CN103349995A - Hydrodesulfurization catalyst taking micro and mesoporous composite molecular sieve as carrier and preparation method thereof - Google Patents
Hydrodesulfurization catalyst taking micro and mesoporous composite molecular sieve as carrier and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a hydrodesulfurization catalyst taking a micro and mesoporous composite molecular sieve as a carrier. The catalyst takes the micro and mesoporous composite molecular sieve ZK-1 as the carrier and at least VIII metal and at least VIB metal as active constituents. A preparation method for the catalyst comprises the following steps: adding an aluminum source into a tetrapropylammonium hydroxide water solution and dropwise adding a silicon source; mixing a mixture with a hexadecyl trimethyl ammonium bromide water solution, crystallizing, and filtering and drying a solid matter to obtain the micro and mesoporous composite molecular sieve ZK-1 carrier; dissolving soluble metal salt of metal in de-ionized water to prepare a metal salt solution; dipping the carrier into the metal salt solution to prepare the hydrodesulfurization catalyst. The micro and mesoporous composite molecular sieve ZK-1 has a pore canal structure combining a three-dimensional short wormlike mesoporous canal with a ZSM-5 microporous canal and has the characteristics of large specific surface, moderate acidity, good hydrothermal stability and the like; the prepared hydrodesulfurization catalyst is large in specific surface area, rich in pore canals and high in dispersity of metal active constituents, and can be used for effectively removing macromolecular sulfur-containing compounds under milder reaction conditions.
Description
Technical field
The present invention relates to a kind ofly make Hydrobon catalyst of carrier and preparation method thereof with Jie's mesoporous-microporous composite molecular sieve new material, belong to petroleum refining and PETROLEUM PROCESSING and catalyst technical field.
Background technology
At present, along with day by day increasing the weight of of environmental pollution, producing low-sulfur or super low-sulfur oil and diesel oil has become the inexorable trend that day by day harsh environmental regulation is satisfied in modern refinery industry.Desulfur technology mainly contains hydrodesulfurization, oxidation sweetening, adsorption desulfurize etc., and wherein hydrodesulfurization technology (HDS) is present industrial most widely used, the most ripe technology.The degree of depth that improves hydrodesulfurization can reduce reaction velocity by improving reaction temperature, reconstructs reactor or adopts more highly active catalyst several respects to set about.Because front several modes can produce the increase energy consumption, reduce treating capacity, increase the various problems such as investment, therefore developing more highly active catalyst becomes effective means.
The research work of depth H DS catalyst mainly is from selecting suitable carrier, improve the loading method of active component and screening the higher component three aspects: expansion of activity.The three is isolated cutting apart, but interpenetrate, a complementary integral body.Carrier is one of chief component of catalyst, plays a part skeleton and support in catalyst, and affect the character of active component, the reactivity worth of regulating catalyst by the interaction with the active component of load; Simultaneously for reaction provides the place, and participate in catalytic reaction directly to a certain extent, therefore select good carrier to play vital effect to preparing high-performance HDS catalyst.
Hydrobon catalyst the most frequently used carrier be γ-A1
2O
3With γ-A1
2O
3The HDS catalyst of doing carrier preparation has good mechanical stability, the advantage such as renewable, with low cost.But, γ-A1
2O
3And very strong interaction is arranged between transition metal oxide, be unfavorable for the HDS reaction.With the zeolite as carrier Kaolinite Preparation of Catalyst, its stronger acidity can promote Methyl transporters or demethylation on the aromatic ring, be conducive to improve the activity of catalyst and reactant, yet the aperture of zeolite is less, suppressed the diffusion of large molecule in the duct, its hydrogenation cracking activity is too high in addition, the easy coking and deactivation of catalyst.In recent years, more and more (the CN 1306885A of research that prepare the HDS catalyst take mesoporous materials such as MCM-41, SBA-15 as carrier, CN 101058074A, CN 101590425A etc.) their high-specific surface area is conducive to the dispersion of metal active constituent, the larger mesoporous diffusion that is conducive to macromolecule substrate.But its unbodied hole wall causes its hydrothermal stability relatively poor, has limited it in industrial application.It is acid strong that mesoporous-microporous composite molecular screen has had micro porous molecular sieve concurrently, and the duct advantage of good hydrothermal stability and mesopore molecular sieve is once researcher's extensive concern occurring just having caused.There is research to think [Catal. Today, 2010,150 (3-4): 218-223; J.Catal., 2010,274(2): 273-286], for some Jie's mesoporous-microporous composite molecular sieve, because its micropore has higher absorption potential to hydrogen molecule, but the efficient adsorption hydrogen molecule, and be delivered to mesoporous part by the duct that is communicated with and carry out selective hydrodesulfurization with thiophenic sulfur, the efficient adsorption of hydrogen can reduce the required temperature and pressure of HDS process, can realize the ultra-deep desulfurization of fuel oil under the operating condition of gentleness, greatly reduces energy consumption of reaction.ZK-1(ZSM-5/KIT-1) Jie's mesoporous-microporous composite molecular sieve is a kind of new multistage porous molecular sieve material (Micropor.Mesopor.Mater. that the inventor synthesizes, 2009,123:221-227.), it has large specific area, the pore passage structure that the ZSM-5 micropore canals combines with the three-dimensional short worm meso-porous duct of KIT-1, suitable acidity and good hydrothermal stability boil 5d in 100 ℃ of boiling water or 700 ℃ of pure water vapour processing 2h still can keep the microcellular structure that is situated between preferably.The ZK-1 molecular sieve utilizes one step of double template crystallization method Hydrothermal Synthesis, and its structure and pattern can be by changing the factor controllings such as crystallization temperature, crystallization time and template ratio.At first, the synthetic used aluminium source of ZK-1 molecular sieve is aluminium isopropoxide, need to dissolve under the ice-water bath condition, and dissolution velocity is slower.In order to be beneficial to the industry amplification and to reduce production costs, in the recent period we respectively take sodium metaaluminate and aluminum sulfate as the aluminium source (sodium metaaluminate and aluminum sulfate can dissolve rapidly at normal temperatures), modulation synthetic method, synthesized the ZK-1 molecular sieve, and obtained satisfied result.ZK-1 Zeolite synthesis step is simple, and good reproducibility is conducive to commercial Application.Result of the test shows that the Hydrobon catalyst of preparation has high catalytic activity take ZK-1 as carrier, can effectively remove the large molecular sulfur compound that the difficulties such as dibenzothiophenes and 4,6-dimethyl Dibenzothiophene remove under relatively mild condition.
Summary of the invention
The purpose of this invention is to provide highly active Hydrobon catalyst of a kind of Large ratio surface and preparation method thereof.The present invention takes following technical scheme to realize:
(1) take TPAOH and softex kw (TPAOH and CTAB) as template, adopt step crystallization method Hydrothermal Synthesis Jie mesoporous-microporous composite molecular sieve ZK-1, crystallization temperature is 90～170 ℃, crystallization time is 2～100h, and crystallization is finished by suction filtration, washing, drying and roasting and obtained the ZK-1 carrier.
(2) take by weighing at least a VIII family and at least a soluble metallic salt that is selected from the metal of group VIB of being selected from, be dissolved in and make salting liquid in the deionized water.Described metallic compound refers to water miscible inorganic salts or the water miscible organic salt of these metals, such as: inorganic salts are nitrate, carbonate, sulfate, chloride, molybdate, tungstates and metatungstate etc., and organic salt is oxalates or acetate etc.
(3) with (1) made carrier impregnation in the described salting liquid of step (2), utilize the methods such as ultrasonic concussion, stirring that metal component is uniformly dispersed at carrier surface, then drying and roasting makes Hydrobon catalyst.Wherein the group VIII metal oxide accounts for the 2-16% that catalyst forms; The group VIB metal oxide accounts for the 5-30% that catalyst forms.
Dipping method in aforesaid (3) step comprises step impregnation method and co-impregnation.
The Hydrobon catalyst that makes in aforesaid (3) step can pass through the method moulding such as compressing tablet, extrusion, spin.
Obtained catalyst is estimated at the minitype high voltage fixed bed reactors.Carrying out presulfurization before carrying out hydrodesulfurization reaction makes the catalyst of oxidation state change sulphided state into.Operating procedure is as follows: with pack into the flat-temperature zone of reactor of broken good oxidized catalyst after the moulding, fill with the porcelain ball at the bed two ends, passes into vulcanizing agent, vulcanized 3～10 hours under 200～400 ℃ of temperature.Vulcanizing agent is 1～10% CS
2Cyclohexane solution.
Catalyst of the present invention has large specific area (600-900m
2/ g) and pore volume (0.6-1.0ml/g), Jie's micropore twin-stage duct feature, suitable acid site distribute and good hydrothermal stability, and metal component is in the carrier surface high degree of dispersion.This catalyst has higher hydrodesulfurization activity, can realize effectively removing sulfur-containing compound under relatively mild reaction condition.For example at reaction pressure 3Mpa, 320 ℃ of reaction temperatures, air speed 3.0h
-1, under the reaction condition of hydrogen-oil ratio 300, the CoMo/ZK-1 catalyst is 94.2% to the desulfurization degree of dibenzothiophenes, is 93.5% to the desulfurization degree of 4,6-dimethyl Dibenzothiophene, apparently higher than the CoMo/ γ-A1 of preparation under the same conditions
2O
3Catalyst.
Description of drawings
Fig. 1 is the N of ZK-1 carrier and CoMo/ZK-1 catalyst
2Adsorption and desorption isotherms;
Fig. 2 A is the micropore size distribution map of ZK-1 carrier and CoMo/ZK-1 catalyst;
Fig. 2 B is the mesoporous graph of pore diameter distribution of ZK-1 carrier and CoMo/ZK-1 catalyst.
In the accompanying drawings, a is the ZK-1 carrier, and b is the CoMo/ZK-1 catalyst.As shown in Figure 1, ZK-1 carrier and CoMo/ZK-1 catalyst all present the feature of IV type Adsorption and desorption isotherms.The ZK-1 molecular sieve is Jie's microcellular structure, is hanging down than nip P/P
0＜0.01 N of place
2The hop of adsorbance is owing to the filling of micropore.At P/P
0Absorption hop during=0.2-0.35 is corresponding to mesoporous capillary condensation, and the hysteresis loop in middle high specific pressure district is the feature of meso-hole structure.After supporting reactive metal, the CoMo/ZK-1 catalyst is to N
2Adsorbance decreases, but still has kept the feature of the Adsorption and desorption isotherms similar to the ZK-1 carrier.
Fig. 2 A and Fig. 2 B are respectively micropore size distribution map and the mesoporous graph of pore diameter distribution of ZK-1 carrier and CoMo/ZK-1 catalyst.As seen from the figure, the ZK-1 carrier is through supporting active component, after dipping and the roasting, its micropore canals and mesopore orbit all do not cave in, still keep complete, the skeleton structure that shows ZK-1 is highly stable, and metal component realized high dispersive at the ZK-1 molecular sieve carrier, and this is highly beneficial for improving catalyst activity.
The specific embodiment
Embodiment 1
1. the preparation of Jie's mesoporous-microporous composite molecular sieve ZK-1 carrier:
(1) aluminium isopropoxide (AIP) is joined in TPAOH (TPAOH) aqueous solution, under ice-water bath, be stirred to AIP and all dissolve.Then be warming up to 25 ℃, stir the lower ethyl orthosilicate (TEOS) that dropwise adds.Mixture at room temperature continues stirred for several hour makes the TEOS hydrolysis.
(2) the CTAB aqueous solution adds continuation stirring 1h in the said mixture, and the mole of final synthetic mixture consists of 60SiO
2: Al
2O
3: 15TPAOH:15CTAB:6000H
2O.
(3) this mixture is changed in the band teflon-lined stainless steel cauldron.Put into baking oven after tightening, at 130 ℃ of static crystallization 48h.
(4) use the vavuum pump suction filtration after crystallization is finished, the deionized water washing is to neutrality, 80 ℃ of dry 12h in baking oven.
(5) sample 550 ℃ of roasting 10h in Muffle furnace directly obtain Hydrogen ZK-1 molecular sieve with removed template method TPAOH and CTAB.
2. take by weighing 0.74g ammonium molybdate ((NH
4)
6Mo
7O
244H
2O) and 0.81g cobalt nitrate (Co (NO
3)
26H
2O), be dissolved in the 150ml deionized water, be made into dipping solution.Take by weighing the former powder of 3.0g ZK-1 and add in the maceration extract, ultrasonic concussion 20min, at 80 ℃ of stirring 3h, 120 ℃ of dryings 12 hours, then roasting 4 hours in air under 500 ℃ made Hydrobon catalyst.
Embodiment 2
1. the preparation of Jie's mesoporous-microporous composite molecular sieve ZK-1 carrier:
(1) sodium metaaluminate is joined in TPAOH (TPAOH) aqueous solution, at room temperature stirring and dissolving.Then dropwise add ethyl orthosilicate (TEOS), mixture at room temperature continues stirred for several hour makes the TEOS hydrolysis.
(2) the CTAB aqueous solution adds continuation stirring 1h in the said mixture, and the mole of final synthetic mixture consists of 60SiO
2: Al
2O
3: 15TPAOH:15CTAB:6000H
2O.
(3) this mixture is changed in the band teflon-lined stainless steel cauldron.Put into baking oven after tightening at 130 ℃ of static crystallization 48h.
(4) use the vavuum pump suction filtration after crystallization is finished, the deionized water washing is to neutrality, 80 ℃ of dry 12h in baking oven.
(5) sample 550 ℃ of roasting 10h in Muffle furnace obtain sodium type ZK-1 with removed template method TPAOH and CTAB.
(6) aqueous ammonium nitrate solution with 0.4mol/l carries out the exchange of three secondary ions to sodium type ZK-1, and obtains Hydrogen ZK-1 in 3 hours 500 ℃ of roastings.
2. take by weighing 0.74g ammonium molybdate ((NH
4)
6Mo
7O
244H
2O) and 0.81g cobalt nitrate (Co (NO
3)
26H
2O), be dissolved in the 150ml deionized water, be made into dipping solution.Take by weighing the former powder of 3.0g ZK-1 and add in the maceration extract, ultrasonic concussion 20min, at 80 ℃ of stirring 3h, 120 ℃ of dryings 12 hours, then roasting 4 hours in air under 500 ℃ made Hydrobon catalyst.
Embodiment 3
1. the preparation of Jie's mesoporous-microporous composite molecular sieve ZK-1 carrier:
(1) aluminum sulfate is joined in TPAOH (TPAOH) aqueous solution, at room temperature stirring and dissolving.Then dropwise add ethyl orthosilicate (TEOS), mixture at room temperature continues stirred for several hour makes the TEOS hydrolysis.
(2) the CTAB aqueous solution adds continuation stirring 1h in the said mixture, and the mole of final synthetic mixture consists of 60SiO
2: Al
2O
3: 20TPAOH:15CTAB:6000H
2O.
(3) this mixture is changed in the band teflon-lined stainless steel cauldron.Put into baking oven after tightening at 170 ℃ of static crystallization 4h.
(4) use the vavuum pump suction filtration after crystallization is finished, the deionized water washing is to neutrality, 80 ℃ of dry 12h in baking oven.
(5) sample 550 ℃ of roasting 10h in Muffle furnace directly obtain Hydrogen ZK-1 with removed template method TPAOH and CTAB.
2. take by weighing 0.74g ammonium molybdate ((NH
4)
6Mo
7O
244H
2O) and 0.81g cobalt nitrate (Co (NO
3)
26H
2O), be dissolved in the 150ml deionized water, be made into dipping solution.Take by weighing the former powder of 3.0g ZK-1 and add in the maceration extract, ultrasonic concussion 20min, at 80 ℃ of stirring 3h, 120 ℃ of dryings 12 hours, then roasting 4 hours in air under 500 ℃ made Hydrobon catalyst.
Embodiment 4
1. the preparation of Jie's mesoporous-microporous composite molecular sieve ZK-1 carrier:
(1) aluminium isopropoxide (AIP) is joined in TPAOH (TPAOH) aqueous solution, under ice-water bath, be stirred to AIP and all dissolve.Then be warming up to 25 ° of C, stir the lower ethyl orthosilicate (TEOS) that dropwise adds.Mixture at room temperature continues stirred for several hour makes the TEOS hydrolysis.
(2) the CTAB aqueous solution adds continuation stirring 1h in the said mixture, and the mole of final synthetic mixture consists of 90SiO
2: Al
2O
3: 22.5TPAOH:22.5CTAB:9000H
2O.
(3) this mixture is changed in the band teflon-lined stainless steel cauldron.Put into baking oven after tightening at 130 ℃ of static crystallization 48h.
(4) use the vavuum pump suction filtration after crystallization is finished, the deionized water washing is to neutrality, 80 ℃ of dry 12h in baking oven.
(5) sample 550 ℃ of roasting 10h in Muffle furnace directly obtain Hydrogen ZK-1 molecular sieve with removed template method TPAOH and CTAB.
2. take by weighing 0.74g ammonium molybdate ((NH
4)
6Mo
7O
244H
2O) and 0.81g cobalt nitrate (Co (NO
3)
26H
2O), be dissolved in the 150ml deionized water, be made into dipping solution.Take by weighing the former powder of 3.0g ZK-1 and add in the maceration extract, ultrasonic concussion 20min, at 80 ℃ of stirring 3h, 120 ℃ of dryings 12 hours, then roasting 4 hours in air under 500 ℃ made Hydrobon catalyst.
Embodiment 5
1. the preparation of Jie's mesoporous-microporous composite molecular sieve ZK-1 carrier:
(1) aluminum sulfate is joined in TPAOH (TPAOH) aqueous solution, at room temperature stirring and dissolving.Then dropwise add ethyl orthosilicate (TEOS), mixture at room temperature continues stirred for several hour makes the TEOS hydrolysis.
(2) the CTAB aqueous solution adds continuation stirring 1h in the said mixture.The mole of final synthetic mixture consists of 60SiO
2: Al
2O
3: 20TPAOH:15CTAB:6000H
2O.
(3) this mixture is changed in the band teflon-lined stainless steel cauldron.Put into baking oven after tightening at 130 ℃ of static crystallization 48h.
(4) use the vavuum pump suction filtration after crystallization is finished, the deionized water washing is to neutrality, 80 ℃ of dry 12h in baking oven.
2. take by weighing 0.74g ammonium molybdate ((NH
4)
6Mo
7O
244H
2O) and 0.81g cobalt nitrate (Co (NO
3)
26H
2O), be dissolved in respectively in the 150ml deionized water and be made into dipping solution.Take by weighing the former powder of 3.0g ZK-1, adopt step impregnation method to prepare the CoMo/ZK-1 catalyst.The order of dipping is Co behind the first Mo, behind the dipping ammonium molybdate solution, 120 ℃ of dryings 12 hours, then floods cobalt nitrate solution, after dipping is finished, and 120 ℃ of dryings 12 hours, then roasting 4 hours in air under 500 ℃.
Embodiment 6
1. the preparation of Jie's mesoporous-microporous composite molecular sieve ZK-1 carrier:
Take sodium metaaluminate as the aluminium source, concrete synthetic method and raw material proportioning are with embodiment 2.
2. take by weighing 0.74g ammonium molybdate ((NH
4)
6Mo
7O
244H
2O) and 0.81g nickel nitrate (Ni (NO
3)
26H
2O), be dissolved in the 150ml deionized water, be made into dipping solution.Take by weighing the former powder of 3.0g ZK-1 and add in the maceration extract, ultrasonic concussion 20min, at 80 ℃ of stirring 3h, 120 ℃ of dryings 12 hours, then roasting 4 hours in air under 500 ℃ made Hydrobon catalyst.
Embodiment 7
1. the preparation of Jie's mesoporous-microporous composite molecular sieve ZK-1 carrier is with the method for embodiment 1.
2. take by weighing 1.13g ammonium metatungstate (3(NH
4)
2O-7WO
36H
2O) and 0.81g nickel nitrate (Ni (NO
3)
26H
2O), be dissolved in the 150ml deionized water, be made into dipping solution.Take by weighing the former powder of 3.0g ZK-1 and add in the maceration extract, ultrasonic concussion 20min, at 80 ℃ of stirring 3h, 120 ℃ of dryings 12 hours, then roasting 4 hours in air under 500 ℃ made Hydrobon catalyst.
Claims (7)
1. the Hydrobon catalyst take Jie's mesoporous-microporous composite molecular sieve as carrier is characterized in that, this catalyst comprises carrier and active component; Take Jie's mesoporous-microporous composite molecular sieve ZK-1 as carrier, take at least a VIII family and at least a group VIB metal as active component.
2. according to Hydrobon catalyst claimed in claim 1, it is characterized in that: described group VIII metal is cobalt, nickel, and described group VIB metal is molybdenum, tungsten.
3. according to claim 1 or 2 described Hydrobon catalysts, it is characterized in that: the weight percentage of described active component in catalyst is: group VIII metal oxide 2-16%; Group VIB metal oxide 5-30%;
4. method for preparing claim 1 or 2 described Hydrobon catalysts, its feature may further comprise the steps:
(1) the aluminium source is joined in the TPAOH aqueous solution, drip the silicon source after the stirring and dissolving; After the hydrolysis of silicon source, said mixture and softex kw aqueous solution are stirred dress still crystallization; After crystallization was finished, with solid content filtration, washing, drying and roasting, mesoporous-microporous composite molecular sieve ZK-1 carrier namely obtained being situated between;
(2) with the soluble metallic salt of at least a group VIII metal and at least a group VIB metal, be dissolved in and make metal salt solution in the deionized water;
(3) with carrier impregnation in the described metal salt solution of step (2), metal component is uniformly dispersed at carrier surface, then drying, roasting make Hydrobon catalyst.
5. method for preparing the described Hydrobon catalyst of claim 3, its feature may further comprise the steps:
(1) the aluminium source is joined in the TPAOH aqueous solution, drip the silicon source after the stirring and dissolving; After the hydrolysis of silicon source, said mixture and softex kw aqueous solution are stirred dress still crystallization; After crystallization was finished, with solid content filtration, washing, drying and roasting, mesoporous-microporous composite molecular sieve ZK-1 carrier namely obtained being situated between;
(2) with the soluble metallic salt of at least a group VIII metal and at least a group VIB metal, be dissolved in and make metal salt solution in the deionized water;
(3) with carrier impregnation in the described metal salt solution of step (2), metal component is uniformly dispersed at carrier surface, then drying, roasting make Hydrobon catalyst.
6. according to the method described in the claim 4, it is characterized in that described aluminium source refers to sodium metaaluminate, aluminium isopropoxide or aluminum sulfate; The silicon source is silester.
7. according to the method described in the claim 5, it is characterized in that described aluminium source refers to sodium metaaluminate, aluminium isopropoxide or aluminum sulfate; The silicon source is silester.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104368376A (en) * | 2014-11-17 | 2015-02-25 | 哈尔滨工业大学 | Deep hydrodesulfurization catalyst preparation method by carrying nickel and tungsten on multistage porous zeolite |
| CN105435831A (en) * | 2015-11-12 | 2016-03-30 | 北京华石联合能源科技发展有限公司 | Microspherical catalyst as well as preparation method and application thereof |
| CN105457668A (en) * | 2015-12-10 | 2016-04-06 | 哈尔滨工业大学 | Method for preparing hydrodesulfurization catalysts with zeolite serving as carriers |
| CN108126751A (en) * | 2017-12-27 | 2018-06-08 | 中海油天津化工研究设计院有限公司 | Molecular sieve supported heteropoly acid alkylating and desulfurizing catalyst of multi-stage porous and preparation method thereof |
| CN113198527A (en) * | 2021-04-25 | 2021-08-03 | 西南化工研究设计院有限公司 | Composite hierarchical pore molecular sieve catalyst for preparing aromatic hydrocarbon from low-carbon alkane and preparation method thereof |
| CN114308116A (en) * | 2021-12-23 | 2022-04-12 | 复旦大学 | Nano nickel-based MFI (melt flow index) crystallite molecular sieve and preparation method and application thereof |
-
2013
- 2013-07-11 CN CN2013102924404A patent/CN103349995A/en active Pending
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104368376A (en) * | 2014-11-17 | 2015-02-25 | 哈尔滨工业大学 | Deep hydrodesulfurization catalyst preparation method by carrying nickel and tungsten on multistage porous zeolite |
| CN105435831A (en) * | 2015-11-12 | 2016-03-30 | 北京华石联合能源科技发展有限公司 | Microspherical catalyst as well as preparation method and application thereof |
| CN105457668A (en) * | 2015-12-10 | 2016-04-06 | 哈尔滨工业大学 | Method for preparing hydrodesulfurization catalysts with zeolite serving as carriers |
| CN108126751A (en) * | 2017-12-27 | 2018-06-08 | 中海油天津化工研究设计院有限公司 | Molecular sieve supported heteropoly acid alkylating and desulfurizing catalyst of multi-stage porous and preparation method thereof |
| CN108126751B (en) * | 2017-12-27 | 2020-11-24 | 中海油天津化工研究设计院有限公司 | Multi-stage pore molecular sieve supported heteropoly acid alkylation desulfurization catalyst and preparation method thereof |
| CN113198527A (en) * | 2021-04-25 | 2021-08-03 | 西南化工研究设计院有限公司 | Composite hierarchical pore molecular sieve catalyst for preparing aromatic hydrocarbon from low-carbon alkane and preparation method thereof |
| CN114308116A (en) * | 2021-12-23 | 2022-04-12 | 复旦大学 | Nano nickel-based MFI (melt flow index) crystallite molecular sieve and preparation method and application thereof |
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