WO2021147809A1 - Procédé de préparation de sb4o5cl2 directement à partir de sb2o3 et d'une solution aqueuse d'acide chlorhydrique - Google Patents

Procédé de préparation de sb4o5cl2 directement à partir de sb2o3 et d'une solution aqueuse d'acide chlorhydrique 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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PCT/CN2021/072442
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Chinese (zh)
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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

Definitions

  • 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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  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

L'invention concerne un procédé de préparation de Sb4O5Cl2 directement à partir de Sb2O3 et d'une solution aqueuse d'acide chlorhydrique, le procédé comportant : la formulation d'une solution aqueuse d'acide chlorhydrique dont la concentration en acide chlorhydrique se situe dans une certaine plage, en tant que solution initiale synthétique, en utilisant de l'acide chlorhydrique et de l'eau ; le chauffage de la solution initiale synthétique jusqu'à une certaine plage de température ; l'ajout de Sb2O3 à la solution initiale synthétique qui a été chauffée à une température appropriée, et la réaction de celle-ci sous agitation constante pendant une certaine durée pour former un cristal de Sb4O5Cl2 ; la séparation du cristal et d'un liquide résiduel de synthèse de la solution aqueuse ; le lavage du cristal avec de l'eau ou de l'éthanol ; et le séchage du cristal lavé pour obtenir le cristal Sb4O5Cl2. Le procédé présente les caractéristiques suivantes : un temps de préparation court, une grande pureté du produit, une faible consommation d'énergie, et aucune émission de liquide et de gaz résiduels pendant la préparation.
PCT/CN2021/072442 2020-01-20 2021-01-18 Procédé de préparation de sb4o5cl2 directement à partir de sb2o3 et d'une solution aqueuse d'acide chlorhydrique WO2021147809A1 (fr)

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CN202010066868.7A CN111233036B (zh) 2020-01-20 2020-01-20 一种由Sb2O3和盐酸水溶液直接制备Sb4O5Cl2的方法

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CN111233036B (zh) * 2020-01-20 2022-07-26 昆明瀚创科技有限公司 一种由Sb2O3和盐酸水溶液直接制备Sb4O5Cl2的方法

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US3148943A (en) * 1962-12-26 1964-09-15 M & T Chemicals Inc Novel process for preparing antimony oxychloride
CN1546732A (zh) * 2003-12-11 2004-11-17 苏州大学 电化学牺牲阳极法制备氯氧化锑
CN1721581A (zh) * 2005-05-18 2006-01-18 武汉大学 氯氧化锑晶体的制备方法
CN101514396A (zh) * 2009-04-03 2009-08-26 郴州市宇腾化工有限公司 从含锡铅阳极泥中分离锡、锑的方法
CN101831551A (zh) * 2010-05-21 2010-09-15 葫芦岛锌业股份有限公司 一种从铅阳极泥中回收金、银、铋、锑和铜的方法
CN103334018A (zh) * 2013-06-19 2013-10-02 山东恒邦冶炼股份有限公司 一种从铅阳极泥中提取锑、铋的处理方法
CN109136578A (zh) * 2018-08-30 2019-01-04 西北矿冶研究院 一种从卡尔多炉渣盐酸浸出液中分离锑和铋的方法
CN111233036A (zh) * 2020-01-20 2020-06-05 昆明瀚创科技有限公司 一种由Sb2O3和盐酸水溶液直接制备Sb4O5Cl2的方法

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