CN108163890A - A kind of preparation method of nanometer sulfo antimony acid antimony - Google Patents
A kind of preparation method of nanometer sulfo antimony acid antimony Download PDFInfo
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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
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M125/00—Lubricating compositions characterised by the additive being an inorganic material
- C10M125/24—Compounds containing phosphorus, arsenic or antimony
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/08—Inorganic acids or salts thereof
- C10M2201/084—Inorganic acids or salts thereof containing sulfur, selenium or tellurium
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/04—Detergent property or dispersant property
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
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Abstract
The present invention discloses a kind of preparation method of nanometer sulfo antimony acid antimony, thioantimonic acid sodium solution is added in the complex solution of trivalent antimony and disperseed using ultrasonic wave, the temperature of the reaction system is controlled to maintain 20 35 DEG C, and it is 6.3 7.8 to control the pH value of the reaction system with hydrochloric acid, ultrasonic wave is continuing with after adding in thioantimonic acid sodium solution and disperses 10 15min, filters to take filter residue, after filter residue potassium sodium tartrate solution and purifying water washing, with 3 5h of ball mill grinding to get；The sulfur content for the antimony sulantimonate that preparation method provided by the invention obtains is few, product is stable, pure, yield is high, performance is good, and particle is nanoscale, has preferable compatibility with lubricant grease, extreme pressure and antiwear performance and greasy property are good, far be more than requirement of the national standard to extreme pressure grease as the various performances of additive, can industrialized production, have a good application prospect.
Description
Technical field
The present invention relates to chemical fields, more particularly relate to a kind of preparation method of nanometer sulfo antimony acid antimony.
Background technology
Antimony sulantimonate is a kind of extreme-pressure anti-wear lubricating grease additive haveing excellent performance, and can significantly improve lubricant grease
Sintering load and load capacity reduce friction coefficient, are widely used in mining machinery, ship and military equipment field.Thio antimony
Sour antimony and all basic fat such as lithium saponify, clay fat, silicone grease and aluminum complex grease etc. have preferable compatibility, to various
Alloy has good lubricant effect including being difficult to the chromium tool steel lubricated and stainless steel etc., and thermal stability is good, is suitable for Gao Zhen
The special circumstances such as sky, high load capacity, radiation use.
Preparing antimony sulantimonate at present, there are mainly three types of methods.First method be using antimony oxide and potassium hydroxide as
Antimony sulantimonate is obtained by the reaction in starting material and schlippe's salt, this method needs a large amount of hydrochloric acid to neutralize, and leads to schlippe's salt point
Solution generates hydrogen sulfide gas and produces sulphur simple substance, causes sulfur content in product higher, corrodes in use by lubriation material,
A large amount of ethyl alcohol washing sulphur need to be consumed, generating hydrogen sulfide deteriorates working condition.Second method is used in ethanol medium
Antimony trihalide and schlippe's salt reaction directly synthesize antimony sulantimonate.Although this method reduces the life of hydrogen sulfide and elemental sulfur
Into, but antimony trihalide easily hydrolyzes, and need to use a large amount of organic solvents, cause waste and the pollution of environment water.The third side
Method is to substitute antimony trihalide using antimony oxide directly to react with schlippe's salt in aqueous solution, and it is less to obtain free sulphur
Antimony sulantimonate, but this method need to carry out in acid condition, schlippe's salt easily hydrolyzes, and yield is caused to decline.
The size of thioantimonic acid antimony particle and the uniformity coefficient of dispersion are larger to Lubrication Properties, with grain diameter
Reduce, the increase of surface atom percentage, surface defect structure increases, nanometer sulfo antimony acid antimony show unique bulk effect,
Quantum size effect and tunnel-effect make its dispersibility and compatibility in basic grease increase significantly, hence it is evident that improve production
The greasy property of product.Therefore, the shortcomings that so overcoming above-mentioned three kinds of preparation methods, nanometer sulfo antimony acid antimony can be prepared by providing one kind
Method, be those skilled in the art's urgent need to resolve a problem.
Invention content
It is an object of the invention to overcome defect of the existing technology, a kind of preparation side of nanometer sulfo antimony acid antimony is provided
Method.
To achieve these goals, the technical solution adopted by the present invention is as follows：
The preparation method of the nanometer sulfo antimony acid antimony of the present invention, includes the following steps：
(1) vulcanized sodium is added under agitation in the purified water that temperature is 50-70 DEG C, adds elemental sulfur and three oxygen
Change two antimony, which is maintained and stirs 20-28min at 55-95 DEG C, is then filtered, obtains filtrate；
(2) filtrate of step (1) in 0-8 DEG C of cryostat, is subjected to crystallisation by cooling 20-30min, detaches crystal and knot
Brilliant mother liquor obtains schlippe's salt coarse crystal；
(3) the schlippe's salt coarse crystal of step (2) is added in the purified water that temperature is 30-45 DEG C, stirs 3-5min
It is filtered, obtains saturation thioantimonic acid sodium solution；
(4) the saturation thioantimonic acid sodium solution of step (3) at 0-5 DEG C is recrystallized, thio antimony is obtained after suction filtration
Sour sodium crystal, then thioantimonic acid sodium crystal is dissolved in purified water, obtain schlippe's salt solution for standby；
(5) it is added in purified water after mixing tartaric acid and sodium chloride, heats the mixed solution under agitation to 35-
65 DEG C, antimony oxide powder is added, is filtered after reacting 15-25min, is taken filtrate, obtain the complex solution of trivalent antimony；
(6) the thioantimonic acid sodium solution of step (4) is pressed 1:The volume ratio of 1.5-2 adds in matching for the trivalent antimony of step (5)
Disperseed in polymer solution and using ultrasonic wave, control the temperature of the reaction system at 20-35 DEG C, and control this anti-with hydrochloric acid
The pH value for answering system is 6.3-7.8, and ultrasonic wave dispersion 10-15min, filtering are continuing with after adding in thioantimonic acid sodium solution
Filter residue is taken, obtains antimony sulantimonate crude product；
(7) the antimony sulantimonate crude product of step (6) is washed 1-2 times with the potassium sodium tartrate solution of a concentration of 3-7g/L
Afterwards, then with purifying water washing 2-3 times；
(8) antimony sulantimonate solid abrasive 3-5h after step (7) is washed with ball mill to get.
Preferably, the molar ratio of antimony oxide, vulcanized sodium and elemental sulfur added in the step (1) is 1:6.15-
6.25:2.02-2.15。
Preferably, the liquid-solid ratio in step (1) reaction system is 5-10mL/g.
Preferably, the molar ratio of step (5) mesotartaric acid and antimony oxide is 5.5-6.5:1.
Preferably, the liquid-solid ratio of the mixed solution of the step (5) is 18-25mL/g.
Preferably, when the step (5) heats the mixed solution containing tartaric acid and sodium chloride under agitation, control
Speed of agitator is 300-800rpm.
Preferably, in the complex solution of the trivalent antimony of the step (5) chlorion a concentration of 2.5-3.5mol/L.
Preferably, a concentration of 75-80g/L of antimony in the thioantimonic acid sodium solution of the step (6)；The complex of trivalent antimony is molten
A concentration of 35-75g/L of antimony in liquid.
Preferably, when thioantimonic acid sodium solution being added in the complex solution of trivalent antimony in the step (6), control is thio
The addition speed of metaantimmonic acid sodium solution is 12-18mL/min.
Preferably, the step (6) using ultrasonic wave to instill thioantimonic acid sodium solution trivalent antimony complex solution
When being disperseed, the frequency for controlling ultrasonic wave is 50-100kHz, power 100-200w.
The present invention is by adopting the above-described technical solution, have the advantages that：
1st, the present invention is reacted with tartaric acid in saturated nacl aqueous solution with antimony oxide, obtained trivalent antimony
Tartaric acid complex solution is all more stable in acid, neutral, alkaline system；The sodium chloride of addition is remarkably improved tartaric acid
To the leaching rate of antimony oxide, raw material availability is improved, reduces production cost；To thioantimonic acid sodium crystal using recrystallization
Method is conducive to improve the degree of purity of schlippe's salt, and impurity can be introduced as few as possible when synthesizing antimony sulantimonate, improves
The stability and degree of purity of product.
2nd, the present invention is in the preparation process of nanometer sulfo antimony acid antimony, and the pH value of control system is 6.3-7.8, in the pH models
Enclose the interior tartaric acid complex solution of thioantimonic acid sodium solution and trivalent antimony synthesis antimony sulantimonate, it is suppressed that schlippe's salt
Decomposition, products obtained therefrom sulfur content is few, and product is stable, pure, and yield is high, and performance is good, suitable for industrialized production.
3rd, the present invention is in the preparation process of nanometer sulfo antimony acid antimony, using ultrasonic wave to the complex solution of trivalent antimony into
Row ultrasonic disperse is conducive to improve dispersed homogeneous degree of the thioantimonic acid sodium solution in the complex solution of trivalent antimony, promotes sulphur
For the synthetic reaction of metaantimmonic acid antimony, the granulation uniformity of antimony sulantimonate crystal improved reduces the grain size of crystal grain；It adopts
Antimony sulantimonate crystal is ground with ball mill, can further reduce the grain diameter of antimony sulantimonate, make its particle
Diameter reaches nanoscale, shows unique bulk effect, quantum size effect and tunnel-effect, makes its dispersion in basic grease
Property and compatibility increase significantly, hence it is evident that improve the greasy property of product.
4th, the present invention washs antimony sulantimonate crude product using potassium sodium tartrate solution and purified water, can inhibit wash water
The raising of pH reduces loss of the antimony sulantimonate in washing process, improves antimony sulantimonate finished product yield.
5th, the thioantimonic acid antimony particle that preparation method provided by the invention obtains is nanoscale, is had preferably with lubricant grease
Compatibility, extreme pressure and antiwear performance and greasy property are good, and national standard is far more than to extreme boundary lubrication as the various performances of additive
The requirement of fat, has a good application prospect.
Specific embodiment
To make the objectives, technical solutions, and advantages of the present invention more comprehensible, preferred embodiment is enumerated below, to this hair
Bright further description.However, it is necessary to illustrate, many details listed in specification are used for the purpose of making reader to this
There are one thorough explanations for the one or more aspects of invention, can also realize the present invention's even without these specific details
These aspects.
Embodiment 1
The preparation method of the nanometer sulfo antimony acid antimony of the present invention, includes the following steps：
(1) 6.15mol vulcanized sodium is added under agitation in the purified water that temperature is 50 DEG C, adds 2.02mol
The reaction system is maintained and stirs 28min at 55 DEG C, then filtered, filtered by elemental sulfur and 1mol antimony oxides
Liquid, the liquid-solid ratio of the reaction system is 10mL/g；
(2) filtrate of step (1) is subjected to crystallisation by cooling 20min in 0 DEG C of cryostat, separation crystal and crystallization are female
Liquid obtains schlippe's salt coarse crystal；
(3) the schlippe's salt coarse crystal of step (2) is added in the purified water that temperature is 45 DEG C, stirring 3min was carried out
Filter, obtains saturation thioantimonic acid sodium solution；
(4) the saturation thioantimonic acid sodium solution of step (3) at 0 DEG C is recrystallized, thioantimonic acid is obtained after suction filtration
Sodium crystal, then thioantimonic acid sodium crystal is dissolved in purified water, the thioantimonic acid sodium solution of a concentration of 75g/L of antimony is obtained, it is spare；
(5) it is added in purified water after mixing 5.5mol tartaric acid and sodium chloride, in the stirring condition that rotating speed is 300rpm
Lower heating mixed solution adds 1mol antimony oxide powder to 35 DEG C, and the liquid-solid ratio for controlling the mixed solution is 18mL/
g；It is filtered after the mixed solution is reacted 25min, takes filtrate, be configured to chlorine ion concentration as 2.5mol/L, a concentration of 75g/L of antimony
Trivalent antimony complex solution；
(6) the thioantimonic acid sodium solution of step (4) is pressed 1:1.5 volume ratio adds in the cooperation of the trivalent antimony of step (5)
In object solution, the addition speed of control thioantimonic acid sodium solution is 12mL/min, and frequency of use is 50kHz, power 100w
Ultrasonic wave disperseed, control the temperature of the reaction system at 20 DEG C, and control the pH value of the reaction system to be with hydrochloric acid
6.3, ultrasonic wave dispersion 10min is continuing with after adding in thioantimonic acid sodium solution, filter residue is filtered to take, obtains antimony sulantimonate
Crude product；
(7) after the antimony sulantimonate crude product of step (6) being washed 2 times with the potassium sodium tartrate solution of a concentration of 3g/L, then
With purifying water washing 3 times；
(8) antimony sulantimonate solid abrasive 3h after step (7) is washed with ball mill to get.
Embodiment 2
The preparation method of the nanometer sulfo antimony acid antimony of the present invention, includes the following steps：
(1) 6.17mol vulcanized sodium is added under agitation in the purified water that temperature is 54 DEG C, adds 2.04mol
The reaction system is maintained and stirs 27min at 60 DEG C, then filtered, filtered by elemental sulfur and 1mol antimony oxides
Liquid, the liquid-solid ratio of the reaction system is 9mL/g；
(2) filtrate of step (1) is subjected to crystallisation by cooling 21min in 1 DEG C of cryostat, separation crystal and crystallization are female
Liquid obtains schlippe's salt coarse crystal；
(3) the schlippe's salt coarse crystal of step (2) is added in the purified water that temperature is 42 DEG C, stirring 3.3min is carried out
Filtering, obtains saturation thioantimonic acid sodium solution；
(4) the saturation thioantimonic acid sodium solution of step (3) at 1 DEG C is recrystallized, thioantimonic acid is obtained after suction filtration
Sodium crystal, then thioantimonic acid sodium crystal is dissolved in purified water, the thioantimonic acid sodium solution of a concentration of 76g/L of antimony is obtained, it is spare；
(5) it is added in purified water after mixing 5.7mol tartaric acid and sodium chloride, in the stirring condition that rotating speed is 400rpm
Lower heating mixed solution adds 1mol antimony oxide powder to 41 DEG C, and the liquid-solid ratio for controlling the mixed solution is 19mL/
g；It is filtered after the mixed solution is reacted 23min, takes filtrate, be configured to chlorine ion concentration as 2.7mol/L, a concentration of 69g/L of antimony
Trivalent antimony complex solution；
(6) the thioantimonic acid sodium solution of step (4) is pressed 1:1.6 volume ratio adds in the cooperation of the trivalent antimony of step (5)
In object solution, the addition speed of control thioantimonic acid sodium solution is 13mL/min, and frequency of use is 60kHz, power 110w
Ultrasonic wave disperseed, control the temperature of the reaction system at 23 DEG C, and control the pH value of the reaction system to be with hydrochloric acid
6.6, ultrasonic wave dispersion 11min is continuing with after adding in thioantimonic acid sodium solution, filter residue is filtered to take, obtains antimony sulantimonate
Crude product；
(7) after the antimony sulantimonate crude product of step (6) being washed 1 time with the potassium sodium tartrate solution of a concentration of 4g/L, then
With purifying water washing 2 times；
(8) antimony sulantimonate solid abrasive 3.3h after step (7) is washed with ball mill to get.
Embodiment 3
The preparation method of the nanometer sulfo antimony acid antimony of the present invention, includes the following steps：
(1) 6.19mol vulcanized sodium is added under agitation in the purified water that temperature is 57 DEG C, adds 2.07mol
The reaction system is maintained and stirs 26min at 66 DEG C, then filtered, filtered by elemental sulfur and 1mol antimony oxides
Liquid, the liquid-solid ratio of the reaction system is 8mL/g；
(2) filtrate of step (1) is subjected to crystallisation by cooling 22min in 2 DEG C of cryostat, separation crystal and crystallization are female
Liquid obtains schlippe's salt coarse crystal；
(3) the schlippe's salt coarse crystal of step (2) is added in the purified water that temperature is 39 DEG C, stirring 3.7min is carried out
Filtering, obtains saturation thioantimonic acid sodium solution；
(4) the saturation thioantimonic acid sodium solution of step (3) at 2 DEG C is recrystallized, thioantimonic acid is obtained after suction filtration
Sodium crystal, then thioantimonic acid sodium crystal is dissolved in purified water, the thioantimonic acid sodium solution of a concentration of 77g/L of antimony is obtained, it is spare；
(5) it is added in purified water after mixing 5.9mol tartaric acid and sodium chloride, in the stirring condition that rotating speed is 500rpm
Lower heating mixed solution adds 1mol antimony oxide powder to 47 DEG C, and the liquid-solid ratio for controlling the mixed solution is 20mL/
g；It is filtered after the mixed solution is reacted 21min, takes filtrate, be configured to chlorine ion concentration as 2.9mol/L, a concentration of 61g/L of antimony
Trivalent antimony complex solution；
(6) the thioantimonic acid sodium solution of step (4) is pressed 1:1.7 volume ratio adds in the cooperation of the trivalent antimony of step (5)
In object solution, the addition speed of control thioantimonic acid sodium solution is 14mL/min, and frequency of use is 70kHz, power 120w
Ultrasonic wave disperseed, control the temperature of the reaction system at 26 DEG C, and control the pH value of the reaction system to be with hydrochloric acid
6.9, ultrasonic wave dispersion 12min is continuing with after adding in thioantimonic acid sodium solution, filter residue is filtered to take, obtains antimony sulantimonate
Crude product；
(7) after the antimony sulantimonate crude product of step (6) being washed 1 time with the potassium sodium tartrate solution of a concentration of 5g/L, then
With purifying water washing 3 times；
(8) antimony sulantimonate solid abrasive 3.6h after step (7) is washed with ball mill to get.
Embodiment 4
The preparation method of the nanometer sulfo antimony acid antimony of the present invention, includes the following steps：
(1) 6.21mol vulcanized sodium is added under agitation in the purified water that temperature is 60 DEG C, adds 2.09mol
The reaction system is maintained and stirs 25min at 73 DEG C, then filtered, filtered by elemental sulfur and 1mol antimony oxides
Liquid, the liquid-solid ratio of the reaction system is 7mL/g；
(2) filtrate of step (1) is subjected to crystallisation by cooling 24min in 4 DEG C of cryostat, separation crystal and crystallization are female
Liquid obtains schlippe's salt coarse crystal；
(3) the schlippe's salt coarse crystal of step (2) is added in the purified water that temperature is 36 DEG C, stirring 4min was carried out
Filter, obtains saturation thioantimonic acid sodium solution；
(4) the saturation thioantimonic acid sodium solution of step (3) at 3 DEG C is recrystallized, thioantimonic acid is obtained after suction filtration
Sodium crystal, then thioantimonic acid sodium crystal is dissolved in purified water, the thioantimonic acid sodium solution of a concentration of 78g/L of antimony is obtained, it is spare；
(5) it is added in purified water after mixing 6.1mol tartaric acid and sodium chloride, in the stirring condition that rotating speed is 600rpm
Lower heating mixed solution adds 1mol antimony oxide powder to 53 DEG C, and the liquid-solid ratio for controlling the mixed solution is 22mL/
g；It is filtered after the mixed solution is reacted 22min, takes filtrate, be configured to chlorine ion concentration as 3.1mol/L, a concentration of 55g/L of antimony
Trivalent antimony complex solution；
(6) the thioantimonic acid sodium solution of step (4) is pressed 1:1.8 volume ratio adds in the cooperation of the trivalent antimony of step (5)
In object solution, the addition speed of control thioantimonic acid sodium solution is 15mL/min, and frequency of use is 80kHz, power 140w
Ultrasonic wave disperseed, control the temperature of the reaction system at 28 DEG C, and control the pH value of the reaction system to be with hydrochloric acid
7.2, ultrasonic wave dispersion 13min is continuing with after adding in thioantimonic acid sodium solution, filter residue is filtered to take, obtains antimony sulantimonate
Crude product；
(7) after the antimony sulantimonate crude product of step (6) being washed 2 times with the potassium sodium tartrate solution of a concentration of 6g/L, then
With purifying water washing 2 times；
(8) antimony sulantimonate solid abrasive 3.9h after step (7) is washed with ball mill to get.
Embodiment 5
The preparation method of the nanometer sulfo antimony acid antimony of the present invention, includes the following steps：
(1) 6.23mol vulcanized sodium is added under agitation in the purified water that temperature is 63 DEG C, adds 2.11mol
The reaction system is maintained and stirs 23min at 80 DEG C, then filtered, filtered by elemental sulfur and 1mol antimony oxides
Liquid, the liquid-solid ratio of the reaction system is 6mL/g；
(2) filtrate of step (1) is subjected to crystallisation by cooling 26min in 6 DEG C of cryostat, separation crystal and crystallization are female
Liquid obtains schlippe's salt coarse crystal；
(3) the schlippe's salt coarse crystal of step (2) is added in the purified water that temperature is 34 DEG C, stirring 4.3min is carried out
Filtering, obtains saturation thioantimonic acid sodium solution；
(4) the saturation thioantimonic acid sodium solution of step (3) at 4 DEG C is recrystallized, thioantimonic acid is obtained after suction filtration
Sodium crystal, then thioantimonic acid sodium crystal is dissolved in purified water, the thioantimonic acid sodium solution of a concentration of 79g/L of antimony is obtained, it is spare；
(5) it is added in purified water after mixing 6.3mol tartaric acid and sodium chloride, in the stirring condition that rotating speed is 700rpm
Lower heating mixed solution adds 1mol antimony oxide powder to 57 DEG C, and the liquid-solid ratio for controlling the mixed solution is 23mL/
g；It is filtered after the mixed solution is reacted 23min, takes filtrate, be configured to chlorine ion concentration as 3.2mol/L, a concentration of 48g/L of antimony
Trivalent antimony complex solution；
(6) the thioantimonic acid sodium solution of step (4) is pressed 1:1.9 volume ratio adds in the cooperation of the trivalent antimony of step (5)
In object solution, the addition speed of control thioantimonic acid sodium solution is 16mL/min, and frequency of use is 90kHz, power 160w
Ultrasonic wave disperseed, control the temperature of the reaction system at 30 DEG C, and control the pH value of the reaction system to be with hydrochloric acid
7.4, ultrasonic wave dispersion 14min is continuing with after adding in thioantimonic acid sodium solution, filter residue is filtered to take, obtains antimony sulantimonate
Crude product；
(7) after the antimony sulantimonate crude product of step (6) being washed 1 time with the potassium sodium tartrate solution of a concentration of 7g/L, then
With purifying water washing 3 times；
(8) antimony sulantimonate solid abrasive 4.2h after step (7) is washed with ball mill to get.
Embodiment 6
The preparation method of the nanometer sulfo antimony acid antimony of the present invention, includes the following steps：
(1) 6.24mol vulcanized sodium is added under agitation in the purified water that temperature is 66 DEG C, adds 2.13mol
The reaction system is maintained and stirs 22min at 88 DEG C, then filtered, filtered by elemental sulfur and 1mol antimony oxides
Liquid, the liquid-solid ratio of the reaction system is 5mL/g；
(2) filtrate of step (1) is subjected to crystallisation by cooling 28min in 7 DEG C of cryostat, separation crystal and crystallization are female
Liquid obtains schlippe's salt coarse crystal；
(3) the schlippe's salt coarse crystal of step (2) is added in the purified water that temperature is 32 DEG C, stirring 4.6min is carried out
Filtering, obtains saturation thioantimonic acid sodium solution；
(4) the saturation thioantimonic acid sodium solution of step (3) is recrystallized at 5 DEG C, thioantimonic acid is obtained after suction filtration
Sodium crystal, then thioantimonic acid sodium crystal is dissolved in purified water, the thioantimonic acid sodium solution of a concentration of 80g/L of antimony is obtained, it is spare；
(5) it is added in purified water after mixing 6.4mol tartaric acid and sodium chloride, in the stirring condition that rotating speed is 800rpm
Lower heating mixed solution adds 1mol antimony oxide powder to 61 DEG C, and the liquid-solid ratio for controlling the mixed solution is 24mL/
g；It is filtered after the mixed solution is reacted 24min, takes filtrate, be configured to chlorine ion concentration as 3.4mol/L, a concentration of 41g/L of antimony
Trivalent antimony complex solution；
(6) the thioantimonic acid sodium solution of step (4) is pressed 1:2 volume ratio adds in the complex of the trivalent antimony of step (5)
In solution, the addition speed of control thioantimonic acid sodium solution is 17mL/min, and frequency of use is 100kHz, power is 180w's
Ultrasonic wave is disperseed, and controls the temperature of the reaction system at 33 DEG C, and it is 7.6 to control the pH value of the reaction system with hydrochloric acid,
Ultrasonic wave dispersion 15min is continuing with after adding in thioantimonic acid sodium solution, filter residue is filtered to take, it is thick to obtain antimony sulantimonate
Product；
(7) after the antimony sulantimonate crude product of step (6) being washed 2 times with the potassium sodium tartrate solution of a concentration of 5g/L, then
With purifying water washing 2 times；
(8) antimony sulantimonate solid abrasive 4.6h after step (7) is washed with ball mill to get.
Embodiment 7
The preparation method of the nanometer sulfo antimony acid antimony of the present invention, includes the following steps：
(1) 6.25mol vulcanized sodium is added under agitation in the purified water that temperature is 70 DEG C, adds 2.15mol
The reaction system is maintained and stirs 20min at 95 DEG C, then filtered, filtered by elemental sulfur and 1mol antimony oxides
Liquid, the liquid-solid ratio of the reaction system is 6mL/g；
(2) filtrate of step (1) is subjected to crystallisation by cooling 30min in 8 DEG C of cryostat, separation crystal and crystallization are female
Liquid obtains schlippe's salt coarse crystal；
(3) the schlippe's salt coarse crystal of step (2) is added in the purified water that temperature is 30 DEG C, stirring 5min was carried out
Filter, obtains saturation thioantimonic acid sodium solution；
(4) the saturation thioantimonic acid sodium solution of step (3) at 4 DEG C is recrystallized, thioantimonic acid is obtained after suction filtration
Sodium crystal, then thioantimonic acid sodium crystal is dissolved in purified water, the thioantimonic acid sodium solution of a concentration of 79g/L of antimony is obtained, it is spare；
(5) it is added in purified water after mixing 6.5mol tartaric acid and sodium chloride, in the stirring condition that rotating speed is 800rpm
Lower heating mixed solution adds 1mol antimony oxide powder to 65 DEG C, and the liquid-solid ratio for controlling the mixed solution is 25mL/
g；It is filtered after the mixed solution is reacted 25min, takes filtrate, be configured to chlorine ion concentration as 3.5mol/L, a concentration of 35g/L of antimony
Trivalent antimony complex solution；
(6) the thioantimonic acid sodium solution of step (4) is pressed 1:2 volume ratio adds in the complex of the trivalent antimony of step (5)
In solution, the addition speed of control thioantimonic acid sodium solution is 18mL/min, and frequency of use is 100kHz, power is 200w's
Ultrasonic wave is disperseed, and controls the temperature of the reaction system at 35 DEG C, and it is 7.8 to control the pH value of the reaction system with hydrochloric acid,
Ultrasonic wave dispersion 15min is continuing with after adding in thioantimonic acid sodium solution, filter residue is filtered to take, it is thick to obtain antimony sulantimonate
Product；
(7) after the antimony sulantimonate crude product of step (6) being washed 2 times with the potassium sodium tartrate solution of a concentration of 6g/L, then
With purifying water washing 2 times；
(8) antimony sulantimonate solid abrasive 5h after step (7) is washed with ball mill to get.
Claims (10)
1. a kind of preparation method of nanometer sulfo antimony acid antimony, which is characterized in that include the following steps：
(1) vulcanized sodium is added under agitation in the purified water that temperature is 50-70 DEG C, adds elemental sulfur and three oxidations two
The reaction system is maintained and stirs 20-28min at 55-95 DEG C, then filtered, obtain filtrate by antimony；
(2) filtrate of step (1) is subjected to crystallisation by cooling 20-30min in 0-8 DEG C of cryostat, separation crystal and crystallization are female
Liquid obtains schlippe's salt coarse crystal；
(3) the schlippe's salt coarse crystal of step (2) is added in the purified water that temperature is 30-45 DEG C, stirring 3-5min is carried out
Filtering, obtains saturation thioantimonic acid sodium solution；
(4) the saturation thioantimonic acid sodium solution of step (3) at 0-5 DEG C is recrystallized, schlippe's salt is obtained after suction filtration
Crystal, then thioantimonic acid sodium crystal is dissolved in purified water, obtain schlippe's salt solution for standby；
(5) it is added in purified water after mixing tartaric acid and sodium chloride, heats the mixed solution under agitation to 35-65
DEG C, antimony oxide powder is added, is filtered after reacting 15-25min, is taken filtrate, obtain the complex solution of trivalent antimony；
(6) the thioantimonic acid sodium solution of step (4) is pressed 1:The volume ratio of 1.5-2 adds in the complex of the trivalent antimony of step (5)
Disperseed in solution and using ultrasonic wave, control the temperature of the reaction system at 20-35 DEG C, and the reactant is controlled with hydrochloric acid
The pH value of system is 6.3-7.8, and ultrasonic wave dispersion 10-15min is continuing with after adding in thioantimonic acid sodium solution, filters to take filter
Slag obtains antimony sulantimonate crude product；
(7) after the antimony sulantimonate crude product of step (6) is washed 1-2 times with the potassium sodium tartrate solution of a concentration of 3-7g/L, then
With purifying water washing 2-3 times；
(8) antimony sulantimonate solid abrasive 3-5h after step (7) is washed with ball mill to get.
2. the preparation method of nanometer sulfo antimony acid antimony according to claim 1, it is characterised in that：Add in the step (1)
The molar ratio of antimony oxide, vulcanized sodium and elemental sulfur entered is 1:6.15-6.25:2.02-2.15.
3. the preparation method of nanometer sulfo antimony acid antimony according to claim 1, it is characterised in that：Step (1) reaction
Liquid-solid ratio in system is 5-10mL/g.
4. the preparation method of nanometer sulfo antimony acid antimony according to claim 1, it is characterised in that：Wine in the step (5)
The molar ratio of stone acid and antimony oxide is 5.5-6.5:1.
5. the preparation method of nanometer sulfo antimony acid antimony according to claim 1, it is characterised in that：The step (5) is mixed
The liquid-solid ratio for closing solution is 18-25mL/g.
6. the preparation method of nanometer sulfo antimony acid antimony according to claim 1, it is characterised in that：The step (5) is being stirred
When the mixed solution containing tartaric acid and sodium chloride is heated under the conditions of mixing, control speed of agitator is 300-800rpm.
7. the preparation method of nanometer sulfo antimony acid antimony according to claim 1, it is characterised in that：The three of the step (5)
A concentration of 2.5-3.5mol/L of chlorion in the complex solution of valency antimony.
8. the preparation method of nanometer sulfo antimony acid antimony according to claim 1, it is characterised in that：The sulphur of the step (6)
For a concentration of 75-80g/L of antimony in metaantimmonic acid sodium solution；A concentration of 35-75g/L of antimony in the complex solution of trivalent antimony.
9. the preparation method of nanometer sulfo antimony acid antimony according to claim 1, it is characterised in that：It will in the step (6)
When thioantimonic acid sodium solution adds in the complex solution of trivalent antimony, the addition speed of control thioantimonic acid sodium solution is 12-18mL/
min。
10. the preparation method of nanometer sulfo antimony acid antimony according to claim 1, it is characterised in that：The step (6) uses
When ultrasonic wave disperses the complex solution for instilling the trivalent antimony of thioantimonic acid sodium solution, the frequency for controlling ultrasonic wave is
50-100kHz, power 100-200w.
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| CN109437298A (en) * | 2019-01-07 | 2019-03-08 | 中南大学 | A kind of preparation method of Sodium thioantimonite nano material |
| CN109437297A (en) * | 2019-01-07 | 2019-03-08 | 中南大学 | A kind of preparation method of the micro-nano multilevel structure material of schlippe's salt |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109437298A (en) * | 2019-01-07 | 2019-03-08 | 中南大学 | A kind of preparation method of Sodium thioantimonite nano material |
| CN109437297A (en) * | 2019-01-07 | 2019-03-08 | 中南大学 | A kind of preparation method of the micro-nano multilevel structure material of schlippe's salt |
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