CN103495427A - Method for using low-temperature plasma to prepare supported metal sulfide catalyst - Google Patents
Method for using low-temperature plasma to prepare supported metal sulfide catalyst Download PDFInfo
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- CN103495427A CN103495427A CN201310489243.1A CN201310489243A CN103495427A CN 103495427 A CN103495427 A CN 103495427A CN 201310489243 A CN201310489243 A CN 201310489243A CN 103495427 A CN103495427 A CN 103495427A
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Abstract
The invention discloses a method for using low-temperature plasma to prepare a supported metal sulfide catalyst and belongs to the technical field of material science. The method is characterized by including: allowing ionization of hydrogen sulfide gas or gas containing hydrogen sulfide through gas discharge to form the low-temperature plasma distributed evenly, and using the low-temperature plasma to interact with supported metal salt precursor to generate metal sulfide. Due to the fact that the catalyst is avoided from being exposed in excessively high temperature, the prepared catalyst is free of thermal agglomeration, so that the catalyst is smaller in particle size and higher in dispersity. The method is suitable for preparation of various sulfide catalysts, metal sulfide can be supported on different materials to prepare various supported catalysts. The method has the advantages of low reaction temperature, low energy consumption, short preparation time and the like. In addition, processing objects are common metal salt, wide involve range is achieved, and the prepared catalyst is applicable to various common heterogeneous reactions.
Description
Technical field
The invention belongs to materials science field, relate to a kind of method of utilizing low temperature plasma to prepare the load type metal sulfide catalyst.
Technical background
Metal sulfide is as a kind of important functional material, and it is widely used in optics, the fields such as catalysis and magnetic device.The current method for preparing load type metal sulfide is by the slaine impregnated carrier, by roasting (generation metal oxide), high temperature vulcanized making.Due to favourable macroscopic property and relatively weak H-S key, the energy barrier of metal oxide vulcanization is usually very little.Although the sulfidation of metal oxide can be carried out at lower temperature, owing to being subject to kinetic limitation, react very slow.Although higher temperature has improved rate of cure, when hot operation brings running cost to increase, also can cause the reunion of active phase, thereby cause particle diameter to increase, decentralization reduces and lattice defect.These all can have influence on the reactivity of catalyst.
The low temperature plasma method that the present invention adopts is widely used in catalyst and synthesizes fields such as reaching material surface modifying.With traditional preparation method, compare, the needed preparation time of lower temperature plasma technology is short, and energy consumption is low, and the catalyst made to have an active component particle diameter little, the decentralization advantages of higher.
The present invention adopts low temperature plasma to prepare the method for load type metal sulfide.Take the dielectric barrier discharge form as example, and dielectric barrier discharge plasma belongs to low temperature plasma, in preparation reaction temperature far below sample the temperature through high-temperature roasting and sulfuration; Reaction unit is simple to operation; Processing object is common metallic salt presoma, has a wide range of applications object.
Summary of the invention
The object of the present invention is to provide a kind of method of utilizing plasma mode to prepare load type metal sulfide, the method is simple to operate, save energy consumption, environmentally friendly, not only can shorten preparation time but also prepared sample and there is the advantages such as the active phase particle decentralization is high, the particle diameter distributed area is narrow, and particle diameter is little.
The present invention is achieved through the following technical solutions:
Plasma is that the 4th kind of material exists form, is rich in the as lively as a cricket high activity species such as atom, molecule and free radical of various ions, electronics, excitation state, is a kind of fluid with electric conductivity.The energy of the high energy particle in plasma is generally several to tens electron-volts (eV), and the activation energy that provides chemical reaction required is provided.The present invention adopts low temperature plasma to prepare different loads type metal sulfide catalyst, and the excited state molecule that utilizes plasma to generate exciting of hydrogen sulfide, ion, free radical etc. interact and generate metal sulfide with metal salt precursor under temperate condition.The method comprises the following steps:
(1) catalyst precarsor of support type metalline is placed in to discharge reactor;
(2) pass at normal temperatures and pressures plasma discharge gas, the high pressure that utilizes high voltage source to provide at the electrode two ends makes gas discharge, and the plasma of formation decomposes slaine, vulcanize.
Described slaine is the formed salt of transition metal.
The gaseous mixture that described plasma discharge gas is hydrogen sulfide gas, hydrogen sulfide and inert gas, hydrogen sulfide and hydrogen.
Course of reaction is described below: high energy electron and hydrogen sulfide molecule generation inelastic collision in low temperature plasma make it excite generation excited state molecule, ion, free radical etc. thereby electron energy is transferred to the latter.Because the chemical property of excited state species in plasma is very active, and metal salt precursor is easy to decompose under excited state species collision effect under plasma.Therefore, under gentle condition, metal salt precursor and hydrogen sulfide Plasma Interaction can generate metal sulfide.The present invention is applicable to multiple sulfide catalyst preparation, such as, nickel sulfide, manganese sulfide, silver sulfide, iron sulfide, cobalt sulfide, zinc sulphide, cadmium sulfide, copper sulfide, molybdenum sulfide, tungsten sulfide etc.In addition, because metal salt mixture easily makes, therefore by this invention technology, can prepare binary or multi-element metal sulfide.Metal sulfide can be used metal and nonmetalloid modification and modification, can utilize too the technology of the present invention to prepare the modified sulphur compound catalyst.
Metal sulfide also can load on multiple different materials and make loaded catalyst, and the carrier used is not particularly limited, and can be material with carbon element, as active carbon, carbon molecular sieve, carbon fiber, CNT, fullerene, Graphene; Can be oxide, as magnesia, silica, cerium oxide, calcium oxide, titanium oxide, aluminium oxide, zirconia; Can be porous material, as one or both and the two or more mixtures in zeolite molecular sieve, mesopore molecular sieve, mesoporous-microporous composite material, high-specific surface area large pore material.
Effect of the present invention and benefit:
With the conventional high-temperature roasting, with high temperature vulcanized process, compare, the present invention adopts the low temperature plasma method to have the advantages such as reaction temperature is low, energy consumption is low, preparation time is short.Owing to having avoided catalyst exposure at too high temperature, therefore the catalyst of preparation not there will be hot agglomeration, thereby particle size is less, and decentralization is higher.Mechanism infers that show is be decomposed and vulcanize the generation metal sulfide under metal salt precursor and energetic plasma direct effect under the gas discharge condition.Because energy directly acts on, slaine decomposes and sulfuration, and energy utilization efficiency is higher, and the active phase granularity of made support type sulfide is more even, and decentralization is higher, and its particle diameter is nanoscale.In addition, processing object is common slaine, and coverage is wide and so long as Powdered getting final product, without specially treated.The operation at normal temperatures and pressures of equipment fortune, operate simpler.
The accompanying drawing explanation
Fig. 1 is dielectric barrier discharge plasma treating apparatus schematic diagram.
In figure: 1 high-field electrode; 2 quartz glass tubes; 3 earthing poles; 4 heat insulation layers; 5 catalyst precarsor beds; 6 the earth; 7 gas vents; 8 gas accesses.
Fig. 2 is CdS and the ZnS x-ray photoelectron energy spectrogram of the alundum (Al2O3) load for preparing of plasma method.Its
In, (a) be the x-ray photoelectron energy spectrogram of CdS, be (b) the x-ray photoelectron energy spectrogram of ZnS.
Fig. 3 is CdS and the ZnS transmission electron microscope picture of the alundum (Al2O3) load for preparing of plasma method.
Wherein, (a) being the transmission electron microscope picture of CdS, is (b) transmission electron microscope picture of ZnS.
Fig. 4 is the metal sulfide X-ray diffraction spectrogram of the different carriers load for preparing of plasma method.
The specific embodiment
Describe by the following examples and by reference to the accompanying drawings the specific embodiment of the present invention in detail.
The loading of catalyst metals sulfide be take the mass fraction of its oxide and is counted 10% as example.
Taking 3 gram particle degree is 40-60 purpose γ-Al
2o
3carrier, get the Cd (NO of 0.80 gram
3)
24H
2o is dissolved in 3 ml deionized water, and this solution is slowly splashed into to carrier and stirs, and at room temperature floods 8 hours, and then in the baking oven of 120 ℃ dry 12 hours, the gained catalyst precarsor was labeled as Cd (NO
3)
2/ Al
2o
3.
Taking 3 gram particle degree is 40-60 purpose SiO
2carrier, get the Cd (NO of 0.80 gram
3)
24H
2o is dissolved in 3 ml deionized water, and this solution is slowly splashed into to carrier and stirs, and at room temperature floods 8 hours, and then in the baking oven of 120 ℃ dry 12 hours, the gained catalyst precarsor was labeled as Cd (NO
3)
2/ SiO
2.
Taking 3 gram particle degree is 40-60 purpose absorbent charcoal carrier, gets the Cd (NO of 0.80 gram
3)
24H
2o is dissolved in 3 ml deionized water, and this solution is slowly splashed into to carrier and stirs, and at room temperature floods 8 hours, and then in the baking oven of 120 ℃ dry 12 hours, the gained catalyst precarsor was labeled as Cd (NO
3)
2/ C.
Taking 3 gram particle degree is 40-60 purpose ZSM-5 zeolite molecular sieve carrier, gets the Cd (NO of 0.80 gram
3)
24H
2o is dissolved in 3 ml deionized water, and this solution is slowly splashed into to carrier and stirs, and at room temperature floods 8 hours, and then in the baking oven of 120 ℃ dry 12 hours, the gained catalyst precarsor was labeled as Cd (NO
3)
2/ ZSM-5.
Taking 3 gram particle degree is 40-60 purpose beta-zeolite molecular sieve carrier, gets the Cd (NO of 0.80 gram
3)
24H
2o is dissolved in 3 ml deionized water, and this solution is slowly splashed into to carrier and stirs, and at room temperature floods 8 hours, and then in the baking oven of 120 ℃ dry 12 hours, the gained catalyst precarsor was labeled as Cd (NO
3)
2/ β zeolite.
Embodiment 6
Taking 3 gram particle degree is 40-60 purpose γ-Al
2o
3carrier, get the Zn (NO of 1.22 grams
3)
26H
2o is dissolved in 3 ml deionized water, and this solution is slowly splashed into to carrier and stirs, and at room temperature floods 8 hours, and then in the baking oven of 120 ℃ dry 12 hours, the gained catalyst precarsor was labeled as Zn (NO
3)
2/ Al
2o
3.
Taking 3 gram particle degree is 40-60 purpose SiO
2carrier, get the Zn (NO of 1.22 grams
3)
26H
2o is dissolved in 3 ml deionized water, and this solution is slowly splashed into to carrier and stirs, and at room temperature floods 8 hours, and then in the baking oven of 120 ℃ dry 12 hours, the gained catalyst precarsor was labeled as Zn (NO
3)
2/ SiO
2.
Embodiment 8
Taking 3 gram particle degree is 40-60 purpose absorbent charcoal carrier, gets the Zn (NO of 1.22 grams
3)
26H
2o is dissolved in 3 ml deionized water, and this solution is slowly splashed into to carrier and stirs, and at room temperature floods 8 hours, and then in the baking oven of 120 ℃ dry 12 hours, the gained catalyst precarsor was labeled as Zn (NO
3)
2/ C.
Embodiment 9
Taking 3 gram particle degree is 40-60 purpose ZSM-5 zeolite molecular sieve carrier, gets the Zn (NO of 1.22 grams
3)
26H
2o is dissolved in 3 ml deionized water, and this solution is slowly splashed into to carrier and stirs, and at room temperature floods 8 hours, and then in the baking oven of 120 ℃ dry 12 hours, the gained catalyst precarsor was labeled as Zn (NO
3)
2/ ZSM-5.
Embodiment 10
Taking 3 gram particle degree is 40-60 purpose beta-zeolite molecular sieve carrier, gets the Zn (NO of 1.22 grams
3)
26H
2o is dissolved in 3 ml deionized water, and this solution is slowly splashed into to carrier and stirs, and at room temperature floods 8 hours, and then in the baking oven of 120 ℃ dry 12 hours, the gained catalyst precarsor was labeled as Zn (NO
3)
2/ β zeolite.
Embodiment 11
Taking 3 gram particle degree is 40-60 purpose γ-Al
2o
3carrier, get the Co (NO of 1.29 grams
3)
26H
2o is dissolved in 3 ml deionized water, and this solution is slowly splashed into to carrier and stirs, and at room temperature floods 8 hours, and then in the baking oven of 120 ℃ dry 12 hours, the gained catalyst precarsor was labeled as Co (NO
3)
2/ Al
2o
3.
Embodiment 12
Taking 3 gram particle degree is 40-60 purpose SiO
2carrier, get the Co (NO of 1.29 grams
3)
26H
2o is dissolved in 3 ml deionized water, and this solution is slowly splashed into to carrier and stirs, and at room temperature floods 8 hours, and then in the baking oven of 120 ℃ dry 12 hours, the gained catalyst precarsor was labeled as Co (NO
3)
2/ SiO
2.
Embodiment 13
Taking 3 gram particle degree is 40-60 purpose absorbent charcoal carrier, gets the Co (NO of 1.29 grams
3)
26H
2o is dissolved in 3 ml deionized water, and this solution is slowly splashed into to carrier and stirs, and at room temperature floods 8 hours, and then in the baking oven of 120 ℃ dry 12 hours, the gained catalyst precarsor was labeled as Co (NO
3)
2/ C.
Embodiment 14
Taking 3 gram particle degree is 40-60 purpose ZSM-5 zeolite molecular sieve carrier, gets the Co (NO of 1.29 grams
3)
26H
2o is dissolved in 3 ml deionized water, and this solution is slowly splashed into to carrier and stirs, and at room temperature floods 8 hours, and then in the baking oven of 120 ℃ dry 12 hours, the gained catalyst precarsor was labeled as Co (NO
3)
2/ ZSM-5.
Embodiment 15
Taking 3 gram particle degree is 40-60 purpose beta-zeolite molecular sieve carrier, gets the Co (NO of 1.29 grams
3)
26H
2o is dissolved in 3 ml deionized water, and this solution is slowly splashed into to carrier and stirs, and at room temperature floods 8 hours, and then in the baking oven of 120 ℃ dry 12 hours, the gained catalyst precarsor was labeled as Co (NO
3)
2/ β zeolite.
Embodiment 16
Taking 3 gram particle degree is 40-60 purpose γ-Al
2o
3carrier, get the Fe (NO of 1.69 grams
3)
39H
2o is dissolved in 3 ml deionized water, and this solution is slowly splashed into to carrier and stirs, and at room temperature floods 8 hours, and then in the baking oven of 120 ℃ dry 12 hours, the gained catalyst precarsor was labeled as Fe (NO
3)
3/ Al
2o
3.
Embodiment 17
Taking 3 gram particle degree is 40-60 purpose SiO
2carrier, get the Fe (NO of 1.69 grams
3)
39H
2o is dissolved in 3 ml deionized water, and this solution is slowly splashed into to carrier and stirs, and at room temperature floods 8 hours, and then in the baking oven of 120 ℃ dry 12 hours, the gained catalyst precarsor was labeled as Fe (NO
3)
3/ SiO
2.
Embodiment 18
Taking 3 gram particle degree is 40-60 purpose absorbent charcoal carrier, gets the Fe (NO of 1.69 grams
3)
39H
2o is dissolved in 3 ml deionized water, and this solution is slowly splashed into to carrier and stirs, and at room temperature floods 8 hours, and then in the baking oven of 120 ℃ dry 12 hours, the gained catalyst precarsor was labeled as Fe (NO
3)
3/ C.
Embodiment 19
Taking 3 gram particle degree is 40-60 purpose ZSM-5 zeolite molecular sieve carrier, gets the Fe (NO of 1.69 grams
3)
39H
2o is dissolved in 3 ml deionized water, and this solution is slowly splashed into to carrier and stirs, and at room temperature floods 8 hours, and then in the baking oven of 120 ℃ dry 12 hours, the gained catalyst precarsor was labeled as Fe (NO
3)
3/ ZSM-5.
Taking 3 gram particle degree is 40-60 purpose beta-zeolite molecular sieve carrier, gets the Fe (NO of 1.69 grams
3)
39H
2o is dissolved in 3 ml deionized water, and this solution is slowly splashed into to carrier and stirs, and at room temperature floods 8 hours, and then in the baking oven of 120 ℃ dry 12 hours, the gained catalyst precarsor was labeled as Fe (NO
3)
3/ β zeolite.
Embodiment 21
Taking 3 gram particle degree is 40-60 purpose γ-Al
2o
3carrier, get the AgNO of 0.49 gram
3be dissolved in 3 ml deionized water, this solution is slowly splashed into to carrier and stirs, at room temperature flood 8 hours, then in the baking oven of 120 ℃ dry 12 hours, the gained catalyst precarsor was labeled as AgNO
3/ Al
2o
3.
Embodiment 22
Taking 3 gram particle degree is 40-60 purpose SiO
2carrier, get the AgNO of 0.49 gram
3be dissolved in 3 ml deionized water, this solution is slowly splashed into to carrier and stirs, at room temperature flood 8 hours, then in the baking oven of 120 ℃ dry 12 hours, the gained catalyst precarsor was labeled as AgNO
3/ SiO
2.
Embodiment 23
Taking 3 gram particle degree is 40-60 purpose absorbent charcoal carrier, gets the AgNO of 0.49 gram
3be dissolved in 3 ml deionized water, this solution is slowly splashed into to carrier and stirs, at room temperature flood 8 hours, then in the baking oven of 120 ℃ dry 12 hours, the gained catalyst precarsor was labeled as AgNO
3/ C.
Embodiment 24
Taking 3 gram particle degree is 40-60 purpose ZSM-5 zeolite molecular sieve carrier, gets the AgNO of 0.49 gram
3be dissolved in 3 ml deionized water, this solution is slowly splashed into to carrier and stirs, at room temperature flood 8 hours, then in the baking oven of 120 ℃ dry 12 hours, the gained catalyst precarsor was labeled as AgNO
3/ ZSM-5.
Embodiment 25
Taking 3 gram particle degree is 40-60 purpose beta-zeolite molecular sieve carrier, gets the AgNO of 0.49 gram
3be dissolved in 3 ml deionized water, this solution is slowly splashed into to carrier and stirs, at room temperature flood 8 hours, then in the baking oven of 120 ℃ dry 12 hours, the gained catalyst precarsor was labeled as AgNO
3/ β zeolite.
Embodiment 26
Taking 3 gram particle degree is 40-60 purpose γ-Al
2o
3carrier, get the Mn (NO that 1.37 gram mass marks are 50%
3)
2the aqueous solution also adds deionized water to 3 milliliter, and this solution is slowly splashed into to carrier and stirs, and at room temperature floods 8 hours, and then in the baking oven of 120 ℃ dry 12 hours, the gained catalyst precarsor was labeled as Mn (NO
3)
2/ Al
2o
3.
Embodiment 27
Taking 3 gram particle degree is 40-60 purpose SiO
2carrier, get the Mn (NO that 1.37 gram mass marks are 50%
3)
2the aqueous solution also adds deionized water to 3 milliliter, and this solution is slowly splashed into to carrier and stirs, and at room temperature floods 8 hours, and then in the baking oven of 120 ℃ dry 12 hours, the gained catalyst precarsor was labeled as Mn (NO
3)
2/ SiO
2.
Embodiment 28
Taking 3 gram particle degree is 40-60 purpose absorbent charcoal carrier, gets the Mn (NO that 1.37 gram mass marks are 50%
3)
2the aqueous solution also adds deionized water to 3 milliliter, and this solution is slowly splashed into to carrier and stirs, and at room temperature floods 8 hours, and then in the baking oven of 120 ℃ dry 12 hours, the gained catalyst precarsor was labeled as Mn (NO
3)
2/ C.
Embodiment 29
Taking 3 gram particle degree is 40-60 purpose ZSM-5 zeolite molecular sieve carrier, gets the Mn (NO that 1.37 gram mass marks are 50%
3)
2the aqueous solution also adds deionized water to 3 milliliter, and this solution is slowly splashed into to carrier and stirs, and at room temperature floods 8 hours, and then in the baking oven of 120 ℃ dry 12 hours, the gained catalyst precarsor was labeled as Mn (NO
3)
2/ ZSM-5.
Taking 3 gram particle degree is 40-60 purpose beta-zeolite molecular sieve carrier, gets the Mn (NO that 1.37 gram mass marks are 50%
3)
2the aqueous solution also adds deionized water to 3 milliliter, and this solution is slowly splashed into to carrier and stirs, and at room temperature floods 8 hours, and then in the baking oven of 120 ℃ dry 12 hours, the gained catalyst precarsor was labeled as Mn (NO
3)
2/ β zeolite.
Embodiment 31
Taking 3 gram particle degree is 40-60 purpose γ-Al
2o
3carrier, get the Cu (NO of 1.01 grams
3)
23H
2o is dissolved in 3 ml deionized water, and this solution is slowly splashed into to carrier and stirs, and at room temperature floods 8 hours, and then in the baking oven of 120 ℃ dry 12 hours, the gained catalyst precarsor was labeled as Cu (NO
3)
2/ Al
2o
3.
Embodiment 32
Taking 3 gram particle degree is 40-60 purpose SiO
2carrier, get the Cu (NO of 1.01 grams
3)
23H
2o is dissolved in 3 ml deionized water, and this solution is slowly splashed into to carrier and stirs, and at room temperature floods 8 hours, and then in the baking oven of 120 ℃ dry 12 hours, the gained catalyst precarsor was labeled as Cu (NO
3)
2/ SiO
2.
Embodiment 33
Taking 3 gram particle degree is 40-60 purpose absorbent charcoal carrier, gets the Cu (NO of 1.01 grams
3)
23H
2o is dissolved in 3 ml deionized water, and this solution is slowly splashed into to carrier and stirs, and at room temperature floods 8 hours, and then in the baking oven of 120 ℃ dry 12 hours, the gained catalyst precarsor was labeled as Cu (NO
3)
2/ C.
Embodiment 34
Taking 3 gram particle degree is 40-60 purpose ZSM-5 zeolite molecular sieve carrier, gets the Cu (NO of 1.01 grams
3)
23H
2o is dissolved in 3 ml deionized water, and this solution is slowly splashed into to carrier and stirs, and at room temperature floods 8 hours, and then in the baking oven of 120 ℃ dry 12 hours, the gained catalyst precarsor was labeled as Cu (NO
3)
2/ ZSM-5.
Embodiment 35
Taking 3 gram particle degree is 40-60 purpose beta-zeolite molecular sieve carrier, gets the Cu (NO of 1.01 grams
3)
23H
2o is dissolved in 3 ml deionized water, and this solution is slowly splashed into to carrier and stirs, and at room temperature floods 8 hours, and then in the baking oven of 120 ℃ dry 12 hours, the gained catalyst precarsor was labeled as Cu (NO
3)
2/ β zeolite.
Embodiment 36
Taking 3 gram particle degree is 40-60 purpose γ-Al
2o
3carrier, get the Ni (NO of 1.30 grams
3)
26H
2o is dissolved in 3 ml deionized water, and this solution is slowly splashed into to carrier and stirs, and at room temperature floods 8 hours, and then in the baking oven of 120 ℃ dry 12 hours, the gained catalyst precarsor was labeled as Ni (NO
3)
2/ Al
2o
3.
Embodiment 37
Taking 3 gram particle degree is 40-60 purpose SiO
2carrier, get the Ni (NO of 1.30 grams
3)
26H
2o is dissolved in 3 ml deionized water, and this solution is slowly splashed into to carrier and stirs, and at room temperature floods 8 hours, and then in the baking oven of 120 ℃ dry 12 hours, the gained catalyst precarsor was labeled as Ni (NO
3)
2/ SiO
2.
Embodiment 38
Taking 3 gram particle degree is 40-60 purpose absorbent charcoal carrier, gets the Ni (NO of 1.30 grams
3)
26H
2o is dissolved in 3 ml deionized water, and this solution is slowly splashed into to carrier and stirs, and at room temperature floods 8 hours, and then in the baking oven of 120 ℃ dry 12 hours, the gained catalyst precarsor was labeled as Ni (NO
3)
2/ C.
Embodiment 39
Taking 3 gram particle degree is 40-60 purpose ZSM-5 zeolite molecular sieve carrier, gets the Ni (NO of 1.30 grams
3)
26H
2o is dissolved in 3 ml deionized water, and this solution is slowly splashed into to carrier and stirs, and at room temperature floods 8 hours, and then in the baking oven of 120 ℃ dry 12 hours, the gained catalyst precarsor was labeled as Ni (NO
3)
2/ ZSM-5.
Taking 3 gram particle degree is 40-60 purpose beta-zeolite molecular sieve carrier, gets the Ni (NO of 1.30 grams
3)
26H
2o is dissolved in 3 ml deionized water, and this solution is slowly splashed into to carrier and stirs, and at room temperature floods 8 hours, and then in the baking oven of 120 ℃ dry 12 hours, the gained catalyst precarsor was labeled as Ni (NO
3)
2/ β zeolite.
Embodiment 41
Taking 3 gram particle degree is 40-60 purpose γ-Al
2o
3carrier, get (the NH of 0.41 gram
4)
6mo
7o
244H
2o is dissolved in 3 ml deionized water, and this solution is slowly splashed into to carrier and stirs, and at room temperature floods 8 hours, and then in the baking oven of 120 ℃ dry 12 hours, the gained catalyst precarsor was labeled as (NH
4)
6mo
7o
24/ Al
2o
3.Embodiment 42
Taking 3 gram particle degree is 40-60 purpose SiO
2carrier, get (the NH of 0.41 gram
4)
6mo
7o
244H
2o is dissolved in 3 ml deionized water, and this solution is slowly splashed into to carrier and stirs, and at room temperature floods 8 hours, and then in the baking oven of 120 ℃ dry 12 hours, the gained catalyst precarsor was labeled as (NH
4)
6mo
7o
24/ SiO
2.Embodiment 43
Taking 3 gram particle degree is 40-60 purpose absorbent charcoal carrier, gets (the NH of 0.41 gram
4)
6mo
7o
244H
2o is dissolved in 3 ml deionized water, and this solution is slowly splashed into to carrier and stirs, and at room temperature floods 8 hours, and then in the baking oven of 120 ℃ dry 12 hours, the gained catalyst precarsor was labeled as (NH
4)
6mo
7o
24/ C.
Embodiment 44
Taking 3 gram particle degree is 40-60 purpose ZSM-5 zeolite molecular sieve carrier, gets (the NH of 0.41 gram
4)
6mo
7o
244H
2o is dissolved in 3 ml deionized water, and this solution is slowly splashed into to carrier and stirs, and at room temperature floods 8 hours, and then in the baking oven of 120 ℃ dry 12 hours, the gained catalyst precarsor was labeled as (NH
4)
6mo
7o
24/ ZSM-5.
Embodiment 45
Taking 3 gram particle degree is 40-60 purpose beta-zeolite molecular sieve carrier, gets (the NH of 0.41 gram
4)
6mo
7o
244H
2o is dissolved in 3 ml deionized water, and this solution is slowly splashed into to carrier and stirs, and at room temperature floods 8 hours, and then in the baking oven of 120 ℃ dry 12 hours, the gained catalyst precarsor was labeled as (NH
4)
6mo
7o
24/ β zeolite.
Embodiment 46
Taking 3 gram particle degree is 40-60 purpose γ-Al
2o
3carrier, get (the NH of 0.38 gram
4)
6w
12o
39be dissolved in 3 ml deionized water, this solution is slowly splashed into to carrier and stirs, at room temperature flood 8 hours, then in the baking oven of 120 ℃ dry 12 hours, the gained catalyst precarsor was labeled as (NH
4)
6w
12o
39/ Al
2o
3.Embodiment 47
Taking 3 gram particle degree is 40-60 purpose SiO
2carrier, get (the NH of 0.38 gram
4)
6w
12o
39be dissolved in 3 ml deionized water, this solution is slowly splashed into to carrier and stirs, at room temperature flood 8 hours, then in the baking oven of 120 ℃ dry 12 hours, the gained catalyst precarsor was labeled as (NH
4)
6w
12o
39/ SiO
2.
Embodiment 48
Taking 3 gram particle degree is 40-60 purpose absorbent charcoal carrier, gets (the NH of 0.38 gram
4)
6w
12o
39be dissolved in 3 ml deionized water, this solution is slowly splashed into to carrier and stirs, at room temperature flood 8 hours, then in the baking oven of 120 ℃ dry 12 hours, the gained catalyst precarsor was labeled as (NH
4)
6w
12o
39/ C.
Embodiment 49
Taking 3 gram particle degree is 40-60 purpose ZSM-5 zeolite molecular sieve carrier, gets (the NH of 0.38 gram
4)
6w
12o
39be dissolved in 3 ml deionized water, this solution is slowly splashed into to carrier and stirs, at room temperature flood 8 hours, then in the baking oven of 120 ℃ dry 12 hours, the gained catalyst precarsor was labeled as (NH
4)
6w
12o
39/ ZSM-5.
Taking 3 gram particle degree is 40-60 purpose beta-zeolite molecular sieve carrier, gets (the NH of 0.38 gram
4)
6w
12o
39be dissolved in 3 ml deionized water, this solution is slowly splashed into to carrier and stirs, at room temperature flood 8 hours, then in the baking oven of 120 ℃ dry 12 hours, the gained catalyst precarsor was labeled as (NH
4)
6w
12o
39/ β zeolite.
Embodiment 51
Taking 3 gram particle degree is 40-60 purpose γ-Al
2o
3carrier, get the CrCl of 1.17 grams
36H
2o is dissolved in 3 ml deionized water, and this solution is slowly splashed into to carrier and stirs, and at room temperature floods 8 hours, and then in the baking oven of 120 ℃ dry 12 hours, the gained catalyst precarsor was labeled as CrCl
3/ Al
2o
3.
Embodiment 52
Taking 3 gram particle degree is 40-60 purpose SiO
2carrier, get the CrCl of 1.17 grams
36H
2o is dissolved in 3 ml deionized water, and this solution is slowly splashed into to carrier and stirs, and at room temperature floods 8 hours, and then in the baking oven of 120 ℃ dry 12 hours, the gained catalyst precarsor was labeled as CrCl
3/ SiO
2.
Embodiment 53
Taking 3 gram particle degree is 40-60 purpose absorbent charcoal carrier, gets the CrCl of 1.17 grams
36H
2o is dissolved in 3 ml deionized water, and this solution is slowly splashed into to carrier and stirs, and at room temperature floods 8 hours, and then in the baking oven of 120 ℃ dry 12 hours, the gained catalyst precarsor was labeled as CrCl
3/ C.
Embodiment 54
Taking 3 gram particle degree is 40-60 purpose ZSM-5 zeolite molecular sieve carrier, gets the CrCl of 1.17 grams
36H
2o is dissolved in 3 ml deionized water, and this solution is slowly splashed into to carrier and stirs, and at room temperature floods 8 hours, and then in the baking oven of 120 ℃ dry 12 hours, the gained catalyst precarsor was labeled as CrCl
3/ ZSM-5.Embodiment 55
Taking 3 gram particle degree is 40-60 purpose beta-zeolite molecular sieve carrier, gets the CrCl of 1.17 grams
36H
2o is dissolved in 3 ml deionized water, and this solution is slowly splashed into to carrier and stirs, and at room temperature floods 8 hours, and then in the baking oven of 120 ℃ dry 12 hours, the gained catalyst precarsor was labeled as CrCl
3/ β zeolite.
Embodiment 56
Taking 3 gram particle degree is 40-60 purpose γ-Al
2o
3carrier, get the Cd (NO of 0.41 gram
3)
24H
2zn (the NO of O and 0.59 gram
3)
26H
2o is dissolved in 3 ml deionized water, and this solution is slowly splashed into to carrier and stirs, and at room temperature floods 8 hours, and then in the baking oven of 120 ℃ dry 12 hours, the gained catalyst precarsor was labeled as Cd (NO
3)
2-Zn (NO
3)
2/ Al
2o
3.
Embodiment 57
Taking 3 gram particle degree is 40-60 purpose SiO
2carrier, get the Cd (NO of 0.41 gram
3)
24H
2zn (the NO of O and 0.59 gram
3)
26H
2o is dissolved in 3 ml deionized water, and this solution is slowly splashed into to carrier and stirs, and at room temperature floods 8 hours, and then in the baking oven of 120 ℃ dry 12 hours, the gained catalyst precarsor was labeled as Cd (NO
3)
2-Zn (NO
3)
2/ SiO
2.
Embodiment 58
Taking 3 gram particle degree is 40-60 purpose absorbent charcoal carrier, gets the Cd (NO of 0.41 gram
3)
24H
2zn (the NO of O and 0.59 gram
3)
26H
2o is dissolved in 3 ml deionized water, and this solution is slowly splashed into to carrier and stirs, and at room temperature floods 8 hours, and then in the baking oven of 120 ℃ dry 12 hours, the gained catalyst precarsor was labeled as Cd (NO
3)
2-Zn (NO
3)
2/ C.
Embodiment 59
Taking 3 gram particle degree is 40-60 purpose ZSM-5 zeolite molecular sieve carrier, gets the Cd (NO of 0.41 gram
3)
24H
2zn (the NO of O and 0.59 gram
3)
26H
2o is dissolved in 3 ml deionized water, and this solution is slowly splashed into to carrier and stirs, and at room temperature floods 8 hours, and then in the baking oven of 120 ℃ dry 12 hours, the gained catalyst precarsor was labeled as Cd (NO
3)
2-Zn (NO
3)
2/ ZSM-5.
Taking 3 gram particle degree is 40-60 purpose beta-zeolite molecular sieve carrier, gets the Cd (NO of 0.41 gram
3)
24H
2zn (the NO of O and 0.59 gram
3)
26H
2o is dissolved in 3 ml deionized water, and this solution is slowly splashed into to carrier and stirs, and at room temperature floods 8 hours, and then in the baking oven of 120 ℃ dry 12 hours, the gained catalyst precarsor was labeled as Cd (NO
3)
2-Zn (NO
3)
2/ β zeolite.
Embodiment 61
Respectively the load type metal salt sample obtained in embodiment 1 to 60 is placed in the quartz glass tube and the cavity between high-field electrode of plasma reactor (Fig. 1), passes into high-purity argon 5 minutes to remove the air in reactor.Control by mass flowmenter, make to pass through beds containing the argon gas mixed air of 10% hydrogen sulfide (also can adopt bright sulfur hydrogen, or hydrogen sulfide and other inert gases, or the gaseous mixture of hydrogen sulfide and hydrogen) with the flow of 80mL/min.Connect the plasma electrical source that connects high-pressure stage, by preparation condition as shown in table 1, make different loads type metal sulfide catalyst.
Table 1 prepares the reaction condition of different loads type metal sulfide catalyst
Prepared load type metal sulfide catalyst x-ray photoelectron power spectrum, X-ray diffraction and transmission electron microscope analysis can draw following analysis result:
The Cd of sulfide, only appearred belonging in x-ray photoelectron energy spectrogram as shown in Figure 2 as can be seen from Figure
2+and Zn
2+characteristic peak, show after slaine is by Cement Composite Treated by Plasma and generated metal sulfide;
Transmission electron microscope picture as shown in Figure 3 can find out in prepared load-type CdS and ZnS that the particle diameter of CdS and ZnS is tiny and be evenly distributed that particle diameter is the 5nm left and right;
X-ray diffraction spectrogram as shown in Figure 4 shows that the metal salt precursor of different carriers load is decomposed fully and generates load type metal sulfide after Cement Composite Treated by Plasma, all observe the diffraction maximum of its corresponding sulfide in spectrogram, there is no other impurity diffraction maximums.
Above-described embodiment has illustrated that the low temperature plasma method is a kind of method that effectively prepares load type metal sulfide.Those skilled in the art are fully aware of, can carry out some modifications and improvement to the present invention, for example, reactor, discharge type and electrode structure are improved, change the metal sulfide loading, be mixed with binary or multi-element metal sulfide by slaine, or metal sulfide is loaded on different materials and makes multiple loaded catalyst, etc.So, only otherwise leave spirit of the present invention, any modification that the present invention is carried out and improve all should be within the scope of the invention.Scope of the present invention proposes in claims.
Claims (10)
1. a method of utilizing low temperature plasma to prepare the load type metal sulfide catalyst, it is characterized in that: make hydrogen sulfide gas, hydrogen sulfide and inert gas mist or hydrogen sulfide and hydrogen mixed gas volume ionization by gas discharge, form equally distributed low temperature plasma; Wherein, slaine is carried on carrier and forms load type metal salt precursor, utilize this low temperature plasma and load type metal salt precursor direct interaction to generate the load type metal sulfide catalyst.
2. method according to claim 1, is characterized in that, the power supply that described gas discharge is used is AC power or dc source.
3. method according to claim 1 and 2, be further characterized in that, the slaine of described load type metal salt precursor is the formed salt of transition metal.
4. method according to claim 1 and 2, be further characterized in that, described load type metal sulfide catalyst is the first subgroup metallic element sulfide, the second subgroup metallic element sulfide, the 6th subgroup metallic element sulfide, the 7th subgroup metallic element sulfide, the 8th Main Group Metal Elements sulfide.
5. method according to claim 4, be further characterized in that, described load type metal sulfide catalyst is that the first subgroup metallic element sulfide is copper sulfide, silver sulfide, aurosulfo; The second subgroup metallic element sulfide is zinc sulphide, cadmium sulfide; The 6th subgroup metallic element sulfide is chromic sulfide, molybdenum sulfide, tungsten sulfide; The 7th subgroup metallic element sulfide is manganese sulfide; The 8th Main Group Metal Elements sulfide is iron sulfide, cobalt sulfide, nickel sulfide, palladium sulfide, platinum sulfide.
6. according to claim 1,2 or 5 described methods, be further characterized in that, described load type metal sulfide catalyst is binary or polynary load type metal sulfide catalyst.
7. according to claim 1,2,5,7 or 8 described methods, be further characterized in that, described load type metal sulfide catalyst is by the load type metal sulfide catalyst of metal and nonmetalloid modification and modification.
8. method according to claim 3, be further characterized in that, described load type metal sulfide catalyst is by the load type metal sulfide catalyst of metal and nonmetalloid modification and modification.
9. method according to claim 4, be further characterized in that, described load type metal sulfide catalyst is by the load type metal sulfide catalyst of metal and nonmetalloid modification and modification.
10. according to claim 1,2,5,7,8 or 9 described methods, be further characterized in that, described carrier is material with carbon element, oxide, porous material, comprises that one or more the mixing in active carbon, carbon molecular sieve, carbon fiber, CNT, fullerene, Graphene, magnesia, silica, cerium oxide, calcium oxide, titanium oxide, aluminium oxide, zirconia, zeolite molecular sieve, mesopore molecular sieve, mesoporous-microporous composite material, high-specific surface area large pore material is used.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101011664A (en) * | 2007-01-09 | 2007-08-08 | 大连理工大学 | Method for preparing metal phosphide hydrogenation refining catalyst by using hydrogen plasma reduction mehtod |
| CN102408095A (en) * | 2011-08-20 | 2012-04-11 | 大连理工大学 | Method of decomposing hydrogen sulfide for preparation of hydrogen and elemental sulfur |
| JP2013028843A (en) * | 2011-07-29 | 2013-02-07 | Kumamoto Univ | Method for producing transition metal sulfide |
-
2013
- 2013-10-17 CN CN201310489243.1A patent/CN103495427B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101011664A (en) * | 2007-01-09 | 2007-08-08 | 大连理工大学 | Method for preparing metal phosphide hydrogenation refining catalyst by using hydrogen plasma reduction mehtod |
| JP2013028843A (en) * | 2011-07-29 | 2013-02-07 | Kumamoto Univ | Method for producing transition metal sulfide |
| CN102408095A (en) * | 2011-08-20 | 2012-04-11 | 大连理工大学 | Method of decomposing hydrogen sulfide for preparation of hydrogen and elemental sulfur |
Non-Patent Citations (3)
| Title |
|---|
| ANJIE WANG ET AL.: "The Synthesis of Metal Phosphides: Reduction of Oxide Precursors in a Hydrogen Plasma", 《ANGEW.CHEM.》, vol. 120, 4 July 2008 (2008-07-04), pages 6141 - 6143 * |
| LU ZHAO ET AL.: "Hydrogen production via decomposition of hydrogen sulfide by synergy of non-thermal plasma and semiconductor catalysis", 《INTERNATIONAL JOURNAL OF HYDROGEN ENERGY》, vol. 38, 3 October 2013 (2013-10-03), pages 14415 - 14423 * |
| 王瑶 等: "过渡金属磷化物氢等离子体还原法制备及其加氢脱硫性能", 《大连理工大学学报》, vol. 51, no. 5, 30 September 2011 (2011-09-30), pages 625 - 630 * |
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