CN105080547A - Catalyst for preparing low carbon olefin through CO hydrogenation, and method for preparing low carbon olefin through CO hydrogenation - Google Patents
Catalyst for preparing low carbon olefin through CO hydrogenation, and method for preparing low carbon olefin through CO hydrogenation Download PDFInfo
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Abstract
The invention provides a catalyst for preparing low carbon olefin through CO hydrogenation. The catalyst comprises 20-80wt% of zirconium, 5-60wt% of iron, 5-40wt% of silicon and 5-30wt% of aluminum. The invention also provides a method for preparing the low carbon olefin through CO hydrogenation. The method is characterized in that a CO-containing raw material is in contact with a hydrogen-containing gas and the catalyst. Compared with routine catalysts, the catalyst provided by the invention has the advantages of good dispersion, simple preparation method, mild reaction conditions, high activity, high selectivity of the low carbon olefin, and good stability.
Description
Technical field
The present invention relates to a kind of catalyst for CO Hydrogenation low-carbon alkene, relate in particular to a kind of Zr-Fe-Si-Al multimetal reforming catalyst that Synthetic holography is low-carbon alkene by a kind of high activity, highly selective and the CO Hydrogenation method for low-carbon alkene.
Background technology
Low-carbon alkene, as basic organic chemical industry raw material, plays a part very important in modern petroleum and chemical industry.Especially ethene and propylene, along with the continuous expansion of increase and the application day by day of its demand, studies widely its synthetic method and shows important day.
The method of preparing low-carbon olefins can be divided into two large classes generally: a class is petroleum path, and another kind of is Non oil-based route.Up to now, the light oil cracking method that still main employing is traditional in the world, namely petroleum path carrys out the low-carbon alkene such as preparing ethylene, propylene.When oil price is soaring, take natural gas as raw material, possess skills and economic attractiveness via the direct or indirect producing light olefins of synthesis gas.As being raw material with natural gas, by method preparing low-carbon olefins technology such as oxidative couplings; With natural gas or coal for waste synthesis gas, synthesis gas is by F-T synthesis (direct method) or via methyl alcohol or dimethyl ether (indirect method) preparing low-carbon olefins technology etc.And be that single step reaction generates object product by the direct preparing low-carbon olefins of synthesis gas, its technological process is simpler than indirect method, more economical.
The catalyst that synthesis gas orientation is converted into low-carbon alkene reaction generally selects Fe as active component, adds some auxiliary agents simultaneously; The normally various types of molecular sieve of carrier of catalyst and activated carbon.Wherein molecular sieve carried catalyst is owing to realizing selecting shape etc. to product by the adjustable pore passage structure of molecular sieve carrier rule, receives publicity in raising selectivity of light olefin.
The Chinese patent application CN1260823A of Exxon Corporation reports the method with modified molecular screen, Synthetic holography being become low-carbon alkene, and it adopts Fe
3(CO)
12/ ZSM-5 modified molecular sieve catalyst, at 260 DEG C, H
2/ CO volume ratio is 3, GHSV is 1000h
-1reaction condition under, the overall selectivity of ethene and propylene is 65%.Effect excellent like this, except the factor of catalyst, also depends on the factor of reaction engineering aspect.
Chinese invention patent application (the application number: 92109866.9) report use high-silica zeolite load Fe-Mn isoreactivity component and achieve the selective of good preparation of low carbon olefines by synthetic gas of Dalian Chemical Physics Research Institute.Catalyst disclosed in it is ferrimanganic metal oxide-molecular sieve (K-Fe-MnO/Silicalite-2) composite catalyst, and CO conversion ratio reaches 70-90%, and C2-C4 olefine selective is 72-74%.But due to the pore structure of molecular sieve can be caused in molecular sieve carried active component to change, and the active metal of outer surface is by the impact of carrier hole structure, high selective unfavorable to obtaining, the effect of carrier can not be not fully exerted.
It is carrier that the Chinese invention patent ZL03109585.2 of Beijing University of Chemical Technology discloses with activated carbon, manganese, copper, zinc, silicon, potassium etc. are the Fe/ activated carbon catalyst of auxiliary agent, for the synthesis of the reaction of gas preparing low-carbon olefins, be 300-400 DEG C in temperature, pressure is 1-2MPa, and synthesis gas air speed is 400-1000h
-1and CO conversion ratio can reach 95% under the condition circulated without unstripped gas, the content of hydrocarbon in gas-phase product is 69.5%, and selective in hydrocarbon of ethene, propylene, butylene reaches more than 68%.But in this catalyst use procedure, coking is serious, can not operate for a long time.
Chinese patent application CN10129384A uses vacuum-impregnated preparation method, and main catalyst component Fe and auxiliary agent are highly dispersed on carrier active carbon, thus obtains very high catalytic activity and good catalytic effect.Be 300-400 DEG C in temperature, pressure is 1-2Mpa, and synthesis gas air speed is 400-1000h
-1process conditions under, CO conversion ratio reaches 95%, and low-carbon alkene accounts for more than 68% of gas-phase product hydro carbons mass content, but at high temperature easy coking deactivation.
Chinese patent application CN1065026A discloses catalyst and the preparation method of preparation of ethylene by use of synthetic gas, adds Nb, Ga, Pr, Sc, In, Yh, Ce, La etc. more than ten plant chemical element, and ethylene selectivity can reach more than 90%, but CO conversion ratio is lower, and the circulation of synthesis gas certainly will increase equipment and operating cost.
Chinese patent application CN103157489A adopts parallel flow precipitation Fe and auxiliary agent to be highly dispersed at self-control basic supports surface, at 200-500 DEG C, and pressure 0-5Mpa, synthesis gas air speed 600-2400h
-1process conditions under, CO conversion ratio reaches 75-85%, and low-carbon alkene accounts for the 50-60% of gas-phase product hydro carbons mass content.But catalyst strength is poor, cannot operate for a long time in paste state bed reactor.
(the Science such as DeJong, 2012,335,835) iron nano-particle is dispersed on the interactive Alpha-alumina of weakness or carbon nano-fiber carrier, synthesis gas is directly transformed and produces C2-C4 light olefin, when CO conversion ratio 80%, it is 50% that low-carbon alkene accounts for hydrocarbon product mass content, and have relatively good anticoking capability, but catalyst preparation process complicated difficult is to realize industrial applications.
For many years, some research teams have attempted exploitation high temperature melting iron catalyst, directly produce the selective of the product of low-carbon alkene for improving F-T synthesis.Chinese patent application CN101757925A provides that a kind of oxide by iron and co-catalyst aluminium oxide, calcium oxide, potassium oxide etc. form, produce low-carbon alkene for the synthesis of gas fused iron catalyst, this catalyst F-T synthesis activity and selectivity is higher, conversion per pass reaches more than 95%, methane selectively is less than 10%, and low-carbon alkene content is more than 35%.But, fused iron catalyst mechanical performance is at high temperature not good, the blocking of beds in fixed-bed operation may be caused, or cause the incrustation of fluid-bed process separation equipment, limit fused iron catalyst generates low-carbon alkene course of reaction application at F-T synthesis.
At present, Repeatability prepared by the catalyst preparing low-carbon alkene of prior art, and industry runs into difficulty in various degree in amplifying.Therefore design the catalyst of new structure, obtain high selectivity of light olefin, significant to the commercial Application of preparation of low carbon olefines by synthetic gas.
Summary of the invention
Object of the present invention mainly provides a kind of good stability and ferrozirconium catalyst synthesis gas being converted into low-carbon alkene that activity is high and selectivity of light olefin is good for the above-mentioned shortcoming of prior art.
For realizing aforementioned object, according to a first aspect of the invention, the invention provides a kind of catalyst for CO Hydrogenation low-carbon alkene, this catalyst comprises: the zirconium of 20-80 % by weight, the iron of 5-60 % by weight, the silicon of 5-40 % by weight and the aluminium of 5-30 % by weight.
According to a second aspect of the invention, the invention provides the method for a kind of CO Hydrogenation for low-carbon alkene, the method comprises: by containing the unstripped gas of CO and hydrogen-containing gas and catalyst exposure, and wherein, described catalyst is catalyst of the present invention.
Compared with conventional catalyst, catalyst provided by the invention has the following advantages: (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, good stability.
Other features and advantages of the present invention are described in detail in detailed description of the invention part subsequently.
Detailed description of the invention
Below the specific embodiment of the present invention is described in detail.Should be understood that, detailed description of the invention described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
As previously mentioned, the invention provides a kind of catalyst for CO Hydrogenation low-carbon alkene, wherein, this catalyst comprises: the zirconium of 20-80 % by weight, the iron of 5-60 % by weight, the silicon of 5-40 % by weight and the aluminium of 5-30 % by weight.
In the present invention, low-carbon alkene refers to the alkene of C2-C4.
Catalyst of the present invention has higher activity and selectivity of light olefin, and for the present invention, further preferred described catalyst comprises: the zirconium of 35-38 % by weight, the iron of 24-39 % by weight, the silicon of 11-24 % by weight and the aluminium of 9-14 % by weight.
Catalyst according to the invention, preferred described catalyst also comprises one or more metals in VIII race's metal beyond deironing, VII B race metal, IV B race metal, VI B race metal, I B race metal, II B race metal and rare earth metal except zirconium, such as, be one or more in manganese, cobalt, cerium, titanium, platinum, molybdenum, ruthenium and palladium.More preferably content is 0.5-15 % by weight.
According to one of the present invention preferred embodiment, preferred described catalyst also comprises one or more metals in VIII race's metal, VII B race metal and the rare earth metal beyond deironing, is preferably selected from one or more in manganese, cobalt, cerium and ruthenium.
According to one of the present invention preferred embodiment, described catalyst also comprise in manganese, cobalt, cerium and ruthenium one or more, and content is 2-13 % by weight.
The preferred embodiment of one according to the present invention, preferred described catalyst also comprises at least two kinds in manganese, cobalt, cerium and ruthenium.
Catalyst according to the invention, described catalyst is alloy catalyst, and more preferably described catalyst is amorphous alloy catalyst.
The present invention to the preparation method of described catalyst without particular/special requirement, such as, as long as meet above-mentioned composition, when catalyst of the present invention is alloy catalyst, as long as carry out formula according to catalyst of the present invention composition to be prepared into alloy catalyst.
And for example, when described catalyst preparing is become amorphous alloy catalyst by needs, its preparation method also can be the customary preparation methods of this area, can adopt any one existing method preparation preparing amorphous alloy catalyst.For the present invention, preferred described amorphous alloy catalyst can be prepared as follows:
By zirconium, iron, silicon, aluminium and or discord deironing beyond VIII race's metal, VII B race metal, one or more METAL HEATING PROCESS in IV B race metal, VI B race metal, I B race metal, II B race metal and rare earth metal except zirconium then cool formation alloy to melting, with aqueous slkali, extracting process is carried out to the alloy after solidification and obtains with extraction section aluminium.Being more preferably will by zirconium, iron, silicon, aluminium and or discord deironing beyond VIII race's metal, VII B race metal, IV B race metal except zirconium, VI B race metal, I B race metal, the fused mass of the alloy that one or more metals in II B race metal and rare earth metal form is to be greater than the cooldown rate rapid curing of 1000 DEG C/S, cured product under agitation adds that to be heated to extraction temperature be in the alkali lye of 10-100 DEG C, aluminium in alloy and alkali are fully reacted, then elimination liquid, solid sample is washed with distilled water to pH and obtains catalyst after 7, the concentration of alkali lye is 2-40 % by weight, the weight ratio of alloy and alkali is 1:1-10.
Preparation method provided by the invention, can adopt atwirl single roller or two roller cooling molten metal, also can adopt the quick cool metal of the mode of spray atomization and deposition more than 1300 DEG C.
In preparation method provided by the invention, described alkali density process is: under agitation add through quick-setting quick cooling alloy and be heated in the alkali lye of extraction temperature, aluminium in alloy and alkali lye are fully reacted, obtain black solid catalyst, extraction temperature is preferably 40-90 DEG C, and alkali concn is preferably 10-20 % by weight, and extraction times is 5-600min, is preferably 30-120min, alloying pellet size is 8-400 order, preferably 80-200 order, is preferably 1:1.5-4 in alloy and the weight ratio of alkali.After alkali density, catalyst sample is washed with distilled water to neutrality, preferably preserves under the condition having indifferent gas or hydrogen shield.
In method provided by the invention, described alkali is solubility highly basic, as the hydroxide of alkali and alkaline earth metal ions, can be NaOH, KOH and Ba (OH)
2in one, be wherein preferably NaOH or KOH.
As previously mentioned, the invention provides the method for a kind of CO Hydrogenation for low-carbon alkene, the method comprises: by containing the unstripped gas of CO and hydrogen-containing gas and catalyst exposure, and described catalyst is catalyst of the present invention.
In the present invention, described hydrogen-containing gas can be the gas containing hydrogen or other hydrogeneous gas, and for the present invention, preferred described hydrogen-containing gas is hydrogen.
According to method of the present invention, the condition of preferably contact comprises: temperature is 200-500 DEG C, is more preferably 280-320 DEG C, and serviceability temperature is 300 DEG C of exemplarily property explanations in an embodiment of the present invention.
According to method of the present invention, described unstripped gas can for the various gases containing carbon monoxide, and can be pure carbon monoxide, also can be gaseous mixture, such as, can be synthesis gas.
According to method of the present invention, the condition of preferably contact comprises: pressure is 0.1-15MPa.
According to method of the present invention, the condition of preferably contact also comprises: H
2be 0.5-10:1 with the mol ratio of CO.
According to method of the present invention, described contact can be carried out in various reactor, such as, can carry out in paste state bed reactor, fixed bed reactors, for the present invention, when described contact is carried out in fixed bed reactors, the condition of contact comprises: 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, in catalyst, each constituent content adopts plasma emission spectrum (ICP) to measure.
Embodiment 1
1.5kg zirconium, 1.0kg iron, 0.5kg cobalt, 0.5kg silicon and 2.5kg aluminium are joined in graphite crucible, it is heated to melting in coreless induction furnace, then this fused solution is sprayed onto a rotating speed from crucible nozzle is on the copper roller of 800 revs/min, logical cooling water in copper roller, throw away along copper roller tangent line after aluminium alloy cools fast with the cooling velocity being greater than 1000 DEG C/s, form flakey band, flakey band is less than 50 microns through being ground to particle diameter, obtains foundry alloy.Slowly joined in the there-necked flask of the potassium hydroxide aqueous solution filling 500 gram 20 % by weight by 50g foundry alloy, controlling its temperature is that 60 DEG C and constant temperature stir 1 hour, stops heating and after stirring, elimination liquid; Be 7 with the distilled water of 100 DEG C washing to pH value.Obtained catalyst is numbered catalyst-1, and the composition of catalyst-1 is in table 1.
Embodiment 2
1.5kg zirconium, 1.0kg iron, 1.0kg silicon and 2.5kg aluminium are joined in graphite crucible, it is heated to melting in coreless induction furnace, then this fused solution is sprayed onto a rotating speed from crucible nozzle is on the copper roller of 800 revs/min, logical cooling water in copper roller, throw away along copper roller tangent line after aluminium alloy cools fast with the cooling velocity being greater than 1000 DEG C/s, form flakey band, flakey band is less than 50 microns through being ground to particle diameter, obtains foundry alloy.Slowly joined in the there-necked flask of the aqueous solution filling 500 gram of 20 % by weight potassium hydroxide by 50g foundry alloy, controlling its temperature is that 60 DEG C and constant temperature stir 1 hour, stops heating and after stirring, elimination liquid; Be 7 with the distilled water of 100 DEG C washing to pH value.Obtained catalyst is numbered catalyst-2, and the composition of catalyst-2 is in table 1.
Embodiment 3
1.5kg zirconium, 1.5kg iron, 0.2kg manganese, 0.5kg silicon and 2.5kg aluminium are joined in graphite crucible, it is heated to melting in coreless induction furnace, then this fused solution is sprayed onto a rotating speed from crucible nozzle is on the copper roller of 800 revs/min, logical cooling water in copper roller, throw away along copper roller tangent line after aluminium alloy cools fast with the cooling velocity being greater than 1000 DEG C/s, form flakey band, flakey band is less than 50 microns through being ground to particle diameter, obtains foundry alloy.Slowly joined in the there-necked flask of the aqueous solution filling 500 gram of 20 % by weight potassium hydroxide by 50g foundry alloy, controlling its temperature is that 60 DEG C and constant temperature stir 1 hour, stops heating and after stirring, elimination liquid; Be 7 with the distilled water of 100 DEG C washing to pH value.Obtained catalyst is numbered catalyst-3, and the composition of catalyst-3 is in table 1.
Embodiment 4
1.5kg zirconium, 1.5kg iron, 0.2kg cerium, 0.5kg silicon and 2.5kg aluminium are joined in graphite crucible, it is heated to melting in coreless induction furnace, then this fused solution is sprayed onto a rotating speed from crucible nozzle is on the copper roller of 800 revs/min, logical cooling water in copper roller, throw away along copper roller tangent line after aluminium alloy cools fast with the cooling velocity being greater than 1000 DEG C/s, form flakey band, flakey band is less than 50 microns through being ground to particle diameter, obtains foundry alloy.Slowly joined in the there-necked flask of the aqueous solution filling 500 gram of 20 % by weight potassium hydroxide by 50g foundry alloy, controlling its temperature is that 60 DEG C and constant temperature stir 1 hour, stops heating and after stirring, elimination liquid; Be 7 with the distilled water of 100 DEG C washing to pH value.Obtained catalyst is numbered catalyst-4, and the composition of catalyst-4 is in table 1.
Embodiment 5
1.5kg zirconium, 1.5kg iron, 0.1kg ruthenium, 0.5kg silicon and 2.5kg aluminium are joined in graphite crucible, it is heated to melting in coreless induction furnace, then this fused solution is sprayed onto a rotating speed from crucible nozzle is on the copper roller of 800 revs/min, logical cooling water in copper roller, throw away along copper roller tangent line after aluminium alloy cools fast with the cooling velocity being greater than 1000 DEG C/s, form flakey band, flakey band is less than 50 microns through being ground to particle diameter, obtains foundry alloy.Slowly joined in the there-necked flask of the aqueous solution filling 500 gram of 20 % by weight potassium hydroxide by 50g foundry alloy, controlling its temperature is that 60 DEG C and constant temperature stir 1 hour, stops heating and after stirring, elimination liquid; Be 7 with the distilled water of 100 DEG C washing to pH value.Obtained catalyst is numbered catalyst-5, and the composition of catalyst-5 is in table 1.
Embodiment 6
1.5kg zirconium, 1.6kg iron, 0.052kg ruthenium, 0.3kg silicon and 2.0kg aluminium are joined in graphite crucible, it is heated to melting in coreless induction furnace, then this fused solution is sprayed onto a rotating speed from crucible nozzle is on the copper roller of 800 revs/min, logical cooling water in copper roller, throw away along copper roller tangent line after aluminium alloy cools fast with the cooling velocity being greater than 1000 DEG C/s, form flakey band, flakey band is less than 50 microns through being ground to particle diameter, obtains foundry alloy.Slowly joined in the there-necked flask of the potassium hydroxide aqueous solution filling 500 gram 20 % by weight by 50g foundry alloy, controlling its temperature is that 90 DEG C and constant temperature stir 1 hour, stops heating and after stirring, elimination liquid; Be 7 with the distilled water of 100 DEG C washing to pH value.Obtained catalyst is numbered catalyst-6, and the composition of catalyst-6 is in table 1.
Embodiment 7
1.5kg zirconium, 1.5kg iron, 0.1kg palladium, 0.5kg silicon and 2.5kg aluminium are joined in graphite crucible, it is heated to melting in coreless induction furnace, then this fused solution is sprayed onto a rotating speed from crucible nozzle is on the copper roller of 800 revs/min, logical cooling water in copper roller, throw away along copper roller tangent line after aluminium alloy cools fast with the cooling velocity being greater than 1000 DEG C/s, form flakey band, flakey band is less than 50 microns through being ground to particle diameter, obtains foundry alloy.Slowly joined in the there-necked flask of the potassium hydroxide aqueous solution filling 500 gram 20 % by weight by 50g foundry alloy, controlling its temperature is that 60 DEG C and constant temperature stir 1 hour, stops heating and after stirring, elimination liquid; Be 7 with the distilled water of 100 DEG C washing to pH value.Obtained catalyst is numbered catalyst-7, and the composition of catalyst-7 is in table 1.
Embodiment 8
1.5kg zirconium, 1.5kg iron, 0.05kg ruthenium, 0.05kg manganese, 0.5kg silicon and 2.5kg aluminium are joined in graphite crucible, it is heated to melting in coreless induction furnace, then this fused solution is sprayed onto a rotating speed from crucible nozzle is on the copper roller of 800 revs/min, logical cooling water in copper roller, throw away along copper roller tangent line after aluminium alloy cools fast with the cooling velocity being greater than 1000 DEG C/s, form flakey band, flakey band is less than 50 microns through being ground to particle diameter, obtains foundry alloy.Slowly joined in the there-necked flask of the potassium hydroxide aqueous solution filling 500 gram 20 % by weight by 50g foundry alloy, controlling its temperature is that 60 DEG C and constant temperature stir 1 hour, stops heating and after stirring, elimination liquid; Be 7 with the distilled water of 100 DEG C washing to pH value.Obtained catalyst is numbered catalyst-8, and the composition of catalyst-8 is in table 1.
Embodiment 9
1.5kg zirconium, 1.5kg iron, 0.013kg cobalt, 0.09kg cerium, 0.5kg silicon and 2.5kg aluminium are joined in graphite crucible, it is heated to melting in coreless induction furnace, then this fused solution is sprayed onto a rotating speed from crucible nozzle is on the copper roller of 800 revs/min, logical cooling water in copper roller, throw away along copper roller tangent line after aluminium alloy cools fast with the cooling velocity being greater than 1000 DEG C/s, form flakey band, flakey band is less than 50 microns through being ground to particle diameter, obtains foundry alloy.Slowly joined in the there-necked flask of the potassium hydroxide aqueous solution filling 500 gram 20 % by weight by 50g foundry alloy, controlling its temperature is that 60 DEG C and constant temperature stir 1 hour, stops heating and after stirring, elimination liquid; Be 7 with the distilled water of 100 DEG C washing to pH value.Obtained catalyst is numbered catalyst-9, and the composition of catalyst-9 is in table 1.
Embodiment 10
1.5kg zirconium, 1.5kg iron, 0.075kg ruthenium, 0.03kg cerium, 0.5kg silicon and 2.5kg aluminium are joined in graphite crucible, it is heated to melting in coreless induction furnace, then this fused solution is sprayed onto a rotating speed from crucible nozzle is on the copper roller of 800 revs/min, logical cooling water in copper roller, throw away along copper roller tangent line after aluminium alloy cools fast with the cooling velocity being greater than 1000 DEG C/s, form flakey band, flakey band is less than 50 microns through being ground to particle diameter, obtains foundry alloy.Slowly joined in the there-necked flask of the potassium hydroxide aqueous solution filling 500 gram 20 % by weight by 50g foundry alloy, controlling its temperature is that 60 DEG C and constant temperature stir 1 hour, stops heating and after stirring, elimination liquid; Be 7 with the distilled water of 100 DEG C washing to pH value.Obtained catalyst is numbered catalyst-10, and the composition of catalyst-10 is in table 1.
Comparative example 1-4
According to the method Kaolinite Preparation of Catalyst of embodiment 5, unlike, the catalyst composition prepared is in table 1.
Table 1
| Embodiment | Catalyst is numbered | Catalyst forms |
| 1 | Catalyst-1 | Zr 36.6Fe 24.4Co 12.1Si 12.2Al 14.7 |
| 2 | Catalyst-2 | Zr 37.5Fe 25.0Si 23.7Al 13.8 |
| 3 | Catalyst-3 | Zr 35.7Fe 38.1Mn 4.8Si 11.9Al 9.5 |
| 4 | Catalyst-4 | Zr 36.1Fe 35.9Ce 4.3Si 12.5Al 11.2 |
| 5 | Catalyst-5 | Zr 35.8Fe 36.4Ru 2.4Si 11.7Al 13.7 |
| 6 | Catalyst-6 | Zr 40.0Fe 42.2Ru 1.4Si 7.7Al 8.7 |
| 7 | Catalyst-7 | Zr 35.8Fe 36.4Pd 2.4Si 11.7Al 13.7 |
| 8 | Catalyst-8 | Zr 35.8Fe 36.4Mn 1.2Ru 1.2Si 11.7Al 13.7 |
| 9 | Catalyst-9 | Zr 35.8Fe 36.4Co 0.3Ce 2.1Si 11.7Al 13.7 |
| 10 | Catalyst-10 | Zr 35.8Fe 36.4Ru 1.8Ce 0.6Si 11.7Al 13.7 |
| Comparative example 1 | D1 | Zr 45.8Fe 40.4Al 13.8 |
| Comparative example 2 | D2 | Zr 43.2Fe 44.0Si 12.8 |
| Comparative example 3 | D3 | Zr 49.5Fe 50.5 |
| Comparative example 4 | D4 | Zr 55.0Fe 45.0 |
* subscript represents the weight percentage of metal.
Test case 1-10
This test case illustrates and adopts catalyst provided by the invention, carries out the situation of CO hydrogenation reaction in fixed bed reactors.
At Catalyst packing 0.5g, reaction temperature is 300 DEG C, and reaction pressure is 0.5MPa, reaction time 100h, H
2/ CO=2, air speed 6000h
-1process conditions under react, reaction result is in table 2 or table 3.
Test case 11
This test case illustrates and adopts catalyst provided by the invention, carries out the situation of CO hydrogenation reaction in fixed bed reactors.
Carry out according to the method for test case 1-10, unlike, temperature is 330 DEG C, and reaction result is in table 3.
Table 2
Table 3
As can be seen from the result of table 2 and table 3, catalyst of the present invention is used for co hydrogenation and prepares low-carbon alkene, active high and selective good.
Test case 12-13
This test case illustrates and adopts catalyst provided by the invention, carries out the situation of CO hydrogenation reaction in fixed bed reactors.
At Catalyst packing 0.5g, reaction temperature is 300 DEG C, and reaction pressure is 0.5MPa, H
2/ CO=2, air speed 6000h
-1process conditions under react, reaction result is in table 4.
As can be seen from data in table 4, when catalyst of the present invention is used for CO hydrogenation reaction, there is higher activity, and after reaction for a long time, activity has no decline, this shows, catalyst stability of the present invention is also better.
Table 4
Test comparison example 1-4
In fixed bed reactors, carry out CO hydrogenation reaction according to the method for test case 1-10, unlike the use of catalyst be D1-D4, reaction result is in table 5.
Table 5
More than describe the preferred embodiment of the present invention in detail, but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention, can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to scope of the present invention.
It should be noted that in addition, each the concrete technical characteristic described in above-mentioned detailed description of the invention, in reconcilable situation, can be combined by any suitable mode.
In addition, also can be combined between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (11)
1. for a catalyst for CO Hydrogenation low-carbon alkene, it is characterized in that, this catalyst comprises: the zirconium of 20-80 % by weight, the iron of 5-60 % by weight, the silicon of 5-40 % by weight and the aluminium of 5-30 % by weight.
2. catalyst according to claim 1, wherein, described catalyst comprises: the zirconium of 35-38 % by weight, the iron of 24-39 % by weight, the silicon of 11-24 % by weight and the aluminium of 9-14 % by weight.
3. catalyst according to claim 2, wherein, described catalyst also comprises one or more metals in VIII race's metal beyond deironing, VII B race metal, IV B race metal, VI B race metal, I B race metal, II B race metal and rare earth metal except zirconium, and content is 0.5-15 % by weight.
4. catalyst according to claim 3, wherein, described catalyst also comprises one or more metals in manganese, cobalt, cerium and ruthenium, and content is 2-13 % by weight.
5. catalyst according to claim 3, wherein, described catalyst also comprises at least two kinds of metals in manganese, cobalt, cerium and ruthenium.
6. according to the catalyst in claim 1-5 described in any one, wherein, described catalyst is alloy catalyst.
7. catalyst according to claim 6, wherein, described catalyst is amorphous alloy catalyst.
8. CO Hydrogenation is for a method for low-carbon alkene, and the method comprises: by containing the unstripped gas of CO and hydrogen-containing gas and catalyst exposure, and it is characterized in that, described catalyst is the catalyst in claim 1-7 described in any one.
9. method according to claim 8, wherein, the condition of contact comprises: temperature is 200-500 DEG C.
10. method according to claim 9, wherein, described unstripped gas is synthesis gas, and the condition of contact comprises: temperature is 280-320 DEG C, and pressure is 0.1-15MPa, H
2be 0.5-10:1 with the mol ratio of CO.
11. methods according to Claim 8 in-10 described in any one, wherein, described contact is carried out in fixed bed reactors, and the condition of contact comprises: air speed is 500-100000h
-1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410222221.3A CN105080547B (en) | 2014-05-23 | 2014-05-23 | The catalyst and a kind of CO Hydrogenations of producing light olefins are hydrogenated with for the method for low-carbon alkene for CO |
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| 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 |
| CN107774298A (en) * | 2016-08-30 | 2018-03-09 | 中国石油化工股份有限公司 | Porous metals/molecular sieve composite catalyst, its preparation method and the purposes in preparing low-carbon olefin |
| CN107774281A (en) * | 2016-08-30 | 2018-03-09 | 中国石油化工股份有限公司 | The catalyst and preparation method and the method for co hydrogenation producing light olefins of a kind of co hydrogenation producing light olefins |
| CN109647292A (en) * | 2017-10-10 | 2019-04-19 | 中国石油化工股份有限公司 | A method of using fluidized bed by preparing low-carbon olefin |
| 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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| 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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