CN104056629A - Catalyst used in preparation of low-carbon alcohol by synthesis gas, as well as preparation method and application of catalyst - Google Patents
Catalyst used in preparation of low-carbon alcohol by synthesis gas, as well as preparation method and application of catalyst Download PDFInfo
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Abstract
The invention provides a catalyst used in preparation of low-carbon alcohol by a synthesis gas by using flake graphite or graphene as a carrier, a preparation method of the catalyst and application of the catalyst to preparation of the low-carbon alcohol. The catalyst is used for synthesizing the low-carbon alcohol by using the synthesis gas, and has the characteristics of high CO conversion rate, good selectivity of 2-carbon or more-carbon alcohol, good low-temperature activity, and the like. The preparation and treatment process is simple and suitable for industrialized production. According to the basic preparation principle, all metal ions, especially copper ions and cobalt ions in a catalyst precursor are uniformly mixed by controlling a coprecipitation condition; because metal and graphite have a strong interaction, Cu-Co nanometer alloy can be highly dispersed on a graphite flake after reduction, and thus particle sintering caused by migration of the CuCo alloy can be effectively prevented.
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 processed, its preparation method and application.
Background technology
Along with the consumption day by day of petroleum resources, energy problem constantly aggravates, and develops new energy system extremely urgent.By synthesis gas (CO, the H of natural gas or coal or the production of reproducible biomass resource
2) prepare low-carbon alcohols (refer to containing two carbon atoms or above alcohol) and caused great concern, its using value at fuel and chemical field also highlights day by day.Low-carbon alcohols can substitute controversial MTBE and the larger lead tetraethide of toxicity as petroleum additive as the power fuel of high-quality, goes out the higher alcohols of price such as second, third, fourth and amylalcohol by low-carbon alcohols is separable simultaneously.In addition, low-carbon alcohols can also be as one of means of coal liquefaction, realize the alkylation of coal and solubilization and as liquefied petroleum gas substitute etc.
In low carbon alcohol by synthetic gas reaction, be often attended by methyl alcohol, hydro carbons and CO
2deng the generation of accessory substance, so the key of synthesis of low-carbon alcohol technology is the catalyst that exploitation has excellent activity, selective and stability.At present, formate low-carbon alcohol catalyst has four kinds: the noble metal catalyst that the Rh of take is representative, and the catalst for synthesis of methanol of modification, Mo is catalyst based, the FT synthetic catalyst of modification.Wherein, though take the hydrogenation activity that noble metal catalyst that Rh is representative had, alcohol is selectively better; But it is expensive, easily by CO
2its application that the feature limits such as poisoned.The methanol synthesis catalyst operating condition of modification is harsh, and product still take methyl alcohol as main, so be eliminated gradually.Though the catalyst with base of molybdenum of modification has unique anti-sulphur, can avoid costly deep desulfuration, and moisture less in product, low-carbon alcohols content is higher, but the hydrogen-carbon ratio of unstripped gas is required harsh, must be between 1.0～1.1, and this catalyst promoter very easily forms carbonyls with CO, cause the loss of its constituent element, thereby its stability is restricted.
The fischer-tropsch synthetic catalyst of modification mainly take Cu-Fe and Cu-Co catalyst based as main.During Cu-Fe is catalyst based, because Fe has higher water gas shift reaction activity, make to contain more water in product, hydrocarbon selective is higher simultaneously.In Cu-Co is catalyst based, Co is to the highest active element in FT reaction, Co series catalysts has Water gas shift/WGS insensitive, and in course of reaction, be difficult for the advantages such as carbon distribution is poisoning, Cu is conducive to generate alcohol, and the synergy of Cu and Co can improve the active of catalyst and contain two and two above carbon atom alcohol (C
2+alcohol) selective, so Cu-Co is catalyst based is considered to up-and-coming formate low-carbon alcohol catalyst.But C in product
2+alcohol is selectively still on the low side, does not still have industrial production and is worth.
At present, the synthetic catalyst based preparation method of CuCo is mainly infusion process.
As document [Journal of Catalysis, 2012,286:51-61] has been reported a series of xCuyCo/ γ-Al that prepare with co-impregnation
2o
3, (x=0～0.5).When x=y=1, after calcining afterproduct reduces at 673K temperature, formed γ-Al
2o
3load copper cobalt nano-particle.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 selectively 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, after reduction, obtain independent Cu and Co metallic particles, and Active components distribution is uneven, thereby has weakened the synergy between Cu-Co, be unfavorable for the generation of low-carbon alcohols.
In recent years, layered double hydroxide (Layered Double Hydroxides, LDHs), claims again houghite, have been a great concern the lamellar compound that it is comprised 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 be replaced by the metal ion of other similar radius, have adjustable sex change; Be subject to the minimum effects of lattice orientation effect and lattice energy, laminate metal ion can reach being uniformly distributed of molecular level simultaneously; The thermal decomposition of LDHs has structural topology effect, can make product of roasting 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.
In prior art, there is a key issue in Cu-Co bimetallic catalyst: sintering, because Cu-Co content is higher, nanometer Cu-Co Particle Phase, apart near, is easily merged into bulky grain, then inactivation.During by preparation, add other components, as Zn, Mg etc., can dilute Cu-Co, improve anti-sintering, but dilution is unfavorable for Cu-Co alloy, form, so selectively decline.Also can select other carrier, as ZrO
2, SiO
2deng supporting Cu-Co catalyst, still exist carrier and Cu-Co that the problems such as solid phase reaction, preparation difficulty occur.
Summary of the invention
The present invention is intended to the technological deficiency for prior art, and a kind of catalyst for the synthesis of gas low-carbon alcohols processed, its preparation method and application that flake graphite or Graphene be carrier of take is provided.
For realizing above technical purpose, the present invention by the following technical solutions:
For the synthesis of a catalyst for gas low-carbon alcohols processed, it is characterized in that being formed by metal ingredient and graphite composition, described metal ingredient is to contain Cu, Co, Al
2o
3blending constituent, simultaneously above-mentioned each component meets following relation: the mass fraction of graphite composition in metal ingredient and graphite composition gross mass is 0.3～30%; The mass fraction of Cu in metal ingredient is 2～25%; The mass fraction of Co in metal ingredient is 3～45%; The surplus of metal ingredient is Al
2o
3.
Preferably, described metal ingredient also comprises auxiliary agent, and described auxiliary agent is the component that contains in Zn, Mn, Mg, Ca, Ni, Fe, Cr one or more, and the mass fraction of described auxiliary agent in described metal ingredient be not higher than 70%.
Preferably, the sheet graphite oxide reduction that described graphite composition is no more than 1000nm by thickness obtains.
Preferably, the sheet graphite oxide reduction that described graphite composition is no more than 100nm by thickness obtains.
Preferably, described graphite composition is obtained by graphene oxide reduction.
Meanwhile, the present invention also provides a kind of preparation method of above-mentioned catalyst, and its concrete steps are as follows:
1) under ice bath, stirring condition by 98% (w/w) H
2sO
4, graphite powder, sodium nitrate, potassium permanganate mix, then it is kept 1～3 hour under-5～5 ℃ of conditions, then be warming up to 30～40 ℃ and kept stirring 10～180min, then add wherein the first deionized water to dilute, in this process, keep mixture temperature in 100 ℃ of following reaction 1～5h, then add wherein 30% (w/w) hydrogen peroxide stirring reaction, 1～120min, then add wherein again the second deionized water preparation to become the mixed liquor that graphite concentration is 0.5～20g/L, be graphite oxide, above-mentioned 98% (w/w) H
2sO
4, graphite powder, sodium nitrate, potassium permanganate, the first deionized water, 30% (w/w) hydrogen peroxide mass ratio be (90～95): (1～2.2): (0.9～1.4): (6～7.5): (130～170): (25～35).
2) according to the mol ratio of copper nitrate, cobalt nitrate, aluminum nitrate, auxiliary agent nitrate total amount, be 1:(0.3～3): (1～6): (0～3), mentioned component is added in deionized water and is made into the mixed solution that total ion concentration is 0.01-2mol/L, be designated as the first mixed solution; By Na
2cO
3be mixed with the second mixed solution with NaOH, and in the molar concentration that guarantees NaOH in the second mixed solution and the first mixed solution all the ratio of cation molar concentration sums be (1～5): 1, guarantee Na in the second mixed solution simultaneously
2cO
3molar concentration and the first mixed solution in all the ratio of bivalent cation molar concentration sums be (1～5): 1; Above-mentioned the first mixed solution and the second mixed solution stream are joined to step 1) in the graphite oxide that obtains, controlling pH value is 8～11, after dropwising, the first mixed solution stops dripping, by mixture, in temperature, be to process 6～48h under 60～130 ℃ of conditions, then collect solid phase washing to neutral, the more fully dry compound that obtains;
3) by step 2) compound that obtains is 300～8000h-passing into air speed
1reducibility gas exist under, temperature is reduction 0.5～6h 200～600 ℃ within the scope of, thereby described in obtaining for the synthesis of the catalyst of gas low-carbon alcohols processed, wherein reducibility gas is the gas that includes in hydrogen, carbon monoxide, methane one or more.
Except said method, can also be following method:
1) under ice bath, stirring condition to 98% (w/w) H
2sO
4in add graphite powder, sodium nitrate, potassium permanganate, after mixing, it is kept 1～3 hour under-5～5 ℃ of conditions, then be warming up to 30～40 ℃ and kept stirring 10～60min, then add wherein the first deionized water to dilute, in this process, keep mixture temperature in 100 ℃ of following reaction 1～5h, then add wherein 30% (w/w) hydrogen peroxide stirring reaction, 1～10min, then add wherein again the second deionized water preparation to become the mixed liquor that graphite concentration is 0.5～20g/L, be graphite oxide, above-mentioned 98% (w/w) H
2sO
4, graphite powder, sodium nitrate, potassium permanganate, the first deionized water, 30% (w/w) hydrogen peroxide mass ratio be (90～95): (1～2.2): (0.9～1.4): (6～7.5): (130～170): (25～35).
2) according to the mol ratio of copper nitrate, cobalt nitrate, aluminum nitrate, auxiliary agent nitrate total amount, be 1:(0.3～3): (1～6): (0～3), mentioned component is added in deionized water and is made into the mixed solution that total ion concentration is 0.01-2mol/L, be designated as the first mixed solution; By Na
2cO
3be mixed with the second mixed solution with NaOH, and in the molar concentration that guarantees NaOH in the second mixed solution and the first mixed solution all the ratio of bivalent cation molar concentration sums be (1～5): 1, in the molar concentration that simultaneously guarantees NaOH in the second mixed solution and the first mixed solution, all the ratio of bivalent cation molar concentration sums is (1～5): 1; Above-mentioned the first mixed solution is mixed with the second mixed solution stream, controlling pH value is 8～11, after dropwising, the first mixed solution stops dripping, by mixture, in temperature, be to process 6～48h under 60～130 ℃ of conditions, then this mixture is joined to step 1) fully stir in the graphite oxide that obtains, then collect solid phase washing to neutral, the more fully dry compound that obtains;
3) by step 2) compound that obtains is 300～8000h passing into air speed
-1reducibility gas exist under, temperature is reduction 0.5～6h 200～600 ℃ within the scope of, thereby described in obtaining for the synthesis of the catalyst of gas low-carbon alcohols processed, wherein reducibility gas is the gas that includes in hydrogen, carbon monoxide, methane one or more.
For above-mentioned two kinds of methods, can there is following optimal way:
Preferably, step 3) utilizing reducibility gas to process compound can also comprise the following steps before: by compound roasting under inert gas shielding.
Above-mentioned by compound roasting following concrete steps more preferably under inert gas shielding: sintering temperature is 300～800 ℃, and roasting time is 0.5～10h, and inert gas composition comprises one or more in nitrogen, argon gas, helium.
The present invention simultaneously also provides a kind of above-mentioned catalyst for catalyzing and synthesizing gas, to prepare the application of low-carbon alcohols, comprise the following steps: with the described catalyst contact conditions for the synthesis of gas low-carbon alcohols processed under, with 200～350 ℃, the condition of 1～6MPa, in reactor, take air speed as 500～8000
-1pass into mol ratio for (0.5～3): 1 hydrogen and carbon mono oxide mixture.
The method for preparing catalyst of technique scheme, step 1) prepared its lamellar spacing of graphite oxide, between 1000nm to 1 atomic layer, is mainly distributed between 10～100nm.
Technique scheme tool has the following advantages: by coprecipitation, prepare graphite oxide-houghite presoma, reduction obtains that Nanometer Copper cobalt dual-metal catalyst realizes.Control deposition condition and can realize the even mixing of each metal ion, particularly copper ion and cobalt ions in catalyst precursor; After reduction, owing to having strong interaction between metal and graphite, Cu-Co Nanoalloy can high degree of dispersion on graphite flake/alkene, can effectively avoid or slow down the sintering of Cu-Co alloying pellet.The Cu-Co active component making like this, has high specific activity surface area, and carrier and additive can suppress the sintering of active component.The outstanding advantage of this catalyst is that low-carbon alcohols is selective and low temperature active is all higher, and preparation is simple, and cost is low, has industrial application value.
Accompanying drawing explanation
Fig. 1 is that in the embodiment of the present invention 1, prepared catalyst, after calcining, reduces afterwards and reaction XRD curve afterwards, and XRD is that cobalt target records; In figure: a is that catalyst precursor is through the XRD curve after 500 ℃ of calcinings; B is the XRD curve of 450 ℃ of catalyst after reduction 3h; C is for the catalyst after reduction is through the XRD curve after reaction.* represent the diffraction maximum of Co-Cu alloy, ● represent CuCo
2o
4;
Fig. 2 is that the prepared catalyst precursor of example 1 of the present invention is with 5%H
2/ Ar is reducing gases, after being warming up to 450 ℃ of reduction 3h, at scale, is the TEM figure under 2nm with 10 ℃/min; In figure, d=0.208nm is interplanar distance.Due to (111) interplanar distance d=0.208nm of Co0.52Cu0.48, so this crystal face belongs to CuCo alloy (111) crystal face;
Fig. 3 is that the catalyst that example 1 of the present invention makes is the stability curve of 255 ℃ of reactions in temperature; In figure: selective trend over time that curve a is alcohols; Curve b is the conversion ratio trend over time of CO; Curve c is the selectively trend over time of alkane; Curve d is CO in product
2selectively trend over time;
Fig. 4 is the graphite oxide scanning electron microscope (SEM) photograph of the embodiment of the present invention 1 preparation; As we can see from the figure, its graphite flake layer thickness is greatly about 30nm left and right.
The specific embodiment
[embodiment 1]
In dry container, add 98% dense H
2sO
4, in ice bath, under stirring, add graphite, stir, add sodium nitrate, potassium permanganate, and mixture temperature is controlled to 0 ℃ of maintenance stirring 2.8h; Then mixture is remained on to 31～33 ℃ of left and right, stir 25min; Then to mixed liquor, add deionized water dilution, in this process, mixture temperature remains on below 100 ℃, and reaction 4h, takes out reactor, adds the first deionized water dilution, then adds 30% hydrogen peroxide, stirs 8min; Then carry out high speed centrifugation separation, and with deionized water wash in filtrate without SO
4 2-, at 80 ℃, dry 24h, makes graphite oxide.Add deionized water, the graphite oxide dispersion liquid that compound concentration is 7g/L; Wherein, each reactant quality ratio is, 98% dense H
2sO
4: graphite: sodium nitrate: potassium permanganate: the first deionized water: hydrogen peroxide=92:2:1:7:150:33 of 30%.
By the mol ratio of copper nitrate, cobalt nitrate and aluminum nitrate, be that 2:4:3 is made into the mixing salt solution that total metal concentration is 1mol/L, be designated as solution A; Press 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.The volumetric usage of solution A and solution B is 1.Solution A and solution B stream are joined containing in the reactor of above-mentioned graphite oxide dispersion liquid, and to control pH value be 9.5, after A solution dropwises, in temperature, be aging 12h under 80 ℃ of conditions, after product Separation of Solid and Liquid, washing is to neutral, through dry 24h at 80 ℃ of temperature, obtain the compound of houghite presoma and graphite oxide;
Get catalyst precursor prepared by said method and add in Muffle furnace, roasting 4h in 500 ℃ of temperature, nitrogen atmosphere, gets roasting afterproduct in reactor, in reactor, passes into H
2volume fraction is 5% hydrogen, argon gas gaseous mixture, with the heating rate of 10 ℃/min, rises to 450 ° of reduction 3h, passes into H after naturally cooling to room temperature
2with the synthesis gas that the mol ratio of CO is 2:1, by boost in pressure, be 3MPa, the volume space velocity of synthesis gas is set to 3900h
-1, temperature setting is set to 240 ℃-300 ℃.Adopt SP3410 gas-chromatography to carry out on-line testing, the distribution variation with temperature of the conversion ratio of CO and each product is as shown in table 1.Can find out, CO conversion ratio and low-carbon alcohols are selectively all very high.
The catalyst precursor prepared from said method can find out through the XRD figure after reduction, and catalyst precursor occurs alloy diffraction maximum after reducing, and illustrates and has formed alloy, and the size that calculates alloy by Scherrer formula is between 3-10nm.In reacted XRD, still there is alloy diffraction maximum, CuCo alloy stable existence is described, the separation of phase does not occur, directly illustrated that catalyst stability is good.
Table 1
[embodiment 2]
The preparation method of graphite oxide is identical with embodiment 1.
By the mol ratio of copper nitrate, cobalt nitrate, zinc nitrate, aluminum nitrate, be that 2:2:1:3 is made into the mixing salt solution that total metal concentration is 1mol/L, be designated as solution A; Press c (Na
2cO
3)=1.0mol/L and c (NaOH)=3.2mol/L is made into mixed ammonium/alkali solutions and is designated as B.The volumetric usage of solution A and solution B is 1.3.Solution A and solution B stream are joined in the reactor that 1.5L concentration is 3g/L graphite oxide dispersion liquid, and to control pH value be 9.7, after A solution dropwises, in temperature, be aging 12h under 60 ℃ of conditions, after product Separation of Solid and Liquid, washing is to neutral, through dry 14h at 80 ℃ of temperature, obtain the compound of houghite presoma and graphite oxide;
Get catalyst precursor prepared by said method and add in Muffle furnace, roasting 3h in 550 ℃ of temperature, nitrogen atmosphere, gets roasting afterproduct in reactor, in reactor, passes into H
2volume fraction is 5% hydrogen, argon gas gaseous mixture, with the heating rate of 5 ℃/min, rises to 450 ° of reduction 3h, passes into H after naturally cooling to room temperature
2with the synthesis gas that the mol ratio of CO is 2:1, by boost in pressure, be 3MPa, the volume space velocity of synthesis gas is set to 3900h
-1, temperature setting is set to 290 ℃.Adopt SP3410 gas-chromatography to carry out on-line testing, the conversion ratio of CO and the distribution of each product are as shown in table 2.
[embodiment 3]
The preparation method of graphite oxide is identical with embodiment 1.
By the mol ratio of copper nitrate, cobalt nitrate, calcium nitrate, aluminum nitrate, be that 2:4:0.6:3 is made into the mixing salt solution that total metal concentration is 0.5mol/L, be designated as solution A; Press c (Na
2cO
3)=1.0mol/L and c (NaOH)=1.5mol/L is made into mixed ammonium/alkali solutions and is designated as B.The volumetric usage of solution A and solution B is 1.1.It is in the reactor of 5g/L graphite oxide dispersion liquid that solution A and solution B stream are added to 1L concentration, and to control pH value be 8, after A solution dropwises, in temperature, be aging 12h under 70 ℃ of conditions, after product Separation of Solid and Liquid, washing is to neutral, through dry 48h at 80 ℃ of temperature, obtain the compound of houghite presoma and graphite oxide;
Get catalyst precursor prepared by said method and add in Muffle furnace, roasting 4h in 500 ℃ of temperature, nitrogen atmosphere, joins roasting afterproduct in reactor, in reactor, passes into H
2volume fraction is 5% hydrogen, argon gas gaseous mixture, with the heating rate of 8 ℃/min, rises to 400 ° of reduction 3h, passes into H after naturally cooling to room temperature
2with the synthesis gas that the mol ratio of CO is 2:1, by boost in pressure, be 3MPa, the volume space velocity of synthesis gas is set to 7800h
-1, temperature setting is set to 270 ℃.Adopt SP3410 gas-chromatography to carry out on-line testing, the conversion ratio of CO and the distribution of each product are as shown in table 2.
[embodiment 4]
The preparation method of graphite oxide is identical with embodiment 1.
By the mol ratio of copper nitrate, cobalt nitrate, manganese nitrate, aluminum nitrate, be that 1:1:0.1:1 is made into the mixing salt solution that total metal concentration is 2mol/L, be designated as solution A; Press c (Na
2cO
3)=3mol/L and c (NaOH)=7mol/L is made into mixed ammonium/alkali solutions and is designated as B.The volumetric usage of solution A and solution B is 1.5.It is in the reactor of 4g/L graphite oxide dispersion liquid that solution A and solution B stream are added to 1.5mL concentration, and to control pH value be 9.After A solution dropwises, in temperature, be aging 10h under 75 ℃ of conditions, after product Separation of Solid and Liquid, washing, to neutral, through dry 20h at 85 ℃ of temperature, obtains the compound of houghite presoma and graphite oxide;
Get catalyst precursor prepared by said method and join in reactor, take volume space velocity as 3000h
-1pass into H
2volume fraction is 3% hydrogen, argon gas gaseous mixture, with the heating rate of 1 ℃/min, rises to 350 ° of reduction 3h, passes into H after naturally cooling to room temperature
2with the synthesis gas that the mol ratio of CO is 2:1, by boost in pressure, be 3MPa, the volume space velocity of synthesis gas is set to 3900h
-1, temperature setting is set to 260 ℃.Adopt SP3410 gas-chromatography to carry out on-line testing, the conversion ratio of CO and the changes in distribution of each product are as shown in table 2.
[embodiment 5]
The preparation method of graphite oxide is identical with embodiment 1.
By the mol ratio of copper nitrate, cobalt nitrate, nickel nitrate, aluminum nitrate, be that 1:2:0.1:1 is made into the mixing salt solution that total metal concentration is 0.3mol/L, be designated as solution A; Press c (Na
2cO
3)=0.3mol/L and c (NaOH)=1mol/L is made into mixed ammonium/alkali solutions and is designated as B.The volumetric usage of solution A and solution B is 0.8.It is in the reactor of 8g/L graphite oxide dispersion liquid that solution A and solution B stream are added to 0.5L concentration, containing in the reactor of above-mentioned graphite oxide colloidal sol, and to control pH value be 9.0, after A solution dropwises, in temperature, be aging 20h under 70 ℃ of conditions, after product Separation of Solid and Liquid, washing is to neutral, through dry 20h at 75 ℃ of temperature, obtains the compound of houghite presoma and graphite oxide.
Get catalyst precursor prepared by said method and add in Muffle furnace, roasting 5h in 500 ℃ of temperature, nitrogen atmosphere, joins roasting afterproduct in reactor, take volume space velocity as 2000h
-1pass into H
2volume fraction is 3% hydrogen, argon gas gaseous mixture, with the heating rate of 5 ℃/min, rises to 450 ° of reduction 3h, passes into H after naturally cooling to room temperature
2with the synthesis gas that the mol ratio of CO is 2:1, by boost in pressure, be 2MPa, the volume space velocity of synthesis gas is set to 4800h
-1, temperature setting is set to 260 ℃.Adopt SP3410 gas-chromatography to carry out on-line testing, the conversion ratio of CO and the changes in distribution of each product are as shown in table 2.
[embodiment 6]
The preparation method of graphite oxide is identical with embodiment 1.
By the mol ratio of copper nitrate, cobalt nitrate, calcium nitrate, chromic nitrate, aluminum nitrate, be that 1:1:0.1:0.1:1 is made into the mixing salt solution that total metal concentration is 0.1mol/L, be designated as solution A; Press c (Na
2cO
3)=0.15mol/L and c (NaOH)=0.3mol/L is made into mixed ammonium/alkali solutions and is designated as B.The volumetric usage of solution A and solution B is 1.It is in the reactor of 2g/L graphite oxide dispersion liquid that solution A and solution B stream are added to 1L concentration, and to control pH value be 8.5, after A solution dropwises, in temperature, be aging 20h under 100 ℃ of conditions, after product Separation of Solid and Liquid, washing is to neutral, through dry 20h at 75 ℃ of temperature, obtain the compound of houghite presoma and graphite oxide.
Get catalyst prepared by said method and pack in reactor, take volume space velocity as 3000h
-1pass into H
2volume fraction is 5% hydrogen, argon gas gaseous mixture, with the heating rate of 10 ℃/min, rises to 440 ° of reduction 5h, passes into H after naturally cooling to room temperature
2with the synthesis gas that the mol ratio of CO is 2:1, by boost in pressure, be 3MPa, the volume space velocity of synthesis gas is set to 3900h
-1, temperature setting is set to 300 ℃.Adopt SP3410 gas-chromatography to carry out on-line testing, the conversion ratio of CO and the distribution of each product are as shown in table 2.
[embodiment 7]
The preparation method of graphite oxide is identical with embodiment 1.
By the mol ratio of copper nitrate, cobalt nitrate, magnesium nitrate, aluminum nitrate, be that 1:1:1:1 is made into the mixing salt solution that total metal concentration is 0.5mol/L, be designated as solution A; Press c (Na
2cO
3)=1mol/L and c (NaOH)=1.8mol/L is made into mixed ammonium/alkali solutions and is designated as B.The volumetric usage of solution A and solution B is 1.It is in the reactor of 3g/L graphite oxide dispersion liquid that solution A and solution B stream are added to 1.5L concentration, and to control pH value be 10, after A solution dropwises, in temperature, be aging 12h under 70 ℃ of conditions, after product Separation of Solid and Liquid, washing is to neutral, through dry 48h at 80 ℃ of temperature, obtain the compound of houghite presoma and graphite oxide;
Get catalyst precursor prepared by said method and add in Muffle furnace, roasting 4h in 500 ℃ of temperature, nitrogen atmosphere, joins roasting afterproduct in reactor, in reactor, passes into H
2volume fraction is 5% hydrogen, argon gas gaseous mixture, with the heating rate of 8 ℃/min, rises to 400 ° of reduction 3h, passes into H after naturally cooling to room temperature
2with the synthesis gas that the mol ratio of CO is 2:1, by boost in pressure, be 3MPa, the volume space velocity of synthesis gas is set to 7800h
-1, temperature setting is set to 270 ℃.Adopt SP3410 gas-chromatography to carry out on-line testing, the conversion ratio of CO and the distribution of each product are as shown in table 2.
Table 2
Above the embodiment of the present invention is had been described in detail, but described content is only preferred embodiment of the present invention, not in order to limit the present invention.All any modifications of making in application range of the present invention, be equal to and replace and improvement etc., within all should being included in protection scope of the present invention.
Claims (9)
1. for the synthesis of a catalyst for gas low-carbon alcohols processed, it is characterized in that consisting of metal ingredient and graphite composition, described metal ingredient is to contain Cu, Co, Al
2o
3blending constituent, simultaneously above-mentioned each component meets following relation:
The mass fraction of graphite composition in metal ingredient and graphite composition gross mass is 0.3～30%;
The mass fraction of Cu in metal ingredient is 2～25%;
The mass fraction of Co in metal ingredient is 3～45%;
The surplus of metal ingredient is Al
2o
3.
2. a kind of catalyst for the synthesis of gas low-carbon alcohols processed according to claim 1, it is characterized in that described metal ingredient also comprises auxiliary agent, described auxiliary agent is the component that contains in Zn, Mn, Mg, Ca, Ni, Fe, Cr one or more, and the mass fraction of described auxiliary agent in described metal ingredient be not higher than 70%.
3. a kind of catalyst for the synthesis of gas low-carbon alcohols processed according to claim 1, is characterized in that the sheet graphite oxide reduction that described graphite composition is no more than 1000nm by thickness obtains.
4. a kind of catalyst for the synthesis of gas low-carbon alcohols processed according to claim 1, is characterized in that the sheet graphite oxide reduction that described graphite composition is no more than 100nm by thickness obtains.
5. a kind of catalyst for the synthesis of gas low-carbon alcohols processed according to claim 1, is characterized in that described graphite composition is obtained by graphene oxide reduction.
6. the method for preparing catalyst for the synthesis of gas low-carbon alcohols processed as claimed in claim 1, is characterized in that comprising the following steps:
1) under ice bath, stirring condition by 98% (w/w) H
2sO
4, graphite powder, sodium nitrate, potassium permanganate mix, then it is kept 1～3 hour under-5～5 ℃ of conditions, then be warming up to 30～40 ℃ and kept stirring 10～180min, then add wherein the first deionized water to dilute, in this process, keep mixture temperature in 100 ℃ of following reaction 1～5h, then add wherein 30% (w/w) hydrogen peroxide stirring reaction, 1～120min, then add wherein again the second deionized water preparation to become the mixed liquor that graphite concentration is 0.5～20g/L, be graphite oxide, above-mentioned 98% (w/w) H
2sO
4, graphite powder, sodium nitrate, potassium permanganate, the first deionized water, 30% (w/w) hydrogen peroxide mass ratio be (90～95): (1～2.2): (0.9～1.4): (6～7.5): (130～170): (25～35).
2) according to the mol ratio of copper nitrate, cobalt nitrate, aluminum nitrate, auxiliary agent nitrate total amount, be 1:(0.3～3): (1～6): (0～3), mentioned component is added in deionized water and is made into the mixed solution that total ion concentration is 0.01-2mol/L, be designated as the first mixed solution; By Na
2cO
3be mixed with the second mixed solution with NaOH, and in the molar concentration that guarantees NaOH in the second mixed solution and the first mixed solution all the ratio of cation molar concentration sums be (1～5): 1, guarantee Na in the second mixed solution simultaneously
2cO
3molar concentration and the first mixed solution in all the ratio of bivalent cation molar concentration sums be (1～5): 1; Above-mentioned the first mixed solution and the second mixed solution stream are joined to step 1) in the graphite oxide that obtains, controlling pH value is 8～11, after dropwising, the first mixed solution stops dripping, by mixture, in temperature, be to process 6～48h under 60～130 ℃ of conditions, then collect solid phase washing to neutral, the more fully dry compound that obtains;
3) by step 2) compound that obtains is 300～8000h passing into air speed
-1reducibility gas exist under, temperature is reduction 0.5～6h 200～600 ℃ within the scope of, thereby described in obtaining for the synthesis of the catalyst of gas low-carbon alcohols processed, wherein reducibility gas is the gas that includes in hydrogen, carbon monoxide, methane one or more.
7. the method for preparing catalyst for the synthesis of gas low-carbon alcohols processed according to claim 6, is characterized in that step 3) utilize reducibility gas processing compound before further comprising the steps of: by compound roasting under inert gas shielding.
8. the method for preparing catalyst for the synthesis of gas low-carbon alcohols processed according to claim 7; it is characterized in that describedly by compound roasting concrete grammar under inert gas shielding, being: sintering temperature is 300～800 ℃; roasting time is 0.5～10h, and inert gas composition comprises one or more in nitrogen, argon gas, helium.
9. the catalyst as described in claim 1～5 any one is for catalyzing and synthesizing the application that gas is prepared low-carbon alcohols, it is characterized in that comprising the following steps: with the described catalyst contact conditions for the synthesis of gas low-carbon alcohols processed under, with 200～350 ℃, the condition of 1～6MPa, in reactor, take air speed as 500～8000
-1pass into mol ratio for (0.5～3): 1 hydrogen and carbon mono oxide mixture.
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