CN104475106A - Carbon nano tube composite nanometer cobalt-copper alloy catalyst for low-carbon alcohol synthesis and preparation method of carbon nano tube composite nanometer cobalt-copper alloy catalyst - Google Patents
Carbon nano tube composite nanometer cobalt-copper alloy catalyst for low-carbon alcohol synthesis and preparation method of carbon nano tube composite nanometer cobalt-copper alloy catalyst Download PDFInfo
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Abstract
The invention relates to a carbon nano tube composite nanometer cobalt-copper alloy catalyst for low-carbon alcohol synthesis and a preparation method of the carbon nano tube composite nanometer cobalt-copper alloy catalyst. According to the preparation method, firstly Co, Cu, Al and other additives are prepared into hydrotalcite-like structural substances to realize the uniform mixing of Co and Cu; CNTs and a hydrotalcite-like compound are compounded as a precursor of the catalyst, wherein a carbon nano tube is used as a diluent and the CNTs is used as a dispersing agent to prepare the nanometer cobalt-copper alloy catalyst used for preparing low-carbon alcohol from a synthetic gas; the uniform mixing of various metal ions contained in the precursor of the catalyst and copper ions and cobalt ions especially can be realized by controlling a deposition condition; because strong interaction exists between metal and the carbon nano tube, a Cu-Co nanometer alloy can be highly dispersed on the carbon nano tube after reduction, so that the granule sintering, which is caused by migration, of the Cu-Co nanometer alloy is effectively prevented. The prepared Cu-Co active component has the large active specific surface area, and the sintering of the Cu-Co active component can be inhibited by a carrier and the additives.
Description
Technical field
The present invention relates to chemical catalyst technical field, be specifically related to a kind of catalyst for the synthesis of gas low-carbon alcohols, its preparation method and application.
Background technology
Synthesis gas (CO and H can be produced by natural gas or coal or reproducible living beings
2mist), then may production low-carbon alcohols (referring to the alcohol containing two carbon atoms or more) by synthesis gas, low-carbon alcohols has significant application value at fuel and chemical field.Low-carbon alcohols can be used as the power fuel of high-quality, can substitute controversial MTBE and the larger lead tetraethide of toxicity as petroleum additive, simultaneously by low-carbon alcohols separable go out second, third, alcohols that the price such as fourth and amylalcohol is higher.In addition, low-carbon alcohols can also as one of means of coal liquefaction, realize the alkylation of coal and solubilized and as liquefied petroleum gas substitute etc.
Methyl alcohol, hydro carbons and CO is often attended by low carbon alcohol by synthetic gas reaction
2deng the generation of accessory substance, therefore the key of synthesis of low-carbon alcohol technology is the catalyst that exploitation has excellent activity, high selectivity and high stability.At present, the formate low-carbon alcohol catalyst of report has four kinds: the noble metal catalyst taking Rh as representative, the catalst for synthesis of methanol of modification, and Mo is catalyst based, the FT synthetic catalyst of modification.Wherein, though take Rh as the hydrogenation activity that the noble metal catalyst of representative has had, ethanol selectivity is better; But it is expensive, easily by CO
2the feature such as to poison limits its application.The methanol synthesis catalyst operating condition of modification is harsh, and product is still based on methyl alcohol, so be eliminated gradually.Though the catalyst with base of molybdenum of modification has unique resistance to SO_2, costly deep desulfuration can be avoided, and it is moisture less in product, low-carbon alcohols content is higher, but the hydrogen-carbon ratio of unstripped gas is required harsh, must between 1.0 ~ 1.1, and also this catalyst promoter very easily forms carbonyls with CO, cause the loss of its constituent element, thus its stability is restricted.
The fischer-tropsch synthetic catalyst of modification is mainly catalyst based based on Cu-Fe and Co-Cu.During Cu-Fe is catalyst based, because Fe has higher water gas shift reaction activity, make containing more water in product, hydrocarbon selective is higher simultaneously.In Co-Cu is catalyst based, Co is considered to the highest active in FT reaction element, Co series catalysts has Water gas shift/WGS insensitive, and the advantage such as not easily carbon distribution is poisoning in course of reaction, Cu is conducive to generating alcohol, and the synergy of Cu and Co can improve the activity of catalyst and contain two and two or more carbon atom alcohol (C
2+alcohol) selective, therefore Co-Cu is catalyst based is considered to up-and-coming formate low-carbon alcohol catalyst.But C in product
2+alcohol is selective still on the low side, does not still have industrial production and is worth.
During Co-Cu is catalyst based, Cu is upper can methanol, and Co then can increase carbochain and namely become molecule containing two carbon atoms and two or more carbon atom, simultaneously the chemical bond that ruptures again between carbon and oxygen of Co; In other words on Cu after methanol, methanol conversion is the more molecule of carbon atoms again by Co, obtains ethanol, propyl alcohol, butanols etc.; Namely Co-Cu synergy generates low-carbon alcohols.But if only have Cu, product is methyl alcohol; If only have Co, product is methane, ethane, propane, butane etc., and Co makes the C―O bond cleavage of CO and hydrogenation, carbochain increase.So good catalyst should be that Co-Cu phase is close, or form alloy; And independent Cu and independent Co will be avoided to exist as far as possible.Preparation Co-Cu alloy is exactly the key point of technology.
Meanwhile, in Co-Cu catalyst, the particle of Co-Cu is little, otherwise the conversion ratio of CO too low (being exactly active low), so the efficiency of catalyst is just low.Because catalytic reaction is carried out on the surface of CATALYST Co-Cu, particle is large, and specific area is little.The effect of carrier (aluminium oxide etc.) is exactly by Co-Cu dispersion thereon, and Co-Cu granule agglomeration of avoiding and postpone, keeps bigger serface and the granule of Co-Cu.
Document [Journal of Catalysis, 2012,286:51-61] reports a series of xCuyCo/ γ-Al prepared with co-impregnation
2o
3, (x=0 ~ 0.5).As x=y=1, after calcining afterproduct reduces at 673K temperature, define γ-Al
2o
3the copper cobalt nano-particle of load.At 2MPa, 523K and H
2/ CO is under the condition of 2:1, and CO conversion ratio is 16.5%, and hydrocarbon selective is 82.6%, and alcohol is selective is 17.1%, and wherein, methyl alcohol accounts for 35.7% of total alcohol content.Think that catalyst calcination afterproduct prepared by this method is generally the CuO of monocline and the Co of spinel structure
3o
4mixture, obtain independent Cu and Co metallic particles after reduction, and Active components distribution is uneven, thus reduces the synergy between Cu-Co, be unfavorable for the generation of low-carbon alcohols.
Before introducing the precipitation method, first introduce layered double hydroxide (Layered Double Hydroxides, LDHs) and CNT (CNTs).LDHs also known as houghite, the lamellar compound that it is made up of positively charged layers of metal hydroxides and the electronegative anion of interlayer.Its chemical composition can be expressed as [M
2+ 1-xm
3+ x(OH)
2]
x+(A
n-)
x/nmH
2o], wherein, M is metal ion, A
n-for interlayer anion.LDHs has unique character: as laminate metal ion can replace by the metal ion of other similar radius, there is adjustable sex change; Simultaneously by lattice orientation effect and the minimum effects of lattice energy, laminate metal ion can reach being uniformly distributed of molecular level; The thermal decomposition of LDHs has structural topology effect, and product of roasting can be made to keep the equally distributed feature of precursor, and further reduction also can form equally distributed nano-metal particle or Nanoalloy particle.Therefore utilize LDHs to carry out Kaolinite Preparation of Catalyst as presoma, not only can realize being uniformly distributed of each component, be also beneficial to the synergy between active component.
CNTs is by the curling elongated tubular material with carbon element of graphite flake, and it has thermal conductivity, the well mechanical strength of becoming reconciled, and it is even that the high-termal conductivity of CNTs is conducive to reaction bed temperature.CNTs can not in the present invention houghite generation chemical reaction, so as dispersant, can namely play the component in dilution water talcum, and the component generation chemical reaction not in hydrotalcite.
The patent application of application number 201310016666.1 " for the synthesis of the cupric hydrotalcite catalyst of gas mixed alcohol and method for making thereof and application " (CN 103084178A), the technology of preparing core of this catalyst take hydrotalcite as predecessor, Hydrotalcite Precursors is wherein prepared by co-precipitation, then catalyst is obtained through calcining, for higher alcohols synthesis.The theme of this catalyst is the mixed oxide of cupric, and wherein in mixed oxide, the kind of metallic element is a lot, can by hundreds of kind combining form., methyl alcohol selective height high with hydrocarbon selective in the product of this Catalyst Production low-carbon alcohols, and low-carbon alcohols is selective lower; On the catalyst that performance is best, low-carbon alcohols (C
2+alcohol) be no more than 25% mass ratio.
The patent application " preparing low-carbon mixed alcohol by synthetic gas CNT promotes cobalt-copper-based catalysts and preparation method thereof " (CN1669649A) of application number 200410082377.2; By the nitrate potash co-precipitation of copper and cobalt, in precipitation, be mixed into CNTs, prepare the catalyst consisting of copper and cobalt and CNT, this technology is also with paper form report [Xiamen University's journal (natural science edition), the 2005,44th volume, 4th phase, 445 pages].With the mixture that the product of this Catalyst Production low-carbon alcohols is methyl alcohol, low-carbon alcohols and dimethyl ether, wherein dimethyl ether accounts for 30-40wt%.
In addition, patent CN102489301A proposes a kind of structuring copper cobalt-base catalyst and catalyzes and synthesizes the application that gas prepares higher alcohol.Adopt the method growth in situ copper cobalt aluminum hydrotalcite film on aluminum substrates of growth in situ, the copper cobalt-base catalyst of height of formation dispersion after calcining, reduction.3MPa, 300 DEG C, air speed is 8000mLg
cat -1h
-1and H
2/ CO is under the condition of 2:1, and alcohols selectivity is 40%, C
2the content of above higher alcohol accounts for 21%.After 60h stability test, CO conversion ratio is reduced to about 14% by 27%.The low-carbon alcohols of this catalyst visible is selective and stability is all not high, does not still have industrial production and is worth.
By in above-mentioned visible prior art, infusion process is unfavorable for the interaction between Co-Cu, so be unfavorable for that Co-Cu acts synergistically, and low-carbon alcohols selective low.On Cu-contained catalyst prepared by the coprecipitation of having reported for work, low-carbon alcohols selective also lower, or produce the mixture of methyl alcohol, low-carbon alcohols and dimethyl ether etc.
About product cost problem, synthesis gas (CO+H
2) low-carbon alcohols processed product in, methyl alcohol and methane are the most cheap, two times of to be ethanol price be substantially the approximately methyl alcohol of the price as this year (2014) first half of the year, and the price of propyl alcohol, butanols is about three times of methyl alcohol; So require in low-carbon alcohols that the content of ethanol, propyl alcohol, butanols is more high better.
Many documents are also had to be studied the nanometer cobalt copper alloy catalyst for higher alcohols synthesis and to report, but all there is different problems, so simple combination and preparation, the breakthrough to the nanometer cobalt copper alloy catalyst for higher alcohols synthesis really cannot be realized.
Summary of the invention
According to the deficiencies in the prior art, we, through in many ways studying and testing, think and must reach: (1) makes Co, Cu, Al and other additives first form hydrotalcite-like compound material, to realizing the Homogeneous phase mixing of Co, Cu; (2) adopt CNT as diluent, CNT dilutes houghite particle, comprise Co and Cu, and the distance between Co and Cu does not change in houghite particle; Combine both this, while realizing Co-Cu formation alloy, Co-Cu is with form of nanoparticles existence and the long-pending height of particle small specific surface.
The present invention is intended to the technological deficiency for prior art, provides a kind of using CNTs as dispersant, using CNTs and the houghite compound predecessor as catalyst, for the preparation of the nanometer cobalt copper alloy catalyst of low carbon alcohol by synthetic gas; Catalyst is that CNT and aluminium oxide form complex carrier, and nanometer cobalt copper alloy supports and form catalyst on this complex carrier, can contain auxiliary agent in catalyst.
The present invention is realized by following technical solution:
For a nanometer cobalt copper alloy catalyst for the CNT compound of higher alcohols synthesis, it is characterized in that being made up of metal ingredient and carbon nanotube component, described metal ingredient contains Cu, Co, Al
2o
3blending constituent, simultaneously above-mentioned each component meets following relation: the mass fraction of carbon nanotube component in metal ingredient and carbon nanotube component gross mass is 3 ~ 30%; The mass fraction of Cu in metal ingredient is 2%-25%; The mass fraction of Co in metal ingredient is 3%-45%; Al
2o
3mass fraction in metal ingredient is 20%-80%.
Described metal ingredient also comprises additive M, and described additive M refers to one or more in Zn, Mn, Mg, Ca, Ni, Fe, Cr, the mass fraction 0 ~ 75% of affiliated additive in described metal ingredient.
The preparation method of the nanometer cobalt copper alloy catalyst of above-mentioned a kind of CNT compound for higher alcohols synthesis, comprises the following steps:
1) in dry container, CNT is added, 98% (w/w) sulfuric acid, 65% (w/w) nitric acid, after ultrasonic 2-5h, reflux 2-6h at 100 DEG C, filtering and washing, dry 12-48h at 60-100 DEG C, obtains the CNT that acidification is crossed, above-mentioned CNT, 98% (w/w) sulfuric acid, the mass ratio of 65% (w/w) nitric acid is 1:(30-45): (10-15).
2) be 1:(0.4-3 according to the mol ratio of the nitrate of copper nitrate, cobalt nitrate, aluminum nitrate and additive M ion): (1.5-10): (0-14), by one or more in the nitrate of the nitrate of copper, cobalt and aluminium and additive zinc, manganese, magnesium, calcium, nickel, iron and chromium, add in deionized water and be made into the mixed solution that total ion concentration is 0.01-2mol/L, be designated as solution A; By NaOH and Na
2cO
3in the molar concentration of the NaOH in mixed solution and solution A, the ratio of all cation mole concentration sums is (1-5): 1, by the Na in mixed solution
2cO
3molar concentration and solution A in all bivalent cation molar concentration sums than being (1-5): 1, mixed solution is designated as solution B; Solution A and solution B and stream joins step 1) obtain in CNT dispersion liquid, and control ph is 7-11, after solution A dropwises, aging 6h-48h under temperature is 60 DEG C of-130 DEG C of conditions, after product Separation of Solid and Liquid, washing is to neutral, dry 6-48h at temperature 25 DEG C-180 DEG C, obtains catalyst precursor;
3) by step 2) catalyst precursor prepared adds in Muffle furnace, at temperature 300-800 DEG C, inertia (nitrogen, argon gas or helium, or its gaseous mixture) roasting 0.5-10h in atmosphere, join in reactor by the catalyst precursor after roasting, be 300-8000h with volume space velocity in reactor
-1pass into reducing gases, after temperature 200-600 DEG C of reduction 0.5-6h, obtain the nanometer cobalt copper alloy catalyst of the CNT compound for higher alcohols synthesis, described reduction reaction gas is one or both in hydrogen, carbon monoxide and methane, or the gaseous mixture of one or both and inert gas wherein, inert gas wherein in gaseous mixture is nitrogen or argon gas or helium, and in reduction reaction gas, the percentage by volume of inert gas accounts for 1%-99%.
Above-mentioned steps 3) in, can adopt with the following method:
By step 2) catalyst precursor prepared joins in reactor, is 300-8000h in reactor with volume space velocity
-1pass into reducing gases, after temperature 200-600 DEG C of reduction 0.5-6h, obtain the nanometer cobalt copper alloy catalyst of the CNT compound for higher alcohols synthesis, described reduction reaction gas is one or both in hydrogen, carbon monoxide and methane, or the gaseous mixture of one or both and inert gas wherein, inert gas wherein in gaseous mixture is nitrogen or argon gas or helium, and in reduction reaction gas, the percentage by volume of inert gas accounts for 1%-99%.
The application of the nanometer cobalt copper alloy catalyst of the CNT compound for higher alcohols synthesis prepared by the present invention, process for the synthesis of gas synthesis of low-carbon alcohol: catalyst is added in fixed bed reactors, under temperature is 200-350 DEG C and pressure is 1-6MPa condition, be 500-8000h with air speed in reactor
-1pass into mol ratio for (0.5-3): the hydrogen of 1 and Co mixed gas.
The invention has the beneficial effects as follows, prepare houghite/carbon nanotube precursor by coprecipitation, reduction obtains Nanometer Copper cobalt dual-metal catalyst to realize.Control the Homogeneous phase mixing that deposition condition can realize each metal ion, particularly copper ion and cobalt ions in catalyst precursor; Owing to there is strong interaction between metal and CNT, after reduction, Cu-Co Nanoalloy can high degree of dispersion on the carbon nanotubes, the particle sintering simultaneously can effectively avoiding Cu-Co alloy to cause due to migration.Cu-Co active component obtained like this, has high specific surface area active, and carrier and additive can the sintering of inhibit activities component.The advantage that this catalyst is given prominence to is that low-carbon alcohols is selective and low temperature active is all higher, stability is higher, when 260 DEG C, CO conversion ratio can reach more than 50%, low-carbon alcohols is selective reaches more than 50%, when 280 DEG C, catalyst experiences 192 hours stability tests, stable in catalytic performance, active component not easy-sintering is grown up, and preparation is simple, cost is low, has industrial application value.
Accompanying drawing explanation
Fig. 1 is the XRD curve of catalyst precursor obtained in example 1.XRD is that cobalt target records.
Fig. 2 is the XRD curve of catalyst precursor after 500 degree of calcinings after 500 degree of reduction obtained in example 1.
Fig. 3 is that catalyst obtained by example 1 is at 280 degree of stability inferior test curves.
Fig. 4 is the SEM figure of catalyst precursor obtained in example 1.
Fig. 5 is the TEM figure of catalyst precursor after 500 DEG C of calcinings, 450 DEG C of reduction obtained in example 1.
[embodiment 1]
CNT is added in dry container, 98% (w/w) sulfuric acid, 65% (w/w) nitric acid, after ultrasonic 2h, reflux 2h at 100 DEG C, filtering and washing, dry 12h at 60 DEG C, obtains the CNT that acidification is crossed, above-mentioned CNT, 98% (w/w) sulfuric acid, the mass ratio of 65% (w/w) nitric acid is 1:30:10.It is scattered in 15L deionized water to take 25g CNT, obtains carbon nano tube dispersion liquid;
Be the mixing salt solution that 1:2:1.5 is made into that total metal concentration is 1mol/L by the mol ratio of copper nitrate, cobalt nitrate and aluminum nitrate, be designated as solution A; By c (Na
2cO
3)=0.66mol/L and c (NaOH)=4.1mol/L is made into mixed ammonium/alkali solutions and is designated as B.Solution A and solution B and stream joins in the reactor containing above-mentioned carbon nano tube dispersion liquid, and control ph is 9.5, after solution A dropwises, aging 12h under temperature is 80 DEG C of conditions, after product Separation of Solid and Liquid, washing is to neutral, through dry 24h at temperature 80 DEG C, obtain carbon nanotube loaded houghite presoma;
Getting catalyst precursor prepared by said method adds in Muffle furnace, and roasting 4h in temperature 500 DEG C, nitrogen atmosphere, gets roasting afterproduct in reactor, in reactor, pass into H
2volume fraction is hydrogen, the argon gas gaseous mixture of 5%, rises to 500 ° of reduction 6h, pass into H after naturally cooling to room temperature with the heating rate of 10 DEG C/min
2be the synthesis gas of 2:1 with the mol ratio of CO, be 3MPa by boost in pressure, the volume space velocity of synthesis gas is set to 3900h
-1, temperature is set to 260 DEG C-290 DEG C.Adopt SP3410 gas-chromatography to carry out on-line testing, the conversion ratio of CO and the distribution variation with temperature of each product as shown in table 1.Can find out, CO conversion ratio and low-carbon alcohols selective all very high.Meanwhile, the stability test of this catalyst under 280 degree (Fig. 3), as can be seen from Fig., this catalyst stability is good.
As can be seen from XRD figure (Fig. 1) of catalyst precursor prepared by said method, having there is the characteristic diffraction peak of hydrotalcite in curve, shows that hydrotalcite is formed.XRD figure (Fig. 2) after reduction, has the diffraction maximum of alloy after can finding out reduction.Scheme (Fig. 4) from the SEM of catalyst precursor, can find out that sheet hydrotalcite is uniformly along carbon nano tube growth, size is between 30-70nm.As can be seen from the TEM (Fig. 5) of catalyst precursor after reduction prepared by said method, after reduction, there is the lattice fringe of alloy, illustrate and define alloy.
Table 1
[embodiment 2]
CNT is added in dry container, 98% (w/w) sulfuric acid, 65% (w/w) nitric acid, after ultrasonic 3h, reflux 3h at 100 DEG C, filtering and washing, dry 20h at 70 DEG C, obtains the CNT that acidification is crossed, above-mentioned CNT, 98% (w/w) sulfuric acid, the mass ratio of 65% (w/w) nitric acid is 1:35:10.It is scattered in 15L deionized water to take 2g CNT, obtains carbon nano tube dispersion liquid;
Be the mixing salt solution that 1:2:1.5:2 is made into that total metal concentration is 1mol/L by the mol ratio of copper nitrate, cobalt nitrate, aluminum nitrate, zinc nitrate, be designated as solution A; By c (Na
2cO
3)=0.58mol/L and c (NaOH)=1.0mol/L is made into mixed ammonium/alkali solutions and is designated as B.Solution A and solution B and stream joins 1.5L concentration is in the reactor of 2.7g/L carbon nano tube dispersion liquid, and control ph is 9.7, after solution A dropwises, aging 12h under temperature is 70 DEG C of conditions, after product Separation of Solid and Liquid, washing is to neutral, through dry 14h at temperature 80 DEG C, obtain houghite presoma;
Getting catalyst precursor prepared by said method adds in Muffle furnace, and roasting 4h in temperature 500 DEG C, nitrogen atmosphere, gets roasting afterproduct in reactor, in reactor, pass into H
2volume fraction is hydrogen, the argon gas gaseous mixture of 5%, rises to 500 ° of reduction 3h, pass into H after naturally cooling to room temperature with the heating rate of 5 DEG C/min
2be the synthesis gas of 2:1 with the mol ratio of CO, be 4MPa by boost in pressure, the volume space velocity of synthesis gas is set to 3900h
-1, temperature is set to 200 DEG C.Adopt SP3410 gas-chromatography to carry out on-line testing, the conversion ratio of CO and the distribution of each product as shown in table 2.
[embodiment 3]
CNT is added in dry container, 98% (w/w) sulfuric acid, 65% (w/w) nitric acid, after ultrasonic 4h, reflux 4h at 100 DEG C, filtering and washing, dry 24h at 80 DEG C, obtains the CNT that acidification is crossed, above-mentioned CNT, 98% (w/w) sulfuric acid, the mass ratio of 65% (w/w) nitric acid is 1:40:10.It is scattered in 15L deionized water to take 15g CNT, obtains carbon nano tube dispersion liquid;
Be the mixing salt solution that 1:2:6:2 is made into that total metal concentration is 0.5mol/L by the mol ratio of copper nitrate, cobalt nitrate, aluminum nitrate, magnesium nitrate, be designated as solution A; Mixed ammonium/alkali solutions is made into by c (Na2CO3)=1.35mol/L and c (NaOH)=2.5mol/L.Solution A and solution B and stream adds 1.0L concentration is in the reactor of 3.0g/L carbon nano tube dispersion liquid, and control ph is 10.5, after solution A dropwises, aging 24h under temperature is 60 DEG C of conditions, after product Separation of Solid and Liquid, washing is to neutral, through dry 48h under temperature 70 C, obtain houghite presoma;
Getting catalyst precursor prepared by said method adds in Muffle furnace, and roasting 5h in temperature 600 DEG C, nitrogen atmosphere, joins in reactor by roasting afterproduct, in reactor, pass into H
2volume fraction is hydrogen, the argon gas gaseous mixture of 5%, rises to 500 ° of reduction 4h, pass into H after naturally cooling to room temperature with the heating rate of 5 DEG C/min
2be the synthesis gas of 2:1 with the mol ratio of CO, be 3MPa by boost in pressure, the volume space velocity of synthesis gas is set to 7800h-1, and temperature is set to 290 DEG C.Adopt SP3410 phase chromatogram to carry out on-line testing, the conversion ratio of CO and the distribution of each product as shown in table 2
[embodiment 4]
CNT is added in dry container, 98% (w/w) sulfuric acid, 65% (w/w) nitric acid, after ultrasonic 5h, reflux 6h at 100 DEG C, filtering and washing, dry 36h at 80 DEG C, obtains the CNT that acidification is crossed, above-mentioned CNT, 98% (w/w) sulfuric acid, the mass ratio of 65% (w/w) nitric acid is 1:45:10.It is scattered in 15L deionized water to take 10g CNT, obtains carbon nano tube dispersion liquid;
Be the mixing salt solution that 1:2:9:14:12 is made into that total metal concentration is 1.5mol/L by the mol ratio of copper nitrate, cobalt nitrate, aluminum nitrate, ferric nitrate, manganese nitrate, be designated as solution A; By c (Na
2cO
3)=1.9mol/L and c (NaOH)=3.0mol/L is made into mixed ammonium/alkali solutions and is designated as B.Solution A and solution B and stream adds 1.5L concentration is in the reactor of 4.2g/L carbon nano tube dispersion liquid, and control ph is 8.5, after solution A dropwises, aging 20h under temperature is 75 DEG C of conditions, after product Separation of Solid and Liquid, washing is to neutral, through dry 24h under temperature 70 C, obtain houghite presoma;
Getting catalyst precursor prepared by said method adds in Muffle furnace, and roasting 3h in temperature 650 DEG C, nitrogen atmosphere, joins in reactor by roasting afterproduct, in reactor, pass into H
2volume fraction is hydrogen, the argon gas gaseous mixture of 5%, rises to 600 ° of reduction 3h, pass into H after naturally cooling to room temperature with the heating rate of 5 DEG C/min
2be the synthesis gas of 2:1 with the mol ratio of CO, be 5MPa by boost in pressure, the volume space velocity of synthesis gas is set to 8000h
-1, temperature is set to 270 DEG C.Adopt SP3410 gas-chromatography to carry out on-line testing, the conversion ratio of CO and the distribution of each product as shown in table 2.
[embodiment 5]
CNT is added in dry container, 98% (w/w) sulfuric acid, 65% (w/w) nitric acid, after ultrasonic 5h, reflux 2h at 100 DEG C, filtering and washing, dry 48h at 100 DEG C, obtains the CNT that acidification is crossed, above-mentioned CNT, 98% (w/w) sulfuric acid, the mass ratio of 65% (w/w) nitric acid is 1:45:15.It is scattered in 15L deionized water to take 20g CNT, obtains carbon nano tube dispersion liquid;
Be the mixing salt solution that 2:1:9:14 is made into that total metal concentration is 0.01mol/L by the mol ratio of copper nitrate, cobalt nitrate, aluminum nitrate, nickel nitrate, be designated as solution A; By c (Na
2cO
3)=0.01mol/L and c (NaOH)=0.02mol/L is made into mixed ammonium/alkali solutions and is designated as B.Solution A and solution B and stream adds 0.5L concentration is in the reactor of 6g/L carbon nano tube dispersion liquid, and control ph is 10.0, after solution A dropwises, aging 15h under temperature is 90 DEG C of conditions, after product Separation of Solid and Liquid, washing is to neutral, through dry 20h under temperature 70 C, obtain houghite presoma.
Getting catalyst precursor prepared by said method joins in reactor, take volume space velocity as 3000h
-1pass into H
2volume fraction is hydrogen, the argon gas gaseous mixture of 5%, rises to 550 ° of reduction 5h, pass into H after naturally cooling to room temperature with the heating rate of 10 DEG C/min
2be the synthesis gas of 2:1 with the mol ratio of CO, be 2MPa by boost in pressure, the volume space velocity of synthesis gas is set to 4800h
-1, temperature is set to 350 DEG C.Adopt SP3410 gas-chromatography to carry out on-line testing, the conversion ratio of CO and the changes in distribution of each product as shown in table 2.
[embodiment 6]
CNT is added in dry container, 98% (w/w) sulfuric acid, 65% (w/w) nitric acid, after ultrasonic 5h, reflux 5h at 90 DEG C, filtering and washing, dry 40h at 100 DEG C, obtains the CNT that acidification is crossed, above-mentioned CNT, 98% (w/w) sulfuric acid, the mass ratio of 65% (w/w) nitric acid is 1:45:15.It is scattered in 15L deionized water to take 18g CNT, obtains carbon nano tube dispersion liquid;
Be the mixing salt solution that 1:0.4:10:0.3:0.3 is made into that total metal concentration is 2.0mol/L by the mol ratio of copper nitrate, cobalt nitrate, aluminum nitrate, calcium nitrate, chromic nitrate, be designated as solution A; By c (Na
2cO
3)=2.6mol/L and c (NaOH)=4.2mol/L is made into mixed ammonium/alkali solutions and is designated as B.Solution A and solution B and stream adds 1.5L concentration is in the reactor of 0.7g/L carbon nano tube dispersion liquid, and control ph is 8, after solution A dropwises, aging 24h under temperature is 100 DEG C of conditions, after product Separation of Solid and Liquid, washing is to neutral, through dry 20h at temperature 80 DEG C, obtains houghite presoma.
Getting catalyst prepared by said method to load in reactor, take volume space velocity as 2000h
-1pass into H
2volume fraction is hydrogen, the argon gas gaseous mixture of 5%, rises to 600 ° of reduction 5h, pass into H after naturally cooling to room temperature with the heating rate of 7 DEG C/min
2be the synthesis gas of 2:1 with the mol ratio of CO, be 6MPa by boost in pressure, the volume space velocity of synthesis gas is set to 5000h
-1, temperature is set to 240 DEG C.Adopt SP3410 gas-chromatography to carry out on-line testing, the conversion ratio of CO and the distribution of each product as shown in table 2.
Table 2
Claims (8)
1. for a CNT composite Nano copper-cobalt alloy catalyst for higher alcohols synthesis, it is characterized in that each component and mass content as follows:
Metal is composed as follows:
Cu：2％-25％；
Co：3％-45％；
Al
2O
3：20％-80％；
Carbon nanotube component be metal composition and carbon nanotube component gross mass in mass fraction be 3 ~ 30%.
2. catalyst as claimed in claim 1, is characterized in that being added with one or more in additive Zn, Mn, Mg, Ca, Ni, Fe or Cr in described metal ingredient, and content is less than 75% of metal composition.
3. the preparation method of catalyst described in claim 1 or 2, is characterized in that comprising the following steps:
1) in container, add CNT, the concentrated sulfuric acid and red fuming nitric acid (RFNA), after ultrasonic 2-5h, reflux 2-6h at 100 DEG C, filtering and washing, and dry 12-48h at 60-100 DEG C, obtains the CNT that acidification is crossed;
2) by one or more in the nitrate of the nitrate of copper, cobalt and aluminium and additive zinc, manganese, magnesium, calcium, nickel, iron and chromium, add in deionized water and be made into the mixed solution that total ion concentration is 0.01-2mol/L, be designated as solution A;
By NaOH and Na
2cO
3solution mixing is designated as solution B; In the molar concentration of NaOH wherein and solution A, the ratio of all cation mole concentration sums is (1-5): 1; Na
2cO
3molar concentration and solution A in all bivalent cation molar concentration sum than being (1-5): 1;
Solution A and solution B and stream joins step 1) in the carbon nano tube dispersion liquid that obtains, and utilize B solution control ph for 7-11, after solution A dropwises, 6h-48h is left standstill under temperature is 60 DEG C of-130 DEG C of conditions, after product Separation of Solid and Liquid, washing is to neutral, dry 6-48h at temperature 25 DEG C-180 DEG C, obtains catalyst precursor;
3) by step 2) catalyst precursor prepared adds in Muffle furnace, and at temperature 300-800 DEG C, roasting 0.5-10h in inert atmosphere, join in reactor by the catalyst precursor after roasting, be 300-8000h with volume space velocity in reactor
-1pass into reducing gases, after temperature 200-600 DEG C of reduction 0.5-6h, obtain the CNT composite Nano copper-cobalt alloy catalyst for higher alcohols synthesis.
4. method as claimed in claim 3, step 3 described in its feature) adopt with the following method:
By step 2) catalyst precursor prepared joins in reactor, is 300-8000h in reactor with volume space velocity
-1pass into reducing gases, after temperature 200-600 DEG C of reduction 0.5-6h, obtain the CNT composite Nano copper-cobalt alloy catalyst for higher alcohols synthesis.
5. method as claimed in claim 3, the concentrated sulfuric acid described in its feature is 98% sulfuric acid, and red fuming nitric acid (RFNA) is 65% nitric acid; CNT: 98% sulfuric acid: the mass ratio of 65% nitric acid is 1:(30-45): (10-15).
6. the method as described in claim 3 or 4, reduction reaction gas described in its feature is one or both in hydrogen, carbon monoxide or methane; Or the gaseous mixture of one or both and inert gas wherein, the inert gas wherein in gaseous mixture is nitrogen or argon gas or helium, and in reduction reaction gas, the percentage by volume of inert gas accounts for 1%-99%.
7. method as claimed in claim 3, the nitrate of copper, cobalt and aluminium described in its feature and additive are 1:(0.4-3 according to the mol ratio of the nitrate of copper nitrate, cobalt nitrate, aluminum nitrate and additive M ion): (1.5-10): (0-14).
8. the catalyst of claim 1 or 2 is used for the method for higher alcohols synthesis, it is characterized in that: added by catalyst in fixed bed reactors, under temperature is 200-350 DEG C and pressure is 1-6MPa condition, is 500-8000h in reactor with air speed
-1pass into mol ratio for (0.5-3): the hydrogen of 1 and Co mixed gas.
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