CN112210786A - Method for electrochemically preparing sulfur powder - Google Patents
Method for electrochemically preparing sulfur powder Download PDFInfo
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- CN112210786A CN112210786A CN202010987988.0A CN202010987988A CN112210786A CN 112210786 A CN112210786 A CN 112210786A CN 202010987988 A CN202010987988 A CN 202010987988A CN 112210786 A CN112210786 A CN 112210786A
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- C25B1/00—Electrolytic production of inorganic compounds or non-metals
Abstract
The invention provides a method for electrochemically preparing sulfur powder. The method takes soluble salt containing ammonium radicals, sulfate radicals, persulfate radicals and halogen anions and soluble salt containing negative divalent sulfur as electrolyte, takes graphite foil or graphite rod as an electrode, and prepares the sulfur powder by one step by adopting an electrochemical method. Because the double graphite foils or the graphite rods are respectively used as the anode and the cathode, the use of the noble metal electrode is reduced, and the cost is effectively reduced; the device can be implemented simply in a common beaker or glass vessel; the preparation method is green and environment-friendly, simple in equipment, short in operation time, convenient to operate, simple in process and easy to amplify.
Description
Technical Field
The invention relates to the technical field of controllable preparation of elemental sulfur materials, in particular to a method for electrochemically preparing sulfur powder.
Background
Sulfur is a non-metallic element, one of the oxygen group elements (via group via), and is located in the third period of the periodic table. Elemental sulphur is generally a yellow crystal, also known as sulphur. The allotropes of elemental sulfur are various, including orthorhombic sulfur, monoclinic sulfur, and elastic sulfur. The sulfur element generally exists in the form of sulfide, sulfate or simple substance in nature, and is widely distributed in nature, and the content of the sulfur element in the universe is ranked tenth and is about 0.002%. The sulfur abundance content in the crust ranks seventeenth, and is about 0.048% (by mass). Elemental sulfur is poorly soluble in water, slightly soluble in ethanol, and readily soluble in carbon disulfide. Sulfur is an important constituent element of protein in human body, and has important significance for human life activities. Sulphur is mainly used in the production of fertilizers, gunpowder, lubricants, insecticides and antifungal agents.
At present, the preparation method of elemental sulfur is divided into a chemical method and a microbiological method. The chemical method for preparing elemental sulfur can be divided into: adding sulfurous acid (H) to the hydrogen sulfuric acid2SO3+2H2S＝3S↓+3H2O) or by introduction of sulfur dioxide (SO)2+2H2S＝3S↓+2H2O), introducing hydrogen sulfuric acid (2 KMnO) into the acidic potassium permanganate4+5H2S+3H2SO4＝K2SO4+2MnSO4+5S↓+8H2O), introducing hydrogen sulfide (2H) into sulfurous acid2S+H2SO3＝3S↓+3H2O), sulfide reaction with acid (5H)2S+2HNO3＝5S↓+N2+6H2O) and the application of pyrite, carbon and oxygen in high-temperature environment (3 FeS)2+12C+8O2＝6S↓+Fe3O4+12 CO). The method uses inflammable and explosive (H)2S、K2MnO4) And strong oxidizing property (HNO)3) The substances of (2) are reactants and the generation of toxic by-products (CO), and the conditions limit the preparation of sulfur powder and are not beneficial to industrial production. The microbiological process is mainly to contact an aqueous solution containing hydrosulphide with oxidised sulphide-oxidising bacteria under anaerobic conditions, wherein elemental sulphur is produced and reduced sulphide-oxidising bacteria are obtained. The method has high requirements on reaction equipment, and the production of byproducts needs further separation and purification.
At present, most of existing methods for preparing sulfur powder need high temperature, have high requirements on equipment and complex process, and increase production cost. Moreover, in the production and preparation process, flammable and explosive substances with strong oxidizing property are used, so that the controllability is poor and the environment is greatly damaged. These factors limit the preparation of the existing sulfur powder, so that the development of a method for preparing sulfur powder which is environment-friendly, simple in process and capable of being produced in a large scale is urgently needed.
Disclosure of Invention
The invention aims to provide a method for preparing sulfur powder, which is green and environment-friendly, simple in equipment, short in operation time, convenient to operate, simple in process and easy to amplify, and aims to overcome the defects of the prior art for preparing sulfur powder.
In order to achieve the above purpose, the technical scheme provided by the invention is as follows: a method of electrochemically preparing a sulfur powder, comprising the steps of:
dissolving one or more of soluble salts containing ammonium radicals, sulfate radicals, persulfate radicals and halogen anions and soluble salts containing negative divalent sulfur in deionized water to form electrolyte;
putting double graphite electrodes into the electrolyte, and connecting square wave voltage, and reacting until the reaction is finished;
washing the reacted electrolyte for many times to obtain light yellow powder;
the pale yellow powder obtained was dried.
Alternatively, for the one method of electrochemically preparing a sulfur powder, the soluble salts comprising ammonium, sulfate, persulfate, and halide anions comprise: one or more of ammonium sulfate, potassium sulfate, sodium sulfate, ammonium oxalate, ammonium persulfate, potassium persulfate, sodium persulfate, ammonium fluoride, sodium fluoride, potassium chloride, sodium chloride, ammonium chloride, potassium bromide, sodium bromide, ammonium bromide, potassium iodide, sodium iodide and ammonium iodide;
the soluble salt containing ammonium radicals, sulfate radicals, persulfate radicals and halogen anions adopts an aqueous solution form, and the concentration is 0.01-10 mol/L.
Alternatively, for the method of electrochemically preparing a sulfur powder, the soluble salt containing negative divalent sulfur includes: one or more of sodium sulfide, potassium sulfide, thiourea and thioacetamide;
the soluble salt containing the negative divalent sulfur adopts a water solution form, and the concentration is 0.1-10 mol/L.
Optionally, for one of said processes for electrochemically preparing sulfur powder, said dual graphite electrode comprises a graphite rod or a graphite foil, said graphite foil having a thickness greater than 0.5 mm; the distance between the two graphite electrodes is 1 cm-3 cm.
Optionally, for the method for electrochemically preparing sulfur powder, the volume of the deionized water is 200mL to 500 mL.
Optionally, for the method for electrochemically preparing the sulfur powder, the voltage of the square wave voltage is 6V-20V, and the time for positive and negative voltage conversion is 10 s-50 s.
Optionally, for the method for electrochemically preparing the sulfur powder, the reaction temperature is 0-80 ℃.
Optionally, for the method for electrochemically preparing sulfur powder, the reaction time is 0.5h to 8 h.
Optionally, for the method for electrochemically preparing sulfur powder, the cleaning manner includes one or more of centrifugation, suction filtration and dialysis.
Optionally, for the method for electrochemically preparing sulfur powder, the drying manner includes one or more of natural drying, normal pressure heating drying, vacuum drying, spray drying or freeze drying.
Alternatively, for one of the described methods of electrochemically preparing sulfur powder, the area ratio between the two graphite electrodes is 1: 1.
Compared with the prior art, the invention has at least the following beneficial effects: according to the invention, as the double graphite electrodes are respectively used as the anode and the cathode, the use of the noble metal electrode is reduced, the cost is effectively reduced, and the preparation method of the sulfur powder is expanded; the method is simple to operate, can be implemented in a common beaker or glass ware, and avoids the defects of high toxicity of the required raw materials, high danger in the operation process and the like in the prior art; the method is environment-friendly, simple in equipment, convenient to operate, mild in condition, good in repeatability, low in cost and easy to amplify, so that the preparation of the sulfur powder is safer and more reliable and has high cost performance; in addition, the product prepared by the invention has high quality, good performance and wide application range.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a diagram illustrating the electrochemical production of sulfur powder according to a first embodiment of the present invention;
FIG. 2 is an optical microscope photograph of an electrochemically prepared sulfur powder in accordance with one embodiment of the present invention;
FIG. 3 is a diagram of the electrochemical production of sulfur powder according to example two of the present invention;
FIG. 4 is an optical microscope photograph of an electrochemically prepared sulfur powder in example two of the present invention;
FIG. 5 is a diagram of the electrochemical production of sulfur powder in example III of the present invention;
FIG. 6 is an optical microscope photograph of an electrochemically prepared sulfur powder in example III of the present invention;
FIG. 7 is a diagram of the product of electrochemical preparation of sulfur powder in example four of the present invention;
FIG. 8 is an optical microscope photograph of an electrochemically prepared sulfur powder in example four of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The terms "first," "second," "third," "fourth," and the like in the description and in the claims, as well as in the drawings, if any, are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used is interchangeable under appropriate circumstances such that the embodiments of the invention described herein are capable of operation in sequences other than those illustrated or described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
The technical solution of the present invention will be described in detail below with specific examples. The following several specific embodiments may be combined with each other, and details of the same or similar concepts or processes may not be repeated in some embodiments.
The method of the embodiment of the invention comprises the following steps:
step S101, dissolving one or more of soluble salts containing ammonium radicals, sulfate radicals, persulfate radicals and halogen anions and soluble salts containing negative divalent sulfur in deionized water to form electrolyte;
step S102, putting double graphite electrodes into the electrolyte, and then putting square wave voltage into the electrolyte to react until the reaction is finished;
step S103, washing the reacted electrolyte for multiple times to obtain light yellow powder;
in step S104, the obtained pale yellow powder is dried.
Further, the salt containing ammonium, sulfate, persulfate and halogen anion used in the electrolyte comprises: one or more of ammonium sulfate, potassium sulfate, sodium sulfate, ammonium oxalate, ammonium persulfate, potassium persulfate, sodium persulfate, ammonium fluoride, sodium fluoride, potassium chloride, sodium chloride, ammonium chloride, potassium bromide, sodium bromide, ammonium bromide, potassium iodide, sodium iodide and ammonium iodide, but not limited to these.
Furthermore, the concentration of the aqueous solution of ammonium, sulfate, persulfate and halogen anions used in the electrolyte is 0.01-10 mol/L.
Further, the soluble salt containing divalent negative sulfur used in the electrolyte comprises: one or more of sodium sulfide, potassium sulfide, thiourea and thioacetamide, but not limited to the above.
Furthermore, the concentration of the aqueous solution containing the negative divalent sulfur used in the electrolyte is 0.1-10 mol/L.
Further, the graphite is one or more of a graphite rod or a graphite foil, and the thickness of the graphite foil is more than 0.5 mm.
Further, the volume of the deionized water is 200 mL-500 mL.
Further, the voltage of the alternating current power supply is between 6V and 20V, and the time for positive and negative voltage conversion is between 10s and 50 s.
Further, the temperature of the electrochemical stripping is 0-80 ℃.
Further, the time of the electrochemical stripping is 30 min-12 h.
Furthermore, the cleaning mode is one or more of methods such as centrifugation, suction filtration, dialysis and the like.
Further, the drying mode is one or more of natural drying, normal-pressure heating drying, vacuum drying, spray drying or freeze drying.
Further, the distance between the two graphite electrodes is 1 cm-3 cm.
Further, the area ratio between the two graphite electrodes is 1: 1.
Example 1
Referring to fig. 1 and 2, fig. 1 is a diagram illustrating a product of electrochemically preparing sulfur powder according to a first embodiment of the present invention, and fig. 2 is a diagram illustrating an optical microscope illustrating the electrochemically preparing sulfur powder according to the first embodiment of the present invention.
In this example, 0.1mol/L ammonium sulfate was dissolved in 300mL deionized water, and 0.1mol/L thiourea was added and dissolved by stirring to form an electrolyte.
Then, a graphite foil electrode with the specification of 5cm long, 6cm wide and 0.5mm thick is placed into the electrolyte, a 10V alternating current power supply is connected, the anode and the cathode of the power supply are changed every 30s, and the time consumption in the embodiment is about 2 hours.
And then, the substrate is washed again for a plurality of times, for example, 3 times, by using absolute ethyl alcohol and deionized water.
Finally, drying was carried out in a vacuum drying oven at 60 ℃.
The powder produced was yellowish and was judged to be a sulfur powder.
As can be seen from fig. 2, the prepared sulfur powder is in the micron scale.
Example 2
Referring to fig. 3 and 4, fig. 3 is a product of electrochemically preparing sulfur powder according to a first embodiment of the present invention, and fig. 4 is an optical microscope image of electrochemically preparing sulfur powder according to a first embodiment of the present invention.
In this example, 0.1mol/L ammonium oxalate was dissolved in 300mL deionized water, and 0.1mol/L thioacetamide was added and stirred to dissolve the ammonium oxalate to form an electrolyte.
Then, a graphite foil electrode with the specification of 5cm long, 6cm wide and 0.5mm thick is placed into the electrolyte, a 10V alternating current power supply is connected, the anode and the cathode of the power supply are changed every 30s, and the time consumption in the embodiment is about 2 hours.
And then, the substrate is washed again for a plurality of times, for example, 3 times, by using absolute ethyl alcohol and deionized water.
Finally, drying was carried out in a vacuum drying oven at 60 ℃.
The powder produced was yellowish and was judged to be a sulfur powder.
As can be seen from fig. 4, the prepared sulfur powder is in the micron scale.
Example 3
Referring to fig. 5 and 6, fig. 5 is a product of electrochemically preparing sulfur powder according to a first embodiment of the present invention, and fig. 6 is an optical microscope image of electrochemically preparing sulfur powder according to a first embodiment of the present invention.
In this example, 0.1mol/L sodium chloride was dissolved in 300mL of deionized water, and then 0.1mol/L sodium sulfide was added and stirred to dissolve it, thereby forming an electrolyte.
Then, a graphite foil electrode with the specification of 5cm long, 6cm wide and 0.5mm thick is placed into the electrolyte, a 10V alternating current power supply is connected, the anode and the cathode of the power supply are changed every 30s, and the time consumption in the embodiment is about 2 hours.
And then, the substrate is washed again for a plurality of times, for example, 3 times, by using absolute ethyl alcohol and deionized water.
Finally, drying was carried out in a vacuum drying oven at 60 ℃.
The powder produced was yellowish and was judged to be a sulfur powder.
As can be seen from fig. 6, the prepared sulfur powder is in the micron scale.
Example 4
Referring to fig. 7 and 8, fig. 7 is a product of electrochemically preparing sulfur powder according to a first embodiment of the present invention, and fig. 8 is an optical microscope image of electrochemically preparing sulfur powder according to a first embodiment of the present invention.
In this example, 0.1mol/L ammonium oxalate was dissolved in 300mL deionized water, and then 0.1mol/L potassium sulfide was added and stirred to dissolve it, thereby forming an electrolyte.
Then, a graphite foil electrode with the specification of 5cm long, 6cm wide and 0.5mm thick is placed into the electrolyte, a 10V alternating current power supply is connected, the anode and the cathode of the power supply are changed every 30s, and the time consumption in the embodiment is about 2 hours.
And then, the substrate is washed again for a plurality of times, for example, 3 times, by using absolute ethyl alcohol and deionized water.
Finally, drying was carried out in a vacuum drying oven at 60 ℃.
The powder produced was yellowish and was judged to be a sulfur powder.
As can be seen from fig. 8, the prepared sulfur powder was in the micron size range.
In summary, in the method for preparing sulfur powder by electrochemical stripping provided by the embodiment of the invention, soluble salts containing ammonium, sulfate, persulfate and halogen anions and soluble salts containing negative divalent sulfur are used as electrolyte, and graphite foil or graphite rod is used as an electrode, and the sulfur powder is prepared by one step by an electrochemical method. Because the double graphite is respectively used as the anode and the cathode, the use cost of the noble metal electrode is effectively reduced. The inventive device can be implemented simply in a common beaker or glass vessel. The preparation method has the advantages of environmental protection, simple equipment, short operation time, convenient operation, simple process, easy amplification and the like.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A method for electrochemically producing a sulfur powder, comprising the steps of:
dissolving one or more of soluble salts containing ammonium radicals, sulfate radicals, persulfate radicals and halogen anions and soluble salts containing negative divalent sulfur in deionized water to form electrolyte;
putting double graphite electrodes into the electrolyte, and connecting square wave voltage, and reacting until the reaction is finished;
washing the reacted electrolyte for many times to obtain light yellow powder;
the pale yellow powder obtained was dried.
2. The method of claim 1, wherein the soluble salts comprising ammonium, sulfate, persulfate, and halide anions comprise: one or more of ammonium sulfate, potassium sulfate, sodium sulfate, ammonium oxalate, ammonium persulfate, potassium persulfate, sodium persulfate, ammonium fluoride, sodium fluoride, potassium chloride, sodium chloride, ammonium chloride, potassium bromide, sodium bromide, ammonium bromide, potassium iodide, sodium iodide and ammonium iodide;
the soluble salt containing ammonium radicals, sulfate radicals, persulfate radicals and halogen anions adopts an aqueous solution form, and the concentration is 0.01-10 mol/L.
3. The method of claim 1, wherein the soluble salt containing divalent negative sulfur comprises: one or more of sodium sulfide, potassium sulfide, thiourea and thioacetamide;
the soluble salt containing the negative divalent sulfur adopts a water solution form, and the concentration is 0.1-10 mol/L.
4. The method of claim 1, wherein the dual graphite electrodes comprise graphite rods or graphite foils, the graphite foils having a thickness greater than 0.5 mm; the distance between the two graphite electrodes is 1 cm-3 cm.
5. The method of claim 1, wherein the volume of the deionized water is 200mL to 500 mL.
6. The method of claim 1, wherein the square wave voltage has a voltage of 6V-20V and the time for the positive and negative voltage transformation is 10 s-50 s.
7. The method of claim 1, wherein the reaction temperature is 0-80 ℃.
8. The process for electrochemical preparation of sulfur powder according to claim 1, wherein the reaction time is 0.5 to 8 hours.
9. The method for electrochemically preparing sulfur powder as claimed in claim 1, wherein the cleaning manner comprises one or more of centrifugation, suction filtration and dialysis.
10. The method of claim 1, wherein the drying manner comprises one or more of natural drying, atmospheric heating drying, vacuum drying, spray drying or freeze drying.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4191620A (en) * | 1978-11-13 | 1980-03-04 | Union Oil Company Of California | Electrochemical conversion of sulfur-containing anions to sulfur |
| US5019227A (en) * | 1989-11-09 | 1991-05-28 | The Texas A&M University System | Electrochemical method for producing hydrogen and sulfur |
| US20120273365A1 (en) * | 2011-01-27 | 2012-11-01 | Joshi Ashok V | Electrochemical conversion of alkali sulfate into useful chemical products |
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2020
- 2020-09-18 CN CN202010987988.0A patent/CN112210786A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4191620A (en) * | 1978-11-13 | 1980-03-04 | Union Oil Company Of California | Electrochemical conversion of sulfur-containing anions to sulfur |
| US5019227A (en) * | 1989-11-09 | 1991-05-28 | The Texas A&M University System | Electrochemical method for producing hydrogen and sulfur |
| US20120273365A1 (en) * | 2011-01-27 | 2012-11-01 | Joshi Ashok V | Electrochemical conversion of alkali sulfate into useful chemical products |
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