CN111233036A - Made of Sb2O3Direct preparation of Sb with aqueous hydrochloric acid4O5Cl2Method (2) - Google Patents
Made of Sb2O3Direct preparation of Sb with aqueous hydrochloric acid4O5Cl2Method (2) Download PDFInfo
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Abstract
The invention relates to a composite material made of Sb2O3Direct preparation of Sb with aqueous hydrochloric acid4O5Cl2The method of (1) preparing hydrochloric acid aqueous solution containing a certain hydrochloric acid concentration range by using hydrochloric acid and water as initial synthesis solution; heating the synthesis starting solution to a temperature range; and Sb2O3Adding into the initial liquid, reacting for a while under stirring to form Sb4O5Cl2A crystal; and separating said crystals and synthesis tails from said aqueous solution; washing the crystal with water or ethanol; drying the washed crystal to obtain the Sb4O5Cl2And (4) crystals. The process has the characteristics of short preparation time, high product purity, low energy consumption and no waste liquid or waste gas emission in the preparation process.
Description
Technical Field
The invention belongs to the field of inorganic chemical industry and nonferrous metallurgy, mainly relates to a preparation method of an antimony compound product, and particularly relates to Sb4O5Cl2The preparation method of (1).
Background
Sb4O5Cl2The zinc sulfate is one of two important intermediate substances which enable a chlorine-antimony flame-retardant synergistic system to generate a flame-retardant effect in a combustion process, and is also an important component of an activating agent in a method for purifying a zinc sulfate aqueous solution to remove nickel, cobalt and germanium.
Albeit Sb4O5Cl2The content of the halogen-free halogen-antimony flame retardant is lower than that of SbOCl, the flame retardant effect is slightly poor when the halogen-free halogen-antimony flame retardant is used as a flame retardant alone, but the halogen-antimony flame retardant has excellent flame retardant synergistic performance when the halogen-free halogen-antimony flame retardant is used in combination with halogen. It can reduce the pigment consumption in colour plastics, has less influence on the transparency of high polymer, and has Sb2O3And sodium antimonate and the like which do not have special performance of common antimony flame retardant additives. In addition, some studies have shown that Sb4O5Cl2The method has potential application in the fields of batteries and the like. Due to the preparation process, the discharge amount of wastewater is large, the production cost is high, the industrial application of the wastewater is hindered, and the industrial application of the wastewater is not reported yet.
Most commonly prepared Sb4O5Cl2Method [1 ]]Preparation of Sb by hydrolysis of aqueous hydrochloric acid solution containing antimony trichloride4O5Cl2The method comprises the following specific processes:
first, leaching Sb with hydrochloric acid aqueous solution2O3Obtaining hydrochloric acid aqueous solution of antimony trichloride, controlling the hydrochloric acid concentration of the aqueous solution of antimony trichloride to be more than 2.5mol/l for preventing hydrolysis, and adding water into the aqueous solution to obtain Sb4O5Cl2And the concentration of the hydrolyzed liquid-controlled hydrogen chloride is 0.5-0.6 mol/l.
The method has the advantages of simple process, mild reaction conditions and the biggest defect that the amount of produced wastewater is large, in order to obtain high hydrolysis rate, the acidity of hydrolyzed liquid needs to be controlled, a large amount of water is usually added, if the hydrolysis rate needs to be more than 98%, and the addition amount of water is 8-10 times of that of the aqueous solution of hydrochloric acid containing antimony. The typical hydrolysis waste liquid contains 0.5 mol/L of hydrogen chloride and 0.3g/L of Sb, except that about 20 percent of mother liquid is used for preparing a leaching solution, and the rest is neutralized by lime to produce dilute calcium chloride waste water to be discharged. The process results in high production cost and serious environmental pollution. In order to avoid the production of large amounts of waste water, some patents have been proposed in order to develop processes with low waste water yield, and the following patents are introduced:
chinese patent publication No. CN1721581A discloses a method for preparing Sb4O5Cl2The method of (1). The method takes antimony trichloride as a raw material and directly prepares Sb by hydrothermal reaction4O5Cl2The yield reaches 99 percent, and the product purity is high.
The preparation method comprises the steps of adding antimony trichloride into a reactor, adding water, adjusting the pH value to be 2, sealing, keeping the temperature of 120-140 ℃ for 20-30 hours, cooling to room temperature, filtering to obtain colorless and transparent granular crystals, washing with water, and drying in vacuum to obtain Sb4O5Cl2And (4) crystals. The method is simple, long in reaction time and high in temperature, expensive antimony trichloride is used as a raw material, and industrial production is not easy to realize.
Chinese patent CN1546732A discloses a method for preparing antimony trichloride aqueous solution by electrochemical dissolution of antimony anode and further preparing Sb by hydrolysis of the aqueous solution4O5Cl2The method of (1). The key point of the invention is that the metal antimony is dissolved by adopting an electrochemical dissolution method to prepare the hydrochloric acid aqueous solution of antimony trichloride, and in the specification of the patent, Sb is directly obtained by stirring the antimony-containing aqueous solution obtained by electrolysis4O5Cl2However, no water is added to the hydrolysis stage, nor is there any disclosure of the Sb product of this process4O5Cl2The yield of (a). Apparently, Sb was prepared according to the hydrolysis method4O5Cl2Principle of (1), high Sb could not be obtained without adding water4O5Cl2Yield, which will generate a large amount of waste liquid after adding water.
Chinese patent application No. 201710440652.0 discloses submicron rod-like Sb4O5Cl2The simple hydrothermal preparation method. First SbCl3Mixing with deionized water, and magnetically stirring to obtain SbCl3Dissolve and obtain a milky white suspensionAdding deionized water and L-cysteine into the turbid solution; continuously carrying out magnetic stirring to obtain white turbid liquid; then transferring the white suspension into a high-pressure reaction kettle, carrying out hydrothermal reaction for 10-15 hours at the temperature of 100-150 ℃, separating and drying to obtain the final product of submicron rod-like Sb4O5Cl2Submicron rod-shaped Sb prepared by the method4O5Cl2The material has fine particle size, diameter of 400-700 nm, length of 4-10 μm, and uniform particle size. The method adopts high-pressure hydrolysis method using antimony trichloride as raw material, and is not easy for industrial production for the same reasons.
U.S. Pat. No. 3148943 proposes a process for preparing SbOCl in 1962 by using antimony trichloride and Sb in an aqueous hydrochloric acid medium2O3The reaction mainly comprises the following steps:
SbCl3+Sb2O3＝3SbOCl
when the concentration of the added hydrochloric acid is 30-40% (weight percent) based on the concentration of the hydrochloric acid in the solution, and the molar ratio of the added hydrochloric acid is added, stirring and reacting for 1 hour at the reflux temperature of 110 ℃ to prepare SbOCl crystals, wherein the yield is 77.5%. The crystals contained 70.7% antimony (theoretical 70.5%) and 20.3% chlorine (theoretical 20.5%). When the concentration of hydrochloric acid is lower than 30%, the product is not SbOCl and may be Sb4O5Cl2The present inventors have found that Sb4O5Cl2The above method can be used to prepare the compound in a hydrochloric acid solution with the concentration of less than 30%, and the typical range of hydrochloric acid is 14-26% (weight percent). However, this method uses antimony trichloride and Sb2O3Preparation of Sb as raw Material4O5Cl2Because of the high price of antimony trichloride, Sb is prepared by the method4O5Cl2High raw material cost is inevitably brought, in addition, the concentration and the temperature of the adopted hydrochloric acid are high, and the operating environment and the equipment corrosion prevention requirements are high. These deficiencies have led to the patent not being reported to date for industrial applications.
U.S. Pat. No. 3,79493,1965 proposes adding Sb to saturated solution of antimony chloride with high-temperature hydrochloric acid2O3The method for preparing SbOCl is characterized in that Sb is added into hydrochloric acid water medium containing antimony at the temperature of 110 ℃ under the condition of over 30 percent of excessive hydrochloric acid concentration2O3And hydrogen chloride gas at normal pressure. This process is a process for preparing SbOCl, although only Sb is used2O3The SbOCl is prepared by the method and hydrogen chloride gas, when mother liquor is returned, the yield of the SbOCl can reach more than 90 percent, but the method has high reaction temperature, high hydrochloric acid concentration, higher hydrogen chloride gas cost and inconvenient use; of course, further hydrolysis of SbOCl obtained in this patent can also be used to prepare Sb4O5Cl2，But the cost is further increased, and the defects cause that the patent is not reported to have industrial application so far.
Citations
1. Antimony, Zhao Tian Yuan, Metallurgical Press, 1987, p572-573
Disclosure of Invention
The invention aims to:
1. provides a simple Sb easy for industrial production4O5Cl2The method of (1).
2. The production process does not discharge waste water and waste gas.
3. Product Sb4O5Cl2The yield and the purity of the product are high.
4. The production process has mild conditions and is easy to control.
5. The method provides raw material guarantee for the method which is applied by the inventor and is named as the method for purifying the zinc sulfate aqueous solution to remove nickel, cobalt and germanium.
Other objects the following description will be further read by those skilled in the art.
The invention relates to a composition of Sb2O3Direct preparation of Sb with aqueous hydrochloric acid4O5Cl2The method of (2), characterized by: preparing hydrochloric acid aqueous solution containing a certain hydrochloric acid concentration range by using hydrochloric acid and water as synthetic initial solution; heating the synthesis starting solution to a temperature range; and Sb2O3Adding into a container heated to a proper temperatureIn the synthetic initial liquid, reacting for a period of time under the condition of continuous stirring to form Sb4O5Cl2A crystal; and separating said crystals and synthesis tails from said aqueous solution; washing the crystal with water or ethanol; drying the washed crystal to obtain the Sb4O5Cl2And (4) crystals.
Adding concentrated hydrochloric acid and water into the synthesis tail solution to adjust the concentration of hydrochloric acid to prepare synthesis initial solution, and returning the synthesis initial solution to the Sb4O5Cl2And (4) preparing crystals.
Prepared Sb4O5Cl2The crystal is a five-face wedge-shaped body, wherein the bottom of the crystal is rectangular, two faces of the crystal are triangular, and two faces of the crystal are trapezoidal; the Sb4O5Cl2The crystal consists of the five-face wedge-shaped monocrystal and the polycrystal, and the average grain size is 10-30 microns.
The Sb2O3Is industrial Sb2O3The purity is at least over 99.00 percent.
The Sb2O3The ratio of addition per mole of Sb2O3At least with 2mol of HCl in solution, then 1mol of Sb is formed4O5Cl2A crystal;
the preparation of Sb4O5Cl2The process reaction temperature of the crystal is 30-70 ℃, and preferably 40-60 ℃.
The concentration range of the certain hydrochloric acid is 0.20-1.5 mol/l, preferably 0.45-1 mol/l; the concentration of the concentrated hydrochloric acid is at least more than 20% (weight percentage), and preferably 30-37%.
The reaction time is at least 15 minutes, and preferably 40-60 minutes.
The separation is filtration and centrifugal separation, preferably centrifugal separation.
The preparation of Sb4O5Cl2The crystal synthesis process mainly comprises the steps of preparing a synthesis initial solution at least containing 0.45-1 mol/l of aqueous hydrogen chloride medium; heating the synthetic initial solution to reach the temperature of 30-60 ℃;adding Sb2O3Adding the mixture into a synthetic initial solution heated to 30-60 ℃; sb2O3The ratio of addition per mole of Sb2O3At least with 2mol of HCl in the solution, and then 1mol of Sb is formed4O5Cl2A crystal; stirring and reacting for 0.25-1 hour and then forming Sb4O5Cl2A crystal; separating Sb from the synthesis starting solution4O5Cl2A crystal; washing the produced Sb with water4O5Cl2A crystal; drying the washed crystal to obtain the Sb4O5Cl2A crystal; all the obtained synthesis tail liquid and washing liquid are returned to the preparation of the synthesis initial liquid; adding concentrated hydrochloric acid containing 30-37% of the returned synthesis tail liquid and water to adjust the concentration of HCl in the solution to 0.45-1 mol/l for the next Sb4O5Cl2Preparing crystals; no waste liquid is discharged in the preparation process.
The above process is further described below in order to understand the present invention.
As can be seen from the above-mentioned background art related patents and documents, Sb4O5Cl2Except for the conventional hydrolysis method, no method for quickly preparing Sb exists4O5Cl2The hydrolysis method has high production cost and wastewater treatment cost due to the discharge of a large amount of wastewater containing hydrochloric acid and antimony, which directly results in the process being incapable of economically producing Sb4O5Cl2It is no Sb on the market4O5Cl2The main reason for the availability of the product. And adopts Sb2O3Direct preparation of Sb by reaction with hydrochloric acid4O5Cl2The related patents adopt high hydrochloric acid concentration and high temperature, which results in that the patents cannot be applied to industrial production.
Depending on the concentration of HCl in solution and the potential for aqueous HCl and Sb2O3Several reactions occur as follows.
When the solution HCl content is high, the reaction is as follows:
6H++6Cl-+Sb2O3＝2SbCl3+3H2O (1)
the reaction is Sb2O3The dissolution reaction of (3). To complete the reaction, the acid concentration is H+The free acid concentration is generally greater than 1 mol/l. At low free acid concentrations, Sb2O3The dissolution was incomplete.
The hydrochloric acid-antimony trichloride aqueous solution obtained in the reaction 1 is subjected to the following reaction when water is added:
4SbCl3+5H2O＝Sb4O5Cl2+10HCl (2)
it is apparent from reactions 1 and 2 that antimony trichloride is only Sb2O3Production of Sb4O5Cl2Adding reactions 1 and 2 to obtain the following reaction:
2Sb2O3+2H++2Cl-＝Sb4O5Cl2+H2O (3)
apparently, from the viewpoint of chemical reaction, reaction (3) is to use Sb2O3Preparation of Sb4O5Cl2The shortest route of (2). Preparation of Sb Using reaction 34O5Cl2Not only can cancel Sb2O3Production of SbCl by dissolution3The process of the aqueous solution can also avoid the problem of a large amount of low-concentration hydrochloric acid wastewater generated by a hydrolysis method. From the viewpoint of reaction (3), it is clear that the higher the hydrochloric acid concentration, the more easily the reaction proceeds, but from the viewpoint of reaction 2, too high a hydrochloric acid concentration is clearly disadvantageous for Sb4O5Cl2And (4) generating. Direct preparation of Sb using high concentrations of hydrochloric acid as mentioned in the above patents2O3In order to obtain higher Sb4O5Cl2High-temperature operating conditions cannot be adopted for the yield. U.S. Pat. No. 3148943 found Sb4O5Cl2Sb may be used2O3And less than 30% hydrochloric acid, typically in the range of 14 to 26% by weight, but at a temperature of 110 ℃.
Obviously, Sb is directly used2O3The reaction with the hydrochloric acid aqueous solution is the process route with the lowest cost, but in the published patent, the acidity and the preparation temperature are higher, so that Sb is enabled to be prepared4O5Cl2The higher the cost of preparation, because the higher the HCl concentration of the solution, the more adverse the Sb4O5Cl2Formation of Sb not obtainable at room temperature at a relatively high acidity4O5Cl2To obtain Sb4O5Cl2Higher hydrolysis temperatures have to be used, which leads to a considerable increase in the equipment and processing costs.
The inventors have surprisingly found that Sb4O5Cl2Sb may be used2O3With a low concentration of hydrochloric acid, from Sb2O3Directly reacting with hydrochloric acid aqueous solution to generate Sb4O5Cl2The proper temperature for the reaction is generally required to be higher than 30 ℃, for example, 40-60 ℃. An excessively high temperature will lead to an increase in cost. The possible reactions of this method are as follows:
2Sb2O3+2H++2Cl-＝Sb4O5Cl2+H2O (5)
the initial solution for synthesizing the aqueous medium is prepared from concentrated hydrochloric acid and water, and the concentration of the hydrochloric acid is 30% or 30-40%. The typical content of the hydrochloric acid which is easily obtained commercially is 30-37%, while the concentration of the hydrogen chloride in the used hydrochloric acid aqueous solution is very low, and the synthesis tail solution and the concentrated hydrochloric acid are easily used for adjusting the hydrochloric acid concentration range required by the synthesis tail solution.
In the examples of the present invention, Sb4O5Cl2The yield of the method is close to 100%, and the produced synthetic tail liquid contains 50-100 mg/l of antimony, and the method is characterized in that all the synthetic tail liquid can be added into industrial concentrated hydrochloric acid (30-40%) to prepare dilute hydrochloric acid aqueous solution required by reaction.
Sb used2O3Is industrial Sb2O3In Sb2O3The content is more than 99 percent, and the content is not required to be increased in generalAnd (5) one-step purification. Industrial hydrochloric acid can be used as the hydrochloric acid. Of course, if desired, the invention can be used to prepare highly pure Sb4O5Cl2The product, the reagent used should be relatively pure, such as analytically pure.
Preferably 2 moles of hydrogen chloride and 2 moles of Sb2O3Can produce 1mol of Sb4O5Cl2And (5) producing the product. Typically every 2 moles of Sb2O32 moles of hydrogen chloride may be utilized. The total amount of hydrogen chloride in the hydrochloric acid added preferably should exceed the theoretical amount, expressed as Sb2O3All generated Sb4O5Cl2The concentration of the hydrogen chloride in the end point solution is 0.11-0.68 mol/l. In the examples of the present invention, 2 moles of hydrogen chloride and 2 moles of Sb2O3Essentially equimolar reaction. If Sb is present2O3In excess, the product is exposed to unreacted Sb2O3And (4) pollution.
Hydrochloric acid does not lead to product contamination in the stated ranges, since excess hydrogen chloride remains in the synthesis tail, in which Sb is present3+The content of ions is low, generally lower than 100mg/l, irrespective of the variations in hydrogen chloride solution brought about by the dissolution of antimony. When the concentration of the hydrogen chloride in the solution exceeds a control range, the composition, the morphology and the yield of the product are greatly influenced.
Preheating the prepared hydrochloric acid aqueous solution to a specified temperature, and then adding Sb2O3Adding into hydrochloric acid aqueous solution preheated to a specified temperature range, and adding Sb under stirring2O3. Preferably, Sb2O3Should be dispersed in the solution uniformly by means of mechanical stirring or the like, the temperature may be generally 30 to 70 ℃, although the low temperature is advantageous for reducing the operation cost and the heating energy consumption, the heating temperature should be below 40 ℃, but the too low temperature will cause the reaction to slow, preferably 40 to 60 ℃. Too low a temperature, for example less than 20 ℃, would require cooling of the solution at higher temperatures, which would lead to increased costs, and it is clear that higher temperatures, for example 90 ℃, are chosen, although they may accelerate the reaction, but would lead to an increase in costsThe reaction conditions are deteriorated, for example, the escape of hydrogen chloride gas from the solution is also increased at high temperature, the working environment for filtration is also deteriorated during liquid-solid separation, and the selection of lower reaction temperature is favorable for the selection of equipment material.
After the addition of the raw materials is completed, the temperature of the slurry is maintained at 40 to 60 ℃, for example, 50 ℃ under stirring, and at this temperature, the reaction can be completed in a relatively short time (15 to 60 minutes), generally within 40 minutes. The lower the temperature, the longer the time to complete the reaction.
As the reaction proceeds, Sb2O3Conversion to Sb4O5Cl2Crystals are precipitated from the liquid phase. After completion of the reaction, Sb was formed4O5Cl2It can be separated from the solution by filtration or centrifugation. If desired, this product may be washed with water, ethanol or the like to remove the reaction solution entrained with the crystals, but from the viewpoint of environmental protection, it is apparent that washing the product with water is a preferred option because the wash water can be returned to the solution preparation system. Because the solution contains less chloride ions, only the volatilized gas needs to be absorbed by water in the drying process, and the pollution caused by a small amount of hydrogen chloride gas can be avoided. The used aqueous solution absorbing the hydrogen chloride can be returned to the liquid preparation process, so that the environmental pollution caused by a small amount of hydrogen chloride gas is avoided.
We have found that Sb prepared by the process of the present invention4O5Cl2The crystal method has the yield of almost 100 percent, and the invention has the characteristics that: the synthetic tail liquid containing a small amount of antimony can be completely returned to the preparation section for recycling, and antimony is hardly lost. The small losses of solution, which are the water carried over by the product and the water lost by evaporation of the solution during the reaction, can be compensated by adding small amounts of water, and by this means a closed solution circuit in the preparation process can be achieved, i.e. no waste water is discharged. In this way, Sb is produced4O5Cl2Yields can be maximized, generally close to theoretical amounts, while effluent production can be avoided. Meanwhile, because the reaction temperature is low, the hydrogen chloride in the solution is not easy to volatilize, and the production environment isBetter and less corrosion to equipment, and can select low-temperature anticorrosive materials, such as polypropylene plastics to manufacture the preparation reactor, which is obviously beneficial to industrial production. The average grain size of the crystal obtained by the process provided by the invention is 10-30 microns, the grain size can be controlled in a required range by the process provided by the invention, and the solution can be recycled for multiple times.
The beneficial effects produced by the invention are as follows:
1. general production of Sb4O5Cl2The mature processes are all hydrolysis processes, which result in the production of large amounts of waste water, which directly results in commercially unavailable Sb4O5Cl2The method avoids the generation of waste water, greatly improves the utilization rate of hydrochloric acid, and simultaneously avoids the loss of antimony caused by antimony contained in tail liquid, and the recovery rate of antimony is close to 100% and the utilization rate of hydrochloric acid is close to 100%. So that Sb is prepared at low cost in industry4O5Cl2It becomes possible.
2. Because the preparation temperature is lower, the heating energy consumption is lower, the production operation condition is better, and the corrosion prevention of equipment is easy to solve.
It is apparent that the method of the present invention is applied to Sb4O5Cl2The upgrading of the industrial production of Sb plays a role in promoting4O5Cl2Applications in other fields are provided. Meanwhile, the method provides raw material guarantee for industrial application of the method for purifying the zinc sulfate aqueous solution to remove nickel, cobalt and germanium.
Drawings
FIG. 1 is a typical Sb4O5Cl2Crystal XRD pattern.
FIG. 2 is a typical Sb4O5Cl2SEM image of (d).
FIG. 3 Sb produced by multiple circulating liquids of synthetic tail liquid4O5Cl2XRD pattern.
FIG. 4 Sb produced by multiple cycles of synthetic tail liquid4O5Cl2SEM image.
Fig. 5 is a partially enlarged view of fig. 4.
Detailed Description
Sb produced by the process4O5Cl2The XRD pattern and SEM pattern of a typical crystal form product of the crystal are shown in figure 1 and figure 2, the crystal form is a five-face wedge-shaped body, the bottom of the five-face wedge-shaped body is rectangular, two faces of the five-face wedge-shaped body are triangular, two faces of the five-face wedge-shaped body are trapezoidal, and the five-face wedge-shaped body has a clear crystal face. Under the condition that the solution is recycled for multiple times, the XRD (X-ray diffraction) diagram and the SEM (scanning electron microscope) diagram of the product are shown in figure 3 and figure 4, as can be seen from figure 4, most crystal grains are polycrystal with edges due to impurity accumulation and are mixed with a small amount of crystal particles under typical conditions, the crystal grains of the product have various defects, including growth lines, cracks, twin crystals, continuous crystals, holes and the like, but both the crystal grains have clear crystal faces. FIG. 5 is a partial enlarged view of FIG. 3, in which growth striations, continuous crystals, twin crystals and hole defects due to the accumulation of impurities after the circulation of the synthetic tail liquid can be more clearly observed. As can be seen from FIGS. 1 and 3, the products produced under both conditions were Sb-free4O5Cl2The XRD standard patterns are well coincided, which indicates that the product produced after the mother solution is circulated for many times is still Sb4O5Cl2。
For further explanation of the present invention, the following examples are given by way of illustration, and unless otherwise specified, the proportions in the following examples are by weight.
Example 1
In order to further illustrate the content of the invention, the invention is further described in the following examples.
In this example, the process according to the invention is carried out in a 2000 ml glass beaker with a mechanical paddle, thermostatted water bath. The hydrochloric acid adopts industrial hydrochloric acid (37.5%) and water adopts drinking water. 1000 ml of an aqueous solution containing 0.6mol/l of hydrochloric acid was prepared. Heating to 30 deg.C, stirring and adding 111 g Sb2O3(purity > 99.00%) is added to the liquid, Sb2O3After the addition, the temperature is kept at 30 ℃ and the stirring reaction is carried out for 1 hour to complete the Sb reaction4O5Cl2And (4) preparation reaction of crystals. After the reaction is finished, the obtained slurry is filtered. Sb4O5Cl2The crystalline product was washed with 30 ml of water. Then dried to constant weight in a vacuum drying oven with a water pumping system. Yield 135.2 g (98.6% yield) of Sb4O5Cl2And (4) crystals. The crystal contained 76.2% antimony (theoretical 76.35%) and 11.31% chlorine (theoretical 11.11%). X-ray diffraction test shows that the product is Sb4O5Cl2. The produced synthesis tail liquid is 933 ml, the chlorine content is 0.22mol/L, and the antimony content is 0.032 g/L.
As can be seen from example 1: sb of the invention4O5Cl2The yield of the crystal is high, and the purity is high. Furthermore, the process has high reaction speed and is easy to operate.
Example 2
In this example, the process according to the invention is carried out in a 2000 ml glass beaker with a mechanical paddle, thermostatted water bath. Firstly, 1000 ml of aqueous solution containing 0.45mol/l of hydrochloric acid is prepared, analytically pure hydrochloric acid is used as a reagent, and distilled water is used as water. The solution was heated to 55 ℃ and 90 g of Sb were added with stirring2O3(purity > 99.00%) is added to the liquid, Sb2O3After the addition, the temperature is kept at 55 ℃ and the stirring reaction is carried out for 40 minutes to complete the Sb reaction4O5Cl2And (4) preparation reaction of crystals. After the reaction, the slurry was filtered. Sb4O5Cl2The crystalline product was washed with 30 ml of water. Then dried to constant weight in a vacuum drying oven with a water pumping system. Yield 106.4 g Sb4O5Cl2And (4) crystals. The crystal contained 76.34% antimony (theoretical 76.35%) and 11.12% chlorine (theoretical 11.11%). X-ray diffraction test shows that the product is Sb4O5Cl2. The particle size is 10-30 microns. The produced synthetic tail liquid is 925 ml, the chlorine content is 0.31mol/l, and the antimony content is 0.052 g/l. Sb produced in this example4O5Cl2The crystal has an XRD pattern shown in figure 1 and an SEM pattern shown in figure 2, and a typical crystal form is a pentahedral wedge with a rectangular bottom surface and has clear crystallization angles.
Example 3
In this embodiment, an example according to the invention is in oneWith mechanical stirring paddle, thermostatic water bath, in a 2000 ml plastic beaker. The hydrochloric acid adopts industrial hydrochloric acid (37.5%) and water adopts drinking water. 1000 ml of an aqueous solution containing 0.76mol/l hydrochloric acid was first prepared. The solution was heated to 40 ℃ and 120 g of Sb were added with stirring2O3(purity > 99.00%) is added to the liquid, Sb2O3After the addition, the temperature is kept at 40 ℃ and the stirring reaction is carried out for 1 hour to complete the Sb reaction4O5Cl2And (4) preparation reaction of crystals. After the reaction, the slurry was filtered. Sb4O5Cl2The crystalline product was washed with 30 ml of water. Then dried to constant weight in a vacuum drying oven with a water pumping system. Yield 130.1 g Sb4O5Cl2And (4) crystals. The crystalline antimony 76.31% (theoretical 76.35%) contains 11.22% (theoretical 11.11%) chlorine. X-ray diffraction test shows that the product is Sb4O5Cl2. The produced synthetic tail liquid is 925 ml, the chlorine content is 0.34mol/l, and the antimony content is 0.058 g/l. This example illustrates that the hydrochloric acid reaction solution can still yield acceptable finished products at a lower liquid-to-solid ratio.
Example 4
In this example, the process according to the invention is carried out in a 200 ml glass beaker with a mechanical stirrer, thermostatted water bath. The hydrochloric acid adopts industrial hydrochloric acid (37.5%) and water adopts drinking water. 1000 ml of an aqueous solution containing 0.91mol/l hydrochloric acid was first prepared. The solution was heated to 70 ℃ and 111 g of Sb were added with stirring2O3(purity > 99.00%) is added to the liquid, Sb2O3After the addition, the temperature is kept at 70 ℃ and the stirring reaction is carried out for 15 minutes to complete the Sb reaction4O5Cl2And (4) preparation reaction of crystals. After the reaction, the slurry was filtered. Sb4O5Cl2The crystalline product was washed with 30 ml of water. Then dried to constant weight in a vacuum drying oven with a water pumping system. Yield 108.5 g Sb4O5Cl2And (4) crystals. The crystalline antimony 76.31% (theoretical 76.35%) contains 11.07% (theoretical 11.11%) chlorine. X-ray diffraction test shows that the product is Sb4O5Cl2. The particle size is 1030 microns. The produced synthetic tail liquid is 925 ml, the chlorine content is 0.53mol/l, and the antimony content is 0.075 g/l.
Example 5
This example describes the example of multiple recycling of the synthetic tail liquid produced by the present invention, and 20 times of synthetic tail liquid recycling experiments were performed. The hydrochloric acid adopts industrial hydrochloric acid (37.5%) and water adopts drinking water. The experimental equipment was carried out in a 3000 ml polypropylene plastic beaker placed in a thermostatic water bath, and the stirring was carried out with a teflon mechanical stirring paddle at 60 ℃ for 45 minutes. 2000 ml of a solution containing 0.6mol/l hydrochloric acid were prepared as in example 1, 235 g of Sb being added each time2O3(purity is more than 99.00%), after the reaction is finished, the obtained slurry is filtered, the crystal product is washed by 30 ml of water, and then the crystal product is dried to constant weight in a vacuum drying oven with a water pumping system to obtain Sb4O5Cl2Crystals and synthesis tail liquid. And (3) returning all the synthesis tail liquid and the washing water obtained each time to prepare a solution before preparation, adding 36 wt% of concentrated hydrochloric acid and water into the synthesis tail liquid obtained by each filtration, adding 67-70 ml of concentrated hydrochloric acid, adding water to adjust the volume of the solution to 2000 ml, and adjusting the chlorine concentration of the solution to 0.6 mol/l. The volume of the synthetic tail liquid in multiple cycles is 1870-1901 ml, the chloride ion concentration of the produced synthetic tail liquid is 0.19-0.20 mol/l, the antimony content is 0.045-0.061g/l, and the produced crystal is 251.7-260.7 g (the yield is 97.5-101.1%) of Sb4O5Cl2And (4) crystals. The crystal contains 76.24-76.45% (theory 76.35%) of antimony and 10.91-11.13% (theory 11.11%) of chlorine. X-ray diffraction test shows that the product is Sb4O5Cl2. As is apparent from this example, although the solution is recycled for 20 times, the antimony and chlorine content and yield of the product are not affected, but the morphology of the crystal is changed, but the change does not affect the use of the method in the related cobalt-removing purification method patents proposed by the present inventors, and Sb is used in the two patents of the present inventors entitled "method for removing nickel, cobalt and germanium by purifying aqueous solution of zinc sulfate" and "method for continuously and deeply removing nickel, cobalt and germanium by purifying aqueous solution of zinc sulfate" and "method for controlling the same4O5Cl2Sb prepared by adopting circulating solution4O5Cl2。
Sb prepared by 20 cycles of synthetic tail liquid in this example4O5Cl2The XRD pattern of the mixed sample is shown in fig. 4. Sb4O5Cl2The SEM image of the crystal is shown in FIG. 3.
Finally, the above embodiments and figures are only intended to illustrate the technical solution of the invention and not to limit it, and although the invention has been described in detail by way of the description and the above embodiments, a person skilled in the art will understand that various changes in form and detail can be made therein without departing from the scope of the invention as defined by the claims.
Claims (10)
1. Made of Sb2O3Direct preparation of Sb with aqueous hydrochloric acid4O5Cl2The method of (2), characterized by: preparing hydrochloric acid aqueous solution containing a certain hydrochloric acid concentration range by using hydrochloric acid and water as synthetic initial solution; heating the synthesis starting solution to a temperature range; and Sb2O3Adding into the initial liquid, reacting for a while under stirring to form Sb4O5Cl2A crystal; and separating said crystals and synthesis tails from said aqueous solution; washing the crystal with water or ethanol; drying the washed crystal to obtain the Sb4O5Cl2And (4) crystals.
2. The process of claim 1, wherein: adding concentrated hydrochloric acid and water into the synthesis tail solution to adjust the concentration of hydrochloric acid to prepare synthesis initial solution, and returning the synthesis initial solution to the Sb4O5Cl2And (4) preparing crystals.
3. The process of claim 1 or 2, wherein: prepared Sb4O5Cl2The crystal is a five-face wedge-shaped body, wherein the bottom is rectangular,two surfaces are triangular and two surfaces are trapezoidal; the Sb4O5Cl2The crystal consists of the five-face wedge-shaped monocrystal and the polycrystal, and the average grain size is 10-30 microns.
4. The process of claim 1 or 2, wherein: the Sb2O3Is industrial Sb2O3The purity is at least over 99.00 percent.
5. The process of claim 1 or 2, wherein: the Sb2O3The ratio of addition per mole of Sb2O3At least with 2mol of HCl in solution, then 1mol of Sb is formed4O5Cl2And (4) crystals.
6. The process of claim 1 or 2, wherein: the preparation of Sb4O5Cl2The process reaction temperature of the crystal is 30-70 ℃, and preferably 40-60 ℃.
7. The process according to claim 1 or 2, characterized in that: the concentration range of the certain hydrochloric acid is 0.20-1.5 mol/l, preferably 0.45-1 mol/l; the concentration of the concentrated hydrochloric acid is 30-37% (weight percent).
8. The process according to claim 1 or 2, characterized in that: the reaction time is at least 15 minutes, and preferably 40-60 minutes.
9. The process according to claim 1 or 2, characterized in that: the separation is filtration and centrifugal separation, preferably centrifugal separation.
10. The process according to claim 1 or 2, characterized in that: the preparation of Sb4O5Cl2The crystal synthesis process mainly comprises the steps of preparing a synthesis initial solution at least containing 0.45-1 mol/l of aqueous hydrogen chloride medium; addingHeating the synthesis initial solution to reach the temperature of 30-60 ℃; adding Sb2O3Adding the mixture into a synthetic initial solution heated to 30-60 ℃; sb2O3The ratio of addition per mole of Sb2O3At least with 2mol of HCl in the solution, and then 1mol of Sb is formed4O5Cl2A crystal; stirring and reacting for 0.25-1 hour and then forming Sb4O5Cl2A crystal; separating Sb from the synthesis starting solution4O5Cl2A crystal; washing the produced Sb with water4O5Cl2A crystal; drying the washed crystal to obtain the Sb4O5Cl2A crystal; all the obtained synthesis tail liquid and washing liquid are returned to the preparation of the synthesis initial liquid; adding concentrated hydrochloric acid containing 30-37% of the returned synthesis tail liquid and water to adjust the concentration of HCl in the solution to 0.45-1 mol/l for the next Sb4O5Cl2Preparing crystals; no waste liquid is discharged in the preparation process.
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| PCT/CN2021/072442 WO2021147809A1 (en) | 2020-01-20 | 2021-01-18 | Method for preparing sb4o5cl2 directly from sb2o3 and aqueous hydrochloric acid solution |
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