CN104056629B - A kind of catalyst for low carbon alcohol by synthetic gas, its preparation method and application - Google Patents
A kind of catalyst for low carbon alcohol by synthetic gas, its preparation method and application Download PDFInfo
- Publication number
- CN104056629B CN104056629B CN201410271568.7A CN201410271568A CN104056629B CN 104056629 B CN104056629 B CN 104056629B CN 201410271568 A CN201410271568 A CN 201410271568A CN 104056629 B CN104056629 B CN 104056629B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- graphite
- gas
- mixed solution
- synthetic gas
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention provides a kind of catalyst for low carbon alcohol by synthetic gas, its preparation method with flake graphite or Graphene as carrier and utilize its application preparing low-carbon alcohols.This catalyst for by synthesizing low-carbon alcohol from synthetic gas, has that CO conversion ratio is higher, the selectivity of carbon 2 and above alcohol is good, the preferable feature of low temperature active.Its preparation and processing procedure industrialized production simple, applicable.The ultimate principle of preparation is by controlling Coprecipitation, it is achieved the uniform mixing of each metal ion, particularly copper ion and cobalt ion in catalyst precursor；Owing to there is strong interaction between metal and graphite, after reduction, Cu Co Nanoalloy can be highly dispersed on graphite flake, can be effectively prevented from the granule sintering that CuCo alloy causes due to migration.
Description
Technical field
The present invention relates to technical field of chemical engineering catalysts, be specifically related to a kind of catalysis for low carbon alcohol by synthetic gas
Agent, 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 and has compeled at eyebrow
Eyelash.Synthesis gas (CO, the H produced by natural gas or coal or reproducible biomass resource2) prepare low-carbon (LC)
Alcohol (referring to containing two carbon atoms or above alcohol) causes greatly concern, and it should fuel and chemical field
The most day by day highlight with being worth.Low-carbon alcohols can serve as the power fuel of high-quality, can substitute as petroleum additive
Controversial MTBE and the bigger lead tetraethyl of toxicity, simultaneously by low-carbon alcohols may separate out second, third, fourth
The alcohols higher with prices such as amylalcohols.It addition, one of low-carbon alcohols means being also used as coal liquefaction, it is achieved coal
Alkylation and solubilized and as liquefied petroleum gas succedaneum etc..
Low carbon alcohol by synthetic gas reaction is often attended by methanol, hydro carbons and CO2Deng the generation of by-product, therefore
Synthesis of low-carbon alcohol technology it is crucial that exploitation has the catalyst of excellent activity, selectivity and stability.At present,
Formate low-carbon alcohol catalyst has four kinds: the noble metal catalyst with Rh as representative, modified synthesizing methanol catalysis
Agent, Mo base catalyst, modified FT synthetic catalyst.Wherein, the noble metal catalyst with Rh as representative
Though the hydrogenation activity having had, alcohol selectivity is preferable；But it is expensive, easily by CO2The feature such as poison limits
Its application.Modified methanol synthesis catalyst operating condition is harsh, and product is still based on methanol, then by
Gradually it is eliminated.Though modified catalyst with base of molybdenum has the resistance to SO_2 of uniqueness, can avoid costly deep desulfuration,
And aqueous less in product, low-carbon alcohols content is higher, but the hydrogen-carbon ratio of unstripped gas is required harshness, it is necessary to
Between 1.0～1.1, and this catalyst promoter easily forms carbonyl compound with CO, causes the stream of its constituent element
Lose, thus its stability is restricted.
Modified fischer-tropsch synthetic catalyst is mainly based on Cu-Fe and Cu-Co base catalyst.Cu-Fe base is catalyzed
In agent, owing to Fe has higher water gas shift reaction activity so that containing more water in product, with
Time hydrocarbon selective higher.In Cu-Co base catalyst, Co is the element the highest to activity in FT reaction,
Co series catalysts has Water gas shift/WGS insensitive, and is difficult to the advantages such as carbon distribution poisoning in course of reaction,
Cu is conducive to generating alcohol, and the synergism of Cu and Co can improve the activity of catalyst and containing two and two
Above carbon atom alcohol (C2+Alcohol) selectivity, therefore Cu-Co base catalyst is considered as up-and-coming conjunction
Become low-carbon alcohol catalyst.But C in product2+Alcohol selectivity is the most on the low side, does not the most have commercial production valency
Value.
At present, the preparation method of synthesis CuCo base catalyst is mainly infusion process.
As document [Journal of Catalysis, 2012,286:51-61] reports prepared with co-impregnation
Series xCuyCo/ γ-Al2O3, (x=0～0.5).As x=y=1, calcining afterproduct reduces at a temperature of 673K
Afterwards, γ-Al is defined2O3Load copper cobalt nano-particle.At 2MPa, 523K and H2/ CO is 2:1
Under conditions of, CO conversion ratio is 16.5%, and hydrocarbon selective is 82.6%, and alcohol selectivity is 17.1%, its
In, methanol accounts for the 35.7% of total alcohol content.Think that catalyst calcination afterproduct prepared by this method is general
CuO and the Co of spinel structure for monocline3O4Mixture, obtain after reduction single Cu and
Co metallic particles, and Active components distribution is uneven, thus reduce the synergism between Cu-Co, unfavorable
Generation in low-carbon alcohols.
In recent years, layered double hydroxide (Layered Double Hydroxides, LDHs), also known as
Houghite, has been a great concern, and it is electronegative by positively charged layers of metal hydroxides and interlayer
Anion composition lamellar compound.Its chemical composition is represented by
[M2+ 1-xM3+ x(OH)2]x+(An-)x/n·mH2O], wherein, M is metal ion, An-For interlayer anion.LDHs
There is the character of uniqueness: as laminate metal ion can be replaced by the metal ion of other similar radius, have
Adjustable degeneration；Simultaneously by the minimum effects of lattice orientation effect and lattice energy, laminate metal ion can reach
Being uniformly distributed of molecular level；The thermal decomposition of LDHs has structural topology effect, it is possible to product of roasting is protected
Holding the equally distributed feature of precursor, further reduction also can form equally distributed nano-metal particle or nanometer is closed
Gold grain.Prepare catalyst hence with LDHs as presoma, not only can realize the equal of each component
Even distribution, the synergism being additionally favorable between active component.
In prior art, there is a key issue in Cu-Co bimetallic catalyst: sintering, due to Cu-Co
Content is higher, and nanometer Cu-Co granule, at a distance of near, be easily merged into bulky grain, then inactivate.By preparation
Time add other components, such as Zn, Mg etc., Cu-Co can be diluted, improve anti-sintering, but dilute unfavorable
Being formed in Cu-Co alloy, then selectivity declines.Also may select other carrier, such as ZrO2、SiO2Deng load
Carry Cu-Co catalyst, but there is carrier, with Cu-Co, the problem such as solid state reaction, preparation difficulty occurs.
Summary of the invention
It is contemplated that for the technological deficiency of prior art, it is provided that a kind of with flake graphite or Graphene as carrier
The catalyst for low carbon alcohol by synthetic gas, its preparation method and application.
For realizing above technical purpose, the present invention by the following technical solutions:
A kind of catalyst for low carbon alcohol by synthetic gas, it is characterised in that be made up of metal ingredient and graphite content,
Described metal ingredient is containing Cu, Co, Al2O3Blending constituent, the most above-mentioned each component meet with ShiShimonoseki
System: graphite content mass fraction in metal ingredient with graphite content gross mass is 0.3～30%；Cu is at gold
The mass fraction belonged in composition is 2～25%；Co mass fraction in metal ingredient is 3～45%；Metal becomes
The surplus divided is Al2O3。
Preferably, described metal ingredient also include auxiliary agent, described auxiliary agent be containing Zn, Mn, Mg, Ca,
The component of one or more in Ni, Fe, Cr, described auxiliary agent mass fraction in described metal ingredient is the highest
In 70%.
Preferably, the lamellar graphite oxide reduction that described graphite content is less than 1000nm by thickness obtains.
Preferably, the lamellar graphite oxide reduction that described graphite content is less than 100nm by thickness obtains.
Preferably, described graphite content is obtained by graphene oxide reduction.
Meanwhile, present invention also offers the preparation method of a kind of above-mentioned catalyst, it specifically comprises the following steps that
1) by 98% (w/w) H under ice bath, stirring condition2SO4, graphite powder, sodium nitrate, potassium permanganate mix
Close uniformly, then it is kept 1～3 hour under the conditions of-5～5 DEG C, be then warming up to 30～40 DEG C of holdings
Stirring 10～180min, is then added thereto to the first deionized water and is diluted, and keeps mixture during this
Temperature is in less than 100 DEG C reactions 1～5h, is then added thereto to the stirring reaction of 30% (w/w) hydrogen peroxide
1～120min, be added thereto to the most again the second deionized water preparation become graphite concentration be 0.5～20g/L mixed
Close liquid, be graphite oxide, above-mentioned 98% (w/w) H2SO4, graphite powder, sodium nitrate, potassium permanganate,
One deionized water, the mass ratio of 30% (w/w) hydrogen peroxide are
(90～95): (1～2.2): (0.9～1.4): (6～7.5): (130～170): (25～35).
2) according to copper nitrate, cobalt nitrate, aluminum nitrate, the mol ratio of auxiliary agent nitrate total amount it is
1:(0.3～3): (1～6): (0～3), mentioned component is added in deionized water to be made into total ion concentration be 0.01-2mol/L
Mixed solution, be designated as the first mixed solution；By Na2CO3It is configured to the second mixed solution with NaOH, and
Ensure in the second mixed solution in the molar concentration of NaOH and the first mixed solution all cation mole concentration
The ratio of sum is (1～5): 1, ensures Na in the second mixed solution simultaneously2CO3Molar concentration mix molten with first
In liquid, the ratio of whole bivalent cation molar concentration sums is (1～5): 1；Above-mentioned first mixed solution and second are mixed
Closing solution stream and join step 1) in the graphite oxide that obtains, control ph is 8～11, when the first mixing
Stop dropping after solution dropping, mixture is processed under the conditions of temperature is 60～130 DEG C 6～48h, then
Collect solid phase and wash to neutral, being more fully dried to obtain complex；
3) by step 2) complex that obtains is 300～8000h being passed through air speed-1Reducibility gas in the presence of,
Temperature reduces 0.5～6h in the range of being 200～600 DEG C, thus obtains the described catalysis for low carbon alcohol by synthetic gas
Agent, wherein reducibility gas is to include the gas of one or more in hydrogen, carbon monoxide, methane.
In addition to the method described above, it is also possible to be following method:
1) to 98% (w/w) H under ice bath, stirring condition2SO4Middle addition graphite powder, sodium nitrate, permanganic acid
Potassium, keeps it 1～3 hour under the conditions of-5～5 DEG C after mix homogeneously, is then warming up to 30～40 DEG C of guarantors
Hold stirring 10～60min, be then added thereto to the first deionized water and be diluted, during this, keep mixing
Thing temperature is in less than 100 DEG C reactions 1～5h, is then added thereto to the stirring reaction of 30% (w/w) hydrogen peroxide
1～10min, be added thereto to the most again the second deionized water preparation become graphite concentration be 0.5～20g/L mixed
Close liquid, be graphite oxide solution, above-mentioned 98% (w/w) H2SO4, graphite powder, sodium nitrate, potassium permanganate,
First deionized water, the mass ratio of 30% (w/w) hydrogen peroxide are
(90～95): (1～2.2): (0.9～1.4): (6～7.5): (130～170): (25～35).
2) according to copper nitrate, cobalt nitrate, aluminum nitrate, the mol ratio of auxiliary agent nitrate total amount it is
1:(0.3～3): (1～6): (0～3), mentioned component is added in deionized water to be made into total ion concentration be 0.01-2mol/L
Mixed solution, be designated as the first mixed solution；By Na2CO3It is configured to the second mixed solution with NaOH, and
Ensure in the second mixed solution in the molar concentration of NaOH and the first mixed solution all bivalent cations mole
The ratio of concentration sum is (1～5): 1, ensures that in the second mixed solution, the molar concentration of NaOH mixes with first simultaneously
In solution, the ratio of whole bivalent cation molar concentration sums is (1～5): 1；By above-mentioned first mixed solution and second
Mixed solution also flows mixing, and control ph is 8～11, stops dropping after the first mixed solution dropping,
Mixture is processed under the conditions of temperature is 60～130 DEG C 6～48h, then adds this mixture to step 1)
The graphite oxide obtained is sufficiently stirred for, then collects solid phase and wash to neutral, being more fully dried to obtain compound
Thing；
3) by step 2) complex that obtains is 300～8000h being passed through air speed-1Reducibility gas in the presence of,
Temperature reduces 0.5～6h in the range of being 200～600 DEG C, thus obtains the described catalysis for low carbon alcohol by synthetic gas
Agent, wherein reducibility gas is to include the gas of one or more in hydrogen, carbon monoxide, methane.
For above two method, can there is a following optimal way:
Preferably, step 3) utilize reducibility gas can also comprise the following steps before processing complex: will
Complex roasting under inert gas shielding.
Above-mentioned by complex, under inert gas shielding, roasting can step the most in detail below: roasting
Temperature is 300～800 DEG C, and roasting time is 0.5～10h, and noble gas component comprises nitrogen, argon, helium
In one or more.
Present invention also offers a kind of above-mentioned catalyst simultaneously and prepare the application of low-carbon alcohols for catalyzing and synthesizing gas, bag
Include following steps: with described under the catalyst contact condition of low carbon alcohol by synthetic gas, with 200～350 DEG C,
The condition of 1～6MPa is 500～8000 with air speed in reactor-1Be passed through mol ratio for (0.5～3): the hydrogen of 1 and
Carbon mono oxide mixture.
The method for preparing catalyst of technique scheme, step 1) prepared by its lamellar spacing of graphite oxide exist
Between 1000nm to 1 atomic layer, it is distributed mainly between 10～100nm.
Technique scheme has the advantage for preparing graphite oxide-houghite presoma by coprecipitation,
Reduction obtains what Nanometer Copper cobalt dual-metal catalyst realized.Control deposition condition and can realize catalyst precursor
In the uniform mixing of each metal ion, particularly copper ion and cobalt ion；After reduction, due to metal and graphite it
Between there is strong interaction, Cu-Co Nanoalloy can be highly dispersed on graphite flake/alkene, can be effectively
Avoid or slow down the sintering of Cu-Co alloying pellet.The Cu-Co active component so prepared, has high work
Property specific surface area, carrier and additive can the sintering of inhibitory activity component.The advantage that this catalyst highlights is low-carbon (LC)
Alcohol selectivity and low temperature active are the highest, and preparation is simple, low cost, has industrial application value.
Accompanying drawing explanation
Fig. 1 be catalyst obtained in the embodiment of the present invention 1 after calcining, after reduction and react it
After XRD curve, XRD is that cobalt target records；In figure: a is that catalyst precursor is through 500 DEG C of calcinings
After XRD curve；B is the XRD curve of the catalyst after 450 DEG C of reduction 3h；C is urging after reducing
Agent XRD curve after reaction.* the diffraction maximum of Co-Cu alloy is represented, ● represent CuCo2O4；
Fig. 2 is that the catalyst precursor obtained by present example 1 is with 5%H2/ Ar is reducing gases, with 10 DEG C
TEM figure after/min is warming up to 450 DEG C of reduction 3h, under scale is 2nm；D=0.208nm in figure
For interplanar distance.Due to (111) interplanar distance d=0.208nm of Co0.52Cu0.48, so this crystal face is returned
Belong to (111) crystal face of CuCo alloy；
Fig. 3 is that the prepared catalyst of present example 1 is at the stability curves that temperature is 255 DEG C of reactions；In figure:
Curve a is the selectivity trend over time of alcohols；Curve b be the conversion ratio of CO over time
Trend；Curve c is the selectivity trend over time of alkane；Curve d is CO in product2Selectivity
Trend over time；
Fig. 4 is the graphite oxide scanning electron microscope (SEM) photograph of the embodiment of the present invention 1 preparation；From the figure, it can be seen that its stone
Ink sheet layer thickness is about at about 30nm.
Detailed description of the invention
[embodiment 1]
The dense H of 98% is added in dry container2SO4, in ice bath, under stirring, add graphite, stirring, add
Sodium nitrate, potassium permanganate, and control mixture temperature to be kept stirring for 2.8h at 0 DEG C；Then mixture is protected
Hold at about 31～33 DEG C, stir 25min；Then deionized water dilution is added to mixed liquor, in the process
Mixture temperature is maintained at less than 100 DEG C, reacts 4h, takes out reactor, adds the first deionized water dilution,
Add the hydrogen peroxide of 30%, stir 8min；Then carry out high speed centrifugation separation, and be washed with deionized water
Wash to filtrate without SO4 2-, at 80 DEG C, it is dried 24h, prepares graphite oxide solution.Add deionized water,
Compound concentration is the graphite oxide dispersion of 7g/L；Wherein, each reactant mass ratio is, the dense H of 98%2SO4:
Graphite: sodium nitrate: potassium permanganate: the first deionized water: the hydrogen peroxide=92:2:1:7:150 of 30%:
33。
It is that to be made into total metal concentration be the mixed of 1mol/L to 2:4:3 by the mol ratio of copper nitrate, cobalt nitrate and aluminum nitrate
Close saline solution, be designated as solution A；By c (Na2CO3)=0.66mol/L and c (NaOH)=4.1mol/L joins
Mixed ammonium/alkali solutions is become to be designated as B.The volumetric usage of solution A and solution B is 1.Solution A and solution B also
Stream joins in the reactor containing above-mentioned graphite oxide dispersion, and control ph is 9.5, and solution A drips
After, aging 12h under the conditions of temperature is 80 DEG C, after product solid-liquid separation, washing is to neutral, through in temperature
It is dried 24h at 80 DEG C, obtains the complex of houghite presoma and graphite oxide；
Take in catalyst precursor addition Muffle furnace prepared by said method, in temperature 500 DEG C, nitrogen atmosphere
Roasting 4h, takes roasting afterproduct in reactor, in reactor
It is passed through H2Volume fraction is hydrogen, the argon gaseous mixture of 5%, rises to 450 ° with the heating rate of 10 DEG C/min
Reduction 3h, is passed through H after naturally cooling to room temperature2With the synthesis gas that mol ratio is 2:1 of CO, pressure is carried
Being upgraded to 3MPa, the volume space velocity of synthesis gas is set to 3900h-1, temperature is set to 240 DEG C-300 DEG C.Adopt
Carrying out on-line testing by SP3410 gas chromatogram, the distribution of the conversion ratio of CO and each product is with the change of temperature
Change as shown in table 1.It can be seen that CO conversion ratio and low-carbon alcohols selectivity are the highest.
XRD figure after reduction of the catalyst precursor prepared from the above is it can be seen that catalyst
There is alloy diffraction maximum after reduction in presoma, illustrates to define alloy, is calculated by Scherrer formula
The size of alloy is between 3-10nm.Reacted XRD still has alloy diffraction maximum, CuCo is described
, not there is the separation of phase, directly illustrate that catalyst stability is good in alloy stable existence.
Table 1
[embodiment 2]
The preparation method of graphite oxide is same as in Example 1.
It is that 2:2:1:3 is made into total metal concentration and is by copper nitrate, cobalt nitrate, zinc nitrate, the mol ratio of aluminum nitrate
The mixing salt solution of 1mol/L, is designated as solution A；By c (Na2CO3)=1.0mol/L and c (NaOH)=3.2mol/L
It 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
And stream joins in the reactor that 1.5L concentration is 3g/L graphite oxide dispersion, and control ph is 9.7,
After solution A dropping, aging 12h under the conditions of temperature is 60 DEG C, after product solid-liquid separation, washing is to neutral,
Through being dried 14h at temperature 80 DEG C, obtain the complex of houghite presoma and graphite oxide；
Take in catalyst precursor addition Muffle furnace prepared by said method, in temperature 550 DEG C, nitrogen atmosphere
Roasting 3h, takes roasting afterproduct in reactor, in reactor
It is passed through H2Volume fraction is hydrogen, the argon gaseous mixture of 5%, rises to 450 ° with the heating rate of 5 DEG C/min
Reduction 3h, is passed through H after naturally cooling to room temperature2With the synthesis gas that mol ratio is 2:1 of CO, pressure is carried
Being upgraded to 3MPa, the volume space velocity of synthesis gas is set to 3900h-1, temperature is set to 290 DEG C.Use SP341
0 gas chromatogram carries out on-line testing, and 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 same as in Example 1.
It is that 2:4:0.6:3 is made into total metal concentration and is by copper nitrate, cobalt nitrate, calcium nitrate, the mol ratio of aluminum nitrate
The mixing salt solution of 0.5mol/L, is designated as solution A；By c (Na2CO3)=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.Solution
A and solution B flowing adds in the reactor that 1L concentration is 5g/L graphite oxide dispersion, and control ph
It is 8, after solution A dropping, aging 12h under the conditions of temperature is 70 DEG C, washs after product solid-liquid separation
To neutral, through being dried 48h at temperature 80 DEG C, obtain the complex of houghite presoma and graphite oxide；
Take in catalyst precursor addition Muffle furnace prepared by said method, in temperature 500 DEG C, nitrogen atmosphere
Roasting 4h, joins in reactor by roasting afterproduct, in reactor
It is passed through H2Volume fraction is hydrogen, the argon gaseous mixture of 5%, rises to 400 ° with the heating rate of 8 DEG C/min
Reduction 3h, is passed through H after naturally cooling to room temperature2With the synthesis gas that mol ratio is 2:1 of CO, pressure is carried
Being upgraded to 3MPa, the volume space velocity of synthesis gas is set to 7800h-1, temperature is set to 270 DEG C.Use SP341
0 gas chromatogram carries out on-line testing, and 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 same as in Example 1.
It is that 1:1:0.1:1 is made into total metal concentration and is by copper nitrate, cobalt nitrate, manganese nitrate, the mol ratio of aluminum nitrate
The mixing salt solution of 2mol/L, is designated as solution A；By c (Na2CO3)=3mol/L and c (NaOH)=7mol/L
It is made into mixed ammonium/alkali solutions and is designated as B.The volumetric usage of solution A and solution B is 1.5.Solution A and solution B
And flow in the reactor that addition 1.5mL concentration is 4g/L graphite oxide dispersion, and control ph is 9.A
After solution dropping, aging 10h under the conditions of temperature is 75 DEG C, after product solid-liquid separation, washing is to neutral,
Through being dried 20h at temperature 85 DEG C, obtain the complex of houghite presoma and graphite oxide；
Take catalyst precursor prepared by said method and join in reactor,
With volume space velocity as 3000h-1It is passed through H2Volume fraction is hydrogen, the argon gaseous mixture of 3%, with 1 DEG C/min
Heating rate rise to 350 ° reduction 3h, be passed through H after naturally cooling to room temperature2It is 2:1 with the mol ratio of CO
Synthesis gas, be 3MPa by boost in pressure, the volume space velocity of synthesis gas is set to 3900h-1, temperature is arranged
It it is 260 DEG C.SP3410 gas chromatogram is used to carry out on-line testing, the conversion ratio of CO and dividing of each product
Cloth change is as shown in table 2.
[embodiment 5]
The preparation method of graphite oxide is same as in Example 1.
It is that 1:2:0.1:1 is made into total metal concentration and is by copper nitrate, cobalt nitrate, nickel nitrate, the mol ratio of aluminum nitrate
The mixing salt solution of 0.3mol/L, is designated as solution A；By c (Na2CO3)=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.Solution A
With solution B and flow add 0.5L concentration be 8g/L graphite oxide dispersion reactor in, containing above-mentioned oxidation stone
In the reactor of ink colloidal sol, and control ph is 9.0, after solution A dropping, is 70 DEG C of bars in temperature
Aging 20h under part, after product solid-liquid separation, washing is to neutral, through being dried 20h at temperature 75 DEG C, obtains class
Hydrotalcite precursor and the complex of graphite oxide.
Take in catalyst precursor addition Muffle furnace prepared by said method, in temperature 500 DEG C, nitrogen atmosphere
Roasting 5h, joins in reactor by roasting afterproduct,
With volume space velocity as 2000h-1It is passed through H2Volume fraction is hydrogen, the argon gaseous mixture of 3%, with 5 DEG C/min
Heating rate rise to 450 ° reduction 3h, be passed through H after naturally cooling to room temperature2It is 2:1 with the mol ratio of CO
Synthesis gas, be 2MPa by boost in pressure, the volume space velocity of synthesis gas is set to 4800h-1, temperature is arranged
It it is 260 DEG C.SP3410 gas chromatogram is used to carry out on-line testing, the conversion ratio of CO and dividing of each product
Cloth change is as shown in table 2.
[embodiment 6]
The preparation method of graphite oxide is same as in Example 1.
It is that 1:1:0.1:0.1:1 is made into by copper nitrate, cobalt nitrate, calcium nitrate, chromic nitrate, the mol ratio of aluminum nitrate
Total metal concentration is the mixing salt solution of 0.1mol/L, is designated as solution A；By c (Na2CO3)=0.15mol/L
It is made into mixed ammonium/alkali solutions is designated as B with c (NaOH)=0.3mol/L.Solution A and the volumetric usage of solution B
It is 1.Solution A and solution B and flow and add in the reactor that 1L concentration is 2g/L graphite oxide dispersion,
And control ph is 8.5, after solution A dropping, aging 20h, product under the conditions of temperature is 100 DEG C
After solid-liquid separation, washing is to neutral, through being dried 20h at temperature 75 DEG C, obtains houghite presoma and oxygen
The complex of graphite.
Take in catalyst loading reactor prepared by said method, with volume space velocity as 3000h-1It is passed through H2Body
Fraction is hydrogen, the argon gaseous mixture of 5%, rises to 440 ° of reduction 5h with the heating rate of 10 DEG C/min,
It is passed through H after naturally cooling to room temperature2With the synthesis gas that mol ratio is 2:1 of CO, it is 3MP by boost in pressure
A, the volume space velocity of synthesis gas is set to 3900h-1, temperature is set to 300 DEG C.Use SP3410 gas phase color
Spectrum carries out on-line testing, and 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 same as in Example 1.
It is that 1:1:1:1 is made into total metal concentration and is by copper nitrate, cobalt nitrate, magnesium nitrate, the mol ratio of aluminum nitrate
The mixing salt solution of 0.5mol/L, is designated as solution A；By c (Na2CO3)=1mol/L and c (NaOH)=1.8mol/L
It 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
And flow in the reactor that addition 1.5L concentration is 3g/L graphite oxide dispersion, and control ph is 10, A
After solution dropping, aging 12h under the conditions of temperature is 70 DEG C, after product solid-liquid separation, washing is to neutral,
Through being dried 48h at temperature 80 DEG C, obtain the complex of houghite presoma and graphite oxide；
Take in catalyst precursor addition Muffle furnace prepared by said method, in temperature 500 DEG C, nitrogen atmosphere
Roasting 4h, joins in reactor by roasting afterproduct, in reactor
It is passed through H2Volume fraction is hydrogen, the argon gaseous mixture of 5%, rises to 400 ° with the heating rate of 8 DEG C/min
Reduction 3h, is passed through H after naturally cooling to room temperature2With the synthesis gas that mol ratio is 2:1 of CO, pressure is carried
Being upgraded to 3MPa, the volume space velocity of synthesis gas is set to 7800h-1, temperature is set to 270 DEG C.Use SP341
0 gas chromatogram carries out on-line testing, and 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 described in detail, but described content has been only presently preferred embodiments of the present invention,
Not in order to limit the present invention.All any amendment, equivalents made in the application range of the present invention and changing
Enter, should be included within the scope of the present invention.
Claims (8)
1. the catalyst for low carbon alcohol by synthetic gas, it is characterised in that being made up of metal ingredient and graphite content, wherein graphite content is flake graphite or Graphene, and described metal ingredient is containing Cu, Co, Al2O3Blending constituent, the most above-mentioned each component meets following relation:
Graphite content mass fraction in metal ingredient with graphite content gross mass is 0.3 ~ 30%；
Cu mass fraction in metal ingredient is 2 ~ 25%；
Co mass fraction in metal ingredient is 3 ~ 45%；
The surplus of metal ingredient is Al2O3；
The lamellar graphite oxide reduction that described flake graphite is less than 1000nm by thickness obtains.
A kind of catalyst for low carbon alcohol by synthetic gas the most according to claim 1, it is characterized in that described metal ingredient also includes auxiliary agent, described auxiliary agent is containing the component of one or more in Zn, Mn, Mg, Ca, Ni, Fe, Cr, and described auxiliary agent mass fraction in described metal ingredient is not higher than 70%.
A kind of catalyst for low carbon alcohol by synthetic gas the most according to claim 1, it is characterised in that the lamellar graphite oxide reduction that described graphite content is less than 100nm by thickness obtains.
A kind of catalyst for low carbon alcohol by synthetic gas the most according to claim 1, it is characterised in that described graphite content is obtained by graphene oxide reduction.
5. the method for preparing catalyst being used for low carbon alcohol by synthetic gas as claimed in claim 2, it is characterised in that comprise the following steps:
1) by 98% (w/w) H under ice bath, stirring condition2SO4, graphite powder, sodium nitrate, potassium permanganate mix homogeneously, then it is kept 1 ~ 3 hour under the conditions of-5 ~ 5 DEG C, then it is warming up to 30 ~ 40 DEG C and is kept stirring for 10 ~ 180min, then it is added thereto to the first deionized water be diluted, mixture temperature is kept to be in less than 100 DEG C reaction 1 ~ 5h during this, then it is added thereto to 30% (w/w) hydrogen peroxide stirring reaction 1 ~ 120min, it is added thereto to the second deionized water preparation the most again and becomes the mixed liquor that graphite concentration is 0.5 ~ 20g/L, it is graphite oxide solution, above-mentioned 98% (w/w) H2SO4, graphite powder, sodium nitrate, potassium permanganate, the first deionized water, the mass ratio of 30% (w/w) hydrogen peroxide be (90 ~ 95): (1 ~ 2.2): (0.9 ~ 1.4): (6 ~ 7.5): (130 ~ 170): (25 ~ 35)；
2) it is 1:(0.3 ~ 3 according to copper nitrate, cobalt nitrate, aluminum nitrate, the mol ratio of auxiliary agent nitrate total amount): (1 ~ 6): (0 ~ 3), mentioned component is added in deionized water and be made into the mixed solution that total ion concentration is 0.01-2mol/L, be designated as the first mixed solution；By Na2CO3It is configured to the second mixed solution with NaOH, and ensures in the second mixed solution that in the molar concentration of NaOH and the first mixed solution, all the ratio of cation mole concentration sums is (1 ~ 5): 1, ensure Na in the second mixed solution simultaneously2CO3Molar concentration and the first mixed solution in the ratio of whole bivalent cation molar concentration sums be (1 ~ 5): 1；Above-mentioned first mixed solution and the second mixed solution stream are joined in the graphite oxide solution that step 1) obtains, control ph is 8 ~ 11, dropping is stopped after the first mixed solution dropping, mixture is processed under the conditions of temperature is 60 ~ 130 DEG C 6 ~ 48h, then collect solid phase and wash to neutral, being more fully dried to obtain complex；
3) by step 2) complex that obtains is 300 ~ 8000h being passed through air speed-1Reducibility gas in the presence of, temperature reduce 0.5 ~ 6h in the range of being 200 ~ 600 DEG C, thus obtain the described catalyst for low carbon alcohol by synthetic gas, wherein reducibility gas is to include the gas of one or more in hydrogen, carbon monoxide, methane.
Method for preparing catalyst for low carbon alcohol by synthetic gas the most according to claim 5, it is characterised in that step 3) is further comprising the steps of before utilizing reducibility gas to process complex: by complex roasting under inert gas shielding.
Method for preparing catalyst for low carbon alcohol by synthetic gas the most according to claim 6; it is characterized in that described by complex roasting under inert gas shielding method particularly includes: sintering temperature is 300 ~ 800 DEG C; roasting time is 0.5 ~ 10h, and noble gas component comprises one or more in nitrogen, argon, helium.
8. the catalyst as described in any one of claim 1 ~ 4 prepares the application of low-carbon alcohols for catalyzing and synthesizing gas, it is characterized in that comprising the following steps: with described under the catalyst contact condition of low carbon alcohol by synthetic gas, with 200 ~ 350 DEG C, the condition of 1 ~ 6MPa in reactor with air speed for 500 ~ 8000h-1It is passed through mol ratio for (0.5 ~ 3): the hydrogen of 1 and carbon mono oxide mixture.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410271568.7A CN104056629B (en) | 2014-06-17 | 2014-06-17 | A kind of catalyst for low carbon alcohol by synthetic gas, its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410271568.7A CN104056629B (en) | 2014-06-17 | 2014-06-17 | A kind of catalyst for low carbon alcohol by synthetic gas, its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104056629A CN104056629A (en) | 2014-09-24 |
| CN104056629B true CN104056629B (en) | 2016-08-17 |
Family
ID=51544735
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410271568.7A Active CN104056629B (en) | 2014-06-17 | 2014-06-17 | A kind of catalyst for low carbon alcohol by synthetic gas, its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104056629B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104475106A (en) * | 2014-12-15 | 2015-04-01 | 天津大学 | 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 |
| CN106140192A (en) * | 2015-04-22 | 2016-11-23 | 裴彦鹏 | One improves the selective catalyst of synthesis gas converted product and preparation method thereof and application |
| CN105536853B (en) * | 2016-02-01 | 2020-06-26 | 辽宁恒顺达新材料有限公司 | Molecular sieve catalyst for preparing low-carbon mixed alcohol from synthesis gas |
| CN106582700A (en) * | 2016-11-29 | 2017-04-26 | 中国科学院山西煤炭化学研究所 | Graphene-supported catalyst for preparation of low-carbon mixed alcohol from syngas, preparation method and application |
| CN107413348B (en) * | 2017-04-11 | 2020-11-03 | 太原理工大学 | Catalyst, preparation method thereof and method for synthesizing isobutanol |
| CN110327937A (en) * | 2019-07-26 | 2019-10-15 | 郑州轻工业学院 | Active component and carrier synergistic effect catalyst and its preparation method and application for one-step method from syngas preparation low-carbon alcohols |
| CN113600208B (en) * | 2021-08-30 | 2023-08-15 | 浙江工业大学 | CuCoMn/Al 2 O 3 Catalyst, preparation method and application thereof |
| WO2023173348A1 (en) * | 2022-03-17 | 2023-09-21 | 无锡东恒新能源科技有限公司 | Synthesis method for layered catalyst for fluidized bed |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1124887C (en) * | 2002-01-16 | 2003-10-22 | 厦门大学 | Carbon nanometer tube copper-base dmethanol synthesis promoting catalyst and its preparing method |
| CN100335170C (en) * | 2004-12-31 | 2007-09-05 | 厦门大学 | Promoting cobalt-copper base catalyst for preparation of low carbon mixed alcohol-carbon nano tube from synthetic gas and preparing method thereof |
| US20130211147A1 (en) * | 2011-09-02 | 2013-08-15 | Michael Cheiky | Low pressure dimethyl ether synthesis catalyst |
| CN103084178B (en) * | 2013-01-17 | 2015-06-03 | 中国科学院上海高等研究院 | Copper-contained hydrotalcite-based catalyst for preparing mixed alcohol by using synthesis gas as well as preparation method and application thereof |
| CN103143361B (en) * | 2013-03-29 | 2014-12-03 | 北京化工大学 | Graphene-promoted hydrotalcite-based denitration catalyst and preparation method thereof |
-
2014
- 2014-06-17 CN CN201410271568.7A patent/CN104056629B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN104056629A (en) | 2014-09-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104056629B (en) | A kind of catalyst for low carbon alcohol by synthetic gas, its preparation method and application | |
| Wang et al. | Designing 3d dual transition metal electrocatalysts for oxygen evolution reaction in alkaline electrolyte: Beyond oxides | |
| Jing et al. | Recent advances in synergistic effect promoted catalysts for preferential oxidation of carbon monoxide | |
| Tabakova et al. | CO-free hydrogen production over Au/CeO2–Fe2O3 catalysts: Part 1. Impact of the support composition on the performance for the preferential CO oxidation reaction | |
| Gobara et al. | Nanocrystalline spinel ferrite for an enriched production of hydrogen through a solar energy stimulated water splitting process | |
| Aider et al. | Improvement of catalytic stability and carbon resistance in the process of CO2 reforming of methane by CoAl and CoFe hydrotalcite-derived catalysts | |
| Zhang et al. | Fast start-up structured CuFeMg/Al2O3 catalyst applied in microreactor for efficient hydrogen production in methanol steam reforming | |
| Torimoto et al. | Effects of alloying for steam or dry reforming of methane: a review of recent studies | |
| Niakolas et al. | Study of the synergistic interaction between nickel, gold and molybdenum in novel modified NiO/GDC cermets, possible anode materials for CH4 fueled SOFCs | |
| Han et al. | Highly selective conversion of CO 2 to methanol on the CuZnO–ZrO 2 solid solution with the assistance of plasma | |
| Dasireddy et al. | Cu–Mn–O nano-particle/nano-sheet spinel-type materials as catalysts in methanol steam reforming (MSR) and preferential oxidation (PROX) reaction for purified hydrogen production | |
| CN109395735B (en) | Methanation catalyst, preparation method thereof and method for preparing methane by using methanation catalyst | |
| Asthana et al. | Direct conversion of syngas to DME: synthesis of new Cu-based hybrid catalysts using Fehling’s solution, elimination of the calcination step | |
| CN104549283A (en) | Carbon fiber compound nano copper cobalt alloy catalyst for low-carbon alcohol synthesis and preparation method of catalyst | |
| Wu et al. | Recent progresses in the design and fabrication of highly efficient Ni-based catalysts with advanced catalytic activity and enhanced anti-coke performance toward CO2 reforming of methane | |
| Tian et al. | CO2 hydrogenation to methanol over Pd/MnO/In2O3 catalyst | |
| CN104475106A (en) | 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 | |
| Abdalla et al. | The effects of WO3 addition to NiO/ZrO2 oxygen carriers for chemical looping combustion of methane | |
| Xie et al. | Zn‐Al hydrotalcite‐derived CoxZnyAlOz catalysts for hydrogen generation by auto‐thermal reforming of acetic acid | |
| CN110773214A (en) | Carbon layer embedded iron carbide, preparation method thereof and application of carbon layer embedded iron carbide as Fischer-Tropsch synthesis catalyst | |
| Santana et al. | Influence of Al, Cr, Ga, or Zr as promoters on the performance of Cu/ZnO catalyst for CO2 hydrogenation to methanol | |
| Wu et al. | High‐Efficiency Oxygen Evolution Reaction: Controllable Reconstruction of Surface Interface | |
| Jampaiah et al. | Enhanced water-gas shift reaction performance of MOF-derived Cu/CeO2 catalysts for hydrogen purification | |
| Wang et al. | Trace ultrafine Ru nanoparticles on Ni/Al hydrotalcite-derived oxides supports as extremely active catalysts for N-ethylcarbazole hydrogenation | |
| Song et al. | Doped Mn modulates the local charge distribution of cobalt-based spinel catalysts to promote the availability of ligand lattice oxygen for complete oxidation of methane |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |