CN106745245B - A kind of preparation method of sodium pyroantimonate and sodium metaantimonate - Google Patents
A kind of preparation method of sodium pyroantimonate and sodium metaantimonate Download PDFInfo
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- CN106745245B CN106745245B CN201611028518.1A CN201611028518A CN106745245B CN 106745245 B CN106745245 B CN 106745245B CN 201611028518 A CN201611028518 A CN 201611028518A CN 106745245 B CN106745245 B CN 106745245B
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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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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Abstract
The invention discloses the preparation methods of a kind of sodium pyroantimonate and sodium metaantimonate, sodium hydroxide and antimony oxide water is dissolved in first sufficiently to react, it is passed through ozone again, it is fully oxidized, recrystallization, centrifugation, drying obtain sodium pyroantimonate, then the crystallization water of sodium pyroantimonate is removed by microwave, pH value, drying are finally adjusted, neutral sodium metaantimonate is obtained.The present invention uses ozone as oxidant, and oxidation effectiveness is good, and the crystallization water of sodium pyroantimonate is removed by microwave, can adjust sodium metaantimonate to avoid the sodium metaantimonate high temperature xanthochromia of generation to neutrality, be more suitable for fire retardant for Polymer Processing.Simple production process of the invention, the reaction time is short, and technical process environmental protection, production cost is low, and low energy consumption, and sodium pyroantimonate and the sodium metaantimonate purity is high being prepared, whiteness is high, and pH is in neutrality, and can be used as fire retardant and is widely applied in plastic cement field.
Description
Technical field
The present invention relates to the preparation methods of a kind of sodium pyroantimonate and sodium metaantimonate, belong to fire proofing technical field.
Background technique
Sodium pyroantimonate is a kind of rising fine chemical product, can be used as high-grade glass clarifying agent and decoloration
Agent, material fire retardants etc., production capacity is only second to antimony oxide in antimony system, China converted products.The antimony resource storage in China is abundant,
Efficient and rational utilize is of great significance for the industrial development in China.
When sodium pyroantimonate is used as fire retardant, have many advantages, such as that additive amount is few, good flame retardation effect, and by sodium pyroantimonate dehydration system
Standby obtained sodium metaantimonate has temperature tolerance more better than sodium pyroantimonate and flame retarding efficiency.Traditional antimony oxide flame retardant is used for
When PET resin matrix, antimony oxide has catalytic degradation effect to PET, and plastic cement physical property is caused to decline, and influence material uses the longevity
Life, sodium pyroantimonate and sodium metaantimonate are completely absent the problem.
The production technology of sodium pyroantimonate can be divided into pyrogenic process and two kinds of wet process, wherein wet processing reaction raw materials conversion ratio compared with
Height, energy consumption is lower, domestic using most at present.During wet production sodium pyroantimonate, sodium nitrate, peroxidating are generally used
Hydrogen, chlorine or air etc. are used as oxidant, but all in place of Shortcomings: when 1) using sodium nitrate as oxidant, in process of production
Carcinogenic nitrogen oxides can be generated, environmental pollution is serious, and product quality is poor；2) right when using hydrogen peroxide as oxidant
The requirement of raw material is high, high production cost；3) when using chlorine as oxidant, production technology is complicated, and investment is big, corrodes to equipment tight
Weight, can also generate a large amount of waste water；4) when using air as oxidant, oxidation efficiency is lower, unstable product quality, the production cycle
It is long, it can also generate a large amount of sodium thiosulfate byproducts.
Sodium metaantimonate is to be dehydrated to obtain by sodium pyroantimonate high-temperature calcination mostly, and not only energy consumption is high, but also high temperature can also be led
Deflection sodium antimonate product xanthochromia, product whiteness are low.
Summary of the invention
The purpose of the present invention is to provide the preparation methods of a kind of sodium pyroantimonate and sodium metaantimonate.
The technical solution used in the present invention is:
A kind of preparation method of sodium pyroantimonate the following steps are included:
1) reaction kettle is added in sodium hydroxide and water, adds antimony oxide, 80~120 DEG C of isothermal reactions 0.5~3 are small
When；
2) 30~50 DEG C are cooled to, is passed through ozone while stirring, is carried out oxidation reaction 3~7 hours；
3) 80~120 DEG C are warming up to, is stood still for crystals, is centrifuged, it is dry, obtain sodium pyroantimonate.
Sodium hydroxide described in step 1), antimony oxide mass ratio be 1:(2.6~3.5).
The mass ratio of the gross mass and water of sodium hydroxide described in step 1) and antimony oxide is (1.0~1.3): 1.
Reaction temperature described in step 1) is 90~100 DEG C.
The temperature of crystallization described in step 3) is 90~100 DEG C, and crystallization time is 0.5~1 hour.
The temperature of drying described in step 3) is 100~120 DEG C.
A kind of preparation method of sodium metaantimonate the following steps are included:
1) sodium pyroantimonate is sloughed into the crystallization water by microwave；
2) pH adjusting agent is added, adjusts pH value to neutrality, dehydration and drying obtains sodium metaantimonate.
The frequency of microwave described in step 1) is 300~30000MHz.
PH adjusting agent described in step 2 is phosphoric acid, sulfuric acid, acetic acid, ammonium phosphate, ammonium sulfate, at least one in polyphosphoric acid
Kind.
The temperature of dehydration and drying described in step 2 is 100~120 DEG C.
The beneficial effects of the present invention are: simple production process of the invention, the reaction time is short, technical process environmental protection, production
At low cost, low energy consumption, and sodium pyroantimonate and the sodium metaantimonate purity is high being prepared, whiteness is high, and pH is in neutrality, and can be used as fire retardant
It is widely applied in plastic cement field.
1) for the present invention using ozone as oxidant, oxidizing potential of the ozone in alkaline solution reaches 2.07V, is higher than chlorine and mistake
The oxidizing potential of hydrogen oxide, oxidation effectiveness is good, reduces trivalent antimony residual, improves product purity；
2) present invention is using ozone as oxidant, instead of the corrosivity hyperoxia agent such as chlorine, and does not need vulcanized sodium exudation
Agent etc., reduces by-product, the ozone fast decoupled under basic reaction conditions, will not be to air born pollution；
3) present invention prepares sodium metaantimonate using the mode of microwave dehydration, does not need to carry out high-temperature baking operation, can not only
It consumes low, but also xanthochromia can occur because of high temperature to avoid product, product whiteness is high；
4) sodium metaantimonate is adjusted to neutrality using pH adjusting agent by the present invention, to downstream plastic cement when avoiding as fire retardant
Modification application generate adverse effect.
Specific embodiment
A kind of preparation method of sodium pyroantimonate the following steps are included:
1) reaction kettle is added in sodium hydroxide and water, adds antimony oxide, 80~120 DEG C of isothermal reactions 0.5~3 are small
When；
2) 30~50 DEG C are cooled to, is passed through ozone while stirring, is carried out oxidation reaction 3~7 hours；
3) 80~120 DEG C are warming up to, is stood still for crystals, is centrifuged, it is dry, obtain sodium pyroantimonate.
Preferably, the mass ratio of sodium hydroxide, antimony oxide described in step 1) is 1:(2.6~3.5).
Preferably, the mass ratio of the gross mass of sodium hydroxide and antimony oxide described in step 1) and water be (1.0~
1.3): 1.
Preferably, the temperature of reaction described in step 1) is 90~100 DEG C.
Preferably, the temperature of crystallization described in step 3) is 90~100 DEG C, and crystallization time is 0.5~1 hour.
Preferably, the temperature of drying described in step 3) is 100~120 DEG C.
A kind of preparation method of sodium metaantimonate the following steps are included:
1) sodium pyroantimonate is sloughed into the crystallization water by microwave；
2) pH adjusting agent is added, adjusts pH value to neutrality, dehydration and drying obtains sodium metaantimonate.
Preferably, the frequency of microwave described in step 1) is 300~30000MHz.
Preferably, pH adjusting agent described in step 2 is phosphoric acid, in sulfuric acid, acetic acid, ammonium phosphate, ammonium sulfate, polyphosphoric acid
It is at least one.
Preferably, the temperature of dehydration and drying described in step 2 is 100~120 DEG C.
The present invention will be further explained combined with specific embodiments below and explanation.
Embodiment 1:
145L pure water and 48kg sodium hydroxide are added in 500L reaction kettle, stirring and dissolving, add the oxidation of 140kg tri- two
Antimony stirs evenly, and is warming up to 95 DEG C of isothermal reactions 1 hour, is cooled to 30 DEG C after reaction, is passed through ozone while stirring, permanent
Temperature reaction 3.5 hours, is warming up to 95 DEG C after reaction, stands still for crystals 1 hour, is centrifugated, liquid reuse, and washing solid produces
110 DEG C of drying after object is approximately equal to 7 to pH, obtain sodium pyroantimonate.
Sodium pyroantimonate microwave dehydration will be prepared, dehydration temperaturre≤250 DEG C obtain sodium metaantimonate semi-finished product, then will be inclined
Reaction kettle is added in sodium antimonate semi-finished product, and pure water is added to solid content 50%, stirs evenly, phosphoric acid is added and is adjusted to pH=7, centrifugation point
From liquid reuse, 100 DEG C of solid product drying obtain sodium metaantimonate.
After tested, the content of trivalent antimony is 0.13% in sodium metaantimonate, whiteness 95%, pH value 7.5.(note: trivalent antimony contains
Amount is tested by titration, and whiteness is tested by the test test of whiteness instrument, pH value by pH meter.)
Embodiment 2:
145L pure water and 48kg sodium hydroxide are added in 500L reaction kettle, stirring and dissolving, add the oxidation of 140kg tri- two
Antimony stirs evenly, and is warming up to 95 DEG C of isothermal reactions 1.5 hours, is cooled to 30 DEG C after reaction, is passed through ozone while stirring,
Isothermal reaction 6 hours, it is warming up to 98 DEG C after reaction, stands still for crystals 0.5 hour, is centrifugated, liquid reuse, washes solid
100 DEG C of drying after product is approximately equal to 7 to pH, obtain sodium pyroantimonate.
Sodium pyroantimonate microwave dehydration will be prepared, dehydration temperaturre≤250 DEG C obtain sodium metaantimonate semi-finished product, then will be inclined
Reaction kettle is added in sodium antimonate semi-finished product, and pure water is added to solid content 50%, stirs evenly, sulfuric acid is added and is adjusted to pH=7, centrifugation point
From liquid reuse, 110 DEG C of solid product drying obtain sodium metaantimonate.
After tested, the content of trivalent antimony is 0.09% in sodium metaantimonate, whiteness 96%, pH value 7.6.
Embodiment 3:
145L pure water and 40kg sodium hydroxide are added in 500L reaction kettle, stirring and dissolving, add the oxidation of 140kg tri- two
Antimony stirs evenly, and is warming up to 90 DEG C of isothermal reactions 3 hours, is cooled to 50 DEG C after reaction, is passed through ozone while stirring, permanent
Temperature reaction 7 hours, is warming up to 90 DEG C after reaction, stands still for crystals 1 hour, is centrifugated, liquid reuse, washes solid product
100 DEG C of drying, obtain sodium pyroantimonate after being approximately equal to 7 to pH.
Sodium pyroantimonate microwave dehydration will be prepared, dehydration temperaturre≤250 DEG C obtain sodium metaantimonate semi-finished product, then will be inclined
Reaction kettle is added in sodium antimonate semi-finished product, and pure water is added to solid content 50%, stirs evenly, acetic acid is added and is adjusted to pH=7, centrifugation point
From liquid reuse, 120 DEG C of solid product drying obtain sodium metaantimonate.
After tested, the content of trivalent antimony is 0.17% in sodium metaantimonate, whiteness 94%, pH value 7.0.
Embodiment 4:
194L pure water and 54kg sodium hydroxide are added in 500L reaction kettle, stirring and dissolving, add the oxidation of 140kg tri- two
Antimony stirs evenly, and is warming up to 100 DEG C of isothermal reactions 0.5 hour, is cooled to 40 DEG C after reaction, is passed through ozone while stirring,
Isothermal reaction 3 hours, it is warming up to 100 DEG C after reaction, stands still for crystals 0.5 hour, is centrifugated, liquid reuse, washing is solid
120 DEG C of drying after body product is approximately equal to 7 to pH, obtain sodium pyroantimonate.
Sodium pyroantimonate microwave dehydration will be prepared, dehydration temperaturre≤250 DEG C obtain sodium metaantimonate semi-finished product, then will be inclined
Reaction kettle is added in sodium antimonate semi-finished product, and pure water is added to solid content 50%, stirs evenly, phosphoric acid is added and is adjusted to pH=7, centrifugation point
From liquid reuse, 100 DEG C of solid product drying obtain sodium metaantimonate.
After tested, the content of trivalent antimony is 0.10% in sodium metaantimonate, whiteness 96%, pH value 7.6.
Comparative example:
145L pure water and 48kg sodium hydroxide are added in 500L reaction kettle, stirring and dissolving, add the oxidation of 140kg tri- two
Antimony stirs evenly, and is warming up to 95 DEG C of isothermal reactions 1 hour, is cooled to 50 DEG C after reaction, is continuously added dropwise 27% in 10 hours
Hydrogenperoxide steam generator carry out oxidation reaction, temperature control 98 DEG C are warming up at 50~60 DEG C, after oxidation, stand still for crystals 1
Hour, centrifuge separation, washing solid product to pH is approximately equal to 7, and drying obtains sodium pyroantimonate.
Sodium pyroantimonate is prepared in above-mentioned steps and is heated to 400 DEG C, calcined dehydration obtains sodium metaantimonate.
After tested, the content of trivalent antimony is 0.50% in sodium metaantimonate, whiteness 90%, pH value 10.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (6)
1. a kind of preparation method of sodium pyroantimonate, it is characterised in that: the following steps are included:
1) reaction kettle is added in sodium hydroxide and water, adds antimony oxide, 80~120 DEG C isothermal reaction 0.5~3 hour；
2) 30~50 DEG C are cooled to, is passed through ozone while stirring, is carried out oxidation reaction 3~7 hours；
3) 80~120 DEG C are warming up to, is stood still for crystals, is centrifuged, it is dry, obtain sodium pyroantimonate.
2. the preparation method of sodium pyroantimonate according to claim 1, it is characterised in that: sodium hydroxide described in step 1),
The mass ratio of antimony oxide is 1:(2.6~3.5).
3. the preparation method of sodium pyroantimonate according to claim 1, it is characterised in that: sodium hydroxide described in step 1) and
The gross mass of antimony oxide and the mass ratio of water are (1.0~1.3): 1.
4. the preparation method of sodium pyroantimonate according to claim 1, it is characterised in that: reaction temperature described in step 1) is
90~100 DEG C.
5. the preparation method of sodium pyroantimonate according to claim 1, it is characterised in that: the temperature of crystallization described in step 3)
It is 90~100 DEG C, crystallization time is 0.5~1 hour.
6. the preparation method of sodium pyroantimonate according to claim 1, it is characterised in that: the temperature of drying described in step 3)
It is 100~120 DEG C.
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| CN108455669A (en) * | 2018-04-23 | 2018-08-28 | 长沙烨星锑业有限公司 | A kind of preparation method of schlippe's salt |
| CN112390288A (en) * | 2020-10-23 | 2021-02-23 | 如皋市丹凤纺织有限公司 | Production process of curing agent for yarn impregnation |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN87102082A (en) * | 1987-09-09 | 1988-02-24 | 株洲市化工研究所 | A kind of production technique for preparing refined granular sodium pyroantimonate |
| CN104229850A (en) * | 2014-08-29 | 2014-12-24 | 福建鸿丰纳米科技有限公司 | Method and device for producing nano calcium carbonate by microwave drying |
| CN105858724A (en) * | 2016-05-16 | 2016-08-17 | 中南大学 | Method of using solution atomization method to prepare superfine Sb oxide |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1077177A (en) * | 1992-04-06 | 1993-10-13 | 唐铁桥 | Wet process for preparing soduim antimonate |
| CN100371253C (en) * | 2005-05-13 | 2008-02-27 | 河南科技大学 | Tech. of producing sodium antimonate by purified stibium trioxide |
| CN105540665B (en) * | 2016-02-04 | 2017-06-09 | 株洲安特新材料科技有限公司 | A kind of high temperature reaction stove of utilization sodium pyroantimonate dehydration production sodium metaantimonate |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN87102082A (en) * | 1987-09-09 | 1988-02-24 | 株洲市化工研究所 | A kind of production technique for preparing refined granular sodium pyroantimonate |
| CN104229850A (en) * | 2014-08-29 | 2014-12-24 | 福建鸿丰纳米科技有限公司 | Method and device for producing nano calcium carbonate by microwave drying |
| CN105858724A (en) * | 2016-05-16 | 2016-08-17 | 中南大学 | Method of using solution atomization method to prepare superfine Sb oxide |
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Effective date of registration: 20200805 Address after: 100085, Beijing, Haidian District international science and Technology Pioneer Park, building 101, room 0201, room 8 Patentee after: Zhang Naibin Address before: 100085, Beijing, Haidian District international science and Technology Pioneer Park, building 101, room 0201, room 8 Co-patentee before: STAR-BETTER (SHANGHAI) CHEMICAL MATERIALS Co.,Ltd. Patentee before: STAR-BETTER (BEIJING) CHEMICAL MATERIALS Co.,Ltd. |
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Denomination of invention: A preparation method of sodium pyroantimonate and sodium metaantimonate Effective date of registration: 20220629 Granted publication date: 20190402 Pledgee: Zhongguancun Beijing technology financing Company limited by guarantee Pledgor: Zhang Naibin Registration number: Y2022990000386 |
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