CN103214035B - Method for preparing antimony thioantimonate based on stable reaction system - Google Patents
Method for preparing antimony thioantimonate based on stable reaction system Download PDFInfo
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Abstract
The invention provides a method for preparing antimony thioantimonate based on a stable reaction system, belonging to the technical field of preparation for chemical products. The method comprises the following steps of: preparing a high-concentration Sb<3+> ion conjugate solution, which is not hydrolyzed under acidic, alkali and neutral conditions, by using antimony white as a raw material through acidification and conjugation; preparing sodium thioantimonate under alkali conditions; and then reacting the Sb<3+> ion conjugate solution and a sodium thioantimonate solution to prepare antimony thioantimonate. By using the method, the problems that antimony halide is hydrolyzed under alkali conditions and sodium thioantimonate is decomposed when being in contact with acid are solved; and the obtained antimony thioantimonate is high in purity and good in performance, and can be used as an extreme pressure antiwear additive for lubricating grease and a solid lubricant. The preparation process is simple, clean and stable, no side reaction occurs in the preparation course, the yield is high, the product is pure, the performance is good, and the method is suitable for industrial production.
Description
Technical field
The present invention relates to a kind of method preparing antimony sulantimonate, special for relating to a kind of method preparing antimony sulantimonate based on stable reaction system; Belong to Chemicals preparing technical field.
Technical background
Antimony sulantimonate is a kind of reddish-brown amorphous powder, is soluble in alkali, is insoluble to organic solvent and mineral acid.Antimony sulantimonate is a kind of lubricating oil and grease additive, has excellent extreme-pressure anti-wear lubricating performance, can increase substantially bearing load and the antiwear property of grease, be much better than traditional WS
2, MoS
2and graphite, comprise lithium saponify, silicone fat, clay fat and aluminum complex grease etc. with various basic fat and all there is good consistency, to traditional MoS
2the chromium tool steel and the stainless steel capital that are difficult to lubrication have good lubricant effect.
More typical antimony sulantimonate synthetic method has three kinds.First method is with Sb
2o
3be starting raw material and Na with KOH
3sbS
49H
2o is obtained by reacting thioantimonic acid antimony product; The method disadvantage need neutralize with hydrochloric acid, causes Na
3sbS
4decompose and produce H
2s gas also along with the generation of elementary sulfur, causes sulphur content in product higher, in use corrodes lubricated material, need consume a large amount of washing with alcohol sulphur, produces H
2s makes working condition worsen.Second method uses SbX in ethanol medium
3(Cl, F) and Na
2sbS
49H
2o reacts, and directly synthesizes antimony sulantimonate.Although the method decreases H
2the generation of S and element S, obtains sulphur content lower than the thioantimonic acid antimony product of 1%, but employs the SbX of easily hydrolysis
3, a large amount of organic solvent need be used, bring organic solvent and reclaim problem.The third method adopts stable ANTIMONY TRIOXIDE SB 203 99.8 PCT to replace antimony trihalide to make reagent, in aqueous direct and Na
2sbS
49H
2o is obtained by reacting the SbSbS that free sulphur content is less than 1%
4, productive rate is about 90%.This method is reacted in acid condition, and the problem of schlippe's salt hydrolysis does not solve, and causes productive rate to decline.
Many scientific workers of China have done much research, and Du Xinling etc. use sodium antimonate and sodium sulphite direct reaction to prepare schlippe's salt, then stable antimony chloride and thioantimonic acid sodium solution are joined HCl-NaCl-H lentamente
2in O system, antimony sulantimonate is prepared in reaction, and the method synthesizes antimony sulantimonate in acid system, the problem of inevitable schlippe's salt acid decomposition.Patent 201210047888.5 has been applied for before contriver, with sodium antimonate and stibium trioxide for raw material, adopt sodium sulphite to leach sodium antimonate and obtain quinquevalence antimony solution, the sodium chloride solution of hydrochloric acid leaching stibium trioxide is adopted to produce trivalent antimony solution, then two kinds of solution are slowly joined a buffer system containing tensio-active agent, take ultrasonic stirring to carry out precipitation from homogeneous solution, the precipitation produced obtains nanometer sulfo antimony acid antimony product through ageing in tartaric acid solution, dispersion, rinsing, oven dry.The method needs the strict feed rate controlling quinquevalence antimony solution and trivalent antimony solution, adopt ultrasonic wave accelerated reaction simultaneously, be that antimony sulantimonate generates fast, antimony sulantimonate ageing in tartaric acid solution of generation, coordinates the complete butter of antimony with being mixed in antimony sulantimonate surface of unreacted.Although this patent can obtain the high product of purity, reaction system is unstable, and operation is many, complicated operation.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, provide a kind of method preparing antimony sulantimonate based on stable reaction system; Solve the problem of antimony halides hydrolyzed under basic conditions or schlippe's salt acid decomposition or the complicated operation existed in existing antimony sulantimonate preparation process.
A kind of method preparing antimony sulantimonate based on stable reaction system of the present invention, comprises the following steps:
Step one: Sb
3+the conjugate solutions preparation of ion
In the ratio adding 1 gram of stibium trioxide in the mixing solutions of every 4-6ml hydrochloric acid and sodium-chlor, stibium trioxide is added in the mixing solutions of hydrochloric acid and sodium-chlor and react, the concentration of described hydrochloric acid is 4.5-6.5mol/L, sodium chloride concentration is 1.5-3.4mol/L, obtain butter of antimony solution, in gained butter of antimony solution, add multi-hydroxy carboxy acid's solution again, the mol ratio controlling multi-hydroxy carboxy acid and antimony is 1.7-2.0:1, obtains Sb
3+the conjugate solutions of ion; Adjust the pH value of conjugate solutions to 6.5-7.5, obtain reserve liquid;
Step 2: the preparation of antimony sulantimonate
Thioantimonic acid sodium solution containing antimony 70-110g/L is added in step one gained reserve liquid and precipitates, filter, obtain antimony sulantimonate; Or
The thioantimonic acid sodium solution and step one gained reserve liquid that contain antimony 70-110g/L are added drop-wise in medium simultaneously and precipitate, filter, obtain antimony sulantimonate, described medium is water, and the volume of medium is the 8-10% of overall solution volume;
During precipitation, the temperature controlling solution is 20-30 DEG C, pH value is that in 6.5-8.0, reaction solution, trivalent antimony and antimonic mol ratio are 1.0-1.1:1.
A kind of method preparing antimony sulantimonate based on stable reaction system of the present invention, thioantimonic acid sodium solution containing antimony 70-110g/L described in step one is prepared by following proposal: in the ratio adding 1 gram of stibium trioxide in every 3-4ml sodium hydroxide solution, stibium trioxide is added in sodium hydroxide solution and leaches, hydrogen peroxide oxidation is added while leaching, through cooling after oxidation, crystallization, filtration obtains sodium antimonate, sodium antimonate being added concentration is react in the sodium sulfide solution of 250-351g/L again, the mol ratio controlling sodium antimonate and sodium sulphite is 1:4.2-4.8, temperature of reaction is 90-95 DEG C, after having reacted, reaction solution is cooled, crystallization, filter to obtain schlippe's salt solid, add water in schlippe's salt solid again, obtain the thioantimonic acid sodium solution containing antimony 70-110g/L, the concentration of described sodium hydroxide solution is 200-300g/L, and extraction temperature is 80-90 DEG C, and the consumption of hydrogen peroxide is 1.3-1.5 times of theoretical amount, and the mass percentage concentration of hydrogen peroxide is 27-30%.
A kind of method preparing antimony sulantimonate based on stable reaction system of the present invention, in step one, the reaction times of hydrochloric acid soln and stibium trioxide is 40-60min, and the concentration controlling antimony during reaction is 140-210g/L; Described multi-hydroxy carboxy acid is selected from tartrate, at least one in citric acid and oxalic acid; Sb
3+the pH value of ion complex solution is regulated and controled by sodium hydroxide, and in reserve liquid, the concentration of antimony is 60-75g/L.
A kind of method preparing antimony sulantimonate based on stable reaction system of the present invention, in step 2, the pH value of reaction solution is regulated and controled by hydrochloric acid; The time of precipitation is 1-2h.
A kind of method preparing antimony sulantimonate based on stable reaction system of the present invention, the extraction time of stibium trioxide is 3-4h, and leach liquor is 5-10 DEG C through cooled temperature; When sodium antimonate and sodium sulphite react, the concentration controlling antimony in solution is 80-125g/L, and the time that sodium antimonate and sodium sulphite react is 2-3h, and reaction solution is through cooled temperature≤5 DEG C.
A kind of method preparing antimony sulantimonate based on stable reaction system of the present invention, prepared antimony sulantimonate obtains antimony sulantimonate finished product through rinsing, oven dry, pulverizing, screening, finished appearance is red-brown powder, and antimony content is 65.1-65.4%, and sulphur content is 34.2-34.6%.
Principle of the present invention and beneficial effect
The present invention's dissolving with hydrochloric acid antimonous oxide obtains butter of antimony, coordinates Sb with multi-hydroxy carboxy acid
3+ion, the Sb of generation
3+ionic complex is all stable at acidity, neutrality and alkaline system; In the preparation process of antimony sulantimonate, the pH value of the hierarchy of control is 6.5-8.0, with thioantimonic acid sodium solution and Sb in this pH value range
3+the conjugate solutions synthesis antimony sulantimonate of ion, completely inhibit the decomposition of schlippe's salt and the hydrolysis of butter of antimony, products obtained therefrom is sulfur-bearing and antimony sulfide not, and product is stable, pure, and productive rate is high, performance good, pollution-free, does not need with an organic solvent to clean.
Preparation technology of the present invention is simple, clean, stable, and without side reaction in preparation process, productive rate is high, and product is pure, performance good, is suitable for suitability for industrialized production.
Accompanying drawing explanation
The X-ray diffraction spectrogram of the antimony sulantimonate of accompanying drawing 1 prepared by embodiment 1;
Can find out that from accompanying drawing 1 crystallization of antimony sulantimonate has obvious characteristic peak.
Embodiment
Following examples are intended to the present invention instead of limitation of the invention further are described.
Embodiment 1
(1) sodium antimonate is prepared
In the NaOH solution of 315mL200g/L, add stibium trioxide 105g, at 85 DEG C, leach 3.5h, constantly drip 30wt% hydrogen peroxide 123mL during leaching, cooling, crystallization, filtration obtain sodium antimonate 169 grams, and after cooling, the temperature of solution is 5-10 DEG C.
(2) thioantimonic acid sodium solution is prepared
Adopt 722g nine water cure sodium to dissolve and be made into 668mL solution, then the sodium antimonate 169 grams that step (1) obtains is added, control temperature of reaction 95 DEG C, stirring reaction 3.0h, be cooled to less than 5 DEG C, filter, obtain nine water schlippe's salt crystallization 255.08g, this crystallization is configured to 923mL, containing the thioantimonic acid sodium solution of antimony 70g/L.
(3) butter of antimony solution is prepared with hydrochloric acid leaching stibium trioxide.
37wt% concentrated hydrochloric acid 870mL and 155.3gNaCl adds water and is made into 1600mL solution, adds stibium trioxide 402g, and temperature is room temperature, stirs 40min, filters, and obtains the butter of antimony solution containing antimony 210g/L.
(4) transition of butter of antimony solution.
Take 219g tartrate, join above-mentioned 500mL, antimony concentration is in the butter of antimony solution of 210g/L, is made into 1750mL solution after dissolving, adds solid NaOH adjust ph to 6.5, is cooled to less than 40 DEG C, obtains stable 60g/L trivalent antimony solution.
(5) the thioantimonic acid sodium solution 200mL that step (2) obtains is joined in the trivalent antimony solution that step (4) obtains, trivalent antimony liquor capacity is 234ml, in reinforced process, the feed rate of constant flow pump is about 8mL/min, the temperature of whole process control reaction system is 30 DEG C, pH value is 7.0, and rear continuation of having fed in raw material filters to obtain antimony sulantimonate filter cake after stirring 40min.
(6) by step (5) gained antimony sulantimonate filter cake through superheated water rinsing, oven dry, pulverizing, screening, obtain thioantimonic acid antimony product, its quality is 41.4g, productive rate is 97%, outward appearance is red-brown powder, and antimony content is 65.3%, and sulphur content is 34.3%, the XRD detected result of antimony sulantimonate is shown in Fig. 1, and its concrete composition is in table 1.
Obtained thioantimonic acid antimony product is made an addition in 0# universal lithium base grease, adopt MRS-10A type four ball frictional testing machines according to its last non seizure load of GB/T3142 standard testing (oil film strength), spot value and frictional coefficient is ground according to the abrading-ball of SH/T0204 test under 392N load, the long abrasive stick part of 1450r/min and 30min, find that the antimony sulantimonate frictional coefficient of interpolation 1.5% is reduced to 0.057 by 0.069, oil film strength brings up to 107kg by 71kg, and various performance is far more than MoS
2with the requirement of national standard to extreme pressure grease.
Antimony sulantimonate component list prepared by table 1. embodiment 1
Embodiment 2
(1) sodium antimonate is prepared
In the NaOH solution of 440mL250g/L, add stibium trioxide 110g, at 80 DEG C, leach 4h, constantly drip 27wt% hydrogen peroxide 132mL in leaching process, cooling, crystallization, filtration obtain sodium antimonate 180 grams, and after cooling, the temperature of solution is 5-10 DEG C.
(2) thioantimonic acid sodium solution is prepared
Adopt 840g nine water cure sodium to dissolve and be made into 900mL solution, then the 180g sodium antimonate that step (1) obtains is added, control temperature of reaction 95 DEG C, stirring reaction 2.5h, be cooled to less than 5 DEG C, filter, obtain nine water schlippe's salt crystallization 250g, this crystallization is formulated as 745mL solution, obtains the thioantimonic acid sodium solution containing antimony 85g/L.
(3) butter of antimony solution is prepared with hydrochloric acid leaching stibium trioxide.
37wt% concentrated hydrochloric acid 870mL and 177gNaCl adds water and is made into 2000mL solution, adds stibium trioxide 400g, and temperature is room temperature, stirs 50min, filters, and obtains the butter of antimony solution containing antimony 167g/L.
(4) transition of trivalent antimony solution.
Take 329g citric acid, join above-mentioned 628mL, antimony concentration is in the butter of antimony solution of 167g/L, is made into 1500mL solution after dissolving, adds solid NaOH adjust ph to 7.0, is cooled to less than 40 DEG C, obtains stable 70g/L trivalent antimony solution.
(5) the thioantimonic acid sodium solution 200mL that step (2) obtains is joined in the trivalent antimony solution that step (4) obtains, trivalent antimony liquor capacity is 255ml, in reinforced process, the feed rate of constant flow pump is about 8mL/min, the temperature of whole process control reaction system is 20 DEG C, pH value is 6.5, and rear continuation of having fed in raw material filters to obtain antimony sulantimonate filter cake after stirring 40min.
(6) by step (5) gained antimony sulantimonate filter cake through superheated water rinsing, oven dry, pulverizing, screening, obtain thioantimonic acid antimony product, its quality is 50.60g, and productive rate is 97.5%, and outward appearance is red-brown powder, and antimony content is 65.4%, and sulphur content is 34.4%.
By obtained antimony sulantimonate product application in lithium soap grease, adopt MRS-10A type four ball frictional testing machines according to its last non seizure load of GB/T3142 standard testing (oil film strength), spot value and frictional coefficient is ground according to the abrading-ball of SH/T0204 test under 392N load, the long abrasive stick part of 1450r/min and 30min, find that the antimony sulantimonate frictional coefficient adding 1.5wt% is reduced to 0.055 by 0.069, oil film strength brings up to 100kg by 71kg, and various performance is far more than MoS
2with the requirement of national standard to extreme pressure grease.
Embodiment 3
(1) sodium antimonate is prepared
In the NaOH solution of 375mL300g/L, add stibium trioxide 125g, at 90 DEG C, leach 3h, slowly drip 30wt% hydrogen peroxide 145mL in leaching process, cooling, crystallization, filtration obtain sodium antimonate 205g, and after cooling, the temperature of solution is 5-10 DEG C.
(2) thioantimonic acid sodium solution is prepared
Adopt 837g nine water cure sodium to dissolve and be made into 780mL solution, then add the 195g sodium antimonate that step (1) obtains.Control temperature of reaction 90 DEG C, stirring reaction 2.5h, is cooled to less than 5 DEG C, filters, obtains nine water schlippe's salt crystallization 297g, this crystallization is formulated as 752mL, containing the thioantimonic acid sodium solution of antimony 100g/L.
(3) butter of antimony solution is prepared with hydrochloric acid leaching stibium trioxide.
37wt% concentrated hydrochloric acid 870mL and 155.3gNaCl adds water and is made into 1600mL solution, adds stibium trioxide 402g, and temperature is room temperature, stirs 40min, filters, and obtains the butter of antimony solution containing antimony 210g/L.
(4) transition of trivalent antimony solution
Take 255g oxalic acid, join above-mentioned 500mL, antimony concentration is in the butter of antimony solution of 210g/L, be made into 1300mL solution after dissolving, add solid NaOH adjust ph to 6.5, constant volume is 1400mL, be cooled to less than 40 DEG C, obtain the stable trivalent antimony solution containing antimony 75g/L.
(5) the thioantimonic acid sodium solution 200mL that step (2) obtains is joined in the trivalent antimony solution that step (4) obtains, trivalent antimony liquor capacity is 293mL, in reinforced process, the feed rate of constant flow pump is about 8mL/min, the temperature of whole process control reaction system is 25 DEG C, pH value is 7.0, and rear continuation of having fed in raw material filters to obtain antimony sulantimonate filter cake after stirring 40min.
(6) by step (5) gained antimony sulantimonate filter cake through superheated water rinsing, oven dry, pulverizing, screening, obtain thioantimonic acid antimony product, its quality is 59.80g, and productive rate is 98%, and outward appearance is red-brown powder, and antimony content is 65.2%, and sulphur content is 34.6%.
By obtained antimony sulantimonate product application in 0# lithium soap grease, adopt MRS-10A type four ball frictional testing machines according to its last non seizure load of GB/T3142 standard testing (oil film strength), grind spot value and frictional coefficient according to the abrading-ball of SH/T0204 test under 392N load, the long abrasive stick part of 1450r/min and 30min.Find that the antimony sulantimonate frictional coefficient adding 1.5wt% is reduced to 0.055 by 0.069, oil film strength brings up to 103kg by 71kg, and various performance is far more than MoS
2with the requirement of national standard to extreme pressure grease.
Embodiment 4
(1) sodium antimonate is prepared
In the NaOH solution of 500mL300g/L, add stibium trioxide 125g, at 85 DEG C, leach 3.5h, slowly drip 30wt% hydrogen peroxide 136mL in leaching process, cooling, crystallization, filtration obtain sodium antimonate 205g, and after cooling, the temperature of solution is 5-10 DEG C.
(2) thioantimonic acid sodium solution is prepared
Adopt 870g nine water cure sodium to dissolve and be made into 940mL solution, then add the 205g sodium antimonate that step (1) obtains.Control temperature of reaction 95 DEG C, stirring reaction 2.0h, is cooled to less than 5 DEG C, filters, obtains nine water schlippe's salt crystallization 294.80g, this crystallization is formulated as 691mL solution, obtains the quinquevalence antimony solution containing antimony 108g/L.
(3) trivalent antimony solution is prepared with hydrochloric acid leaching stibium trioxide.
37wt% concentrated hydrochloric acid 758mL and 400gNaCl adds water and is made into 2000mL solution, adds stibium trioxide 333g, and temperature is room temperature, stirs 60min, filters, and obtains the trivalent antimony solution containing antimony 141g/L.
(4) transition of trivalent antimony solution.
Take 87.20g tartrate and 111.63g citric acid, join above-mentioned 500mL, concentration is in the trivalent antimony solution of 141g/L antimony, solid NaOH adjust ph is added to 7.5 after dissolving, constant volume is 940mL, is cooled to less than 40 DEG C, obtains the trivalent antimony solution of stable 75g/L.
(5) the thioantimonic acid sodium solution 200mL that step (2) obtains is joined in the trivalent antimony solution that step (4) obtains, trivalent antimony liquor capacity is 302mL, in reinforced process, the feed rate of constant flow pump is about 8mL/min, the temperature of whole process control reaction system is 26 DEG C, pH value is 8.0, and rear continuation of having fed in raw material filters to obtain antimony sulantimonate filter cake after stirring 40min.
(6) by step (5) gained antimony sulantimonate filter cake through superheated water rinsing, oven dry, pulverizing, screening, obtain thioantimonic acid antimony product, its quality is 64.5g, and productive rate is 98%, and outward appearance is red-brown powder, and antimony content is 65.1%, and sulphur content is 34.3%.
By obtained antimony sulantimonate product application in 0# lithium soap grease, its last non seizure load (oil film strength) tested by employing MRS-10A type four ball frictional testing machines and the abrading-ball under 392N load, the long abrasive stick part of 1450r/min and 30min grinds spot value and frictional coefficient changing conditions, find that the antimony sulantimonate frictional coefficient adding 1.5wt% is reduced to 0.054 by 0.069, oil film strength brings up to 100kg by 71kg, and various performance is far more than MoS
2with the requirement of national standard to extreme pressure grease.
Embodiment 5
(1) sodium antimonate is prepared
In the NaOH solution of 385mL280g/L, add stibium trioxide 110g, at 80 DEG C, leach 4h, slowly drip 30wt% hydrogen peroxide 111mL in leaching process, cooling, crystallization, filtration obtain sodium antimonate 180 grams, and after cooling, the temperature of solution is 5-10 DEG C.
Adopt 840g nine water cure sodium to dissolve and be made into 1080mL solution, then the 180g sodium antimonate that step (1) obtains is added, control temperature of reaction 95 DEG C, stirring reaction 3.0h, be cooled to less than 5 DEG C, filter, obtain nine water schlippe's salt crystallization 223g, this crystallization is formulated as 664mL solution, obtains the thioantimonic acid sodium solution containing antimony 85g/L.
(3) butter of antimony solution is prepared with hydrochloric acid leaching stibium trioxide.
37wt% concentrated hydrochloric acid 870mL and 177gNaCl adds water and is made into 2000mL solution, adds stibium trioxide 400g, and temperature is room temperature, stirs 50min, filters, and obtains the butter of antimony solution containing antimony 167g/L.
(4) transition of trivalent antimony solution.
Take 166g citric acid, 129g tartrate joins above-mentioned 630mL, and antimony concentration is in the butter of antimony solution of 167g/L, solid NaOH adjust ph is added to 7.5 after dissolving, constant volume is 1500mL solution, is cooled to less than 40 DEG C, obtains the trivalent antimony solution of stable 70g/L.
(5) the 255ml trivalent antimony solution that thioantimonic acid sodium solution 200mL step (2) obtained and step (4) obtain joins in 40ml water simultaneously, in reinforced process, the feed rate of constant flow pump is about 8mL/min, the temperature of whole process control reaction system is 30 DEG C, pH value is 7.5, and rear continuation of having fed in raw material filters to obtain antimony sulantimonate filter cake after stirring 40min.
(6) by step (5) gained antimony sulantimonate filter cake through superheated water rinsing, oven dry, pulverizing, screening, obtain thioantimonic acid antimony product, its quality is 50.6g, and productive rate is 97.5%, and outward appearance is red-brown powder, and antimony content is 65.2%, and sulphur content is 34.4%.
By obtained antimony sulantimonate product application in lithium soap grease, adopt MRS-10A type four ball frictional testing machines according to its last non seizure load of GB/T3142 standard testing (oil film strength), spot value and frictional coefficient is ground according to the abrading-ball of SH/T0204 test under 392N load, the long abrasive stick part of 1450r/min and 30min, find that the antimony sulantimonate frictional coefficient adding 1.5wt% is reduced to 0.051 by 0.069, oil film strength brings up to 102kg by 71kg, and various performance is far more than MoS
2with the requirement of national standard to extreme pressure grease.
Embodiment 6
(1) sodium antimonate is prepared
In the NaOH solution of 500mL300g/L, add stibium trioxide 125g while stirring, at 85 DEG C, leach 3h, leaching adds 30wt% hydrogen peroxide 130mL simultaneously and is oxidized, and cooling, crystallization, filtration obtain sodium antimonate 205g, and after cooling, the temperature of solution is 5-10 DEG C.
(2) thioantimonic acid sodium solution is prepared
Adopt 870g nine water cure sodium to dissolve and be made into 940mL solution, then add the 205g sodium antimonate that step (1) obtains.Control temperature of reaction 93 DEG C, stirring reaction 2h, is cooled to less than 5 DEG C, filters, obtains nine water schlippe's salt crystallization 281.80g, this crystallization is formulated as 648mL solution, obtains the quinquevalence antimony solution containing antimony 110g/L.
(3) trivalent antimony solution is prepared with hydrochloric acid leaching stibium trioxide.
37wt% concentrated hydrochloric acid 870mL and 155.3gNaCl adds water and is made into 1600mL solution, adds stibium trioxide 402g, and temperature is room temperature, stirs 40min, filters, and obtains the trivalent antimony solution containing antimony 210g/L.
(4) transition of trivalent antimony solution.
Take 139g oxalic acid and 153g citric acid, join above-mentioned 500mL, concentration is in the trivalent antimony solution of 210g/L antimony, be made into 1300mL solution after dissolving, add solid NaOH adjust ph to 7.5, constant volume is 1400mL, be cooled to less than 40 DEG C, obtain the trivalent antimony solution of stable 75g/L.
(5) the trivalent antimony solution 431mL that thioantimonic acid sodium solution 267mL step (2) obtained and step (4) obtain, join in 55mL deionized water with constant flow pump with the feed rate of 8mL/min respectively, the temperature of whole process control reaction system is 30 DEG C, pH value is 7.0, and rear continuation of having fed in raw material filters to obtain antimony sulantimonate filter cake after stirring 40min.
(6) by step (5) gained antimony sulantimonate filter cake through superheated water rinsing, oven dry, pulverizing, screening, obtain thioantimonic acid antimony product, its quality is 86.9g, and productive rate is 97%, and outward appearance is red-brown powder, and antimony content is 65.1%, and sulphur content is 34.3%.
By obtained antimony sulantimonate product application in 0# lithium soap grease, adopt MRS-10A type four ball frictional testing machines according to its last non seizure load of GB/T3142 standard testing (oil film strength), grind spot value and frictional coefficient according to the abrading-ball of SH/T0204 test under 392N load, the long abrasive stick part of 1450r/min and 30min.Find that the antimony sulantimonate frictional coefficient adding 1.5wt% is reduced to 0.052 by 0.069, oil film strength brings up to 105kg by 71kg, and various performance is far more than MoS
2with the requirement of national standard to extreme pressure grease.
Claims (4)
1. prepare a method for antimony sulantimonate based on stable reaction system, it is characterized in that comprising the steps:
Step one: Sb
3+the conjugate solutions preparation of ion
In the ratio adding 1 gram of stibium trioxide in the mixing solutions of every 4-6mL hydrochloric acid and sodium-chlor, stibium trioxide is added in the mixing solutions of hydrochloric acid and sodium-chlor and react, the concentration of described hydrochloric acid is 4.5-6.5 mol/L, sodium chloride concentration is 1.5-3.4 mol/L, obtain butter of antimony solution, in gained butter of antimony solution, add multi-hydroxy carboxy acid's solution again, the mol ratio controlling multi-hydroxy carboxy acid and antimony is 1.7-2.0:1, obtains high density Sb
3+the conjugate solutions of ion; Adjust the pH value of conjugate solutions to 6.5-7.5, obtain reserve liquid; The reaction times of hydrochloric acid soln and stibium trioxide is 40-60min, and the concentration controlling antimony during reaction is 140-210g/L; Described multi-hydroxy carboxy acid is selected from tartrate, at least one in citric acid and oxalic acid; Sb
3+the pH value of ion complex solution is regulated and controled by sodium hydroxide, and in reserve liquid, the concentration of antimony is 60-75g/L;
Step 2: the preparation of antimony sulantimonate
Thioantimonic acid sodium solution containing antimony 70-110 g/L is added in step one gained reserve liquid and precipitates, filter, obtain antimony sulantimonate; Or
The thioantimonic acid sodium solution and step one gained reserve liquid that contain antimony 70-110 g/L are added drop-wise in water simultaneously and precipitate, filter, obtain antimony sulantimonate;
During precipitation, the temperature controlling solution is 20-30 DEG C, pH value is that in 6.5-8.0, reaction solution, trivalent antimony and antimonic mol ratio are 1.0-1.1:1.
2. a kind of method preparing antimony sulantimonate based on stable reaction system according to claim 1, is characterized in that: in step 2, and the pH value of reaction solution is regulated and controled by hydrochloric acid; The time of precipitation is 1-2h.
3. a kind of method preparing antimony sulantimonate based on stable reaction system according to claim 1 and 2, it is characterized in that the described thioantimonic acid sodium solution containing antimony 70-110 g/L is prepared by following proposal: in the ratio adding 1 gram of stibium trioxide in every 3-4mL sodium hydroxide solution, stibium trioxide is added in sodium hydroxide solution and leaches, hydrogen peroxide oxidation is added while leaching, through cooling after oxidation, obtain sodium antimonate, sodium antimonate being added concentration is react in the sodium sulfide solution of 250-351g/L again, the mol ratio controlling sodium antimonate and sodium sulphite is 1:4.2-4.8, the concentration controlling antimony in solution is 80-125 g/L, temperature of reaction is 90-95 DEG C, after having reacted, reaction solution is cooled, obtain schlippe's salt solid, again schlippe's salt solid is dissolved in water, obtain the thioantimonic acid sodium solution containing antimony 70-110 g/L, the concentration of described sodium hydroxide solution is 200-300g/L, and extraction temperature is 80-90 DEG C, and the consumption of hydrogen peroxide is 1.3-1.5 times of theoretical amount, and the mass percentage concentration of hydrogen peroxide is 27%-30%.
4. a kind of method preparing antimony sulantimonate based on stable reaction system according to claim 3, is characterized in that: the extraction time of stibium trioxide in sodium hydroxide solution is 3-4h, and leach liquor is cooled to 5-10 DEG C, and crystallization, filtration obtain sodium antimonate; The time that sodium antimonate and sodium sulphite react is 2-3h, and reaction solution is cooled to temperature≤5 DEG C, crystallization, filters to obtain schlippe's salt solid.
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| CN108130156A (en) * | 2017-12-29 | 2018-06-08 | 广西生富锑业科技股份有限公司 | A kind of preparation method of modified antimony sulantimonate |
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