CN103934040A - Preparation method of metal catalyst with high selectivity and high dispersion - Google Patents
Preparation method of metal catalyst with high selectivity and high dispersion Download PDFInfo
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Abstract
The invention discloses a preparation method of a metal catalyst with high selectivity and high dispersion, and relates to a preparation method of a metal catalyst. The method can be used for preparing a series of nanoscale, reduction-free and high-dispersion metal catalysts, and adopts base metal including Cu, Ag, Au, Ni, Fe and Co, and noble metal including Pt, Pd, Rh, Ru and Ir, the prepared Ru/H-beta molecular sieve based catalyst has good fischer-tropsch reactivity, meanwhile, the reactivity of a C5-C11 liquid state product (comprising main ingredient of a gasoline blending agent) is 70% of that of a full product, and the ratio of isoparaffin to n-alkanes in the product is as high as 5 to 1. The dispersing degree of noble metal Ru in the prepared Ru/H-beta molecular sieve based catalyst is 40%, the particle size of metal Ru is 1-2 nanometers, the catalyst is not subjected to extra reduction treatment, and the reduction degree of metal Ru in the prepared Ru/H-beta molecular sieve based catalyst is higher than 90%.
Description
Technical field
The present invention relates to a kind of preparation method of metallic catalyst, particularly relate to the preparation method of the metallic catalyst of a kind of high selectivity, high dispersive.
Background technology
Gasoline, outward appearance is transparency liquid, main component is C4～C12 aliphatic hydrocarbon and cyclic hydrocar-bons compound.In the gasoline standard of China, allow to contain a small amount of compound fragrant hydrocarbon.Gasoline is mainly used in internal combustion engine and car engine.As the important indicator of weighing the good and bad standard of gasoline, there are the anti-knock properties of gasoline and the compression ratio of gasoline.And the anti-knock properties of gasoline directly represent with the octane number of gasoline., have on the vaporizer gasoline engine that high-octane gasoline can be applied to high compression ratio meanwhile, significantly improve the power of engine, reduce fuel consumption, improve the thermal efficiency.The octane number of gasoline is to stipulate like this: the anti-knock properties of isooctane are better, and octane number regulation is 100, and the anti-knock properties of normal heptane are poor, and octane number is returned and is decided to be 0.The mensuration of octane number is that to take isooctane and normal heptane be ideal fuels, and the knock intensity that ideal fuels mixture is produced is identical with comparative fuel, and in ideal fuels, the shared percentage by volume of isooctane is exactly the octane number of comparative fuel so.Octane number is higher, and gasoline anti-knock properties are better.Grade and the price of gasoline are also just distinguished by octane number.Therefore, improve gasoline quality, increase gasoline added value, in original gasoline fraction, adding high-octane gasoline blender is current industrial high-quality gasoline industry development trend.
Industrial gasoline is mainly made by petroleum fractionating or heavy end cracking.Crude oil produces gasoline component through processes such as distillation, catalytic cracking, thermal cracking, hydrocracking, catalytic reformings.But the high speed development along with World Economics, the worsening shortages of petroleum resources, developing rapidly of the day by day serious and living beings technology of environmental pollution, Fischer-Tropsch synthetic (Fischer-Tropsch synthesis: be a kind of important technical process of liquid fuel and high valuable chemicals by coal, natural gas, living beings indirect reformer) has caused the extensive concern [1,2] of countries in the world again.Resource characteristic in conjunction with China " rich coal, oil starvation, weak breath " [3], the coal chemical technology of coal as waste petroleum-type product take in development, implement oil and replace strategy, being the key subjects that are related to the economic long-term stability development of China and energy security, is also the inevitable choice that realizes country's " replace oil with coal " strategy.But Fischer-Tropsch product is very complicated, adopt different iron-baseds, cobalt-based or noble metal catalyst, the selective difference of liquid product is larger.Wherein, cobalt-based and noble metal catalyst reactivity are stable and be difficult for generation carbon distribution, cause inactivation; Insensitive to water gas shift reaction, there is lower CO
2and CH
4selective, carbon atom utilization rate is higher; In product, oxygenatedchemicals is less; There is the higher chain growth factor, be conducive to synthetic long carbochain hydrocarbon compound.Meanwhile, molecular sieve has the fatty ability of the long carbon of cut-out as the main catalyst of heavy oil cracking one of (molecular sieve commercial Application the most successful example), alkene and the isoparaffin of generation short carbon chain.In conjunction with noble metal catalyst and the bifunctional FTS catalyst of molecular sieve, via Fischer-Tropsch synthesis path, can optionally generate the saturated alkane of the high isomery ratio of C5～C11.Resulting product can be used as gasoline blender and joins in petroleum distillate, thereby improves greatly the octane number of oil, improves quality and the added value of product.
Metallic catalyst be in solid catalyst, study the earliest, the most deep, be simultaneously also a kind of catalyst that obtains the most extensive use.According to price category, metallic catalyst comprises base metal catalysts, as: Ni, Cu, Co, Fe etc.; And noble metal catalyst, as: Pt, Pd, Ru, Rh etc.At present, the preparation method of metallic catalyst mainly comprises chemical method and Physical.Wherein in chemical method, mainly contain infusion process, coprecipitation, homogeneous precipitation method, sol-gel process and microemulsion method etc.; Physical has vapour deposition process, atomic deposition method, sputtering method and solid-phase grinding method.In chemical method, in coprecipitation method and homogeneous precipitation method preparation ground metallic catalyst preparation process, reaction condition is gentle, easily control, and equipment investment is little, and the metal granularity of preparation is uniformly dispersed controlled.And prepared catalyst activity in catalytic reaction is higher, therefore extensive use aborning.But, adopting coprecipitation method and homogeneous precipitation method to prepare in the process of metallic catalyst, owing to extensively having adopted more cheap metal nitrate presoma, there is a large amount of waste water containing nitrate anion to produce, the very big impact that environment is caused, environment is unfriendly.Therefore, in the today of implementing Green Chemistry, advocating green synthetic chemistry, develop a kind of simple, free of contamination metallic catalyst preparation method is very necessary.For noble metal catalyst, due to its expensive price, generally select vapour deposition process, atomic deposition method or sputtering method preparation.Object obtains the noble metal catalyst of high degree of dispersion, thereby saves the consumption of noble metal catalyst.
List of references:
[1]?A.Y.?Khodakov,?W.?Chu,?P.?Fongarland,?Advances?in?the?Development?of?Novel?Cobalt?Fischer-Tropsch?Catalysts?for?Synthesis?of?Long-Chain?Hydrocarbons?and?Clean?Fuels,?Chem.?Rev.?107?(2007)?1692-1744.
[2]?Q.H.?Zhang,?W.P.?Deng,?Y.?Wang,?Recent?Advances?in?Understanding?the?Key?Catalyst?Factors?for?Fischer-Tropsch?Synthesis,?J.?Energy?Chem.?22?(2013)?27-38.
[3] alkene industry " 12 " development plan and petrochemical industry and chemical industry " 12 " development plan, the Ministry of Industry and Information Technology.
Summary of the invention
The object of the present invention is to provide the preparation method of the metallic catalyst of a kind of high selectivity, high dispersive, it is active that Ru/H-beta catalyst prepared by this method shows splendid fischer-tropsch reaction, simultaneously the selective of C5-C11 liquid product is 70% of full product, wherein in product isoparaffin with the ratio of n-alkane up to 5:1.The decentralization of noble metal Ru is 40%; The particle size of Ru metal is 1-2 nanometer.
The object of the invention is to be achieved through the following technical solutions:
A preparation method for the metallic catalyst of high selectivity, high dispersive, described method comprises selects one or more different metals and noble metal, as Cu, Ag, Au, Ni, Co, Fe, Pt, Pd, Rh, Ru, Ir, precursor salt, the salt that nitrate or acetate etc. contains above-mentioned metallic element, and a certain organic acid that contains carboxyl, as formic acid, acetic acid, propionic acid, ethanedioic acid, citric acid, amion acetic acid, EDTA, or amino acid etc., or glucose, cellulose are raw material; By metal precursor and the organic acid or the glucose that contain carboxyl, cellulose dissolution is in deionized water, and the 5-500 that the volume of deionized water is volume of mixture doubly; Under room temperature condition, stir 5-30 minute, until the presoma of salt dissolves completely with the organic acid that contains carboxyl, wherein metal ion is 0.3-10 with the molar ratio range of the carboxyl functional group containing, working concentration is that to be adjusted to pH value scope be 4-9 to the ammoniacal liquor of 14-28%, make the complete clear of solution, without precipitation or cotton-shaped muddy deposits yields; 4-20 hour refluxes within the scope of 60-90 degree celsius temperature; After the complete chelating of raw material, within the scope of 30-80 degree celsius temperature, slowly steam water, until deionized water evaporates completely, obtain chelating, the uniform presoma of color; Precursor powder and different carriers, as Al
20
3, SiO
2, ZnO, ZrO
2, CeO
2, La
2o
3, TiO
2, Fe
2o
3, MgO, MnO2, Cr
2o
3deng, or the molecular sieve that contains Different Silicon aluminum ratio and Different Pore Structures; Or active carbon, carbon pipe, Graphene material with carbon element physical mixed, at ambient temperature, air ambient, grinds 10-30 minute; Wherein to account for the quality dispersion range of whole mixt be 0.5-80wt% to the quality of precursor powder; At inert atmosphere, as argon gas or nitrogen, or be that both arbitrary proportions mix, roasting at 200-700 ℃ of condition temperature range; In the process of roasting, the metallic salt-organic acid after chelating or glucose, cellulose presoma progressively decomposes, and slowly releases reducibility gas, as CH
4, H
2, CO, these gases are as the metal cation in the reducing agent reduction chelate of original position, as Cu, Ag, Au, Ni, Co, Fe, Pt, Pd, Rh, Ru, Ir, is simple metal; After roasting, when temperature, be down to room temperature or use additive method to reduce environment temperature, temperature range is born 80-25 ℃, under condition, adopts 1%-5%O
2product with noble gas mixtures after by roasting, after passivation 1-50 hour, can obtain prepared catalyst.
The preparation method of described a kind of high selectivity, the metallic catalyst of high dispersive, described being dried in temperature range is dry under 80-120 degrees celsius, be 3-50 hour drying time.
Advantage of the present invention and effect are:
The present invention proposes a series of brand-new, nanoscales, (wherein base metal comprises Cu, Ag, Au, Ni, Fe, Co to exempt from the preparation method of metallic catalyst of reduction, high dispersive; Noble metal is Pt, Pd, Rh, Ru, Ir).It is active that prepared Ru/H-beta catalyst shows splendid fischer-tropsch reaction, and the selective of C5-C11 liquid product (main component of gasoline blender) is 70% of full product simultaneously, wherein in product isoparaffin with the ratio of n-alkane up to 5:1.Prepared Ru/H-beta catalyst, the decentralization of noble metal Ru is 40%; The particle size of Ru metal is 1-2 nanometer; Catalyst is not processed through extra reduction, and the reduction degree that records Ru via hydrogen temperature programmed reduction is higher than 90%.
Accompanying drawing explanation
Fig. 1 is the schematic surface that the metallic high dispersive in the prepared metallic catalyst of the present invention is distributed in carrier.
The specific embodiment
Below in conjunction with accompanying drawing illustrated embodiment, the invention will be further described.
The size of gasoline antiknock ability is relevant with chemical composition.Shock resistance best (being that knock tendency is minimum) with aromatic hydrocarbons, cycloalkane and branched isoparaffin take second place, and alkene takes second place again, and in alkane, the shock resistance of positive structure (straight chain) alkane is little.But the aromatic hydrocarbons in gasoline component is because incomplete oxidation burning very easily produces carcinogenic substance, to environment.Therefore, the Fischer-Tropsch synthetic of target is mainly cycloalkane and branched isoparaffin.
1. the preparation of base metal catalysts: select different base metals (as Cu, Ag, Au, Ni, Co, Fe) and precursor (salt that nitrate or acetate etc. contain above-mentioned metallic element) and the organic acid that contains carboxyl (as formic acid, acetic acid, propionic acid, ethanedioic acid, citric acid, amion acetic acid, EDTA, or amino acid etc.) or glucose, cellulose be raw material.Metal precursor and the organic acid or the glucose (cellulose) that contain carboxyl are dissolved in deionized water, and wherein metal ion is 0.3-10 with the molar ratio range of the carboxyl functional group containing, and uses ammoniacal liquor to be adjusted to suitable pH value, and pH value scope is 4-9.The 60-120 ℃ of Powdered presoma forming after dry 3-100 hour.Precursor powder and different carriers are (as Al
20
3, SiO
2, ZnO, ZrO
2, CeO
2, La
2o
3, TiO
2, Fe
2o
3, MgO, MnO2, Cr
2o
3etc., or the molecular sieve that contains Different Silicon aluminum ratio and Different Pore Structures; Or active carbon, carbon pipe, the material with carbon elements such as Graphene) physical mixed, wherein to account for the quality dispersion range of whole mixt be 0.5-80wt% to the quality of precursor powder, in air at room temperature environment, grinds evenly.Get the product that mixes of part, roasting at 200-700 ℃ of inert atmosphere (as argon gas or nitrogen) condition temperature range.After roasting, when temperature is down to room temperature or is used additive method to reduce under environment temperature (temperature range is born 80-25 ℃) condition, employing 1%-5%O
2product with noble gas mixtures after by roasting, passivation a period of time (1-50 hour).After passivation, and can obtain prepared catalyst.
2. the preparation of noble metal catalyst: select different noble metals (as Pt, Pd, Rh, Ru, Ir) precursor (salt that nitrate or acetate etc. contain above-mentioned metallic element) and the organic acid that contains carboxyl are (as formic acid, acetic acid, propionic acid, ethanedioic acid, citric acid, amion acetic acid, EDTA, or amino acid etc.) or glucose, cellulose be raw material.Metal precursor and the organic acid or the glucose (cellulose) that contain carboxyl are dissolved in deionized water, and wherein metal ion is 0.3-10 with the molar ratio range of the carboxyl functional group containing, and uses ammoniacal liquor to be adjusted to suitable pH value, and pH value scope is 4-9.The 60-120 ℃ of Powdered presoma forming after dry 3-100 hour.Precursor powder and different carriers are (as Al
20
3, SiO
2, ZnO, ZrO
2, CeO
2, La
2o
3, TiO
2, Fe
2o
3, MgO, MnO2, Cr
2o
3etc., or the molecular sieve that contains Different Silicon aluminum ratio and Different Pore Structures; Or active carbon, carbon pipe, the material with carbon elements such as Graphene) physical mixed, wherein to account for the quality dispersion range of whole mixt be 0.1-20wt% to the quality of precursor powder, in air at room temperature environment, grinds evenly.Get the product that mixes of part, roasting at 200-700 ℃ of inert atmosphere (as argon gas or nitrogen) condition temperature range.After roasting, when temperature is down to room temperature or is used additive method to reduce under environment temperature (temperature range is born 80-25 ℃) condition, employing 1%-5%O
2product with noble gas mixtures after by roasting, passivation a period of time (1-50 hour).After passivation, and can obtain prepared catalyst.
As shown in Figure 1, the surface that is distributed in carrier of the metallic high dispersive in prepared metallic catalyst.Like this, can improve significantly the decentralization of metal.The metal dispersity that the method for the decentralization employing hydrogen chemisorbed of prepared various metals catalyst metals is measured is between 20% to 40%.
It is presoma that acetic acid ruthenium is selected in the preparation of the Ru/H-β metallic catalyst of high dispersive, and citric acid is as chelating agent, H-beta-molecular sieve SiO
2/ Al
2o
3=27, adopt the method in 1, the load capacity of calculating Ru according to theory is 2wt%.Ru ion and citric acid mol ratio are 1:3, and it is 7.0 that 14% concentration ammoniacal liquor regulates pH, are uniformly dissolved latter 70 degrees Celsius and reflux 4 hours, at 70 degrees Celsius, steam water.Presoma and H-beta-molecular sieve physical mixed 400 degrees Celsius of roastings of argon atmosphere 3 hours, are down to 25 degrees Celsius of uses when temperature and are contained 1%O after grinding evenly
2n
2passivation 4 hours.After passivation, take out catalyst called after Ru/H-β-1.As reference, adopt conventional infusion process preparation, and Ru/H-beta catalyst called after Ru/H-β-2 after reducing in pure hydrogen.Take dealkylation reaction condition as follows: reaction temperature 533 K, pressure 1.0 MPa, catalyst quality 1 g, noble metal Ru load capacity 2 wt%, reaction time 15 h, synthesis gas composition CO/H
2=1/2, W/F (CO+H
2+ Ar)=10 ghmol
-1.Adopt metallic catalyst prepared by this brand-new method and adopt fischer-tropsch reaction activity and the product of the catalyst of same composition prepared by conventional method to distribute as shown in table 1.By contrast, can be clearly seen that adopt metallic catalyst prepared by this new method due to the decentralization of noble metal Ru hand over high, so the conversion ratio of reactivity and CO is traditional catalyst 1.5 times.Isoparaffin is promoted to 4.7 with the ratio of n-alkane by 3.6, and in liquid product, octane number can be greatly improved like this.
The fischer-tropsch reaction activity of table 1 different catalysts and product distribute
Get stable reaction data, reaction condition: reaction temperature: 533 K; Pressure: 1.0 MPa; Catalyst quality: 1 g; Noble metal Ru load capacity: 2 wt%; Reaction time: 15 h; Synthesis gas composition CO/H
2=1/2, W/F (CO+H
2+ Ar)=10 ghmol
-1.C
iso/ C
n: isoparaffin and n-alkane mol ratio that carbon number is greater than 3; C
ole/ C
n: alkene and n-alkane mol ratio that carbon number is greater than 3.
Claims (2)
1. a preparation method for the metallic catalyst of high selectivity, high dispersive, is characterized in that, described method comprises selects one or more different metals and noble metal, as Cu, Ag, Au, Ni, Co, Fe, Pt, Pd, Rh, Ru, Ir, precursor salt, the salt that nitrate or acetate etc. contain above-mentioned metallic element, and a certain organic acid that contains carboxyl, as formic acid, acetic acid, propionic acid, ethanedioic acid, citric acid, amion acetic acid, EDTA, or amino acid etc., or glucose, cellulose are raw material; By metal precursor and the organic acid or the glucose that contain carboxyl, cellulose dissolution is in deionized water, and the 5-500 that the volume of deionized water is volume of mixture doubly; Under room temperature condition, stir 5-30 minute, until the presoma of salt dissolves completely with the organic acid that contains carboxyl, wherein metal ion is 0.3-10 with the molar ratio range of the carboxyl functional group containing, working concentration is that to be adjusted to pH value scope be 4-9 to the ammoniacal liquor of 14-28%, make the complete clear of solution, without precipitation or cotton-shaped muddy deposits yields; 4-20 hour refluxes within the scope of 60-90 degree celsius temperature; After the complete chelating of raw material, within the scope of 30-80 degree celsius temperature, slowly steam water, until deionized water evaporates completely, obtain chelating, the uniform presoma of color; Precursor powder and different carriers, as Al
20
3, SiO
2, ZnO, ZrO
2, CeO
2, La
2o
3, TiO
2, Fe
2o
3, MgO, MnO2, Cr
2o
3deng, or the molecular sieve that contains Different Silicon aluminum ratio and Different Pore Structures; Or active carbon, carbon pipe, Graphene material with carbon element physical mixed, at ambient temperature, air ambient, grinds 10-30 minute; Wherein to account for the quality dispersion range of whole mixt be 0.5-80wt% to the quality of precursor powder; At inert atmosphere, as argon gas or nitrogen, or be that both arbitrary proportions mix, roasting at 200-700 ℃ of condition temperature range; In the process of roasting, the metallic salt-organic acid after chelating or glucose, cellulose presoma progressively decomposes, and slowly releases reducibility gas, as CH
4, H
2, CO, these gases are as the metal cation in the reducing agent reduction chelate of original position, as Cu, Ag, Au, Ni, Co, Fe, Pt, Pd, Rh, Ru, Ir, is simple metal; After roasting, when temperature, be down to room temperature or use additive method to reduce environment temperature, temperature range is born 80-25 ℃, under condition, adopts 1%-5%O
2product with noble gas mixtures after by roasting, after passivation 1-50 hour, can obtain prepared catalyst.
2. the preparation method of the metallic catalyst of a kind of high selectivity according to claim 1, high dispersive, is characterized in that, described being dried in temperature range is dry under 80-120 degrees celsius, and be 3-50 hour drying time.
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| CN108067249A (en) * | 2017-03-29 | 2018-05-25 | 天津大学 | A kind of high dispersive is in platinum based catalyst of carrier silicas and its preparation method and application |
| CN108067249B (en) * | 2017-03-29 | 2020-08-18 | 天津大学 | Platinum-based catalyst highly dispersed in carrier silicon dioxide and preparation method and application thereof |
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