CN104549352B - The catalyst and its application method of synthesis gas production low-carbon alkene - Google Patents
The catalyst and its application method of synthesis gas production low-carbon alkene Download PDFInfo
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Abstract
The present invention relates to the catalyst and its application method of a kind of synthesis gas production low-carbon alkene, 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 present invention uses a kind of catalyst that low-carbon alkene is produced for synthesis gas, by weight percentage including following components：A) 5~50% ferro element or its oxide；B) 4~20% selected from manganese and zirconium at least one element or its oxide；C) 1~10% bismuth element or its oxide；D) 25~90% carrier, in terms of vehicle weight number, including following components（1）15~40 parts of alpha-aluminium oxides；（2）1~45 part of calcium oxide；（3）1~5 part of titanium dioxide；（4）1~20 part of technical scheme of potassium oxide, preferably solves the problem, can be used for the industrial production of fixed bed synthesis gas preparing low-carbon olefins.
Description
Technical field
The present invention relates to the catalyst and its application method of a kind of synthesis gas production low-carbon alkene.
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 that synthesis gas produces CO conversion ratios in low-carbon alkene technology in the prior art
The low problem of selectivity of light olefin in low and product, there is provided a kind of new synthesis gas produces the catalyst of low-carbon alkene and its makes
With method, when the catalyst is used for the reaction of fixed bed preparation of low carbon olefines by synthetic gas, with low-carbon (LC) alkene in CO high conversion rates and product
Hydrocarbon-selective advantage high.
In order to solve the above technical problems, the technical solution adopted by the present invention is as follows：One kind produces low-carbon (LC) alkene for synthesis gas
The catalyst of hydrocarbon, by weight percentage including following components：
A) 5~50% ferro element or its oxide；
B) 4~20% selected from manganese and zirconium at least one element or its oxide；
C) 1~10% bismuth element or its oxide；
D) 25~90% carrier, in terms of vehicle weight number, including following components（1）15~40 parts of Alpha-aluminas；（2）
1~45 part of calcium oxide；（3）1~5 part of titanium dioxide；（4）1~20 part of potassium oxide.
In above-mentioned technical proposal, the oxide of iron is di-iron trioxide in catalyst, in terms of catalyst weight percent, is contained
The preferred scope of amount is 10~40%；The oxide of manganese and zirconium is respectively manganese oxide and zirconium oxide in catalyst, with catalyst weight
Percentages, the preferred scope of content is 10~20%；The oxide of the bismuth described in catalyst is bismuth oxide, with catalyst weight
Amount percentages, the preferred scope of content is 1~5%.
In above-mentioned technical proposal, composite oxide carrier is high by Alpha-alumina, powdered whiting, titanium dioxide and potassium carbonate
Prepared by temperature sintering, calculated with vehicle weight number, and the preferred scope of Alpha-alumina content is 20~40 parts；Calcium oxide content it is excellent
It is 10~40 parts to select scope；The preferred scope of content of titanium dioxide is 3~5 parts；The preferred scope of potassium oxide content is 1~10
Part.
In above-mentioned technical proposal, synthesis gas used produces the preparation method of light olefins catalyst, comprises the following steps：
（1）Compound G is obtained after the mixed-powder of Alpha-alumina, powdered whiting and titanium dioxide is carried out into ball milling mixing
It is stand-by；
（2）By in potassium carbonate addition deionized water, until completely dissolved, carried out in the above-mentioned compound G of addition kneaded and formed
And drying, crushing and screening prepares composite oxide carrier H after high temperature sintering, cooling after drying；
（3）By molysite, manganese salt or zirconates and bismuth salt, it is dissolved in water deionized water and is made mixed solution I；
（4）Under the conditions of the kPa of vacuum 1 ~ 80, above-mentioned mixed solution I be impregnated in into the compound of forming in step (2)
On oxide carrier H catalyst precarsor J；
（5）Required catalyst will be obtained after catalyst precarsor J dryings, roasting.
In above-mentioned technical proposal, the preferred scope of high temperature sintering temperature is 1100~1600 DEG C, and high temperature sintering temperature is more
Preferred scope is 1200~1400 DEG C, and the preferred scope of sintering time is 1~6 hour, the more preferably scope of sintering time for 2~
4 hours, the preferred scope of the sintering temperature in step (5) was 450 ~ 750 DEG C, and the preferred scope of roasting time is 1.0 ~ 4.5 small
When.
A kind of method that synthesis gas produces low-carbon alkene, with synthesis gas as raw material, H2Mol ratio with CO is 1 ~ 3, anti-
It is 250 ~ 400 DEG C to answer temperature, and reaction pressure is 1.0 ~ 3.0Mpa, and feed gas volume air speed is 500 ~ 5000h-1Under conditions of, it is former
Material gas contains C with catalyst haptoreaction generation2~C4Alkene.
The catalyst that the inventive method is used is prepared by vacuum impregnation technology, can make active component and auxiliary agent high uniformity
Complex sintered Oxide-supports are scattered in, increase improves the conversion ratio of CO exposed to the quantity of the active sites of carrier surface.
Transient metal Mn or Zr are introduced in the catalyst that the inventive method is used as catalyst promoter, can be with modulation activity
The electron valence state of component Fe, particularly introduces main group metal Bi, can not only be urged with modulation active component electron valence state, and enhancing
The interaction strength of agent active component and carrier, so as to be conducive to improving the selectivity of light olefin of catalyst.
Calcium oxide and potassium oxide are added in the catalyst complex carrier that the inventive method is used, catalyst is not only greatly reduced
Surface acidity, improves selectivity of light olefin, and improves anti-carbon effect, reduces area carbon generation；Introduced in carrier suitable
Amount titanium dioxide, as stabilizer, high temperature sintering is molded together with Alpha-alumina, is improved while keeping carrier loose structure and urged
The mechanical strength and heat endurance of agent.
The reaction condition of synthesis gas production low-carbon alkene is as follows：With H2It is raw material, H with the synthesis gas that CO is constituted2With CO's
Mol ratio be 1 ~ 3, reaction temperature be 250 ~ 400 DEG C, reaction pressure be 1.0 ~ 3.0Mpa, feed gas volume air speed be 500 ~
5000h-1Under conditions of, unstripped gas is contacted with above-mentioned catalyst, achieves preferable technique effect：CO conversion ratios up to 99.8%,
3.8% is improved than prior art；Selectivity of the low-carbon alkene in hydrocarbon is improved up to 75.9% than prior art
7.9%, more detailed result sees attached list.
The present invention is described further for the following examples, and protection scope of the present invention does not receive these embodiments
Limitation.
Specific embodiment
【Embodiment 1】
Weigh 45.0 grams of Alpha-aluminas（Al2O3）Powder and 40.1 grams of powdered whitings（CaCO3）Powder and 3.4 grams of titanium dioxide
（TiO2）Powder is well mixed, and grinds mixed 1 hour in ball mill, is made compound G stand-by；Weigh 11.5 grams of potassium carbonate
（K2CO3）, 30 ml deionized waters are added, until completely dissolved, add in the mixed compound G of above-mentioned mill, carry out kneading extruding
Shaping；Sintered 2 hours at a temperature of 1300 DEG C after drying, be made complex carrier, crushing and screening is into 60~80 mesh systems after cooling
It is standby go out composite oxide carrier H；By 101.2 grams of Fe(NO3)39H2Os, 25.2 gram 50% of manganese nitrate solution, 10.4 gram of five hydration
Bismuth nitrate, is dissolved in 35.0 grams of deionized waters and is made mixed solution I；Under conditions of vacuum 80kPa, by above-mentioned mixed solution
I impregnated on 70.0 grams of composite oxide carrier H for having prepared to obtain catalyst precarsor J；The catalyst precarsor J for having impregnated exists
Dried under the conditions of 110 DEG C, be then calcined, 600 DEG C of sintering temperature, roasting time 2h, that is, the synthesis gas production needed for obtaining
The catalyst of low-carbon alkene.Obtained catalyst by weight percentage, comprising following components：20% Fe2O3, 5% MnO, 5%
Bi2O3, 40% α-Al2O3, 20% CaO, 3% TiO2, 7% K2O；Obtained catalyst carries out synthesis gas life under certain condition
Low-carbon alkene reaction is produced, experimental result is listed in table 1.
【Embodiment 2】
Weigh 63.1 grams of Alpha-aluminas（Al2O3）Powder and 8.0 grams of powdered whitings（CaCO3）Powder and 9.0 grams of titanium dioxide
（TiO2）Powder is well mixed, and grinds mixed 1 hour in ball mill, is made compound G stand-by；Weigh 19.8 grams of potassium carbonate
（K2CO3）, 30 ml deionized waters are added, until completely dissolved, add in the mixed compound G of above-mentioned mill, carry out kneading extruding
Shaping；Sintered 2 hours at a temperature of 1300 DEG C after drying, be made complex carrier, crushing and screening is into 60~80 mesh systems after cooling
It is standby go out composite oxide carrier H；By 253.0 grams of Fe(NO3)39H2Os, 100.9 gram 50% of manganese nitrate solution, 10.4 gram of five hydration
Bismuth nitrate, is dissolved in 35.0 grams of deionized waters and is made mixed solution I；Under conditions of vacuum 80kPa, by above-mentioned mixed solution
I impregnated on 25.0 grams of composite oxide carrier H for having prepared to obtain catalyst precarsor J；The catalyst precarsor J for having impregnated exists
Dried under the conditions of 110 DEG C, be then calcined, 600 DEG C of sintering temperature, roasting time 2h, that is, the synthesis gas production needed for obtaining
The catalyst of low-carbon alkene.Obtained catalyst by weight percentage, comprising following components：50% Fe2O3, 20% MnO, 5%
Bi2O3, 17.5% α-Al2O3, 1.25% CaO, 2.5% TiO2, 3.75% K2O；Obtained catalyst enters under certain condition
Row synthesis gas production low-carbon alkene reaction, experimental result is listed in table 1.
【Embodiment 3】
Weigh 18.6 grams of Alpha-aluminas（Al2O3）Powder and 59.9 grams of powdered whitings（CaCO3）Powder and 0.7 gram of titanium dioxide
（TiO2）Powder is well mixed, and grinds mixed 1 hour in ball mill, is made compound G stand-by；Weigh 20.8 grams of potassium carbonate
（K2CO3）, 30 ml deionized waters are added, until completely dissolved, add in the mixed compound G of above-mentioned mill, carry out kneading extruding
Shaping；Sintered 2 hours at a temperature of 1300 DEG C after drying, be made complex carrier, crushing and screening is into 60~80 mesh systems after cooling
It is standby go out composite oxide carrier H；By 25.3 grams of Fe(NO3)39H2Os, 20.2 gram 50% of manganese nitrate solution, 2.1 gram of five hydration nitre
Sour bismuth, is dissolved in 35.0 grams of deionized waters and is made mixed solution I；Under conditions of vacuum 80kPa, by above-mentioned mixed solution I
Impregnated on 90.0 grams of composite oxide carrier H for having prepared to obtain catalyst precarsor J；The catalyst precarsor J for having impregnated is 110
Dried under the conditions of DEG C, be then calcined, 600 DEG C of sintering temperature, roasting time 2h, that is, the synthesis gas production low-carbon (LC) needed for obtaining
The catalyst of alkene.Obtained catalyst by weight percentage, comprising following components：5% Fe2O3, 4% MnO, 1% Bi2O3,
25% α-Al2O3, 45% CaO, 1% TiO2, 19% K2O；It is low that obtained catalyst carries out synthesis gas production under certain condition
Carbene hydrocarbon reaction, experimental result is listed in table 1.
【Embodiment 4】
Weigh 24.0 grams of Alpha-aluminas（Al2O3）Powder and 73.6 grams of powdered whitings（CaCO3）Powder and 1.0 grams of titanium dioxide
（TiO2）Powder is well mixed, and grinds mixed 1 hour in ball mill, is made compound G stand-by；Weigh 1.4 grams of potassium carbonate（K2CO3）,
30 ml deionized waters are added, until completely dissolved, is added in the mixed compound G of above-mentioned mill, carry out kneading extrusion forming；Dry
Sintered 2 hours at a temperature of 1300 DEG C after dry, be made complex carrier, crushing and screening is prepared compound into 60~80 mesh after cooling
Oxide carrier H；It is molten by 50.5 grams of Fe(NO3)39H2Os, 50.5 gram 50% of manganese nitrate solution, 20.8 gram of five nitric hydrate bismuth
Mixed solution I is made in 35.0 grams of deionized waters；Under conditions of vacuum 80kPa, above-mentioned mixed solution I impregnated in
On 70.0 grams of composite oxide carrier H for having prepared catalyst precarsor J；The catalyst precarsor J for having impregnated is in 110 DEG C of conditions
Lower drying, is then calcined, 600 DEG C of sintering temperature, roasting time 2h, that is, the synthesis gas production low-carbon alkene needed for obtaining
Catalyst.Obtained catalyst by weight percentage, comprising following components：10% Fe2O3, 10% MnO, 10% Bi2O3, 25%
α-Al2O3, 43% CaO, 1% TiO2, 1% K2O；Obtained catalyst carries out synthesis gas production low-carbon (LC) alkene under certain condition
Hydrocarbon reaction, experimental result is listed in table 1.
【Embodiment 5】
Weigh 34.8 grams of Alpha-aluminas（Al2O3）Powder and 31.0 grams of powdered whitings（CaCO3）Powder and 8.7 grams of titanium dioxide
（TiO2）Powder is well mixed, and grinds mixed 1 hour in ball mill, is made compound G stand-by；Weigh 25.5 grams of potassium carbonate
（K2CO3）, 30 ml deionized waters are added, until completely dissolved, add in the mixed compound G of above-mentioned mill, carry out kneading extruding
Shaping；Sintered 2 hours at a temperature of 1300 DEG C after drying, be made complex carrier, crushing and screening is into 60~80 mesh systems after cooling
It is standby go out composite oxide carrier H；By 202.4 grams of Fe(NO3)39H2Os, 50.5 gram 50% of manganese nitrate solution, 10.4 gram of five hydration
Bismuth nitrate, is dissolved in 35.0 grams of deionized waters and is made mixed solution I；Under conditions of vacuum 80kPa, by above-mentioned mixed solution
I impregnated on 45.0 grams of composite oxide carrier H for having prepared to obtain catalyst precarsor J；The catalyst precarsor J for having impregnated exists
Dried under the conditions of 110 DEG C, be then calcined, 600 DEG C of sintering temperature, roasting time 2h, that is, the synthesis gas production needed for obtaining
The catalyst of low-carbon alkene.Obtained catalyst by weight percentage, comprising following components：40% Fe2O3, 10% MnO, 5%
Bi2O3, 20% α-Al2O3, 10% CaO, 5% TiO2, 10% K2O；Obtained catalyst carries out synthesis gas under certain condition
Production low-carbon alkene reaction, experimental result is listed in table 1.
【Embodiment 6】
Weigh 23.8 grams of Alpha-aluminas（Al2O3）Powder and 73.7 grams of powdered whitings（CaCO3）Powder and 1.0 grams of titanium dioxide
（TiO2）Powder is well mixed, and grinds mixed 1 hour in ball mill, is made compound G stand-by；Weigh 1.5 grams of potassium carbonate（K2CO3）,
30 ml deionized waters are added, until completely dissolved, is added in the mixed compound G of above-mentioned mill, carry out kneading extrusion forming；Dry
Sintered 2 hours at a temperature of 1300 DEG C after dry, be made complex carrier, crushing and screening is prepared compound into 60~80 mesh after cooling
Oxide carrier H；It is molten by 50.6 grams of Fe(NO3)39H2Os, 100.9 gram 50% of manganese nitrate solution, 10.4 gram of five nitric hydrate bismuth
Mixed solution I is made in 35.0 grams of deionized waters；Under conditions of vacuum 80kPa, above-mentioned mixed solution I impregnated in
On 65.0 grams of composite oxide carrier H for having prepared catalyst precarsor J；The catalyst precarsor J for having impregnated is in 110 DEG C of conditions
Lower drying, is then calcined, 600 DEG C of sintering temperature, roasting time 2h, that is, the synthesis gas production low-carbon alkene needed for obtaining
Catalyst.Obtained catalyst by weight percentage, comprising following components：10% Fe2O3, 20% MnO, 5% Bi2O3, 23%
α-Al2O3, 40% CaO, 1% TiO2, 1% K2O；Obtained catalyst carries out synthesis gas production low-carbon (LC) alkene under certain condition
Hydrocarbon reaction, experimental result is listed in table 1.
【Embodiment 7】
Weigh 45.0 grams of Alpha-aluminas（Al2O3）Powder and 40.1 grams of powdered whitings（CaCO3）Powder and 3.4 grams of titanium dioxide
（TiO2）Powder is well mixed, and grinds mixed 1 hour in ball mill, is made compound G stand-by；Weigh 11.5 grams of potassium carbonate
（K2CO3）, 30 ml deionized waters are added, until completely dissolved, add in the mixed compound G of above-mentioned mill, carry out kneading extruding
Shaping；Sintered 2 hours at a temperature of 1300 DEG C after drying, be made complex carrier, crushing and screening is into 60~80 mesh systems after cooling
It is standby go out composite oxide carrier H；By 101.2 grams of Fe(NO3)39H2Os, 17.4 gram of five nitric hydrate zirconium, 10.4 gram of five nitric hydrate
Bismuth, is dissolved in 35.0 grams of deionized waters and is made mixed solution I；Under conditions of vacuum 80kPa, by the leaching of above-mentioned mixed solution I
Stain on 70.0 grams of composite oxide carrier H for having prepared catalyst precarsor J；The catalyst precarsor J for having impregnated is at 110 DEG C
Under the conditions of dry, be then calcined, 600 DEG C of sintering temperature, roasting time 2h, that is, obtain needed for synthesis gas production low-carbon (LC) alkene
The catalyst of hydrocarbon.Obtained catalyst by weight percentage, comprising following components：20% Fe2O3, 5% ZrO2, 5% Bi2O3,
40% α-Al2O3, 20% CaO, 3% TiO2, 7% K2O；It is low that obtained catalyst carries out synthesis gas production under certain condition
Carbene hydrocarbon reaction, experimental result is listed in table 1.
【Embodiment 8】
Weigh 45.0 grams of Alpha-aluminas（Al2O3）Powder and 40.1 grams of powdered whitings（CaCO3）Powder and 3.4 grams of titanium dioxide
（TiO2）Powder is well mixed, and grinds mixed 1 hour in ball mill, is made compound G stand-by；Weigh 11.5 grams of potassium carbonate
（K2CO3）, 30 ml deionized waters are added, until completely dissolved, add in the mixed compound G of above-mentioned mill, carry out kneading extruding
Shaping；Sintered 2 hours at a temperature of 1300 DEG C after drying, be made complex carrier, crushing and screening is into 60~80 mesh systems after cooling
It is standby go out composite oxide carrier H；By 25.3 grams of Fe(NO3)39H2Os, 69.7 gram of five nitric hydrate zirconium, 10.4 gram of five nitric hydrate
Bismuth, is dissolved in 35.0 grams of deionized waters and is made mixed solution I；Under conditions of vacuum 80kPa, by the leaching of above-mentioned mixed solution I
Stain on 70.0 grams of composite oxide carrier H for having prepared catalyst precarsor J；The catalyst precarsor J for having impregnated is at 110 DEG C
Under the conditions of dry, be then calcined, 600 DEG C of sintering temperature, roasting time 2h, that is, obtain needed for synthesis gas production low-carbon (LC) alkene
The catalyst of hydrocarbon.Obtained catalyst by weight percentage, comprising following components：5% Fe2O3, 20% ZrO2, 5% Bi2O3,
40% α-Al2O3, 20% CaO, 3% TiO2, 7% K2O；It is low that obtained catalyst carries out synthesis gas production under certain condition
Carbene hydrocarbon reaction, experimental result is listed in table 1.
【Embodiment 9】
Weigh 45.0 grams of Alpha-aluminas（Al2O3）Powder and 40.1 grams of powdered whitings（CaCO3）Powder and 3.4 grams of titanium dioxide
（TiO2）Powder is well mixed, and grinds mixed 1 hour in ball mill, is made compound G stand-by；Weigh 11.5 grams of potassium carbonate
（K2CO3）, 30 ml deionized waters are added, until completely dissolved, add in the mixed compound G of above-mentioned mill, carry out kneading extruding
Shaping；Sintered 2 hours at a temperature of 1300 DEG C after drying, be made complex carrier, crushing and screening is into 60~80 mesh systems after cooling
It is standby go out composite oxide carrier H；By 75.9 grams of Fe(NO3)39H2Os, 34.8 gram of five nitric hydrate zirconium, 10.4 gram of five nitric hydrate
Bismuth, is dissolved in 35.0 grams of deionized waters and is made mixed solution I；Under conditions of vacuum 80kPa, by the leaching of above-mentioned mixed solution I
Stain on 70.0 grams of composite oxide carrier H for having prepared catalyst precarsor J；The catalyst precarsor J for having impregnated is at 110 DEG C
Under the conditions of dry, be then calcined, 600 DEG C of sintering temperature, roasting time 2h, that is, obtain needed for synthesis gas production low-carbon (LC) alkene
The catalyst of hydrocarbon.Obtained catalyst by weight percentage, comprising following components：15% Fe2O3, 10% ZrO2, 5% Bi2O3,
40% α-Al2O3, 20% CaO, 3% TiO2, 7% K2O；It is low that obtained catalyst carries out synthesis gas production under certain condition
Carbene hydrocarbon reaction, experimental result is listed in table 1.
【Embodiment 10】
Weigh 45.0 grams of Alpha-aluminas（Al2O3）Powder and 40.1 grams of powdered whitings（CaCO3）Powder and 3.4 grams of titanium dioxide
（TiO2）Powder is well mixed, and grinds mixed 1 hour in ball mill, is made compound G stand-by；Weigh 11.5 grams of potassium carbonate
（K2CO3）, 30 ml deionized waters are added, until completely dissolved, add in the mixed compound G of above-mentioned mill, carry out kneading extruding
Shaping；Sintered 6 hours at a temperature of 1100 DEG C after drying, be made complex carrier, crushing and screening is into 60~80 mesh systems after cooling
It is standby go out composite oxide carrier H；By 101.2 grams of Fe(NO3)39H2Os, 25.2 gram 50% of manganese nitrate solution, 10.4 gram of five hydration
Bismuth nitrate, is dissolved in 35.0 grams of deionized waters and is made mixed solution I；Under conditions of vacuum 80kPa, by above-mentioned mixed solution
I impregnated on 70.0 grams of composite oxide carrier H for having prepared to obtain catalyst precarsor J；The catalyst precarsor J for having impregnated exists
Dried under the conditions of 110 DEG C, be then calcined, 600 DEG C of sintering temperature, roasting time 2h, that is, the synthesis gas production needed for obtaining
The catalyst of low-carbon alkene.Obtained catalyst by weight percentage, comprising following components：20% Fe2O3, 5% MnO, 5%
Bi2O3, 40% α-Al2O3, 20% CaO, 3% TiO2, 7% K2O；Obtained catalyst carries out synthesis gas life under certain condition
Low-carbon alkene reaction is produced, experimental result is listed in table 1.
【Embodiment 11】
Weigh 45.0 grams of Alpha-aluminas（Al2O3）Powder and 40.1 grams of powdered whitings（CaCO3）Powder and 3.4 grams of titanium dioxide
（TiO2）Powder is well mixed, and grinds mixed 1 hour in ball mill, is made compound G stand-by；Weigh 11.5 grams of potassium carbonate
（K2CO3）, 30 ml deionized waters are added, until completely dissolved, add in the mixed compound G of above-mentioned mill, carry out kneading extruding
Shaping；Sintered 1 hour at a temperature of 1600 DEG C after drying, be made complex carrier, crushing and screening is into 60~80 mesh systems after cooling
It is standby go out composite oxide carrier H；By 101.2 grams of Fe(NO3)39H2Os, 25.2 gram 50% of manganese nitrate solution, 8.3 gram of five hydration nitre
Sour bismuth, 1.6 grams of magnesium nitrate hexahydrates, are dissolved in 35.0 grams of deionized waters and are made mixed solution I；In the condition of vacuum 80kPa
Under, above-mentioned mixed solution I be impregnated in on 70.0 grams of composite oxide carrier H for having prepared to obtain catalyst precarsor J；Impregnate
Catalyst precarsor J under the conditions of 110 DEG C dry, be then calcined, 600 DEG C of sintering temperature, roasting time 2h obtains institute
The synthesis gas for needing produces the catalyst of low-carbon alkene.Obtained catalyst by weight percentage, comprising following components：20%
Fe2O3, 5% MnO, 4% Bi2O3, 1% MgO, 40% α-Al2O3, 20% CaO, 3% TiO2, 7% K2O；Obtained catalyst exists
Synthesis gas production low-carbon alkene reaction is carried out under certain condition, experimental result is listed in table 1.
【Embodiment 12】
Catalyst obtained in Example 1, other are constant, only change reaction condition, carry out preparation of low carbon olefines by synthetic gas, real
Test result and be listed in table 2.
【Comparative example 1】
Weigh 45.0 grams of Alpha-aluminas（Al2O3）Powder and 40.1 grams of powdered whitings（CaCO3）Powder and 3.4 grams of titanium dioxide
（TiO2）Powder is well mixed, and grinds mixed 1 hour in ball mill, is made compound G stand-by；Weigh 11.5 grams of potassium carbonate
（K2CO3）, 30 ml deionized waters are added, until completely dissolved, add in the mixed compound G of above-mentioned mill, carry out kneading extruding
Shaping；Sintered 2 hours at a temperature of 1300 DEG C after drying, be made complex carrier, crushing and screening is into 60~80 mesh systems after cooling
It is standby go out composite oxide carrier H；By 101.2 grams of Fe(NO3)39H2Os, 50.5 gram 50% of manganese nitrate solution, it is dissolved in 35.0 grams and goes
Mixed solution I is made in ionized water；Under conditions of vacuum 80kPa, above-mentioned mixed solution I impregnated in 70.0 grams and prepared
On good composite oxide carrier H catalyst precarsor J；The catalyst precarsor J for having impregnated is dried under the conditions of 110 DEG C, then
It is calcined, 600 DEG C of sintering temperature, roasting time 2h, that is, the synthesis gas needed for obtaining produces the catalyst of low-carbon alkene.It is obtained
Catalyst by weight percentage, comprising following components：20% Fe2O3, 10% MnO, 40% α-Al2O3, 20% CaO, 3%
TiO2, 7% K2O；Obtained catalyst carries out synthesis gas production low-carbon alkene reaction under certain condition, and experimental result is listed in
Table 1.
【Comparative example 2】
Weigh 45.0 grams of Alpha-aluminas（Al2O3）Powder and 40.1 grams of powdered whitings（CaCO3）Powder and 3.4 grams of titanium dioxide
（TiO2）Powder is well mixed, and grinds mixed 1 hour in ball mill, is made compound G stand-by；Weigh 11.5 grams of potassium carbonate
（K2CO3）, 30 ml deionized waters are added, until completely dissolved, add in the mixed compound G of above-mentioned mill, carry out kneading extruding
Shaping；Sintered 2 hours at a temperature of 1300 DEG C after drying, be made complex carrier, crushing and screening is into 60~80 mesh systems after cooling
It is standby go out composite oxide carrier H；By 50.6 grams of Fe(NO3)39H2Os, 25.2 gram 50% of manganese nitrate solution, 31.2 gram of five hydration nitre
Sour bismuth, is dissolved in 35.0 grams of deionized waters and is made mixed solution I；Under conditions of vacuum 80kPa, by above-mentioned mixed solution I
Impregnated on 70.0 grams of composite oxide carrier H for having prepared to obtain catalyst precarsor J；The catalyst precarsor J for having impregnated is 110
Dried under the conditions of DEG C, be then calcined, 600 DEG C of sintering temperature, roasting time 2h, that is, the synthesis gas production low-carbon (LC) needed for obtaining
The catalyst of alkene.Obtained catalyst by weight percentage, comprising following components：10% Fe2O3, 5% MnO, 15%
Bi2O3, 40% α-Al2O3, 20% CaO, 3% TiO2, 7% K2O；Obtained catalyst carries out synthesis gas life under certain condition
Low-carbon alkene reaction is produced, experimental result is listed in table 1.
【Comparative example 3】
Weigh 44.3 grams of Alpha-aluminas（Al2O3）Powder and 39.5 grams of powdered whitings（CaCO3）Powder is well mixed, in ball
Mill is mixed 1 hour in grinding machine, is made compound G stand-by；Weigh 16.2 grams of potassium carbonate（K2CO3）, 30 ml deionized waters are added, treat
After CL, add in the mixed compound G of above-mentioned mill, carry out kneading extrusion forming；Burnt at a temperature of 1300 DEG C after drying
Knot 2 hours, is made complex carrier, and crushing and screening prepares composite oxide carrier H into 60~80 mesh after cooling；By 30.4 gram nine
Nitric hydrate iron, 7.6 gram 50% of manganese nitrate solution, 3.1 gram of five nitric hydrate bismuth, be dissolved in 35.0 grams of deionized waters be made it is mixed
Close solution I；Under conditions of vacuum 80kPa, above-mentioned mixed solution I be impregnated in into 70.0 grams of composite oxides for having prepared
On carrier H catalyst precarsor J；The catalyst precarsor J for having impregnated is dried under the conditions of 110 DEG C, is then calcined, roasting temperature
600 DEG C of degree, roasting time 2h, that is, the synthesis gas needed for obtaining produces the catalyst of low-carbon alkene.Obtained catalyst is with weight
Percentages, comprising following components：20% Fe2O3, 5% MnO, 5% Bi2O3, 40% α-Al2O3, 20% CaO, 10% K2O；Institute
Obtained catalyst carries out synthesis gas production low-carbon alkene reaction under certain condition, and experimental result is listed in table 1.
【Comparative example 4】
Weigh 47.6 grams of Alpha-aluminas（Al2O3）Powder and 31.8 grams of powdered whitings（CaCO3）Powder and 11.9 grams of titanium dioxide
（TiO2）Powder is well mixed, and grinds mixed 1 hour in ball mill, is made compound G stand-by；Weigh 8.7 grams of potassium carbonate（K2CO3）,
30 ml deionized waters are added, until completely dissolved, is added in the mixed compound G of above-mentioned mill, carry out kneading extrusion forming；Dry
Sintered 2 hours at a temperature of 1300 DEG C after dry, be made complex carrier, crushing and screening is prepared compound into 60~80 mesh after cooling
Oxide carrier H；By 30.4 grams of Fe(NO3)39H2Os, 7.6 gram 50% of manganese nitrate solution, 3.1 gram of five nitric hydrate bismuth, it is dissolved in
Mixed solution I is made in 35.0 grams of deionized waters；Under conditions of vacuum 80kPa, above-mentioned mixed solution I impregnated in 70.0
On gram composite oxide carrier H for having prepared catalyst precarsor J；The catalyst precarsor J for having impregnated does under the conditions of 110 DEG C
It is dry, be then calcined, 600 DEG C of sintering temperature, roasting time 2h, that is, the synthesis gas needed for obtaining produces the catalysis of low-carbon alkene
Agent.Obtained catalyst by weight percentage, comprising following components：20% Fe2O3, 5% MnO, 5% Bi2O3, 40% α-
Al2O3, 15% CaO, 10% TiO2, 5% K2O；Obtained catalyst carries out synthesis gas production low-carbon alkene under certain condition
Reaction, 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 1.7MPa
The ml of loaded catalyst 3
Catalyst loading 1000 hours-1
Raw material proportioning (mole) H2/ CO=1.6/1
Table 1
Table 2
* the appreciation condition for changing compared with the condition described in table 1.
Claims (10)
1. it is a kind of for synthesis gas produce low-carbon alkene catalyst, the catalyst with vacuum impregnation technology prepare, with weight percent
Include following components than meter：
A) 5~50% ferro element or its oxide；
B) 4~20% selected from manganese and zirconium at least one element or its oxide, with the electrovalence of modulation active component iron
State；
C) 1~10% bismuth element or its oxide；
D) 25~90% carrier, in terms of vehicle weight number, including (1) 15~40 part of Alpha-alumina of following components；(2) 1~
45 parts of calcium oxide；(3) 1~5 parts of titanium dioxide；(4) 1~20 parts of potassium oxides.
2. it is according to claim 1 for synthesis gas produce low-carbon alkene catalyst, it is characterised in that described catalysis
The oxide of iron is di-iron trioxide in agent, and in terms of catalyst weight percent, content is 10~40%.
3. it is according to claim 1 for synthesis gas produce low-carbon alkene catalyst, it is characterised in that described catalysis
The oxide of manganese and zirconium is respectively manganese oxide and zirconium oxide in agent, and in terms of catalyst weight percent, content is 10~20%.
4. it is according to claim 1 for synthesis gas produce low-carbon alkene catalyst, it is characterised in that described catalysis
The oxide of the bismuth described in agent is bismuth oxide, and in terms of catalyst weight percent, content is 1~5%.
5. it is according to claim 1 for synthesis gas produce low-carbon alkene catalyst, it is characterised in that described α-oxygen
Change aluminium in terms of vehicle weight number, content is 20~40 parts.
6. it is according to claim 1 for synthesis gas produce low-carbon alkene catalyst, it is characterised in that described oxidation
In terms of vehicle weight number, content is 10~40 parts to calcium.
7. it is according to claim 1 for synthesis gas produce low-carbon alkene catalyst, it is characterised in that described dioxy
Change titanium in terms of vehicle weight number, content is 3~5 parts.
8. it is according to claim 1 for synthesis gas produce low-carbon alkene catalyst, it is characterised in that described oxidation
In terms of vehicle weight number, content is 1~10 part to potassium.
9. it is according to claim 1 for synthesis gas produce low-carbon alkene catalyst, it is characterised in that the carrier by
Prepared by Alpha-alumina, powdered whiting, titanium dioxide and potassium carbonate high temperature sintering, sintering temperature is 1100~1600 DEG C, sintering
Time is 1~6 hour.
10. a kind of method that synthesis gas produces low-carbon alkene, with synthesis gas as raw material, H2It is 1~3 with the mol ratio of CO, in reaction
Temperature is 250~400 DEG C, and reaction pressure is 1.0~3.0Mpa, and feed gas volume air speed is 500~5000h-1Under conditions of, it is former
Material gas contains C with the catalyst haptoreaction generation described in any one of claim 1~92~C4Alkene.
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| CN101757925A (en) * | 2009-12-31 | 2010-06-30 | 浙江工业大学 | Fused iron catalyst for producing light olefins from syngas and preparation method and application thereof |
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