CN112062109B - Preparation of S by using dielectric barrier discharge low-temperature plasma4N4Method (2) - Google Patents

Preparation of S by using dielectric barrier discharge low-temperature plasma4N4Method (2) Download PDF

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CN112062109B
CN112062109B CN202010857589.2A CN202010857589A CN112062109B CN 112062109 B CN112062109 B CN 112062109B CN 202010857589 A CN202010857589 A CN 202010857589A CN 112062109 B CN112062109 B CN 112062109B
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dielectric barrier
barrier discharge
plasma reactor
temperature plasma
discharge low
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CN112062109A (en
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宁平
薛宇
陈鹏
马懿星
王学谦
王郎郎
宁致远
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Kunming University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
    • C01B21/086—Compounds containing nitrogen and non-metals and optionally metals containing one or more sulfur atoms
    • C01B21/0865—Binary compounds of nitrogen with sulfur
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
    • B01J2219/00718—Type of compounds synthesised
    • B01J2219/00745—Inorganic compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J2219/0894—Processes carried out in the presence of a plasma
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses a preparation method of low-temperature plasma by using dielectric barrier dischargeS4N4The method comprises the steps of quantitatively introducing gases such as carbonyl sulfide and/or carbon disulfide into a dielectric barrier discharge low-temperature plasma reactor by using a gas mass flow meter, reacting at room temperature to generate elemental sulfur and S, wherein the plasma voltage is 10-15 kV and the frequency is 8-10 k Hz4N4Evacuating the gas after the plasma reaction, flushing the reactor with liquid nitrogen, and reacting the S produced in the reactor4N4Collecting and converting part of the elemental sulphur of the residue to S4N4Then purifying by extraction and evaporation to obtain pure S4N4. S obtained by the method4N4High purity, stable performance, simple operation at room temperature and low operation cost. The method has the advantages of simple process, high feasibility and good economic and environmental benefits.

Description

Preparation of S by using dielectric barrier discharge low-temperature plasma4N4Method (2)
Technical Field
The invention belongs to the technical field of preparation of inorganic compound materials, and particularly relates to a method for preparing S by using dielectric barrier discharge low-temperature plasma4N4The method of (1).
Background
S4N4(tetrathionitrid) is a synthetic pure single crystal inorganic polymer, bright orange solid, melting point 458K, insoluble in water and organic solvents, stable in air, slightly collided, and explosive.
S4N4Can be sublimated at low pressure to generate S under the condition of 523K and catalyst2N2Which can polymerize at room temperature to form a black solid, composition (SN)x。
S4N4It has been synthesized as early as 1910, but pure single crystalline inorganic polymers were not produced until 2009. It not only has brass metallic luster and metallic conductivity, but also is a one-dimensional body which is close to a plane bond in a crystal,are parallel to each other, and generate conductivity along the flowing of bond electrons, and the conductivity is 600-2000 omega at room temperature-1cm-1. And exhibits superconductivity at a low temperature of 0.26K! It is the first covalent polymer with metallic conductivity and also the first covalent polymer that does not contain metal and exhibits superconductivity. The structure and bonding of the material are special, the material is the most main material for preparing other compounds containing S-N bonds, and a brand new possibility is developed for solid physicists considering electrical properties, so that the material becomes the focus of research.
At present, S4N4The preparation method mainly comprises the following steps:
1) the conventional preparation is to react S with dry ammonia2Cl2And extracting with dioxane to obtain relatively pure S4N4；
2) A more recent approach is to utilize [ (Me)3Si)2N]2S is introduced into an S-N bond, and lithium bis amide and SCl2Prepared by reaction of [ (Me)3Si)2N]2S, from prepared [ (Me)3Si)2N]2S and SCl2And SO2Cl2Reaction of the mixture to prepare S4N4. For example, CN 110402235A discloses an S4N4A process for preparing the metal halide adduct of (1), using S2Cl2Reacting with gaseous ammonia in anhydrous solvent to obtain crude S4N4Without purification, the crude S4N4Adding into alcoholic solution of metal halide and stirring until there is no S4N4Residual, obtaining S by removing alcohol4N4The metal halide adduct of (a);
3) low temperature plasma technology can be used to prepare and modify materials. For example, CN 201710236441.5 discloses a method for preparing a two-dimensional structure carbon nitride compound by using low-temperature plasma, in which a solid precursor of the carbon nitride compound is placed in the plasma, then plasma discharge gas is introduced, a direct current or alternating current voltage is applied to an electrode, the precursor is treated and decomposed, and the decomposed product is the finished product. The method is a technique for synthesizing a product by regenerating a carbon nitride compound applied to a solid by plasma gas discharge.
Preparation of S by conventional method4N4By-product NH is generated in the process4Cl, while the dioxane used for the extraction belongs to the group of micro-toxins, which are irritating to the skin, eyes and respiratory system and may cause damage to the liver, kidneys and nervous system. With [ (Me)3Si)2N]2S to prepare S4N4The method of (1), wherein LiCl, (CH) is a by-product3)3SiCl and SO2Etc. while SCl2It has pungent odor, and can react violently with water, and has strong irritation to eye and respiratory mucosa, and severe skin burn. Has certain potential safety hazard. The low-temperature plasma has some excellent effects in material preparation, and has no research and application in S, N compound synthesis. CN 201710236441.5 discloses a method for preparing materials by reacting solid substances with plasma gas discharge, in which carbon and nitrogen compounds can be obtained by low-temperature plasma, and carbon source and nitrogen source are derived from solid precursor. Generally, the efficiency of the reaction of the solid phase is relatively low.
In summary, the current S4N4The preparation process is complex, and the [ (Me) is utilized in a traditional preparation mode or a new mode3Si)2N]2S to prepare S4N4Toxic medicines are used, the operation is improper, the injury is easy, the preparation process has the problems of more byproducts, unsatisfactory reaction efficiency, high preparation cost and the like.
Therefore, S was developed4N4New synthesis techniques and methods, overcoming the above-mentioned drawbacks or deficiencies, are S4N4The need for advances in synthesis technology.
Disclosure of Invention
The invention aims to provide a method for preparing S by using Dielectric Barrier Discharge (DBD) low-temperature plasma4N4The method uses a sulfur-containing gas source and nitrogen as raw materials through dielectric barrier discharge low-temperature plasma, and under the conditions of specific discharge structure and discharge characteristicsTo make it generate S4N4. The method has the advantages of simple operation, safety, environmental protection, low cost of raw materials and high conversion efficiency.
The technical scheme of the invention is as follows:
the method utilizes a gas mass flowmeter to quantitatively introduce carbonyl sulfide or carbon disulfide into a coaxial dielectric barrier discharge low-temperature plasma reactor for reaction, and the airspeed of the gas is 10000-20000 h-1The plasma voltage is 10-15 kV, and the frequency is 8-10 k Hz.
The DBD dielectric barrier reactor can be a coaxial dielectric barrier discharge low-temperature plasma reactor or a parallel plate type dielectric barrier discharge low-temperature plasma reactor. The coaxial reactor is a quartz tube with the outer diameter of 16-20 mm, the high-voltage electrode is a stainless steel bar with the diameter of 10-12 mm, and a stainless steel mesh is wound on the outer wall of the quartz tube to serve as an outer electrode; a high-voltage electrode of the parallel plate type dielectric barrier discharge low-temperature plasma reactor adopts a group of stainless steel plates or copper plates, and the distance between the plates is 0.3-3 mm.
The method comprises the following operation steps:
A. introducing carbon-based sulfur and carbon disulfide into a dielectric barrier discharge low-temperature plasma reactor by using a gas flowmeter for reaction;
B. after the reaction is finished, exhausting the gas in the plasma reactor;
C. flushing the plasma reactor with liquid ammonia;
D. extracting and purifying to obtain high-purity S4N4。
The pressure condition of the plasma discharge gas is normal pressure, and the temperature condition is normal temperature.
The plasma in the invention does not need precursor compound, and has the advantages of simple operation, short time consumption, high efficiency and the like.
The concentration of the residual reactant in the exhaust gas after the reaction is lower than 0.8-1 mg/m3。
The invention has the following advantages:
high-energy electricity generated by plasma under high-voltage dischargeNitrogen, COS and CS2The gas is ionized and dissociated to promote the gas to be ionized and dissociated to generate free radicals, and plasma with coexisting molecules, excited molecules and ion free radicals is formed. The plasma species are chemically active and are prone to chemical reactions. Generation of S4N4And elemental S, then dissolving S by using liquid ammonia4N4And reacts with the simple substance S to generate S4N4. Then extracting, distilling and purifying to obtain high-purity S4N4。
The invention is to degrade carbonyl sulfide, carbon disulfide and other gases by low-temperature plasma through a coaxial dielectric barrier discharge low-temperature plasma reactor at room temperature and prepare S4N4No secondary pollution, S4N4The yield can reach more than 90%.
The invention utilizes the high reaction activity of low-temperature plasma, reacts at room temperature, and utilizes carbonyl sulfide, carbon disulfide and other atmospheric pollutants to prepare high-purity S4N4Not only solves the problem of secondary pollution, but also prepares high-purity S4N4For subsequent use. The method has simple process, high feasibility and good economic and environmental benefits.
Detailed Description
The technical solution of the present invention will be more fully described with reference to the following examples, but the present invention is not limited in any way, and any modifications or alterations based on the teaching of the present invention are within the scope of the present invention.
Example 1
(1) Under the laboratory conditions, gas is COS, nitrogen is balance gas, the COS and the nitrogen are introduced into the dielectric barrier discharge low-temperature plasma reactor through a gas mass flow meter, the reactor adopts a coaxial dielectric barrier discharge low-temperature plasma reactor in the example, the outer diameter of the reactor is 16mm, the high-voltage electrode is a stainless steel bar with the diameter of 10mm, and a stainless steel mesh is wound on the outer wall of the quartz tube to serve as an outer electrode.
(2) The space velocity of the gas is 10000h-1Regulation, etcThe plasma voltage was 10k V, the frequency was 8 khz, the reaction was run, and after the reaction was complete, the gas in the plasma reactor was evacuated, at which point the carbonyl sulfide removal rate was 99.7%.
(3) Flushing the plasma reactor with liquid ammonia, followed by distillation and collection of S4N4，S4N4The yield reaches 91.9 percent.
Example 2
(1) Under laboratory conditions, the gas is CS2Nitrogen as balance gas, adding CS2And nitrogen is introduced into the dielectric barrier discharge low-temperature plasma reactor through a gas mass flowmeter, the coaxial dielectric barrier discharge low-temperature plasma reactor is adopted in the embodiment, the outer diameter of the quartz tube is 18mm, the high-voltage electrode is a stainless steel bar with the diameter of 11mm, and a stainless steel mesh is wound on the outer wall of the quartz tube to be used as an outer electrode.
(2) The space velocity of the gas is 15000h-1And adjusting the plasma voltage to be 13k V and the frequency to be 9k Hz, carrying out reaction, and exhausting the gas in the plasma reactor after the reaction is finished, wherein the removal rate of carbonyl sulfide is 99.2 percent.
(3) Flushing the plasma reactor with liquid ammonia, followed by distillation and collection of S4N4，S4N4The yield reaches 90.6 percent.
Example 3
(1) Under laboratory conditions, the gas is CS2COS mixed gas and nitrogen as balance gas, adding CS2The COS mixed gas and the nitrogen are introduced into the dielectric barrier discharge low-temperature plasma reactor through a gas mass flowmeter, the coaxial dielectric barrier discharge low-temperature plasma reactor adopted in the embodiment adopts a quartz tube with the outer diameter of 20mm, the high-voltage electrode is a stainless steel bar with the diameter of 12mm, and a stainless steel mesh is wound on the outer wall of the quartz tube to serve as an outer electrode.
(2) The space velocity of the gas is 20000h-1And adjusting the plasma voltage to be 15k V and the frequency to be 10k Hz, carrying out reaction, and evacuating the gas in the plasma reactor after the reaction is finished, wherein the removal rate of carbonyl sulfide is 99.5 percent.
(3) Flushing plasma with liquid ammoniaDaughter reactor, then extracting and collecting S4N4，S4N4The yield reaches 91.2 percent.
Example 4
(1) Under laboratory conditions, the gas is CS2COS mixed gas and nitrogen as balance gas, adding CS2The COS mixed gas and the nitrogen are introduced into the dielectric barrier discharge low-temperature plasma reactor through a gas mass flowmeter, in the embodiment, the parallel plate type dielectric barrier discharge low-temperature plasma reactor is adopted, a group of stainless steel plates or copper plates are adopted as high-voltage electrodes, and the distance between the two plates is 0.3-3 mm.
(2) The space velocity of the gas is 20000h-1And adjusting the plasma voltage to be 14k V and the frequency to be 9k Hz, carrying out the reaction, and exhausting the gas in the plasma reactor after the reaction is finished, wherein the removal rate of the carbonyl sulfide is 98.5 percent.
(3) Flushing the plasma reactor with liquid ammonia, then extracting and collecting S4N4，S4N4The yield reaches 90.4 percent.

Claims (6)

1. A method for preparing S4N4 by using dielectric barrier discharge low-temperature plasma is characterized in that:
s1, taking nitrogen as balance gas, and quantitatively introducing carbonyl sulfide and/or carbon disulfide gas into the dielectric barrier discharge low-temperature plasma reactor for reaction by using a gas flowmeter; the airspeed of the gas introduced into the dielectric barrier discharge low-temperature plasma reactor is 10000-20000 h-1(ii) a The voltage used by the dielectric barrier discharge low-temperature plasma reactor is 10-15 k V, and the frequency is 8-10 k Hz; the pressure condition of the gas for reaction in the dielectric barrier discharge low-temperature plasma reactor is normal pressure, and the temperature condition is normal temperature;
s2, after the reaction is finished, exhausting the gas in the plasma reactor;
s3, flushing the plasma reactor with liquid ammonia;
s4, extracting and purifying to obtain high-purity S4N4。
2. Preparation S according to claim 14N4The method of (2), characterized by:
and the gas introduced into the dielectric barrier discharge low-temperature plasma reactor in the S1 is COS.
3. Preparation S according to claim 14N4The method of (2), characterized by:
the gas introduced into the dielectric barrier discharge low-temperature plasma reactor in the S1 is CS2。
4. Preparation S according to claim 14N4The method of (2), characterized by:
the gas introduced into the dielectric barrier discharge low-temperature plasma reactor in the S1 is CS2Mixed gas with COS.
5. Preparation S according to claim 14N4The method of (2), characterized by:
the dielectric barrier discharge low-temperature plasma reactor adopts a quartz tube with the outer diameter of 16-20 mm, a high-voltage electrode of the dielectric barrier discharge low-temperature plasma reactor is a stainless steel bar with the diameter of 10-12 mm, and a stainless steel net is wound on the outer wall of the quartz tube to serve as an outer electrode.
6. Preparation S according to claim 14N4The method of (2), characterized by:
the dielectric barrier discharge low-temperature plasma reactor adopts a parallel plate type dielectric barrier discharge low-temperature plasma reactor, the high-voltage electrode of the dielectric barrier discharge low-temperature plasma reactor adopts a group of stainless steel plates or copper plates, and the plate interval is 0.3-3 mm.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107915213A (en) * 2017-11-23 2018-04-17 武汉大学 A kind of method that tetrasulfur tetranitride is prepared by disulphur dichloride ammonification
CN110402235A (en) * 2017-03-14 2019-11-01 英国国防部 Prepare the method for the metal halide adduct of S4N4 and by the mark visualization method and equipment on object

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110402235A (en) * 2017-03-14 2019-11-01 英国国防部 Prepare the method for the metal halide adduct of S4N4 and by the mark visualization method and equipment on object
CN107915213A (en) * 2017-11-23 2018-04-17 武汉大学 A kind of method that tetrasulfur tetranitride is prepared by disulphur dichloride ammonification

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