CN106031871A - Iron-based catalyst for low-carbon olefin production through CO2 hydrogenation, and preparation and applications thereof - Google Patents
Iron-based catalyst for low-carbon olefin production through CO2 hydrogenation, and preparation and applications thereof Download PDFInfo
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Abstract
The present invention provides an iron-based catalyst for low-carbon olefin production through CO2 hydrogenation, wherein the main active component of the catalyst is Fe3O4, the auxiliary agent is added or is not added, and is an oxide, the content of the auxiliary agent accounts for 0-30% of the total mass of the catalyst, and the auxiliary agent is one or more than two selected from the oxide of Si, Al, Mn, K, Cu, Na, Zr, V, Zn and Ce. The present invention further provides a preparation method and applications of the catalyst. According to the present invention, the catalyst has the following beneficial effects that 1) the particles have characteristics of regular spherical shape, uniform spatial distribution, and narrow size distribution; 2) the raw materials are inexpensive and easy to obtain, and the preparation method has characteristics of simpleness and low cost, and is suitable for industrial production; 3) the catalyst has characteristics of high mechanical strength, good wear resistance and compression resistance, and is suitable for the fixed bed, the fluidized bed and the slurry bed; 4) the CO2 hydrogenation activity and the low-carbon olefin selectivity are high, the single-pass conversion rate can achieve more than 40%, the methane selectivity in the hydrocarbon product is lower than 15%, the low-carbon olefin selectivity is higher than 40%, the alkene/alkane ratio (O/P) is 2-12, and the yield of the low-carbon olefin can achieve 10-60 g/m<3> (CO2+H2).
Description
Technical field
The invention belongs to CO2Hydrogenation produces light olefins catalyst field, is specifically related to a kind of CO2Hydrogenation
Take the ferrum-based catalyst of low-carbon alkene and preparation thereof and application.
Background technology
CO2Being the most cheap in carbon one family and rich in natural resources, reserves are the abundantest on earth.Along with people
The development of class society, the usage amount of fossil energy sharply increases, CO in air2Content day by day increase,
This not only exacerbates greenhouse effect, also result in huge carbon resource waste.Carry out CO2Trans-utilization is studied,
Change harmful to treasure, no matter from economic benefit, or in social benefit, suffer from significance.
Low-carbon alkene is important industrial chemicals, currently mainly derives from naphtha pyrolysis.Along with crude oil price
Continuous rise and environmental problem increasingly serious, from CO2The research of catalytic hydrogenation preparing low-carbon olefins starts
Scientific worker is caused to pay close attention to widely.Research shows, CO2Hydrogenation typically experiences two steps for Hydrocarbon,
First CO2Occurring Reversed Water-gas Shift to produce CO, then CO is again through F-T synthesis hydrocarbon compound.Fe
Base catalyst all shows higher activity to Reversed Water-gas Shift and Fischer-Tropsch synthesis, and cheap,
Therefore at CO2Hydro-conversion research in receive significant attention.It is presently used for CO2Hydrogenation is for low carbene
The catalyst of hydrocarbon is broadly divided into following a few class:
(1) Fe catalyst Lu Zhen lifts and waits [gas chemical industry, 1993,18 (1): 23-27] with Fe/AC to CO2
Hydrogenation synthesizing low carbon alkene is studied.At 320 DEG C, 650h-1、H2/CO2=0.95, under pressure 1.5MPa,
CO2Conversion ratio be 37.5%, C2 =～C3 =Selectivity be 34.2%.Huang Youmei etc. [Journal of Molecular Catalysis, 1995,
9 (1): 78-80] use " substep backflow infusion process " by Fe3(CO)12Load to prepare on carrier Fe3/ZSM-5
Catalyst, substantially improves C2 =～C3 =Selectivity, improve CO2Conversion ratio.Normal pressure, 260 DEG C
Under, Ar/H2/CO2=91:6:3, air speed 1000h-1Under the conditions of, C2 =～C3 =Selectivity reach 96.6%, CO2
Conversion ratio reach 16.3%.
(2) Fe-Mn catalyst Tian Zhijian etc. [the 7th the whole nation catalysis academic meeting paper summary collection, 1994,6:
92] Fe-Mn/ activated-carbon catalyst is prepared, in temperature 345 DEG C, pressure 2.0MPa, air speed 1200h-1、
H2/CO2React under the conditions of=4, obtain CO2Conversion ratio be 53.01%, C2 =～C4 =Selectivity be 34.3%；
And the Fe-Mn/Silicalite-2 catalyst prepared, CO under identical reaction condition2Conversion ratio be 35.4%,
C2 =～C4 =Selectivity be 56.7%.
(3) prepared by K-Fe-MnO catalyst Xu Long child etc. [gas chemical industry, 1995,20 (5): 6-10]
K-Fe-MnO composite catalyst, and investigated different carriers to CO2The impact of hydrogenation reaction performance.Find
345 DEG C, pressure 2.0MPa, air speed 1200h-1, H2/CO2Under the conditions of=4, K-Fe-MnO/Al2O3Upper CO2
Conversion ratio be 50.3%, C2 =～C4 =Selectivity be 17.8%；On K-Fe-MnO/Silicalite-2 catalyst
CO2Conversion ratio be 35.2%, C2 =～C4 =Selectivity be 65.9%；On K-Fe-MnO/MgO catalyst
CO2Conversion ratio be 28.4%, C2 =～C4 =Selectivity be 62.7%, consider and can be seen that Silicalite-2
Carrier effect is good.
(4) Fe-Co bimetallic catalyst Liu Yun grain husk etc. [chemistry of fuel journal, 1999,27 (2): 145-149] grind
Study carefully under normal pressure CO on Fe-Co bimetallic catalyst2The reaction of catalytic hydrogenation synthesizing low-carbon alkene, at ferrum cobalt
Mol ratio 67:33, reaction temperature 350 DEG C, under the conditions of reaction velocity 5000mL/ (g h), CO2Conversion ratio reaches
28.1%, C2+Selectivity reaches 11.6%, ethylenic alkoxy rate 5.4.Result shows, the carbonization being added with beneficially ferrum of cobalt,
Improve CO2Conversion ratio, reduces CO selectivity, improves methane selectively, and the interpolation of amounts of cobalt promotees
Enter the carbon dioxide conversion to hydrocarbon.Li Mengqing etc. [Hebei University of Technology's journal, 2000,29 (2): 39-43] are right
CO on Fe-Co-K catalyst2Hydrogenation synthesizing low carbon alkene is studied, and result shows, normal pressure, 350 DEG C,
H2/CO2Under the conditions of=3, relative Fe-Co catalyst, add CO after a small amount of K2Conversion ratio is by 22.2%
It is increased to 28.8%, C2～C3The ethylenic alkoxy rate of hydrocarbon is increased to 17.4 by 2.2, finds that the addition of Mn is to alkene simultaneously
Hydrocarbon yield has no significant effect.
(5) Fe-Ni bimetallic catalyst Liu Yun grain husk etc. [chemistry of fuel journal, 1999,27 (5): 447-450] research
CO on Fe-Ni bimetallic catalyst under normal pressure2The reaction of catalytic hydrogenation synthesizing low-carbon alkene, has investigated not
With nickel content to CO2Conversion ratio and the impact of selectivity of product, result shows, the interpolation of a small amount of nickel promotes
The reduction of ferrum in catalyst, the carbonization of ferrum improves CO2Conversion ratio and olefine selective.When adding 1% nickel,
Reaction temperature 350 DEG C, under the conditions of reaction velocity 5000mL/ (g h), CO2Conversion ratio is 32.6%, in product
Olefine selective reaches 5.3%, and ethylenic alkoxy rate is 4.7.
Above-mentioned catalyst system and catalyzing is at CO2Hydrogenation preparing low-carbon olefins aspect all achieves preferably progress, it is thus achieved that relatively
High-low carbon olefine selective, but the subject matter that catalyst exists is: and (1) products distribution is wider, methane and C5+
Hydrocarbon content is high；(2) catalyst preparation cost is higher, the most unfavorable to industrialization；(3) loaded catalyst activity
The highest；(4) some experiments are to be similar in the little reactor of differential reactor to carry out, the reaction of product ethylene secondary
Not not embodying, be once evaluated on integral reactor, experimental result is it is possible that large change.With
In CO2The problem that the catalyst emphasis of alkene processed is to be solved is the effective of the secondary hydrogenation of alkene and products distribution
Control, thus CO2The key technology of hydrogenation preparing low-carbon olefins is design and exploitation high activity, just carbene
The catalyst of hydrocarbon-selective.
Summary of the invention
The technical problem to be solved is to existing catalyst size wider distribution, is prepared as
The problems such as this height, hydrocarbon product distribution are wide, it is provided that a kind of for CO2The iron-based catalysis of hydrogenation preparing low-carbon olefins
Agent and preparation thereof and application.
The technical scheme is that
The main active component of catalyst of the present invention is Fe3O4, adding or without auxiliary agent, auxiliary agent is oxidation
Thing, the content of auxiliary agent accounts for the 0～30% of catalyst gross mass.
Main active component Fe in described catalyst3O4Mean diameter be 25nm.
Described auxiliary agent is the one in the oxide of Si, Al, Mn, K, Cu, Na, Zr, V, Zn, Ce
Or it is two or more；In catalyst, the more excellent content of auxiliary agent accounts for the 0.1～15% of catalyst gross mass.
Described auxiliary agent is SiO2、Al2O3、MnO2、K2O、CuO、Na2O、ZrO2、V2O5、ZnO、
CeO2In one or more.
Catalyst is ground, tabletting, excessively 20～40 mesh sieves, obtains ferrum-based catalyst finished product.
Catalyst can use one of following three kinds of processes to prepare；
Catalyst uses coprecipitation: comprise the following steps:
(1) according to catalyst composition and ratio, Fe (III) salt of Fe (II) salt of solubility, solubility is mixed,
Form saline solution, Fe (III) concentration 0.05～1mol/L in saline solution, and add HCl solution, HCl concentration
5～12.1mol/L；Mol ratio 2:(1～3 of Fe (III) and Fe (II) in saline solution)；
(2) in (1), aqueous slkali is added；Gradually pH value=0～5 of solution is adjusted to alkaline ph values=9～12；
After dropping, aging 1～10h；
(3), after reaction terminates, magnetic field absorption, centrifugal or sucking filtration method is utilized sedimentation products to be divided from (2)
From, and sedimentation products deionized water is fully washed, dry, i.e. prepare the Fe without auxiliary agent3O4Catalyst；
Or, catalyst uses one-step synthesis: comprise the following steps:
(1) according to catalyst composition and ratio, by Fe (II) salt of solubility, Fe (III) salt of solubility, help
Agent source mixes, and forms saline solution, Fe (III) concentration 0.05～1mol/L in saline solution, and adds HCl solution,
HCl concentration 5～12.1mol/L；Mol ratio 2:(1～3 of Fe (III) and Fe (II) in saline solution)；Auxiliary agent source be Si,
The soluble-salt of one or two or more kinds in Al, Mn, Cu, Zr, V, Zn, Ce, or, auxiliary agent source is
Containing in Si, Al, Mn, Cu, Zr, V, Zn, Ce one or two or more kinds, and can react with water
Organic substance, auxiliary agent source be preferably the nitrate of Si, Al, Mn, Cu, Zr, V, Zn, Ce, acetate,
One or two or more kinds in chloride, vanadate, silicate, tetraethyl orthosilicate, Ludox；
(2) in (1), aqueous slkali is added；Gradually pH value=0～5 of solution is adjusted to alkaline ph values=9～12；
After dropping, aging 1～10h；
(3), after reaction terminates, magnetic field absorption, centrifugal or sucking filtration method is utilized sedimentation products to be divided from (2)
From, and sedimentation products deionized water is fully washed, dry, roasting or do not carry out roasting, sintering temperature
300～500 DEG C, roasting time 2～24h, i.e. prepare the ferrum-based catalyst containing auxiliary agent；
Or, catalyst uses Co deposited synthesis Fe3O4, then use infusion process to add auxiliary agent: to include following
Step:
(1) according to catalyst composition and ratio, Fe (III) salt of Fe (II) salt of solubility, solubility is mixed,
Form saline solution, Fe (III) concentration 0.05～1mol/L in saline solution, and add HCl solution, HCl concentration
5～12.1mol/L；Mol ratio 2:(1～3 of Fe (III) and Fe (II) in saline solution)；
(2) in (1), aqueous slkali is added；Gradually pH value=0～5 of solution is adjusted to alkaline ph values=9～12；
After dropping, aging 1～10h；
(3), after reaction terminates, magnetic field absorption, centrifugal or sucking filtration method is utilized sedimentation products to be divided from (2)
From, and sedimentation products deionized water is fully washed, dry, i.e. prepare active component Fe3O4；
(4) using infusion process that with active ingredient combinations, builder salts is formed catalyst, detailed process is: by institute
Need the amount of builder salts needed for auxiliary agent content, computational theory, be made into the aqueous solution of builder salts, will (3) be prepared into
The Fe arrived3O4Incipient impregnation is in solution, through stirring, stand, drying, calcination procedure, and sintering temperature
300～500 DEG C, roasting time 2～24h, i.e. prepare the ferrum-based catalyst containing auxiliary agent.
Fe (II) salt of step (1) solubility, Fe (III) salt of solubility refer to be dissolved in the salt compounds of water,
It is preferably one or two or more kinds in chlorate, nitrate, acetate；Builder salts is to be dissolved in the salt of water
One or two or more kinds in compounds, preferably chlorate, nitrate, acetate.
In the step (2) of three kinds of methods aqueous slkali refer to regulate solution ph aqueous slkali, preferably NaOH,
KOH、Na2CO3、K2CO3, one or two or more kinds in ammonia；Alkaline concentration is 0.1～10mol/L.
For CO2Hydrogenation preparing low-carbon olefins, reaction condition is: H2/CO2=1.0～8.0, reaction temperature is
250～450 DEG C, reaction pressure is 0.01～10.0MPa, and air speed is 500～50000mL/ (h gcat)。
Described low-carbon alkene refers to C2～C4Alkene, i.e. ethylene, propylene, butylene.
This catalyst is applied to containing CO2Gas, described gas refer to industrial waste gas, vehicle exhaust,
The CO absorbed in coal combustion exhaust and sea water2Deng.
Present invention have an advantage that
(1) the iron oxides presoma in catalyst of the present invention is with Fe3O4Form exists, and particles spatial distribution is all
One, in regular spherical pattern, narrow size distribution, mean diameter is 25nm；
(2) catalyst preparation materials of the present invention is cheap and easy to get, and preparation method is simple, catalyst low cost, is suitable for
In industrialized production；
(3) catalytic mechanical intensity of the present invention is high, has good wearability.It is suitable for fixed bed, fluid bed
Apply with slurry bed system；
(4) catalyst CO of the present invention2Hydrogenation activity and selectivity of light olefin are higher, and conversion per pass is up to 40%
Above, methane selectively be less than 15%, selectivity of light olefin be higher than 40%, ethylenic alkoxy rate (O/P)=2～12,
Yield of light olefins is up to 10～60g/m3(CO2+H2)。
Detailed description of the invention
The technology of the present invention details is by the detailed description in addition of following embodiment.It should be noted that lifted embodiment,
Its effect simply further illustrates the technical characteristic of the present invention rather than limits the present invention.
Embodiment 1
By 15.81g FeCl3·6H2O, 6.27g FeCl2·4H2O, by Fe3+:Fe2+The mixed in molar ratio of=65:35
Become the saline solution that Fe concentration is about 1mol/L, and add the 12.1mol/L HCl solution of 2.5mL.60 DEG C,
Under stirring condition, at the uniform velocity add the 1.5mol/L NaOH solution of 180mL.In about 1.5h, by solution
PH value is adjusted to about 10.0 by acidity.After dropping, keep temperature to continue stirring 1h, be finally cooled to
Room temperature.After reaction terminates, utilize magnetic field absorption sedimentation products to be separated, and fully wash with deionized water,
At 60 DEG C dry, i.e. prepare catalyst sample, sample is ground, tabletting and cross 20～40 mesh sieve standby
With.Fe3O4Synthetic reaction equation be:
Fe2++2Fe3++8OH–→Fe(OH)2+2Fe(OH)3→Fe3O4+4H2O。
Reducing condition: under normal pressure, pure H2In, temperature is 350 DEG C, and air speed is 1500mL/ (h gcat), reduction
Time 12h.Reaction condition: H2/CO2=3.0, temperature is 280～400 DEG C, and pressure is 3.0MPa, and air speed is
2000mL/(h·gcat), investigate the reaction temperature impact on catalyst performance, test result (being shown in Table 1) shows,
Along with reaction temperature raises, CO2Conversion ratio is gradually increased, C2 =～C4 =Selectivity and ethylenic alkoxy rate first raise and drop afterwards
Low, this catalyst shows the CO of excellence within the temperature range of being investigated all the time2Hydrogenation.
Embodiment 2
Weigh catalyst sample 1.0g prepared by embodiment 1 method, be evaluated in fixed bed reactors:
Reducing condition: under normal pressure, pure H2In, temperature is 350 DEG C, and air speed is 1500mL/ (h gcat), the recovery time
12h.Reaction condition: H2/CO2=3.0, temperature is 320 DEG C, and pressure is 0.1～5.0MPa, and air speed is
2000mL/(h·gcat), investigate the reaction pressure impact on catalyst performance, test result (being shown in Table 2) shows,
Along with reaction pressure raises, CO2Conversion ratio is gradually increased, and CO selectivity and C2 =～C4 =Selectivity is gradually
Reduce.
Embodiment 3
Weigh catalyst sample 0.4g prepared by embodiment 1 method, be evaluated in fixed bed reactors:
Reducing condition: under normal pressure, pure H2In, temperature is 350 DEG C, and air speed is 1500mL/ (h gcat), the recovery time
12h.Reaction condition: H2/CO2=3.0, temperature is 320 DEG C, and pressure is 3.0MPa, and air speed is
2000～20000mL/ (h gcat), investigate the impact on catalyst performance of the unstripped gas air speed, test result (is shown in Table
3) show, C2 =～C4 =Selectivity first gradually rises along with air speed increases and starts afterwards to reduce, and in air speed is
8000mL/(h·gcat) time reach maximum；This catalyst is at 20000mL/ (h gcat) under air speed, still keep high CO2
Conversion ratio (31.8%) and high C2 =～C4 =Selectivity (45.7%).
Embodiment 4
By 15.81g FeCl3·6H2O, 6.27g FeCl2·4H2O and 1.02g Na2SiO3·9H2O, presses
Fe3+:Fe2+: the molar ratio of Si=65:35:4 becomes 100mL mixing salt solution, and adds the 12.1 of 2.5mL
Mol/L HCl solution, 60 DEG C, under stirring condition, the 1.5mol/L NaOH at the uniform velocity adding 180mL is molten
Liquid.In about 1.5h, the pH value of solution is adjusted to about 10.0 by acidity.After being added dropwise to complete, keep temperature
Degree continues stirring 1h, is finally cooled to room temperature.After reaction terminates, magnetic field absorption is utilized sedimentation products to be separated,
And fully wash with deionized water, dry at 60 DEG C, i.e. prepared Fe-Si nanometer by one-step synthesis
Composite catalyst, sample is ground, tabletting and cross after 20～40 mesh sieves standby.Reducing condition: under normal pressure,
Pure H2In, temperature is 350 DEG C, and air speed is 1500mL/ (h gcat), recovery time 12h.Reaction condition:
H2/CO2=3.0, temperature is 300～400 DEG C, and pressure is 3.0MPa, and air speed is 2000mL/ (h gcat), investigate
The reaction temperature impact on catalyst performance, test result (being shown in Table 4) shows, along with reaction temperature raises,
CO2Conversion ratio is gradually increased, C2 =～C4 =Selectivity first raises and reduces afterwards.
Embodiment 5
Weigh the Fe that 4.0g is produced by embodiment 1 method3O4Sample, weighs 0.157g KNO3, it is made into
The KNO of 0.647mol/L3Solution, by above-mentioned Fe3O4Sample incipient impregnation is in above-mentioned KNO3In solution,
Stirring, standing 12h, dry, 400 DEG C of roasting 3h at 120 DEG C, the most ground, tabletting and excessively 20～40
Mesh sieve.Reducing condition: under normal pressure, pure H2In, temperature is 350 DEG C, and air speed is 1500mL/ (h gcat), also
Former time 12h.Reaction condition: H2/CO2=3.0, temperature is 280～380 DEG C, and pressure is 3.0MPa, air speed
For 2000mL/ (h gcat), investigate the reaction temperature impact on catalyst performance, test result (being shown in Table 5) table
Bright, along with reaction temperature raises, CO2Conversion ratio is gradually increased, C2 =～C4 =Selectivity and ethylenic alkoxy rate first raise
Rear reduction.
Embodiment 6
Weigh the Fe that 4.0g is produced by embodiment 1 method3O4Sample, weighs 0.376g Cu (NO3)2·3H2O,
It is made into the Cu (NO of 0.647mol/L3)2Solution, by above-mentioned Fe3O4Sample incipient impregnation is in above-mentioned
Cu(NO3)2In solution, stir, stand 12h, dry at 120 DEG C, 400 DEG C of roasting 3h, after through grinding
Mill, tabletting and 20～40 mesh sieves excessively.Reducing condition: under normal pressure, pure H2In, temperature is 350 DEG C, air speed
For 1500mL/ (h gcat), recovery time 12h.Reaction condition: H2/CO2=3.0, temperature is 280～380 DEG C,
Pressure is 3.0MPa, and air speed is 2000mL/ (h gcat), investigate the reaction temperature impact on catalyst performance,
Test result (being shown in Table 6) shows, along with reaction temperature raises, and CO2Conversion ratio is gradually increased, C2 =～C4 =Select
Property and ethylenic alkoxy rate first raise and reduce afterwards.
Embodiment 7
Weigh the Fe that 4.0g is produced by embodiment 1 method3O4Sample, weighs 0.463g Zn (NO3)2·6H2O,
It is made into the Zn (NO of 0.647mol/L3)2Solution, by above-mentioned Fe3O4Sample incipient impregnation is in above-mentioned Zn (NO3)2
In solution, stir, stand 12h, dry at 120 DEG C, 400 DEG C of roasting 3h, the most ground, tabletting
And cross 20～40 mesh sieves.Reducing condition: under normal pressure, pure H2In, temperature is 350 DEG C, and air speed is
1500mL/(h·gcat), recovery time 12h.Reaction condition: H2/CO2=3.0, temperature is 280～380 DEG C, pressure
Power is 3.0MPa, and air speed is 2000mL/ (h gcat), investigate the reaction temperature impact on catalyst performance,
Test result (being shown in Table 7) shows, along with reaction temperature raises, and CO2Conversion ratio is gradually increased, C2 =～C4 =Select
Property is gradually lowered.
Comparative example 1
The preparation of precipitated iron catalyst: weigh 72.72g Fe (NO3)3·9H2O is made into 200mL concentration
Fe (the NO of 0.9mol/L3)3Solution, 80 DEG C, under stirring condition, at the uniform velocity add 250mL mass fraction
It it is the ammonia spirit of 5%.In about 2h, the pH value of solution is adjusted to about 9.0.After dropping, will
The aging 2h of precipitation obtained, then carries out filtering, washing then at 120 DEG C of drying, and at 400 DEG C of roasting 3h,
I.e. prepare catalyst sample.Reducing condition: under normal pressure, pure H2In, temperature is 350 DEG C, and air speed is
1500mL/(h·gcat), recovery time 12h.Reaction condition: H2/CO2=3.0, temperature is 280～380 DEG C, pressure
Power is 3.0MPa, and air speed is 2000mL/ (h gcat), investigate the reaction temperature impact on catalyst performance,
Test result (being shown in Table 8) shows, along with reaction temperature raises, and CO2Conversion ratio is gradually increased, in hydrocarbon products
C2 =～C4 =Selectivity is consistently lower than 1%, and CH4Selectivity is higher than 57%, this explanation routine precipitation Fe catalysis
Agent is at CO2Poor-performing in hydrogenation reaction.
Comparative example 2
The preparation of precipitated iron catalyst: weigh 72.72g Fe (NO3)3·9H2O is made into 200mL concentration
Fe (the NO of 0.9mol/L3)3Solution, 80 DEG C, under stirring condition, at the uniform velocity add the 1.5mol/L of 200mL
Na2CO3Solution.In about 2h, the pH value of solution is adjusted to about 9.0.After dropping, will obtain
The aging 2h of precipitation, then carry out filtering, washing then at 120 DEG C of drying, and at 400 DEG C of roasting 3h, i.e.
Prepare catalyst sample.Reducing condition: under normal pressure, pure H2In, temperature is 350 DEG C, and air speed is
1500mL/(h·gcat), recovery time 12h.Reaction condition: H2/CO2=3.0, temperature is 280～380 DEG C, pressure
Power is 3.0MPa, and air speed is 2000mL/ (h gcat), investigate the reaction temperature impact on catalyst performance,
Test result (being shown in Table 9) shows, along with reaction temperature raises, and CO2Conversion ratio is gradually increased, in hydrocarbon products
C2 =～C4 =Selectivity is consistently lower than 37%, and CH4Selectivity is higher than 20%, and this shows routine is being precipitated Fe
After the preparation method of catalyst improves, its reactivity worth is still below the reactivity worth of catalyst in embodiment 1.
Embodiment result
Table 1 reaction temperature CO upper to ferrum-based catalyst (nanoscale Fe)2The impact of hydrogenation reaction performance
Table 2 reaction pressure CO upper to ferrum-based catalyst (nanoscale Fe)2The impact of hydrogenation reaction performance
Table 3 unstripped gas air speed CO upper to ferrum-based catalyst (nanoscale Fe)2The impact of hydrogenation reaction performance
Table 4 reaction temperature CO upper to ferrum-based catalyst (nanoscale Fe-Si)2The impact of hydrogenation reaction performance
Table 5 reaction temperature CO upper to ferrum-based catalyst (nanoscale Fe-K)2The impact of hydrogenation reaction performance
Table 6 reaction temperature CO upper to ferrum-based catalyst (nanoscale Fe-Cu)2The impact of hydrogenation reaction performance
Table 7 reaction temperature CO upper to ferrum-based catalyst (nanoscale Fe-Zn)2The impact of hydrogenation reaction performance
Comparative example result
Table 8 reaction temperature is to CO on precipitation Fe catalyst2The impact of hydrogenation reaction performance
Table 9 reaction temperature is to CO on precipitation Fe catalyst2The impact of hydrogenation reaction performance
Claims (10)
1. a CO2The ferrum-based catalyst of hydrogenation preparing low-carbon olefins, it is characterised in that: the main activity of catalyst
Component is Fe3O4, adding or without auxiliary agent, auxiliary agent is oxide, the content of auxiliary agent accounts for catalyst gross mass
0～30%.
Ferrum-based catalyst the most according to claim 1, it is characterised in that: described auxiliary agent is Si, Al,
One or more in the oxide of Mn, K, Cu, Na, Zr, V, Zn, Ce；Catalyst helps
The more excellent content of agent accounts for the 0.1～15% of catalyst gross mass.
Ferrum-based catalyst the most according to claim 1 and 2, it is characterised in that: described auxiliary agent is SiO2、
Al2O3、MnO2、K2O、CuO、Na2O、ZrO2、V2O5、ZnO、CeO2In one or both with
On.
4. according to the arbitrary described ferrum-based catalyst of claims 1 to 3, it is characterised in that: catalyst is ground,
Tabletting, excessively 20～40 mesh sieves, obtain ferrum-based catalyst finished product.
5. the preparation method of ferrum-based catalyst described in a claim 1, it is characterised in that:
Catalyst can use one of following three kinds of processes to prepare；
Catalyst uses coprecipitation: comprise the following steps:
(1) according to catalyst composition and ratio, Fe (III) salt of Fe (II) salt of solubility, solubility is mixed,
Form saline solution, Fe (III) concentration 0.05～1mol/L in saline solution, and add HCl solution, HCl concentration
5～12.1mol/L；Mol ratio 2:(1～3 of Fe (III) and Fe (II) in saline solution)；
(2) in (1), aqueous slkali is added；Gradually pH value=0～5 of solution is adjusted to alkaline ph values=9～12；
After dropping, aging 1～10h；
(3), after reaction terminates, magnetic field absorption, centrifugal or sucking filtration method is utilized sedimentation products to be divided from (2)
From, and sedimentation products deionized water is fully washed, dry, i.e. prepare the Fe without auxiliary agent3O4Catalyst；
Or, catalyst uses one-step synthesis: comprise the following steps:
(1) according to catalyst composition and ratio, by Fe (II) salt of solubility, Fe (III) salt of solubility, help
Agent source mixes, and forms saline solution, Fe (III) concentration 0.05～1mol/L in saline solution, and adds HCl solution,
HCl concentration 5～12.1mol/L；Mol ratio 2:(1～3 of Fe (III) and Fe (II) in saline solution)；Auxiliary agent source be Si,
The soluble-salt of one or two or more kinds in Al, Mn, Cu, Zr, V, Zn, Ce, or, auxiliary agent source is
Containing in Si, Al, Mn, Cu, Zr, V, Zn, Ce one or two or more kinds, and can react with water
Organic substance, auxiliary agent source be preferably the nitrate of Si, Al, Mn, Cu, Zr, V, Zn, Ce, acetate,
One or two or more kinds in chloride, vanadate, silicate, tetraethyl orthosilicate, Ludox；
(2) in (1), aqueous slkali is added；Gradually pH value=0～5 of solution is adjusted to alkaline ph values=9～12；
After dropping, aging 1～10h；
(3), after reaction terminates, magnetic field absorption, centrifugal or sucking filtration method is utilized sedimentation products to be divided from (2)
From, and sedimentation products deionized water is fully washed, dry, roasting or do not carry out roasting, sintering temperature
300～500 DEG C, roasting time 2～24h, i.e. prepare the ferrum-based catalyst containing auxiliary agent；
Or, catalyst uses Co deposited synthesis Fe3O4, then use infusion process to add auxiliary agent: to include following
Step:
(1) according to catalyst composition and ratio, Fe (III) salt of Fe (II) salt of solubility, solubility is mixed,
Form saline solution, Fe (III) concentration 0.05～1mol/L in saline solution, and add HCl solution, HCl concentration
5～12.1mol/L；Mol ratio 2:(1～3 of Fe (III) and Fe (II) in saline solution)；
(2) in (1), aqueous slkali is added；Gradually pH value=0～5 of solution is adjusted to alkaline ph values=9～12；
After dropping, aging 1～10h；
(3), after reaction terminates, magnetic field absorption, centrifugal or sucking filtration method is utilized sedimentation products to be divided from (2)
From, and sedimentation products deionized water is fully washed, dry, i.e. prepare active component Fe3O4；
(4) using infusion process that with active ingredient combinations, builder salts is formed catalyst, detailed process is: by institute
Need the amount of builder salts needed for auxiliary agent content, computational theory, be made into the aqueous solution of builder salts, will (3) be prepared into
The Fe arrived3O4Incipient impregnation is in solution, through stirring, stand, drying, calcination procedure, and sintering temperature
300～500 DEG C, roasting time 2～24h, i.e. prepare the ferrum-based catalyst containing auxiliary agent.
The preparation method of catalyst the most according to claim 5, it is characterised in that: step (1) solubility
Fe (II) salt, Fe (III) salt of solubility refer to be dissolved in the salt compounds of water, preferably chlorate, nitric acid
One or two or more kinds in salt, acetate；Builder salts is to be dissolved in the salt compounds of water, preferably chlorine
Change one or two or more kinds in salt, nitrate, acetate.
The preparation method of catalyst the most according to claim 5, it is characterised in that: the step of three kinds of methods
(2) in, aqueous slkali refers to regulate the aqueous slkali of solution ph, preferably NaOH, KOH, Na2CO3、K2CO3、
One or two or more kinds in ammonia；Alkaline concentration is 0.1～10mol/L.
8. the application of the arbitrary described catalyst of Claims 1 to 4, it is characterised in that: for CO2Hydrogenation
Preparing low-carbon olefins, reaction condition is: H2/CO2=1.0～8.0, reaction temperature is 250～450 DEG C, reaction pressure
Power is 0.01～10.0MPa, and air speed is 500～50000mL/ (h gcat)。
The application of catalyst the most according to claim 8, it is characterised in that: described low-carbon alkene refers to C2～C4
Alkene, i.e. ethylene, propylene, butylene.
The application of catalyst the most according to claim 8, it is characterised in that: this catalyst is applied to contain
There is CO2Gas, described gas refer in industrial waste gas, vehicle exhaust, coal combustion exhaust and sea water absorb
CO2Deng.
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