CN103464159B - Copper-iron based catalyst and application thereof in preparing low mixed alcohols by catalyzing synthesis gas - Google Patents
Copper-iron based catalyst and application thereof in preparing low mixed alcohols by catalyzing synthesis gas Download PDFInfo
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Abstract
The invention discloses a copper-iron based catalyst in the technical field of catalyst preparation and application thereof in preparing low mixed alcohols by catalyzing synthesis gas. According to the invention, a copper-magnesium-iron hydrotalcite precursor is prepared by a nucleation-crystallization isolating method, and then the copper-magnesium-iron hydrotalcite precursor is roasted and then subjected to reduction treatment to obtain the copper-iron based catalyst of highly dispersed nanoparticles. The catalyst has the characteristics that the catalytic active ingredients are highly dispersed, the catalytic active ingredients have strong interaction with one another, and are high in stability, and as a result, the activity and selectivity of the catalyst are improved. After the copper-iron based catalyst is applied to preparing low mixed alcohols from the synthesis gas, the CO conversion rate is high, and the selectivity and space time yield of the low mixed alcohols are also improved; besides, the conversion rate of CO for synthesizing low mixed alcohols through CO hydrogenation is 56.89% and the selectivity of alcohols is 49.07%.
Description
Technical field
The invention belongs to catalyst preparation technical field, be specifically related to a kind of copper ferrum-based catalyst and be applied to catalyze and synthesize gas and prepare MAS.
Background technology
Energy development and environmental protection have become two great strategy themes of human society survival and development.As coal producer the biggest in the world, the energy resource structure feature of the few oil of the rich coal of China is more obvious.From the angle of the utilization of resources and environmental protection, Efficient Conversion clean coal and biomass energy preparation " green fuel " MAS have important strategic importance and application prospect.Low-carbon alcohols, or claim MAS, generally refer to C
1-C
5alcohol-based mixtures.Low-carbon alcohols has very high octane number, and it is explosion-proof, anti-seismic performance is superior.Have and make CO in vehicle exhaust, the content of oxynitrides and hydrocarbon reduces 30%-50%, and the lead tetraethide larger with the alternative toxicity of gasoline blending and oneself controversial methyl tertiary butyl ether(MTBE), reduce greenhouse gases CO
2discharge, be conducive to the advantages such as environmental protection.
Since 20 beginnings of the century, software engineering researchers invent goes out multiple different low-carbon alcohol catalyst system, but totally it seems that the deficiency that there is the aspects such as active, selective, stability and economy, the catalyst of exploitation high activity and high selectivity are still the difficult point and key studied.There is good catalytic activity by noble metal catalyst (mainly Rh catalyst) in the catalyst of the direct synthesis of low-carbon alcohol of synthesis gas at present, but expensively limit its application industrially.Therefore non-metallic catalyst, comprises modification catalyst for methanol, modifies F-T synthetic catalyst and Mo is catalyst based just arouses widespread concern.In these non-precious metal catalysts, modify F-T synthetic catalyst (CuCo, CuFe catalyst) and be considered to desirable mixed alcohol synthetic catalyst.But such catalyst also exists the easy passivation of catalyst at present, and in product, alcohol is selective low, the problems such as poor catalyst stability.
In recent years, hydrotalcite (LDHs), due to its adjustable chemical composition and special structure, is considered to a kind of well heterogeneous catalyst.LDHs is the layered inorganic material that a class has special construction, and hydrotalcite composition structural formula is: [M
2+ 1-xm
3+ x(OH)
2] (A
n-)
x/nmH
2o, wherein M
2+and M
3+be respectively divalence and trivalent metal cation, be positioned at A on main body laminate
n-be interlayer exchangeable anions, x is M
3+/ (M
2++ M
3+) molar ratio, m is the mole of intermediary water molecule.Layer structure due to uniqueness and impact, the divalence on LDHs laminate and the mutual high degree of dispersion of trivalent metal cation by lattice orientation effect.Homodisperse metal oxide can obtained after high-temperature roasting and reduction, or metal/metal oxide composition.This feature of LDHs is utilized to obtain multicomponent, the load type metal nanocatalyst of high dispersive and special appearance.If therefore with copper Mg-Fe ball for precursor, the copper magnesium ferrum-based catalyst of the even high dispersive of catalytic active component can be obtained after high-temperature roasting reduction, can strong interaction be had between catalytic active component, be expected to improve the selective of CO conversion ratio and MAS.
Summary of the invention
Object of the present invention aims to provide a kind of copper ferrum-based catalyst and is applied to catalyze and synthesize gas prepares MAS.The present invention adopts nucleation crystallization isolation method to prepare copper Mg-Fe ball precursor, then reduction treatment after its roasting is obtained the copper ferrum-based catalyst of high-dispersion nano particle.This catalyst activity component high degree of dispersion, there is strong interaction between catalytic active component, stability is high, and the activity and selectivity of catalyst is improved.
First the salting liquid of cupric magnesium iron and aqueous slkali mix rapidly by the present invention in full back-mixing rotating liquid-film reactor, violent circulation stirring, realize the coprecipitation reaction of salting liquid and aqueous slkali, the instantaneous abundant contact of reactant is made by the linear velocity controlling reactor rotor, collision, become instantaneous the completing of nuclear reaction and form a large amount of nucleus, after by slurries crystallization at a certain temperature in another container, then nucleus synchronous growth, ensure the uniformity of crystalline size in crystallization process, by the hydrotalcite precursor of gained under certain conditions after roasting reduction, obtain the dispersed copper ferrum-based catalyst having nano particle.Be applied to synthesis gas and prepare MAS, have good effect.
The preparation method of copper ferrum-based catalyst of the present invention is specific as follows:
(1) Cu is taken respectively
2+soluble inorganic salt 2-20g, Mg
2+soluble inorganic salt 2-20g, Fe
3+soluble inorganic salt 3-20g in 100-200ml deionized water, stir make it dissolve completely; Take NaOH5-10g respectively, Na
2cO
34-10g, in 100-200ml deionized water, stirs and makes it dissolve completely;
(2) two kinds of solution that step (1) obtains are added nucleation in rotating liquid-film reactor simultaneously and after the 2-3min that circulates, slurries are placed in water heating kettle, crystallization 24-48h at the temperature of 100-200 DEG C, filter, then spend deionized water product to the pH value of washings and be less than 8, then obtain copper Mg-Fe ball precursor through 50-80 DEG C of dry 12-24h;
(3) the copper Mg-Fe ball precursor that step (2) is obtained is placed in Muffle furnace, is warming up to 400-600 DEG C with the heating rate of 1-10 DEG C/min, insulation 2-6h, naturally cools to room temperature afterwards; Then reduction treatment is carried out to it, reducing condition is: pass into hydrogen and nitrogen mixed gas that hydrogen and nitrogen volume ratio are 0.05-0.2, flow velocity is that 20-80ml/min, 1-10 DEG C/min is warmed up to 200-500 DEG C, insulation 0.5-6h, cools to room temperature after reduction terminates and obtains copper ferrum-based catalyst.
Described Cu
2+soluble inorganic salt be copper chloride, copper nitrate; Described Mg
2+soluble inorganic salt be magnesium chloride, magnesium nitrate; Described Fe
3+soluble inorganic salt be iron chloride, ferric nitrate.
Copper ferrum-based catalyst of the present invention is used for catalyzing and synthesizing gas and prepares MAS, and concrete reaction condition is: the copper ferrum-based catalyst amount of fill of above-mentioned preparation is 0.01-5g, reaction temperature 100-500 DEG C, reaction pressure 1-6MPa, and the synthesis gas passed into is H
2be the H of 0.5-3.0 with CO volume ratio
2with CO mist, corresponding air speed is GHSV=1000-10000h
-1, reaction time 10-100h.
Air speed of the present invention is pass into the volume of gas and the ratio of catalyst quality in the unit time.
Compared with prior art, the invention has the advantages that:
1. catalyst of the present invention adopts nucleation crystallization isolation method to prepare hydrotalcite precursor, and the method is easy to operation, and reproducible, crystallite dimension is homogeneous, and this catalyst is applicable to catalyze and synthesize gas synthesizing low-carbon mixed alcohol.
2. the present invention is using hydrotalcite as precursor, after roasting, catalytic active component obtains high degree of dispersion, under given conditions after reduction, obtain homodisperse nano particle, achieve the even height dispersion of catalytic active component, there is strong interaction between catalytic active component, improve the selective of CO conversion ratio and alcohol.
3. the catalyst that prepared by the present invention is structural catalyst, this catalyst activity is high and stable, and CO conversion ratio is high, and the selective and space-time yield of MAS also increases, the conversion ratio of the CO of CO hydrogenation synthesizing low carbon mixed alcohol is 56.89%, and the selective of alcohol is 49.07%.
Accompanying drawing explanation
Fig. 1 is the XRD figure of copper ferrum-based catalyst prepared by embodiment 1;
Fig. 2 is the XRD figure of copper ferrum-based catalyst prepared by embodiment 2;
Fig. 3 is the XRD figure of copper ferrum-based catalyst prepared by embodiment 3;
Fig. 4 is the HREM figure of copper ferrum-based catalyst prepared by embodiment 2.
Detailed description of the invention
Below in conjunction with embodiment, the invention will be further described, instead of limit the scope of the invention.
Embodiment 1
1. take Cu (NO respectively
3)
23H
2o4g, Mg (NO
3)
26H
2o12.8g, Fe (NO
3)
39H
2o13.4g, in 100ml deionized water, stirs and makes it dissolve completely; Take NaOH6.4g respectively, Na
2cO
37.1g, in 100ml deionized water, stirs and makes it dissolve completely;
2. two kinds of solution step 1 obtained add fast nucleation in rotating liquid-film reactor by certain flow rate simultaneously, and after the 2min that circulates, mixed liquor is placed in water heating kettle, at the temperature of 100 DEG C, then crystallization 48h. spends deionized water much filtrate and makes the pH value of washings be less than 8, then obtains copper Mg-Fe ball precursor through 60 DEG C of dry 24h.
3. the copper Mg-Fe ball precursor that step 2 is obtained is placed in Muffle furnace, is warmed up to 500 DEG C with 2 DEG C/min, insulation 6h, Temperature fall is to room temperature; Then reduction treatment is carried out, reducing condition is: pass into hydrogen and nitrogen mixed gas that hydrogen and nitrogen volume ratio are 0.05, flow velocity is 40mL/min, is warmed up to 350 DEG C with 2 DEG C/min, insulation 4h, cools to room temperature after reduction terminates and obtains structuring copper ferrum-based catalyst.As can be seen from XRD, after reduction, there is the diffraction maximum of elemental copper and fe.
Use the copper ferrum-based catalyst of above-mentioned preparation to prepare MAS for catalyzing and synthesizing gas, concrete reaction condition is: the copper ferrum-based catalyst amount of fill of above-mentioned preparation is 4g, reaction temperature 300 DEG C, reaction pressure 4MPa, and the synthesis gas passed into is H
2be the H of 2.0 with CO volume ratio
2with CO mist, corresponding air speed is GHSV=2000h
-1, reaction time 24h.
Product is by being equipped with TCD and FID dual detector, and the GC-2014 type gas chromatograph of two chromatographic column does on-line analysis.TCD detector is for analyzing N
2, CO and CH
4, fid detector for analyzing all the other alkane, alcohol and oxygenatedchemicals.Evaluation result: CO conversion ratio is 63.22%, the selective of total alcohol is 32.77%.
Embodiment 2
1. take Cu (NO respectively
3)
23H
2o9.1g, Mg (NO
3)
26H
2o9.6g, Fe (NO
3)
39H
2o10.1g, in 100ml deionized water, stirs and makes it dissolve completely; Take NaOH6.4g respectively, Na
2cO
35.3g, in 100ml deionized water, stirs and makes it dissolve completely;
2. two kinds of solution step 1 obtained add fast nucleation in rotating liquid-film reactor by certain flow rate simultaneously, and after the 2min that circulates, mixed liquor is placed in water heating kettle, at the temperature of 100 DEG C, then crystallization 48h. spends deionized water much filtrate and makes the pH value of washings be less than 8, then obtains copper Mg-Fe ball precursor through 60 DEG C of dry 24h.
3. the copper Mg-Fe ball precursor that step 2 is obtained is placed in Muffle furnace, is warmed up to 500 DEG C with 2 DEG C/min, insulation 6h, Temperature fall is to room temperature; Then reduction treatment is carried out, reducing condition is: pass into hydrogen and nitrogen mixed gas that hydrogen and nitrogen volume ratio are 0.05, flow velocity is 40mL/min, is warmed up to 350 DEG C with 2 DEG C/min, insulation 4h, cools to room temperature after reduction terminates and obtains structuring copper ferrum-based catalyst.As can be seen from XRD, after reduction, there is the diffraction maximum of elemental copper and fe.
Use the copper ferrum-based catalyst of above-mentioned preparation to prepare MAS for catalyzing and synthesizing gas, concrete reaction condition is: the copper ferrum-based catalyst amount of fill of above-mentioned preparation is 4g, reaction temperature 300 DEG C, reaction pressure 4MPa, and the synthesis gas passed into is H
2be the H of 2.0 with CO volume ratio
2with CO mist, corresponding air speed is GHSV=2000h
-1, reaction time 24h.
Product is by being equipped with TCD and FID dual detector, and the GC-2014 type gas chromatograph of two chromatographic column does on-line analysis.TCD detector is for analyzing N
2, CO and CH
4, fid detector for analyzing all the other alkane, alcohol and oxygenatedchemicals.Evaluation result: CO conversion ratio is 56.89%, the selective of total alcohol is 49.07%.
Embodiment 3
1. take Cu (NO respectively
3)
23H
2o12.1g, Mg (NO
3)
26H
2o7.7g, Fe (NO
3)
39H
2o8.1g, in 100ml deionized water, stirs and makes it dissolve completely; Take NaOH6.4g respectively, Na
2cO
34.2g, in 100ml deionized water, stirs and makes it dissolve completely;
2. two kinds of solution step 1 obtained add nucleation in rotating liquid-film reactor simultaneously, and after the 2min that circulates, mixed liquor is placed in water heating kettle, at the temperature of 100 DEG C, then crystallization 48h. spends deionized water much filtrate and makes the pH value of washings be less than 8, then obtains copper Mg-Fe ball precursor through 60 DEG C of dry 24h.
3. the copper Mg-Fe ball precursor that step 2 is obtained is placed in Muffle furnace, is warmed up to 500 DEG C with 2 DEG C/min, insulation 6h, Temperature fall is to room temperature; Then reduction treatment is carried out, reducing condition is: pass into hydrogen and nitrogen mixed gas that hydrogen and nitrogen volume ratio are 0.05, flow velocity is 40mL/min, is warmed up to 350 DEG C with 2 DEG C/min, insulation 4h, cools to room temperature after reduction terminates and obtains structuring copper ferrum-based catalyst.As can be seen from XRD, after reduction, there is the diffraction maximum of elemental copper and fe.
Use the copper ferrum-based catalyst of above-mentioned preparation to prepare MAS for catalyzing and synthesizing gas, concrete reaction condition is: the copper ferrum-based catalyst amount of fill of above-mentioned preparation is 4g, reaction temperature 300 DEG C, reaction pressure 4MPa, and the synthesis gas passed into is H
2be the H of 2.0 with CO volume ratio
2with CO mist, corresponding air speed is GHSV=2000h
-1, reaction time 24h.
Product is by being equipped with TCD and FID dual detector, and the GC-2014 type gas chromatograph of two chromatographic column does on-line analysis.TCD detector is for analyzing N
2, CO and CH
4, fid detector for analyzing all the other alkane, alcohol and oxygenatedchemicals.Evaluation result: CO conversion ratio is 50.32%, the selective of total alcohol is 45.75%.
Embodiment 4
1. take Cu (NO respectively
3)
23H
2o12.1g, Mg (NO
3)
26H
2o7.7g, Fe (NO
3)
39H
2o8.1g, in 100ml deionized water, stirs and makes it dissolve completely; Take NaOH6.4g respectively, Na
2cO
34.2g, in 100ml deionized water, stirs and makes it dissolve completely;
2. two kinds of solution step 1 obtained add nucleation in rotating liquid-film reactor simultaneously, and after the 2min that circulates, mixed liquor is placed in water heating kettle, at the temperature of 100 DEG C, then crystallization 48h. spends deionized water much filtrate and makes the pH value of washings be less than 8, then obtains copper Mg-Fe ball precursor through 60 DEG C of dry 24h.
3. the copper Mg-Fe ball precursor that step 2 is obtained is placed in Muffle furnace, is warmed up to 500 DEG C with 2 DEG C/min, insulation 6h, Temperature fall is to room temperature; Then carry out reduction treatment, reducing condition is: pass into hydrogen and nitrogen mixed gas that hydrogen and nitrogen volume ratio are 0.05, flow velocity is 40mL/min, is warmed up to 350 DEG C with 2 DEG C/min, and insulation 4h, cools to room temperature after reduction terminates and obtain copper ferrum-based catalyst.As can be seen from XRD, after reduction, there is the diffraction maximum of elemental copper and fe.For making the metal in copper ferrum-based catalyst more disperse, and strengthening catalytic performance, adding the montmorillonite of 6wt%, making mixed catalyst.
Use the mixed catalyst of above-mentioned preparation to prepare MAS for catalyzing and synthesizing gas, concrete reaction condition is: above-mentioned mixed catalyst amount of fill is 4g, reaction temperature 300 DEG C, reaction pressure 4MPa, and the synthesis gas passed into is H
2be the H of 2.0 with CO volume ratio
2with CO mist, corresponding air speed is GHSV=2000h
-1, reaction time 24h.
Product is by being equipped with TCD and FID dual detector, and the GC-2014 type gas chromatograph of two chromatographic column does on-line analysis.TCD detector is for analyzing N
2, CO and CH
4, fid detector for analyzing all the other alkane, alcohol and oxygenatedchemicals.Evaluation result: CO conversion ratio is 56.41%, the selective of total alcohol is 45.12%.
Claims (3)
1. a preparation method for copper ferrum-based catalyst, is characterized in that, its preparation method is specific as follows:
(1) Cu is taken respectively
2+soluble inorganic salt 2-20g, Mg
2+soluble inorganic salt 2-20g, Fe
3+soluble inorganic salt 3-20g in 100-200mL deionized water, stir make it dissolve completely; Take NaOH 5-10g respectively, Na
2cO
34-10g, in 100-200mL deionized water, stirs and makes it dissolve completely;
(2) two kinds of solution that step (1) obtains are added nucleation in rotating liquid-film reactor simultaneously and after the 2-3min that circulates, slurries are placed in water heating kettle, crystallization 24-48h at the temperature of 100-200 DEG C, filter, then spend deionized water product to the pH value of washings and be less than 8, then obtain copper Mg-Fe ball precursor through 50-80 DEG C of dry 12-24h;
(3) the copper Mg-Fe ball precursor that step (2) is obtained is placed in Muffle furnace, is warming up to 400-600 DEG C with the heating rate of 1-10 DEG C/min, insulation 2-6h, naturally cools to room temperature afterwards; Then reduction treatment is carried out to it, reducing condition is: pass into hydrogen and nitrogen mixed gas that hydrogen and nitrogen volume ratio are 0.05-0.2, flow velocity is that 20-80mL/min, 1-10 DEG C/min is warmed up to 200-500 DEG C, insulation 0.5-6h, cools to room temperature after reduction terminates and obtains copper ferrum-based catalyst.
2. preparation method according to claim 1, is characterized in that, described Cu
2+soluble inorganic salt be copper chloride, copper nitrate; Described Mg
2+soluble inorganic salt be magnesium chloride, magnesium nitrate; Described Fe
3+soluble inorganic salt be iron chloride, ferric nitrate.
3. the copper ferrum-based catalyst that method according to claim 1 and 2 prepares catalyzes and synthesizes the application that gas prepares MAS, it is characterized in that, its concrete reaction condition is: described copper ferrum-based catalyst amount of fill is 0.01-5g, reaction temperature 100-500 DEG C, reaction pressure 1-6MPa, the synthesis gas passed into is H
2be the H of 0.5-3.0 with CO volume ratio
2with CO mist, corresponding air speed is GHSV=1000-10000h
-1, reaction time 10-100h.
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| CN105903472B (en) * | 2016-05-23 | 2018-08-03 | 北京化工大学 | A kind of equally distributed CoCu catalyst of synthesis gas ethyl alcohol and higher alcohol |
| CN108465468B (en) * | 2018-03-21 | 2021-03-12 | 西安工程大学 | Preparation method of catalyst for preparing low-carbon alcohol from synthesis gas |
| CN110183592B (en) * | 2019-04-23 | 2021-06-29 | 莆田学院 | Nano-copper/silver hydrotalcite-like conductive composite material and preparation method thereof |
| CN111229286B (en) * | 2020-03-24 | 2021-03-23 | 吉林大学 | Catalytic material, preparation method thereof and photocatalyst |
| CN112916010B (en) * | 2021-01-26 | 2022-09-16 | 北京化工大学 | Cu for selective hydrogenation of alkyne y /MMgO x Catalyst and preparation method thereof |
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