CN103071541B - A kind of preparation method of load type metal catalyst of highly disperse active center - Google Patents
A kind of preparation method of load type metal catalyst of highly disperse active center Download PDFInfo
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- CN103071541B CN103071541B CN201310020756.8A CN201310020756A CN103071541B CN 103071541 B CN103071541 B CN 103071541B CN 201310020756 A CN201310020756 A CN 201310020756A CN 103071541 B CN103071541 B CN 103071541B
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Abstract
The invention discloses a kind of preparation method of load type metal catalyst of highly disperse active center, adopt the infusion process improved: after the pretreatment of catalyst conventional carrier drying, the polyfunctional compound of dipping containing two or more parent hydroxy functional group, impregnating metal saline solution again after drying; Or, by the carrier direct impregnation without finishing at the aqueous metal salt of polyfunctional compound containing two or more parent hydroxy functional group; Drying and calcining obtain metal load type catalyst again.By improve infusion process and complexing infusion process, the effect in carrier and activated centre can be improved, polyfunctional compound consumption few and be easy to control, preparation process is simple and reliable, is the new way preparing effective catalyst; By catalyst prepared by complexing infusion process, metal active constituent is evenly distributed in catalyst surface, and decentralization increases, and active component size tunable is within 10nm, and domain size distribution is adjustable.
Description
Technical field:
The invention belongs to catalyst technical field, be specifically related to a kind of preparation method of load type metal catalyst of highly disperse active center.
Background technology:
Loaded catalyst is catalyst conventional in chemical industry, and metal active constituent can be distributed to the surface of catalyst more uniformly.The catalyst common metal consumption of support type is less, and preparation process is simply easy to control.The common method preparing loaded catalyst comprises infusion process, ion-exchange, sol-gal process and coprecipitation etc.In order to prepare more high degree of dispersion, more highly active catalyst, new preparation method continues to bring out.Such as: utilize cold/hot plasma to prepare ultra-fine grain catalyst, plasma sputtering cocatalyst active component deposition preparation high dispersive, highly active catalyst, but need special plasma apparatus in preparation process, high voltage is there is in process, certain vacuum system, catalyst preparing scale limited (CatalysisToday Volume72 (2002), 173-184).Utilize ion-exchanger to make carrier, introduce active component with the form of counter ion, the load type metal catalyst of preparation high dispersive, Large ratio surface; Carrier is commonly used as various molecular sieve; Catalyst metal loadings amount prepared by ion-exchange is less, need repeatedly to exchange and just can reach higher exchange degree and load capacity, cation simultaneously in catalyst carrier is difficult to be completely displaced all the time, detrimental effect is played to some reaction, the method is subject to restriction (the Catalysis Today Volume77 (2003) of kind of carrier in addition, 299-314 and Chemical Engineering Journal209 (2012), 652-660); Sol-gal process refers to that metal organic or inorganic compound solidifies through solution, colloidal sol and gel, then forms the method for oxide or other compound solids through Overheating Treatment.The catalyst uniformity of preparation is high, and course of reaction simply easily controls, and catalyst has high dispersive, the good aperture of high-ratio surface sum, and in preparation process, reaction temperature is low, and crystal formation and the granularity of nano particle are controlled; But a large amount of use metallo-organic compound or organic matter gel in actual application, higher (the Angewandte Chemie Volume35 (1996) of Catalyst Production cost, 1420-1436 and Catalysis Today Volume137 (2008), 132-143); (the Chemical Reviews Volume102 (2002) such as Philippe Serp, 3085-3128) review chemical vapour deposition technique and prepare loaded catalyst (i.e. gas phase impregnation-decomposition method), be deposited on again on carrier after the vaporization of metal active precursor, finally heat roasting gas to decompose, compared with conventional infusion process, metal active constituent distribution is more even, and active raising is a lot, but metal premise calls is easily vaporized, be easy to decompose.Metal precursor conventional in real process is metal carbonyl, because toxicity is comparatively large, needs the preparation condition of anhydrous and oxygen-free, is unfavorable for large-scale application.
Summary of the invention:
The object of this invention is to provide a kind of preparation method utilizing complexing infusion process to prepare the load type metal catalyst at highly disperse active center.
The present invention is achieved by the following technical programs:
Adopt the infusion process improved, concrete steps are as follows:
After the pretreatment of catalyst conventional carrier drying, dipping is containing two or more parent hydroxy functional group (such as hydroxyl, carboxyl, amino, aldehyde radical etc.) polyfunctional compound 6 ~ 24h and at 50 ~ 150 DEG C the dry carrier obtaining finishing for 6 ~ 24 hours, then by the carrier impregnation aqueous metal salt 6 ~ 24h of finishing;
Or, in aqueous metal salt, directly add the polyfunctional compound containing two or more parent hydroxy functional group, the aqueous metal salt 6 ~ 24h of the polyfunctional compound of two or more parent hydroxy functional group will be contained without the pretreated carrier direct impregnation of a finishing drying;
By the catalyst after above-mentioned impregnating metal saline solution, at 50-100 DEG C of Rotary drying 10 ~ 24h, at 100 ~ 200 DEG C after dry 10 ~ 24 hours, calcine 2 ~ 4 hours at 300 ~ 800 DEG C, heating rate controls to obtain metal load type catalyst at 1 ~ 10 DEG C/min;
The mol ratio of the metal of described aqueous metal salt and the polyfunctional compound containing two or more parent hydroxy functional group is between 1:0.5 ~ 1:10; The mass percent of described content of metal wt%(activity component metal and conventional carrier) be 1 ~ 40%, be preferably 1 ~ 25%.
The conventional carrier of described catalyst comprises metal oxide carrier (such as Al
2o
3), nonmetal oxide carrier (such as SiO
2) or the carrier such as molecular sieve (such as MCM-41).
The dry pretreatment of described catalyst carrier refers to metal oxide carrier or nonmetal oxide carrier dry 6-24 hour at 100 ~ 200 DEG C; Molecular sieve carrier burns 2 ~ 6h and removes template at 550 DEG C.
The described polyfunctional compound containing two or more parent hydroxy functional group is preferably ethylenediamine or citric acid, lactic acid, ethylene glycol, sorbierite, glucose, glycerine, BDO.
Slaine in described aqueous metal salt, as the active component of metal load type catalyst, comprises Co (NO
3)
26H
2o, Cu (NO
3)
23H
2o or Ni (NO
3)
26H
2the slaines such as O.
Of the present invention have following beneficial effect:
1) by infusion process and the complexing infusion process of improvement, utilize the characteristic of carrier parent hydroxyl, utilize the polyfunctional compound containing close hydroxyl and carrier, interaction between metal ion, first flood in catalyst carrier in catalyst preparation process or directly add at aqueous metal salt containing two or more parent hydroxy functional group (hydroxyl, carboxyl, amino, aldehyde radical) polyfunctional compound, polyfunctional compound consumption few and be easy to control, preparation process is simple and reliable, is to prepare the simple and practical new approach of effective catalyst.
2) by catalyst prepared by complexing infusion process, can improve the effect in carrier and activated centre, metal active constituent is evenly distributed in catalyst surface, and decentralization increases, the active component size tunable of the metal carrying catalyst of high dispersive is within 10nm, and domain size distribution can regulate.
Accompanying drawing illustrates:
Fig. 1 is the XRD spectra of the catalyst of different metal load capacity;
Fig. 2 is the XRD spectra of the catalyst that different sintering temperature obtains;
Fig. 3 is the XRD spectra of the catalyst that different ethylene glycol consumption obtains;
Fig. 4 and Fig. 5 is the XRD spectra of the catalyst that different alcohols obtains;
Fig. 6 is the XRD spectra of the catalyst that different how close hydroxy compounds obtains;
Fig. 7, Fig. 8, Fig. 9 and Figure 10 are the XRD spectras of the catalyst that different metal and carrier obtain;
Wherein, 2 θ represent the angle of diffraction of XRD
Detailed description of the invention:
Below further illustrate of the present invention, instead of limitation of the present invention.Slaine in the polyfunctional compound of the conventional carrier of described catalyst, close hydroxy functional group or aqueous metal salt for following embodiment, and is not restricted to this.
Embodiment 1: the impact of content of metal
Take 2.5g graininess 40-60 order commercial vectors SiO
2at 120 DEG C, drying 12 hours, for subsequent use.Under room temperature, add ethylene glycol (glycol is abbreviated as EG) and flood SiO
2carrier 6h, then at 50 DEG C dry 24 hours, obtains the carrier of finishing.Under room temperature, on the carrier of finishing, dipping is containing 2.4692g Co (NO
3)
26H
2the aqueous solution of O, floods 12 hours, 90 DEG C of Rotary dryings 12 hours, and 120 DEG C of dryings 12 hours, after dry, sample is placed in Muffle furnace 400 DEG C of roastings 2 hours, and heating rate 2 DEG C/min, obtains the Co/SiO of 10% load
2catalyst, changes Co (NO
3)
26H
2the consumption of O, repeat said process, gained catalyst is designated as 1%Co-SiO
2, 10%Co-SiO
2, 20%Co-SiO
2, 25%Co-SiO
2, 30%Co-SiO
2, 40%Co-SiO
2.Corresponding XRD spectra is shown in Fig. 1, can draw from figure, and content of metal is when below 25wt%, and metal active centres is at carrier S iO
2load very even, decentralization is very high; Particle size is very little, to such an extent as to XRD spectra superiors disappears completely or very disperse, and content of metal is when 25wt%, and particle diameter is calculated as 3.7nm; Content of metal is when 30wt% and 40wt%, and particle diameter is calculated as 12.8nm and 15.2nm; And not through the carrier of ethylene glycol finishing, Co
3o
4diffraction maximum obviously ((d) XRD diffraction maximum see Fig. 4), particle diameter is calculated as 16.3nm.
Embodiment 2: the impact of sintering temperature
Implementation step and condition with embodiment 1, commercial vectors SiO
2drying 24 hours at 100 DEG C, with 10% load C o/SiO
2catalyst is example.Under room temperature, add ethylene glycol (EG) and flood SiO
2carrier 24h, then at 150 DEG C dry 6 hours, obtains the carrier of finishing.Carrier impregnation Co (the NO of finishing ethylene glycol
3)
26H
2flood 20 hours after O, 50 DEG C of Rotary dryings 24 hours, 200 DEG C of dryings 10 hours, after dry, sample is placed in Muffle furnace 300 DEG C, 400 DEG C, 500 DEG C, 600 DEG C, 700 DEG C, 800 DEG C roastings 2 hours, heating rate 2 DEG C/min.Corresponding XRD spectra is shown in Fig. 2, and the sample activity center of sintering temperature below 600 DEG C is at carrier S iO
2load very even, decentralization is very high, and XRD diffraction maximum disappears completely; The sintering temperature of more than 600 DEG C, occur very disperse XRD diffraction maximum, particle diameter is calculated as 4.9-5.2nm.
Embodiment 3: the impact of ethylene glycol consumption
Take 2.5g graininess 40-60 order commercial vectors SiO
2at 200 DEG C, drying 6 hours, for subsequent use.Under room temperature, on carrier, dipping is containing 2.4692g Co (NO
3)
26H
2the glycol water of O, floods 6 hours, at 60 DEG C of Rotary drying 20h, and drying 24 hours at 100 DEG C; After dry, sample is placed in Muffle furnace 400 DEG C of roastings 2 hours, and heating rate 2 DEG C/min, obtains 10% load C o/SiO
2catalyst; Metal wherein in slaine and the mol ratio of ethylene glycol are respectively: 1:0.5,1:1,1:2,1:4,1:6,1:10.Corresponding XRD spectra is shown in Fig. 3, can draw from figure, and when in aqueous metal salt, metal and ethylene glycol molar ratio are less than 1:1, metal active centres is at carrier S iO
2load very even, decentralization is very high, and XRD diffraction maximum disappears completely; Ratio is when 1:1, and occur very disperse XRD diffraction maximum, particle diameter is calculated as 4.7nm; Ratio is 1:0.5, and occur clear sharp-pointed XRD diffraction maximum, particle diameter is calculated as 15.2nm.
Embodiment 4: the impact of other alcohols
Implementation step and condition with embodiment 3, with 10% load C o/SiO
2catalyst is example, adds monohydroxy compound ethanol (ethanol) in the solution of dipping, and in water, content is that 20%(metal and alcohols molar ratio are less than 1:1), at 60 DEG C of Rotary drying 24h, drying 10 hours at 120 DEG C; In addition, other adds polyol sorbierite (sorbitol), glucose (glucose), glycerine (glycerol), 1,4-butanediol (1,4-butanediol), in water, content is that 10%(metal and alcohols molar ratio are less than 1:1), at 80 DEG C of Rotary drying 12h, drying 12 hours at 150 DEG C; Other step is shown in embodiment 3.Corresponding XRD spectra is shown in Fig. 4,5, can draw from figure, although ethanol content is 20% in water, hydroxy radical content is then calculated and is equivalent to 10% ethylene glycol, but after monodentate ligand, do not have unnecessary hydroxyl and carrier to combine, between metal ion and carrier, do not produce interaction, the particle diameter of metal active centres is comparatively large, and particle diameter is calculated as 15.8nm.When use polyol sorbierite, glucose, glycerine, 1, when 4-butanediol is as additive, after multiple tooth coordination, also residual hydroxyl and carrier combine, produce between metal ion and carrier and interact, metal active centres can be scattered in carrier surface well, or XRD diffraction maximum disappears very disperse completely, and particle diameter calculates at below 3nm.
Embodiment 5: the impact of other how close hydroxy compounds
Implementation step and condition with embodiment 3, with 10% load C o/SiO
2catalyst is example, the function groups compound containing two or more parent hydroxyl functional group is added: ethylenediamine (ethylenediamine), citric acid (citric acid), lactic acid (lactic acid), urea (urea) in the solution of dipping, in water, content is that 10%(metal and alcohols molar ratio are less than 1:1), at 70 DEG C of Rotary drying 16h, drying 10 hours at 120 DEG C; Other step is shown in embodiment 3.Corresponding XRD spectra is shown in Fig. 6, can draw from figure, other function groups compound containing two or more parent hydroxyl functional group plays the effect of polyol equally, metal active centres can be scattered in carrier surface well, or XRD diffraction maximum disappears very disperse completely, particle diameter calculates at below 4.9nm.But the interpolation of inorganic matter urea, may be lower due to the decomposition temperature of urea, and well can not control the interphase interaction of metal ion and carrier, the interaction of generation is more weak, the particle diameter of metal active centres is comparatively large, and particle diameter is calculated as 9.7nm.
Embodiment 6: the impact of other metal and carrier
Take 8g graininess 40-60 order commercial vectors SiO
2at 120 DEG C, drying 12 hours, for subsequent use.Under room temperature, on carrier, dipping is containing 4.5621gCu (NO
3)
23H
2o and 1.1721g glycol water, floods 24 hours, at 100 DEG C of Rotary drying 10h, and drying 10 hours at 200 DEG C; After dry, sample is placed in Muffle furnace 400 DEG C of roastings 4 hours, heating rate 1 DEG C/min, and obtaining load capacity is 15%Cu/SiO
2catalyst.Corresponding XRD spectra is shown in Fig. 7, and can draw from figure, metal active centres is at carrier S iO
2upper load very even, decentralization is very high, and the very disperse of XRD diffraction maximum, particle diameter is calculated as 6.8nm, and the catalyst particle size not having improved infusion process to prepare is 39.7nm.
Take 5g graininess 40-60 order commercial vectors Al
2o
3or 100-200 order molecular sieve MCM-41, at 200 DEG C and 550 DEG C dry 10 and 6 hours respectively.Under room temperature, on carrier, dipping is containing 4.9546g Ni (NO
3)
26H
2o and 1.0575g glycol water, floods 10 hours, at 70 DEG C of Rotary drying 24h, and drying 12 hours at 120 DEG C; After dry, sample is placed in Muffle furnace 400 DEG C of roastings 4 hours, heating rate 10 DEG C/min, and obtaining load capacity is 20% catalyst.Corresponding XRD spectra is shown in Fig. 8,9, and can draw from figure, metal active centres is at carrier A l
2o
3very even with load on molecular sieve MCM-41, decentralization is very high, and the very disperse of XRD diffraction maximum, particle diameter is calculated as 5.0nm and 3.2nm, and the catalyst particle size not having improved infusion process to prepare is 14.3nm and 48nm.Reducing ethylene glycol addition makes Ni:EG molar ratio be 1:0.5, and the 20%Ni-MCM-41 catalyst XRD spectra of preparation is shown in Figure 10, occurs the diffraction maximum of W metal after 450 DEG C of hydrogen reducings, and corresponding XRD diffraction maximum still compares disperse; Reduce the consumption of ethylene glycol, the declines between complex solution and carrier, peak intensity significantly improves, and particle diameter is calculated as 3.9nm.
Claims (6)
1. a preparation method for the load type metal catalyst at highly disperse active center, is characterized in that adopting following steps:
After the pretreatment of a, catalyst conventional carrier drying, polyfunctional compound 6 ~ the 24h of dipping containing two or more parent hydroxy functional group and at 50 ~ 150 DEG C the dry carrier obtaining finishing for 6 ~ 24 hours, then by the carrier impregnation aqueous metal salt 6 ~ 24h of finishing; The described polyfunctional compound containing two or more parent hydroxy functional group is selected from ethylene glycol, sorbierite, glucose, glycerine, BDO;
Or, in aqueous metal salt, directly add the polyfunctional compound containing two or more parent hydroxy functional group, the aqueous metal salt 6 ~ 24h of the polyfunctional compound of two or more parent hydroxy functional group will be contained without the pretreated carrier direct impregnation of a finishing drying;
B, by the catalyst after above-mentioned impregnating metal saline solution, at 50-100 DEG C of Rotary drying 10 ~ 24h, at 100 ~ 200 DEG C after dry 10 ~ 24 hours, calcine 2 ~ 4 hours at 300 ~ 800 DEG C, heating rate controls to obtain metal load type catalyst at 1 ~ 10 DEG C/min;
The mol ratio of the metal of described aqueous metal salt and the polyfunctional compound containing two or more parent hydroxy functional group is between 1:0.5 ~ 1:10; Described content of metal wt% is 1 ~ 40%.
2. the preparation method of the load type metal catalyst at highly disperse active center according to claim 1, is characterized in that the conventional carrier of described catalyst is selected from metal oxide carrier, nonmetal oxide carrier or molecular sieve.
3. the preparation method of the load type metal catalyst at highly disperse active center according to claim 2, is characterized in that described metal oxide carrier is Al
2o
3, nonmetal oxide carrier is SiO
2, molecular sieve carrier is MCM-41.
4. the preparation method of the load type metal catalyst at highly disperse active center according to claim 1, is characterized in that the slaine in described aqueous metal salt, is selected from Co (NO
3)
26H
2o, Cu (NO
3)
23H
2o or Ni (NO
3)
26H
2o.
5. the preparation method of the load type metal catalyst at highly disperse active center according to claim 1, is characterized in that described content of metal wt% is 1 ~ 25%.
6. the preparation method of the load type metal catalyst at highly disperse active center according to claim 1, it is characterized in that the active component particle diameter of described metal load type catalyst is within 10nm, and domain size distribution is adjustable.
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| CN109201045A (en) * | 2017-06-29 | 2019-01-15 | 深圳光启高等理工研究院 | A kind of carbon based metal catalyst and its preparation method and application |
| CN108187713A (en) * | 2017-12-07 | 2018-06-22 | 中国科学院上海高等研究院 | A kind of nitrogen co-doped carbon nano-tube catalyst of copper and its preparation method and application |
| CN108212201B (en) * | 2017-12-07 | 2021-12-21 | 中国科学院上海高等研究院 | Catalyst with copper nanoparticles loaded on molecular sieve, and preparation method and application thereof |
| CN110064420B (en) * | 2018-01-23 | 2021-11-30 | 中国石油天然气股份有限公司 | Oxidation state continuous reforming catalyst and preparation method thereof |
| CN110064392B (en) * | 2018-01-23 | 2021-11-30 | 中国石油天然气股份有限公司 | Oxidized state semi-regenerated reforming catalyst and preparation method thereof |
| WO2021208013A1 (en) * | 2020-04-16 | 2021-10-21 | 萧建兴 | Method for manufacturing catalyst reactant for high-efficiency catalysis in thermal reaction |
| CN111530444B (en) * | 2020-06-01 | 2023-10-27 | 四川泸天化股份有限公司 | Catalyst for synthesizing long-chain alpha-olefin, preparation method and application thereof |
| CN113929058B (en) * | 2021-09-28 | 2023-08-22 | 浙江师范大学 | Catalyst carrier for preparing chlorine by catalytic oxidation of fluorine-containing HCl gas, and preparation method and application thereof |
| CN114950474B (en) * | 2022-04-26 | 2024-03-22 | 陕西延长石油（集团）有限责任公司 | Method for regulating and controlling metal active center dispersity of metal supported catalyst by using complex precursor |
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| CN1074631A (en) * | 1992-01-24 | 1993-07-28 | 北京大学 | Loading type butadiene catalyst made by butylene oxidation dehydrogen |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1074631A (en) * | 1992-01-24 | 1993-07-28 | 北京大学 | Loading type butadiene catalyst made by butylene oxidation dehydrogen |
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