 abstract description 14
- NSBGJRFJIJFMGW-UHFFFAOYSA-N trisodium;stiborate Chemical compound [Na+].[Na+].[Na+].[O-][Sb]([O-])([O-])=O NSBGJRFJIJFMGW-UHFFFAOYSA-N 0.000 abstract description 14
- 239000000047 product Substances 0.000 abstract description 12
- 230000003647 oxidation Effects 0.000 abstract description 9
- 230000001590 oxidative effect Effects 0.000 abstract description 3
- 239000002244 precipitate Substances 0.000 abstract description 3
- 239000013078 crystal Substances 0.000 abstract description 2
- 230000006872 improvement Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000010419 fine particle Substances 0.000 abstract 1
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 abstract 1
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 description 18
- 238000003756 stirring Methods 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 10
- 239000012065 filter cake Substances 0.000 description 9
- 238000009826 distribution Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 229920003023 plastic Polymers 0.000 description 7
- 239000004033 plastic Substances 0.000 description 7
- 239000003513 alkali Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 230000002378 acidificating effect Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000004064 recycling Methods 0.000 description 5
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 5
- 239000012265 solid product Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 229910000410 antimony oxide Inorganic materials 0.000 description 2
- 238000000889 atomisation Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- WCTAGTRAWPDFQO-UHFFFAOYSA-K trisodium;hydrogen carbonate;carbonate Chemical compound [Na+].[Na+].[Na+].OC([O-])=O.[O-]C([O-])=O WCTAGTRAWPDFQO-UHFFFAOYSA-K 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- KEQXNNJHMWSZHK-UHFFFAOYSA-L 1,3,2,4$l^{2}-dioxathiaplumbetane 2,2-dioxide Chemical compound [Pb+2].[O-]S([O-])(=O)=O KEQXNNJHMWSZHK-UHFFFAOYSA-L 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 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
- 239000002253 acid Substances 0.000 description 1
- 150000001462 antimony Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 239000008395 clarifying agent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- -1 for example Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000011084 recovery Methods 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
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- YEAUATLBSVJFOY-UHFFFAOYSA-N tetraantimony hexaoxide Chemical compound O1[Sb](O2)O[Sb]3O[Sb]1O[Sb]2O3 YEAUATLBSVJFOY-UHFFFAOYSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G30/00—Compounds of antimony
- C01G30/02—Antimonates; Antimonites
- C01G30/023—Antimonates; Antimonites of ammonium, alkali or alkaline-earth metals or magnesium
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
- C03C1/004—Refining agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/51—Particles with a specific particle size distribution
- C01P2004/52—Particles with a specific particle size distribution highly monodisperse size distribution
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Geochemistry & Mineralogy (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
本发明公开了一种降低焦锑酸钠粒度的制备方法，包括以下步骤：步骤(1)：三氧化二锑、双氧水预先进行氧化反应；步骤(2)：步骤(1)反应结束后，向反应体系中投加表面活性剂和氢氧化钠，进行沉淀反应；沉淀反应结束后经固液分离、洗涤、干燥处理，得到细粒径的焦锑酸钠。本发明以三氧化二锑为原料，用双氧水充分氧化三氧化二锑，并加入表面活性剂促进晶粒的细化，然后加入氢氧化钠溶液进行充分反应，所产生的沉淀经洗涤，得到最终产品超细焦锑酸钠。本发明与传统工艺相比，采用先加双氧水氧化，再加氢氧化钠反应；而传统工艺则是先加氢氧化钠，再加双氧水。传统工艺得到的焦锑酸钠粒度一般为40um左右，而本发明在晶粒粒度上有非常大的改善。The invention discloses a preparation method for reducing the particle size of sodium pyroantimonate, which comprises the following steps: step (1): pre-oxidizing antimony trioxide and hydrogen peroxide; A surfactant and sodium hydroxide are added into the reaction system to carry out a precipitation reaction; after the precipitation reaction is completed, solid-liquid separation, washing and drying are carried out to obtain sodium pyroantimonate with fine particle size. The invention uses antimony trioxide as a raw material, fully oxidizes antimony trioxide with hydrogen peroxide, adds a surfactant to promote the refinement of crystal grains, and then adds sodium hydroxide solution to fully react, and the resulting precipitate is washed to obtain the final Products ultra-fine pyro sodium antimonate. Compared with the traditional process, the present invention adopts hydrogen peroxide to be added for oxidation first, and then sodium hydroxide is added for reaction; while the traditional process is to add sodium hydroxide first, and then add hydrogen peroxide. The particle size of sodium pyroantimonate obtained by the traditional process is generally about 40um, and the present invention has a very large improvement in the particle size.
Description
Technical Field
The invention relates to a preparation method of superfine sodium pyroantimonate, which is widely used for flame retardant materials and belongs to the technical field of flame retardant materials.
Background
Sodium pyroantimonate is a white powder with granular and equiaxed crystals, is resistant to high temperature and does not decompose at 1000 ℃, and can be used as a high-grade glass clarifying agent and decoloring agent, a flame retardant for plastics and textiles, a milk-white agent for enamels and ceramics and an opaque coating for casting paints. The capacity of antimony series processed products in China is only inferior to that of antimony oxide. Along with the development of science and technology, the glass is required to be clarified and the atomization prevention level is higher, the flame retardant effect of the plastic is better, and correspondingly, higher requirements are also put forward on the performance of the sodium antimonate. The granularity is one of important indexes, the surface atom percentage is increased along with the reduction of the particle size of the particles, the surface defect structure is increased, the dispersibility and the compatibility of the superfine sodium antimonate in plastics and glass are incomparable with those of common sodium antimonate, and various performances of the product are obviously improved. When the granularity of the sodium antimonate is less than 2um, the clarification and atomization prevention capability of the automobile glass is improved by 10 times, and the flame retardant effect of the plastic is close to 100 percent.
At present, the domestic production method of sodium pyroantimonate mainly comprises four methods, namely, a sodium nitrate oxidation method; ② hydrogen peroxide oxidation method; thirdly, a chlorine gas oxidation method; air oxidation method. These methods all relate to the preparation method of common sodium antimonate, and do not relate to the control of the form and structure of sodium antimonate. The method is characterized in that a hydrogen peroxide oxidation method is widely used in industry, antimony white is used as a raw material, sodium hydroxide is used as a solvent, hydrogen peroxide is used as an oxidant, and a sodium pyroantimonate product is obtained by direct synthesis. For example, chinese patent publication No. CN87102082 discloses a production process for preparing fine granular sodium pyroantimonate, which belongs to a chemical inorganic salt process. The invention is characterized in that Sb2O3 and NaOH are synthesized into sodium antimonite in H2O2Is converted into Na by the action of2H2Sb2O7·5H2And O. Wherein the concentration of NaOH is 27-35%, the reaction temperature is 85-95 ℃, the drying temperature is 100 +/-2 ℃, and the stirring speed is 80-90 r/min. The reaction is carried out under normal pressure, the product is formed into granules by controlling the reaction condition, and then the granules are washed, dried, tested and packaged.
The sodium antimonate produced by the existing method has the particle size of 20-40 um, large particles, wide particle size distribution range, low flame retardant effect on plastics and low level for preventing glass from being atomized. How to successfully prepare the superfine sodium pyroantimonate effectively is still a problem which is faced by the inventor and the technical personnel in the field and needs to be solved urgently.
Disclosure of Invention
In order to solve the technical problem of overlarge particle size of the existing sodium pyroantimonate, the invention provides a preparation method for reducing the particle size of the sodium pyroantimonate, and aims to reduce the particle size of the obtained sodium pyroantimonate.
The invention also comprises the sodium pyroantimonate with the ultrafine grain size prepared by the preparation method.
A preparation method for reducing the particle size of sodium pyroantimonate comprises the following steps:
step (1): carrying out oxidation reaction on antimony trioxide and hydrogen peroxide in advance;
step (2): after the reaction in the step (1) is finished, adding a surfactant and sodium hydroxide into a reaction system to perform a precipitation reaction; after the precipitation reaction is finished, carrying out solid-liquid separation, washing and drying treatment to obtain the fine-particle-size sodium pyroantimonate.
The inventor initiatively provides a preparation method for reducing the granularity of the sodium pyroantimonate. The method overcomes the traditional synthetic thought that the prior art firstly carries out alkali (sodium hydroxide) leaching and then carries out oxidation, originally carries out oxidation reaction on the antimony trioxide and the hydrogen peroxide in advance, and then carries out precipitation reaction with the sodium hydroxide under the action of the surfactant; the idea of the invention can unexpectedly solve the technical problem of overlarge particle size of the prepared material in the prior art, and can prepare the sodium pyroantimonate with superfine particle size.
Different from the prior art of generating sodium antimonate by reacting with sodium hydroxide in advance and then oxidizing the sodium antimonate into sodium pyroantimonate, the method oxidizes trivalent Sb into pentavalent Sb in advance and then performs precipitation reaction with a large amount of alkali; the technical problem of overlarge product granularity can be unexpectedly solved by changing a synthesis line and a synthesis thought.
In the step (1), the pH of the solution system before the oxidation reaction is controlled to be less than or equal to 13.
The present inventors have found through extensive practice that controlling the pH of step (1), particularly within the pH range described, unexpectedly further reduces the particle size of the resulting sodium pyroantimonate.
In the invention, the solution before oxidation reaction refers to a mixed solution obtained by mixing antimony trioxide, hydrogen peroxide and a selective solvent (water).
In an embodiment of the oxidation reaction of the present invention, in step (1), the solution system before the oxidation reaction is an acidic system.
Preferably, in the step (1), the pH of the solution system before the oxidation reaction is 2 or more and 7 or less. The inventors have also found that controlling the pH under acidic to neutral conditions helps to further reduce the particle size of the sodium pyroantimonate; the granularity of the product can be reduced to about 1um, and the effect is outstanding.
In the present invention, when the oxidation reaction is carried out under acidic conditions, the pH may be adjusted to be acidic by using an acid, for example, sulfuric acid.
In another embodiment of the oxidation reaction of the present invention, the oxidation reaction is carried out under alkaline conditions; in the step (1), the pH of the solution system before the oxidation reaction is greater than 7 and less than or equal to 13.
In the present invention, the oxidation process can be carried out at a pH with a small amount of alkali added, and the effect of reducing the particle size of the obtained product is unexpectedly achieved, but the effect of reducing the particle size is slightly inferior to that under acidic conditions.
In the step (1), the pH value of a solution system before oxidation reaction is adjusted to be within the range by sodium hydroxide, wherein the weight of the sodium hydroxide added in the step (1) is not higher than 2.0 percent of the weight of the added sodium hydroxide in the step (2); preferably 0.5-2.0%; further preferably 2%. In the invention, a small amount of alkali (less than 2% of the total alkali amount) is added in the step (1), and the method is mainly used for controlling the pH value in the oxidation reaction process and promoting the oxidation reaction process. The method of the invention is beneficial to obtaining the superfine sodium pyroantimonate by controlling the reaction process of the sodium pyroantimonate growth process and adding the required alkali step by step in the reaction process. The process has high yield, no three-waste pollution and narrow product granularity distribution.
In the step (1), the weight ratio of the hydrogen peroxide to the antimony trioxide is preferably 1: 0.5-1.
Preferably, the concentration of the hydrogen peroxide is preferably 15-60%; industrial hydrogen peroxide can be used.
In the present invention, controlling the verified oxidation temperature at the stated pH can help to further reduce the particle size of the resulting sodium pyroantimonate.
Preferably, in step (1), the temperature of the oxidation reaction is 30 to 100 ℃.
Further preferably, in the step (1), the temperature of the oxidation reaction is 60 to 80 ℃.
Under the conditions of the oxidation reaction temperature and the pH value, the preferable oxidation reaction time is 0.5-4 h; further preferably 1 to 4 hours.
And after the oxidation reaction is finished, adding a surfactant and supplementing a large amount of sodium hydroxide into the oxidation reaction system to perform a precipitation reaction.
The adding sequence of the surfactant and the supplemented sodium hydroxide has no requirement, and the surfactant and the supplemented sodium hydroxide are preferably mixed and added into an oxidation reaction system.
The research shows that the particle size of the obtained sodium pyroantimonate can be further reduced by the proper type of the surfactant and the addition amount of the surfactant.
Preferably, the surfactant is at least one of ethylene glycol, cetyl trimethyl ammonium bromide, isopropyl alcohol, glycerin, tartaric acid, sorbitan, polyethylene glycol, polyvinyl alcohol, and sodium lauryl sulfate.
In the step (2), the mass ratio of the surfactant to the antimony trioxide is 1: 100-120.
Preferably, in the step (2), the sodium hydroxide is preferably supplemented in the form of a solution, and preferably, in the step (2), the concentration of the added solution of the sodium hydroxide is preferably 100-480 g/L.
In the step (2), the mass ratio of the sodium hydroxide to the antimony trioxide is 1: 1.5-2.
Preferably, in the step (2), the temperature of the precipitation reaction is 80-120 ℃; further preferably 90 to 100 ℃.
The time of the precipitation reaction is preferably 1 to 3 hours.
And after the precipitation reaction is finished, carrying out solid-liquid separation to obtain a sodium pyroantimonate filter cake.
In the invention, after the precipitation reaction is finished, the solid part (sodium pyroantimonate filter cake) obtained by solid-liquid separation is ultrasonically dispersed in a buffer solution with the pH value of 8.0-9.0, and the ultrasonic dispersion time is 0.5-2.0 h; the solid is then isolated and subjected to a subsequent washing step. This preferred ultrasonic dispersion treatment can further contribute to the reduction of the particle size.
The buffer solution is sodium bicarbonate-sodium carbonate solution with the pH value of 8.0-9.0.
Washing and drying the sodium pyroantimonate filter cake or the solid obtained by solid-liquid separation after ultrasonic dispersion to obtain the sodium pyroantimonate with superfine particle size.
And after ultrasonic dispersion in the buffer solution, carrying out solid-liquid separation to obtain a solid, washing the obtained solid with pure water, and drying the washed solid to obtain the superfine sodium pyroantimonate.
Preferably, the drying temperature is 80 to 100 ℃.
A more preferred preparation method of the present invention comprises the steps of:
a) adding antimony trioxide and a certain amount of pure water into a reaction kettle, fully dispersing to obtain slurry, slowly adding hydrogen peroxide into the slurry at a certain flow rate, controlling the pH value to be 2-13, and carrying out oxidation reaction for 1-4 hours at the temperature of 60-80 ℃.
b) Preparing 2-6mol/L NaOH solution, adding appropriate amount of surfactant, slowly adding into the above solution at a certain flow rate, heating to 80-120 deg.C (preferably 90-100 deg.C), reacting at constant temperature for 1-3 hr, and filtering. The surfactant is at least one of ethylene glycol, cetyl trimethyl ammonium bromide, isopropanol, glycerol, tartaric acid, sorbitan, polyethylene glycol, polyvinyl alcohol and sodium dodecyl sulfate.
c) Adding the filtered solid matter (i.e. sodium pyroantimonate filter cake) into buffer solution with pH value of 8.0-9.0, and ultrasonically dispersing at normal temperature for 0.5-2.0 h.
d) Filtering, rinsing, drying at 80-100 ℃, crushing and screening the sodium antimonate obtained in the step (c) to obtain the sodium antimonate.
The invention also discloses the sodium pyroantimonate prepared by the preparation method, and the particle size of the sodium pyroantimonate is less than 10 um.
The invention also includes the use of said sodium pyroantimonate as a flame retardant or as a glass refining agent.
Advantageous effects
The invention provides a preparation method capable of reducing the particle size of the obtained sodium pyroantimonate for the first time, wherein antimony trioxide and hydrogen peroxide are subjected to oxidation reaction in advance, and then are subjected to precipitation reaction with sodium hydroxide; the idea of the invention can unexpectedly solve the technical problem of overlarge particle size of the prepared material in the prior art, and can prepare the sodium pyroantimonate with superfine particle size.
In the invention, the pH value in the oxidation reaction process is controlled, so that the particle size of the obtained sodium pyroantimonate can be unexpectedly further reduced, and the conversion rate of antimony oxide can be further improved.
The process of the invention is that the inventor comprehensively controls the whole preparation process by various methods and means, reaction solution is slowly added into a reaction system for synthesis by accurate flow control, the temperature of precipitation is controlled, and the type of the surfactant suitable for the process of the invention is particularly selected and the specific required dosage is determined, so that the sodium antimonate with the granularity of 1.7-2.3 microns and the standard deviation of the granularity of less than 15 percent is finally prepared. The invention also adopts an ultrasonic chemical method to disperse the solid in the buffer solution, and utilizes the principle of ultrasonic cavitation to generate very high temperature in the interface area around small air bubbles in a very short time, thereby providing a special critical environment for the adsorption of the surfactant, leading the surfactant to be adsorbed on the surfaces of particles to form a compact protective layer, inhibiting the generation of agglomeration of the precipitate in the subsequent washing and drying processes, leading the precipitate to have high uniform dispersibility and providing a good way for preparing narrow particle size distribution. In addition, the improvement of the invention is that in the ultrasonic dispersion and washing process, the pH value is controlled to be 8.0-9.0, and the pH value is deviated from the isoelectric point of the sodium pyroantimonate, so that the surface of the sodium pyroantimonate is charged, sodium antimonate particles mutually repel and agglomeration is inhibited, and the product obtained by the process of the invention is stable, pure, high in yield and good in performance.
In conclusion, the process has the advantages of good comprehensive recovery, high yield, no three-waste pollution and the like, the product is mainly used for a flame retardant of plastics and a clarifier of glass, the particle size is 1.7-2.3 microns, and the product has good compatibility with plastics and glass and reaches various performance indexes.
Drawings
FIG. 1 is a graph showing the particle size distribution of sodium pyroantimonate obtained in example 1;
FIG. 2 is a graph showing the particle size distribution of sodium pyroantimonate obtained in example 2;
FIG. 3 is a graph showing the particle size distribution of sodium pyroantimonate obtained in example 3;
FIG. 4 is a particle size distribution diagram of sodium pyroantimonate obtained in comparative example 1;
FIG. 5 is a graph showing the particle size distribution of sodium pyroantimonate obtained in comparative example 2.
Detailed Description
In the following examples and comparative examples, the buffer solution was a sodium bicarbonate-sodium carbonate buffer solution, and the pH was 8 to 9.
Example 1:
adding 50Kg of antimony trioxide and 200L of pure water into a 500L reaction kettle, uniformly stirring, adding 70L of hydrogen peroxide (with the concentration of 30%), uniformly stirring, controlling the pH to 7, heating to 70 ℃, reacting at a constant temperature (oxidation reaction) for 2 hours, heating to 90 ℃ after the reaction is finished, adding sodium hydroxide (the adding amount of which is 0.6 time of that of the antimony trioxide) and surfactant sodium dodecyl sulfate (0.5Kg) while stirring, and reacting at a constant temperature (90 ℃), wherein
And (3) 1.5 hours, ultrasonically dispersing the filter cake after the reaction is finished (ultrasonically dispersing the filter cake in a buffer solution with the pH value of 8-9 for 30min), then cooling and crystallizing, washing with pure water until the washing liquid is neutral, centrifugally separating, recycling the liquid, washing the solid product with water, and drying at the temperature of 80-90 ℃ to obtain the sodium pyroantimonate.
The test result is shown in figure 1, the particle size of the sodium pyroantimonate is 8.06um, the whiteness is 96 percent, and the pH value is 7.48. (Note: whiteness is measured by whiteness tester and pH is measured by pH meter.)
Example 2:
adding 50Kg of antimony trioxide and 200L of pure water into a 500L reaction kettle, uniformly stirring, adding 70L of hydrogen peroxide, uniformly stirring, adjusting the pH to 13 through sodium hydroxide, heating to 70 ℃ for reacting at a constant temperature for 2 hours, heating to 90 ℃ after the reaction is finished, adding sodium hydroxide (the addition amount of the sodium hydroxide is 0.6 times of that of the antimony trioxide) and sodium dodecyl sulfate (0.5Kg) serving as a surfactant while stirring, reacting at the constant temperature for 1.5 hours, ultrasonically dispersing filter cakes (ultrasonically dispersing in a buffer solution with the pH of 8.0-9.0) after the reaction is finished, cooling, crystallizing, centrifugally separating, recycling liquid, washing solid products with water, and drying at the temperature of 80-90 ℃ to obtain sodium pyroantimonate.
The test result is shown in figure 2, the particle size of the sodium pyroantimonate is 6.06um, the whiteness is 78 percent, and the PH value is 7.32. (Note: whiteness is measured by whiteness tester and pH is measured by pH meter.)
Example 3:
adding 50Kg of antimony trioxide and 200L of pure water into a 500L reaction kettle, uniformly stirring, adding 70L of hydrogen peroxide, uniformly stirring, adjusting the pH to 2, heating to 70 ℃ for reacting at a constant temperature for 2 hours, heating to 90 ℃ after the reaction is finished, adding sodium hydroxide (the addition is 0.6 time of that of the antimony trioxide) and sodium dodecyl sulfate (0.5Kg) as a surfactant while stirring, reacting at the constant temperature for 1.5 hours, ultrasonically dispersing filter cakes (dispersing in the buffer solution) after the reaction is finished, cooling, crystallizing, centrifugally separating, recycling liquid, washing solid products with water, and drying at the temperature of 80-90 ℃ to obtain sodium pyroantimonate.
The test result is shown in figure 3, the particle size of the sodium pyroantimonate is 1.45um, the whiteness is 98 percent, and the pH value is 7.12. (Note: whiteness is measured by whiteness tester and pH is measured by pH meter.)
Comparative example 1:
the method is characterized in that a surfactant is not added, and the specific operation is as follows:
adding 50kg of antimony trioxide and 200L of pure water into a 500L reaction kettle, uniformly stirring, adding 70L of hydrogen peroxide, uniformly stirring, adjusting the pH to 7, heating to 70 ℃ for reacting at a constant temperature for 2 hours, heating to 90 ℃ after the reaction is finished, adding sodium hydroxide (the adding amount is 0.6 times of that of the antimony trioxide) while stirring, reacting at the constant temperature for 1.5 hours, ultrasonically dispersing filter cakes after the reaction is finished, cooling, crystallizing, centrifugally separating, recycling liquid, washing solid products with water, and drying at 80-90 ℃ to obtain sodium pyroantimonate.
The test result is shown in figure 4, the particle size of the sodium pyroantimonate is 12.40um, the whiteness is 98 percent, and the pH value is 7.78. (Note: whiteness is measured by whiteness tester and pH is measured by pH meter.)
Comparative example 2:
compared with the embodiment 1, the difference is that the sodium hydroxide is added firstly, and then the hydrogen peroxide is added, and the specific operation is as follows:
adding 50Kg of antimony trioxide and 200L of pure water into a 500L reaction kettle, uniformly stirring, adding 30Kg of sodium hydroxide, uniformly stirring, heating to 90 ℃ for reacting at constant temperature for 1.5 hours, cooling to 70 ℃ after the reaction is finished, adding hydrogen peroxide (with the concentration of 30%; 70L) while stirring, reacting at constant temperature for 2.0 hours, cooling for crystallization, performing centrifugal separation, recycling liquid, washing a solid product with water, and drying at 80-90 ℃ to obtain the sodium pyroantimonate.
The test result is shown in figure 5, the particle size of the sodium pyroantimonate is 39.62um, the whiteness is 98 percent, and the pH value is 7.78. (Note: whiteness is measured by a whiteness measuring instrument, and pH is measured by a pH meter.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (7)
1. A preparation method for reducing the granularity of sodium pyroantimonate is characterized by comprising the following steps: the method comprises the following steps:
step (1): carrying out oxidation reaction on antimony trioxide and hydrogen peroxide in advance; wherein the pH of the solution system before the oxidation reaction is controlled to be less than or equal to 13; the temperature of the oxidation reaction is 30-100 ℃; the reaction time is 0.5-4 h;
step (2): after the reaction in the step (1) is finished, adding a surfactant and sodium hydroxide into a reaction system to perform a precipitation reaction; after the precipitation reaction is finished, carrying out solid-liquid separation, washing and drying treatment to obtain fine-grain-size sodium pyroantimonate;
the surfactant is at least one of ethylene glycol, cetyl trimethyl ammonium bromide, isopropanol, glycerol, tartaric acid, sorbitan, polyethylene glycol, polyvinyl alcohol and sodium dodecyl sulfate;
the mass ratio of the surfactant to the antimony trioxide is 1: 100-120;
the mass ratio of the added sodium hydroxide to the added antimony trioxide is 1: 1.5-2;
the temperature of the precipitation reaction is 80-120 ℃.
2. The method of claim 1, wherein the particle size reduction comprises the steps of: in the step (1), the pH of the solution system before the oxidation reaction is 2 or more and 7 or less.
3. The method of claim 1, wherein the particle size reduction comprises the steps of: in the step (1), the pH value of a solution system before oxidation reaction is more than 7 and less than or equal to 13; and (3) adjusting the pH value of the solution system before oxidation reaction to be in the range by using sodium hydroxide, wherein the added sodium hydroxide in the step (1) is not higher than 2% of the added sodium hydroxide in the step (2) in weight.
4. The method of any one of claims 1 to 3, wherein the method comprises the following steps: in the step (1), the temperature of the oxidation reaction is 60-80 ℃; the reaction time is 1-4 h.
5. The method of claim 1, wherein the particle size reduction comprises the steps of: in the step (2), the temperature of the precipitation reaction is 90-100 ℃.
6. The method of claim 1, wherein the particle size reduction comprises the steps of: in the step (2), ultrasonically dispersing a solid part obtained by solid-liquid separation after the precipitation reaction is finished in a buffer solution with the pH value of 8.0-9.0, wherein the ultrasonic dispersion time is 0.5-2.0 h; the solid is then isolated and subjected to a subsequent washing step.
7. The application of the sodium pyroantimonate prepared by the preparation method of any one of claims 1 to 6 is characterized in that the sodium pyroantimonate is used as a flame retardant or a glass clarifier.
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