CN103934040B - The preparation method of the metallic catalyst of a kind of high selectivity, high dispersive - Google Patents
The preparation method of the metallic catalyst of a kind of high selectivity, high dispersive Download PDFInfo
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Abstract
A preparation method for the metallic catalyst of high selectivity, high dispersive, relates to a kind of preparation method of metallic catalyst, and the method is a series of nanoscale, exempt to reduce, the preparation method of the metallic catalyst of high dispersive, wherein base metal comprises Cu, Ag, Au, Ni, Fe, Co; Noble metal is Pt, Pd, Rh, Ru, Ir; It is active that prepared Ru/H-beta-molecular sieve 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 the ratio of isoparaffin and n-alkane up to 5:1.Prepared Ru/H-beta-molecular sieve catalyst, the decentralization of noble metal Ru is 40%; The particle size of metal Ru is 1-2 nanometer; Catalyst is without extra reduction treatment, and in prepared Ru/H-beta-molecular sieve catalyst, the reduction degree of metal Ru 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 metallic catalyst of a kind of high selectivity, high dispersive.
Background technology
Gasoline, outward appearance is transparency liquid, and main component is C4 ~ C12 aliphatic hydrocarbon and cyclic hydrocarbon composition.Allow containing a small amount of compound fragrant hydrocarbon in the gasoline standard of China.Gasoline is mainly used in internal combustion engine and car engine.The anti-knock properties of gasoline and the compression ratio of gasoline is had as the important indicator weighing the good and bad standard of gasoline.And the anti-knock properties of gasoline directly represent with the octane number of gasoline.Meanwhile, there is high-octane gasoline and can be applied on the vaporizer gasoline engine of high compression ratio, significantly improve the power of engine, reduce fuel consumption, improve the thermal efficiency.The octane number of gasoline specifies like this: the anti-knock properties of isooctane are better, and octane number is defined as 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 the knock intensity that ideal fuels mixture is produced is identical with comparative fuel, and the percentage by volume so in ideal fuels shared by isooctane is exactly the octane number of comparative fuel with isooctane and normal heptane for ideal fuels.Octane number is higher, and anti-knock characteristic of gasoline is better.The grade of gasoline and price are also distinguished by octane number height.Therefore, improve gasoline quality, increase gasoline added value, in original gasoline fraction, add high-octane gasoline blender is current industrial high-quality gasoline industry development trend.
Industrial gasoline obtains primarily of petroleum fractionating or heavy end cracking.Crude oil produces gasoline component through processes such as distillation, catalytic cracking, thermal cracking, hydrocracking, catalytic reformings.But along with the high speed development of World Economics, the worsening shortages of petroleum resources, developing rapidly of the day by day serious and living beings technology of environmental pollution, F-T synthesis (Fischer-Tropschsynthesis: a kind of important technical process by coal, natural gas, living beings indirect reformer being liquid fuel and high valuable chemicals) causes the extensive concern [1,2] of countries in the world again.In conjunction with the resource characteristic of China " rich coal, oil starvation, weak breath " [3], development take coal as the coal chemical technology of waste petroleum-type product, implement oil and replace strategy, being the key subjects of the economic long-term stability development of relation China and energy security, is also the inevitable choice realizing 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 stablized and not easily produce 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 synthesis Long carbon chain hydrocarbon compound.Meanwhile, molecular sieve has as the dominant catalyst of heavy oil cracking (one of the most successful example of molecular sieve commercial Application) ability cutting off Long carbon chain hydro carbons, generates alkene and the isoparaffin of short carbon chain.Optionally can generate the saturated alkane of C5 ~ C11 height Isomer ratio via F-T synthesis path in conjunction with noble metal catalyst and the bifunctional FTS catalyst of molecular sieve.The product obtained can join in petroleum distillate as gasoline blender, thus improves the octane number of oil greatly, improves quality and the added value of product.
Metallic catalyst be study the earliest in solid catalyst, the most deep, be also simultaneously a kind of catalyst obtaining 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 mainly contain infusion process, coprecipitation, homogeneous precipitation method, sol-gel process and microemulsion method etc. in chemical method; Physical has vapour deposition process, atom deposition method, sputtering method and solid-phase sequencing.In chemical method, it is gentle that coprecipitation method and homogeneous precipitation method prepare reaction condition in ground metallic catalyst preparation process, and easily control, and equipment investment is little, the metal particle size of preparation is uniformly dispersed controlled.And prepared catalyst activity in catalytic reaction is higher, therefore extensive use aborning.But prepare in the process of metallic catalyst at employing coprecipitation method and homogeneous precipitation method, owing to being widely used more cheap metal nitrate presoma, have a large amount of waste water containing nitrate anion to produce, to the extreme influence that environment causes, environment is unfriendly.Therefore, implementing Green Chemistry, advocating today of green synthetic chemistry, develop a kind of simple, free of contamination metallic catalyst preparation method is very necessary.For noble metal catalyst, due to the price of its costliness, vapour deposition process, atom deposition method or sputtering method is generally selected to prepare.Object obtains the noble metal catalyst of high degree of dispersion, thus saves the consumption of noble metal catalyst.
Bibliography:
[1]A.Y.Khodakov,W.Chu,P.Fongarland,AdvancesintheDevelopmentofNovelCobaltFischer-TropschCatalystsforSynthesisofLong-ChainHydrocarbonsandCleanFuels,Chem.Rev.107(2007)1692-1744.
[2]Q.H.Zhang,W.P.Deng,Y.Wang,RecentAdvancesinUnderstandingtheKeyCatalystFactorsforFischer-TropschSynthesis,J.EnergyChem.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 the ratio of isoparaffin and 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 containing above-mentioned metallic element such as nitrate or acetate, and a certain organic acid containing 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 containing carboxyl or glucose, cellulose dissolution is in deionized water, and the volume of deionized water is 5-500 times of volume of mixture; 5-30 minute is stirred under room temperature condition, until the presoma of salt dissolves completely with the organic acid containing carboxyl, wherein metal ion is 0.3-10 with the molar ratio range of the carboxyl functional group contained, working concentration is that to be adjusted to pH value range be 4-9 to the ammoniacal liquor of 14-28%, make the complete clear of solution, without precipitation or cotton-shaped muddy produce life; Reflux 4-20 hour in 60-90 degree Celsius temperature range; After the complete chelating of raw material, in 30-80 degree Celsius temperature range, slowly steam water, until deionized water is evaporated 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 contain the molecular sieve of Different Silicon aluminum ratio and Different Pore Structures; Or active carbon, carbon pipe, graphene carbon Material Physics mixes, at ambient temperature, air ambient, grinding 10-30 minute; Wherein the quality of precursor powder accounts for the mass-dispersion scope of whole mixt is 0.5-80wt%; At inert atmosphere, as argon gas or nitrogen, or be both arbitrary proportion mixing, roasting at Conditions Temperature scope 200-700 DEG C; 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, 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, are simple metal; After roasting, when temperature is down to room temperature or is used additive method to reduce environment temperature, temperature range bears 80-25 DEG C, under condition, adopts 1%-5%O
2with noble gas mixtures by the product after roasting, after passivation 1-50 hour, prepared catalyst can be obtained.
The preparation method of described a kind of high selectivity, the metallic catalyst of high dispersive, described drying is dry under temperature range is 80-120 degrees celsius, and drying time is 3-50 hour.
Advantage of the present invention and effect are:
The present invention proposes a series of completely newly, nanoscale, exempt to reduce, (wherein base metal comprises Cu, Ag, Au, Ni, Fe, Co for the preparation method of the metallic catalyst of 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 the ratio of isoparaffin and 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, without extra reduction treatment, records the reduction degree of Ru higher than 90% via hydrogen temperature programmed reduction.
Accompanying drawing explanation
Metallic high dispersive in the metallic catalyst of Fig. 1 prepared by the present invention is distributed in the schematic surface of carrier.
Detailed description of the invention
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.With the shock resistance of aromatic hydrocarbons best (namely knock tendency is minimum), cycloalkane and branched isoparaffin take second place, and third, in alkane, the shock resistance of positive structure (straight chain) alkane is little for alkene.But the aromatic hydrocarbons in gasoline component burns due to incomplete oxidation and 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 metal (as Cu, Ag, Au, Ni, Co, Fe) and the precursor salt of above-mentioned metallic element (nitrate or the acetate etc. containing) and the organic acid containing 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.Be dissolved in deionized water by metal precursor and the organic acid containing carboxyl or glucose (cellulose), wherein metal ion is 0.3-10 with the molar ratio range of the carboxyl functional group contained, and use ammoniacal liquor to be adjusted to suitable pH value, pH value range is 4-9.The 60-120 DEG C of Powdered presoma formed 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 contain the molecular sieve of Different Silicon aluminum ratio and Different Pore Structures; Or active carbon, carbon pipe, the material with carbon elements such as Graphene) physical mixed, wherein the quality of precursor powder accounts for the mass-dispersion scope of whole mixt is 0.5-80wt%, and in air at room temperature environment, grinding is evenly.Get the product that part mixes, roasting at inert atmosphere (as argon gas or nitrogen) Conditions Temperature scope 200-700 DEG C.After roasting, under temperature is down to room temperature or is used additive method to reduce environment temperature (temperature range bears 80-25 DEG C) condition, employing 1%-5%O
2with noble gas mixtures by the product after roasting, passivation a period of time (1-50 hour).After passivation, and prepared catalyst can be obtained.
2. the preparation of noble metal catalyst: select different noble metal (as Pt, Pd, Rh, Ru, Ir) precursor (salt containing above-mentioned metallic element such as nitrate or acetate) and the organic acid containing 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.Be dissolved in deionized water by metal precursor and the organic acid containing carboxyl or glucose (cellulose), wherein metal ion is 0.3-10 with the molar ratio range of the carboxyl functional group contained, and use ammoniacal liquor to be adjusted to suitable pH value, pH value range is 4-9.The 60-120 DEG C of Powdered presoma formed 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 contain the molecular sieve of Different Silicon aluminum ratio and Different Pore Structures; Or active carbon, carbon pipe, the material with carbon elements such as Graphene) physical mixed, wherein the quality of precursor powder accounts for the mass-dispersion scope of whole mixt is 0.1-20wt%, and in air at room temperature environment, grinding is evenly.Get the product that part mixes, roasting at inert atmosphere (as argon gas or nitrogen) Conditions Temperature scope 200-700 DEG C.After roasting, under temperature is down to room temperature or is used additive method to reduce environment temperature (temperature range bears 80-25 DEG C) condition, employing 1%-5%O
2with noble gas mixtures by the product after roasting, passivation a period of time (1-50 hour).After passivation, and prepared catalyst can be obtained.
As shown in Figure 1, the surface being distributed in carrier of the metallic high dispersive in prepared metallic catalyst.Like this, the decentralization of metal can be improved significantly.The decentralization of prepared various metals catalyst metals adopts the metal dispersity of the method mensuration of hydrogen chemisorption between 20% to 40%.
The preparation of the Ru/H-β metallic catalyst of high dispersive selects acetic acid ruthenium to be presoma, citric acid as chelating agent, H-beta-molecular sieve SiO
2/ Al
2o
3=27, adopting the method in 1, is 2wt% according to the load capacity of theory calculate Ru.Ru ion and citric acid mol ratio are 1:3, and 14% concentration ammoniacal liquor regulates pH to be 7.0, are uniformly dissolved rear 70 degrees Celsius of backflows 4 hours, steam water at 70 degrees Celsius.Presoma and H-beta-molecular sieve physical mixed are ground evenly, argon atmosphere 400 degrees Celsius of roastings 3 hours, be down to 25 degrees Celsius use containing 1%O when temperature
2n
2passivation 4 hours.Catalyst called after Ru/H-β-1 is taken out after passivation.As reference, conventional infusion process is adopted to prepare, and the Ru/H-beta catalyst called after Ru/H-β-2 in pure hydrogen after reduction.Take dealkylation reaction condition as follows: reaction temperature 533K, pressure 1.0MPa, catalyst quality 1g, noble metal Ru load capacity 2wt%, reaction time 15h, synthesis gas composition CO/H
2=1/2, W/F (CO+H
2+ Ar)=10ghmol
-1.The fischer-tropsch reaction of the catalyst of same composition prepared by the metallic catalyst adopting this brand-new method to prepare and employing conventional method is active and product distribution is as shown in table 1.By contrast, can be clearly seen that and adopt the metallic catalyst prepared of this new method to hand over high, so the conversion ratio of reactivity and CO is 1.5 times of traditional catalyst due to the decentralization of noble metal Ru.The ratio of isoparaffin and n-alkane is promoted to 4.7 by 3.6, and in such liquid product, octane number can be greatly improved.
The fischer-tropsch reaction activity of table 1 different catalysts and product distribution
Get stable reaction data, reaction condition: reaction temperature: 533K; Pressure: 1.0MPa; Catalyst quality: 1g; Noble metal Ru load capacity: 2wt%; Reaction time: 15h; Synthesis gas composition CO/H
2=1/2, W/F (CO+H
2+ Ar)=10ghmol
-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 (1)
1. a preparation method for the metallic catalyst of high selectivity, high dispersive, is characterized in that, described method comprises selects Cu, Ag, Au, Ni, Co, Fe, Pt, Pd, Rh, Ru, one or more different base metals in Ir and the precursor salt of noble metal, this precursor salt is selected from nitrate containing above-mentioned metallic element or acetate, and a certain formic acid containing carboxyl, acetic acid, propionic acid, ethanedioic acid, citric acid, amion acetic acid, EDTA, or amino acid, or glucose, or cellulose is raw material; By above-mentioned metal precursor salt and the organic acid containing carboxyl or amino acid, or glucose, or cellulose dissolution is in deionized water, and the volume of deionized water is 5-500 times of volume of mixture; 5-30 minute is stirred under room temperature condition, until the presoma of salt and the organic acid containing carboxyl, or amino acid, or glucose, or cellulose dissolves completely, wherein metal ion is 0.3-10 with the molar ratio range of carboxyl functional group contained, and working concentration is that to be adjusted to pH value range be 4-9 to the ammoniacal liquor of 14-28%, make the complete clear of solution, without precipitation or cotton-shaped muddy produce life; Reflux 4-20 hour in 60-90 degree Celsius temperature range; After the complete chelating of raw material, in 30-80 degree Celsius temperature range, slowly steam water, until deionized water is evaporated completely, obtain chelating, the uniform presoma of color; The precursor powder of gained and different carriers Al
2o
3, SiO
2, ZnO, ZrO
2, CeO
2, La
2o
3, TiO
2, Fe
2o
3, MgO, MnO
2, Cr
2o
3, or contain the molecular sieve of Different Silicon aluminum ratio and Different Pore Structures; Or active carbon, carbon pipe, graphene carbon Material Physics mixes, at ambient temperature, air ambient, grinding 10-30 minute; Wherein the quality of precursor powder accounts for the 0.5-80wt% of whole mixt quality; At inert atmosphere argon gas or nitrogen, or be both arbitrary proportion mixing, roasting at Conditions Temperature scope 200-700 DEG C; In the process of roasting, the metallic salt-organic acid after chelating or glucose, cellulose presoma progressively decomposes, and slowly releases reducibility gas CH
4, H
2, CO, these gases are as the metal cation Cu in the reducing agent reduction chelate of original position, and Ag, Au, Ni, Co, Fe, Pt, Pd, Rh, Ru, Ir are simple metal; After roasting, when temperature is down to room temperature or is used additive method to reduce environment temperature, temperature range bears 80-25 DEG C, under condition, adopts 1%-5%O
2with noble gas mixtures by the product after roasting, after passivation 1-50 hour, prepared catalyst can be obtained.
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| CN104923287A (en) * | 2015-05-13 | 2015-09-23 | 北京化工大学 | Microporous molecular sieve based catalyst for ammonia removal and preparation method therefor and application thereof |
| CN106492759B (en) * | 2016-11-21 | 2021-03-26 | 浙江农林大学 | Preparation method of silver oxide/graphene oxide composite material capable of efficiently co-capturing radioactive or highly toxic anions and cations |
| CN106975505B (en) * | 2017-03-03 | 2019-11-15 | 华南理工大学 | A kind of carbon material supported Pd catalyst of nitrating and the preparation method and application thereof is in Catalytic Hydrogenation of Nitrobenzene reaction |
| 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 |
| CN107051461B (en) | 2017-05-02 | 2020-05-08 | 江南大学 | Graphene modified iron-based catalyst, preparation thereof and application thereof in Fischer-Tropsch reaction |
| 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 |
| CN109806881A (en) * | 2017-11-20 | 2019-05-28 | 中国科学院大连化学物理研究所 | A kind of iron-molybdic catalyst and preparation method thereof for prepn. of formaldehyde by oxidation of methanol |
| CN110098412B (en) * | 2019-05-17 | 2020-09-29 | 清华大学深圳研究生院 | Preparation method and application of battery catalyst |
| CN111111723B (en) * | 2020-02-06 | 2023-07-04 | 江南大学 | Iron-based Fischer-Tropsch catalyst and preparation method and application thereof |
| CN114425444B (en) * | 2020-10-14 | 2024-01-26 | 中国石油化工股份有限公司 | Catalyst for synthesizing vinyl acetate by ethylene method and preparation method thereof |
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