CN106607047A - Iron-based catalyst for preparing low-carbon olefins from synthesis gas and application of iron-based catalyst - Google Patents
Iron-based catalyst for preparing low-carbon olefins from synthesis gas and application of iron-based catalyst Download PDFInfo
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Abstract
The invention relates to a method for preparing low-carbon olefins from synthesis gas on an iron-based catalyst and mainly solves the problems that in the prior art, in a reaction of preparation of the low-carbon olefins from the synthesis gas by using a fixed bed, the CO conversion rate is low, and low-carbon olefin selectivity is low. The iron-based catalyst comprises, by weight, 20-70 parts of the iron element or an oxide of the iron element, 4-20 parts of at least one element selected from copper and manganese or an oxide of the at least one element, 4-20 parts of at least one element selected from zinc and zirconium or an oxide of the at least one element, 20-40 parts of the silicon element or an oxide of the silicon element, 1-10 parts of the germanium element or an oxide of the germanium element and 1-10 parts of the iridium element or an oxide of the iridium element. The problems are well solved through adoption of the above technical scheme, and the iron-based catalyst can be used for industrial production of preparing the low-carbon olefins from the synthesis gas by using the fixed bed.
Description
Technical field
The present invention relates to a kind of ferrum-based catalyst of synthesis gas preparing low-carbon olefins and application thereof.
Background technology
Low-carbon alkene refers to alkene of the carbon number less than or equal to 4.Low-carbon alkene with ethylene, propylene as representative is very important basic organic chemical industry raw material, and with the rapid growth of China's economy, for a long time, supply falls short of demand in low-carbon alkene market.At present, the petrochemical industry route that the production of low-carbon alkene is mainly cracked using lighter hydrocarbons (ethane, Petroleum, light diesel fuel), due to the day by day shortage and the long-term run at high level of crude oil price of Global Oil resource, development low-carbon alkene industry relies solely on the tube cracking furnace technique that petroleum light hydrocarbon is raw material and can run into an increasing raw material difficult problem, and low-carbon alkene production technology and raw material must diversification.The direct preparing low-carbon olefins of one-step method from syngas are exactly carbon monoxide and hydrogen under catalyst action, process of the carbon number less than or equal to 4 low-carbon alkene is obtained directly by Fischer-Tropsch synthesis, the technique need not be as indirect method technique from synthesis gas through methanol or dimethyl ether, alkene is prepared further, simplification of flowsheet, greatly reduces investment.Petroleum resources shortage at home, it is current that external dependence degree more and more higher, international oil price constantly rise violently, raw material sources can be widened from synthesis gas producing olefinic hydrocarbons technique, will with crude oil, natural gas, coal and recyclable materials as raw material production synthesis gas, can be based on high cost raw material as Petroleum steam cracking technology in terms of replacement scheme is provided.The coal price of the abundant coal resources of China and relative moderate is refined oil for Development of Coal and provides the good market opportunity using preparation of low carbon olefines by synthetic gas technique.And near the oil gas field that Natural Gas In China enriches, if Gas Prices are cheap, and using the fabulous opportunity of preparation of low carbon olefines by synthetic gas technique.If the coal and natural gas resource of China's abundant can be utilized, by gas making producing synthesis gas (gaseous mixture of carbon monoxide and hydrogen), the substitute energy source for petroleum technology of development preparation of low carbon olefines by synthetic gas, will be significant to solving energy problem of China.
One-step method from syngas producing light olefins technology originates from traditional Fischer-Tropsch synthesis, and the carbon number distribution of traditional Fischer-Tropsch synthetic defers to ASF distributions, and each hydro carbons all has theoretical maximum selectivity, such as C2-C4The selectivity of fraction 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 bigger.Once α values are determined, the selectivity of whole synthetic product is determined that, chain increases probability α values and depends on catalyst composition, granularity and reaction condition etc..In recent years, it has been found that due to the alkene secondary response that alhpa olefin adsorbing again on a catalyst causes, products distribution is distributed away from ideal ASF.F- T synthesis are a kind of strong exothermal reactions, and substantial amounts of reaction heat will promote catalyst carbon deposit reaction easily to generate methane and low-carbon alkanes, cause selectivity of light olefin significantly to decline；Secondly, complicated kinetic factor also causes unfavorable to selectivity synthesis low-carbon alkene；The ASF distributions of Fischer-Tropsch synthetic limit the selectivity of synthesizing low-carbon alkene.The catalyst of F- T synthesis gas producing light olefins is mainly ferrum catalyst series, in order to improve the selectivity of the direct preparing low-carbon olefins of synthesis gas, physics and chemical modification can be carried out to fischer-tropsch synthetic catalyst, such as using the pore passage structure that molecular sieve is suitable, be conducive to low-carbon alkene to diffuse out metal active centres in time, suppress the secondary response of low-carbon alkene；Metal ion dispersibility is improved, also has preferable olefine selective；Support-metal strong interaction change can also improve selectivity of light olefin；The suitable transition metal of addition, can strengthen the bond energy of active component and carbon, suppress methane to generate, improve selectivity of light olefin；Addition electronics accelerating auxiliaries, promote CO chemisorbeds heat to increase, and adsorbance also increases, and hydrogen adsorptive capacity reduces, and as a result selectivity of light olefin increases；Catalyst acid center is eliminated, the secondary response of low-carbon alkene can be suppressed, its selectivity is improved.By the Support effect of catalyst carrier and some transition metal promoters of addition and alkali metal promoter, catalyst performance is can obviously improve, 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, ferrum-Mn catalyst the system supported with the Group IIA such as MgO alkali metal oxide or silica-rich zeolite molecular sieve (or phosphorus aluminum zeolite), auxiliary agent is made with highly basic K or Cs ion, it is 1.0～5.0MPa in preparation of low carbon olefines by synthetic gas reaction pressure, at 300～400 DEG C of reaction temperature, higher activity (CO conversion ratios 90%) and selectivity (selectivity of light olefin 66%) can be obtained.But the catalyst preparation process is complicated, the preparation molding process cost of particularly carrier zeolite molecular sieve is higher, is unfavorable for industrialized production.In the number of patent application 01144691.9 declared by Beijing University of Chemical Technology, laser pyrolysis processes are adopted to be prepared for reference to solid state reaction combination technique with Fe3Fe base nano-catalysts based on C are applied to preparation of low carbon olefines by synthetic gas, and achieve good catalytic effect, and due to needing using laser pyrolysis technology, preparation technology is comparatively laborious, and raw material adopts Fe (CO)5, catalyst cost is very high, and industrialization is difficult.In patent ZL03109585.2 declared by Beijing University of Chemical Technology, adopt vacuum impregnation technology to prepare manganese, copper, zinc silicon, potassium etc. and react for preparation of low carbon olefines by synthetic gas for the Fe/ activated-carbon catalysts of auxiliary agent, under conditions of circulating without unstripped gas, CO conversion ratios 96%, selectivity 68% of the low-carbon alkene in Hydrocarbon.The catalyst preparation using iron salt and auxiliary agent manganese salt be more expensive and less soluble ferric oxalate and manganese acetate, while with ethanol as solvent, the just inevitable cost of material and running cost for increasing catalyst preparation process.For the cost for further reducing catalyst; in its number of patent application 200710063301.9; catalyst adopts common medicine and reagent to prepare, and the iron salt for using is ferric nitrate, and manganese salt is manganese nitrate; potassium salt is potassium carbonate; activated carbon is coconut husk charcoal, can catalyst must flowing nitrogen protection under carry out high-temperature roasting and Passivation Treatment, need special installation; preparation process is complicated, relatively costly.And CO conversion ratio and selectivity of light olefin of the above-mentioned catalyst in fixed bed reaction is relatively low.
The content of the invention
The technical problem to be solved be that in synthesis gas preparing low-carbon olefins technology CO conversion ratios are low in prior art and product in the low problem of selectivity of light olefin, the method that synthesis gas preparing low-carbon olefins on a kind of new ferrum-based catalyst are provided, the method uses new iron-based catalyst, and in having the advantages that CO high conversion rates and product, selectivity of light olefin is high.
To solve above-mentioned technical problem, the technical solution used in the present invention is as follows：A kind of ferrum-based catalyst of synthesis gas preparing low-carbon olefins, including following components in terms of parts by weight：
A) 20～70 parts of ferrum element or its oxide；
B) 4～20 parts of at least one elements or its oxide in copper and manganese；
C) 4～20 parts of at least one elements or its oxide in zinc and zirconium；
D) 20～40 parts of element silicons or its oxide；
E) 1～10 part of Ge element or its oxide；
F) 1～10 part of iridium or its oxide.
In above-mentioned technical proposal, the preferred version of the oxide of ferrum is ferroso-ferric oxide (Fe3O4), the preferred scope of content is 30～60 parts；The preferred version of the oxide of copper and manganese is respectively copper oxide (CuO) and manganese oxide (MnO), and the preferred scope of content is 5～15 parts；The preferred version of the oxide of zinc and zirconium is respectively Zinc Oxide (ZnO) and zirconium dioxide (ZrO2), the preferred scope of content is 5～15 parts；The preferred version of the oxide of silicon is silicon dioxide (SiO2), the preferred scope of content is 20～35 parts；The preferred version of the oxide of germanium is germanium dioxide (GeO2), the preferred scope of content is 1～5 part；The preferred version of the oxide of iridium is yttrium oxide (IrO2), the preferred scope of content is 1～5 part.
In above-mentioned technical proposal, the ferrum-based catalyst preparation method of described preparation of low carbon olefines by synthetic gas is comprised the following steps：
(1) by the oxide of the oxide of ferrum, cupric or manganese, the oxide containing zinc or zirconium, siliceous oxide, germanic oxide, the oxide containing iridium, and grind mixed in ball mill after polyethylene glycol powder mixing, obtain material A；
(2) deionized water is added in material A, carries out kneading and obtain material B；
(3) material C will be obtained after the drying of material B extruded mouldings；
(4) ferrum-based catalyst needed for crushing and screening is obtained will after material C high temperature sinterings, be cooled down.
In above-mentioned technical proposal, the preparation method of described preparation of low carbon olefines by synthetic gas ferrum-based catalyst, in step (1), Polyethylene Glycol consumption is the 2～6% of all raw material gross weights, in step (2), deionized water consumption is the 5～15% of all raw material gross weights, all raw material gross weights are the oxide of ferrum, the oxide of cupric or manganese, the oxide containing zinc or zirconium, siliceous oxide, germanic oxide, the weight of the oxide containing iridium and；The preferred scope that mill is done time is 2～6 hours；The preferred scope of high temperature sintering temperature is 1100～1400 DEG C.
In above-mentioned technical proposal, described ferrum-based catalyst is reacted for fixed bed preparation of low carbon olefines by synthetic gas, with synthesis gas as raw material, H2Mol ratio with CO is 1～3, is 250～400 DEG C in reaction temperature, and reaction pressure is 1.0～3.0Mpa, and feed gas volume air speed is 500～5000h-1Under conditions of, unstripped gas is generated containing C with the catalyst haptoreaction2～C4Alkene.
The inventive method is using introducing transition metal Cu or Mn, transition metal Zn or Zr, nonmetallic Si in catalyst activity component, and main group metal Ge and transition metal Ir do catalyst promoter, can be with the electron valence state of modulation active component Fe, so as to be conducive to the selectivity of the CO conversion ratios and low-carbon alkene that improve catalyst, particularly when Ge and Ir is added, due to the synergism between Ge and Ir and other active components and auxiliary agent, the activity of catalyst can effectively be discharged, the selectivity of the conversion ratio and low-carbon alkene of CO is improved, good technique effect is achieved.
Using active component, co-catalysis component are uniformly mixed, Jing high temperature sinterings obtain the catalyst that high intensity is high, heat stability is good to the inventive method, even if having crushed in use but being unlikely to crush, can keep stablizing for catalyst activity.
The inventive method is using the addition bonding pore creating material Polyethylene Glycol in catalyst preparation, as Polyethylene Glycol has big specific surface and abundant pore structure, which is easily made to react the carbon dioxide abjection for generating at high temperature with oxygen, leave a void on a catalyst, the pore structure of increase catalyst, reduces inside diffusional resistance.
The reaction condition of synthesis gas preparing low-carbon olefins is as follows：With H2With CO composition synthesis gas be raw material, H2Mol ratio with CO is 1～3, is 250～400 DEG C in reaction temperature, and reaction pressure is 1.0～3.0Mpa, and feed gas volume air speed is 500～5000h-1Under conditions of, unstripped gas is contacted with above-mentioned ferrum-based catalyst, achieves preferable technique effect：CO conversion ratios improve 3.6% than prior art up to 99.6%；Selectivity of the low-carbon alkene in Hydrocarbon improves 9.9% than prior art up to 77.9%, and more detailed result sees attached list.
The present invention is described further for the following examples, and protection scope of the present invention is not limited to these embodiments restrictions.
Specific embodiment
【Embodiment 1】
Weigh 40.0 grams of ferroso-ferric oxide (Fe3O4), 12.0 grams of copper oxides (CuO), 12.0 grams of Zinc Oxide (ZnO), 28.0 grams of silicon dioxide (SiO2), 4.0 grams of germanium oxide (GeO2) and 4.0 grams of yttrium oxide (IrO2) six kinds of raw materials and percentage by weight is 4% 4 grams of polyethylene glycol powder based on raw material total amount, mill is mixed 4 hours in the ball mill；Based on raw material total amount, 10 grams of the deionized water of add weight percentage ratio 10% is added in the mixed material of mill, is mediated to soft shape；Kneaded material is sent in banded extruder, makes the strip of a diameter of 5mm, and cuts into the column that length is 20mm, after drying naturally, sends in drying equipment, standby in 120 DEG C of dryings 8 hours；By dried precursor, send in high temperature furnace, calcine 4.0 hours in 1300 DEG C, crushing and screening is into 60～80 mesh, that is, the slug type preparation of low carbon olefines by synthetic gas catalyst needed for obtaining after cooling.Obtained catalyst by weight percentage, comprising following components：40%Fe2O3, 12%CuO, 12%ZnO, 28%SiO2, 4%GeO2, 4%IrO2；Obtained catalyst is fixed a preparation of low carbon olefines by synthetic gas under certain reaction condition, and experimental result is listed in table 1.
【Embodiment 2】
Weigh 51.0 grams of ferroso-ferric oxide (Fe3O4), 3.0 grams of copper oxides (CuO), 3.0 grams of Zinc Oxide (ZnO), 42.0 grams of silicon dioxide (SiO2), 0.5 gram of germanium oxide (GeO2) and 0.5 gram of yttrium oxide (IrO2) six kinds of raw materials and percentage by weight is 2% 2 grams of polyethylene glycol powder based on raw material total amount, mill is mixed 4 hours in the ball mill；Based on raw material total amount, 10 grams of the deionized water of add weight percentage ratio 10% is added in the mixed material of mill, is mediated to soft shape；Kneaded material is sent in banded extruder, makes the strip of a diameter of 5mm, and cuts into the column that length is 20mm, after drying naturally, sends in drying equipment, standby in 120 DEG C of dryings 8 hours；By dried precursor, send in high temperature furnace, calcine 4.0 hours in 1300 DEG C, crushing and screening is into 60～80 mesh, that is, the slug type preparation of low carbon olefines by synthetic gas catalyst needed for obtaining after cooling.Obtained catalyst by weight percentage, comprising following components：51%Fe2O3, 3%CuO, 3%ZnO, 42%SiO2, 0.5%GeO2, 0.5%IrO2；Obtained catalyst is fixed a preparation of low carbon olefines by synthetic gas under certain reaction condition, and experimental result is listed in table 1.
【Embodiment 3】
Weigh 18.0 grams of ferroso-ferric oxide (Fe3O4), 21.0 grams of copper oxides (CuO), 21.0 grams of Zinc Oxide (ZnO), 18.0 grams of silicon dioxide (SiO2), 11.0 grams of germanium oxide (GeO2) and 11.0 grams of yttrium oxide (IrO2) six kinds of raw materials and percentage by weight is 6% 6 grams of polyethylene glycol powder based on raw material total amount, mill is mixed 4 hours in the ball mill；Based on raw material total amount, 10 grams of the deionized water of add weight percentage ratio 10% is added in the mixed material of mill, is mediated to soft shape；Kneaded material is sent in banded extruder, makes the strip of a diameter of 5mm, and cuts into the column that length is 20mm, after drying naturally, sends in drying equipment, standby in 120 DEG C of dryings 8 hours；By dried precursor, send in high temperature furnace, calcine 4.0 hours in 1300 DEG C, crushing and screening is into 60～80 mesh, that is, the slug type preparation of low carbon olefines by synthetic gas catalyst needed for obtaining after cooling.Obtained catalyst by weight percentage, comprising following components：18%Fe2O3, 21%CuO, 21%ZnO, 18%SiO2, 11%GeO2, 11%IrO2；Obtained catalyst is fixed a preparation of low carbon olefines by synthetic gas under certain reaction condition, and experimental result is listed in table 1.
【Embodiment 4】
Weigh 72.0 grams of ferroso-ferric oxide (Fe3O4), 4.0 grams of copper oxides (CuO), 4.0 grams of Zinc Oxide (ZnO), 18.0 grams of silicon dioxide (SiO2), 1.0 grams of germanium oxide (GeO2) and 1.0 grams of yttrium oxide (IrO2) six kinds of raw materials and percentage by weight is 4% 4 grams of polyethylene glycol powder based on raw material total amount, mill is mixed 4 hours in the ball mill；Based on raw material total amount, 5 grams of the deionized water of add weight percentage ratio 5% is added in the mixed material of mill, is mediated to soft shape；Kneaded material is sent in banded extruder, makes the strip of a diameter of 5mm, and cuts into the column that length is 20mm, after drying naturally, sends in drying equipment, standby in 120 DEG C of dryings 8 hours；By dried precursor, send in high temperature furnace, calcine 4.0 hours in 1300 DEG C, crushing and screening is into 60～80 mesh, that is, the slug type preparation of low carbon olefines by synthetic gas catalyst needed for obtaining after cooling.Obtained catalyst by weight percentage, comprising following components：72%Fe2O3, 4%CuO, 4%ZnO, 18%SiO2, 1%GeO2, 1%IrO2；Obtained catalyst is fixed a preparation of low carbon olefines by synthetic gas under certain reaction condition, and experimental result is listed in table 1.
【Embodiment 5】
Weigh 28.0 grams of ferroso-ferric oxide (Fe3O4), 5.0 grams of copper oxides (CuO), 5.0 grams of Zinc Oxide (ZnO), 42.0 grams of silicon dioxide (SiO2), 10.0 grams of germanium oxide (GeO2) and 10.0 grams of yttrium oxide (IrO2) six kinds of raw materials and percentage by weight is 4% 4 grams of polyethylene glycol powder based on raw material total amount, mill is mixed 4 hours in the ball mill；Based on raw material total amount, 15 grams of the deionized water of add weight percentage ratio 15% is added in the mixed material of mill, is mediated to soft shape；Kneaded material is sent in banded extruder, makes the strip of a diameter of 5mm, and cuts into the column that length is 20mm, after drying naturally, sends in drying equipment, standby in 120 DEG C of dryings 8 hours；By dried precursor, send in high temperature furnace, calcine 4.0 hours in 1300 DEG C, crushing and screening is into 60～80 mesh, that is, the slug type preparation of low carbon olefines by synthetic gas catalyst needed for obtaining after cooling.Obtained catalyst by weight percentage, comprising following components：28%Fe2O3, 5%CuO, 5%ZnO, 42%SiO2, 10%GeO2, 10%IrO2；Obtained catalyst is fixed a preparation of low carbon olefines by synthetic gas under certain reaction condition, and experimental result is listed in table 1.
【Embodiment 6】
Weigh 33.0 grams of ferroso-ferric oxide (Fe3O4), 15.0 grams of copper oxides (CuO), 15.0 grams of Zinc Oxide (ZnO), 35.0 grams of silicon dioxide (SiO2), 1.0 grams of germanium oxide (GeO2) and 1.0 grams of yttrium oxide (IrO2) six kinds of raw materials and percentage by weight is 4% 4 grams of polyethylene glycol powder based on raw material total amount, mill is mixed 4 hours in the ball mill；Based on raw material total amount, 10 grams of the deionized water of add weight percentage ratio 10% is added in the mixed material of mill, is mediated to soft shape；Kneaded material is sent in banded extruder, makes the strip of a diameter of 5mm, and cuts into the column that length is 20mm, after drying naturally, sends in drying equipment, standby in 120 DEG C of dryings 8 hours；By dried precursor, send in high temperature furnace, calcine 4.0 hours in 1000 DEG C, crushing and screening is into 60～80 mesh, that is, the slug type preparation of low carbon olefines by synthetic gas catalyst needed for obtaining after cooling.Obtained catalyst by weight percentage, comprising following components：33%Fe2O3, 15%CuO, 15%ZnO, 35%SiO2, 1%GeO2, 1%IrO2；Obtained catalyst is fixed a preparation of low carbon olefines by synthetic gas under certain reaction condition, and experimental result is listed in table 1.
【Embodiment 7】
Weigh 30.0 grams of ferroso-ferric oxide (Fe3O4), 10.0 grams of copper oxides (CuO), 10.0 grams of Zinc Oxide (ZnO), 40.0 grams of silicon dioxide (SiO2), 5.0 grams of germanium oxide (GeO2) and 5.0 grams of yttrium oxide (IrO2) six kinds of raw materials and percentage by weight is 4% 4 grams of polyethylene glycol powder based on raw material total amount, mill is mixed 4 hours in the ball mill；Based on raw material total amount, 10 grams of the deionized water of add weight percentage ratio 10% is added in the mixed material of mill, is mediated to soft shape；Kneaded material is sent in banded extruder, makes the strip of a diameter of 5mm, and cuts into the column that length is 20mm, after drying naturally, sends in drying equipment, standby in 120 DEG C of dryings 8 hours；By dried precursor, send in high temperature furnace, calcine 4.0 hours in 1600 DEG C, crushing and screening is into 60～80 mesh, that is, the slug type preparation of low carbon olefines by synthetic gas catalyst needed for obtaining after cooling.Obtained catalyst by weight percentage, comprising following components：30%Fe2O3, 10%CuO, 10%ZnO, 40%SiO2, 5%GeO2, 5%IrO2；Obtained catalyst is fixed a preparation of low carbon olefines by synthetic gas under certain reaction condition, and experimental result is listed in table 1.
【Embodiment 8】
Weigh 60.0 grams of ferroso-ferric oxide (Fe3O4), 5.0 grams of copper oxides (CuO), 5.0 grams of Zinc Oxide (ZnO), 20.0 grams of silicon dioxide (SiO2), 5.0 grams of germanium oxide (GeO2) and 5.0 grams of yttrium oxide (IrO2) six kinds of raw materials and percentage by weight is 4% 4 grams of polyethylene glycol powder based on raw material total amount, mill is mixed 4 hours in the ball mill；Based on raw material total amount, 10 grams of the deionized water of add weight percentage ratio 10% is added in the mixed material of mill, is mediated to soft shape；Kneaded material is sent in banded extruder, makes the strip of a diameter of 5mm, and cuts into the column that length is 20mm, after drying naturally, sends in drying equipment, standby in 120 DEG C of dryings 8 hours；By dried precursor, send in high temperature furnace, calcine 4.0 hours in 1100 DEG C, crushing and screening is into 60～80 mesh, that is, the slug type preparation of low carbon olefines by synthetic gas catalyst needed for obtaining after cooling.Obtained catalyst by weight percentage, comprising following components：60%Fe2O3, 5%CuO, 5%ZnO, 20%SiO2, 5%GeO2, 5%IrO2；Obtained catalyst is fixed a preparation of low carbon olefines by synthetic gas under certain reaction condition, and experimental result is listed in table 1.
【Embodiment 9】
Weigh 40.0 grams of ferroso-ferric oxide (Fe3O4), 12.0 grams of manganese oxide (MnO), 12.0 grams of Zinc Oxide (ZnO), 28.0 grams of silicon dioxide (SiO2), 4.0 grams of germanium oxide (GeO2) and 4.0 grams of yttrium oxide (IrO2) six kinds of raw materials and percentage by weight is 4% 4 grams of polyethylene glycol powder based on raw material total amount, mill is mixed 4 hours in the ball mill；Based on raw material total amount, 10 grams of the deionized water of add weight percentage ratio 10% is added in the mixed material of mill, is mediated to soft shape；Kneaded material is sent in banded extruder, makes the strip of a diameter of 5mm, and cuts into the column that length is 20mm, after drying naturally, sends in drying equipment, standby in 120 DEG C of dryings 8 hours；By dried precursor, send in high temperature furnace, calcine 4.0 hours in 1400 DEG C, crushing and screening is into 60～80 mesh, that is, the slug type preparation of low carbon olefines by synthetic gas catalyst needed for obtaining after cooling.Obtained catalyst by weight percentage, comprising following components：40%Fe2O3, 12%MnO, 12%ZnO, 28%SiO2, 4%GeO2, 4%IrO2；Obtained catalyst is fixed a preparation of low carbon olefines by synthetic gas under certain reaction condition, and experimental result is listed in table 1.
【Embodiment 10】
Weigh 40.0 grams of ferroso-ferric oxide (Fe3O4), 12.0 grams of copper oxides (CuO), 12.0 grams of zirconium oxide (ZrO2), 28.0 grams of silicon dioxide (SiO2), 4.0 grams of germanium oxide (GeO2) and 4.0 grams of yttrium oxide (IrO2) six kinds of raw materials and percentage by weight is 4% 4 grams of polyethylene glycol powder based on raw material total amount, mill is mixed 4 hours in the ball mill；Based on raw material total amount, 10 grams of the deionized water of add weight percentage ratio 10% is added in the mixed material of mill, is mediated to soft shape；Kneaded material is sent in banded extruder, makes the strip of a diameter of 5mm, and cuts into the column that length is 20mm, after drying naturally, sends in drying equipment, standby in 120 DEG C of dryings 8 hours；By dried precursor, send in high temperature furnace, calcine 4.0 hours in 1300 DEG C, crushing and screening is into 60～80 mesh, that is, the slug type preparation of low carbon olefines by synthetic gas catalyst needed for obtaining after cooling.Obtained catalyst by weight percentage, comprising following components：40%Fe2O3, 12%CuO, 12%ZrO2, 28%SiO2, 4%GeO2, 4%IrO2；Obtained catalyst is fixed a preparation of low carbon olefines by synthetic gas under certain reaction condition, and experimental result is listed in table 1.
【Embodiment 11】
Weigh 40.0 grams of ferroso-ferric oxide (Fe3O4), 12.0 grams of manganese oxide (MnO), 12.0 grams of zirconium oxide (ZrO2), 28.0 grams of silicon dioxide (SiO2), 4.0 grams of germanium oxide (GeO2) and 4.0 grams of yttrium oxide (IrO2) six kinds of raw materials and percentage by weight is 4% 4 grams of polyethylene glycol powder based on raw material total amount, mill is mixed 4 hours in the ball mill；Based on raw material total amount, 10 grams of the deionized water of add weight percentage ratio 10% is added in the mixed material of mill, is mediated to soft shape；Kneaded material is sent in banded extruder, makes the strip of a diameter of 5mm, and cuts into the column that length is 20mm, after drying naturally, sends in drying equipment, standby in 120 DEG C of dryings 8 hours；By dried precursor, send in high temperature furnace, calcine 4.0 hours in 1300 DEG C, crushing and screening is into 60～80 mesh, that is, the slug type preparation of low carbon olefines by synthetic gas catalyst needed for obtaining after cooling.Obtained catalyst by weight percentage, comprising following components：40%Fe2O3, 12%MnO, 12%ZrO2, 28%SiO2, 4%GeO2, 4%IrO2；Obtained catalyst is fixed a preparation of low carbon olefines by synthetic gas under certain reaction condition, and 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, and experimental result is listed in table 2.
【Comparative example 1】
Weigh 40.0 grams of ferroso-ferric oxide (Fe3O4), 12.0 grams of copper oxides (CuO), 12.0 grams of Zinc Oxide (ZnO), 32.0 grams of silicon dioxide (SiO2) and 4.0 grams of yttrium oxide (IrO2) five kinds of raw materials and percentage by weight is 4% 4 grams of polyethylene glycol powder based on raw material total amount, mill is mixed 4 hours in the ball mill；Based on raw material total amount, 10 grams of the deionized water of add weight percentage ratio 10% is added in the mixed material of mill, is mediated to soft shape；Kneaded material is sent in banded extruder, makes the strip of a diameter of 5mm, and cuts into the column that length is 20mm, after drying naturally, sends in drying equipment, standby in 120 DEG C of dryings 8 hours；By dried precursor, send in high temperature furnace, calcine 4.0 hours in 1300 DEG C, crushing and screening is into 60～80 mesh, that is, the slug type preparation of low carbon olefines by synthetic gas catalyst needed for obtaining after cooling.Obtained catalyst by weight percentage, comprising following components：40%Fe2O3, 12%CuO, 12%ZnO, 32%SiO2, 4%IrO2；Obtained catalyst is fixed a preparation of low carbon olefines by synthetic gas under certain reaction condition, and experimental result is listed in table 1.
【Comparative example 2】
Weigh 40.0 grams of ferroso-ferric oxide (Fe3O4), 12.0 grams of copper oxides (CuO), 12.0 grams of Zinc Oxide (ZnO), 21.0 grams of silicon dioxide (SiO2), 11.0 grams of germanium oxide (GeO2) and 4.0 grams of yttrium oxide (IrO2) six kinds of raw materials and percentage by weight is 4% 4 grams of polyethylene glycol powder based on raw material total amount, mill is mixed 4 hours in the ball mill；Based on raw material total amount, 10 grams of the deionized water of add weight percentage ratio 10% is added in the mixed material of mill, is mediated to soft shape；Kneaded material is sent in banded extruder, makes the strip of a diameter of 5mm, and cuts into the column that length is 20mm, after drying naturally, sends in drying equipment, standby in 120 DEG C of dryings 8 hours；By dried precursor, send in high temperature furnace, calcine 4.0 hours in 1300 DEG C, crushing and screening is into 60～80 mesh, that is, the slug type preparation of low carbon olefines by synthetic gas catalyst needed for obtaining after cooling.Obtained catalyst by weight percentage, comprising following components：40%Fe2O3, 12%CuO, 12%ZnO, 21%SiO2, 11%GeO2, 4%IrO2；Obtained catalyst is fixed a preparation of low carbon olefines by synthetic gas under certain reaction condition, and experimental result is listed in table 1.
【Comparative example 3】
Weigh 40.0 grams of ferroso-ferric oxide (Fe3O4), 12.0 grams of copper oxides (CuO), 12.0 grams of Zinc Oxide (ZnO), 32.0 grams of silicon dioxide (SiO2) and 4.0 grams of germanium oxide (GeO2) five kinds of raw materials and percentage by weight is 4% 4 grams of polyethylene glycol powder based on raw material total amount, mill is mixed 4 hours in the ball mill；Based on raw material total amount, 10 grams of the deionized water of add weight percentage ratio 10% is added in the mixed material of mill, is mediated to soft shape；Kneaded material is sent in banded extruder, makes the strip of a diameter of 5mm, and cuts into the column that length is 20mm, after drying naturally, sends in drying equipment, standby in 120 DEG C of dryings 8 hours；By dried precursor, send in high temperature furnace, calcine 4.0 hours in 1300 DEG C, crushing and screening is into 60～80 mesh, that is, the slug type preparation of low carbon olefines by synthetic gas catalyst needed for obtaining after cooling.Obtained catalyst by weight percentage, comprising following components：40%Fe2O3, 12%CuO, 12%ZnO, 32%SiO2, 4%GeO2；Obtained catalyst is fixed a preparation of low carbon olefines by synthetic gas under certain reaction condition, and experimental result is listed in table 1.
【Comparative example 4】
Weigh 40.0 grams of ferroso-ferric oxide (Fe3O4), 12.0 grams of copper oxides (CuO), 12.0 grams of Zinc Oxide (ZnO), 21.0 grams of silicon dioxide (SiO2), 4.0 grams of germanium oxide (GeO2) and 11.0 grams of yttrium oxide (IrO2) six kinds of raw materials and percentage by weight is 4% 4 grams of polyethylene glycol powder based on raw material total amount, mill is mixed 4 hours in the ball mill；Based on raw material total amount, 10 grams of the deionized water of add weight percentage ratio 10% is added in the mixed material of mill, is mediated to soft shape；Kneaded material is sent in banded extruder, makes the strip of a diameter of 5mm, and cuts into the column that length is 20mm, after drying naturally, sends in drying equipment, standby in 120 DEG C of dryings 8 hours；By dried precursor, send in high temperature furnace, calcine 4.0 hours in 1300 DEG C, crushing and screening is into 60～80 mesh, that is, the slug type preparation of low carbon olefines by synthetic gas catalyst needed for obtaining after cooling.Obtained catalyst by weight percentage, comprising following components：40%Fe2O3, 12%CuO, 12%ZnO, 21%SiO2, 4%GeO2, 11%IrO2；Obtained catalyst is fixed a preparation of low carbon olefines by synthetic gas under certain reaction condition, and experimental result is listed in table 1.
Above-described embodiment with the reducing condition of comparative example is：
450 DEG C of temperature
Pressure normal pressure
Loaded catalyst 3ml
Catalyst loading 1000 hours-1
Also Primordial Qi H2
8 hours recovery times
Reaction condition is：
8 millimeters of fixed bed reactors of φ
310 DEG C of reaction temperature
Reaction pressure 1.6MPa
Loaded catalyst 3ml
Catalyst loading 1200 hours-1
Proportioning raw materials (mole) H2/ CO=1.6/1
Table 1
Table 2
* compared with the condition described in table 1 change appreciation condition.
Claims (10)
1. a kind of ferrum-based catalyst of synthesis gas preparing low-carbon olefins, including following components in terms of parts by weight：
A) 20～70 parts of ferrum element or its oxide；
B) 4～20 parts of at least one elements or its oxide in copper and manganese；
C) 4～20 parts of at least one elements or its oxide in zinc and zirconium；
D) 20～40 parts of element silicons or its oxide；
E) 1～10 part of Ge element or its oxide；
F) 1～10 part of iridium or its oxide.
2. the ferrum-based catalyst of synthesis gas preparing low-carbon olefins according to claim 1, it is characterised in that described ferrum
Oxide be ferroso-ferric oxide, content be 30～60 parts.
3. the ferrum-based catalyst of synthesis gas preparing low-carbon olefins according to claim 1, it is characterised in that described copper
Copper oxide and manganese oxide are respectively with the oxide of manganese, content is 5～15 parts.
4. the ferrum-based catalyst of synthesis gas preparing low-carbon olefins according to claim 1, it is characterised in that described zinc
Zinc Oxide and zirconium oxide are respectively with the oxide of zirconium, content is 5～15 parts.
5. the ferrum-based catalyst of synthesis gas preparing low-carbon olefins according to claim 1, it is characterised in that described silicon
Oxide be silicon dioxide, content be 20～35 parts.
6. the ferrum-based catalyst of synthesis gas preparing low-carbon olefins according to claim 1, it is characterised in that described germanium
Oxide be germanium dioxide, content be 1～5 part.
7. the ferrum-based catalyst of synthesis gas preparing low-carbon olefins according to claim 1, it is characterised in that described iridium
Oxide be iridium dioxide, content be 1～5 part.
8. the preparation method of the ferrum-based catalyst of the synthesis gas preparing low-carbon olefins described in any one of claim 1～7, including
Following steps：
(1) by the oxide of the oxide of ferrum, the cupric or manganese, oxide containing zinc or zirconium, siliceous oxide, germanic
Oxide, grind mixed in ball mill after the oxide containing iridium, and polyethylene glycol powder mixing, obtain material A；
(2) deionized water is added in material A, carries out kneading and obtain material B；
(3) material C will be obtained after the drying of material B extruded mouldings；
(4) ferrum-based catalyst needed for crushing and screening is obtained will after material C high temperature sinterings, be cooled down.
9. the preparation method of the ferrum-based catalyst of synthesis gas preparing low-carbon olefins according to claim 8, its feature exist
It is the 2～6% of all raw material gross weights in described Polyethylene Glycol consumption, the temperature of high temperature sintering is 1000～1600 DEG C.
10. a kind of method of synthesis gas preparing low-carbon olefins, with synthesis gas as raw material, H2Mol ratio with CO is 1～3,
It it is 250～400 DEG C in reaction temperature, reaction pressure is 1.0～3.0Mpa, and feed gas volume air speed is 500～5000h-1Condition
Under, unstripped gas is generated containing C with catalyst haptoreaction described in any one of claim 1～72～C4Alkene.
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| CN111266131A (en) * | 2020-03-02 | 2020-06-12 | 正大能源材料(大连)有限公司 | Catalyst for preparing low-carbon olefin from synthesis gas and preparation method and use method thereof |
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