CN104275189B - Catalyst of high temperature sintering type preparation of low carbon olefines by synthetic gas and preparation method thereof - Google Patents
Catalyst of high temperature sintering type preparation of low carbon olefines by synthetic gas and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of high temperature sintering type preparation of low carbon olefines by synthetic gas catalyst and preparation method thereof, CO conversion ratios are low low with selectivity of light olefin in mainly solving the problems, such as the reaction of preparation of low carbon olefines by synthetic gas present in prior art.The catalyst that the present invention is used is in terms of parts by weight including following components：A) 10~40 parts of ferro elements or its oxide, b) 0.5~10 part of at least one element or its oxide being selected from titanium and chromium；C) 1~10 part of at least one element or its oxide being selected from magnesium and calcium；D) 0.5~10 part of potassium element or its oxide；E) 30~88 parts of technical schemes of carrier alpha-aluminium oxide, preferably solve the problem, can be used for the industrial production of F- T synthesis preparing low-carbon olefins.
Description
Technical field
The present invention relates to a kind of catalyst of high temperature sintering type preparation of low carbon olefines by synthetic gas and preparation method thereof.
Background technology
Low-carbon alkene refers to alkene of the carbon number less than or equal to 4.Low-carbon alkene right and wrong with ethene, propylene as representative
Often important basic organic chemical industry raw material, with the rapid growth of China's economy, for a long time, low-carbon alkene market is not for should
Ask.At present, the production of low-carbon alkene mainly uses lighter hydrocarbons（Ethane, naphtha, light diesel fuel）The petrochemical industry route of cracking, due to
The long-term run at high level of increasingly shortage and crude oil price of Global Oil resource, development low-carbon alkene industry relies solely on petroleum light hydrocarbon
For the tube cracking furnace technique of raw material can run into increasing raw material problem, low-carbon alkene production technology and raw material must be polynary
Change.The direct preparing low-carbon olefins of one-step method from syngas be exactly carbon monoxide and hydrogen under catalyst action, it is anti-by F- T synthesis
The process of low-carbon alkene of the carbon number less than or equal to 4 should be directly obtained, the technique need not be as indirect method technique from conjunction
Into gas through methyl alcohol or dimethyl ether, alkene is further prepared, simplification of flowsheet greatly reduces investment.Petroleum resources are short at home
Lack, it is current that external dependence degree more and more higher, international oil price constantly rise violently, and former material can be widened from synthesis gas producing olefinic hydrocarbons technique
Material source, will produce synthesis gas by raw material of crude oil, natural gas, coal and recyclable materials, can be based on high cost raw material
Such as alternative solution is provided in terms of the steam cracking technology of naphtha.The coal price of the abundant coal resources of China and relative moderate
For Development of Coal is refined oil and provides the good market opportunity using preparation of low carbon olefines by synthetic gas technique.And it is abundant in Natural Gas In China
Oil gas field near, be also the fabulous opportunity using preparation of low carbon olefines by synthetic gas technique if Gas Prices are cheap.If energy
Using the coal and natural gas resource of China's abundant, by gas making producing synthesis gas（The gaseous mixture of carbon monoxide and hydrogen）, hair
The substitute energy source for petroleum technology of preparation of low carbon olefines by synthetic gas is opened up, will be significant to solving energy problem of China.
One-step method from syngas producing light olefins technology originates from traditional Fischer-Tropsch synthesis, traditional Fischer-Tropsch synthetic
Carbon number distribution defer to ASF distribution, each hydro carbons all have theoretical maximum selectivity, such as C2-C4The selectivity of cut is up to
57%, gasoline fraction (C5-C11) selectivity be up to 48%.Chain growth probability α values are bigger, and the selectivity of product heavy hydrocarbon is got over
Greatly.Once α values are determined, the selectivity of whole synthetic product is determined that, chain increase probability α values depend on catalyst constitute,
Granularity and reaction condition etc..In recent years, it has been found that due to the alkene secondary counter that alhpa olefin adsorbing again on a catalyst causes
Should, product distribution is away from ideal ASF distributions.F- T synthesis are a kind of strong exothermal reactions, and substantial amounts of reaction heat will promote catalyst
Carbon deposit reaction is easier generation methane and low-carbon alkanes, causes selectivity of light olefin significantly to decline；Secondly, complicated power
Factor also causes unfavorable to selectivity synthesis low-carbon alkene；The ASF distributions of Fischer-Tropsch synthetic limit synthesizing low-carbon alkene
Selectivity.The catalyst of F- T synthesis gas producing light olefins is mainly iron catalyst series, is directly made to improve synthesis gas
The selectivity of low-carbon alkene is taken, physics and chemical modification can be carried out to fischer-tropsch synthetic catalyst, as utilized molecular sieve suitable
Pore passage structure, is conducive to low-carbon alkene to diffuse out metal active centres in time, suppresses the secondary response of low-carbon alkene；Improve gold
Category ion dispersiveness, also there is preferable olefine selective；Support-metal strong interaction changes can also improve low-carbon alkene choosing
Selecting property；The suitable transition metal of addition, can strengthen the bond energy of active component and carbon, suppress methane generation, improve low-carbon alkene
Selectivity；Addition electronics accelerating auxiliaries, promote CO chemisorbeds heat to increase, and adsorbance also increases, and hydrogen adsorptive capacity reduces, as a result
Selectivity of light olefin increases；Catalyst acid center is eliminated, the secondary response of low-carbon alkene can be suppressed, improve its selectivity.
By the Support effect and addition some transition metal promoters and alkali metal promoter of catalyst carrier, catalyst performance is can obviously improve
Can, develop the fischer-tropsch synthetic catalyst of the novel high-activity high selectivity producing light olefins with the non-ASF distributions of product.
One-step method from syngas is directly produced low-carbon alkene, it has also become one of study hotspot of fischer-tropsch synthetic catalyst exploitation.
In patent CN1083415A disclosed in Dalian Chemiclophysics Inst., Chinese Academy of Sciences, with the Group IIA such as MgO alkali metal oxide or silicon high
Zeolite molecular sieve（Or phosphorus aluminium zeolite）The iron for supporting-Mn catalyst system, makees auxiliary agent, in synthesis gas system with highly basic K or Cs ion
Low-carbon alkene reaction pressure is 1.0 ~ 5.0MPa, at 300 ~ 400 DEG C of reaction temperature, can obtain activity higher（CO conversion ratios
90%）And selectivity（Selectivity of light olefin 66%）.But catalyst preparation process complexity, particularly carrier zeolite molecular sieve
Prepare shaping process cost higher, be unfavorable for industrialized production.The number of patent application that Beijing University of Chemical Technology is declared
In 01144691.9, laser pyrolysis processes combination solid phase reaction combination technique is used to be prepared for Fe3Fe base nano-catalytics based on C
Agent is applied to preparation of low carbon olefines by synthetic gas, and achieves good catalytic effect, due to needing to use laser pyrolysis technology, prepares
Technics comparing is cumbersome, and raw material uses Fe (CO)5, catalyst cost is very high, and industrialization is difficult.It is special that Beijing University of Chemical Technology is declared
In sharp ZL03109585.2, vacuum impregnation technology is used to prepare manganese, copper, zinc silicon, potassium etc. for the Fe/ activated-carbon catalysts of auxiliary agent are used for
Preparation of low carbon olefines by synthetic gas reacts, under conditions of being circulated without unstripped gas, CO conversion ratios 96%, and low-carbon alkene is in hydrocarbon
In selectivity 68%.The molysite and auxiliary agent manganese salt that the catalyst preparation is used are more expensive and less soluble ferric oxalate and acetic acid
Manganese, while with ethanol as solvent, just unavoidably increasing the cost of material and running cost of catalyst preparation process.For further
The cost of catalyst is reduced, in its number of patent application 200710063301.9, catalyst uses common medicine and reagent system
It is standby, the molysite for using be ferric nitrate, manganese salt is manganese nitrate, and sylvite is potassium carbonate, and activated carbon is coconut husk charcoal, can catalyst must stream
High-temperature roasting and Passivation Treatment are carried out under dynamic nitrogen protection, it is necessary to special installation, preparation process is complicated, relatively costly.And it is above-mentioned
CO conversion ratio and selectivity of light olefin of the catalyst in fixed bed reaction are relatively low.
The content of the invention
The technical problems to be solved by the invention are CO conversion ratios in F- T synthesis preparing low carbon olefin hydrocarbon in the prior art
A kind of low problem of selectivity of light olefin in low and product, there is provided new high temperature sintering type preparation of low carbon olefines by synthetic gas catalysis
Agent, it is high with selectivity of light olefin in CO high conversion rates and product when the catalyst is used for the reaction of F- T synthesis low-carbon alkene
Advantage.
In order to solve the above technical problems, the technical solution adopted by the present invention is as follows：A kind of high temperature sintering type synthesis gas system is low
The catalyst of carbon olefin, including following components in terms of parts by weight：
A) 10~40 parts of ferro elements or its oxide；
B) 0.5~10 part of at least one element or its oxide being selected from titanium and chromium；
C) 1~10 part of at least one element or its oxide being selected from magnesium and calcium；
D) 0.5~10 part of potassium element or its oxide；
E) 30~88 parts of carrier Alpha-aluminas.
In above-mentioned technical proposal, preferred scheme be in terms of parts by weight, catalyst also include 0.1~1 part rhenium element or
Its oxide；The preferred scheme of the oxide of iron is magnetic iron ore（Fe3O4）Or bloodstone（Fe2O3）；The oxide of titanium and chromium it is excellent
Scheme respectively titanium oxide and chromium oxide are selected, the preferred scope of content is 8~8.5 parts；The preferred scheme of the oxide of magnesium and calcium
Respectively magnesia and calcium oxide, the preferred scope of content is 1.5~4.5 parts；
In above-mentioned technical proposal, the preparation method of described high temperature sintering type preparation of low carbon olefines by synthetic gas catalyst, including
Following steps：
（1）By the oxide of the oxide of iron, titaniferous or chromium, the oxide containing magnesium or calcium, the salt containing potassium and carrier α-oxygen
Ground in ball mill after at least one mixing in change aluminium, and carbon powder or graphite powder after mixing, obtain material A；
（2）Material B is obtained by deionized water addition material A, mediate；
（3）Material C will be obtained after material B shaping and dryings；
（4）After material C high temperature sinterings, cooling crushing and screening obtains required catalyst.
In above-mentioned technical proposal, the preparation method of described high temperature sintering type preparation of low carbon olefines by synthetic gas catalyst, step
(1) the raw material also oxide including rhenium-containing in；Salt containing potassium is potassium carbonate；Carbon powder or graphite powder consumption are all raw material gross weights
The 2~5% of amount；Deionized water consumption is the 1~10% of all raw material gross weights, and all raw material gross weights are the oxide of iron, contain
The oxide of titanium or chromium, the oxide containing magnesium or calcium, the salt containing potassium, the oxide of rhenium-containing, carrier Alpha-alumina, carbon powder or stone
The weight of ink powder and；The preferred scope that mill is done time is 1 ~ 5 hour；The preferred scope of high temperature sintering temperature is 1200~1800
℃。
In above-mentioned technical proposal, the high temperature sintering type preparation of low carbon olefines by synthetic gas catalyst is used for synthesis of gas produced low-carbon alkene
Hydrocarbon reaction, with synthesis gas as raw material, H2It is 1 ~ 3 with the mol ratio of CO, is 250 ~ 400 DEG C in reaction temperature, reaction pressure is
1.0 ~ 3.0Mpa, feed gas volume air speed is 500 ~ 5000h-1Under conditions of, unstripped gas is generated with the catalyst haptoreaction
Containing C2~C4Alkene.
The inventive method uses and transition metal Ti or Cr, alkaline-earth metal Mg or Ca, alkali is introduced in catalyst activity component
Metal K and transition metal Re, can be with the electron valence state of modulation active component Fe, so as to be conducive to raising to urge used as catalyst promoter
The CO conversion ratios and the selectivity of low-carbon alkene of agent, particularly when transition metal Re is added, due to Re and other activearms
/ synergy, can effectively discharge the activity of catalyst, improve the conversion ratio of CO and the selectivity of low-carbon alkene, obtain
Good technique effect.
The inventive method obtains high-strength using active component, co-catalysis component and carrier are uniformly mixed through high temperature sintering
The good catalyst of degree, heat endurance, even if having crushed in use but being unlikely to crush, can keep catalyst activity
Stabilization.
The inventive method uses and carbon powder or graphite powder is added in catalyst preparation, because carbon powder tool more has big ratio
Surface and abundant pore structure, are more easy to it is reacted generation with oxygen at high temperature carbon monoxide and carbon dioxide on a catalyst
Leave a void, increase the macroporous structure of catalyst, inside diffusional resistance is reduced.Increase carbon powder consumption, can increase outside catalyst
Surface area, improves the reactivity of catalyst.
The use condition of the catalyst is as follows：With H2It is raw material, H with the synthesis gas that CO is constituted2With the mol ratio of CO for 1 ~
3, it is 250 ~ 400 DEG C in reaction temperature, reaction pressure is 1.0 ~ 3.0Mpa, and feed gas volume air speed is 500 ~ 2500h-1Condition
Under, unstripped gas is contacted with fixed bed catalyst, achieves preferable technique effect：CO conversion ratios compare prior art up to 99.6%
Improve 3.6%；Selectivity of the low-carbon alkene in hydrocarbon improves 7.5%, in more detail up to 75.5% than prior art
Result sees attached list.It is a kind of preferable synthesis gas production low-carbon alkene using catalyst F- T synthesis under these conditions
Method.
Below by embodiment, the invention will be further elaborated.
Specific embodiment
【Embodiment 1】
Weigh 19.0 grams of magnetic iron ores（Fe3O4）, 8.0 grams of titanium oxide（TiO2）, 2.5 grams of magnesia（MgO）, 0.9 gram of potassium carbonate
（K2CO3）With 70.0 grams of Alpha-aluminas（α-Al2O3）Five kinds of raw materials and percentage by weight is 3% carbon powder based on raw material total amount
3 grams, grind mixed 2 hours in ball mill；5 grams of the deionized water of add weight percentage 5% is added to and grinds mixed based on raw material total amount
In material, mediated to soft shape；In kneaded material feeding banded extruder, the strip of a diameter of 5mm is made, and cut into
Length is the column of 20mm, standby in 120 DEG C of dryings 8 hours in feeding drying equipment after drying naturally；Before dried
Body, in feeding high temperature furnace, calcines 6.0 hours in 1400 DEG C, and crushing and screening obtains required high temperature into 60 ~ 80 mesh after cooling
Sintered catalyst.Obtained catalyst by weight percentage, comprising following components：19% Fe3O4, 8% TiO2, 2.5%
MgO, 0.5% K2O, 70% α-Al2O3；Obtained catalyst carries out preparation of low carbon olefines by synthetic gas under certain reaction condition,
Experimental result is listed in table 1.
【Embodiment 2】
Weigh 19.0 grams of magnetic iron ores（Fe3O4）, 8.0 grams of titanium oxide（TiO2）, 2.5 grams of magnesia（MgO）, 0.9 gram of potassium carbonate
（K2CO3）, 0.1 gram of rhenium dioxide（ReO2）With 69.9 grams of Alpha-aluminas（α-Al2O3）Six kinds of raw materials and by raw material total amount count weight
Amount percentage is 3% 3 grams of carbon powder, grinds mixed 2 hours in ball mill；Based on raw material total amount add weight percentage 5% go from
5 grams of sub- water is added in the mixed material of mill, is mediated to soft shape；In kneaded material feeding banded extruder, it is made straight
Footpath is the strip of 5mm, and cuts into the column that length is 20mm, after drying naturally, in feeding drying equipment, in 120 DEG C of dryings 8
Hour is standby；By dried precursor, in feeding high temperature furnace, calcined 6.0 hours in 1400 DEG C, after cooling crushing and screening into 60 ~
80 mesh, that is, obtain required high temperature sintering type catalyst.Obtained catalyst by weight percentage, comprising following components：19%
Fe3O4, 8% TiO2, 2.5% MgO, 0.5% K2O, 0.1%ReO2, 69.9% α-Al2O3；Obtained catalyst is certain anti-
Preparation of low carbon olefines by synthetic gas is carried out under the conditions of answering, experimental result is listed in table 1.
【Embodiment 3】
Weigh 19.0 grams of magnetic iron ores（Fe3O4）, 8.0 grams of titanium oxide（TiO2）, 2.5 grams of magnesia（MgO）, 0.9 gram of potassium carbonate
（K2CO3）, 1.0 grams of rhenium dioxides（ReO2）With 70.0 grams of Alpha-aluminas（α-Al2O3）Six kinds of raw materials and by raw material total amount count weight
Amount percentage is 3% 3 grams of carbon powder, grinds mixed 2 hours in ball mill；Based on raw material total amount add weight percentage 5% go from
5 grams of sub- water is added in the mixed material of mill, is mediated to soft shape；In kneaded material feeding banded extruder, it is made straight
Footpath is the strip of 5mm, and cuts into the column that length is 20mm, after drying naturally, in feeding drying equipment, in 120 DEG C of dryings 8
Hour is standby；By dried precursor, in feeding high temperature furnace, calcined 6.0 hours in 1400 DEG C, after cooling crushing and screening into 60 ~
80 mesh, that is, obtain required high temperature sintering type catalyst.Obtained catalyst by weight percentage, comprising following components：19%
Fe3O4, 8% TiO2, 2.5% MgO, 0.5% K2O, 1%ReO2, 69% α-Al2O3；Obtained catalyst is in certain reaction bar
Preparation of low carbon olefines by synthetic gas is carried out under part, experimental result is listed in table 1.
【Embodiment 4】
Weigh 10 grams of magnetic iron ores（Fe2O3）, 0.5 gram of chromium oxide（Cr2O3）, 1 gram of calcium oxide（CaO）, 0.73 gram of potassium carbonate
（K2CO3）With 88 grams of Alpha-aluminas（α-Al2O3）Five kinds of raw materials and percentage by weight grinds mixed in ball mill based on raw material total amount
1 hour；During 5 grams of the deionized water of add weight percentage 5% enters to grind mixed material based on raw material total amount, mediated to softness
Shape；In kneaded material feeding banded extruder, the strip of a diameter of 5mm is made, and cuts into the column that length is 20mm, it is natural
It is standby in 120 DEG C of dryings 8 hours in feeding drying equipment after drying；By dried precursor, in feeding high temperature furnace, in 1600
DEG C calcining 6.0 hours, crushing and screening obtains required high temperature sintering type catalyst into 60 ~ 80 mesh after cooling.Obtained catalysis
Agent by weight percentage, comprising following components：10% Fe2O3, 0.5% Cr2O3, 1% CaO, 0.5% K2O, 88% α-
Al2O3；Obtained catalyst carries out preparation of low carbon olefines by synthetic gas under certain reaction condition, and experimental result is listed in table 1.
【Embodiment 5】
Weigh 40 grams of magnetic iron ores（Fe3O4）, 10 grams of titanium oxide（TiO2）, 10 grams of calcium oxide（CaO）, 14.7 grams of potassium carbonate
（K2CO3）With 30 grams of Alpha-aluminas（α-Al2O3）Five kinds of raw materials and based on raw material total amount percentage by weight 3% carbon powder 1.5
Gram and 1.5 grams of graphite powder, ground in ball mill mixed 5 hours；5 grams of the deionized water of add weight percentage 5% enters based on raw material total amount
In the mixed material of mill, mediated to soft shape；In kneaded material feeding banded extruder, the strip of a diameter of 5mm is made,
And the column that length is 20mm is cut into, it is standby in 120 DEG C of dryings 8 hours in feeding drying equipment after drying naturally；Will be dry
Dry good precursor, in feeding high temperature furnace, calcines 6.0 hours in 1800 DEG C, and crushing and screening obtains institute into 60 ~ 80 mesh after cooling
The high temperature sintering type catalyst for needing.Obtained catalyst by weight percentage, comprising following components：40% Fe3O4, 10%
TiO2, 10% CaO, 10% K2O, 30% α-Al2O3；Obtained catalyst carries out synthesis gas system under certain reaction condition
Low-carbon alkene, experimental result is listed in table 1.
【Embodiment 6】
Weigh 35.5 grams of bloodstone（Fe2O3）, 8.5 grams of chromium oxide（Cr2O3）, 4.2 grams of magnesia（MgO）, 6.2 grams of carbonic acid
Potassium（K2CO3）With 50.0 grams of Alpha-aluminas（α-Al2O3）Five kinds of raw materials and based on raw material total amount percentage by weight 3% carbon powder
3.0 grams, grind mixed 2 hours in ball mill；5 grams of the deionized water of add weight percentage 5% enters to grind mixed thing based on raw material total amount
In material, mediated to soft shape；In kneaded material feeding banded extruder, the strip of a diameter of 5mm, and cut growth are made
The column for 20mm is spent, it is standby in 120 DEG C of dryings 8 hours in feeding drying equipment after drying naturally；By dried precursor,
In feeding high temperature furnace, calcined 6.0 hours in 1200 DEG C, crushing and screening obtains required high temperature sintering into 60 ~ 80 mesh after cooling
Type catalyst.Obtained catalyst by weight percentage, comprising following components：35.5% Fe2O3, 8.5% Cr2O3, 4.2%
MgO, 1.8% K2O, 50% α-Al2O3；Obtained catalyst carries out preparation of low carbon olefines by synthetic gas under certain reaction condition,
Experimental result is listed in table 1.
【Embodiment 7】
Weigh 43.3 grams of magnetic iron ores（Fe3O4）, 8.5 grams of chromium oxide（Cr2O3）, 1.6 grams of calcium oxide（CaO）, 9.7 grams of carbonic acid
Potassium（K2CO3）With 40.0 grams of Alpha-aluminas（α-Al2O3）Five kinds of raw materials and based on raw material total amount percentage by weight 5% carbon powder
5.0 grams, grind mixed 2 hours in ball mill；5 grams of the deionized water of add weight percentage 5% enters to grind mixed thing based on raw material total amount
In material, mediated to soft shape；In kneaded material feeding banded extruder, the strip of a diameter of 5mm, and cut growth are made
The column for 20mm is spent, it is standby in 120 DEG C of dryings 8 hours in feeding drying equipment after drying naturally；By dried precursor,
In feeding high temperature furnace, calcined 6.0 hours in 1400 DEG C, crushing and screening obtains required high temperature sintering into 60 ~ 80 mesh after cooling
Type catalyst.Obtained catalyst by weight percentage, comprising following components：43.3% Fe3O4, 8.5% Cr2O3, 1.6%
CaO, 6.6% K2O, 40% α-Al2O3；Obtained catalyst carries out preparation of low carbon olefines by synthetic gas under certain reaction condition,
Experimental result is listed in table 1.
【Embodiment 8】
Weigh 35.5 grams of bloodstone（Fe2O3）, 8.5 grams of chromium oxide（Cr2O3）, 4.2 grams of magnesia（MgO）, 6.2 grams of carbonic acid
Potassium（K2CO3）With 50.0 grams of Alpha-aluminas（α-Al2O3）Five kinds of raw materials and based on raw material total amount percentage by weight 2% carbon powder
2.0 grams, grind mixed 2 hours in ball mill；5 grams of the deionized water of add weight percentage 5% enters to grind mixed thing based on raw material total amount
In material, mediated to soft shape；In kneaded material feeding banded extruder, the strip of a diameter of 5mm, and cut growth are made
The column for 20mm is spent, it is standby in 120 DEG C of dryings 8 hours in feeding drying equipment after drying naturally；By dried precursor,
In feeding high temperature furnace, calcined 6.0 hours in 1200 DEG C, crushing and screening obtains required high temperature sintering into 60 ~ 80 mesh after cooling
Type catalyst.Obtained catalyst by weight percentage, comprising following components：35.5% Fe2O3, 8.5% Cr2O3, 4.2%
MgO, 1.8% K2O, 50% α-Al2O3；Obtained catalyst carries out preparation of low carbon olefines by synthetic gas under certain reaction condition,
Experimental result is listed in table 1.
【Embodiment 9】
Weigh 35.5 grams of bloodstone（Fe2O3）, 8.5 grams of chromium oxide（Cr2O3）, 4.2 grams of magnesia（MgO）, 6.2 grams of carbonic acid
Potassium（K2CO3）With 50.0 grams of Alpha-aluminas（α-Al2O3）Five kinds of raw materials and based on raw material total amount percentage by weight 5% carbon powder
5.0 grams, grind mixed 2 hours in ball mill；5 grams of the deionized water of add weight percentage 5% enters to grind mixed thing based on raw material total amount
In material, mediated to soft shape；In kneaded material feeding banded extruder, the strip of a diameter of 5mm, and cut growth are made
The column for 20mm is spent, it is standby in 120 DEG C of dryings 8 hours in feeding drying equipment after drying naturally；By dried precursor,
In feeding high temperature furnace, calcined 6.0 hours in 1200 DEG C, crushing and screening obtains required high temperature sintering into 60 ~ 80 mesh after cooling
Type catalyst.Obtained catalyst by weight percentage, comprising following components：35.5% Fe2O3, 8.5% Cr2O3, 4.2%
MgO, 1.8% K2O, 50% α-Al2O3；Obtained catalyst carries out preparation of low carbon olefines by synthetic gas under certain reaction condition,
Experimental result is listed in table 1.
【Embodiment 10】
Weigh 35.5 grams of bloodstone（Fe2O3）, 8.5 grams of chromium oxide（Cr2O3）, 4.2 grams of magnesia（MgO）, 6.2 grams of carbonic acid
Potassium（K2CO3）With 50.0 grams of Alpha-aluminas（α-Al2O3）Five kinds of raw materials and based on raw material total amount percentage by weight 3% carbon powder
3.0 grams, grind mixed 2 hours in ball mill；1 gram of the deionized water of add weight percentage 1% enters to grind mixed thing based on raw material total amount
In material, mediated to soft shape；In kneaded material feeding banded extruder, the strip of a diameter of 5mm, and cut growth are made
The column for 20mm is spent, it is standby in 120 DEG C of dryings 8 hours in feeding drying equipment after drying naturally；By dried precursor,
In feeding high temperature furnace, calcined 6.0 hours in 1200 DEG C, crushing and screening obtains required high temperature sintering into 60 ~ 80 mesh after cooling
Type catalyst.Obtained catalyst by weight percentage, comprising following components：35.5% Fe2O3, 8.5% Cr2O3, 4.2%
MgO, 1.8% K2O, 50% α-Al2O3；Obtained catalyst carries out preparation of low carbon olefines by synthetic gas under certain reaction condition,
Experimental result is listed in table 1.
【Embodiment 11】
Weigh 35.5 grams of bloodstone（Fe2O3）, 8.5 grams of chromium oxide（Cr2O3）, 4.2 grams of magnesia（MgO）, 6.2 grams of carbonic acid
Potassium（K2CO3）With 50.0 grams of Alpha-aluminas（α-Al2O3）Five kinds of raw materials and based on raw material total amount percentage by weight 3% carbon powder
3.0 grams, grind mixed 2 hours in ball mill；10 grams of the deionized water of add weight percentage 10% enters to grind mixed based on raw material total amount
In material, mediated to soft shape；In kneaded material feeding banded extruder, the strip of a diameter of 5mm is made, and cut into
Length is the column of 20mm, standby in 120 DEG C of dryings 8 hours in feeding drying equipment after drying naturally；Before dried
Body, in feeding high temperature furnace, calcines 6.0 hours in 1200 DEG C, and crushing and screening obtains required high temperature into 60 ~ 80 mesh after cooling
Sintered catalyst.Obtained catalyst by weight percentage, comprising following components：35.5% Fe2O3, 8.5% Cr2O3,
4.2% MgO, 1.8% K2O, 50% α-Al2O3；Obtained catalyst carries out synthesis of gas produced low-carbon under certain reaction condition
Alkene, experimental result is listed in table 1.
【Embodiment 12】
The catalyst that embodiment 1 is prepared is used for synthesis gas olefine reaction, and reaction condition and reaction result are shown in Table
2。
【Comparative example 1】
Weigh 35.5 grams of bloodstone（Fe2O3）, 8.5 grams of chromium oxide（Cr2O3）, 4.2 grams of magnesia（MgO）, 6.2 grams of carbonic acid
Potassium（K2CO3）With 50.0 grams of Alpha-aluminas（α-Al2O3）Five kinds of raw materials and based on raw material total amount percentage by weight 1% carbon powder
1.0 grams, grind mixed 2 hours in ball mill；5 grams of the deionized water of add weight percentage 5% enters to grind mixed thing based on raw material total amount
In material, mediated to soft shape；In kneaded material feeding banded extruder, the strip of a diameter of 5mm, and cut growth are made
The column for 20mm is spent, it is standby in 120 DEG C of dryings 8 hours in feeding drying equipment after drying naturally；By dried precursor,
In feeding high temperature furnace, calcined 6.0 hours in 1200 DEG C, crushing and screening obtains required high temperature sintering into 60 ~ 80 mesh after cooling
Type catalyst.Obtained catalyst by weight percentage, comprising following components：35.5% Fe2O3, 8.5% Cr2O3, 4.2%
MgO, 1.8% K2O, 50% α-Al2O3；Obtained catalyst carries out preparation of low carbon olefines by synthetic gas under certain reaction condition,
Experimental result is listed in table 1.
【Comparative example 2】
Weigh 35.5 grams of bloodstone（Fe2O3）, 8.5 grams of chromium oxide（Cr2O3）, 4.2 grams of magnesia（MgO）, 6.2 grams of carbonic acid
Potassium（K2CO3）With 50.0 grams of Alpha-aluminas（α-Al2O3）Five kinds of raw materials and based on raw material total amount percentage by weight 6% carbon powder
6.0 grams, grind mixed 2 hours in ball mill；5 grams of the deionized water of add weight percentage 5% enters to grind mixed thing based on raw material total amount
In material, mediated to soft shape；In kneaded material feeding banded extruder, the strip of a diameter of 5mm, and cut growth are made
The column for 20mm is spent, it is standby in 120 DEG C of dryings 8 hours in feeding drying equipment after drying naturally；By dried precursor,
In feeding high temperature furnace, calcined 6.0 hours in 1200 DEG C, crushing and screening obtains required high temperature sintering into 60 ~ 80 mesh after cooling
Type catalyst.Obtained catalyst by weight percentage, comprising following components：35.5% Fe2O3, 8.5% Cr2O3, 4.2%
MgO, 1.8% K2O, 50% α-Al2O3；Obtained catalyst carries out preparation of low carbon olefines by synthetic gas under certain reaction condition,
Experimental result is listed in table 1.
【Comparative example 3】
Weigh 35.5 grams of bloodstone（Fe2O3）, 8.5 grams of chromium oxide（Cr2O3）, 4.2 grams of magnesia（MgO）, 6.2 grams of carbonic acid
Potassium（K2CO3）With 50.0 grams of Alpha-aluminas（α-Al2O3）Five kinds of raw materials and based on raw material total amount percentage by weight 3% carbon powder
3.0 grams, ground in ball mill after mixing 1 ~ 2 hour；Mediated again to soft shape；In kneaded material feeding banded extruder, system
Into the strip of a diameter of 5mm, and the column that length is 20mm is cut into, after drying naturally, in feeding drying equipment, in 120 DEG C
Dry 8 hours standby；By dried precursor, in feeding high temperature furnace, calcined 6.0 hours in 1200 DEG C, crushing and screening after cooling
Into 60 ~ 80 mesh, that is, obtain required high temperature sintering type catalyst.Obtained catalyst by weight percentage, comprising with the following group
Point：35.5% Fe2O3, 8.5% Cr2O3, 4.2% MgO, 1.8% K2O, 50% α-Al2O3；Obtained catalyst is certain anti-
Preparation of low carbon olefines by synthetic gas is carried out under the conditions of answering, experimental result is listed in table 1.
【Comparative example 4】
Weigh 35.5 grams of bloodstone（Fe2O3）, 8.5 grams of chromium oxide（Cr2O3）, 4.2 grams of magnesia（MgO）, 6.2 grams of carbonic acid
Potassium（K2CO3）With 50.0 grams of Alpha-aluminas（α-Al2O3）Five kinds of raw materials and based on raw material total amount percentage by weight 3% carbon powder
3.0 grams, grind mixed 2 hours in ball mill；12 grams of the deionized water of add weight percentage 12% enters to grind mixed based on raw material total amount
In material, mediated to soft shape；In kneaded material feeding banded extruder, the strip of a diameter of 5mm is made, and cut into
Length is the column of 20mm, standby in 120 DEG C of dryings 8 hours in feeding drying equipment after drying naturally；Before dried
Body, in feeding high temperature furnace, calcines 6.0 hours in 1200 DEG C, and crushing and screening obtains required high temperature into 60 ~ 80 mesh after cooling
Sintered catalyst.Obtained catalyst by weight percentage, comprising following components：35.5% Fe2O3, 8.5% Cr2O3,
4.2% MgO, 1.8% K2O, 50% α-Al2O3；Obtained catalyst carries out synthesis of gas produced low-carbon under certain reaction condition
Alkene, experimental result is listed in table 1.
Above-described embodiment is with the reducing condition of comparative example：
450 DEG C of temperature
Pressure normal pressure
The ml of loaded catalyst 3
Catalyst loading 1000 hours-1
Also Primordial Qi H2
8 hours recovery times
Reaction condition is：
8 millimeters of fixed bed reactors of φ
340 DEG C of reaction temperature
Reaction pressure 1.2MPa
The ml of loaded catalyst 3
Catalyst loading 1000 hours-1
Raw material proportioning (mole) H2/ CO=1.5/1
Table 1
Table 2
* the appreciation condition for changing compared with the condition described in table 1.
Claims (8)
1. a kind of high temperature sintering type preparation of low carbon olefines by synthetic gas catalyst, including following components in terms of parts by weight：
A) 10~40 parts of ferro elements or its oxide；
B) 0.5~10 part is selected from titanium elements or its oxide；
C) 1~10 part of at least one element or its oxide being selected from magnesium and calcium；
D) 0.5~10 part of potassium element or its oxide；
E) 30~88 parts of carrier Alpha-aluminas；
In terms of parts by weight, catalyst also includes 0.1~1 part of rhenium element or its oxide.
2. high temperature sintering type preparation of low carbon olefines by synthetic gas catalyst according to claim 1, it is characterised in that described iron
Oxide be magnetic iron ore (Fe3O4) or bloodstone (Fe2O3)。
3. high temperature sintering type preparation of low carbon olefines by synthetic gas catalyst according to claim 1, it is characterised in that the titanium is
Titanium oxide, content is 8~8.5 parts.
4. high temperature sintering type preparation of low carbon olefines by synthetic gas catalyst according to claim 1, it is characterised in that described magnesium
Magnesia and calcium oxide are respectively with the oxide of calcium, content is 1.5~4.5 parts.
5. the preparation method of the high temperature sintering type preparation of low carbon olefines by synthetic gas catalyst described in any one of Claims 1 to 4, including
Following steps：
(1) by the oxide of iron, containing titanyl compound, the oxide containing magnesium or calcium, the salt containing potassium, rhenium-containing oxide and carrier
Grind mixed in ball mill after at least one mixing in Alpha-alumina, and carbon powder or graphite powder, obtain material A；
(2) in deionized water addition material A, will mediate and obtain material B；
(3) material C will be obtained after material B shaping and dryings；
(4) will cool down crushing and screening and obtain required catalyst after material C high temperature sinterings, the temperature of high temperature sintering for 1200~
1800℃。
6. the preparation method of high temperature sintering type preparation of low carbon olefines by synthetic gas catalyst according to claim 5, its feature exists
In described carbon powder or graphite powder consumption is all raw material gross weights 2~5%.
7. the preparation method of high temperature sintering type preparation of low carbon olefines by synthetic gas catalyst according to claim 5, its feature exists
In described deionized water consumption be the 1~10% of all raw material gross weights.
8. the high temperature sintering type preparation of low carbon olefines by synthetic gas catalyst described in any one of Claims 1 to 4 is used for synthesis gas system
Low-carbon alkene reacts, with synthesis gas as raw material, H2It is 1~3 with the mol ratio of CO, is 250~400 DEG C in reaction temperature, reaction
Pressure is 1.0~3.0Mpa, and feed gas volume air speed is 500~5000h-1Under conditions of, unstripped gas is contacted with the catalyst
Reaction generation contains C2~C4Alkene.
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