CN105753052A - Synthesis method of supported MoS2 catalyst - Google Patents
Synthesis method of supported MoS2 catalyst Download PDFInfo
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- CN105753052A CN105753052A CN201410775951.6A CN201410775951A CN105753052A CN 105753052 A CN105753052 A CN 105753052A CN 201410775951 A CN201410775951 A CN 201410775951A CN 105753052 A CN105753052 A CN 105753052A
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Abstract
The invention relates to a synthesis method of a supported MoS2 catalyst. The method comprises the following steps: preparing a macropore-mesopore-micropore composite hierarchical pore aluminum phosphate AFI molecular sieve carrier at normal pressure or a low authigenic pressure through adopting an ionothermal synthesis technology; and dipping the prepared hierarchical pore aluminum phosphate AFI molecular sieve carrier in a sulfur-containing mother liquor, drying the immersed carrier, and carrying out high temperature roasting to prepare the hierarchical pore molecular sieve supported MoS2 catalyst. The ionothermal synthesis technology has the advantages of recovery and repeated use of an ionic liquid, low synthesis cost, no discharge of acids, alkalis or waste liquids in the synthesis process, and environmental protection. The hierarchical pore molecular sieve supported MoS2 catalyst prepared in the invention has the advantages of large specific surface area, large pore volume, and potential application values in hydrodesulfurization, hydrocracking and other catalytic reactions.
Description
Technical field
The present invention relates to a kind of support type MoS2The synthetic method of catalyst, more particularly to a kind of MoS molecular sieve supported for multi-stage porous aluminum phosphate AFI2The synthetic method of catalyst.
Background technology
With the quick growth of China's economic, intermediate oil demand is continuously increased.And petroleum resources shortage at present, crude oil heaviness and in poor quality are day by day serious, and environmental requirement improves day by day, therefore develops efficient heavy oil transformation technology, and the fuel preparing cleaning is particularly important.Heavy oil transformation technology, adopts Co, Mo or Ni isoreactivity component to be carried on carrier more.Conventional carrier is generally aluminium oxide, silicon dioxide, micro porous molecular sieve and amorphous silica-alumina etc..The present invention relates to the MoS that a kind of multi-stage porous AFI structure is molecular sieve carried2The preparation of catalyst, carrier comprises foramen magnum-mesoporous-micropore, be therefore more beneficial for reactant diffusion and with the contacting of catalyst active center position, and then improve the activity of catalysis.
AFI structure aluminium phosphate molecular sieve (http://www.iza-structure.org/databases/) there is one-dimensional oval twelve-ring straight hole road, aperture size is 0.73nm × 0.73nm.LiBaojun (NewJ.Chem., 2014,38,3078 3083) reports the synthetic method of a kind of multi-stage porous AFI structure molecular sieve.DannyVerboekend (Chem.Mater.2014,26,4552-4562) reports utilization acid or AFI crystal is modified by alkali liquor, with the method preparing multi-stage porous AFI structure molecular sieve.But, said method is all the synthesis when hydro-thermal or alcohol heat, and some process also needs to add strong acid or strong basicity solvent.Crystallization of Zeolite process under high pressure carries out, and consersion unit investment is big, complex process, operating difficulties；Crystallization of Zeolite process needs to use organic formwork agent, expensive, is difficult to reclaim, and synthesis cost is high；After crystallization terminates, it is necessary to filtration washing zeolite product, the waste reaction solution of phosphoric acid and organic formwork agent, surfactant and Organic Alcohol etc. cannot reclaim, and environment directly causes after discharge severe contamination and harm.
Ion process for thermosynthesizing is a kind of novel Zeolite synthesis method, and it is that to adopt ionic liquid or low-temperature eutectic salt be reaction medium or a kind of synthetic method simultaneously as template, and ionic liquid is a kind of fusing point low temperature molten salt near room temperature.Ion thermal synthesis molecular sieve has plurality of advantages, as: Zeolite synthesis reaction can carry out in uncovered non-pressure vessel；There are great potentiality in the molecular sieve of synthesizing new structure and composition；Synthesis condition is gentle；Ionic liquid is recyclable, repeatable utilization, environmental friendliness etc..There are many documents about ion full-boiled process synthesis of molecular sieve and patent report at present.A kind of method of ion thermal synthesis aluminum phosphate or silicoaluminophosphamolecular molecular sieves disclosed in CN1850606A, this method ionic liquid is as reaction medium, add organic amine and control the crystallization process of molecular sieve as auxiliary template agent, thus improving the selectivity of purpose product.The preparation method that CN103318906 discloses the molecular screen membrane with AFI structure that a kind of Woelm Alumina supports.DamienYK (SolidStateSciences25 (2013) 63) reports the method preparation utilizing ion thermal synthesis and has the AFI structure molecular sieve of sheet-like morphology.Due to multi-stage porous composite molecular screen material, potential using value, the synthesis of current multi-stage porous molecular sieve, remain one of important research direction.But, up to now, the preparation method of multi-stage porous molecular sieve is not perfect, also without the report of ion thermal synthesis multi-stage porous AFI structure phosphate aluminium molecular sieve, and there is no multi-stage porous AFI molecular sieve as MoS2The report of carrier.
Micro porous molecular sieve system introducing mesoporous and macropore, prepares multi-stage porous composite molecular screen carrier, be more beneficial for absorption and the diffusion of reactant and product, it is possible to reducing catalyst carbon deposition, thus improving such MoS2The catalytic performance of catalyst.The present invention by, in macropore and mesoporous introducing AFI structure aluminium phosphate molecular sieve system, preparing multi-stage porous compound AFI structure phosphate aluminium molecular sieve carrier, adopts incipient impregnation method, by MoS by ion thermal synthesis method2Support on multi-stage porous molecular sieve carrier, prepare multi-stage porous load MoS2Catalyst, this catalyst can be used for the field such as heavy-oil hydrogenation and desulfurization.
Summary of the invention
It is an object of the invention to provide a kind of support type MoS2The synthetic method of catalyst, more particularly to a kind of MoS molecular sieve supported for multi-stage porous aluminum phosphate AFI2The synthetic method of catalyst, it is characterised in that adopting the synthetic method of ion heat to prepare the AFI molecular sieve carrier of foramen magnum-mesoporous-micropore compound, building-up process carries out at ambient pressure, and operating condition is gentle, and building-up process is discharged without acid-base waste fluid.And adopt equi-volume impregnating by MoS2Support on multi-stage porous AFI molecular sieve, to improving the catalytic performance such as catalyst hydrogenation and desulfurization.
For achieving the above object, the present invention adopts the following technical scheme that:
The synthetic method adopting ion heat prepares multi-stage porous AFI molecular sieve, then be impregnated in by sulphur-containing mother solution on prepared multi-stage porous molecular sieve carrier, and then the MoS that multi-stage porous is molecular sieve supported is prepared in drying and high-temperature roasting2Catalyst, building-up process includes:
A) multi-stage porous AFI molecular sieve is prepared: ionic liquid is warming up to 80-100 DEG C as raw material mixing temperature, phosphorous raw material, aluminum-containing raw material, organic amine and Fluohydric acid. raw material is added in ionic liquid, it is uniformly mixed to obtain precursor mixture, precursor mixture is heated, crystallization under normal pressure or self-generated pressure, crystallization temperature is 100 DEG C-200 DEG C, it is preferred that crystallization temperature is 150～200 DEG C；Crystallization time 10-600min, it is preferred that crystallization time is 1-5 hour.；After crystallization terminates, reactant mixture being cooled to room temperature, add water, filter, with water or ethanol, sample is washed, room temperature-120 DEG C dries, and the solid sample obtained is multi-stage porous AFI structure aluminium phosphate molecular sieve；Collect waste reaction solution, in Rotary Evaporators, the solvent of moisture therein and washing molecular sieve is steamed, reclaim ionic liquid.
Adopt X-ray powder diffraction that this molecular sieve structure is carried out structural analysis, determine its structure by comparing with XRD powder diffraction data storehouse.Utilize SEM and N2Physical absorption-desorption method determines hole type and distribution.
Al in precursor mixture2O3:P2O5: HF: organic amine: the ratio of ionic liquid (aluminum and phosphorus represent according to the form of its oxide) is 1:0.1～10:0.01～0.1:0.1～100:10～1000 for (mol ratio) molar ratio；Preferred Al2O3:P2O5: HF acid: organic amine: ionic liquid (aluminum and phosphorus represent according to the form of its oxide) be preferably in a proportion of (mol ratio) 1:0.5～5:0.05～0.5:0.1～5:5～100, described Fluohydric acid. mass concentration is 30%-50%.
The cation of above-mentioned synthetic method intermediate ion liquid be alkyl replace imidazol ion [Rim]+in one or two or more kinds, [Rim]+On replace alkyl be C1-C8 alkyl in one or two or more kinds, the anion of ionic liquid is: Br-, Cl-, I-, BF4 -、PO4 3-In one or two or more kinds；Phosphorous raw material adopts one or two or more kinds of phosphoric acid, ammonium phosphate, monoammonium phosphate and ammonium dihydrogen phosphate；Aluminum-containing raw material adopts one or two or more kinds of aluminum isopropylate., boehmite, hydrated alumina, aluminum sulfate and aluminum nitrate；Organic amine adopts 1,6-hexamethylene diamine, ethanolamine, Propanolamine, one or two or more kinds of morpholine and Methylimidazole..
Above-mentioned steps A) in preferred raw material mixing temperature be 80～100 DEG C；Preferred crystallization temperature is 150～200 DEG C, it is preferred that crystallization time is for being not less than 1 hour, and heating can adopt traditional thermal source mode of heating, as: baking oven for heating, oil bath is heated, it would however also be possible to employ microwave heating.
B) dipping and roasting, MoS2Support step as follows:
1. adopt incipient impregnation method, by four thio ammonium molybdate solution impregnation that concentration is 0.001g～10g/ml on synthesized multi-stage porous AFI molecular sieve carrier；
2. the catalyst room temperature after dipping is dried, transfer to 70 DEG C of vacuum drying ovens, vacuum drying；
3., by dried catalyst, it is placed in tube furnace, at N2Roasting under atmosphere, sintering temperature 200～600 DEG C, heats 0.5～24h, prepares MoS molecular sieve supported for multi-stage porous AFI2Catalyst.
The beneficial effect of this method:
The MoS that the multi-stage porous AFI structure aluminium phosphate molecular sieve of synthesis supports2Catalyst, carrier has micropore, mesoporous and macropore, it is simple to reactant mass transfer and with active center MoS2Haptoreaction, can be applicable to, in the hydro-conversion of heavy oil and poor oil, have good application prospect.Carrier building-up process adopts ion process for thermosynthesizing, and crystallization process can carry out under low vapor pressure at normal pressure or relatively, and reaction unit need not use high-pressure bottle, and process economics is strong, easy-to-operate；Not using the organic formwork agent of costliness in building-up process, ionic liquid can reclaim, and synthesis cost is low, and building-up process is discharged without soda acid, environmental friendliness.
Accompanying drawing explanation
Fig. 1 is powder X-ray diffraction (XRD) spectrogram of sample in the embodiment of the present invention 1.
Fig. 2 a is the XRD spectra of sample in the embodiment of the present invention 2, b be SEM photograph, c is physical absorption desorption isotherm.
Detailed description of the invention
The present invention is described further for below example, but the invention is not limited in below example, the aluminum-containing raw material in the present invention is only for aluminum isopropylate., but in practical operation, as long as meeting the condition of the present invention, use other several raw materials can also reach the effect of the present invention.
Embodiment 1
At 80 DEG C, being sequentially added into 1.5g phosphoric acid, 0.88g aluminum isopropylate., 0.4g ethanolamine and the Fluohydric acid. that 0.05g mass concentration is 40% mixes in 33g1-butyl-3-methy limidazolium ionic liquid, stirring obtains precursor mixture to uniform.Said mixture is transferred in the stainless steel cauldron with polytetrafluoro liner, it is then placed in crystallization in the baking oven of 150 DEG C, crystallization was taken out after 6 hours, cooling reactor, then adds 200ml deionized water, supersound washing by reactant mixture, reactant is filtered, obtain white solid, with deionized water repeated washing three times, and use 50ml washing with alcohol.Final white solid is placed in 110 DEG C of baking ovens and dries, finally give white powdery solids, determine through XRD, as shown in Figure 1, can observe the characteristic diffraction peak that 2 θ angles are 7.6,20.5,21.1 and 22.5 degree, it was shown that prepared sample is the former powder of AFI structure aluminium phosphate molecular sieve.Moisture in filtrate after washing and solvent are steamed by Rotary Evaporators, reclaims ionic liquid.
Embodiment 2
At 80 DEG C, being sequentially added into 1.8g phosphoric acid, 1.0g aluminum isopropylate., 0.5g ethanolamine and the Fluohydric acid. that 0.05g mass concentration is 40% mixes in 20g1-butyl-3-methy limidazolium ionic liquid, stirring obtains precursor mixture to uniform.Said mixture is transferred in the stainless steel cauldron with polytetrafluoro liner, it is then placed in crystallization in the baking oven of 160 DEG C, crystallization was taken out after 4 hours, cooling reactor, then adds 300ml deionized water, supersound washing by reactant mixture, reactant is filtered, obtain white solid, with deionized water repeated washing three times, and use 50ml washing with alcohol.Final white solid is placed in 110 DEG C of baking ovens and dries, finally give white powdery solids, determine through XRD test, as shown in Figure 2, can observe the characteristic diffraction peak that 2 θ angles are 7.6,20.5,21.1 and 22.5 degree, show that prepared sample is that the former powder of AFI structure aluminium phosphate molecular sieve utilizes SEM to can observe the cluster that the crystal accumulation that prepared sample is bar shaped becomes, have abundant macropore between crystal and mesoporous.Physical absorption-desorption curve, can observe the existence of hysteresis loop, it was demonstrated that prepared sample has mesoporous.Comprehensive XRD, SEM and physical absorption characterization result, it can be verified that product is multi-stage porous aluminum phosphate AFI molecular sieve.Moisture in filtrate after washing and solvent are steamed by Rotary Evaporators, reclaims ionic liquid.
Embodiment 3
By on multi-stage porous AFI molecular sieve carrier synthesized in 0.4 gram of embodiment 2 for the four thio ammonium molybdate solution impregnation that 0.5ml concentration is 0.01g/ml.Catalyst room temperature after dipping is dried, transfers to 70 DEG C of vacuum drying ovens, dry 4 hours.By dried catalyst, it is placed in tube furnace, at N2When purging, it is warming up to 450 DEG C, keeps 8h, prepare MoS molecular sieve supported for multi-stage porous AFI2Catalyst.
Claims (10)
1. a support type MoS2The synthetic method of catalyst, it is characterised in that: detailed process is: preparation sulphur-containing mother solution, and sulphur-containing mother solution adopts equi-volume impregnating impregnated on prepared multi-stage porous AFI molecular sieve carrier, and dry roasting prepares MoS molecular sieve supported for multi-stage porous AFI2Catalyst.
2. the synthetic method described in claim 1, it is characterized in that: adopt the synthetic method of ion heat to prepare multi-stage porous AFI molecular sieve, detailed process is: at 80～100 DEG C, phosphorous raw material, aluminum-containing raw material, organic amine and Fluohydric acid. is added in ionic liquid, stir to obtain precursor mixture, by prepared precursor mixture heating crystallization, after crystallization terminates, separate solid product and obtain multi-stage porous AFI structure aluminium phosphate molecular sieve.
3. the synthetic method described in claim 2, it is characterised in that: (aluminium element and P elements represent according to the form of its oxide) Al in precursor mixture2O3:P2O5: Fluohydric acid.: organic amine: the molar ratio of ionic liquid is 1:0.1～10:0.001～1.0:0.1～100:0.1～1000；Preferred molar ratio example is 1:0.5～5:0.05～0.5:0.1～5:5～100；Described Fluohydric acid. mass concentration is 30%-50%.
4. the synthetic method described in claim 2, it is characterised in that: the cation of ionic liquid is the imidazol ion [Rim] that alkyl replaces+In one or two or more kinds, [Rim]+On replace alkyl be C1-C8 alkyl in one or two or more kinds；The anion of ionic liquid is: Br-、Cl-、I-、BF4 -、PO4 3-In one or two or more kinds.
5. the synthetic method described in claim 2, it is characterised in that: phosphorous raw material is one or two or more kinds of phosphoric acid, ammonium phosphate, monoammonium phosphate and ammonium dihydrogen phosphate.
6. the synthetic method described in claim 2, it is characterised in that: aluminum-containing raw material is one or two or more kinds of aluminum isopropylate., boehmite, hydrated alumina, aluminum sulfate and aluminum nitrate.
7. the synthetic method described in claim 2, it is characterised in that: organic amine is 1,6-hexamethylene diamine, ethanolamine, Propanolamine, one or two or more kinds of morpholine and Methylimidazole..
8. the synthetic method described in claim 2, it is characterised in that: crystallization temperature is 100 DEG C-200 DEG C, it is preferred that crystallization temperature is 150～200 DEG C；Crystallization time 10-600min, it is preferred that crystallization time is 1-5 hour.
9. the synthetic method described in claim 1, it is characterised in that: sulphur-containing mother solution is four thio ammonium molybdate solution, and concentration is 0.001g～10g/ml.
10. the synthetic method described in claim 1, it is characterised in that: sintering temperature is 200～600 DEG C, and roasting time is 0.5～24h；Roasting needs at N2Carry out under atmosphere.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106622298A (en) * | 2016-11-15 | 2017-05-10 | 天津大学 | Layered multi-metal molybdenum sulfide catalyst and preparation method |
| CN111057030A (en) * | 2019-12-03 | 2020-04-24 | 天津大学 | Preparation method and application of hydrotalcite-based sulfide catalyst for synthesizing gamma-valerolactone |
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| CN1850606A (en) * | 2006-06-07 | 2006-10-25 | 中国科学院大连化学物理研究所 | Method for preparing AlPO4 or SAPO molecular sieve |
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| JPH0226642A (en) * | 1988-05-19 | 1990-01-29 | Shell Internatl Res Maatschappij Bv | Manufacture of catalyst particle and catalyst particle produced thereby |
| CN1850606A (en) * | 2006-06-07 | 2006-10-25 | 中国科学院大连化学物理研究所 | Method for preparing AlPO4 or SAPO molecular sieve |
| CN101417247A (en) * | 2007-10-26 | 2009-04-29 | 中国石油化工股份有限公司 | Porous propping agent combination and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106622298A (en) * | 2016-11-15 | 2017-05-10 | 天津大学 | Layered multi-metal molybdenum sulfide catalyst and preparation method |
| CN111057030A (en) * | 2019-12-03 | 2020-04-24 | 天津大学 | Preparation method and application of hydrotalcite-based sulfide catalyst for synthesizing gamma-valerolactone |
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