WO2021147809A1 - Method for preparing sb4o5cl2 directly from sb2o3 and aqueous hydrochloric acid solution - Google Patents

Method for preparing sb4o5cl2 directly from sb2o3 and aqueous hydrochloric acid solution Download PDF

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WO2021147809A1
WO2021147809A1 PCT/CN2021/072442 CN2021072442W WO2021147809A1 WO 2021147809 A1 WO2021147809 A1 WO 2021147809A1 CN 2021072442 W CN2021072442 W CN 2021072442W WO 2021147809 A1 WO2021147809 A1 WO 2021147809A1
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hydrochloric acid
crystals
solution
water
liquid
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张旭
张云彭
沈庆峰
耿惠
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昆明瀚创科技有限公司
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G30/00—Compounds of antimony
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer

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  • the invention belongs to the fields of inorganic chemical industry and non-ferrous metallurgy, and mainly relates to a preparation method of antimony compound products, in particular to a preparation method of Sb 4 O 5 Cl 2 .
  • Sb 4 O 5 Cl 2 is one of the two important intermediate substances that make the chlorine-antimony flame-retardant synergistic system produce a flame-retardant effect during the combustion process. At the same time, it is also called "a zinc sulfate aqueous solution purification system" which the inventor applied An important part of the activator in the method of removing nickel, cobalt and germanium.
  • Sb 4 O 5 Cl 2 Although the content of Sb 4 O 5 Cl 2 is lower than that of SbOCl, the flame retardant effect is slightly worse when used as a flame retardant alone, but it also has excellent halogen-antimony flame retardant synergistic performance when used in conjunction with halogen. It can reduce the amount of pigments in colored plastics, has little effect on the transparency of polymers, and has special properties that are not available in common antimony flame retardant additives such as Sb 2 O 3 and sodium antimonate. In addition, some studies have shown that Sb 4 O 5 Cl 2 has potential applications in batteries and other fields. Due to the preparation process, large waste water discharge and high production cost hinder its industrial application, and its industrial application has not been reported yet.
  • Sb 2 O 3 is leached with hydrochloric acid aqueous solution to obtain the hydrochloric acid aqueous solution of antimony trichloride.
  • the hydrochloric acid concentration of the antimony trichloride aqueous solution should be controlled above 2.5mol/l to prevent hydrolysis.
  • Add water to this solution to obtain Sb 4 O 5 Cl 2 the concentration of hydrogen chloride in the liquid after hydrolysis is controlled to be 0.5 to 0.6 mol/l.
  • Chinese Patent Publication No. CN1721581A discloses a method for preparing Sb 4 O 5 Cl 2 .
  • the method uses antimony trichloride as a raw material to directly prepare Sb 4 O 5 Cl 2 through a hydrothermal reaction, the yield reaches 99%, and the product purity is high.
  • the preparation method is to add antimony trichloride into the reactor, add water, adjust the pH to 2, seal, keep at 120-140°C for 20-30 hours, then cool to room temperature and filter to obtain colorless and transparent granular crystals , Washed with water and dried in vacuum to obtain Sb 4 O 5 Cl 2 crystals.
  • the method is relatively simple, has a long reaction time and a high temperature, and needs to use relatively expensive antimony trichloride as a raw material, which is not easy for industrial production.
  • Chinese patent CN1546732A discloses a method for preparing an aqueous solution of antimony trichloride by electrochemical dissolution with an antimony anode, and further preparing Sb 4 O 5 Cl 2 by hydrolysis of the aqueous solution.
  • the core of the invention is to use electrochemical dissolution method to dissolve metal antimony to prepare an aqueous hydrochloric acid solution of antimony trichloride.
  • Sb 4 O 5 Cl is directly obtained by stirring the antimony-containing aqueous solution obtained by electrolysis. 2.
  • no water was added to the hydrolysis section, and the yield of Sb 4 O 5 Cl 2 produced by this method was not disclosed.
  • a high yield of Sb 4 O 5 Cl 2 cannot be obtained without adding water, and a large amount of waste liquid will be generated after adding water.
  • Chinese Patent Application No. 201710440652.0 discloses a simple hydrothermal preparation method of submicron rod-shaped Sb 4 O 5 Cl 2.
  • the method is a high-pressure hydrolysis method using antimony trichloride as a raw material, and for the same reasons as above, it is not easy to industrially produce.
  • US Patent 3148943 proposed a method for preparing SbOCl in 1962.
  • the method adopted is to react antimony trichloride and Sb 2 O 3 in a hydrochloric acid aqueous medium.
  • the main reactions are as follows:
  • the typical range of hydrochloric acid is 14 to 26% (weight percentage).
  • this method uses antimony trichloride and Sb 2 O 3 as raw materials to prepare Sb 4 O 5 Cl 2. Due to the high price of antimony trichloride, the use of this method to prepare Sb 4 O 5 Cl 2 will inevitably lead to high raw material costs. , The concentration and temperature of hydrochloric acid used are relatively high, and the operating environment and equipment anti-corrosion requirements are high.
  • the purpose of the present invention is:
  • the production process does not discharge waste water and waste gas.
  • the present invention is a method for directly preparing Sb 4 O 5 Cl 2 from Sb 2 O 3 and an aqueous hydrochloric acid solution, which is characterized in that: an aqueous hydrochloric acid solution containing a certain range of hydrochloric acid concentration is prepared with hydrochloric acid and water as a synthesis initial liquid; The initial liquid is heated to a certain temperature range; and Sb 2 O 3 is added to the synthetic initial liquid that has been heated to an appropriate temperature, and reacts for a period of time under constant stirring to form Sb 4 O 5 Cl 2 crystals; and Separate the crystals and synthesis tail liquid from the aqueous solution; wash the crystals with water or ethanol; dry the washed crystals to obtain the Sb 4 O 5 Cl 2 crystals.
  • the synthetic tail liquid is added with concentrated hydrochloric acid and water to adjust the concentration of hydrochloric acid and then formulated into a synthetic initial liquid, which is returned to the preparation of the Sb 4 O 5 Cl 2 crystal.
  • the prepared Sb 4 O 5 Cl 2 crystal is a five-sided wedge, in which the bottom is rectangular, the two faces are triangular, and the two faces are trapezoidal; the Sb 4 O 5 Cl 2 crystal is composed of the five faces
  • the wedge-shaped body is composed of single crystals and polycrystals, with an average particle size of 10-30 microns.
  • the Sb 2 O 3 is industrial Sb 2 O 3 with a purity of at least 99.00%.
  • the ratio of the addition of Sb 2 O 3 is that every mole of Sb 2 O 3 reacts with at least 2 moles of HCl in the solution, and then 1 mole of Sb 4 O 5 Cl 2 crystals are formed;
  • the reaction temperature of the process for preparing Sb 4 O 5 Cl 2 crystals is 30 to 70°C, preferably 40 to 60°C.
  • the certain concentration of hydrochloric acid ranges from 0.20 to 1.5 mol/l, preferably 0.45 to 1 mol/l; the concentration of concentrated hydrochloric acid is at least 20% or more (weight percentage), preferably 30 to 37%.
  • the reaction period is at least 15 minutes, preferably 40-60 minutes.
  • the separation is filtration and centrifugal separation, preferably centrifugal separation.
  • the process for preparing Sb 4 O 5 Cl 2 crystals mainly consists of preparing a synthesis initial solution containing at least 0.45 to 1 mol/l hydrogen chloride aqueous solution; heating the synthesis initial solution to a temperature of 30 to 60°C; adding Sb 2 O 3 to In the initial synthesis solution heated to 30-60°C; Sb 2 O 3 is added at a ratio of at least 2 moles of HCl in the solution per mole of Sb 2 O 3 to form 1 mole of Sb 4 O 5 Cl 2 crystals; the reaction was stirred for 0.25 to 1 hour and then formed Sb 4 O 5 Cl 2 crystals; separating Sb 4 O 5 Cl 2 crystals from the synthesis of the starting solution; washed with water output Sb 4 O 5 Cl 2 crystals; after washing The crystals are dried to obtain the Sb 4 O 5 Cl 2 crystals; the obtained synthesis tail liquid and washing liquid are all returned to the preparation of the synthesis initial liquid; the returned synthesis tail liquid is added with 30 to 37% concentrated hydrochloric
  • This reaction is the dissolution reaction of Sb 2 O 3.
  • the free acid concentration in terms of H + is generally greater than 1 mol/l.
  • the dissolution of Sb 2 O 3 is not complete.
  • reaction (3) is the shortest way to prepare Sb 4 O 5 Cl 2 from Sb 2 O 3.
  • Using reaction 3 to prepare Sb 4 O 5 Cl 2 can not only eliminate the process of dissolving Sb 2 O 3 to produce SbCl 3 aqueous solution, but also avoid the problem of large amounts of low-concentration hydrochloric acid wastewater produced by the hydrolysis method. From the perspective of reaction (3), it is obvious that the higher the concentration of hydrochloric acid, the easier the reaction is, but from the perspective of reaction 2, too high a concentration of hydrochloric acid is obviously not conducive to the formation of Sb 4 O 5 Cl 2.
  • Sb 4 O 5 Cl 2 can be reacted with Sb 2 O 3 and low-concentration hydrochloric acid.
  • Sb 2 O 3 reacts directly with aqueous hydrochloric acid to produce Sb 4 O 5 Cl 2.
  • the appropriate temperature for the reaction is generally It is required to be greater than 30°C, for example, 40-60°C. Too high temperature will increase the cost.
  • the possible reactions of this method are as follows:
  • the synthetic initial liquid of the aqueous medium of the present invention is prepared by using concentrated hydrochloric acid and water, and the concentration of hydrochloric acid is 30%, or 30-40%.
  • concentration of hydrochloric acid that is easily commercially available is typically 30% to 37%, and the concentration of hydrogen chloride in the aqueous hydrochloric acid solution used is very low, and it is easy to use synthetic tail liquid and concentrated hydrochloric acid to adjust to the required hydrochloric acid concentration range for synthetic tail liquid.
  • the yield of Sb 4 O 5 Cl 2 is close to 100%, and the produced synthetic tail liquid contains 50-100 mg/l antimony.
  • a feature of the present invention is that all the synthetic tail liquid can be added to the industrial concentration.
  • Hydrochloric acid (30-40%) is used to prepare the dilute aqueous hydrochloric acid solution required for the reaction.
  • the Sb 2 O 3 used is industrial Sb 2 O 3 , and the content in terms of Sb 2 O 3 is greater than 99%, and no further purification is usually required.
  • Industrial hydrochloric acid can be used for hydrochloric acid.
  • the reagents used should be relatively pure reagents such as analytical reagents.
  • 2 moles of hydrogen chloride and 2 moles of Sb 2 O 3 can produce 1 mole of Sb 4 O 5 Cl 2 product.
  • 2 moles of hydrogen chloride can be used for every 2 moles of Sb 2 O 3.
  • the total amount of hydrogen chloride in the preferentially added hydrochloric acid should exceed the theoretical amount.
  • Sb 4 O 5 Cl 2 is completely generated.
  • the hydrogen chloride concentration in the terminal solution is 0.11 to 0.68 mol/l.
  • 2 moles of hydrogen chloride and 2 moles of Sb 2 O 3 are basically equimolar reactions. If Sb 2 O 3 is excessive, the product will be contaminated with unreacted Sb 2 O 3.
  • the hydrochloric acid within the stated range will not cause product contamination, because excessive hydrogen chloride will remain in the synthesis tail liquid.
  • the content of Sb 3+ ions is low, usually less than 100mg/ l, the change of hydrogen chloride in the solution caused by the dissolution of antimony can be ignored.
  • concentration of hydrogen chloride in the solution exceeds the control range, the composition, morphology and yield of the product will be greatly affected.
  • Sb 2 O 3 should be uniformly dispersed in the solution by means of mechanical stirring or similar devices.
  • the temperature can generally be 30 ⁇ 70°C. Although the low temperature is helpful to reduce the operating cost and heating energy consumption, the heating temperature should be 40°C. Below, but too low temperature will slow down the reaction, preferably 40-60°C. If the temperature is too low, such as less than 20°C, the solution needs to be cooled when the temperature is higher, which will increase the cost.
  • the temperature of the slurry is maintained at 40 ⁇ 60°C under stirring, for example 50°C. At this temperature, the reaction can be completed in a relatively short time (15 ⁇ 60 minutes), generally within 40 minutes Finished within. The lower the temperature, the longer the time to complete the reaction.
  • Sb 2 O 3 is transformed into Sb 4 O 5 Cl 2 crystals and precipitated out of the liquid phase.
  • the generated Sb 4 O 5 Cl 2 can be separated from the solution by filtration or centrifugation. If necessary, this product can be washed.
  • the washing can use water, ethanol, etc. to remove the reaction solution contained in the crystals.
  • washing water can be returned to the dosing system . Since the solution contains less chloride ions, only water is needed to absorb the volatilized gas during the drying process to avoid the pollution caused by a small amount of hydrogen chloride gas.
  • the used aqueous solution that has absorbed hydrogen chloride can be returned to the liquid preparation process, which avoids environmental pollution caused by a small amount of hydrogen chloride gas.
  • a feature of the present invention is that all the synthetic tail liquid containing a small amount of antimony can be returned to the preparation section for recycling. There is almost no loss. A small amount of solution loss is the water carried by the product and the water loss caused by the evaporation of the solution during the reaction. These losses can be compensated by adding a small amount of water. Through this method, the solution in the preparation process can be closed, that is, no discharge. Wastewater. In this way, the yield of Sb 4 O 5 Cl 2 produced can be maximized, generally close to the theoretical amount, while avoiding the production of waste liquid.
  • the hydrogen chloride in the solution is not easy to volatilize, the production environment is better and the equipment is less corroded, and low-temperature anti-corrosion materials can be selected, such as polypropylene plastic to make the reactor, which is obviously beneficial to industrial production.
  • the average particle size of the crystals obtained in the process proposed by the present invention is 10-30 microns, the process invented can control the particle size within the required range, and the solution can be recycled for multiple times.
  • the method of the present invention clearly play a role in promoting industrial production upgrading 2 Sb 4 O 5 Cl, provides the possibility to use Sb 4 O 5 Cl 2 in the other areas. At the same time, it also provides a raw material guarantee for the industrial application of the "a method for purifying and removing nickel, cobalt and germanium" from an aqueous zinc sulfate solution applied by the inventor.
  • Figure 1 is a typical XRD pattern of Sb 4 O 5 Cl 2 crystal.
  • Figure 2 is a typical SEM image of Sb 4 O 5 Cl 2.
  • Fig. 5 is a partial enlarged view of Fig. 4.
  • the typical XRD pattern of the crystal product is shown in Fig. 1, and the SEM picture is shown in Fig. 2.
  • the crystal form is a five-sided wedge with a rectangular bottom and two triangular faces. Each face is trapezoidal, with clear crystal faces.
  • the XRD pattern of the product is shown in Figure 3, and the SEM image is shown in Figure 4. It can be seen from Figure 4 that due to the accumulation of impurities, most of the crystal grains are polycrystalline with ridges, and a small amount of typical conditions are also mixed.
  • Fig. 5 is a partial enlarged view of Fig. 3, which can more clearly observe the growth lines, continuous crystals, twins, and pore defects caused by the accumulation of impurities after the synthetic tail liquid is circulated. It can be seen from Figures 1 and 3 that the products produced under the two conditions are in good agreement with the standard Sb 4 O 5 Cl 2 XRD pattern, indicating that the product produced after multiple cycles of the mother liquor is still Sb 4 O 5 Cl 2 .
  • the example according to the present invention is implemented in a 2000 ml glass beaker with a mechanical stirring blade and a constant temperature water bath.
  • Industrial hydrochloric acid (37.5%) is used for hydrochloric acid
  • drinking water is used for water.
  • the Sb 4 O 5 Cl 2 crystal product was washed with 30 ml of water. Then it is dried to constant weight in a vacuum drying oven with a water extraction system. 135.2 grams (yield rate of 98.6%) of Sb 4 O 5 Cl 2 crystals were produced. The crystal contains 76.2% of antimony (76.35% of theory) and 11.31% of chlorine (11.11% of theory). X-ray diffraction test showed that the product was Sb 4 O 5 Cl 2 .
  • the produced synthetic tail liquid is 933 ml, the chlorine content is 0.22 mol/L, and the antimony content is 0.032 g/l.
  • Example 1 It can be seen from Example 1 that the Sb 4 O 5 Cl 2 crystal of the present invention has a high yield and high purity. Furthermore, this process has a fast reaction speed and is easy to operate.
  • the example according to the present invention is implemented in a 2000 ml glass beaker with a mechanical stirring blade and a constant temperature water bath.
  • the example according to the present invention is implemented in a 2000 ml plastic beaker with a mechanical stirring blade and a constant temperature water bath.
  • Industrial hydrochloric acid (37.5%) is used for hydrochloric acid
  • drinking water is used for water.
  • the example according to the present invention is implemented in a 200 ml glass beaker with a mechanical stirring blade and a constant temperature water bath.
  • Industrial hydrochloric acid (37.5%) is used for hydrochloric acid
  • drinking water is used for water.
  • the Sb 4 O 5 Cl 2 crystal product was washed with 30 ml of water. Then it is dried to constant weight in a vacuum drying oven with a water extraction system. 108.5 grams of Sb 4 O 5 Cl 2 crystals were produced. The crystal contains 76.31% of antimony (76.35% of theory) and 11.07% of chlorine (11.11% of theory). X-ray diffraction test showed that the product was Sb 4 O 5 Cl 2 .
  • the particle size is 10-30 microns.
  • the produced synthetic tail liquid is 925 ml, the chlorine content is 0.53 mol/l, and the antimony content is 0.075 g/l.
  • This example describes an example in which the synthetic tail liquid produced by the present invention is recycled for multiple times, and a total of 20 synthetic tail liquid recycling experiments have been carried out.
  • Industrial hydrochloric acid (37.5%) is used for hydrochloric acid, and drinking water is used for water.
  • the experimental equipment was carried out in a 3000 ml polypropylene plastic beaker placed in a constant temperature water bath. The stirring was carried out with a PTFE mechanical stirring paddle, the temperature was 60°C, and the reaction time was 45 minutes.
  • the obtained slurry is filtered, and the crystal product is treated with 30 ml of water.
  • the product is washed, and then dried to a constant weight in a vacuum drying box with a water pumping system to obtain Sb 4 O 5 Cl 2 crystals and synthesis tail liquid.
  • Add 36% by weight concentrated hydrochloric acid and water to the synthetic tail liquid obtained from each filtration add 67-70 ml of concentrated hydrochloric acid, and add water to make the solution
  • the volume is adjusted to 2000 ml, and the chlorine concentration of the solution is adjusted to 0.6 mol/l.
  • the volume of the synthetic tail liquid in multiple cycles is 1870 ⁇ 1901ml, the chloride ion concentration of the produced synthetic tail liquid is 0.19 ⁇ 0.20mol/l, the antimony content is 0.045-0.061g/l, and the crystals produced are 251.7 ⁇ 260.7 grams (yield rate of 97.5-101.1%) Sb 4 O 5 Cl 2 crystals.
  • the crystal contains 76.24-76.45% of antimony (76.35% of theory) and 10.91-11.13% of chlorine (11.11% of theory).
  • X-ray diffraction test showed that the product was Sb 4 O 5 Cl 2 .
  • the XRD pattern of the Sb 4 O 5 Cl 2 mixed sample prepared by 20 cycles of synthetic tail liquid circulation in this example is shown in Fig. 4.
  • the SEM image of the Sb 4 O 5 Cl 2 crystal is shown in Figure 3.

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Abstract

Disclosed is a method for preparing Sb4O5Cl2 directly from Sb2O3 and an aqueous hydrochloric acid solution, the method involving: formulating an aqueous hydrochloric acid solution having a hydrochloric acid concentration in a certain range as a synthetic initial solution using hydrochloric acid and water; heating the synthetic initial solution to a certain temperature range; adding Sb2O3 to the synthetic initial solution that has been heated to an appropriate temperature, and reacting same under constant stirring for a period of time to form a Sb4O5Cl2 crystal; separating the crystal and a synthesis tail liquid from the aqueous solution; washing the crystal with water or ethanol; and drying the washed crystal to obtain the Sb4O5Cl2 crystal. The process has the characteristics of a short preparation time, a high product purity, a low energy consumption, and no waste liquid and waste gas emission during preparation.

Description

一种由Sb2O3和盐酸水溶液直接制备Sb4O5Cl2的方法 A method for directly preparing Sb4O5Cl2 from Sb2O3 and hydrochloric acid aqueous solution 技术领域Technical field
本发明属于无机化工和有色冶金领域，主要涉及一种锑化合物的产品制备方法，具体地说是涉及一种Sb 4O 5Cl 2的制备方法。 The invention belongs to the fields of inorganic chemical industry and non-ferrous metallurgy, and mainly relates to a preparation method of antimony compound products, in particular to a preparation method of Sb 4 O 5 Cl 2 .
背景技术Background technique
Sb 4O 5Cl 2是使氯-锑阻燃协效体系在燃烧过程中产生阻燃效应的两种重要中间物质之一，同时，也是本发明人申请的名为“一种硫酸锌水溶液净化除镍钴锗的方法”中活化剂的重要组成部分。 Sb 4 O 5 Cl 2 is one of the two important intermediate substances that make the chlorine-antimony flame-retardant synergistic system produce a flame-retardant effect during the combustion process. At the same time, it is also called "a zinc sulfate aqueous solution purification system" which the inventor applied An important part of the activator in the method of removing nickel, cobalt and germanium.
虽然Sb4O5Cl 2中的含量比SbOCl低，单独作阻燃剂使用时，阻燃效果稍差，但它与卤素配合使用时，同样具有优异的卤-锑阻燃协效性能。它能降低彩色塑料中的色料用量，对高聚物的透明度影响较小，具有Sb 2O 3、锑酸钠等常用锑系阻燃助剂所没有的特殊性能。此外，一些研究表明，Sb 4O 5Cl 2在电池等领域也有潜在的应用可能。由于制备工艺的原因，废水排放量大、生产成本高，阻碍了其工业应用,其工业应用尚未见报道。 Although the content of Sb 4 O 5 Cl 2 is lower than that of SbOCl, the flame retardant effect is slightly worse when used as a flame retardant alone, but it also has excellent halogen-antimony flame retardant synergistic performance when used in conjunction with halogen. It can reduce the amount of pigments in colored plastics, has little effect on the transparency of polymers, and has special properties that are not available in common antimony flame retardant additives such as Sb 2 O 3 and sodium antimonate. In addition, some studies have shown that Sb 4 O 5 Cl 2 has potential applications in batteries and other fields. Due to the preparation process, large waste water discharge and high production cost hinder its industrial application, and its industrial application has not been reported yet.
最常见的制备Sb 4O 5Cl 2的方法[1]为含三氯化锑的盐酸水溶液水解制备Sb 4O 5Cl 2，该方法的具体过程如下： The most common method for preparing Sb 4 O 5 Cl 2 [1] is to prepare Sb 4 O 5 Cl 2 by hydrolyzing an aqueous hydrochloric acid solution containing antimony trichloride. The specific process of this method is as follows:
首先用盐酸水溶液浸出Sb 2O 3得到三氯化锑的盐酸水溶液，三氯化锑水溶液溶液的盐酸浓度为防止水解应控制在2.5mol/l以上，在此溶液中加水即可获得Sb 4O 5Cl 2，水解后液控制氯化氢浓度为0.5～0.6mol/l。 Firstly, Sb 2 O 3 is leached with hydrochloric acid aqueous solution to obtain the hydrochloric acid aqueous solution of antimony trichloride. The hydrochloric acid concentration of the antimony trichloride aqueous solution should be controlled above 2.5mol/l to prevent hydrolysis. Add water to this solution to obtain Sb 4 O 5 Cl 2 , the concentration of hydrogen chloride in the liquid after hydrolysis is controlled to be 0.5 to 0.6 mol/l.
该方法的优点为过程简单，反应条件温和，最大的不足是产出的废水量较大，为了获得较高的水解率，需控制水解后液的酸度，常需加入大量的水，如需达到98％以上的水解率，通常水的加入量为含锑的盐酸水溶液的8～10倍。典型的水解废液含氯化氢0.5摩尔/升，Sb 0.3g/l，除20％左右的母液配制浸出液外，其余用石灰中和产出稀氯化钙废水排放。这种工艺导致生产成本高，环境污染严重。为避免产出大量废水，提出了一些专利，以期开发出低废水产率的工艺，以下介绍相关专利：The advantages of this method are simple process and mild reaction conditions. The biggest disadvantage is the large amount of waste water produced. In order to obtain a higher hydrolysis rate, the acidity of the hydrolyzed liquid needs to be controlled, and a large amount of water is often added. With a hydrolysis rate above 98%, the amount of water usually added is 8-10 times that of the antimony-containing hydrochloric acid aqueous solution. A typical hydrolysis waste liquid contains 0.5 mol/l of hydrogen chloride and 0.3 g/l of Sb. Except for the leachate prepared with about 20% of the mother liquor, the rest is neutralized with lime to produce dilute calcium chloride wastewater for discharge. This process leads to high production costs and serious environmental pollution. In order to avoid the production of a large amount of waste water, some patents have been proposed in order to develop a process with low waste water yield. The relevant patents are introduced below:
中国专利公开号CN1721581A公开了一种制备Sb 4O 5Cl 2的方法。该方法以三氯化锑为原料，通过水热反应直接制备Sb 4O 5Cl 2，产率达到了99％，产物纯度高。 Chinese Patent Publication No. CN1721581A discloses a method for preparing Sb 4 O 5 Cl 2 . The method uses antimony trichloride as a raw material to directly prepare Sb 4 O 5 Cl 2 through a hydrothermal reaction, the yield reaches 99%, and the product purity is high.
其制备方法为将三氯化锑加入反应器中，加入水，调节pH等于2，密封，在120～140℃恒温20～30小时，然后冷却至室温，过滤，得到无色透明的颗粒状晶体，用水洗涤，真空干燥即得Sb 4O 5Cl 2晶体。该方法较为简单，反应时间长，温度高，且需采用较为昂贵的三氯化锑为原料，不易工业化生产。 The preparation method is to add antimony trichloride into the reactor, add water, adjust the pH to 2, seal, keep at 120-140°C for 20-30 hours, then cool to room temperature and filter to obtain colorless and transparent granular crystals , Washed with water and dried in vacuum to obtain Sb 4 O 5 Cl 2 crystals. The method is relatively simple, has a long reaction time and a high temperature, and needs to use relatively expensive antimony trichloride as a raw material, which is not easy for industrial production.
中国专利CN1546732A公开了一种采用锑阳极电化学溶解制备三氯化锑水溶液，进一步由水溶液水解制备Sb 4O 5Cl 2的方法。该发明的核心是采用电化学溶解的方法溶解金属锑制备三氯化锑的盐酸水溶液，在该专利的说明书中，采用将电解得到的含锑水溶液采用搅拌的方法直接获得了Sb 4O 5Cl 2，但其中水解段未加入水，也未公开采用该方法产品Sb 4O 5Cl 2的产率。显然，根据水解法制备Sb 4O 5Cl 2的原理，不加入水时无法获得高的Sb 4O 5Cl 2产率，加水后又将产生大量废液。 Chinese patent CN1546732A discloses a method for preparing an aqueous solution of antimony trichloride by electrochemical dissolution with an antimony anode, and further preparing Sb 4 O 5 Cl 2 by hydrolysis of the aqueous solution. The core of the invention is to use electrochemical dissolution method to dissolve metal antimony to prepare an aqueous hydrochloric acid solution of antimony trichloride. In the specification of this patent, Sb 4 O 5 Cl is directly obtained by stirring the antimony-containing aqueous solution obtained by electrolysis. 2. However, no water was added to the hydrolysis section, and the yield of Sb 4 O 5 Cl 2 produced by this method was not disclosed. Obviously, according to the principle of preparing Sb 4 O 5 Cl 2 by the hydrolysis method, a high yield of Sb 4 O 5 Cl 2 cannot be obtained without adding water, and a large amount of waste liquid will be generated after adding water.
中国专利申请号201710440652.0公开了一种亚微米棒状Sb 4O 5Cl 2的简单水热制备方法。首先将SbCl 3与去离子水混合，然后进行磁力搅拌使SbCl 3溶解并得到乳白色的悬浊液，再加入去离子水和L-半胱氨酸；继续进行磁力搅拌，得到白色悬浊液；然后将白色悬浊液转移至高压反应釜中，于100～150℃下水热反应10～15小时，分离干燥得到最终产物亚微米棒状Sb 4O 5Cl 2，该方法制备的亚微米棒状Sb 4O 5Cl 2，材料颗粒粒径细小，直径约为400～700纳米，长度约4～10微米，粒径均一。该方法为采用三氯化锑为原料的高压水解法，同上述原因，不易工业生产。 Chinese Patent Application No. 201710440652.0 discloses a simple hydrothermal preparation method of submicron rod-shaped Sb 4 O 5 Cl 2. First mix SbCl 3 with deionized water, then perform magnetic stirring to dissolve SbCl 3 and obtain a milky white suspension, then add deionized water and L-cysteine; continue magnetic stirring to obtain a white suspension; Then the white suspension was transferred to an autoclave, and hydrothermally reacted at 100-150°C for 10-15 hours, separated and dried to obtain the final product, submicron rod-like Sb 4 O 5 Cl 2 , the sub-micron rod-like Sb 4 prepared by this method O 5 Cl 2 , the particle size of the material is small, the diameter is about 400-700 nanometers, the length is about 4-10 microns, and the particle size is uniform. The method is a high-pressure hydrolysis method using antimony trichloride as a raw material, and for the same reasons as above, it is not easy to industrially produce.
美国专利3148943于1962年提出了一种制备SbOCl的方法，其采用的方法为在盐酸水介质中采用三氯化锑和Sb 2O 3反应，主要反应如下： US Patent 3148943 proposed a method for preparing SbOCl in 1962. The method adopted is to react antimony trichloride and Sb 2 O 3 in a hydrochloric acid aqueous medium. The main reactions are as follows:
SbCl 3+Sb 2O 3＝3SbOCl SbCl 3 +Sb 2 O 3 ＝3SbOCl
在配入的盐酸浓度为以溶液中计的盐酸浓度为30～40％(重量百分)时，在上述反应的摩尔比加入量的情况下，在110℃的回流温度下搅拌反应1小时，制备出了SbOCl晶体，产出率77.5％。晶体含锑70.7％(理论70.5％)、含氯20.3％(理论20.5％)。而当盐酸浓度低于30％产物不是SbOCl，可能是Sb 4O 5Cl 2，该发明发现Sb 4O 5Cl 2可以采用上述方法在低于30％的盐酸溶液中制备，盐酸的典型范围是14～26％(重量百分比)。但此方法采用三氯化锑和Sb 2O 3为原料制备Sb 4O 5Cl 2，由于三氯化锑价格高，采用此方法制备Sb 4O 5Cl 2必然带来高的原料成本，此外，所采用的盐酸浓度及温度均较高，操作环境及设备防腐要求较高。这些不足导致 该专利迄今为止未见工业应用报道。 When the mixed hydrochloric acid concentration is 30-40% (weight percent) of the hydrochloric acid concentration in the solution, in the case of the molar ratio of the above-mentioned reaction, the reaction is stirred at a reflux temperature of 110°C for 1 hour, SbOCl crystals were prepared with a yield rate of 77.5%. The crystal contains 70.7% of antimony (70.5% of theory) and 20.3% of chlorine (20.5% of theory). When the hydrochloric acid concentration is lower than 30%, the product is not SbOCl, but may be Sb 4 O 5 Cl 2. The invention found that Sb 4 O 5 Cl 2 can be prepared in a hydrochloric acid solution lower than 30% by the above method. The typical range of hydrochloric acid is 14 to 26% (weight percentage). However, this method uses antimony trichloride and Sb 2 O 3 as raw materials to prepare Sb 4 O 5 Cl 2. Due to the high price of antimony trichloride, the use of this method to prepare Sb 4 O 5 Cl 2 will inevitably lead to high raw material costs. , The concentration and temperature of hydrochloric acid used are relatively high, and the operating environment and equipment anti-corrosion requirements are high. These shortcomings have resulted in no industrial application reports of this patent so far.
美国专利3179493，1965提出了一种采用高温盐酸的氯化锑饱和液加入Sb 2O 3制备SbOCl的方法，该方法在30％以上的过剩盐酸浓度，110℃下，采用在含锑的盐酸水介质中加入Sb 2O 3和氯化氢气体在常压下制备了SbOCl。该方法为制备SbOCl的方法，该方法虽然仅使用了Sb 2O 3和氯化氢气体制备出SbOCl，在返回母液时，SbOCl产率可达90％以上，但该发明反应温度高、盐酸浓度高，氯化氢气体成本较高、使用不便；当然，采用这个专利所获SbOCl进一步水解也可以制备出Sb 4O 5Cl 2，但成本将进一步提高，这些不足导致该专利迄今为止也未见工业应用报道。 U.S. Patent 3179493, 1965 proposed a method for preparing SbOCl by adding Sb 2 O 3 to a saturated antimony chloride solution of high-temperature hydrochloric acid. SbOCl was prepared by adding Sb 2 O 3 and hydrogen chloride gas into the medium under normal pressure. This method is a method for preparing SbOCl. Although this method only uses Sb 2 O 3 and hydrogen chloride gas to prepare SbOCl, the SbOCl yield can reach more than 90% when returning to the mother liquor, but the invention has high reaction temperature and high concentration of hydrochloric acid. Hydrogen chloride gas is expensive and inconvenient to use. Of course, Sb 4 O 5 Cl 2 can be prepared by further hydrolysis of SbOCl obtained in this patent, but the cost will be further increased. These shortcomings have led to no industrial application reports in this patent so far.
引用文献Citation
1、《锑》，赵天从，冶金工业出版社，1987，p572-5731. "Antimony", Zhao Tiancong, Metallurgical Industry Press, 1987, p572-573
发明内容Summary of the invention
本发明目的是：The purpose of the present invention is:
1、提供一种简单的、易于工业化生产的Sb 4O 5Cl 2的方法。 1. Provide a simple and easy-to-industrial production method of Sb 4 O 5 Cl 2 .
2、生产工艺不排放废水和废气。2. The production process does not discharge waste water and waste gas.
3、产物Sb 4O 5Cl 2的产率高，纯度高。 3. The product Sb 4 O 5 Cl 2 has high yield and high purity.
4、生产过程条件温和，易于控制。4. The production process conditions are mild and easy to control.
5、为本发明人申请的名为“一种硫酸锌水溶液净化除镍钴锗的方法”中所述的方法提供原料保障。5. It provides raw material guarantee for the method described in "A method for purifying and removing nickel, cobalt and germanium from aqueous zinc sulfate solution" applied by the inventor.
其他的目标对于本领域的技术人员，可以进一步阅读下列的描述。Other objectives For those skilled in the art, you can further read the following description.
本发明一种由Sb 2O 3和盐酸水溶液直接制备Sb 4O 5Cl 2的方法，其特征在于：采用盐酸和水配制含有一定盐酸浓度范围的盐酸水溶液作为合成初始液；将所述的合成初始液加热到一定温度范围；并且将Sb 2O 3加入到已加热到适当温度下的合成初始液中，在不断搅拌状态下反应一段时间，形成Sb 4O 5Cl 2晶体；并且从所述的水溶液中分离所述的晶体和合成尾液；将所述的晶体采用水或乙醇洗涤；将所述的洗涤过的晶体进行干燥即得到所述的Sb 4O 5Cl 2晶体。 The present invention is a method for directly preparing Sb 4 O 5 Cl 2 from Sb 2 O 3 and an aqueous hydrochloric acid solution, which is characterized in that: an aqueous hydrochloric acid solution containing a certain range of hydrochloric acid concentration is prepared with hydrochloric acid and water as a synthesis initial liquid; The initial liquid is heated to a certain temperature range; and Sb 2 O 3 is added to the synthetic initial liquid that has been heated to an appropriate temperature, and reacts for a period of time under constant stirring to form Sb 4 O 5 Cl 2 crystals; and Separate the crystals and synthesis tail liquid from the aqueous solution; wash the crystals with water or ethanol; dry the washed crystals to obtain the Sb 4 O 5 Cl 2 crystals.
将所述的合成尾液加入浓盐酸和水调整盐酸浓度再配制成合成初始液，返回所述的Sb 4O 5Cl 2晶体制备。 The synthetic tail liquid is added with concentrated hydrochloric acid and water to adjust the concentration of hydrochloric acid and then formulated into a synthetic initial liquid, which is returned to the preparation of the Sb 4 O 5 Cl 2 crystal.
所制备的Sb 4O 5Cl 2晶体为五面楔形体，其中底部为矩形，两个面为三角形、两个面为梯型；所述的Sb 4O 5Cl 2晶体由所述的五面楔形体单晶体和多晶体组成，平均粒度在10～30微米。 The prepared Sb 4 O 5 Cl 2 crystal is a five-sided wedge, in which the bottom is rectangular, the two faces are triangular, and the two faces are trapezoidal; the Sb 4 O 5 Cl 2 crystal is composed of the five faces The wedge-shaped body is composed of single crystals and polycrystals, with an average particle size of 10-30 microns.
所述的Sb 2O 3为工业Sb 2O 3，纯度至少在99.00％以上。 The Sb 2 O 3 is industrial Sb 2 O 3 with a purity of at least 99.00%.
所述Sb 2O 3添加的比率为每摩尔Sb 2O 3至少与溶液中的2摩尔HCl反应，然后形成1摩尔的Sb 4O 5Cl 2晶体； The ratio of the addition of Sb 2 O 3 is that every mole of Sb 2 O 3 reacts with at least 2 moles of HCl in the solution, and then 1 mole of Sb 4 O 5 Cl 2 crystals are formed;
所述的制备Sb 4O 5Cl 2晶体的工艺反应温度为30～70℃，优选40～60℃。 The reaction temperature of the process for preparing Sb 4 O 5 Cl 2 crystals is 30 to 70°C, preferably 40 to 60°C.
所述的一定盐酸浓度范围是0.20～1.5mol/l，优选0.45～1mol/l；所述的浓盐酸浓度为至少20％以上(重量百分比)，优选30～37％。The certain concentration of hydrochloric acid ranges from 0.20 to 1.5 mol/l, preferably 0.45 to 1 mol/l; the concentration of concentrated hydrochloric acid is at least 20% or more (weight percentage), preferably 30 to 37%.
所述的反应一段时间至少为15分钟，优选40～60分钟。The reaction period is at least 15 minutes, preferably 40-60 minutes.
所述的分离为过滤、离心分离，优选离心分离。The separation is filtration and centrifugal separation, preferably centrifugal separation.
所述制备Sb 4O 5Cl 2晶体的工艺主要由配制至少含有0.45～1mol/l氯化氢水溶液介质的合成初始液；加热该合成初始液，使温度达到30～60℃；加入Sb 2O 3到已加热到30～60℃的合成初始液中；Sb 2O 3添加的比率为每摩尔Sb 2O 3至少和溶液中的2摩尔HCl反应，然后形成1摩尔的Sb 4O 5Cl 2晶体；搅拌反应0.25～1小时然后形成Sb 4O 5Cl 2晶体；从所述的合成初始液中分离Sb 4O 5Cl 2晶体；采用水洗涤产出的Sb 4O 5Cl 2晶体；将洗涤后的晶体干燥得到所述的Sb 4O 5Cl 2晶体；将所获得的合成尾液和洗液全部返回合成初始液的配制；将返回的合成尾液加入含30～37％的浓盐酸和水将溶液HCl浓度调整为0.45～1mol/l用于下一次的Sb 4O 5Cl 2晶体制备；制备过程无废液排放。 The process for preparing Sb 4 O 5 Cl 2 crystals mainly consists of preparing a synthesis initial solution containing at least 0.45 to 1 mol/l hydrogen chloride aqueous solution; heating the synthesis initial solution to a temperature of 30 to 60°C; adding Sb 2 O 3 to In the initial synthesis solution heated to 30-60°C; Sb 2 O 3 is added at a ratio of at least 2 moles of HCl in the solution per mole of Sb 2 O 3 to form 1 mole of Sb 4 O 5 Cl 2 crystals; the reaction was stirred for 0.25 to 1 hour and then formed Sb 4 O 5 Cl 2 crystals; separating Sb 4 O 5 Cl 2 crystals from the synthesis of the starting solution; washed with water output Sb 4 O 5 Cl 2 crystals; after washing The crystals are dried to obtain the Sb 4 O 5 Cl 2 crystals; the obtained synthesis tail liquid and washing liquid are all returned to the preparation of the synthesis initial liquid; the returned synthesis tail liquid is added with 30 to 37% concentrated hydrochloric acid and water The HCl concentration of the solution is adjusted to 0.45-1mol/l for the next preparation of Sb 4 O 5 Cl 2 crystals; there is no waste liquid discharge during the preparation process.
为了理解本发明所述的内容，以下对上述过程进一步说明。In order to understand the content of the present invention, the above process is further described below.
从上述背景技术相关专利和文献可以看出，Sb 4O 5Cl 2的制备除常规的水解法外，尚无一种快速制备Sb 4O 5Cl 2的方法，而水解法由于要排放大量的含盐酸和锑的废水，生产成本及废水处理费用较高，这直接导致了该工艺无法经济地生产Sb 4O 5Cl 2，这是市场上尚无Sb 4O 5Cl 2产品可供出售的主要原因。而采用Sb 2O 3和盐酸反应直接制备Sb 4O 5Cl 2的相关专利所采用的所采用的盐酸浓度及温度均较高，这导致了这些专利无法应用于工业生产。 From the above background art documents and patents, in addition to conventional external preparation hydrolysis Sb 4 O 5 Cl 2 method, and a quick way no Sb 4 O 5 Cl 2 were prepared and hydrolysis due to large emissions of waste water containing hydrochloric acid and antimony, higher production costs and wastewater treatment costs, which led directly to the process can not be economically produced Sb 4 O 5 Cl 2, which is on the market yet Sb 4 O 5 Cl 2 products available for sale main reason. However, related patents using Sb 2 O 3 and hydrochloric acid to directly prepare Sb 4 O 5 Cl 2 use relatively high hydrochloric acid concentration and temperature, which makes these patents unable to be applied to industrial production.
根据溶液HCl的浓度和盐酸水溶液可能和Sb 2O 3发生如下几个反应。 Depending on the concentration of the HCl solution and the aqueous hydrochloric acid solution, the following reactions may occur with Sb 2 O 3.
溶液HCl含浓度高时反应为：When the concentration of HCl is high, the reaction is:
6H ++6Cl -+Sb 2O 3＝2SbCl 3+3H 2O    (1) 6H + + 6Cl - + Sb 2 O 3 = 2SbCl 3 + 3H 2 O (1)
此反应是Sb 2O 3的溶解反应。要使上述反应完全，酸浓度以H +计的游离酸浓度一般大于1mol/l。游离酸浓度低时，Sb 2O 3溶解不完全。 This reaction is the dissolution reaction of Sb 2 O 3. To make the above reaction complete, the free acid concentration in terms of H + is generally greater than 1 mol/l. When the free acid concentration is low, the dissolution of Sb 2 O 3 is not complete.
反应1所获的盐酸-三氯化锑水溶液，在加入水时，发生如下反应：The hydrochloric acid-antimony trichloride aqueous solution obtained in reaction 1, when water is added, the following reaction occurs:
4SbCl 3+5H 2O＝Sb 4O 5Cl 2+10HCl    (2) 4SbCl 3 +5H 2 O=Sb 4 O 5 Cl 2 +10HCl (2)
从反应1和2可以明显看出，三氯化锑只是Sb 2O 3生产Sb 4O 5Cl 2的一个中间产物，将反应1和2相加即得到如下反应： It can be clearly seen from reactions 1 and 2 that antimony trichloride is only an intermediate product of Sb 2 O 3 to produce Sb 4 O 5 Cl 2. Adding reactions 1 and 2 can get the following reaction:
2Sb 2O 3+2H ++2Cl -＝Sb 4O 5Cl 2+H 2O     (3) 2Sb 2 O 3 + 2H + + 2Cl - = Sb 4 O 5 Cl 2 + H 2 O (3)
显然，从化学反应的角度看，反应(3)是采用Sb 2O 3制备Sb 4O 5Cl 2的最短途径。采用反应3制备Sb 4O 5Cl 2不仅可取消Sb 2O 3溶解生产SbCl 3水溶液的过程，还可避免水解法产生的大量低浓度盐酸废水的问题。从反应(3)的角度看，显然盐酸浓度越高反应越易反应，但从反应2的角度看，过高的盐酸浓度明显不利于Sb 4O 5Cl 2的生成。如上述专利所提及的采用高浓度盐酸和直接制备Sb 2O 3的工艺，为了获得较高的Sb 4O 5Cl 2产率，不得以采用了高温的操作条件。美国专利3148943发现Sb 4O 5Cl 2可以采用Sb 2O 3和低于30％的盐酸溶液中制备，盐酸的典型范围是14～26％(重量百分比)，但要求温度为110℃。 Obviously, from a chemical reaction point of view, reaction (3) is the shortest way to prepare Sb 4 O 5 Cl 2 from Sb 2 O 3. Using reaction 3 to prepare Sb 4 O 5 Cl 2 can not only eliminate the process of dissolving Sb 2 O 3 to produce SbCl 3 aqueous solution, but also avoid the problem of large amounts of low-concentration hydrochloric acid wastewater produced by the hydrolysis method. From the perspective of reaction (3), it is obvious that the higher the concentration of hydrochloric acid, the easier the reaction is, but from the perspective of reaction 2, too high a concentration of hydrochloric acid is obviously not conducive to the formation of Sb 4 O 5 Cl 2. As mentioned in the above patent, the process of using high-concentration hydrochloric acid and directly preparing Sb 2 O 3 , in order to obtain a higher yield of Sb 4 O 5 Cl 2 , high-temperature operating conditions must not be used. US Patent 3,148,943 found that Sb 4 O 5 Cl 2 can be prepared from Sb 2 O 3 and a hydrochloric acid solution of less than 30%. The typical range of hydrochloric acid is 14 to 26% (weight percentage), but the temperature is required to be 110°C.
显然，直接采用Sb 2O 3和盐酸水溶液反应是成本最低的工艺路径，但在已公开的专利中，由于采用的酸度、制备温度均较高，使得Sb 4O 5Cl 2制备成本较高，原因在于溶液的HCl浓度越高，越不利于Sb 4O 5Cl 2的生成，在较高的酸度下常温不能获得Sb 4O 5Cl 2，为了获得Sb 4O 5Cl 2不得不采用较高的水解温度，而在高温下水解则导致了设备及加工成本大幅度升高。 Obviously, directly using Sb 2 O 3 to react with an aqueous hydrochloric acid solution is the lowest cost process. However, in the published patents, due to the higher acidity and preparation temperature used, the preparation cost of Sb 4 O 5 Cl 2 is higher. the reason is that higher HCl concentration of the solution, the less conducive to the formation Sb 4 O 5 Cl 2, the normal temperature can not be obtained at high acidity Sb 4 O 5 Cl 2, in order to obtain Sb 4 O 5 Cl 2 had to use higher The hydrolysis temperature is high, and hydrolysis at high temperature has led to a substantial increase in equipment and processing costs.
本发明人意外发现，Sb 4O 5Cl 2可以采用Sb 2O 3和低浓度的盐酸反应，由Sb 2O 3直接和盐酸水溶液反应生成Sb 4O 5Cl 2，该反应的适当温度，一般要求大于30℃，比如说40～60℃。过高的温度将导致成本增加。此方法可能的反应如下： The inventors unexpectedly discovered that Sb 4 O 5 Cl 2 can be reacted with Sb 2 O 3 and low-concentration hydrochloric acid. Sb 2 O 3 reacts directly with aqueous hydrochloric acid to produce Sb 4 O 5 Cl 2. The appropriate temperature for the reaction is generally It is required to be greater than 30°C, for example, 40-60°C. Too high temperature will increase the cost. The possible reactions of this method are as follows:
2Sb 2O 3+2H ++2Cl -＝Sb 4O 5Cl 2+H 2O    (5) 2Sb 2 O 3 + 2H + + 2Cl - = Sb 4 O 5 Cl 2 + H 2 O (5)
本发明所述的水溶液介质的合成初始液使用浓盐酸和水配制，盐酸浓度为30％，或30～40％。容易从商业上获得的盐酸浓度典型含量为30～37％，而所使用的盐酸水溶液中氯化氢浓度很低，很容易使用合成尾液和浓盐酸调整到合成尾液所需的盐酸浓度范围。The synthetic initial liquid of the aqueous medium of the present invention is prepared by using concentrated hydrochloric acid and water, and the concentration of hydrochloric acid is 30%, or 30-40%. The concentration of hydrochloric acid that is easily commercially available is typically 30% to 37%, and the concentration of hydrogen chloride in the aqueous hydrochloric acid solution used is very low, and it is easy to use synthetic tail liquid and concentrated hydrochloric acid to adjust to the required hydrochloric acid concentration range for synthetic tail liquid.
在本发明的实施例中，Sb 4O 5Cl 2的产率接近100％，产出的合成尾液含锑为50～100mg/l本发明的一个特征是可以将全部合成尾液加入工业浓盐酸(30～40％)配制反应所需的稀盐酸水溶液。 In the embodiment of the present invention, the yield of Sb 4 O 5 Cl 2 is close to 100%, and the produced synthetic tail liquid contains 50-100 mg/l antimony. A feature of the present invention is that all the synthetic tail liquid can be added to the industrial concentration. Hydrochloric acid (30-40%) is used to prepare the dilute aqueous hydrochloric acid solution required for the reaction.
所使用的Sb 2O 3为工业Sb 2O 3，以Sb 2O 3计的含量大于99％，通常不需要进一步提纯。盐酸可以使用工业盐酸。当然如需采用本发明制备高纯的Sb 4O 5Cl 2产品，所使用的试剂应使用较纯的试剂如分析纯。 The Sb 2 O 3 used is industrial Sb 2 O 3 , and the content in terms of Sb 2 O 3 is greater than 99%, and no further purification is usually required. Industrial hydrochloric acid can be used for hydrochloric acid. Of course, if the present invention is used to prepare high-purity Sb 4 O 5 Cl 2 products, the reagents used should be relatively pure reagents such as analytical reagents.
优先地2摩尔氯化氢和2摩尔的Sb 2O 3可产出1摩尔的Sb 4O 5Cl 2产品。典型每2摩尔Sb 2O 3可利用2摩尔的氯化氢。优先地加入的盐酸中氯化氢的总量应该超过理论量，按Sb 2O 3全部生成Sb 4O 5Cl 2，终点溶液中的氯化氢浓度为0.11～0.68mol/l。在本发明的实施例中，2摩尔的氯化氢和2摩尔的Sb 2O 3基本上是等摩尔反应。如果Sb 2O 3过量，产品会受到未反应的Sb 2O 3污染。 Preferably, 2 moles of hydrogen chloride and 2 moles of Sb 2 O 3 can produce 1 mole of Sb 4 O 5 Cl 2 product. Typically, 2 moles of hydrogen chloride can be used for every 2 moles of Sb 2 O 3. The total amount of hydrogen chloride in the preferentially added hydrochloric acid should exceed the theoretical amount. According to Sb 2 O 3, Sb 4 O 5 Cl 2 is completely generated. The hydrogen chloride concentration in the terminal solution is 0.11 to 0.68 mol/l. In the embodiment of the present invention, 2 moles of hydrogen chloride and 2 moles of Sb 2 O 3 are basically equimolar reactions. If Sb 2 O 3 is excessive, the product will be contaminated with unreacted Sb 2 O 3.
而盐酸在所述的范围内不会导致产品受到污染，因为过量的氯化氢会留在合成尾液中，在所述的合成尾液中，Sb 3+离子的含量较低，通常低于100mg/l，可不考虑由锑溶解带来的溶液氯化氢的变化。当溶液中的氯化氢浓度超过控制范围时，将导致产物的成分、形貌以及产率受到较大影响。 The hydrochloric acid within the stated range will not cause product contamination, because excessive hydrogen chloride will remain in the synthesis tail liquid. In the synthesis tail liquid, the content of Sb 3+ ions is low, usually less than 100mg/ l, the change of hydrogen chloride in the solution caused by the dissolution of antimony can be ignored. When the concentration of hydrogen chloride in the solution exceeds the control range, the composition, morphology and yield of the product will be greatly affected.
配制好的盐酸水溶液中，先进行预热到指定温度，然后将Sb 2O 3加入到已预热到指定温度范围的盐酸水溶液中，在搅拌条件下，加入Sb 2O 3。最好，Sb 2O 3应该借助于机械搅拌或类似装置均匀地分散在溶液中，温度一般可以为30～70℃，虽然温度低有利于降低操作成本和加热能耗，加热温度应该在40℃以下，但过低的温度将导致反应变慢，最好是40～60℃。过低的温度，比如小于20℃，则在气温较高时，需要对溶液进行冷却，这会导致成本升高，显然选择较高的温度如90℃，虽然可以使反应加速，但会导致反应条件恶化，比如说在高温下氯化氢气体从溶液的逸出也将加剧,液固分离时过滤工作环境也将变差，而且选择较低的反应温度有利于设备材质的选择。 Formulated in aqueous hydrochloric acid, first preheated to a specified temperature, Sb 2 O 3 was then added to the aqueous hydrochloric acid has been preheated to the specified temperature range, with stirring, was added Sb 2 O 3. Preferably, Sb 2 O 3 should be uniformly dispersed in the solution by means of mechanical stirring or similar devices. The temperature can generally be 30～70℃. Although the low temperature is helpful to reduce the operating cost and heating energy consumption, the heating temperature should be 40℃. Below, but too low temperature will slow down the reaction, preferably 40-60°C. If the temperature is too low, such as less than 20°C, the solution needs to be cooled when the temperature is higher, which will increase the cost. Obviously choosing a higher temperature such as 90°C can accelerate the reaction, but it will cause the reaction. Conditions deteriorate, for example, the escape of hydrogen chloride gas from the solution at high temperatures will also increase, the working environment of filtration during liquid-solid separation will also become worse, and the choice of a lower reaction temperature is conducive to the choice of equipment materials.
当原料加完后，在搅拌下将料浆温度维持在40～60℃，比如说50℃，在此温度下，反应可在相当短的时间(15～60分钟)完成，一般可在40分钟内完成。温度越低，完成反应的时间越长。When the raw materials are added, the temperature of the slurry is maintained at 40～60℃ under stirring, for example 50℃. At this temperature, the reaction can be completed in a relatively short time (15～60 minutes), generally within 40 minutes Finished within. The lower the temperature, the longer the time to complete the reaction.
随着反应的进行，Sb 2O 3转化为Sb 4O 5Cl 2晶体，并从液相中沉析出来。反应完 成后，生成的Sb 4O 5Cl 2就可以采用过滤或离心从溶液中分离出来。如果需要，这个产物可进行洗涤，洗涤可以采用水、乙醇等以除去晶体夹杂的反应溶液，但从环境保护的角度，显然采用水洗涤产品是较优的选择，因为洗水可返回配液系统。由于溶液含氯离子较少，烘干过程中仅需对挥发出来的气体采用水吸收即可以避免少量氯化氢气体带来的污染。所使用的吸收了氯化氢的水溶液可以返回到配液工序，这避免了少量氯化氢气体对环境的污染。 As the reaction proceeds, Sb 2 O 3 is transformed into Sb 4 O 5 Cl 2 crystals and precipitated out of the liquid phase. After the reaction is completed, the generated Sb 4 O 5 Cl 2 can be separated from the solution by filtration or centrifugation. If necessary, this product can be washed. The washing can use water, ethanol, etc. to remove the reaction solution contained in the crystals. However, from the perspective of environmental protection, it is obvious that washing with water is a better choice, because the washing water can be returned to the dosing system . Since the solution contains less chloride ions, only water is needed to absorb the volatilized gas during the drying process to avoid the pollution caused by a small amount of hydrogen chloride gas. The used aqueous solution that has absorbed hydrogen chloride can be returned to the liquid preparation process, which avoids environmental pollution caused by a small amount of hydrogen chloride gas.
我们发现，采用本发明的制备Sb 4O 5Cl 2晶体的方法，产率可以达到几乎100％，本发明的一个特点是：含有少量锑的合成尾液全部可返回到制备段循环使用，锑几乎不损失。少量的溶液损失为产品带出的水和反应过程中溶液的蒸发导致的水的损失，这些损失可以通过加入少量水即可弥补，通过这样的方法，可以实现制备过程的溶液闭路，即不排放废水。采用这种方式，产出的Sb 4O 5Cl 2产率可最大化，一般来说接近理论量，同时可避免产出废液。同时由于反应温度低，溶液中的氯化氢也不易挥发，生产环境较好及设备腐蚀均较少，且可选择低温防腐材料,比如说聚丙烯塑料制造制备反应器，显然这对工业生产有利。本发明所提出的工艺过程所获晶体平均粒度10-30微米，所发明的工艺可将粒度控制在所需的范围内，溶液可多次循环使用。 We have found that using the method for preparing Sb 4 O 5 Cl 2 crystals of the present invention, the yield can reach almost 100%. A feature of the present invention is that all the synthetic tail liquid containing a small amount of antimony can be returned to the preparation section for recycling. There is almost no loss. A small amount of solution loss is the water carried by the product and the water loss caused by the evaporation of the solution during the reaction. These losses can be compensated by adding a small amount of water. Through this method, the solution in the preparation process can be closed, that is, no discharge. Wastewater. In this way, the yield of Sb 4 O 5 Cl 2 produced can be maximized, generally close to the theoretical amount, while avoiding the production of waste liquid. At the same time, due to the low reaction temperature, the hydrogen chloride in the solution is not easy to volatilize, the production environment is better and the equipment is less corroded, and low-temperature anti-corrosion materials can be selected, such as polypropylene plastic to make the reactor, which is obviously beneficial to industrial production. The average particle size of the crystals obtained in the process proposed by the present invention is 10-30 microns, the process invented can control the particle size within the required range, and the solution can be recycled for multiple times.
本发明所产生的有益的效果：The beneficial effects produced by the present invention:
1、一般生产Sb 4O 5Cl 2成熟的工艺均为水解法，这导致了大量废水的产生，这是直接导致商业上不能获取Sb 4O 5Cl 2的重要原因，而采用本发明所述的方法，避免了废水的产生并大幅度提高了盐酸的利用率，同时也避免了尾液含锑导致的锑损失，采用这种方法，锑的回收率接近100％，盐酸的利用率也接近100％。使得工业上低成本制备Sb 4O 5Cl 2成为可能。 1. Generally, the mature processes for producing Sb 4 O 5 Cl 2 are all hydrolysis methods, which leads to the production of a large amount of waste water, which is an important reason why Sb 4 O 5 Cl 2 cannot be obtained commercially. The method avoids the production of waste water and greatly improves the utilization rate of hydrochloric acid. At the same time, it also avoids the loss of antimony caused by the antimony contained in the tail liquid. With this method, the recovery rate of antimony is close to 100%, and the utilization rate of hydrochloric acid is also close to 100%. It is possible to prepare Sb 4 O 5 Cl 2 at low cost in industry.
2、由于制备的温度较低，加热的能耗较低，生产作业条件较好，设备防腐易于解决。2. Because the preparation temperature is low, the heating energy consumption is low, the production operation conditions are better, and the equipment anticorrosion is easy to solve.
采用本发明的方法显然对Sb 4O 5Cl 2的工业化生产的升级起到推动作用，为Sb 4O 5Cl 2在其他领域内的应用提供了可能。同时也为本发明人申请的名为“一种硫酸锌水溶液净化除镍钴锗的方法”在工业上的应用提供了原料保障。 The method of the present invention clearly play a role in promoting industrial production upgrading 2 Sb 4 O 5 Cl, provides the possibility to use Sb 4 O 5 Cl 2 in the other areas. At the same time, it also provides a raw material guarantee for the industrial application of the "a method for purifying and removing nickel, cobalt and germanium" from an aqueous zinc sulfate solution applied by the inventor.
附图说明Description of the drawings
图1为典型的Sb 4O 5Cl 2晶体XRD图。 Figure 1 is a typical XRD pattern of Sb 4 O 5 Cl 2 crystal.
图2为典型的Sb 4O 5Cl 2的SEM图。 Figure 2 is a typical SEM image of Sb 4 O 5 Cl 2.
图3合成尾液多次循环液体产出的Sb 4O 5Cl 2XRD图。 Fig. 3 XRD pattern of Sb 4 O 5 Cl 2 produced by multiple cycles of synthetic tail liquid.
图4合成尾液多次循环产出的Sb 4O 5Cl 2SEM图。 Figure 4 SEM image of Sb 4 O 5 Cl 2 produced by multiple cycles of synthetic tail liquid.
图5为图4局部放大图。Fig. 5 is a partial enlarged view of Fig. 4.
具体实施方式Detailed ways
本工艺生产的Sb 4O 5Cl 2晶体，典型的晶型产物XRD图见图1，SEM图见图2，其晶型为五面楔形体，其中底部为矩形，两个面为三角形、两个面为梯型，具有清晰的结晶面。在溶液多次循环使用的条件下，产品XRD图见图3，SEM图见图4，由图4可见，由于杂质累积，大部分晶粒为带有棱的多晶体，也混有少量典型条件下晶型颗粒，产品晶粒存在多种缺陷，包括生长纹，裂隙，孪晶，连晶、孔洞等缺陷，但两种晶粒均有清晰的结晶面。图5是图3的局部放大图，可更清晰的观察到由于合成尾液循环后杂质累积产生的生长纹，连晶，孪晶，孔洞缺陷。由图1，3可看出，两种条件下产出的产物均和Sb 4O 5Cl 2XRD标准图谱吻合良好，说明母液多次循环后产出的产物仍为Sb 4O 5Cl 2。 For the Sb 4 O 5 Cl 2 crystal produced by this process, the typical XRD pattern of the crystal product is shown in Fig. 1, and the SEM picture is shown in Fig. 2. The crystal form is a five-sided wedge with a rectangular bottom and two triangular faces. Each face is trapezoidal, with clear crystal faces. Under the condition of repeated use of the solution, the XRD pattern of the product is shown in Figure 3, and the SEM image is shown in Figure 4. It can be seen from Figure 4 that due to the accumulation of impurities, most of the crystal grains are polycrystalline with ridges, and a small amount of typical conditions are also mixed. Lower crystal grains, the product grains have many defects, including growth lines, cracks, twins, continuous crystals, holes and other defects, but both crystal grains have clear crystal planes. Fig. 5 is a partial enlarged view of Fig. 3, which can more clearly observe the growth lines, continuous crystals, twins, and pore defects caused by the accumulation of impurities after the synthetic tail liquid is circulated. It can be seen from Figures 1 and 3 that the products produced under the two conditions are in good agreement with the standard Sb 4 O 5 Cl 2 XRD pattern, indicating that the product produced after multiple cycles of the mother liquor is still Sb 4 O 5 Cl 2 .
为对本发明进一步解释，以下结合实施例进行说明，除特别说明，下列实施例中的比例均为重量比。In order to further explain the present invention, the following description will be given in conjunction with the examples. Unless otherwise specified, the proportions in the following examples are all weight ratios.
实施例1Example 1
为了进一步说明本发明的内容，以下在实施例中对本发明进一步描述。In order to further illustrate the content of the present invention, the present invention will be further described in the following embodiments.
在此实施例中，根据本发明举例是在一个带机械搅拌桨、恒温水浴的2000毫升的玻璃烧杯中实施的。盐酸采用工业盐酸(37.5％)、水采用生活饮用水。配制含0.6mol/l盐酸的水溶液1000毫升。加热至30℃，在搅拌下将111克Sb 2O 3(纯度＞99.00％)加入到液体中，Sb 2O 3加完后，保持温度在30℃保温搅拌反应1小时以完成Sb 4O 5Cl 2晶体的制备反应。反应结束后，所获料浆采用过滤。Sb 4O 5Cl 2晶体产品用30毫升水洗涤产物。然后在在带水抽气系统的真空干燥箱内干燥至恒重。产出135.2克(产出率98.6％)Sb 4O 5Cl 2晶体。晶体含锑76.2％(理论76.35％)含氯11.31％(理论11.11％)。X射线衍射测试显示产物为Sb 4O 5Cl 2。产出的合成尾液为933毫升，含氯为0.22mol/L，含锑0.032g/l。 In this embodiment, the example according to the present invention is implemented in a 2000 ml glass beaker with a mechanical stirring blade and a constant temperature water bath. Industrial hydrochloric acid (37.5%) is used for hydrochloric acid, and drinking water is used for water. Prepare 1000 ml of an aqueous solution containing 0.6 mol/l hydrochloric acid. Heat to 30°C, add 111 grams of Sb 2 O 3 (purity> 99.00%) to the liquid under stirring. After the Sb 2 O 3 is added, keep the temperature at 30°C and stir for 1 hour to complete the Sb 4 O 5 Preparation reaction of Cl 2 crystals. After the reaction, the obtained slurry is filtered. The Sb 4 O 5 Cl 2 crystal product was washed with 30 ml of water. Then it is dried to constant weight in a vacuum drying oven with a water extraction system. 135.2 grams (yield rate of 98.6%) of Sb 4 O 5 Cl 2 crystals were produced. The crystal contains 76.2% of antimony (76.35% of theory) and 11.31% of chlorine (11.11% of theory). X-ray diffraction test showed that the product was Sb 4 O 5 Cl 2 . The produced synthetic tail liquid is 933 ml, the chlorine content is 0.22 mol/L, and the antimony content is 0.032 g/l.
从实施例1可以看出：本发明的Sb 4O 5Cl 2晶体的产出率高、且纯度高。更进一步的，这个工艺过程反应速度快、易于操作。 It can be seen from Example 1 that the Sb 4 O 5 Cl 2 crystal of the present invention has a high yield and high purity. Furthermore, this process has a fast reaction speed and is easy to operate.
实施例2Example 2
在此实施例中，根据本发明举例是在一个带机械搅拌桨、恒温水浴的2000毫升的玻璃烧杯中实施的。首先配制含0.45mol/l盐酸的水溶液1000毫升，试剂采用分析纯盐酸，水采用蒸馏水。将此溶液加热到55℃，在搅拌下将90克Sb 2O 3(纯度＞99.00％)加入到液体中，Sb 2O 3加完后，保持温度在55℃保温搅拌反应40分钟以完成Sb 4O 5Cl 2晶体的制备反应。反应结束后，将料浆过滤。Sb 4O 5Cl 2晶体产品用30毫升水洗涤产物。然后在在带水抽气系统的真空干燥箱内干燥至恒重。产出106.4克Sb 4O 5Cl 2晶体。晶体含锑76.34％(理论76.35％)含氯11.12％(理论11.11％)。X射线衍射测试显示产物为Sb 4O 5Cl 2。粒度在10～30微米。产出的合成尾液为925毫升，含氯为0.31mol/l，含锑0.052g/l。本实施例产出的Sb 4O 5Cl 2晶体，XRD图见图1，SEM图见图2，其典型晶型为矩形底面的五面楔形体，具有清晰的结晶角。 In this embodiment, the example according to the present invention is implemented in a 2000 ml glass beaker with a mechanical stirring blade and a constant temperature water bath. First, prepare 1000 ml of an aqueous solution containing 0.45mol/l hydrochloric acid, use analytically pure hydrochloric acid as reagent, and use distilled water as water. Heat this solution to 55°C, add 90 grams of Sb 2 O 3 (purity> 99.00%) to the liquid under stirring. After the Sb 2 O 3 is added, keep the temperature at 55°C and stir for 40 minutes to complete the Sb. 4 O 5 Cl 2 crystal preparation reaction. After the reaction, the slurry was filtered. The Sb 4 O 5 Cl 2 crystal product was washed with 30 ml of water. Then it is dried to constant weight in a vacuum drying oven with a water extraction system. 106.4 g of Sb 4 O 5 Cl 2 crystals were produced. The crystal contains 76.34% of antimony (76.35% of theory) and 11.12% of chlorine (11.11% of theory). X-ray diffraction test showed that the product was Sb 4 O 5 Cl 2 . The particle size is 10-30 microns. The produced synthetic tail liquid is 925 ml, the chlorine content is 0.31 mol/l, and the antimony content is 0.052 g/l. The XRD pattern of the Sb 4 O 5 Cl 2 crystal produced in this example is shown in Fig. 1, and the SEM picture is shown in Fig. 2. The typical crystal form is a five-sided wedge with a rectangular bottom surface and has a clear crystal angle.
实施例3Example 3
在此实施例中，根据本发明举例是在一个带机械搅拌桨、恒温水浴的，2000毫升的塑料烧杯中实施的。盐酸采用工业盐酸(37.5％)、水采用生活饮用水。首先配制含0.76mol/l盐酸的水溶液1000毫升。将此溶液加热到40℃，在搅拌下将120克Sb 2O 3(纯度＞99.00％)加入到液体中，Sb 2O 3加完后，保持温度在40℃保温搅拌反应1小时以完成Sb 4O 5Cl 2晶体的制备反应。反应结束后，将料浆过滤。Sb 4O 5Cl 2晶体产品用30毫升水洗涤产物。然后在在带水抽气系统的真空干燥箱内干燥至恒重。产出130.1克Sb 4O 5Cl 2晶体。晶体含锑76.31％(理论76.35％)含氯11.22％(理论11.11％)。X射线衍射测试显示产物为Sb 4O 5Cl 2。产出的合成尾液为925毫升，含氯为0.34mol/l，含锑0.058g/l。此实施例说明在较低的液固比下，盐酸反应液仍能产出合格的成品。 In this embodiment, the example according to the present invention is implemented in a 2000 ml plastic beaker with a mechanical stirring blade and a constant temperature water bath. Industrial hydrochloric acid (37.5%) is used for hydrochloric acid, and drinking water is used for water. First prepare 1000 ml of an aqueous solution containing 0.76 mol/l hydrochloric acid. Heat this solution to 40°C, add 120 grams of Sb 2 O 3 (purity> 99.00%) to the liquid under stirring. After the Sb 2 O 3 is added, keep the temperature at 40°C and stir for 1 hour to complete the Sb. 4 O 5 Cl 2 crystal preparation reaction. After the reaction, the slurry was filtered. The Sb 4 O 5 Cl 2 crystal product was washed with 30 ml of water. Then it is dried to constant weight in a vacuum drying oven with a water extraction system. 130.1 grams of Sb 4 O 5 Cl 2 crystals were produced. The crystal contains 76.31% of antimony (76.35% of theory) and 11.22% of chlorine (11.11% of theory). X-ray diffraction test showed that the product was Sb 4 O 5 Cl 2 . The produced synthetic tail liquid is 925 ml, the chlorine content is 0.34 mol/l, and the antimony content is 0.058 g/l. This example shows that at a lower liquid-to-solid ratio, the hydrochloric acid reaction solution can still produce qualified products.
实施例4Example 4
在此实施例中，根据本发明举例是在一个带机械搅拌桨、恒温水浴的200毫升的玻璃烧杯中实施的。盐酸采用工业盐酸(37.5％)、水采用生活饮用水。首先配制含0.91mol/l盐酸的水溶液1000毫升。将此溶液加热到70℃，在搅拌下将111克Sb 2O 3(纯度＞99.00％)加入到液体中，Sb 2O 3加完后，保持温度在70℃保温搅拌反应15分钟以完成Sb 4O 5Cl 2晶体的制备反应。反应结束后，将料浆过 滤。Sb 4O 5Cl 2晶体产品用30毫升水洗涤产物。然后在在带水抽气系统的真空干燥箱内干燥至恒重。产出108.5克Sb 4O 5Cl 2晶体。晶体含锑76.31％(理论76.35％)含氯11.07％(理论11.11％)。X射线衍射测试显示产物为Sb 4O 5Cl 2。粒度在10～30微米。产出的合成尾液为925毫升，含氯为0.53mol/l，含锑0.075g/l。 In this embodiment, the example according to the present invention is implemented in a 200 ml glass beaker with a mechanical stirring blade and a constant temperature water bath. Industrial hydrochloric acid (37.5%) is used for hydrochloric acid, and drinking water is used for water. First, prepare 1000 ml of an aqueous solution containing 0.91 mol/l hydrochloric acid. Heat this solution to 70°C, add 111 grams of Sb 2 O 3 (purity> 99.00%) to the liquid under stirring. After the Sb 2 O 3 is added, keep the temperature at 70°C and stir for 15 minutes to complete the Sb. 4 O 5 Cl 2 crystal preparation reaction. After the reaction, the slurry was filtered. The Sb 4 O 5 Cl 2 crystal product was washed with 30 ml of water. Then it is dried to constant weight in a vacuum drying oven with a water extraction system. 108.5 grams of Sb 4 O 5 Cl 2 crystals were produced. The crystal contains 76.31% of antimony (76.35% of theory) and 11.07% of chlorine (11.11% of theory). X-ray diffraction test showed that the product was Sb 4 O 5 Cl 2 . The particle size is 10-30 microns. The produced synthetic tail liquid is 925 ml, the chlorine content is 0.53 mol/l, and the antimony content is 0.075 g/l.
实施例5Example 5
本实施例描述了本发明产出的合成尾液多次循环使用的实例，共进行了20次合成尾液循环利用实验。盐酸采用工业盐酸(37.5％)、水采用生活饮用水。实验设备是在置于恒温水浴中的3000毫升聚丙烯塑料烧杯中进行的，搅拌采用聚四氟机械搅拌桨，温度为60℃，反应时间为45分钟。首先按实施例1配制含盐酸0.6mol/l的溶液2000毫升，每次加入235克Sb 2O 3(纯度＞99.00％)，反应结束后，将所获料浆过滤，晶体产品用30毫升水洗涤产物，然后在在带水抽气系统的真空干燥箱内干燥至恒重，得到Sb 4O 5Cl 2晶体和合成尾液。将每次得到的合成尾液和洗水全部返回配制制备前液，将每次过滤获得的合成尾液加入36％重量百分比的浓盐酸和水，加入67～70毫升浓盐酸，补加水将溶液体积调至2000毫升，将溶液的氯浓度调至0.6mol/l。多次循环中合成尾液的体积为1870～1901毫升，产出的合成尾液的氯离子浓度为0.19～0.20mol/l，含锑为0.045-0.061g/l，产出的晶体为251.7～260.7克(产出率97.5～101.1％)Sb 4O 5Cl 2晶体。晶体含锑76.24～76.45％(理论76.35％)含氯10.91～11.13％(理论11.11％)。X射线衍射测试显示产物为Sb 4O 5Cl 2。从本实施例可以明显看出，尽管溶液循环使用了20次，但产品含锑和氯和产率均未受到影响，只是晶体的形貌产生了一些变异，但这不影响其在本发明人所提出的相关净化除钴方法专利中的使用，在本发明人申请的名为“一种硫酸锌水溶液净化除镍钴锗的方法”和名为“一种硫酸锌溶液连续深度净化除镍钴锗的设备及控制方法”两个专利中，使用的Sb 4O 5Cl 2均为采用循环溶液制备的Sb 4O 5Cl 2。 This example describes an example in which the synthetic tail liquid produced by the present invention is recycled for multiple times, and a total of 20 synthetic tail liquid recycling experiments have been carried out. Industrial hydrochloric acid (37.5%) is used for hydrochloric acid, and drinking water is used for water. The experimental equipment was carried out in a 3000 ml polypropylene plastic beaker placed in a constant temperature water bath. The stirring was carried out with a PTFE mechanical stirring paddle, the temperature was 60°C, and the reaction time was 45 minutes. First, prepare 2000 ml of a solution containing 0.6 mol/l of hydrochloric acid according to Example 1, and add 235 g of Sb 2 O 3 (purity> 99.00%) each time. After the reaction, the obtained slurry is filtered, and the crystal product is treated with 30 ml of water. The product is washed, and then dried to a constant weight in a vacuum drying box with a water pumping system to obtain Sb 4 O 5 Cl 2 crystals and synthesis tail liquid. Return the synthetic tail liquid and washing water obtained each time to the pre-preparation solution, add 36% by weight concentrated hydrochloric acid and water to the synthetic tail liquid obtained from each filtration, add 67-70 ml of concentrated hydrochloric acid, and add water to make the solution The volume is adjusted to 2000 ml, and the chlorine concentration of the solution is adjusted to 0.6 mol/l. The volume of the synthetic tail liquid in multiple cycles is 1870～1901ml, the chloride ion concentration of the produced synthetic tail liquid is 0.19～0.20mol/l, the antimony content is 0.045-0.061g/l, and the crystals produced are 251.7～ 260.7 grams (yield rate of 97.5-101.1%) Sb 4 O 5 Cl 2 crystals. The crystal contains 76.24-76.45% of antimony (76.35% of theory) and 10.91-11.13% of chlorine (11.11% of theory). X-ray diffraction test showed that the product was Sb 4 O 5 Cl 2 . It can be clearly seen from this example that although the solution has been recycled 20 times, the product contains antimony and chlorine and the yield is not affected, but the crystal morphology has some variation, but this does not affect its use in the present inventors. The use of the proposed related purification and cobalt removal method patents is named "a method for purifying and removing nickel, cobalt and germanium from zinc sulfate aqueous solution" and "a method for continuous and deep purification of nickel and cobalt by zinc sulfate solution" applied by the inventor. germanium apparatus and control method, "both patents, the use of Sb 4 O 5 Cl 2 were prepared using the circulating solution Sb 4 O 5 Cl 2.
本实施例20次合成尾液循环制备的Sb 4O 5Cl 2混合样品的XRD图见图4。Sb 4O 5Cl 2晶体的SEM图见图3。 The XRD pattern of the Sb 4 O 5 Cl 2 mixed sample prepared by 20 cycles of synthetic tail liquid circulation in this example is shown in Fig. 4. The SEM image of the Sb 4 O 5 Cl 2 crystal is shown in Figure 3.
最终，以上实施例和图仅用于说明本发明的技术方案而非限制，尽管通过说明书及上述实施例已经对本发明进行了详细的描述，但本领域技术人员应当理解，可以在形式上和细节上对其做出各种各样的改变，而不偏离本发明权利要求书所 限定的范围。In the end, the above embodiments and figures are only used to illustrate the technical solutions of the present invention and not to limit it. Although the present invention has been described in detail through the specification and the above embodiments, those skilled in the art should understand that it can be in form and detail. Various changes have been made to it without departing from the scope defined by the claims of the present invention.

Claims (10)

  1. 一种由Sb 2O 3和盐酸水溶液直接制备Sb 4O 5Cl 2的方法，其特征在于：采用盐酸和水配制含有一定盐酸浓度范围的盐酸水溶液作为合成初始液；将所述的合成初始液加热到一定温度范围；并且将Sb 2O 3加入到已加热到适当温度下的合成初始液中，在不断搅拌状态下反应一段时间，形成Sb 4O 5Cl 2晶体；并且从所述的水溶液中分离所述的晶体和合成尾液；将所述的晶体采用水或乙醇洗涤；将所述的洗涤过的晶体进行干燥即得到所述的Sb 4O 5Cl 2晶体。 A method for directly preparing Sb 4 O 5 Cl 2 from Sb 2 O 3 and an aqueous hydrochloric acid solution, which is characterized in that: an aqueous hydrochloric acid solution containing a certain range of hydrochloric acid concentration is prepared with hydrochloric acid and water as a synthesis initial liquid; Heat to a certain temperature range; and add Sb 2 O 3 to the initial synthesis liquid heated to an appropriate temperature, and react for a period of time under constant stirring to form Sb 4 O 5 Cl 2 crystals; and from the aqueous solution Separate the crystals and the synthetic tail liquid in the process; wash the crystals with water or ethanol; dry the washed crystals to obtain the Sb 4 O 5 Cl 2 crystals.
  2. 如权利要求1所述的工艺，其特征在于：将所述的合成尾液加入浓盐酸和水调整盐酸浓度再配制成合成初始液，返回所述的Sb 4O 5Cl 2晶体制备。 The process according to claim 1, characterized in that: adding concentrated hydrochloric acid and water to the synthesis tail liquid to adjust the concentration of hydrochloric acid and then preparing the synthesis initial liquid, returning to the preparation of the Sb 4 O 5 Cl 2 crystal.
  3. 如权利要求1或2所述的工艺，其特征在于：所制备的Sb 4O 5Cl 2晶体为五面楔形体，其中底部为矩形，两个面为三角形、两个面为梯型；所述的Sb 4O 5Cl 2晶体由所述的五面楔形体单晶体和多晶体组成，平均粒度在10～30微米。 The process according to claim 1 or 2, characterized in that: the prepared Sb 4 O 5 Cl 2 crystal is a five-sided wedge-shaped body, wherein the bottom is a rectangle, the two faces are triangular, and the two faces are trapezoidal; The Sb 4 O 5 Cl 2 crystals are composed of the five-sided wedge single crystals and polycrystals, and the average particle size is 10-30 microns.
  4. 如权利要求1或2所述的工艺，其特征在于：所述的Sb 2O 3为工业Sb 2O 3，纯度至少在99.00％以上。 The process according to claim 1 or 2, wherein the Sb 2 O 3 is industrial Sb 2 O 3 with a purity of at least 99.00%.
  5. 如权利要求1或2所述的工艺，其特征在于：所述Sb 2O 3添加的比率为每摩尔Sb 2O 3至少与溶液中的2摩尔HCl反应，然后形成1摩尔的Sb 4O 5Cl 2晶体。 The process according to claim 1 or 2, characterized in that: the ratio of the addition of Sb 2 O 3 is that each mole of Sb 2 O 3 reacts with at least 2 moles of HCl in the solution to form 1 mole of Sb 4 O 5 Cl 2 crystals.
  6. 如权利要求1或2所述的工艺，其特征在于：所述的制备Sb 4O 5Cl 2晶体的工艺反应温度为30～70℃，优选40～60℃。 The process according to claim 1 or 2, wherein the reaction temperature of the process for preparing Sb 4 O 5 Cl 2 crystals is 30 to 70°C, preferably 40 to 60°C.
  7. 根据权利要求1或2所述的工艺，其特征在于：所述的一定盐酸浓度范围是0.20～1.5mol/l，优选0.45～1mol/l；所述的浓盐酸浓度为30～37％(重量％)。The process according to claim 1 or 2, characterized in that: the concentration range of the certain hydrochloric acid is 0.20～1.5mol/l, preferably 0.45-1mol/l; the concentration of the concentrated hydrochloric acid is 30～37% (weight %).
  8. 根据权利要求1或2所述的工艺，其特征在于：所述的反应一段时间至少为15分钟，优选40～60分钟。The process according to claim 1 or 2, wherein the reaction period is at least 15 minutes, preferably 40-60 minutes.
  9. 根据权利要求1或2所述的工艺，其特征在于：所述的分离为过滤、离心分离，优选离心分离。The process according to claim 1 or 2, wherein the separation is filtration, centrifugal separation, preferably centrifugal separation.
  10. 根据权利要求1或2所述的工艺，其特征在于：所述制备Sb 4O 5Cl 2晶体的工艺主要由配制至少含有0.45～1mol/l氯化氢水溶液介质的合成初始液；加热该合成初始液，使温度达到30～60℃；加入Sb 2O 3到已加热到30～60℃的合成初始液中；Sb 2O 3添加的比率为每摩尔Sb 2O 3至少和溶液中的2摩尔HCl反应，然后形成1摩尔的Sb 4O 5Cl 2晶体；搅拌反应0.25～1小时然后形成Sb 4O 5Cl 2晶体；从所述的合成初始液中分离Sb 4O 5Cl 2晶体；采用水洗涤产出的Sb 4O 5Cl 2晶体；将洗 涤后的晶体干燥得到所述的Sb 4O 5Cl 2晶体；将所获得的合成尾液和洗液全部返回合成初始液的配制；将返回的合成尾液加入含30～37％的浓盐酸和水将溶液HCl浓度调整为0.45～1mol/l用于下一次的Sb 4O 5Cl 2晶体制备；制备过程无废液排放。 The process according to claim 1 or 2, characterized in that: the process for preparing Sb 4 O 5 Cl 2 crystals mainly consists of preparing a synthesis initial solution containing at least 0.45-1 mol/l hydrogen chloride aqueous solution; heating the synthesis initial solution to a temperature 30 ~ 60 ℃; was added Sb 2 O 3 to have been heated to the synthesis starting solution 30 ~ 60 ℃ in; the ratio of Sb 2 O 3 added per mole of Sb 2 O 3 is at least a solution of 2 moles of HCl the reaction, then forming a mole of Sb 4 O 5 Cl 2 crystals; the reaction was stirred for 1 h and then formed - 0.25 Sb 4 O 5 Cl 2 crystals; separating Sb 4 O 5 Cl 2 crystals from the synthesis of the starting solution; with water Wash the produced Sb 4 O 5 Cl 2 crystals; dry the washed crystals to obtain the Sb 4 O 5 Cl 2 crystals; return the obtained synthesis tail liquid and washing liquid to the preparation of the synthesis initial liquid; Add 30-37% concentrated hydrochloric acid and water to the synthetic tail liquid to adjust the HCl concentration of the solution to 0.45-1 mol/l for the next preparation of Sb 4 O 5 Cl 2 crystals; no waste liquid is discharged during the preparation process.
PCT/CN2021/072442 2020-01-20 2021-01-18 Method for preparing sb4o5cl2 directly from sb2o3 and aqueous hydrochloric acid solution WO2021147809A1 (en)

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