CN102408095B - A method for decomposing hydrogen sulfide to prepare hydrogen and elemental sulfur - Google Patents

A method for decomposing hydrogen sulfide to prepare hydrogen and elemental sulfur Download PDF

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CN102408095B
CN102408095B CN2011102405121A CN201110240512A CN102408095B CN 102408095 B CN102408095 B CN 102408095B CN 2011102405121 A CN2011102405121 A CN 2011102405121A CN 201110240512 A CN201110240512 A CN 201110240512A CN 102408095 B CN102408095 B CN 102408095B
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CN102408095A (en
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王安杰
赵璐
金亮
王瑶
李翔
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Dalian University of Technology
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Abstract

The invention discloses a method of decomposing hydrogen sulfide for preparation of hydrogen and elemental sulfur, which belongs to the technical field of hydrogen production and gas purification. The invention is characterized in that: hydrogen sulfide or gas containing hydrogen sulfide is subjected to ionization through blockage of discharge by using a medium so as to form uniformly distributed non-equilibrium plasma, and hydrogen sulfide spontaneously decomposes into hydrogen and elemental sulfur in the plasma; when there is a photocatalyst in the plasma, energy in the photons of the photocatalyst can be utilized to promote decomposition of hydrogen sulfide, and complete conversion can be realized under proper conditions. All the frequently used solid photocatalysts can be used in the above mentioned process, e.g., titanium oxide, cerium oxide, zirconia, zinc oxide, cadmium oxide, copper oxide, molybdena, tungsten oxide, zinc sulfide, cadmium sulfide, copper sulfide, molybdenum sulfide, tungsten sulfide and a mixture composed of two or more selected from the above-mentioned photocatalysts; the photocatalysts can also be loaded on a porous material to prepare load type catalysts. The method provided in the invention is especially applicable to treatment of gas containing hydrogen sulfide in the industries of natural gas, petroleum and coal chemistry and is also applicable to preparation of hydrogen and elemental sulfur through dissociation of gas containing hydrogen sulfide in the fields of metallurgy, sea and the like. The method has no special requirements for or restriction on the source and composition of gas; thus, the method has universality to preparation of hydrogen through decomposition of hydrogen sulfide.

Description

一种分解硫化氢制备氢气和单质硫的方法A method for decomposing hydrogen sulfide to prepare hydrogen and elemental sulfur

技术领域 technical field

本发明属于制氢和气体纯化技术领域,涉及一种将有害的硫化氢分解为无毒的单质硫同时获得氢气的方法。The invention belongs to the technical field of hydrogen production and gas purification, and relates to a method for decomposing harmful hydrogen sulfide into nontoxic elemental sulfur and simultaneously obtaining hydrogen.

技术背景 technical background

硫化氢是一种剧毒、恶臭的无色气体,不仅危害人体健康,而且会引起金属等材料的腐蚀,因此需要就地进行无害化处理。天然气、石油、煤和矿产加工工业产生大量含硫化氢气体,目前主要通过克劳斯(Claus)法将其部分氧化为单质硫和水:Hydrogen sulfide is a highly toxic, foul-smelling, colorless gas that not only endangers human health, but also causes corrosion of metals and other materials, so it needs to be treated in situ. Natural gas, petroleum, coal and mineral processing industries produce a large amount of hydrogen sulfide-containing gas, which is currently partially oxidized into elemental sulfur and water mainly through the Claus method:

H2S+3/2O2→SO2+H2OH 2 S+3/2O 2 →SO 2 +H 2 O

2H2S+SO2→3/xSx+2H2O2H 2 S+SO 2 →3/xS x +2H 2 O

虽然克劳斯工艺可以实现硫化氢无害化,但却使具有更高附加值的氢资源转化为水,浪费了宝贵的资源。显然,若能将硫化氢分解,则不仅可以使硫化氢无害化,而且可以得到高附加值的氢气和无毒的单质硫。理论上讲,在常见的非金属氢化物(水、氨和硫化氢)中,硫化氢的解离能最低,因而硫化氢热分解制氢最容易。然而,硫化氢的分解反应受热力学平衡限制,在低温下只有很低的平衡转化率(钱欣平,凌忠钱,周吴,岑可法,燃料化学学报,2005,33(6),722-725)。比如,1000℃时硫化氢的转化率仅为20%,1200℃的转化率为38%(Slimane R.B.,GasTIPS,2004,30-34)。为了产生局部高温,有许多研究者采用了超绝热法分解硫化氢,但其能耗仍然很高。为了打破化学反应平衡限制,有许多研究者采用了膜反应技术,但耐高温且耐硫的膜材料的开发和应用成为实现技术突破的关键。硫化氢分解制氢和硫的反应还可以通过电化学和光催化等方法实现,但存在操作步骤多或者反应效率低的缺点。Although the Claus process can achieve harmless hydrogen sulfide, it converts hydrogen resources with higher added value into water, wasting precious resources. Obviously, if hydrogen sulfide can be decomposed, not only can hydrogen sulfide be made harmless, but also high value-added hydrogen and non-toxic elemental sulfur can be obtained. Theoretically speaking, among the common non-metallic hydrides (water, ammonia and hydrogen sulfide), hydrogen sulfide has the lowest dissociation energy, so the thermal decomposition of hydrogen sulfide to produce hydrogen is the easiest. However, the decomposition reaction of hydrogen sulfide is limited by the thermodynamic equilibrium, and the equilibrium conversion rate is only very low at low temperature (Qian Xinping, Ling Zhongqian, Zhou Wu, Cen Kefa, Journal of Fuel Chemistry, 2005, 33(6), 722-725) . For example, the conversion rate of hydrogen sulfide is only 20% at 1000°C and 38% at 1200°C (Slimane R.B., GasTIPS, 2004, 30-34). In order to generate local high temperature, many researchers have adopted super adiabatic method to decompose hydrogen sulfide, but the energy consumption is still high. In order to break the limitation of chemical reaction balance, many researchers have adopted membrane reaction technology, but the development and application of high temperature and sulfur resistant membrane materials have become the key to achieving technological breakthroughs. The reaction of hydrogen sulfide decomposition to produce hydrogen and sulfur can also be realized by electrochemical and photocatalytic methods, but there are disadvantages of many operation steps or low reaction efficiency.

当硫化氢作为一种氢源用于制氢时,微量硫化氢的残留会在应用时带来许多严重问题。氢气主要用于燃料电池和化学工业的还原剂,由于在这两种场合中都用到贵金属作催化剂,而硫化氢极易使贵金属中毒而失去活性。在现有的硫化氢热解制氢的方法中,由于受热力学平衡的限制不可能实现完全转化,必然涉及产物氢与反应物硫化氢的分离,而含硫化氢气体的分离操作非常苛刻,而且很难实现完全分离。因此,硫化氢的完全分解技术才是一种理想制氢技术。When hydrogen sulfide is used as a hydrogen source for hydrogen production, the residual traces of hydrogen sulfide will cause many serious problems during application. Hydrogen is mainly used as a reducing agent in fuel cells and chemical industries. Since precious metals are used as catalysts in these two occasions, hydrogen sulfide can easily poison precious metals and lose their activity. In the existing hydrogen sulfide pyrolysis hydrogen production method, due to the limitation of thermodynamic equilibrium, it is impossible to achieve complete conversion, which must involve the separation of product hydrogen and reactant hydrogen sulfide, and the separation operation of hydrogen sulfide-containing gas is very harsh, and It is difficult to achieve complete separation. Therefore, the complete decomposition technology of hydrogen sulfide is an ideal hydrogen production technology.

发明内容 Contents of the invention

本发明提供了一种分解硫化氢制备氢气和单质硫的方法,在介质阻挡放电和光催化协同作用下,可以使硫化氢高效分解,在适宜条件下硫化氢可以100%转化为氢气和单质硫。The invention provides a method for decomposing hydrogen sulfide to prepare hydrogen and elemental sulfur. Under the synergy of dielectric barrier discharge and photocatalysis, hydrogen sulfide can be efficiently decomposed, and hydrogen sulfide can be 100% converted into hydrogen and elemental sulfur under suitable conditions.

本发明解决技术问题采用的技术方案如下:The technical solution adopted by the present invention to solve technical problems is as follows:

等离子体是物质的第四态,富含离子、电子、激发态的原子、分子及自由基等极活泼的高活性物种,是一种具有导电性的气体。本发明采用常压操作的介质阻挡放电的等离子体与催化剂结合,利用等离子体对硫化氢的激发和催化剂对反应的促进实现硫化氢的完全分解。等离子体中的高能粒子的能量一般为几至几十电子伏特(eV),足以提供化学反应所需的活化能。此外,等离子体为非平衡状态,因而可以打破硫化氢分解反应的热力学平衡限制。再者,等离子体中含有体相均匀分布的大量光子,通过光催化不仅可以有效利用这部分能源,而且可以提高反应的转化效率,从而实现低能耗、高效率分解硫化氢生产高纯氢气和单质硫。Plasma is the fourth state of matter, rich in ions, electrons, excited atoms, molecules and free radicals and other extremely active and highly active species, and is a conductive gas. The invention adopts the combination of dielectric barrier discharge plasma and catalyst operated at normal pressure, and utilizes the excitation of hydrogen sulfide by plasma and the promotion of reaction by catalyst to realize the complete decomposition of hydrogen sulfide. The energy of high-energy particles in the plasma is generally several to tens of electron volts (eV), which is sufficient to provide the activation energy required for chemical reactions. In addition, the plasma is in a non-equilibrium state, which can break the thermodynamic equilibrium limit of the hydrogen sulfide decomposition reaction. Furthermore, the plasma contains a large number of photons uniformly distributed in the bulk phase. Photocatalysis can not only effectively use this part of energy, but also improve the conversion efficiency of the reaction, so as to achieve low energy consumption and high-efficiency decomposition of hydrogen sulfide to produce high-purity hydrogen and elemental substances. sulfur.

具体说来硫化氢的完全分解通过介质阻挡放电和光催化协同实现:介质阻挡放电使硫化氢或者含硫化氢的气体电离,形成均匀分布的非平衡等离子体,硫化氢在等离子体中自发分解为氢气和单质硫;当等离子体中有光催化剂时,硫化氢的转化率会显著提高,适宜条件下可以实现完全转化。介质阻挡放电既可以使用交流电源,也可以使用直流电源。等离子体区域装填的光催化剂为固体颗粒和粉末,而具有光催化活性的固体光催化剂都适用本发明。比如,氧化钛、氧化铈、氧化锆、氧化锌、氧化镉、氧化铜、氧化钼、氧化钨、硫化锌、硫化镉、硫化铜、硫化钼、硫化钨,以及由它们组成的两种或者两种以上的混合物。光催化剂可以用金属和非金属元素改性和修饰,以提高催化反应性能。Specifically, the complete decomposition of hydrogen sulfide is realized through the cooperation of dielectric barrier discharge and photocatalysis: dielectric barrier discharge ionizes hydrogen sulfide or a gas containing hydrogen sulfide to form a uniformly distributed non-equilibrium plasma, and hydrogen sulfide spontaneously decomposes into hydrogen in the plasma and elemental sulfur; when there is a photocatalyst in the plasma, the conversion rate of hydrogen sulfide will be significantly improved, and complete conversion can be achieved under suitable conditions. Dielectric barrier discharge can use either AC power or DC power. The photocatalysts filled in the plasma region are solid particles and powders, and the solid photocatalysts with photocatalytic activity are applicable to the present invention. For example, titanium oxide, cerium oxide, zirconium oxide, zinc oxide, cadmium oxide, copper oxide, molybdenum oxide, tungsten oxide, zinc sulfide, cadmium sulfide, copper sulfide, molybdenum sulfide, tungsten sulfide, and two or more of them mixture of the above. Photocatalysts can be modified and decorated with metal and nonmetal elements to enhance the performance of catalytic reactions.

具有光催化活性的组分也可以负载在多孔材料上制成负载型催化剂,所使用的载体没有特殊限制,可以是活性炭、碳分子筛、碳纳米管、碳纤维、石墨烯、富勒烯、氧化硅、氧化铝、硅铝酸盐、磷酸盐、碳酸盐、氧化镁、氧化钛、氧化钙、氧化锆、氧化铈、沸石分子筛、介孔分子筛、介-微孔复合材料、高比表面积大孔材料、高分子聚合物和多孔金属中的一种或两种及两种以上的混合物,优选形状为球形、条形、三叶草状、四叶草状、片状、齿球状。制备方法可以采用传统的浸渍法、共沉淀法、沉积法和溅射法等。Components with photocatalytic activity can also be supported on porous materials to make supported catalysts. The carrier used is not particularly limited, and can be activated carbon, carbon molecular sieves, carbon nanotubes, carbon fibers, graphene, fullerene, silicon oxide , alumina, aluminosilicate, phosphate, carbonate, magnesium oxide, titanium oxide, calcium oxide, zirconium oxide, cerium oxide, zeolite molecular sieve, mesoporous molecular sieve, meso-microporous composite material, high specific surface area macropore One or a mixture of two or more of materials, polymers and porous metals, preferably in the shape of a sphere, a bar, a clover, a four-leaf clover, a sheet, or a toothed ball. The preparation method can adopt traditional dipping method, co-precipitation method, deposition method and sputtering method and the like.

本发明的效果和益处是,该方法不仅可以对硫化氢进行无害化处理,而且可以从硫化氢制备高附加值的氢气。该方法对气体的来源和组成没有特殊要求或者限制,因而对于各种浓度硫化氢的分解制氢具有普适性。The effect and benefit of the present invention are that the method can not only carry out harmless treatment of hydrogen sulfide, but also can prepare high value-added hydrogen from hydrogen sulfide. The method has no special requirements or restrictions on the source and composition of the gas, so it is universally applicable to the decomposition of hydrogen sulfide with various concentrations to produce hydrogen.

附图说明 Description of drawings

图1是介质阻挡放电等离子体中分解硫化氢时CdS/Al2O3光催化剂的活性随反应时间的变化。Fig. 1 shows the change of activity of CdS/Al 2 O 3 photocatalyst with reaction time when hydrogen sulfide is decomposed in dielectric barrier discharge plasma.

具体实施方式 Detailed ways

以下结合技术方案详细叙述本发明的具体实施例。Specific embodiments of the present invention will be described in detail below in conjunction with technical solutions.

实施例1Example 1

催化剂的制备:将市售二氧化钛、二氧化硅和氧化铝固体粉末在压力下成型,然后筛分出20~40目颗粒。Catalyst preparation: commercially available titanium dioxide, silicon dioxide and aluminum oxide solid powders are molded under pressure, and then sieved to obtain 20-40 mesh particles.

实施例2Example 2

称取1.50克粒度为20~40目的γ-Al2O3载体(比表面积270m2/g),取0.40克的Cd(NO3)2·4H2O溶于1.5毫升去离子水中,将此溶液缓慢滴入载体并搅拌均匀,在室温下浸渍8小时,然后于120℃的烘箱中干燥12小时,所得固体在马弗炉中于450℃空气氛围下焙烧5小时后降至室温,所得催化剂标记为CdO/Al2O3。采用同样的方法可以制备ZnO/Al2O3Weigh 1.50 grams of γ-Al 2 O 3 carrier (specific surface area 270 m 2 /g) with a particle size of 20 to 40 meshes, and dissolve 0.40 grams of Cd(NO 3 ) 2 4H 2 O in 1.5 milliliters of deionized water. The solution was slowly dropped into the carrier and stirred evenly, impregnated at room temperature for 8 hours, then dried in an oven at 120°C for 12 hours, and the obtained solid was calcined in a muffle furnace at 450°C in an air atmosphere for 5 hours and then lowered to room temperature. The obtained catalyst Labeled CdO/Al 2 O 3 . ZnO/Al 2 O 3 can be prepared by the same method.

实施例3Example 3

将实施例3中得到的CdO/Al2O3装入硫化用石英管中以30mL/min通入硫化剂(10%H2S/Ar),20分钟内升至400℃并保持100分钟。得到氧化铝负载的含10%(质量分数)硫化镉的催化剂,记作CdS/Al2O3。ZnS/Al2O3采用相同方法制备。Put the CdO/Al 2 O 3 obtained in Example 3 into a quartz tube for vulcanization, pass through a vulcanizing agent (10% H 2 S/Ar) at 30 mL/min, rise to 400° C. within 20 minutes and keep for 100 minutes. A catalyst containing 10% (mass fraction) cadmium sulfide supported on alumina is obtained, which is denoted as CdS/Al 2 O 3 . ZnS/Al 2 O 3 was prepared by the same method.

实施例4Example 4

介质阻挡放电反应器结构:放电电极采用线筒结构,高压极位于管式反应器的轴线上,接地极环绕在石英玻璃管的外壁。高压电极为直径2.5毫米的不锈钢线,接地极为薄铝片。石英管的外径为10毫米。Dielectric barrier discharge reactor structure: the discharge electrode adopts a wire barrel structure, the high voltage electrode is located on the axis of the tubular reactor, and the ground electrode is surrounded by the outer wall of the quartz glass tube. The high-voltage electrode is a stainless steel wire with a diameter of 2.5 mm, and the ground is an extremely thin aluminum sheet. The outer diameter of the quartz tube is 10 mm.

将颗粒催化剂置于石英玻璃管与高压电极间的空腔内,通入氮气5分钟以除去反应器中的氧气。通过质量流量计控制,使含10%硫化氢的氩气混合气以一定的流量通过催化剂床层。接通连接高压极和接地极的等离子体电源,调节电压、电流和频率可以改变输入功率。反应后的气体经过氢氧化钠水溶液和硫酸铜水溶液两段吸收后,尾气中氢气含量用色谱仪在线分析。根据氢气的浓度计算硫化氢的转化率。在100%转化条件下,用醋酸铅试纸进一步验证。The granular catalyst was placed in the cavity between the quartz glass tube and the high-voltage electrode, and nitrogen gas was passed through for 5 minutes to remove the oxygen in the reactor. Controlled by a mass flow meter, the argon gas mixture containing 10% hydrogen sulfide passes through the catalyst bed at a certain flow rate. Turn on the plasma power supply connected to the high voltage electrode and the ground electrode, and adjust the voltage, current and frequency to change the input power. After the reacted gas is absorbed by sodium hydroxide aqueous solution and copper sulfate aqueous solution in two stages, the hydrogen content in the tail gas is analyzed online with a chromatograph. The conversion of hydrogen sulfide was calculated from the concentration of hydrogen. Under the condition of 100% conversion, it was further verified with lead acetate test paper.

表1比较了不同催化剂在相同输入功率条件下硫化氢分解为氢气和单质硫的转化率。反应条件如下:催化剂体积1mL,入口气体流量:10mL/min,反应压力为常压,输入功率为24瓦(55V×0.43A)。可以看出,在等离子体和二氧化钛的协同作用下,硫化氢可以完全转化为氢气和单质硫。沉积在催化剂床层下游的淡黄色硫产品经x-射线粉末衍射分析主要为α相硫磺。使用三种催化剂在反应10小时内均未见转化率下降。Table 1 compares the conversion rate of hydrogen sulfide to hydrogen and elemental sulfur under the same input power conditions of different catalysts. The reaction conditions are as follows: the catalyst volume is 1 mL, the inlet gas flow rate is 10 mL/min, the reaction pressure is normal pressure, and the input power is 24 watts (55V×0.43A). It can be seen that under the synergistic effect of plasma and titanium dioxide, hydrogen sulfide can be completely converted into hydrogen and elemental sulfur. The yellowish sulfur product deposited downstream of the catalyst bed was predominantly alpha-phase sulfur by x-ray powder diffraction analysis. No decrease in conversion was observed within 10 hours of reaction using the three catalysts.

表1在相同输入功率下硫化氢在TiO2、SiO2和Al2O3上分解为氢气和单质硫的转化率Table 1 The conversion ratio of hydrogen sulfide to hydrogen and elemental sulfur on TiO 2 , SiO 2 and Al 2 O 3 under the same input power

  催化剂 Catalyst   TiO2 TiO 2   SiO2 SiO 2   Al2O3 Al 2 O 3   硫化氢转化率,% Conversion rate of hydrogen sulfide, %   100 100   85 85   90 90

实施例5Example 5

采用实施例4中的反应装置和反应步骤进行在固体光催化剂存在条件下硫化氢在等离子体中的分解反应。等离子体放电频率为10kHz,催化剂装填量为1.5mL,反应气(10%H2S和90%Ar的混合气)流速为60mL/min。反应结果如下表:The reaction device and reaction steps in Example 4 were used to carry out the decomposition reaction of hydrogen sulfide in the plasma under the condition of the presence of a solid photocatalyst. The plasma discharge frequency was 10 kHz, the catalyst loading was 1.5 mL, and the reaction gas (a mixture of 10% H 2 S and 90% Ar) flow rate was 60 mL/min. The reaction results are as follows:

表2不同输入功率下等离子体与固体光催化剂协同分解硫化氢的反应性能和产氢能耗Table 2 Reaction performance and hydrogen production energy consumption of plasma and solid photocatalyst synergistically decomposing hydrogen sulfide under different input powers

Figure BDA0000084858260000051
Figure BDA0000084858260000051

Figure BDA0000084858260000061
Figure BDA0000084858260000061

实施例6Example 6

采用实施例4中的反应装置和反应步骤考察了CdS/Al2O3光催化剂在硫化氢分解反应中的活性稳定性。等离子体放电频率为10kHz,催化剂装填量为1.5mL,反应气(10%H2S和90%Ar的混合气)流速为60mL/min。反应结果如图1所示。可见,CdS/Al2O3具有很好的活性稳定性。The activity stability of CdS/Al 2 O 3 photocatalyst in hydrogen sulfide decomposition reaction was investigated by using the reaction device and reaction steps in Example 4. The plasma discharge frequency was 10 kHz, the catalyst loading was 1.5 mL, and the reaction gas (a mixture of 10% H 2 S and 90% Ar) flow rate was 60 mL/min. The reaction result is shown in Figure 1. It can be seen that CdS/Al 2 O 3 has good activity stability.

上述试验结果表明,介质阻挡放电与光催化剂协同不仅可以打破热力学平衡限制实现完全转化,而且能源利用率高,是一种直接分解硫化氢制取氢气和硫磺的有效方法。The above experimental results show that the combination of dielectric barrier discharge and photocatalyst can not only break the limitation of thermodynamic equilibrium to achieve complete conversion, but also has high energy utilization rate. It is an effective method to directly decompose hydrogen sulfide to produce hydrogen and sulfur.

上述实施例以氩气中硫化氢的分解为例说明了介质阻挡放电等离子体与光催化协同实现硫化氢高效分解方法、所使用的催化剂及其制备方法。对本发明可以进行一些修改和改进,例如,对反应器及电极结构进行改进,用金属或非金属及其盐类对载体表面进行改性,或者添加一些金属或非金属对本发明的主催化剂进行一定的改性等。The above-mentioned embodiments take the decomposition of hydrogen sulfide in argon as an example to illustrate the method for efficient decomposition of hydrogen sulfide realized by dielectric barrier discharge plasma and photocatalysis, the catalyst used and its preparation method. Some modifications and improvements can be made to the present invention, for example, the reactor and electrode structures are improved, the carrier surface is modified with metals or nonmetals and their salts, or some metals or nonmetals are added to the main catalyst of the present invention. modification, etc.

Claims (9)

1.一种分解硫化氢制备氢气和单质硫的方法,硫化氢的完全分解通过介质阻挡放电和光催化协同实现,其特征在于:通过介质阻挡放电使硫化氢电离,形成均匀分布的非平衡等离子体,硫化氢在等离子体中自发分解为氢气和单质硫;在等离子体区域中装填具有光催化活性的固体光催化剂,提高硫化氢的转化率。 1. A method for decomposing hydrogen sulfide to prepare hydrogen and elemental sulfur. The complete decomposition of hydrogen sulfide is realized through dielectric barrier discharge and photocatalysis. It is characterized in that hydrogen sulfide is ionized by dielectric barrier discharge to form a uniformly distributed non-equilibrium plasma , hydrogen sulfide spontaneously decomposes into hydrogen and elemental sulfur in the plasma; a solid photocatalyst with photocatalytic activity is filled in the plasma region to increase the conversion rate of hydrogen sulfide. 2.根据权利要求1所述的方法,其特征在于,介质阻挡放电既使用交流电源,也使用直流电源。 2. The method according to claim 1, characterized in that both AC power and DC power are used for dielectric barrier discharge. 3.根据权利要求1所述的方法,其特征还在于,等离子体区域装填的光催化剂为固体颗粒和粉末。 3. The method according to claim 1, further characterized in that the photocatalysts filled in the plasma region are solid particles and powders. 4.根据权利要求1所述的方法,其特征还在于,固体光催化剂包括氧化钛、氧化铈、氧化锆、氧化锌、氧化镉、氧化铜、氧化钼、氧化钨、硫化锌、硫化镉、硫化铜、硫化钼、硫化钨中的一种以及由它们组成的两种或者两种以上的混合物。 4. The method according to claim 1, wherein the solid photocatalyst comprises titanium oxide, cerium oxide, zirconium oxide, zinc oxide, cadmium oxide, copper oxide, molybdenum oxide, tungsten oxide, zinc sulfide, cadmium sulfide, One of copper sulfide, molybdenum sulfide, tungsten sulfide and a mixture of two or more of them. 5.根据权利要求1、3或4所述的方法,其特征还在于,光催化剂用金属和非金属元素改性和修饰,提高催化反应性能。 5. The method according to claim 1, 3 or 4, further characterized in that the photocatalyst is modified and decorated with metal and non-metal elements to improve catalytic performance. 6.根据权利要求1、3或4所述的方法,其特征还在于,具有光催化活性的组分负载在多孔材料上制成负载型催化剂,所使用的载体是活性炭、炭分子筛、碳纳米管、碳纤维、石墨烯、富勒烯、氧化硅、氧化铝、硅铝酸盐、磷酸盐、碳酸盐、氧化镁、氧化钛、氧化钙、氧化锆、氧化铈、沸石分子筛、介孔分子筛、介-微孔复合材料、高分子聚合物、多孔金属中的一种或以及由它们组成的两种或者两种以上的混合物。 6. according to the described method of claim 1,3 or 4, it is also characterized in that, the component loading with photocatalytic activity is made loaded catalyst on porous material, and used carrier is activated carbon, carbon molecular sieve, carbon nanometer Tubes, carbon fibers, graphene, fullerenes, silica, alumina, aluminosilicates, phosphates, carbonates, magnesia, titania, calcia, zirconia, ceria, zeolites, mesoporous molecular sieves , meso-microporous composite material, high molecular polymer, porous metal or a mixture of two or more of them. 7.根据权利要求5所述的方法,其特征还在于,具有光催化活性的组分负载在多孔材料上制成负载型催化剂,所使用的载体是活性炭、炭分子筛、碳纳米管、碳纤维、石墨烯、富勒烯、氧化硅、氧化铝、硅铝酸盐、磷酸盐、碳酸盐、氧化镁、氧化钛、氧化钙、氧化锆、氧化铈、沸石分子筛、介孔分子筛、介-微孔复合材料、高分子聚合物、多孔金属中的一种或以及由它们组成的两种或者两种以上的混合物。 7. method according to claim 5, it is also characterized in that, the component loading with photocatalytic activity is made loaded catalyst on porous material, and used carrier is activated carbon, carbon molecular sieve, carbon nanotube, carbon fiber, Graphene, fullerene, silica, alumina, aluminosilicate, phosphate, carbonate, magnesium oxide, titanium oxide, calcium oxide, zirconium oxide, cerium oxide, zeolite molecular sieve, mesoporous molecular sieve, meso-micro Porous composite material, high molecular polymer, porous metal or a mixture of two or more of them. 8.根据权利要求6所述的方法,其特征还在于,所述的载体为球形、条形、三叶草状、四叶草状、片状、齿球状。 8. The method according to claim 6, further characterized in that, the carrier is in the shape of a sphere, a bar, a clover, a four-leaf clover, a sheet, or a toothed ball. 9.根据权利要求6所述的方法,其特征还在于,制备方法采用浸渍法、共沉淀法、沉积法、溅射法。 9. The method according to claim 6, further characterized in that the preparation method adopts dipping method, co-precipitation method, deposition method and sputtering method.
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