CN103551181A

CN103551181A - Preparation method of binary RuS2 heterogeneous catalyst

Info

Publication number: CN103551181A
Application number: CN201310571564.6A
Authority: CN
Inventors: 赵强; 张千峰; 贾爱铨; 辛志峰
Original assignee: Anhui University of Technology AHUT
Current assignee: Anhui University of Technology AHUT
Priority date: 2013-11-13
Filing date: 2013-11-13
Publication date: 2014-02-05
Anticipated expiration: 2033-11-13
Also published as: CN103551181B

Abstract

The invention discloses a preparation method of a binary RuS2 heterogeneous catalyst, and belongs to the technical field of preparation of a ruthenium catalyst. The catalyst consists of a carrier and an active ingredient, wherein the carrier is any one of ZSM-5, SBA-15, gamma-Al2O3 and SiO2, and the active ingredient is Ru; the preparation method comprises the steps of dissolving RuCl3.3H2O in ethanol, adding the carrier to the ethanol, stirring, uniformly mixing and drying, implementing temperature programming in a high-pressure reaction kettle to 200-220 DEG C, prevulcanizing and drying a prevulcanized black solid in a vacuum drying oven to obtain the binary RuS2 catalyst. The method is simple and feasible, and moderate in reaction condition; and the prepared binary RuS2 catalyst is relatively high in particle granularity and shows a relatively high catalytic activity in a thiofuran desulfurization process, so that binary RuS2 catalyst can realize industrial production.

Description

Binary RuS 2the preparation method of heterogeneous catalyst

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 that easily causes in a large number environmental pollution in combustion process, therefore, further reduces the main direction of studying that sulfur content (lower than 10ppm) has become current desulfurization and sulphur removal work.Current industrial main employing Al ₂o ₃etc. metal formation different-phase catalysts such as oxide carried nickel (Ni), cobalt (Co), molybdenums (Mo), carry out hydrodesulfurization (HDS), to remove the sulfide in fossil fuel.Wherein, nickel (cobalt)/molybdenum catalyst is considered to one of most important catalyst in industry always, and RuS ₂being the highest catalyst of Investigation On Hydrodesulfurizationof of Catalysts Derived in transient metal sulfide, is MoS ₂the substitute that catalyst is best.Experiment has proved RuS ₂be unique metal sulfide that makes dibenzothiophenes hydrodesulfurization generate cyclohexylbenzene, main cause is RuS ₂hydrogenation character different with other sulfide, this character makes RuS ₂in to the hydrogenation of biphenyl, catalytic activity compares MoS ₂or WS ₂exceed approximately five times, therefore, RuS ₂catalyst can effectively be removed the sulfide in fuel.In recent years, the research about preparation sulfuration ruthenium nanostructured has obtained tremendous development.Chinese patent CN1693215A discloses a kind of porous sulfuration ruthenium nanosphere and preparation method thereof, and the method is mainly prepared sulfuration ruthenium nanosphere by porous material.Chinese patent CN1693216A discloses a kind of method for making of vulcanized sodium nano particle, and the method is mainly to use Ultrasonic Radiation to prepare vulcanized sodium particle.

The synthetic of sulfuration ruthenium has a several different methods, and the most frequently used mode is by pure H ₂s gas passes into and contains RuCl ₃suspension in, the solid obtaining is at pure H ₂further sulfuration in S gas, sulfuration finishes rear dry.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.With preparation 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 24 hours under nitrogen protection, gained catalyst is first at room temperature dry to remove liquid, then in the baking oven of 110 ℃ dry 24 hours.For can be better to thiophene desulfurization, this class catalyst need to be at 15ml/min H before using ₂s (15%)/N ₂in atmosphere, at different temperature (300 ℃, 400 ℃, 500 ℃, 700 ℃), carry out presulfurization about 2 hours (referring to Harvey T G, Matheson T W.Hydroprocessing catalysis by supported ruthenium sulphide[J] .Journal of Catalysis.1986,101:253-261).

In above-mentioned preparation method due to H ₂s is strong neurotoxin, and H ₂s gas is serious pollutant, does not industrially generally adopt it as industrial chemicals, and because reaction condition is harsher, energy consumption is higher in addition, so 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 consists of carrier and active component; Described carrier is ZSM-5, SBA-15, γ-Al ₂o ₃and SiO ₂in any; 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 putting into autoclave Program is warming up to 200～220 ℃ and carries out presulfurization, the black solid obtaining after presulfurization is put into vacuum drying chamber and dry, the black solid powder of gained is target product of the present invention: binary RuS ₂catalyst.

Described binary RuS ₂the mass percent of active component Ru in catalyst is (1.16～6.44) %.

Described binary RuS ₂carrier ZSM-5, SBA-15 in catalyst, γ-Al 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 the binary RuS making ₂catalyst is put into autoclave, take ethanol as solvent, adds 0.2g thiophene to carry out desulphurization reaction; Reaction finishes rear sampling by gas chromatographic detection and calculates the conversion ratio of thiophene.

The present invention has following technical characterstic:

(1) the binary RuS that prepared by the present invention ₂catalyst is through XRD determining, there is no obvious XRD diffraction maximum, be indicated as amorphous state, but after 450 ℃ of calcinings, carry out XRD test again, become crystalline structure, (MDI Jade is all mated with intensity in the position at peak with literature value, File no.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 thiophene sweetening process, can realize suitability for industrialized production.

Accompanying drawing explanation:

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 the XRD figure after 4 hours through 450 ℃ of calcinings, with RuS ₂/ ZSM-5 is example, and wherein Ru (wt%) is 5.04%.

The specific embodiment:

Below in conjunction with specific embodiment, the present invention is carried out to more detailed description.

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, stirs 24h final vacuum dry under room temperature.In the autoclave stirring at band, add the above-mentioned catalyst of having dried, (wherein cyclohexane is solvent to add 17mL cyclohexane and 3mL carbon disulfide again, carbon disulfide is the sulphur source in presulfurization), off-response still, the air in use nitrogen replacement reactor at least three times, use again nitrogen in hydrogen exchange reactor at least three times, then regulate Hydrogen Vapor Pressure in reactor to 2MPa, to carry out rapid stirring, be heated to 200 ℃ (3 ℃/min of temperature programming) and maintain 4h.After reaction finishes, treat that autoclave is cooled to room temperature, with ethanol washing for several times, vacuum drying chamber is dried, and gained black solid powder i.e. the RuS that wants ₂catalyst.

In the autoclave stirring at band, add above-mentioned binary RuS ₂catalyst, solvent is ethanol (25mL), add 0.2g thiophene, off-response still, with the air in nitrogen replacement reactor at least three times, then use nitrogen in hydrogen exchange reactor at least three times, adjusting Hydrogen Vapor Pressure is 2MPa, carry out rapid stirring, be heated to 250 ℃ (4 ℃/min of temperature programming) and maintain 24h.After reaction finishes, get product and carry out gas phase analysis after autoclave is cooled to room temperature, thiophene conversion ratio is in Table 1.

The XRD result (seeing accompanying drawing 1) of above-mentioned institute controlling catalyst shows, sample before calcining does not have obvious XRD diffraction maximum, for impalpable structure, but the sample XRD result (seeing accompanying drawing 2) through 450 ℃ of calcinings after 4 hours shows that it is crystalline structure, (MDI Jade is all mated with intensity in the position at peak with literature value, File no.73-1677.), and do not find dephasign peak, the purity that shows 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 under room temperature, stirs 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-Al of O and 485mg ₂o ₃be placed in the single necked round bottom flask of 25mL, add 10mL ethanol, then under room temperature, stir 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 under room temperature, stir 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

1. a binary RuS ₂the preparation method of heterogeneous catalyst, described binary RuS ₂heterogeneous catalyst consists of carrier and active component; Described carrier is ZSM-5, SBA-15, γ-Al ₂o ₃and SiO ₂in any; Described active component is Ru; Described binary RuS ₂the concrete preparation process of heterogeneous catalyst is as follows:

2. a kind of binary RuS according to claim 1 ₂the preparation method of catalyst, is characterized in that described binary RuS ₂the mass percent of active component Ru in catalyst is (1.16～6.44) %.

3. a kind of binary RuS according to claim 1 ₂the preparation method of catalyst, is characterized in that described binary RuS ₂carrier ZSM-5, SBA-15 in catalyst, γ-Al 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.