CN105080547B - The catalyst and a kind of CO Hydrogenations of producing light olefins are hydrogenated with for the method for low-carbon alkene for CO - Google Patents
The catalyst and a kind of CO Hydrogenations of producing light olefins are hydrogenated with for the method for low-carbon alkene for CO Download PDFInfo
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Abstract
The invention provides a kind of catalyst that producing light olefins are hydrogenated with for CO, the catalyst includes：20 80 weight % zirconium, 5 60 weight % iron, 5 40 weight % silicon and 5 30 weight % aluminium.The invention provides a kind of method of CO Hydrogenations for low-carbon alkene, this method includes：Unstripped gas containing CO is contacted with hydrogen-containing gas and catalyst, the catalyst is catalyst of the present invention.Compared with conventional catalyst, the catalyst that the present invention is provided has advantages below：(1) catalyst dispersity can be good, and preparation technology is simple；(2) reaction condition is gentle, and catalyst activity is high and selectivity of light olefin is high, and stability is good.
Description
Technical field
The present invention relates to a kind of catalyst that producing light olefins are hydrogenated with for CO, a kind of high activity, height are related in particular to
The Zr-Fe-Si-Al multimetal reforming catalyst and a kind of CO Hydrogenations of low-carbon alkene are optionally converted synthesis gas to for low-carbon alkene
The method of hydrocarbon.
Background technology
Low-carbon alkene plays very important work as basic organic chemical industry raw material in modern petroleum and chemical industry
With.Especially ethene and propylene, with the increasingly increase and the continuous expansion of application field of its demand, enter to its synthetic method
Row extensive research shows important day.
The method of preparing low-carbon olefins can generally be divided into two major classes：One class is petroleum path, and another kind of is non-petroleum road
Line.So far, still mainly using traditional light oil cracking method, i.e. petroleum path to come preparing ethylene, propylene etc. in the world low
Carbon olefin.In the case where oil price is soaring, using natural gas as raw material, have via the direct or indirect producing light olefins of synthesis gas
There are technology and economic attractiveness.Such as using natural gas as raw material, pass through the method preparing low-carbon olefins technology such as oxidative coupling；With day
Right gas or coal are waste synthesis gas, and synthesis gas is by F- T synthesis (direct method) or via methanol or dimethyl ether (indirect method)
Preparing low-carbon olefins technology etc..And be that single step reaction generates purpose product, its technique stream by the direct preparing low-carbon olefins of synthesis gas
Journey is simpler than indirect method, more economical.
The catalyst that synthesis gas orientation is converted into low-carbon alkene reaction typically selects Fe as active component, while adding one
A little auxiliary agents；The carrier of catalyst is typically various types of molecular sieves and activated carbon.Wherein molecular sieve carried catalyst is due to can
To be realized by the adjustable pore passage structure of molecular sieve carrier rule to the shape-selective etc. of product, in terms of selectivity of light olefin is improved
Attract attention.
The Chinese patent application CN1260823A of Exxon Corporation report converted synthesis gas into modified molecular screen it is low
The method of carbon olefin, it uses Fe3(CO)12/ ZSM-5 modified molecular sieve catalysts, in 260 DEG C, H2/ CO volume ratios are 3, GHSV
For 1000h-1Reaction condition under, the overall selectivity of ethene and propylene is 65%.So excellent effect, except catalyst because
It is plain outer, also rely on the factor in terms of reaction engineering.
Chinese invention patent application (the application number of Dalian Chemical Physics Research Institute：92109866.9) report the high silicon of use
Molecular sieve carried Fe-Mn isoreactivities component realizes the selectivity of preferable preparation of low carbon olefines by synthetic gas.Its disclosed catalyst
For ferrimanganic metal oxide-molecular sieve (K-Fe-MnO/Silicalite-2) composite catalyst, CO conversion ratios reach 70-90%,
C2-C4 olefine selectives are 72-74%.But due to the pore structure of molecular sieve can be caused to send out in molecular sieve carried active component
Life changes, and the active metal of outer surface is not influenceed by carrier hole structure, and the selectivity high to acquisition is unfavorable, the work of carrier
With can not be not fully exerted.
The Chinese invention patent ZL03109585.2 of Beijing University of Chemical Technology is disclosed using activated carbon as carrier, manganese, copper, zinc,
Silicon, potassium etc. are the Fe/ activated carbon catalysts of auxiliary agent, are 300-400 in temperature for the reaction of synthesis gas preparing low-carbon olefins
DEG C, pressure is 1-2MPa, and synthesis gas air speed is 400-1000h-1And CO conversion ratios are reachable under conditions of being circulated without unstripped gas
95%, content of the hydrocarbon in gas-phase product is 69.5%, the selection of ethene, propylene, butylene in hydrocarbon
Property is up to more than 68%.But coking is serious during the catalyst use, it is impossible to long-term operating.
Chinese patent application CN10129384A uses vacuum-impregnated preparation method, makes main catalyst component Fe and helps
Agent is highly dispersed on carrier active carbon, so as to obtain very high catalytic activity and good catalytic effect.It is 300- in temperature
400 DEG C, pressure is 1-2Mpa, and synthesis gas air speed is 400-1000h-1Process conditions under, CO conversion ratios are up to 95%, low-carbon alkene
Account for more than the 68% of gas-phase product hydro carbons mass content, but easy coking deactivation at high temperature.
Chinese patent application CN1065026A discloses the catalyst and preparation method of preparation of ethylene by use of synthetic gas, adds Nb, Ga,
Pr, Sc, In, Yh, Ce, La etc. more than ten plants chemical element, and ethylene selectivity is up to more than 90%, but CO conversion ratios are relatively low, synthesis
The circulation of gas certainly will increase equipment and operating cost.
Fe and auxiliary agent are highly dispersed at self-control alkalescence using parallel flow precipitation and carried by Chinese patent application CN103157489A
Body surface face, in 200-500 DEG C, pressure 0-5Mpa, synthesis gas air speed 600-2400h-1Process conditions under, CO conversion ratios reach 75-
85%, low-carbon alkene accounts for the 50-60% of gas-phase product hydro carbons mass content.But catalyst strength is poor, it is impossible to anti-in slurry bed system
Answer in device and operate for a long time.
Iron nano-particle is dispersed in the interactive alpha-oxidation of weak property by De Jong etc. (Science, 2012,335,835)
On aluminium or carbon nano-fiber carrier, synthesis gas is directly converted and produce C2-C4 light olefins, in CO conversion ratios 80%, low-carbon alkene
It is 50% that hydrocarbon, which accounts for hydrocarbon product mass content, and possesses relatively good anticoking capability, but catalyst preparation process complicated difficult
To realize industrial applications.
For many years, some research teams have attempted to high temperature fused iron catalyst, are directly given birth to for improving F- T synthesis
Produce the selectivity of the product of low-carbon alkene.Chinese patent application CN101757925A provides a kind of oxide by iron and helped and urges
The compositions such as agent aluminum oxide, calcium oxide, potassium oxide, for synthesis gas produce low-carbon alkene fused iron catalyst, the catalyst
F- T synthesis activity and selectivity is higher, and conversion per pass reaches more than 95%, and methane selectively is less than 10%, and low-carbon alkene contains
Amount is more than 35%.But, the mechanical performance of fused iron catalyst at high temperature is not good, may result in fixed-bed operation and is catalyzed
The blocking of agent bed, or the incrustation of fluid-bed process separation equipment is caused, limit fused iron catalyst low in F- T synthesis generation
The application of carbon olefin course of reaction.
At present, the catalyst for preparing low-carbon alkene of prior art is preparing Repeatability, and difference is run into industry amplification
The difficulty of degree.Therefore the catalyst of new structure is designed, high selectivity of light olefin is obtained, to preparation of low carbon olefines by synthetic gas
Commercial Application it is significant.
The content of the invention
It is good and active high and low that the purpose of the present invention provides a kind of stability primarily directed to the disadvantages mentioned above of prior art
The good ferrozirconium catalyst that synthesis gas is converted into low-carbon alkene of carbene hydrocarbon-selective.
To realize object defined above, according to the first aspect of the invention, it is used for CO Hydrogenation low-carbons the invention provides one kind
The catalyst of alkene, the catalyst includes：20-80 weight % zirconium, 5-60 weight % iron, 5-40 weight % silicon and 5-30
Weight % aluminium.
According to the second aspect of the invention, the invention provides a kind of CO Hydrogenations for the method for low-carbon alkene, this method
Including：Unstripped gas containing CO is contacted with hydrogen-containing gas and catalyst, wherein, the catalyst is catalysis of the present invention
Agent.
Compared with conventional catalyst, the catalyst that the present invention is provided has advantages below：(1) catalyst dispersity can be good
Good, preparation technology is simple；(2) reaction condition is gentle, and catalyst activity is high and selectivity of light olefin is high, and stability is good.
Other features and advantages of the present invention will be described in detail in subsequent embodiment part.
Embodiment
The embodiment to the present invention is described in detail below.It should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
As it was previously stated, the invention provides a kind of catalyst that producing light olefins are hydrogenated with for CO, wherein, the catalyst bag
Include：20-80 weight % zirconium, 5-60 weight % iron, 5-40 weight % silicon and 5-30 weight % aluminium.
In the present invention, low-carbon alkene refers to C2-C4 alkene.
The catalyst of the present invention has higher activity and selectivity of light olefin, for the present invention, further preferred institute
Stating catalyst includes：35-38 weight % zirconium, 24-39 weight % iron, 11-24 weight % silicon and 9-14 weight % aluminium.
Catalyst according to the invention, preferably described catalyst also include VIII race's metal in addition to iron, VII B races metal,
One or more metals in IV B races metal, VI B races metal, I B races metal, II B races metal and rare earth metal in addition to zirconium,
One or more for example, in manganese, cobalt, cerium, titanium, platinum, molybdenum, ruthenium and palladium.More preferably content is 0.5-15 weight %.
According to one kind of the present invention preferred embodiment, preferably described catalyst also includes the VIII race gold in addition to iron
One or more metals in category, VII B races metal and rare earth metal, one kind being preferably selected from manganese, cobalt, cerium and ruthenium or many
Kind.
According to the present invention it is a kind of preferred embodiment, the catalyst also include one kind in manganese, cobalt, cerium and ruthenium or
It is a variety of, and content is 2-13 weight %.
According to a kind of preferred embodiment of the present invention, preferably described catalyst also includes in manganese, cobalt, cerium and ruthenium
At least two.
Catalyst according to the invention, the catalyst is alloy catalyst, and more preferably described catalyst closes for amorphous state
Au catalyst.
Preparation method of the invention to the catalyst is without particular/special requirement, as long as meeting above-mentioned composition, such as when this
When the described catalyst of invention is alloy catalyst, urged as long as carrying out formula according to the catalyst composition of the present invention and being prepared into alloy
Agent.
And for example, when needing the catalyst preparation into amorphous alloy catalyst, its preparation method can also be this
The customary preparation methods in field, can be prepared using any one existing method for preparing amorphous alloy catalyst.For
The present invention, preferably described amorphous alloy catalyst can be prepared as follows：
By VIII race's metal, VII B races metal, the IV B races gold in addition to zirconium of zirconium, iron, silicon, aluminium and/or discord in addition to iron
Then one or more METAL HEATING PROCESSs in category, VI B races metal, I B races metal, II B races metal and rare earth metal cool down to melting
Alloy is formed, processing is stripped to the alloy after solidification with aqueous slkali is obtained with extraction section aluminium.More preferably will by zirconium,
VIII race's metal, VII B races metal, the IV B races metal in addition to zirconium, VI B races metal, I B of iron, silicon, aluminium and/or discord in addition to iron
The fused mass for the alloy that one or more metals in race's metal, II B races metal and rare earth metal are constituted with more than 1000 DEG C/
S cooldown rate rapid curing, cured product is added under agitation to be heated in the alkali lye that extraction temperature is 10-100 DEG C, is made
Aluminium in alloy fully reacts with alkali, then filters off liquid, and solid sample is washed with distilled water to pH to obtain catalyst after 7,
The concentration of alkali lye is 2-40 weight %, and the weight ratio of alloy and alkali is 1：1-10.
The preparation method that the present invention is provided, can use atwirl single roller or double roller cooling molten metal, can also adopt
Mode used in more than 1300 DEG C spray atomization and depositions quickly cools down metal.
In the preparation method that the present invention is provided, the alkali density process is：Through quick-setting quick cooling alloy under agitation
In the alkali lye for being heated to extraction temperature, the aluminium in alloy is fully reacted with alkali lye, obtain black solid catalyst, take out
Temperature raising degree is preferably 40-90 DEG C, and alkali concn is preferably 10-20 weight %, and extraction times are 5-600min, are preferably 30-
120min, alloying pellet size is 8-400 mesh, preferably 80-200 mesh, with the weight ratio preferably 1 of alkali in terms of alloy：1.5-4.
After alkali density, catalyst sample is washed with distilled water to neutrality, is preserved preferably under conditions of having indifferent gas or hydrogen shield.
In the method that the present invention is provided, described alkali is soluble highly basic, the hydroxide of such as alkali and alkaline earth metal ions,
Can be NaOH, KOH and Ba (OH)2In one kind, wherein preferably NaOH or KOH.
As it was previously stated, the invention provides a kind of method of CO Hydrogenations for low-carbon alkene, this method includes：By containing CO's
Unstripped gas is contacted with hydrogen-containing gas and catalyst, and the catalyst is catalyst of the present invention.
In the present invention, the hydrogen-containing gas can be containing the gas of hydrogen or other hydrogeneous gases, for this hair
Bright, preferably described hydrogen-containing gas is hydrogen.
With the method for the invention it is preferred to which the condition of contact includes：Temperature is 200-500 DEG C, more preferably 280-320
DEG C, temperature in use is used as exemplary illustration for 300 DEG C in an embodiment of the present invention.
The method according to the invention, the unstripped gas can be the various gases containing carbon monoxide, can be single oxygen
Change carbon, or gaseous mixture, for example, can be synthesis gas.
With the method for the invention it is preferred to which the condition of contact includes：Pressure is 0.1-15MPa.
With the method for the invention it is preferred to which the condition of contact also includes：H2Mol ratio with CO is 0.5-10:1.
The method according to the invention, the contact can be carried out in various reactors, for example can be in slurry reactor
Carried out in device, fixed bed reactors, for the present invention, when the contact is carried out in fixed bed reactors, the condition of contact
Including：Air speed is 500-100000h-1.In the present invention, air speed refers to gas space velocity.
Below by embodiment, the invention will be further described, but content not thereby limiting the invention.
In embodiment, each component content is determined using plasma emission spectrum (ICP) in catalyst.
Embodiment 1
1.5kg zirconiums, 1.0kg iron, 0.5kg cobalts, 0.5kg silicon and 2.5kg aluminium are added in graphite crucible, by it in high frequency
Melting is heated in stove, then the fused solution is sprayed onto at crucible nozzle on the copper roller that a rotating speed is 800 revs/min, is led in copper roller
Cooling water, aluminium alloy forms flakey band to be thrown away after the cooling velocity more than 1000 DEG C/s quickly cooling along copper roller tangent line,
Flakey band it is ground to particle diameter be less than 50 microns, obtain foundry alloy.50g foundry alloys are slowly added into and filled
In the there-necked flask of 500 gram of 20 weight % potassium hydroxide aqueous solution, it is 60 DEG C of simultaneously constant temperature stirring 1 hours to control its temperature, is stopped
After heating and stirring, liquid is filtered off；It is 7 with 100 DEG C of distillation water washings to pH value.Obtained catalyst numbering is catalysis
Agent -1, the composition of catalyst -1 is shown in Table 1.
Embodiment 2
1.5kg zirconiums, 1.0kg iron, 1.0kg silicon and 2.5kg aluminium are added in graphite crucible, it is heated in coreless induction furnace
To melting, then the fused solution is sprayed onto at crucible nozzle on the copper roller that a rotating speed is 800 revs/min, and cooling water is led in copper roller, is closed
Golden liquid forms flakey band, flakey bar to be thrown away after the cooling velocity more than 1000 DEG C/s quickly cooling along copper roller tangent line
With it is ground to particle diameter be less than 50 microns, obtain foundry alloy.50g foundry alloys are slowly added into and fill 500 gram of 20 weight
In the there-necked flask for the aqueous solution for measuring % potassium hydroxide, it is 60 DEG C of simultaneously constant temperature stirring 1 hours to control its temperature, stops heating and stirring
Afterwards, liquid is filtered off；It is 7 with 100 DEG C of distillation water washings to pH value.Obtained catalyst numbering is catalyst -2, catalyst -
2 composition is shown in Table 1.
Embodiment 3
1.5kg zirconiums, 1.5kg iron, 0.2kg manganese, 0.5kg silicon and 2.5kg aluminium are added in graphite crucible, by it in high frequency
Melting is heated in stove, then the fused solution is sprayed onto at crucible nozzle on the copper roller that a rotating speed is 800 revs/min, is led in copper roller
Cooling water, aluminium alloy forms flakey band to be thrown away after the cooling velocity more than 1000 DEG C/s quickly cooling along copper roller tangent line,
Flakey band it is ground to particle diameter be less than 50 microns, obtain foundry alloy.50g foundry alloys are slowly added into and filled
In the there-necked flask of the aqueous solution of 500 gram of 20 weight % potassium hydroxide, it is 60 DEG C of simultaneously constant temperature stirring 1 hours to control its temperature, is stopped
After heating and stirring, liquid is filtered off；It is 7 with 100 DEG C of distillation water washings to pH value.Obtained catalyst numbering is catalysis
Agent -3, the composition of catalyst -3 is shown in Table 1.
Embodiment 4
1.5kg zirconiums, 1.5kg iron, 0.2kg ceriums, 0.5kg silicon and 2.5kg aluminium are added in graphite crucible, by it in high frequency
Melting is heated in stove, then the fused solution is sprayed onto at crucible nozzle on the copper roller that a rotating speed is 800 revs/min, is led in copper roller
Cooling water, aluminium alloy forms flakey band to be thrown away after the cooling velocity more than 1000 DEG C/s quickly cooling along copper roller tangent line,
Flakey band it is ground to particle diameter be less than 50 microns, obtain foundry alloy.50g foundry alloys are slowly added into and filled
In the there-necked flask of the aqueous solution of 500 gram of 20 weight % potassium hydroxide, it is 60 DEG C of simultaneously constant temperature stirring 1 hours to control its temperature, is stopped
After heating and stirring, liquid is filtered off；It is 7 with 100 DEG C of distillation water washings to pH value.Obtained catalyst numbering is catalysis
Agent -4, the composition of catalyst -4 is shown in Table 1.
Embodiment 5
1.5kg zirconiums, 1.5kg iron, 0.1kg rutheniums, 0.5kg silicon and 2.5kg aluminium are added in graphite crucible, by it in high frequency
Melting is heated in stove, then the fused solution is sprayed onto at crucible nozzle on the copper roller that a rotating speed is 800 revs/min, is led in copper roller
Cooling water, aluminium alloy forms flakey band to be thrown away after the cooling velocity more than 1000 DEG C/s quickly cooling along copper roller tangent line,
Flakey band it is ground to particle diameter be less than 50 microns, obtain foundry alloy.50g foundry alloys are slowly added into and filled
In the there-necked flask of the aqueous solution of 500 gram of 20 weight % potassium hydroxide, it is 60 DEG C of simultaneously constant temperature stirring 1 hours to control its temperature, is stopped
After heating and stirring, liquid is filtered off；It is 7 with 100 DEG C of distillation water washings to pH value.Obtained catalyst numbering is catalysis
Agent -5, the composition of catalyst -5 is shown in Table 1.
Embodiment 6
1.5kg zirconiums, 1.6kg iron, 0.052kg rutheniums, 0.3kg silicon and 2.0kg aluminium are added in graphite crucible, by it in height
Melting is heated in frequency stove, then the fused solution is sprayed onto at crucible nozzle on the copper roller that a rotating speed is 800 revs/min, in copper roller
Logical cooling water, aluminium alloy forms flakey bar to be thrown away after the cooling velocity more than 1000 DEG C/s quickly cooling along copper roller tangent line
Band, flakey band it is ground to particle diameter be less than 50 microns, obtain foundry alloy.50g foundry alloys are slowly added into Sheng
Have in the 500 gram of 20 weight % there-necked flask of potassium hydroxide aqueous solution, it is 90 DEG C of simultaneously constant temperature stirring 1 hours to control its temperature, is stopped
After only heating and stir, liquid is filtered off；It is 7 with 100 DEG C of distillation water washings to pH value.Obtained catalyst numbering is catalysis
Agent -6, the composition of catalyst -6 is shown in Table 1.
Embodiment 7
1.5kg zirconiums, 1.5kg iron, 0.1kg palladiums, 0.5kg silicon and 2.5kg aluminium are added in graphite crucible, by it in high frequency
Melting is heated in stove, then the fused solution is sprayed onto at crucible nozzle on the copper roller that a rotating speed is 800 revs/min, is led in copper roller
Cooling water, aluminium alloy forms flakey band to be thrown away after the cooling velocity more than 1000 DEG C/s quickly cooling along copper roller tangent line,
Flakey band it is ground to particle diameter be less than 50 microns, obtain foundry alloy.50g foundry alloys are slowly added into and filled
In the there-necked flask of 500 gram of 20 weight % potassium hydroxide aqueous solution, it is 60 DEG C of simultaneously constant temperature stirring 1 hours to control its temperature, is stopped
After heating and stirring, liquid is filtered off；It is 7 with 100 DEG C of distillation water washings to pH value.Obtained catalyst numbering is catalysis
Agent -7, the composition of catalyst -7 is shown in Table 1.
Embodiment 8
1.5kg zirconiums, 1.5kg iron, 0.05kg rutheniums, 0.05kg manganese, 0.5kg silicon and 2.5kg aluminium are added in graphite crucible,
It is heated to melting in coreless induction furnace, then the fused solution is sprayed onto the copper roller that a rotating speed is 800 revs/min at crucible nozzle
On, cooling water is led in copper roller, aluminium alloy is formed to be thrown away after the cooling velocity more than 1000 DEG C/s quickly cooling along copper roller tangent line
Flakey band, flakey band it is ground to particle diameter be less than 50 microns, obtain foundry alloy.50g foundry alloys is slow
In the there-necked flask for being added to the potassium hydroxide aqueous solution for filling 500 gram of 20 weight %, it is 60 DEG C and constant temperature stirring 1 to control its temperature
Hour, stop after heating and stirring, filter off liquid；It is 7 with 100 DEG C of distillation water washings to pH value.Obtained catalyst is compiled
Number it is catalyst -8, the composition of catalyst -8 is shown in Table 1.
Embodiment 9
1.5kg zirconiums, 1.5kg iron, 0.013kg cobalts, 0.09kg ceriums, 0.5kg silicon and 2.5kg aluminium are added to graphite crucible
In, it is heated to melting in coreless induction furnace, then the fused solution is sprayed onto the copper that a rotating speed is 800 revs/min at crucible nozzle
On roller, cooling water is led in copper roller, aluminium alloy after the cooling velocity more than 1000 DEG C/s quickly cooling along copper roller tangent line to throw away, shape
Into flakey band, flakey band it is ground to particle diameter be less than 50 microns, obtain foundry alloy.50g foundry alloys are delayed
Slowly it is added in the there-necked flask for the potassium hydroxide aqueous solution for filling 500 gram of 20 weight %, controls its temperature to be stirred for 60 DEG C and constant temperature
Mix 1 hour, stop after heating and stirring, filter off liquid；It is 7 with 100 DEG C of distillation water washings to pH value.Obtained catalyst
Numbering is catalyst -9, and the composition of catalyst -9 is shown in Table 1.
Embodiment 10
1.5kg zirconiums, 1.5kg iron, 0.075kg rutheniums, 0.03kg ceriums, 0.5kg silicon and 2.5kg aluminium are added to graphite crucible
In, it is heated to melting in coreless induction furnace, then the fused solution is sprayed onto the copper that a rotating speed is 800 revs/min at crucible nozzle
On roller, cooling water is led in copper roller, aluminium alloy after the cooling velocity more than 1000 DEG C/s quickly cooling along copper roller tangent line to throw away, shape
Into flakey band, flakey band it is ground to particle diameter be less than 50 microns, obtain foundry alloy.50g foundry alloys are delayed
Slowly it is added in the there-necked flask for the potassium hydroxide aqueous solution for filling 500 gram of 20 weight %, controls its temperature to be stirred for 60 DEG C and constant temperature
Mix 1 hour, stop after heating and stirring, filter off liquid；It is 7 with 100 DEG C of distillation water washings to pH value.Obtained catalyst
Numbering is catalyst -10, and the composition of catalyst -10 is shown in Table 1.
Comparative example 1-4
Method according to embodiment 5 prepares catalyst, unlike, the catalyst composition prepared is shown in Table 1.
Table 1
| Embodiment | Catalyst is numbered | Catalyst is constituted |
| 1 | Catalyst -1 | Zr36.6Fe24.4Co12.1Si12.2Al14.7 |
| 2 | Catalyst -2 | Zr37.5Fe25.0Si23.7Al13.8 |
| 3 | Catalyst -3 | Zr35.7Fe38.1Mn4.8Si11.9Al9.5 |
| 4 | Catalyst -4 | Zr36.1Fe35.9Ce4.3Si12.5Al11.2 |
| 5 | Catalyst -5 | Zr35.8Fe36.4Ru2.4Si11.7Al13.7 |
| 6 | Catalyst -6 | Zr40.0Fe42.2Ru1.4Si7.7Al8.7 |
| 7 | Catalyst -7 | Zr35.8Fe36.4Pd2.4Si11.7Al13.7 |
| 8 | Catalyst -8 | Zr35.8Fe36.4Mn1.2Ru1.2Si11.7Al13.7 |
| 9 | Catalyst -9 | Zr35.8Fe36.4Co0.3Ce2.1Si11.7Al13.7 |
| 10 | Catalyst -10 | Zr35.8Fe36.4Ru1.8Ce0.6Si11.7Al13.7 |
| Comparative example 1 | D1 | Zr45.8Fe40.4Al13.8 |
| Comparative example 2 | D2 | Zr43.2Fe44.0Si12.8 |
| Comparative example 3 | D3 | Zr49.5Fe50.5 |
| Comparative example 4 | D4 | Zr55.0Fe45.0 |
* subscript represents the weight percentage of metal.
Test case 1-10
This test case illustrates the catalyst provided using the present invention, and the feelings of CO hydrogenation reactions are carried out in fixed bed reactors
Condition.
In Catalyst packing 0.5g, reaction temperature is 300 DEG C, and reaction pressure is 0.5MPa, reaction time 100h, H2/CO
=2, air speed 6000h-1Process conditions under react, reaction result is shown in Table 2 or table 3.
Test case 11
This test case illustrates the catalyst provided using the present invention, and the feelings of CO hydrogenation reactions are carried out in fixed bed reactors
Condition.
Carried out according to test case 1-10 method, unlike, temperature is 330 DEG C, and reaction result is shown in Table 3.
Table 2
Table 3
The catalyst of the present invention prepares low-carbon alkene for co hydrogenation it can be seen from the result of table 2 and table 3,
Activity is high and selectivity is good.
Test case 12-13
This test case illustrates the catalyst provided using the present invention, and the feelings of CO hydrogenation reactions are carried out in fixed bed reactors
Condition.
In Catalyst packing 0.5g, reaction temperature is 300 DEG C, and reaction pressure is 0.5MPa, H2/ CO=2, air speed 6000h-1
Process conditions under react, reaction result is shown in Table 4.
With higher activity when the catalyst of the present invention is for CO hydrogenation reactions it can be seen from data in table 4, and
React after long-time, activity has no decline, it can thus be seen that the catalyst stability of the present invention is also preferable.
Table 4
Test comparison example 1-4
CO hydrogenation reactions are carried out in fixed bed reactors according to test case 1-10 method, the difference is that the catalysis used
Agent is D1-D4, and reaction result is shown in Table 5.
Table 5
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to the scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, it can be combined by any suitable means.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (10)
1. a kind of catalyst that producing light olefins are hydrogenated with for CO, it is characterised in that the catalyst includes：20-80 weight %'s
Zirconium, 5-60 weight % iron, 5-40 weight % silicon and 5-30 weight % aluminium, the catalyst are alloy catalyst.
2. catalyst according to claim 1, wherein, the catalyst includes：35-38 weight % zirconium, 24-39 weight %
Iron, 11-24 weight % silicon and 9-14 weight % aluminium.
3. catalyst according to claim 2, wherein, the catalyst is also including VIII race's metal in addition to iron, VII B races
One or more in metal, the IV B races metal in addition to zirconium, VI B races metal, I B races metal, II B races metal and rare earth metal
Metal, and content is 0.5-15 weight %.
4. catalyst according to claim 3, wherein, the catalyst also includes one kind or many in manganese, cobalt, cerium and ruthenium
Metal is planted, and content is 2-13 weight %.
5. catalyst according to claim 3, wherein, the catalyst also includes at least two in manganese, cobalt, cerium and ruthenium
Metal.
6. catalyst according to claim 1, wherein, the catalyst is amorphous alloy catalyst.
7. a kind of CO Hydrogenations include for the method for low-carbon alkene, this method：By the unstripped gas containing CO and hydrogen-containing gas and catalysis
Agent is contacted, it is characterised in that the catalyst is the catalyst described in any one in claim 1-6.
8. method according to claim 7, wherein, the condition of contact includes：Temperature is 200-500 DEG C.
9. method according to claim 8, wherein, the unstripped gas is synthesis gas, and the condition of contact includes：Temperature is
280-320 DEG C, pressure is 0.1-15MPa, H2Mol ratio with CO is 0.5-10:1.
10. the method according to any one in claim 7-9, wherein, the contact is carried out in fixed bed reactors,
The condition of contact includes：Air speed is 500-100000h-1。
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| CN107774298B (en) * | 2016-08-30 | 2023-06-09 | 中国石油化工股份有限公司 | Porous metal/molecular sieve composite catalyst, preparation method thereof and application thereof in preparation of low-carbon olefin from synthesis gas |
| CN107774281B (en) * | 2016-08-30 | 2020-10-27 | 中国石油化工股份有限公司 | Catalyst for preparing low-carbon olefin by carbon monoxide hydrogenation, preparation method thereof and method for preparing low-carbon olefin by carbon monoxide hydrogenation |
| CN107051469A (en) * | 2017-04-01 | 2017-08-18 | 李晓瑾 | One kind is based on hydrogenation of carbon dioxide producing light olefins composite catalyst and preparation method thereof |
| CN109647292B (en) * | 2017-10-10 | 2022-03-11 | 中国石油化工股份有限公司 | Method for preparing low-carbon olefin from synthesis gas by adopting fluidized bed |
| CN112619651A (en) * | 2019-09-24 | 2021-04-09 | 中国石油化工股份有限公司 | Preparation method of catalyst for preparing low-carbon olefin from synthesis gas |
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