CN103551181B - Binary RuS 2the preparation method of heterogeneous catalyst - Google Patents
Binary RuS 2the preparation method of heterogeneous catalyst Download PDFInfo
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- CN103551181B CN103551181B CN201310571564.6A CN201310571564A CN103551181B CN 103551181 B CN103551181 B CN 103551181B CN 201310571564 A CN201310571564 A CN 201310571564A CN 103551181 B CN103551181 B CN 103551181B
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Abstract
The present invention discloses a kind of binary RuS
2the preparation method of heterogeneous catalyst, belongs to ruthenium catalyst preparing technical field.This catalyst is made up of carrier and active component, and carrier is ZSM-5, SBA-15, γ-Al
2o
3and SiO
2in any one, active component is Ru, by RuCl
33H
2o is dissolved in ethanol, is put into by carrier wherein, is uniformly mixed post-drying, then puts into autoclave Program and is warming up to 200 ~ 220 DEG C and carries out presulfurization, the black solid obtained is put into vacuum drying chamber and dry obtained binary RuS after presulfurization
2catalyst.The inventive method simple possible, reaction condition is gentle, prepared binary RuS
2catalyst particle purity is higher, and shows higher catalytic activity in rhohene desulfiirization process, can realize suitability for industrialized production.
Description
Technical field:
The invention belongs to ruthenium catalyst preparing technical field, be specifically related to a kind of oxide carried binary RuS
2the preparation method of heterogeneous catalyst.
Background technology:
Fossil fuel can produce the sulfur-containing compound easily causing environmental pollution in a large number in combustion, therefore, reduces the main direction of studying that sulfur content (lower than 10ppm) has become current desulfurization and sulphur removal work further.Current industrial main employing Al
2o
3hydrodesulfurization (HDS) is carried out, to remove the sulfide in fossil fuel etc. metal formation different-phase catalysts such as oxide carried nickel (Ni), cobalt (Co), molybdenums (Mo).Wherein, nickel (cobalt)/molybdenum catalyst is considered to one of most important catalyst in industry always, and RuS
2being the catalyst that in transient metal sulfide, Investigation On Hydrodesulfurizationof of Catalysts Derived is the highest, is MoS
2the substitute that catalyst is best.Experiment proves RuS
2be the metal sulfide that uniquely can make to generate dibenzothiophenes hydrodesulfurization cyclohexylbenzene, main cause is RuS
2hydrogenation character different with other sulfide, this character makes RuS
2catalytic activity compares MoS in the hydrogenation of biphenyl
2or WS
2exceed about five times, therefore, RuS
2catalyst effectively can remove the sulfide in fuel.In recent years, the research about preparation sulfuration ruthenium nanostructured achieves tremendous development.Chinese patent CN1693215A discloses a kind of porous sulfuration ruthenium nanosphere and preparation method thereof, and the method prepares sulfuration ruthenium nanosphere mainly through porous material.Chinese patent CN1693216A discloses a kind of method for making of vulcanized sodium nano particle, and the method mainly uses Ultrasonic Radiation to prepare vulcanized sodium particle.
The synthesis of sulfuration ruthenium has multiple method, and the most frequently used mode is by pure H
2s gas passes into containing RuCl
3suspension in, the solid obtained is at pure H
2further sulfuration in S gas, sulfuration terminates rear drying.The preparation of ruthenium sulphide catalyst is generally with RuCl
33H
2o, Ru (NH
3) Cl
6, Ru
3(CO)
12deng as base stock, with SiO
2, γ-Al
2o
3deng as carrier.To prepare RuS
2/ γ-Al
2o
3catalyst is example, RuCl
33H
2o (7wt%Ru) is dissolved in the water of 2.5 volume multiples, adds γ-Al
2o
3after the suspension that obtains stirring at room temperature 24 hours under nitrogen protection, gained catalyst is first at room temperature dry remove liquid, then drying 24 hours in the baking oven of 110 DEG C.In order to better to rhohene desulfiirization, can need at 15ml/minH before this kind of catalyst use
2s (15%)/N
2at different temperature (300 DEG C, 400 DEG C, 500 DEG C, 700 DEG C), presulfurization 2 hours are carried out (see HarveyTG in atmosphere, MathesonTW.Hydroprocessingcatalysisbysupportedrutheniums ulphide [J] .JournalofCatalysis.1986,101:253-261).
Due to H in above-mentioned preparation method
2s is strong neurotoxin, and H
2s gas is serious pollutant, does not industrially generally adopt it as industrial chemicals, and in addition because reaction condition is harsher, observable index is higher, and therefore the method is not suitable for carrying out suitability for industrialized production.
Summary of the invention:
The present invention is directed to the above-mentioned technical problem that prior art exists, a kind of binary RuS is provided
2the preparation method of heterogeneous catalyst.
Binary RuS provided by the present invention
2the preparation method of heterogeneous catalyst, wherein said binary RuS
2heterogeneous catalyst is made up of carrier and active component; Described carrier is ZSM-5, SBA-15, γ-Al
2o
3and SiO
2in any one; Described active component is Ru; Described binary RuS
2the concrete preparation process of heterogeneous catalyst is as follows:
By RuCl
33H
2o is dissolved in ethanol, described carrier is put into wherein, stir 22 ~ 26h and mix post-drying, then put into autoclave Program to be warming up to 200 ~ 220 DEG C and to carry out presulfurization, the black solid obtained after presulfurization is put into vacuum drying chamber to dry, the black solid powder of gained is target product of the present invention: binary RuS
2catalyst.
Described binary RuS
2the mass percent of the active component Ru in catalyst is (1.16 ~ 6.44) %.
Described binary RuS
2carrier ZSM-5, SBA-15, γ-Al in catalyst
2o
3and SiO
2granularity be respectively: ZSM-5:80 ~ 100 order, SBA-15:120 ~ 140 order, γ-Al
2o
3: 40 ~ 60 orders, SiO
2: 30 ~ 50 orders.
By obtained binary RuS
2autoclave put into by catalyst, is solvent with ethanol, adds 0.2g thiophene and carries out desulphurization reaction; Reaction terminates rear sampling by gas chromatographic detection and calculates the conversion ratio of thiophene.
The present invention has following technical characterstic:
(1) the binary RuS for preparing of the present invention
2catalyst is through XRD determining, there is no obvious XRD diffraction maximum, be indicated as amorphous state, but carry out XRD test again after 450 DEG C of calcinings, then become crystalline structure, (MDIJade is all mated in the position at peak with literature value with intensity, Fileno.73-1677.), do not find dephasign peak, show that the purity of sample is higher, and the curing ruthenium catalyst particle average grain diameter of crystalline form is at 12.5nm ~ 32.4nm.
(2) preparation binary RuS provided by the present invention
2the method simple possible of catalyst, reaction condition is gentle, the binary RuS of preparation
2catalyst particle purity is higher, and shows higher catalytic activity in rhohene desulfiirization process, can realize suitability for industrialized production.
Accompanying drawing illustrates:
Fig. 1 is amorphous RuS of the present invention
2the XRD figure of catalyst, with RuS
2/ ZSM-5 is example, and wherein Ru (wt%) is 5.04%.
Fig. 2 is amorphous RuS of the present invention
2catalyst is schemed through the XRD of 450 DEG C of calcinings after 4 hours, with RuS
2/ ZSM-5 is example, and wherein Ru (wt%) is 5.04%.
Detailed description of the invention:
Below in conjunction with specific embodiment, more detailed description is carried out to the present invention.
Embodiment 1: binary RuS
2the preparation of/ZSM-5 catalyst and hydrodesulfurization activity thereof.Accurately take the RuCl of 15mg
33H
2the ZSM-5 of O and 485mg is placed in the single necked round bottom flask (Ru (wt%) is 1.16%) of 25mL, adds 10mL ethanol, and stirred at ambient temperature 24h final vacuum is dry.In the autoclave that band stirs, add the above-mentioned catalyst of having dried, (its cyclohexane is solvent to add 17mL cyclohexane and 3mL carbon disulfide again, carbon disulfide is the sulphur source in presulfurization), off-response still, with the air in nitrogen replacement reaction kettle at least three times, use nitrogen in hydrogen exchange reactor more at least three times, then Hydrogen Vapor Pressure in reactor is regulated to 2MPa, to carry out rapid stirring, be heated to 200 DEG C (temperature programming 3 DEG C/min) and maintain 4h.After reaction terminates, treat that autoclave is cooled to room temperature, with ethanol washing several, vacuum drying chamber is dried, and gained black solid powder i.e. institute wants RuS
2catalyst.
In the autoclave that band stirs, add above-mentioned binary RuS
2catalyst, solvent is ethanol (25mL), add 0.2g thiophene, off-response still, with the air in nitrogen replacement reaction kettle at least three times, then use nitrogen in hydrogen exchange reactor at least three times, adjustment Hydrogen Vapor Pressure is 2MPa, carry out rapid stirring, be heated to 250 DEG C (temperature programming 4 DEG C/min) and maintain 24h.After reaction terminates, be cooled to until autoclave and get product after room temperature and carry out gas phase analysis, thiophene conversion ratio is in table 1.
The XRD result (see accompanying drawing 1) of above-mentioned institute controlling catalyst shows, sample before calcining does not have obvious XRD diffraction maximum, for impalpable structure, but show that it is crystalline structure through the sample XRD result (see accompanying drawing 2) of 450 DEG C of calcinings after 4 hours, (MDIJade is all mated in the position at peak with literature value with intensity, Fileno.73-1677.), and do not find dephasign peak, show that the purity of sample is higher, and the curing ruthenium catalyst particle average grain diameter of crystalline form is at 12.5nm ~ 32.4nm.
Embodiment 2: binary RuS
2the preparation of/SBA-15 catalyst and hydrodesulfurization activity thereof.Accurately take the RuCl of 15mg
33H
2the SBA-15 of O and 485mg is placed in the single necked round bottom flask of 25mL, adds 10mL ethanol, then stirred at ambient temperature 24h, and vacuum drying chamber is dried.Other conditions and method are with embodiment 1.Prepared catalyst to the conversion ratio of thiophene in table 1.
Embodiment 3: binary RuS
2/ γ-Al
2o
3the preparation of catalyst and hydrodesulfurization activity thereof.Accurately take the RuCl of 15mg
33H
2γ-the Al of O and 485mg
2o
3be placed in the single necked round bottom flask of 25mL, add 10mL ethanol, then stirred at ambient temperature 24h, vacuum drying chamber is dried.Other conditions and method are with embodiment 1.Prepared catalyst to the conversion ratio of thiophene in table 1.
Embodiment 4: binary RuS
2/ SiO
2the preparation of catalyst and hydrodesulfurization activity thereof.Accurately take the RuCl of 15mg
33H
2the SiO of O and 485mg
2be placed in the single necked round bottom flask of 25mL, add 10mL ethanol, then stirred at ambient temperature 24h, vacuum drying chamber is dried.Other conditions and method are with embodiment 1.Prepared catalyst to the conversion ratio of thiophene in table 1.
Table 1 catalyst hydrodesulfurization active
| Embodiment | Carrier | Ru content (wt%) | Thiophene conversion ratio (%) |
| Embodiment 1 | ZSM-5 | 1.16 | 57.61 |
| ZSM-5 | 1.84 | 61.47 | |
| ZSM-5 | 2.7 | 63.12 | |
| ZSM-5 | 3.51 | 69.43 | |
| ZSM-5 | 3.87 | 70.3 | |
| ZSM-5 | 5.04 | 81.65 | |
| ZSM-5 | 6.44 | 75.94 | |
| Embodiment 2 | SBA-15 | 1.16 | 50.12 |
| SBA-15 | 1.84 | 52.24 | |
| SBA-15 | 2.7 | 54.64 | |
| SBA-15 | 3.51 | 58.15 | |
| SBA-15 | 3.87 | 60.12 | |
| SBA-15 | 5.04 | 62.45 | |
| SBA-15 | 6.44 | 85.73 | |
| Embodiment 3 | γ-Al 2O 3 | 1.16 | 60.14 |
| γ-Al 2O 3 | 1.84 | 68.14 | |
| γ-Al 2O 3 | 2.7 | 71.43 | |
| γ-Al 2O 3 | 3.51 | 74.15 | |
| γ-Al 2O 3 | 3.87 | 80.12 | |
| γ-Al 2O 3 | 5.04 | 82.52 | |
| γ-Al 2O 3 | 6.44 | 79.72 | |
| Embodiment 4 | SiO 2 | 1.16 | 40.12 |
| SiO 2 | 1.84 | 42.65 | |
| SiO 2 | 2.7 | 45.64 | |
| SiO 2 | 3.51 | 54.12 | |
| SiO 2 | 3.87 | 56.13 | |
| SiO 2 | 5.04 | 53.57 | |
| SiO 2 | 6.44 | 51.18 |
Claims (2)
1. a binary RuS
2the preparation method of heterogeneous catalyst, described binary RuS
2heterogeneous catalyst is made up of carrier and active component; Described carrier is ZSM-5, SiO
2in any one; Described active component is Ru, and the mass percent of described active component Ru is 1.16 ~ 6.44%; Described binary RuS
2the concrete preparation process of heterogeneous catalyst is as follows:
By RuCl
33H
2o is dissolved in ethanol, described carrier is put into wherein, stir 22 ~ 26h and mix post-drying, then autoclave is put into, take cyclohexane as solvent, carbon disulfide is sulphur source, and presulfurization is carried out in temperature programming to 200 ~ 220 DEG C, the black solid obtained after presulfurization is put into vacuum drying chamber to dry, the black solid powder of gained is binary RuS
2heterogeneous catalyst.
2. a kind of binary RuS according to claim 1
2the preparation method of heterogeneous catalyst, is characterized in that described binary RuS
2carrier ZSM-5, SiO in heterogeneous catalyst
2granularity be respectively: ZSM-5:80 ~ 100 order, SiO
2: 30 ~ 50 orders.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1693215A (en) * | 2005-03-31 | 2005-11-09 | 南京大学 | Multipore ruthenium sulfide nanoball and its preparation process |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1693215A (en) * | 2005-03-31 | 2005-11-09 | 南京大学 | Multipore ruthenium sulfide nanoball and its preparation process |
Non-Patent Citations (1)
| Title |
|---|
| TPR-S analysis of the catalytic behavior of Ru/Al2O3 catalysts in industrial conditions;Perla Castillo-Villalon, et al.;《Catalysis Today》;20050822;第107-108卷;第913-919页 * |
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