CN104843760A - Method for producing precipitated barium sulfate and co-producing manganese chloride - Google Patents
Method for producing precipitated barium sulfate and co-producing manganese chloride Download PDFInfo
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Abstract
The invention discloses a method for producing precipitated barium sulfate and co-producing manganese chloride. The method comprises the following steps: A, preparing a barium chloride solution; B, preparing a manganese sulfate solution; C, dipping the manganese sulfate solution prepared by the step B into the barium chloride solution prepared by the step A to perform replacement reaction; D, filtering the product after performing the replacement reaction by the step C, and respectively collecting filtrate and filter cakes; E, performing SO4<2-> decontamination on the filtrate collected by the step D, filtering the decontaminated filtrate, and distilling to obtain manganese chloride; F, rinsing the filter cakes collected by the step D till no chloride ion, baking the rinsed filter cakes in an oven, grinding and sieving to obtain barium sulfate. When precipitated barium sulfate is prepared, simultaneously a byproduct, namely manganese chloride is recovered. The byproduct is high in added value, the utilization rate of the energy is effectively increased, and relatively high economical benefits can be obtained.
Description
Technical field
The invention belongs to technical field prepared by filler, be specifically related to a kind of method of producing process white coproduction Manganous chloride tetrahydrate.
Background technology
Process white, as a kind of high quality filler and white pigment, is widely used in the industries such as rubber, plastics, paint, ink, papermaking, weaving, pottery, medicine.Traditional barium sulfate production method is saltcake-grey black method, and this method take barite as raw material, after coal reduction roasting, then reacts obtained barium sulfate with sodium sulfate.Because sulphur content is high and particle diameter is large, size-grade distribution is wide in product, limit its range of application.
Be that raw material is prepared process white and carried out more deep research by numerous investigators with bariumchloride, the processing method wherein preparing process white byproduct sodium chloride with bariumchloride/sodium sulfate for raw material replacement(metathesis)reaction is applied more, but because side product chlorinated sodium added value is low, if evaporate its dilute solution, energy consumption is high, adopt the cost of the methods such as ion-exchange higher, all cause deficiency in economic performance.
CN101838010A discloses a kind of method preparing barium sulfate and co-producing sodium chloride: bariumchloride and sodium sulfate replacement(metathesis)reaction obtain barium sulfate and sodium-chlor, obtains product barium sulfate after solid-liquid separation after drying, pulverizing; Byproduct sodium-chlor is obtained after filtrate evaporation.CN101838008A discloses a kind of method that superfine precipitated barium sulfate co-production of hydrochloric prepared by bariumchloride: bariumchloride and sulfuric acid reaction obtain barium sulfate and hydrochloric acid, solid-liquid separation, washing, drying, pulverize to obtain product barium sulfate, filtrate obtains byproduct hydrochloric acid through underpressure distillation.In foregoing invention, by product is respectively sodium-chlor, hydrochloric acid, and because it evaporates costly, self-value is low, adds waste water control expense, overall profit can be caused very low, limits its development.
CN102674468A discloses a kind of method that manganous sulfate of purifying prepares barium sulfate simultaneously: in manganese sulfate solution, first add the impurity such as barium sulphide removing iron ion, again manganous sulfate and barium sulphide replacement(metathesis)reaction are generated manganese sulfide, barium sulfate mixed precipitation, pass into oxygen after solid-liquid separation, making beating washing and manganese sulfide is oxidized to manganous sulfate, solid-liquid separation, hot wash drying obtain byproduct barium sulfate; Filtrate obtains the manganese sulfate product of purifying through removal of impurities, evaporation drying.The weak point of this technique: technical process is complicated, long reaction time, produces waste liquid many.If intermediate product manganese sulfide, barium sulfate mixed precipitation oxidation, washing thoroughly, can not make residual manganese ion in barium sulfate and affect its purity and whiteness.
Manganous chloride tetrahydrate can be used for medicine synthesis and feed auxiliary,
analytical reagent, dyestuff and pigment manufacture; Also for magnesium alloy, aluminum alloy smelting, brownish black brick and tile are produced and pharmacy and drying battery manufacture; Agriculturally also can be used as trace element fertilizer.Main raw material used produced by current domestic existing more than 90% enterprise's Manganous chloride tetrahydrate is manganous carbonate, and almost whole manganous carbonate refines gained in the three wastes given off by Resorcinol (a kind of Organic chemical products) production process, bring because adopting above-mentioned manganous carbonate raw material in a large number reluctant containing benzene organism and bring therefrom other be difficult to the objectionable impurities that detects, the quality product of Manganous chloride tetrahydrate is restricted.
Thus the product that the such added value of barium sulfate and co-produced Manganous chloride tetrahydrate is high, good in economic efficiency how is prepared, it is the target that this area is constantly pursued, wherein, patent CN 102115136 A provides a kind of method that barium sulfate and co-produced Manganous chloride tetrahydrate prepared by bariumchloride waste residue, the mol ratio wherein controlling the material of bariumchloride and manganous sulfate is that 1:0.8-1.2 carries out replacement(metathesis)reaction, then obtains barium sulfate and Manganous chloride tetrahydrate through filtering, washing, dry.The method of barium sulfate and co-produced Manganous chloride tetrahydrate prepared by this invention described bariumchloride waste residue, and the purport of invention is the recycling of bariumchloride waste residue, but do not relate to and reclaim product, the purity of by product and purposes.Involved chemical principle is:
BaS+2HCl＝BaCl2+H2S
BaCl2+ZnSO4＝BaSO4↓+2ZnCl
2
From reaction equation, raw materials used is zinc sulfate, and by product is zinc chloride! Described in this patent: the mol ratio of bariumchloride and manganous sulfate is 1:0.8-1.2.If the mol ratio of bariumchloride and manganous sulfate is less than 1:1 (this patent is 0.8) can cause residual a large amount of bariumchloride in by product, reduce the quality of by product.Conversely, if the mol ratio of bariumchloride and manganous sulfate is 1:1.2, the follow-up measure not removing excessive sulfate radical, will certainly cause in by product and contain a large amount of vitriol, reduce the quality of by product equally.Because the step e in invention: the solution of the chloride containing manganese of step C gained is distilled for Manganous chloride tetrahydrate supersaturated solution, makes Manganous chloride tetrahydrate crystallization, obtain Manganous chloride tetrahydrate product.Wherein do not relate to the content of Manganous chloride tetrahydrate product removal of impurities, so this technique only reaches the object of resource reclaim, but product foreign matter content is high, yields poorly, value-added content of product and economic benefit low.
Summary of the invention
The object of the invention is to propose a kind of novel method preparing process white, with bariumchloride/manganous sulfate for raw material, add dispersion agent 5040 replacement(metathesis)reaction and obtain process white, filtrate evaporation obtains byproduct Manganous chloride tetrahydrate, the water of condensation that evaporation obtains and washing of precipitate water retrieval system, for dissolving raw material, achieve the recycle of water.Median size little (about 0.4 μ), the whiteness high (>=94) of obtained process white product, meet the industry needs such as rubber, plastics, papermaking, coating and plastic-steel.
The present invention is the technical scheme realizing the employing of its object:
Produce a method for process white coproduction Manganous chloride tetrahydrate, comprise the following steps:
A, configuration barium chloride solution: by soluble in water for solid chlorine barium, obtain barium chloride solution, add dispersion agent 5040, stir, for subsequent use;
B, configuration manganese sulfate solution: by soluble in water for solid sulphuric acid manganese, obtain manganese sulfate solution, for subsequent use;
C, replacement(metathesis)reaction: the manganese sulfate solution prepared by step B is added dropwise in barium chloride solution prepared by steps A, carries out replacement(metathesis)reaction;
D, the product after step C replacement(metathesis)reaction to be filtered, collect filtrate and filter cake respectively;
E, by step D collect filtrate carry out SO
4 2-removal of impurities, the filtrate after removal of impurities is distilled after filtering, and obtains Manganous chloride tetrahydrate;
F, by step D collect filter cake be washed with water to without chlorion, the filter cake after washing is placed in baking oven and dries, and grinds, sieves, obtain barium sulfate.
The concentration of the barium chloride solution described in steps A is 0.1-2mol/L, and the add-on of described dispersion agent 5040 is the 0.5-3% of butt barium sulfate, and butt barium sulfate refers to that bariumchloride and manganous sulfate react the product barium sulfate that generates in butt.
The concentration of the manganese sulfate solution described in step B is 0.1-2mol/L.
The pH value of the manganese sulfate solution prepared in rate-determining steps B is 1-3.
In step C replacement(metathesis)reaction, control the excessive 2-5% of manganese sulfate solution.
In step C replacement(metathesis)reaction, control manganese sulfate solution excessive 3%.
In step C replacement(metathesis)reaction, manganese sulfate solution is added dropwise in barium chloride solution under the state stirred, and stirring velocity is 200r/min.
In step C replacement(metathesis)reaction, temperature of reaction controls as 20-60 DEG C.
In step F, the bake out temperature of baking oven is 100-120 DEG C.
The invention has the beneficial effects as follows: chemical reaction of the present invention is: BaCl2+MnSO4=BaSO4 ↓+MnCl
2as can be seen from chemical equation: replacement(metathesis)reaction is reaction with same mole, theoretically, the mol ratio of bariumchloride and manganous sulfate is 1:1, but the present invention controls manganese sulfate solution excessive 3% in replacement(metathesis)reaction, i.e. sulfate radical excessive 3%, to allow barium ion precipitate completely, so just can ensure the purity of barium sulfate, and excessive sulfate radical drips bariumchloride removing by twice, control the point of equivalent in precipitation, do not have excessive barium ion to produce, again because the solubility product of barium sulfate is K
sP=10
-10, that is, in solution, barium sulfate content is 10
-5mol/L, is converted into 2.33 × 10
-3grams per liter, like this, in evaporation and crystal process, does not have barium sulfate and separates out, just ensure that the purity of Manganous chloride tetrahydrate yet.
The present invention with bariumchloride/manganous sulfate for raw material, by adding dispersion agent 5040, make product barium sulfate good dispersity, narrow particle size distribution, high whiteness (see Fig. 2, Fig. 3), median size little (about 0.4 μ), the whiteness high (>=94) of obtained process white product, meet the industry needs such as rubber, plastics, papermaking, coating and plastic-steel.The product Manganous chloride tetrahydrate sulfate radical content that filtrate evaporation obtains is low, purity is high; The water of condensation that evaporation obtains and process white washing water retrieval system, for dissolving raw material, achieve the recycle of water, meet the technological principle of environmental protection.
The present invention with bariumchloride/manganous sulfate for raw material, produce the key problem in technology of process white coproduction Manganous chloride tetrahydrate: one is control suitable pH value, because pH value is too high, manganous hydroxide precipitation can be formed, or be oxidized to 4 brown valency manganic compounds, manganous hydroxide precipitation enters filter cake after filtration with brown insolubles together with barium sulfate, and after dry, manganous hydroxide precipitation is also oxidized to 4 brown valency manganic compounds, and the whiteness of product barium sulfate can reduce greatly; Two is by adding dispersion agent 5040 (Shanghai produces apart from zero Chemical Industry Science Co., Ltd), P5040 is high molecular weight water soluble polymer, it is coated on the surface of barium sulfate particles, the space steric effect of its long chain molecule can the growth velocity of each crystal face of Effective Regulation crystal, promote the formation of spheroidal particle, effectively can stop the reunion of barium sulfate particles simultaneously, so, add appropriate dispersion agent 5040, can make that the particle diameter of product barium sulfate is little, narrow particle size distribution, particle microscopic appearance is torispherical (see Fig. 2, Fig. 3).If addition is excessive, owing to can be wound around between macromolecular chain, can increases the viscosity of solution on the contrary, make barium sulfate particle move relative difficulty, cause barium sulfate particle to be involved together by these macromole, make product cut size large, size-grade distribution is wide.
The present invention also has the following advantages:
1. raw material resources are abundant, cost is low, one of raw material of the present invention is bariumchloride, and the main raw material producing bariumchloride is barite, ore resource is enriched, and product cost can reduce naturally, in Guangxi, Guizhou, Hunan, Hubei, Shaanxi, Fujian abundance, and ore district hydrogeologic condition is simple, silication pelitic siltstone, boundary clear, country rock are firm, field conditions is simple, and the main raw material of manganous sulfate is pyrolusite, its in Hunan, Guangxi, Liaoning, the ground such as Sichuan output reach 63.19%.
2. recyclable side product chlorinated manganese while preparing process white, this by product added value is high, Manganous chloride tetrahydrate can be used for organic chloride catalyst, medicine synthesis and feed auxiliary,
analytical reagent, dyestuff and pigment manufacture, also for magnesium alloy, aluminum alloy smelting, brownish black brick and tile are produced and pharmacy and drying battery manufacture, agriculturally also can be used as trace element fertilizer, the technique that to compare with bariumchloride/sodium sulfate be raw material, by product is technical grade sodium-chlor, because China's Coastal Areas salt (sodium-chlor) aboundresources, so technical grade sodium-chlor is due to just very low containing its added value of impurity, because it is cheap, also have and be used as salt without my good man person for processed food, the danger be detrimental to health, coproduction Manganous chloride tetrahydrate of the present invention improves the utilization ratio of the energy effectively, and higher economic benefit can be obtained, prepared by the present invention, the quality of product is high, barium sulfate price is at 5000 ~ 6000 yuan/ton, Manganous chloride tetrahydrate (anhydrous) price is at 11000 yuan/ton, Manganous chloride tetrahydrate (four water) price is at 8500 yuan/ton, higher economic benefit will inevitably be brought, contrast bariumchloride/sodium sulfate is the technique of raw material, its byproduct technical grade sodium-chlor price is at 260 yuan/ton, the energy that evaporative crystallization operation consumes is substantially identical, and product price difference is huge.
3. this technique environmental protection more: evaporation condensed water and washing of precipitate water can be used for dissolving raw material, achieve the recycle of water, not only water saving, are priorly the reduction of discharge of wastewater.
Moreover the pH value of manganese sulfate solution is strict controlled in the scope of 1-3 by the present invention, makes Mn
2+stable, avoid it form white gum precipitation or be oxidized to brown, and then ensure that in joined solution and avoid there is a large amount of brown insolubles, for the whiteness of the barium sulfate of follow-up preparation provides safeguard.
The present invention must strict temperature control be 20-60 DEG C in the process of replacement(metathesis)reaction, and this is that contriver sums up through long-term creative research, BaSO
4particle is separated out primarily of coring and increment two process compositions from liquid phase, these two processes are all subject to the impact of temperature of reaction, when temperature of reaction is lower, the kinetic energy of molecule is lower, intergranular magnetism is relatively large, nucleation is assembled in easy generation, the molecular surface that particle is also easier to be attached to nucleation is grown up, so the product cut size obtained is larger, or formation colloidal state, make product filtration difficulty, when temperature is 20 ~ 60 DEG C, less and the narrow particle size distribution of products obtained therefrom particle diameter, when temperature of reaction is more than 60 DEG C, product cut size also starts to increase, its reason is: on the one hand because the growth velocity of crystal is greater than its nucleation rate, the pedesis aggravation of molecule, the frequency of collision mutually between particle is increased, on the other hand because temperature raises, cause fine particle to dissolve, and macrobead is grown up gradually.
Contriver is through long-term creative research, in the process of process white coproduction Manganous chloride tetrahydrate, the concentration that strictly will control bariumchloride and manganous sulfate is 0.1mol/L-2mol/L, when the concentration of bariumchloride and manganous sulfate is less than 0.1mol/L, because reactant concn is low, at this moment crystal nucleation rate is less than its growth velocity, causes nucleus to grow fast, and now the particle diameter of product is larger; (2mol/L is greater than), BaSO when reactant concn is higher
4nucleation rate is accelerated, a large amount of nucleus is generated in short period of time, and nucleus growth speed reduces relatively, but the surface energy of nucleus is high, easily to reunite, through long-term creative research and the nucleation rate and the growth velocity that consider particle, must the strict concentration controlling bariumchloride and manganous sulfate be 0.1mol/L-2mol/L.
Accompanying drawing explanation
Fig. 1 is process flow diagram of the present invention.
Fig. 2 is the stereoscan photograph of embodiment 3 products obtained therefrom barium sulfate.
Fig. 3 is the stereoscan photograph of embodiment 6 products obtained therefrom barium sulfate.
Embodiment
The present invention is the utilization ratio improving the energy, increases economic benefit simultaneously, provides a kind of method of producing process white coproduction Manganous chloride tetrahydrate, be further detailed below in conjunction with specific embodiment to the present invention.
Embodiment 1.
A, configuration barium chloride solution: by soluble in water for solid chlorine barium, configuration concentration is the barium chloride solution of 0.6mol/L, takes out 500mL, and the amount of adding P5040 is 0.83 gram, stirs, for subsequent use;
B, configuration manganese sulfate solution: by soluble in water for solid sulphuric acid manganese, configuration concentration is the manganese sulfate solution of 0.6mol/L, and taking out 500mL, is 2.5 with sulfuric acid or salt acid for adjusting pH, for subsequent use;
C, replacement(metathesis)reaction: the manganese sulfate solution prepared by step B is added dropwise under stirring in barium chloride solution prepared by steps A, and controls manganese sulfate solution excessive 3%, and stirring velocity controls, for 200r/min, to carry out replacement(metathesis)reaction under 25 DEG C of temperature condition;
D, the product after step C replacement(metathesis)reaction to be filtered, collect filtrate and filter cake respectively;
E, by step D collect filtrate carry out SO
4 2-removal of impurities, be specially: by gained filtrate at constant temperature 45 DEG C, while stirring be that 0.6mol/L barium chloride solution 15mL stream adds in filtrate and carries out primary sedimentation reaction by the concentration with excessive 3% equimolar amount of manganese sulfate solution, filter after stirring 10min, SO excessive in removing filtrate
4 2-, obtain secondary filtrate, drip barium chloride solution and carry out secondary sedimentation reaction in gained secondary filtrate, to visual inspection less than precipitation, filter, the filter cake obtained and the filter cake of step D merge, filtrate through evaporation, crystallization, dry must the violent 16g of chlorination; Secondary sedimentation removes unnecessary SO in filtrate to ensure
4 2-.
F, by step D and E collect filter cake be washed with water to without chlorion (checking with silver nitrate solution), the filter cake after washing is placed in baking oven in 100 DEG C of oven dry, grinds, sieves, obtain barium sulfate 73.5g.
Embodiment 2
A, configuration barium chloride solution: by soluble in water for solid chlorine barium, configuration concentration is the barium chloride solution of 0.1mol/L, takes out 500mL, and the amount of adding P5040 is 0.14 gram, stirs, for subsequent use;
B, configuration manganese sulfate solution: by soluble in water for solid sulphuric acid manganese, configuration concentration is the manganese sulfate solution of 0.1mol/L, and taking out 500mL, is 1 with salt acid for adjusting pH, for subsequent use;
C, replacement(metathesis)reaction: the manganese sulfate solution prepared by step B is added dropwise under stirring in barium chloride solution prepared by steps A, and controls manganese sulfate solution excessive 3%, and stirring velocity controls, for 200r/min, to carry out replacement(metathesis)reaction under 20 DEG C of temperature condition;
D, the product after step C replacement(metathesis)reaction to be filtered, collect filtrate and filter cake respectively;
E, by step D collect filtrate carry out SO
4 2-removal of impurities, be specially: by gained filtrate at constant temperature 45 DEG C, while stirring be that 0.6mol/L barium chloride solution 15mL stream adds in filtrate and carries out primary sedimentation reaction by the concentration with excessive 3% equimolar amount of manganese sulfate solution, filter after stirring 10min, SO excessive in removing filtrate
4 2-, obtain secondary filtrate, drip barium chloride solution and carry out secondary sedimentation reaction in gained secondary filtrate, to visual inspection less than precipitation, filter, the filter cake obtained and the filter cake of step D merge; Filtrate is through evaporation, crystallization, dry the violent 2.6g of chlorination;
F, by step D and E collect filter cake be washed with water to without chlorion (checking with silver nitrate solution), the filter cake after washing is placed in baking oven in 100 DEG C of oven dry, grinds, sieves, obtain barium sulfate 12.2g.
Embodiment 3
A, configuration barium chloride solution: by soluble in water for solid chlorine barium, configuration concentration is the barium chloride solution of 0.5mol/L, takes out 500mL, and the amount of adding P5040 is 4.16 grams, stirs, for subsequent use;
B, configuration manganese sulfate solution: by soluble in water for solid sulphuric acid manganese, configuration concentration is the manganese sulfate solution of 0.5mol/L, and taking out 500mL, is 1.5 with salt acid for adjusting pH, for subsequent use;
C, replacement(metathesis)reaction: the manganese sulfate solution prepared by step B is added dropwise under stirring in barium chloride solution prepared by steps A, and controls manganese sulfate solution excessive 3%, and stirring velocity controls, for 200r/min, to carry out replacement(metathesis)reaction under 35 DEG C of temperature condition;
D, the product after step C replacement(metathesis)reaction to be filtered, collect filtrate and filter cake respectively;
E, by step D collect filtrate carry out SO
4 2-removal of impurities, be specially: by gained filtrate at constant temperature 45 DEG C, while stirring be that 0.5mol/L barium chloride solution 15mL stream adds in filtrate and carries out primary sedimentation reaction by the concentration with excessive 3% equimolar amount of manganese sulfate solution, filter after stirring 10min, SO excessive in removing filtrate
4 2-, obtain secondary filtrate, drip barium chloride solution and carry out secondary sedimentation reaction in gained secondary filtrate, to visual inspection less than precipitation, filter, the filter cake obtained and the filter cake of step D merge; Filtrate is through evaporation, crystallization, dry the violent 13g of chlorination;
F, by step D and E collect filter cake be washed with water to without chlorion (checking with silver nitrate solution), the filter cake after washing is placed in baking oven in 100 DEG C of oven dry, grinds, sieves, obtain barium sulfate 61.2g.
Embodiment 4
A, configuration barium chloride solution: by soluble in water for solid chlorine barium, configuration concentration is the barium chloride solution of 1mol/L, takes out 500mL, and the amount of adding P5040 is 5.55 grams, stirs, for subsequent use;
B, configuration manganese sulfate solution: by soluble in water for solid sulphuric acid manganese, configuration concentration is the manganese sulfate solution of 1mol/L, and taking out 500mL, is 1.5 with salt acid for adjusting pH, for subsequent use;
C, replacement(metathesis)reaction: the manganese sulfate solution prepared by step B is added dropwise under stirring in barium chloride solution prepared by steps A, and controls manganese sulfate solution excessive 3%, and stirring velocity controls, for 200r/min, to carry out replacement(metathesis)reaction under 25 DEG C of temperature condition;
D, the product after step C replacement(metathesis)reaction to be filtered, collect filtrate and filter cake respectively;
E, by step D collect filtrate carry out SO
4 2-removal of impurities, be specially: by gained filtrate at constant temperature 45 DEG C, while stirring be that 1.0mol/L barium chloride solution 15mL stream adds in filtrate and carries out primary sedimentation reaction by the concentration with excessive 3% equimolar amount of manganese sulfate solution, filter after stirring 10min, SO excessive in removing filtrate
4 2-, obtain secondary filtrate, drip barium chloride solution and carry out secondary sedimentation reaction in gained secondary filtrate, to visual inspection less than precipitation, filter, the filter cake obtained and the filter cake of step D merge; Filtrate is through evaporation, crystallization, dry the violent 26g of chlorination;
F, by step D and E collect filter cake be washed with water to without chlorion (checking with silver nitrate solution), the filter cake after washing is placed in baking oven in 100 DEG C of oven dry, grinds, sieves, obtain barium sulfate 122.4g.
Embodiment 5
A, configuration barium chloride solution: by soluble in water for solid chlorine barium, configuration concentration is the barium chloride solution of 1.5mol/L, takes out 500mL, and the amount of adding P5040 is 4.16 grams, stirs, for subsequent use;
B, configuration manganese sulfate solution: by soluble in water for solid sulphuric acid manganese, configuration concentration is the manganese sulfate solution of 1.5mol/L, and taking out 500mL, is 2.5 with salt acid for adjusting pH, for subsequent use;
C, replacement(metathesis)reaction: the manganese sulfate solution prepared by step B is added dropwise under stirring in barium chloride solution prepared by steps A, and controls manganese sulfate solution excessive 3%, and stirring velocity controls, for 200r/min, to carry out replacement(metathesis)reaction under 50 DEG C of temperature condition;
D, the product after step C replacement(metathesis)reaction to be filtered, collect filtrate and filter cake respectively;
E, by step D collect filtrate carry out SO
4 2-removal of impurities, be specially: by gained filtrate at constant temperature 45 DEG C, while stirring be that 1.5mol/L barium chloride solution 15mL stream adds in filtrate and carries out primary sedimentation reaction by the concentration with excessive 3% equimolar amount of manganese sulfate solution, filter after stirring 10min, SO excessive in removing filtrate
4 2-, obtain secondary filtrate, drip barium chloride solution and carry out secondary sedimentation reaction in gained secondary filtrate, to visual inspection less than precipitation, filter, the filter cake obtained and the filter cake of step D merge; Filtrate is through evaporation, crystallization, dry the violent 39g of chlorination;
F, by step D and E collect filter cake be washed with water to without chlorion (checking with silver nitrate solution), the filter cake after washing is placed in baking oven in 100 DEG C of oven dry, grinds, sieves, obtain barium sulfate 183.6g.
Embodiment 6
A, configuration barium chloride solution: by soluble in water for solid chlorine barium, configuration concentration is the barium chloride solution of 1.8mol/L, takes out 500mL, and the amount of adding P5040 is 7.49 grams, stirs, for subsequent use;
B, configuration manganese sulfate solution: by soluble in water for solid sulphuric acid manganese, configuration concentration is the manganese sulfate solution of 1.8mol/L, and taking out 500mL, is 3 with salt acid for adjusting pH, for subsequent use;
C, replacement(metathesis)reaction: the manganese sulfate solution prepared by step B is added dropwise under stirring in barium chloride solution prepared by steps A, and controls manganese sulfate solution excessive 3%, and stirring velocity controls, for 200r/min, to carry out replacement(metathesis)reaction under 40 DEG C of temperature condition;
D, the product after step C replacement(metathesis)reaction to be filtered, collect filtrate and filter cake respectively;
E, by step D collect filtrate carry out SO
4 2-removal of impurities, be specially: by gained filtrate at constant temperature 45 DEG C, while stirring be that 1.8mol/L barium chloride solution 15mL stream adds in filtrate and carries out primary sedimentation reaction by the concentration with excessive 3% equimolar amount of manganese sulfate solution, filter after stirring 10min, SO excessive in removing filtrate
4 2-, obtain secondary filtrate, drip barium chloride solution and carry out secondary sedimentation reaction in gained secondary filtrate, to visual inspection less than precipitation, filter, the filter cake obtained and the filter cake of step D merge; Filtrate is through evaporation, crystallization, dry the violent 47g of chlorination;
F, by step D and E collect filter cake be washed with water to without chlorion (checking with silver nitrate solution), the filter cake after washing is placed in baking oven in 100 DEG C of oven dry, grinds, sieves, obtain barium sulfate 220.4g.
Embodiment 7
A, configuration barium chloride solution: by soluble in water for solid chlorine barium, configuration concentration is the barium chloride solution of 2mol/L, takes out 500mL, and the amount of adding P5040 is 5.45 grams, stirs, for subsequent use;
B, configuration manganese sulfate solution: by soluble in water for solid sulphuric acid manganese, configuration concentration is the manganese sulfate solution of 2mol/L, and taking out 500mL, is 2.5 with salt acid for adjusting pH, for subsequent use;
C, replacement(metathesis)reaction: the manganese sulfate solution prepared by step B is added dropwise under stirring in barium chloride solution prepared by steps A, and controls manganese sulfate solution excessive 3%, and stirring velocity controls, for 200r/min, to carry out replacement(metathesis)reaction under 45 DEG C of temperature condition;
D, the product after step C replacement(metathesis)reaction to be filtered, collect filtrate and filter cake respectively;
E, by step D collect filtrate carry out SO
4 2-removal of impurities, be specially: by gained filtrate at constant temperature 45 DEG C, while stirring be that 0.5mol/L barium chloride solution 15mL stream adds in filtrate and carries out primary sedimentation reaction by the concentration with excessive 3% equimolar amount of manganese sulfate solution, filter after stirring 10min, SO excessive in removing filtrate
4 2-, obtain secondary filtrate, drip barium chloride solution and carry out secondary sedimentation reaction in gained secondary filtrate, to visual inspection less than precipitation, filter, the filter cake obtained and the filter cake of step D merge; Filtrate is through evaporation, crystallization, dry the violent 52g of chlorination;
F, by step D and E collect filter cake be washed with water to without chlorion (checking with silver nitrate solution), the filter cake after washing is placed in baking oven in 100 DEG C of oven dry, grinds, sieves, obtain barium sulfate 244.9g.
By the Manganous chloride tetrahydrate that obtains in above-described embodiment 1-6 step e mensuration by 5.4 sulphate contents in GB HG/T3816-2006, adopt turbidimetry for Determination wherein SO
4 2content:
Agents useful for same is as follows:
Hydrochloric acid soln: 1+3;
Barium chloride solution: 100g/L;
Vitriol standardized solution: 1mL solution is containing vitriol (SO4
2-) 0.10mg.
Pipette the vitriol standardized solution that 10.00mL prepares by HG/T3696.2 requirement, be placed in 100mL volumetric flask, be diluted with water to scale, shake up.
Take the Manganous chloride tetrahydrate 1.00g of gained in above-mentioned steps E, be placed in 250mL Erlenmeyer flask, add 20mL water dissolution, filter if desired, the manganese chloride solution after dissolving is moved in 50mL colorimetric cylinder, add 1mL hydrochloric acid soln, under 30-35 DEG C of condition, be incubated 10min, add 3mL barium chloride solution, be diluted with water to scale, mixing, compares than turbid solution with standard after placing 30min.
Standard is pipette vitriol standardized solution (1mL solution contains vitriol 0.10mg) by following regulation than turbid solution, with test portion simultaneously with expecting to process.
Acceptable end product: 1.00mL; Salable product: 2.00mL.
Adopt the granularity of the process white product obtained in LS-POP (6) type laser particle size analyzer determination step F, adopt PN-48B type measuring brightness instrument to measure the whiteness of process white product, result is see table 1.
Philips Tacnai F20 TEM type scanning electron microscope is adopted to measure the microscopic appearance of process white product.
Table 1
The median size of process white product is little, and its specific surface area is just large, strong with the bonding force of matrix, more effectively can improve the mechanical property of matrix material; Whiteness high (>=94), for industries such as plastics, plastics, papermaking, coating, paint, can not affect the whiteness of product.The key of this technique controls the sulfate radical content in Manganous chloride tetrahydrate, qualified, illustrates that removal of impurities is thorough.
Claims (9)
1. produce a method for process white coproduction Manganous chloride tetrahydrate, it is characterized in that: comprise the following steps:
A, configuration barium chloride solution: by soluble in water for solid chlorine barium, obtain barium chloride solution, add dispersion agent 5040, stir, for subsequent use;
B, configuration manganese sulfate solution: by soluble in water for solid sulphuric acid manganese, obtain manganese sulfate solution, for subsequent use;
C, replacement(metathesis)reaction: the manganese sulfate solution prepared by step B is added dropwise in barium chloride solution prepared by steps A, carries out replacement(metathesis)reaction;
D, the product after step C replacement(metathesis)reaction to be filtered, collect filtrate and filter cake respectively;
E, by step D collect filtrate carry out SO
4 2-removal of impurities, the filtrate after removal of impurities is distilled after filtering, and obtains Manganous chloride tetrahydrate;
F, by step D collect filter cake be washed with water to without chlorion, the filter cake after washing is placed in baking oven and dries, and grinds, sieves, obtain barium sulfate.
2. a kind of method of producing process white coproduction Manganous chloride tetrahydrate according to claim 1, is characterized in that: the concentration of the barium chloride solution described in steps A is 0.1-2mol/L, and the add-on of described dispersion agent 5040 is the 0.5-3% of butt barium sulfate.
3. a kind of method of producing process white coproduction Manganous chloride tetrahydrate according to claim 1, is characterized in that: the concentration of the manganese sulfate solution described in step B is 0.1-2mol/L.
4. a kind of method of producing process white coproduction Manganous chloride tetrahydrate according to claim 1, is characterized in that: the pH value of the manganese sulfate solution prepared in rate-determining steps B is 1-3.
5. a kind of method of producing process white coproduction Manganous chloride tetrahydrate according to claim 1, is characterized in that: in step C replacement(metathesis)reaction, controls the excessive 2-5% of manganese sulfate solution.
6. a kind of method of producing process white coproduction Manganous chloride tetrahydrate according to claim 5, is characterized in that: in step C replacement(metathesis)reaction, controls manganese sulfate solution excessive 3%.
7. a kind of method of producing process white coproduction Manganous chloride tetrahydrate according to claim 1, is characterized in that: in step C replacement(metathesis)reaction, and manganese sulfate solution is added dropwise in barium chloride solution under the state stirred, and stirring velocity is 200r/min.
8. a kind of method of producing process white coproduction Manganous chloride tetrahydrate according to claim 1, is characterized in that: in step C replacement(metathesis)reaction, and temperature of reaction controls as 20-60 DEG C.
9. a kind of method of producing process white coproduction Manganous chloride tetrahydrate according to claim 1, is characterized in that: in step F, the bake out temperature of baking oven is 100-120 DEG C.
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| CN107117657A (en) * | 2017-06-23 | 2017-09-01 | 中南大学 | The method that high-pure anhydrous manganese chloride is prepared using technical grade sulfuric acid manganese |
| CN114229882A (en) * | 2021-12-31 | 2022-03-25 | 山东利特纳米技术有限公司 | Comprehensive utilization method of waste sulfuric acid and washing wastewater in graphene oxide preparation process |
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