CN106000403A - Fe-based catalyst having high CO hydrogenation reaction activity and low carbon olefin yield and application - Google Patents
Fe-based catalyst having high CO hydrogenation reaction activity and low carbon olefin yield and application Download PDFInfo
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- CN106000403A CN106000403A CN201610324479.3A CN201610324479A CN106000403A CN 106000403 A CN106000403 A CN 106000403A CN 201610324479 A CN201610324479 A CN 201610324479A CN 106000403 A CN106000403 A CN 106000403A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 77
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 34
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 16
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title abstract description 11
- 230000000694 effects Effects 0.000 title abstract description 9
- -1 carbon olefin Chemical class 0.000 title abstract description 4
- 239000002243 precursor Substances 0.000 claims abstract description 16
- 229910052596 spinel Inorganic materials 0.000 claims abstract description 14
- 230000009257 reactivity Effects 0.000 claims abstract description 11
- 239000002245 particle Substances 0.000 claims abstract description 9
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims abstract description 8
- 229910001701 hydrotalcite Inorganic materials 0.000 claims abstract description 8
- 229960001545 hydrotalcite Drugs 0.000 claims abstract description 8
- 230000009467 reduction Effects 0.000 claims abstract description 8
- 229910020068 MgAl Inorganic materials 0.000 claims abstract description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 229910026161 MgAl2O4 Inorganic materials 0.000 claims description 13
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 8
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 238000002425 crystallisation Methods 0.000 claims description 6
- 230000008025 crystallization Effects 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 229910052573 porcelain Inorganic materials 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 238000005086 pumping Methods 0.000 claims description 6
- 230000008859 change Effects 0.000 claims description 5
- 150000001768 cations Chemical class 0.000 claims description 3
- 238000002242 deionisation method Methods 0.000 claims description 3
- 238000011084 recovery Methods 0.000 claims description 3
- 229910052599 brucite Inorganic materials 0.000 claims description 2
- 239000004575 stone Substances 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 34
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 238000009903 catalytic hydrogenation reaction Methods 0.000 abstract description 2
- 239000011029 spinel Substances 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 19
- 238000010438 heat treatment Methods 0.000 description 11
- 150000001336 alkenes Chemical class 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 239000008187 granular material Substances 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 238000010926 purge Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000006004 Quartz sand Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 238000010494 dissociation reaction Methods 0.000 description 4
- 230000005593 dissociations Effects 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000007233 catalytic pyrolysis Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Inorganic materials [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/005—Spinels
-
- B01J35/393—
-
- B01J35/399—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
- C07C1/0425—Catalysts; their physical properties
- C07C1/043—Catalysts; their physical properties characterised by the composition
- C07C1/0435—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof
- C07C1/044—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof containing iron
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/74—Iron group metals
- C07C2523/745—Iron
Abstract
The invention provides a Fe-based catalyst having high CO hydrogenation reaction activity and low carbon olefin yield and application and belongs to the technical field of CO catalytic hydrogenation. The Fe-based catalyst contains an active center Fe uniform in particle size and an inert carrier MgAl spinel. The Fe-based catalyst is prepared after reduction of a hydrotalcite precursor MgAlFe-CO32-LDHs. The obtained Fe-based catalyst catalyzes CO hydrogenation under the reaction conditions of T = 340 DEG C and P = 2.0 MPato prepare low-carbon olefin, and the achievable optimal catalytic properties are as follows: after the catalytic performance is stable, the reactivity can be up to 2.92 mol/gFe h(the amount of converted CO substance on per gram of Fe per unit time), the CO conversion rate can be up to 89.2%, meanwhile the selectivity of the low-carbon olefin in a product can be up to 26.4%, and the yield of the low-carbon olefin can be up to 23.5%.
Description
Technical field
The invention provides and a kind of there is in CO Hydrogenation is for low carbon olefin hydrocarbon relatively high reaction activity and low
The catalyst of olefin yields, is specifically related to that a kind of particle diameter is relatively big, the distribution more uniform Fe base catalyst of ratio,
Belong to CO technical field of catalytic hydrogenation.
Background technology
Low-carbon alkene can be as preparing the raw material of the materials such as polymer, coating, cosmetics, solvent, and it needs
The amount of asking presents the trend of cumulative year after year.And in traditional handicraft, the main catalytic pyrolysis using Petroleum and alkane
The methods such as the dehydrogenation reaction of hydrocarbon prepare low-carbon alkene, but in terms of both approaches is due to environment and economic dispatch
Factor, there is also the biggest defect.Therefore, a kind of route just tool preparing low-carbon alkene efficiently is designed
There is the most great meaning.
At present, problem of energy crisis becomes the most prominent, and coal and oil etc. can not resource amount of storage reduce day by day,
Biomass, as Renewable resource, can become the substitute of future source of energy.Therefore, industrially tend to by
The synthesis gas that biomass prepare sets out, under certain condition synthesizing low-carbon alkene.Although being prepared by synthesis gas
The catalyst technology that low-carbon alkene is the most ripe, but still there is many problem in science and have to be solved,
From the point of view of basic research, in CO hydrogenation reaction activity and product, the regulation and control of yield of light olefins are that CO adds
There is one of problem in science of most critical to be solved in hydrogen field.
According to reaction mechanism, the process of preparing low-carbon olefin firstly the need of active center, CO is carried out
Absorption and dissociate, therefore active center CO adsorb dissociation capability will determine CO be hydrogenated with reactivity
And conversion ratio.And this reaction is the most sensitive for the structure change of Fe base catalyst, active center particle diameter etc. is tied
The change of structure all can possess significant impact for CO absorption dissociation capability.This just requires that we strictly to control
The size of Fe catalyst active center granule so that it is particle diameter is distributed in and is easier to absorption and dissociates in the range of CO,
Thus the reactivity promoting CO to be hydrogenated with, increase the total recovery of low-carbon alkene.
Summary of the invention
It is an object of the invention to synthesize that a kind of particle diameter is relatively big, the distribution more uniform Fe base catalyst of ratio so that it is
CO Hydrogenation is for having relatively high reaction activity and yield of light olefins in low carbon olefin hydrocarbon.
To achieve these goals, the present invention is by the following technical solutions:
A kind of, support type Fe base catalyst that yield of light olefins higher relatively big to CO hydrogenation reaction activity,
It is characterized in that, described catalyst includes that granular size is than more uniform active center Fe and inert carrier MgAl
Spinelle；Described Fe base catalyst is by hydrotalcite precursor MgAlFe-CO3 2--LDHs makes after carrying out reduction
?.Active center is that Fe is stronger to the absorption dissociation capability of CO.
The active center Fe particle diameter of preferred catalyst is 10nm～40nm.
Described catalyst active center Fe load capacity is 20wt%～30wt%.
Further preferred: the precursor MgAlFe-CO of catalyst3 2-Brucite laminate bivalence sun in-LDHs precursor
ION Mg2+, Tricationic select Al3+And Fe3+, bivalent cation and the molar ratio of Tricationic
For (2～4): 1.
Further, described Fe base catalyst is by hydrotalcite precursor MgAlFe-CO3 2--LDHs is at H2Atmosphere
Middle reduction and prepare, reduction temperature controls at 600 DEG C～900 DEG C, and the recovery time controls at 0.5h～2h.
Hydrotalcite precursor MgAlFe-CO3 2--LDHs powder is put among porcelain boat, is then placed on pipe
Near the thermocouple of formula resistance furnace, then by interior for pipe vacuum pumping；Observe overpressure will not become
After change, it is passed through H2, heating schedule is set, makes temperature from ambient be increased to 600 DEG C～900 DEG C, speed
Rate is set to (5-10) DEG C/min, then keeps 0.5h～2h；One section is kept after temperature is down to room temperature
Time, the nitrogen oxygen atmosphere being passed through 1% oxygen keeps 20min, then takes out, obtain Fe-MgAl2O4
Catalyst.
Hydrotalcite precursor MgAlFe-CO3 2—LDHs is prepared as conventional method: weigh
Mg(NO3)2·6H2O、Al(NO3)3·9H2O、Fe(NO3)3·9H2O is dissolved in deionized water together；
Additionally weigh Na2CO3It is dissolved in deionized water with NaOH, and the pH strictly controlling solution is 9.5-10,
It is made to keep constant；Then heat up and carry out crystallization；Through sucking filtration, wash, be dried, grind after, obtain
MgAlFe-CO3 2--LDHs sample.Every 8.5467g Mg (NO3)2·6H2O correspondence 250ml deionization
Water.Every 3.533g Na2CO3Corresponding 3.2g NaOH correspondence 250mL deionization.
With immediate prior art ratio, present invention have the advantage that
1. the support type Fe base catalyst of the present invention is with MgAlFe-CO3 2--LDHs is precursor, due to neatly
Stone veneer metal, with atomic level high degree of dispersion, advantageously forms active center granular size equal after being therefore reduced
The Fe base catalyst of one.Its particle diameter distribution ratio is more uniform, essentially 37nm, and when granular size increases to
Time near 40nm, active center is remarkably reinforced for the absorption dissociation capability of CO, so that CO is added by it
The reactivity of hydrogen reaches 2.92mol/gFeH, the reaction of the similar catalyst will reported apparently higher than other documents
Activity (is a maximum of about of 0.72mol/gFeH), and the yield of low-carbon alkene reaches also can reach 23.5%；
The Fe base catalyst that the present invention obtains, at T=340 DEG C, is catalyzed CO and adds under the reaction condition of P=2.0MPa
Hydrogen prepares low-carbon alkene, and accessible optimum catalytic performance is: when after stable in catalytic performance, reactivity up to
2.92mol/gFeH (amount of the material of the CO converted on every gram of Fe in the unit interval), CO conversion ratio
Up to 89.2%, in product, the selectivity of low-carbon alkene can reach 26.4% simultaneously, and the yield of low-carbon alkene can
Reach 23.5%.The granular size of the present invention is than more uniform big particle diameter Fe base catalyst, it is achieved that CO is hydrogenated with
Prepare the high reaction activity of low-carbon alkene and high yield, and its cost is relatively low, easily prepares.
2. the support type Fe base catalyst of the present invention is at T=340 DEG C, under the reaction condition of P=2.0MPa, urges
Changing performance and can keep stable for a long time, its reactivity and selectivity of light olefin can reach rapidly after the reaction
To a stationary value, and still without significant change after 400 minutes.
3) the support type Fe base method for preparing catalyst of the present invention is simple, and cost is relatively low, is conducive to applying in work
During industry produces.
Accompanying drawing explanation
Fig. 1: MgAlFe-CO3 2--LDHs precursor reduce at different temperatures after XRD curve, wherein
A-600 DEG C, B-700 DEG C, C-800 DEG C, D-900 DEG C；
Fig. 2: MgAlFe-CO3 2-TEM after-LDHs precursor reduces at different temperatures schemes, wherein
A-600 DEG C, B-700 DEG C, C-800 DEG C, D-900 DEG C；Wherein set figure is grain size distribution.
Fig. 3: different-grain diameter Fe-MgAl2O4The CO-FTIR figure of catalyst, wherein A-10.47nm,
B-18.55nm, C-28.53nm, D-37.44nm；
Fig. 4: different-grain diameter Fe-MgAl2O4Catalyst CO conversion ratio versus time curve, wherein
A-10.47nm, B-18.55nm, C-28.53nm, D-37.44nm；
Fig. 5: different-grain diameter Fe-MgAl2O4Catalyst selectivity of light olefin versus time curve, its
Middle A-10.47nm, B-18.55nm, C-28.53nm, D-37.44nm.
Detailed description of the invention
Below in conjunction with embodiment, the present invention will be further described, but the present invention is not limited to following example.
Described Fe base catalyst is applied to the CO Hydrogenation course of reaction for low-carbon alkene.Reaction condition is such as
Under: the catalytic performance test of the Fe base catalyst of load is carried out, instead on miniature tubular type catalyst test apparatus
Should pipe specification d=10mm and l=600mm.Whole device has three gas circuits to constitute.Wherein, the first via is for closing
Becoming gas, its component is mainly Ar:H2: CO=5:47.5:47.5；Second tunnel is N2Gas circuit.N2Available
Check whether device leaks gas, can also after the completion of reaction whole pipeline be purged simultaneously.3rd tunnel is
H2, it is mainly used in the pre-reduction before catalyst reaction.Due to catalyst surface active sites before reactions
There may be a part of oxidized, first should use H the most before the reaction in reaction tube2Carry out pre-reduction treatment.
Can be by H2Flow speed control, at about 40ml/min, then arranges heating schedule, makes temperature from ambient be increased to
About 450 DEG C, heating rate controls at 5 DEG C/about min, then insulation 1 hour.Treat that temperature begins to decline
Time, by H in pipeline2Close, use N2Purge.When temperature drops to reaction temperature (340 DEG C),
Again by the N in pipeline2Closing, be passed through synthesis gas, air volume air speed controls as 3000h-1, pressure rises to 2Mpa,
Then carry out catalytic reaction evaluation.
Embodiment 1
Step A: weigh 8.5467g Mg (NO3)2·6H2O、1.2504g Al(NO3)3·9H2O、5.3867g
Fe(NO3)3·9H2O puts in a beaker, adds in 250mL deionized water and dissolves；Additionally claim
Take 3.533g Na2CO3Put in another beaker with 3.2g NaOH, same add 250mL go from
Sub-water dissolves.Two kinds of solution are slowly dropped among the four-hole boiling flask of 1000ml simultaneously, and strictly
Control the pH of solution so that it is be constantly maintained at 9.5.Then it is warming up to 95 DEG C, keeps entering for 20 hours
Row crystallization.Through sucking filtration, wash, be dried, grind after, just can get MgAlFe-CO3 2--LDHs sample
Product.
Step B: take the MgAlFe-CO of partial mill3 2--LDHs powder is put among porcelain boat, then
It is placed near the thermocouple of tube type resistance furnace, then by interior for pipe vacuum pumping.Observe overpressure
After will not changing, it is passed through H2To recovering normal pressure, and regulate H2Flow is to 40ml/min.Arrange
Heating schedule, makes temperature from ambient be increased to 600 DEG C, and speed is set to 5 DEG C/min, then keeps 30
Minute.Keeping a period of time after temperature is down to room temperature, the nitrogen oxygen atmosphere being passed through 1% oxygen keeps
20min, then takes out, and obtains Fe-MgAl2O4Catalyst.Recorded by ICP, Fe in catalyst
Mass fraction is 25.3%.
Step C: catalyst Fe-MgAl2O4Catalytic performance test on miniature tubular type catalyst test apparatus
Carry out.Weigh the Fe-MgAl that granule is 20～40 mesh of 0.7g2O4Catalyst, loads thermocouple the most anti-
Should be in place of pipe, remainder quartz sand is filled.First by online for catalyst prereduction, it is passed through reducing gases H2,
Volume space velocity is set to 3000h-1, heating rate is that 5 DEG C/min rises to 450 DEG C of holdings 1 hour.Treat temperature
When beginning to decline, by H in pipeline2Close, use N2Purge.Treat that temperature drops to reaction temperature (340 DEG C)
Time, then by the N in pipeline2Closing, be passed through synthesis gas, air volume air speed controls as 3000h-1, pressure rises to
2Mpa, then carries out catalytic reaction evaluation.Catalysate uses gas chromatogram on-line analysis, records reaction steady
Determining conversion ratio under state is 42.1%, and low-carbon alkene overall selectivity is 33.2%, and the reactivity of CO hydrogenation is
1.44mol/gFeH, the yield of low-carbon alkene is 14.0%.
Embodiment 2
Step A: weigh 8.5467g Mg (NO3)2·6H2O、1.2504g Al(NO3)3·9H2O、5.3867g
Fe(NO3)3·9H2O puts in a beaker, adds in 250mL deionized water and dissolves；Additionally claim
Take 3.533g Na2CO3Put in another beaker with 3.2g NaOH, same add 250mL go from
Sub-water dissolves.Two kinds of solution are slowly dropped among the four-hole boiling flask of 1000ml simultaneously, and strictly
Control the pH of solution so that it is be constantly maintained at 9.5.Then it is warming up to 95 DEG C, keeps entering for 20 hours
Row crystallization.Through sucking filtration, wash, be dried, grind after, just can get MgAlFe-CO3 2--LDHs sample
Product.
Step B: take the MgAlFe-CO of partial mill3 2--LDHs powder is put among porcelain boat, then
It is placed near the thermocouple of tube type resistance furnace, then by interior for pipe vacuum pumping.Observe overpressure
After will not changing, it is passed through H2To recovering normal pressure, and regulate H2Flow is to 40ml/min.Arrange
Heating schedule, makes temperature from ambient be increased to 700 DEG C, and speed is set to 5 DEG C/min, then keeps 30
Minute.Keeping a period of time after temperature is down to room temperature, the nitrogen oxygen atmosphere being passed through 1% oxygen keeps
20min, then takes out, and obtains Fe-MgAl2O4Catalyst.Recorded by ICP, Fe in catalyst
Mass fraction is 25.7%.
Step C: catalyst Fe-MgAl2O4Catalytic performance test on miniature tubular type catalyst test apparatus
Carry out.Weigh the Fe-MgAl that granule is 20～40 mesh of 0.7g2O4Catalyst, loads thermocouple the most anti-
Should be in place of pipe, remainder quartz sand is filled.First by online for catalyst prereduction, it is passed through reducing gases H2,
Volume space velocity is set to 3000h-1, heating rate is that 5 DEG C/min rises to 450 DEG C of holdings 1 hour.Treat temperature
When beginning to decline, by H in pipeline2Close, use N2Purge.Treat that temperature drops to reaction temperature (340 DEG C)
Time, then by the N in pipeline2Closing, be passed through synthesis gas, air volume air speed controls as 3000h-1, pressure rises to
2Mpa, then carries out catalytic reaction evaluation.Catalysate uses gas chromatogram on-line analysis, records reaction steady
Determining conversion ratio under state is 59.2%, and low-carbon alkene overall selectivity is 29.8%, and the reactivity of CO hydrogenation is
1.99mol/gFeH, the yield of low-carbon alkene is 17.6%.
Embodiment 3
Step A: weigh 8.5467g Mg (NO3)2·6H2O、1.2504g Al(NO3)3·9H2O、5.3867g
Fe(NO3)3·9H2O puts in a beaker, adds in 250mL deionized water and dissolves；Additionally claim
Take 3.533g Na2CO3Put in another beaker with 3.2g NaOH, same add 250mL go from
Sub-water dissolves.Two kinds of solution are slowly dropped among the four-hole boiling flask of 1000ml simultaneously, and strictly
Control the pH of solution so that it is be constantly maintained at 9.5.Then it is warming up to 95 DEG C, keeps entering for 20 hours
Row crystallization.Through sucking filtration, wash, be dried, grind after, just can get MgAlFe-CO3 2--LDHs sample
Product.
Step B: take the MgAlFe-CO of partial mill3 2--LDHs powder is put among porcelain boat, then
It is placed near the thermocouple of tube type resistance furnace, then by interior for pipe vacuum pumping.Observe overpressure
After will not changing, it is passed through H2To recovering normal pressure, and regulate H2Flow is to 40ml/min.Arrange
Heating schedule, makes temperature from ambient be increased to 800 DEG C, and speed is set to 5 DEG C/min, then keeps 30
Minute.Keeping a period of time after temperature is down to room temperature, the nitrogen oxygen atmosphere being passed through 1% oxygen keeps
20min, then takes out, and obtains Fe-MgAl2O4Catalyst.Recorded by ICP, Fe in catalyst
Mass fraction is 25.8%.
Step C: catalyst Fe-MgAl2O4Catalytic performance test on miniature tubular type catalyst test apparatus
Carry out.Weigh the Fe-MgAl that granule is 20～40 mesh of 0.7g2O4Catalyst, loads thermocouple the most anti-
Should be in place of pipe, remainder quartz sand is filled.First by online for catalyst prereduction, it is passed through reducing gases H2,
Volume space velocity is set to 3000h-1, heating rate is that 5 DEG C/min rises to 450 DEG C of holdings 1 hour.Treat temperature
When beginning to decline, by H in pipeline2Close, use N2Purge.Treat that temperature drops to reaction temperature (340 DEG C)
Time, then by the N in pipeline2Closing, be passed through synthesis gas, air volume air speed controls as 3000h-1, pressure rises to
2Mpa, then carries out catalytic reaction evaluation.Catalysate uses gas chromatogram on-line analysis, records reaction steady
Determining conversion ratio under state is 75.7%, and low-carbon alkene overall selectivity is 28.1%, and the reactivity of CO hydrogenation is
2.52mol/gFeH, the yield of low-carbon alkene is 21.3%.
Embodiment 4
Step A: weigh 8.5467g Mg (NO3)2·6H2O、1.2504g Al(NO3)3·9H2O、5.3867g
Fe(NO3)3·9H2O puts in a beaker, adds in 250mL deionized water and dissolves；Additionally claim
Take 3.533g Na2CO3Put in another beaker with 3.2g NaOH, same add 250mL go from
Sub-water dissolves.Two kinds of solution are slowly dropped among the four-hole boiling flask of 1000ml simultaneously, and strictly
Control the pH of solution so that it is be constantly maintained at 9.5.Then it is warming up to 95 DEG C, keeps entering for 20 hours
Row crystallization.Through sucking filtration, wash, be dried, grind after, just can get MgAlFe-CO3 2--LDHs sample
Product.
Step B: take the MgAlFe-CO of partial mill3 2--LDHs powder is put among porcelain boat, then
It is placed near the thermocouple of tube type resistance furnace, then by interior for pipe vacuum pumping.Observe overpressure
After will not changing, it is passed through H2To recovering normal pressure, and regulate H2Flow is to 40ml/min.Arrange
Heating schedule, makes temperature from ambient be increased to 600 DEG C, and speed is set to 5 DEG C/min, then keeps 30
Minute.Keeping a period of time after temperature is down to room temperature, the nitrogen oxygen atmosphere being passed through 1% oxygen keeps
20min, then takes out, and obtains Fe-MgAl2O4Catalyst.Recorded by ICP, Fe in catalyst
Mass fraction is 26.4%.
Step C: catalyst Fe-MgAl2O4Catalytic performance test on miniature tubular type catalyst test apparatus
Carry out.Weigh the Fe-MgAl that 0.7g granule is 20～40 mesh2O4Catalyst, loads thermocouple and reacts in one's power
In place of pipe, remainder quartz sand is filled.First by online for catalyst prereduction, it is passed through reducing gases H2,
Volume space velocity is set to 3000h-1, heating rate is that 5 DEG C/min rises to 450 DEG C of holdings 1 hour.Treat temperature
When beginning to decline, by H in pipeline2Close, use N2Purge.Treat that temperature drops to reaction temperature (340 DEG C)
Time, then by the N in pipeline2Closing, be passed through synthesis gas, air volume air speed controls as 3000h-1, pressure rises to
2Mpa, then carries out catalytic reaction evaluation.Catalysate uses gas chromatogram on-line analysis, records reaction steady
Determining conversion ratio under state is 89.2%, and low-carbon alkene overall selectivity is 26.4%, and the reactivity of CO hydrogenation is
2.92mol/gFeH, the yield of low-carbon alkene is 23.5%.
Above example only in order to illustrate that technical scheme is not intended to limit, the common skill of art
Art personnel should be appreciated that the detailed description of the invention of the present invention can be modified with reference to above-described embodiment or etc.
With replacing, these all await the reply in application without departing from any amendment of spirit and scope of the invention or equivalent
Within claims.
Claims (9)
1. a support type Fe base catalyst, it is characterised in that catalyst includes the homogeneous active center Fe of granular size and inertia
Carrier MgAl spinelle；Described Fe base catalyst is by hydrotalcite precursor MgAlFe-CO3 2--LDHs after carrying out reduction and
Prepare.
2. according to a kind of support type Fe base catalyst described in claim 1, it is characterised in that the active center Fe particle diameter of catalyst
For 10nm～40nm.
3. according to a kind of support type Fe base catalyst described in claim 1, it is characterised in that described catalyst active center Fe
Load capacity is 20wt%～30wt%.
4. according to a kind of support type Fe base catalyst described in claim 1, it is characterised in that the precursor of catalyst
MgAlFe-CO3 2-Brucite laminate bivalent cation Mg in-LDHs precursor2+, Tricationic select Al3+And Fe3+,
Bivalent cation is (2～4) with the molar ratio of Tricationic: 1.
5. according to a kind of support type Fe base catalyst described in claim 1, it is characterised in that described Fe base catalyst is by neatly
Stone precursor MgAlFe-CO3 2--LDHs is at H2Reduction in atmosphere and prepare, reduction temperature control at 600 DEG C～
900 DEG C, the recovery time controls at 0.5h～2h.
6. according to a kind of support type Fe base catalyst described in claim 1, it is characterised in that hydrotalcite precursor
MgAlFe-CO3 2--LDHs powder is put among porcelain boat, and the thermocouple being then placed on tube type resistance furnace is attached
Closely, then by interior for pipe vacuum pumping；After observation overpressure will not change, it is passed through H2, intensification journey is set
Sequence, makes temperature from ambient be increased to 600 DEG C～900 DEG C, and speed is set to (5-10) DEG C/min, then keeps
0.5h～2h；Keeping a period of time after temperature is down to room temperature, the nitrogen oxygen atmosphere being passed through 1% oxygen keeps
20min, then takes out, and obtains Fe-MgAl2O4Catalyst.
7. according to a kind of support type Fe base catalyst described in claim 1, it is characterised in that hydrotalcite precursor
MgAlFe-CO3 2—The preparation of LDHs: weigh Mg (NO3)2·6H2O、Al(NO3)3·9H2O、
Fe(NO3)3·9H2O is dissolved in deionized water together；Additionally weigh Na2CO3It is dissolved in deionized water with NaOH,
And the pH strictly controlling solution is 9.5-10 so that it is keep constant；Then heat up and carry out crystallization；Through sucking filtration,
Washing, be dried, grind after, obtain MgAlFe-CO3 2--LDHs sample.Every 8.5467g Mg (NO3)2·6H2O
Corresponding 250ml deionized water.Every 3.533g Na2CO3Corresponding 3.2g NaOH correspondence 250mL deionization.
8. according to the support type Fe base catalyst described in any one of claim 1-7 as CO Hydrogenation for the catalyst of low-carbon alkene
Application.
9. according to the support type Fe base catalyst described in any one of claim 1-7 as CO Hydrogenation for the catalyst of low-carbon alkene
Application, it is characterised in that to CO hydrogenation reactivity reach 2.92mol/gFeH, the yield of low-carbon alkene reaches
23.5%.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106268826A (en) * | 2016-07-18 | 2017-01-04 | 山东省科学院能源研究所 | Iron-based composite catalyst and methods for making and using same for the online upgrading of bio oil |
| CN110590488A (en) * | 2019-09-30 | 2019-12-20 | 洛阳师范学院 | Method for preparing low-carbon olefin by hydrogenation of carbon monoxide by using composite hydrogen storage material |
| CN114377677A (en) * | 2020-10-20 | 2022-04-22 | 中国科学院理化技术研究所 | Iron-based catalyst for preparing high-carbon hydrocarbon by light-driven catalytic carbon dioxide hydrogenation, and preparation method and application thereof |
| CN115155585A (en) * | 2022-06-30 | 2022-10-11 | 华东理工大学 | Carbon dioxide capture and catalytic hydrogenation olefin preparation dual-function composite material, preparation method and application |
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| JPH0568883A (en) * | 1991-09-12 | 1993-03-23 | Koji Hashimoto | Amorphous alloy catalyst for carbon dioxide conversion |
| CN103301840A (en) * | 2013-06-04 | 2013-09-18 | 北京化工大学 | Supported high-dispersity Fischer-Tropsch synthesis metal catalyst, preparation method and application |
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| JPH0568883A (en) * | 1991-09-12 | 1993-03-23 | Koji Hashimoto | Amorphous alloy catalyst for carbon dioxide conversion |
| CN103301840A (en) * | 2013-06-04 | 2013-09-18 | 北京化工大学 | Supported high-dispersity Fischer-Tropsch synthesis metal catalyst, preparation method and application |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106268826A (en) * | 2016-07-18 | 2017-01-04 | 山东省科学院能源研究所 | Iron-based composite catalyst and methods for making and using same for the online upgrading of bio oil |
| CN106268826B (en) * | 2016-07-18 | 2018-08-31 | 山东省科学院能源研究所 | Iron-based composite catalyst and methods for making and using same for the online upgrading of bio oil |
| CN110590488A (en) * | 2019-09-30 | 2019-12-20 | 洛阳师范学院 | Method for preparing low-carbon olefin by hydrogenation of carbon monoxide by using composite hydrogen storage material |
| CN110590488B (en) * | 2019-09-30 | 2022-03-22 | 洛阳师范学院 | Method for preparing low-carbon olefin by hydrogenation of carbon monoxide by using composite hydrogen storage material |
| CN114377677A (en) * | 2020-10-20 | 2022-04-22 | 中国科学院理化技术研究所 | Iron-based catalyst for preparing high-carbon hydrocarbon by light-driven catalytic carbon dioxide hydrogenation, and preparation method and application thereof |
| CN114377677B (en) * | 2020-10-20 | 2023-08-01 | 中国科学院理化技术研究所 | Iron-based catalyst for preparing high-carbon hydrocarbon by catalyzing carbon dioxide hydrogenation through light drive, and preparation method and application thereof |
| CN115155585A (en) * | 2022-06-30 | 2022-10-11 | 华东理工大学 | Carbon dioxide capture and catalytic hydrogenation olefin preparation dual-function composite material, preparation method and application |
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