CN105582936B - Slug type preparation of low carbon olefines by synthetic gas catalyst and preparation method thereof - Google Patents
Slug type preparation of low carbon olefines by synthetic gas catalyst and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of slug type preparation of low carbon olefines by synthetic gas catalyst and preparation method thereof, mainly solve the problem of that intensity difference, thermal stability are poor under conditions of use for the low catalyst low with selectivity of light olefin of CO conversion ratios in preparation of low carbon olefines by synthetic gas reaction in the prior art.The catalyst that the present invention uses is in terms of parts by weight including following components：A) 10~70 parts of ferro elements or its oxide；B) 1~10 part of cobalt element or its oxide；C) at least one of calcium and magnesium element or its oxide are selected from for 5~20 parts；D) at least one of silicon and zirconium element or its oxide are selected from for 5~20 parts；E) 15~45 titanium elements or its oxide；F) technical solution of 1~10 phosphide element or its oxide, preferably solves the problems, such as this, the industrial production available for preparation of low carbon olefines by synthetic gas.
Description
Technical field
The present invention relates to a kind of slug type preparation of low carbon olefines by synthetic gas catalyst and preparation method thereof.
Background technology
Low-carbon alkene refers to the alkene that carbon atom number is less than or equal to 4.Using ethylene, propylene as representative low-carbon alkene right and wrong
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
It asks.At present, the petrochemical industry route that the production of low-carbon alkene is mainly cracked using lighter hydrocarbons (ethane, naphtha, light diesel fuel), due to
The long-term run at high level of growing lack and crude oil price of Global Oil resource, development low-carbon alkene industry rely solely on petroleum light hydrocarbon
Tube cracking furnace technique for raw material can encounter increasing raw material problem, and 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 atom number less than or equal to 4 should directly be made, which need not be as indirect method technique from conjunction
Into gas through methanol or dimethyl ether, alkene is further prepared, simplification of flowsheet greatly reduces investment.Petroleum resources are short at home
It lacks, it is current that external dependence degree is higher and higher, international oil price constantly rises violently, selects synthesis gas producing olefinic hydrocarbons technique that can widen former material
Expect source, synthesis gas will be produced by raw material of crude oil, natural gas, coal and recyclable materials, can be based on high cost feedstocks
As naphtha steam cracking technology in terms of provide alternative solution.The coal price of the abundant coal resources of China and relative moderate
It is refined oil for Development of Coal and provides the good market opportunity using preparation of low carbon olefines by synthetic gas technique.And it is enriched in Natural Gas In China
Oil gas field near, if Gas Prices it is cheap and application preparation of low carbon olefines by synthetic gas technique fabulous opportunity.If energy
Using the coal and natural gas resource that China is abundant, pass through gas making producing synthesis gas (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 of great significance to solving energy problem of China.
One-step method from syngas producing light olefins technique functions are derived 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 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 got over
Greatly.Once α values determine, the selectivity of entire synthetic product determines that, chain growth probability α values depend on catalyst composition,
Granularity and reaction condition etc..In recent years, it has been found that the alkene secondary counter caused by alhpa olefin adsorbing again on a catalyst
Should, product distribution is distributed away from ideal ASF.F- T synthesis is a kind of strong exothermal reaction, and a large amount of reaction heat will promote catalyst
Carbon deposit reaction is easier generation methane and low-carbon alkanes, and selectivity of light olefin is caused significantly to decline；Secondly, complicated power
It is unfavorable that factor is also caused 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 and diffuses out metal active centres in time, inhibits the secondary response of low-carbon alkene；Improve gold
Belong to ion dispersibility, also there is preferable olefine selective；Support-metal strong interaction change can also improve low-carbon alkene choosing
Selecting property；Suitable transition metal is added, the bond energy of active component and carbon can be enhanced, inhibits methane generation, improves low-carbon alkene
Selectivity；Electronics accelerating auxiliaries are added, CO chemisorbeds heat is promoted to increase, 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 inhibited, improve its selectivity.
By the Support effect and the certain transition metal promoters of addition and alkali metal promoter of catalyst carrier, catalyst performance can obviously improve
Can, develop the fischer-tropsch synthetic catalyst of the highly selective producing light olefins of novel high-activity being distributed with the non-ASF of product.
One-step method from syngas directly produces low-carbon alkene, it has also become one of research hotspot of fischer-tropsch synthetic catalyst exploitation.
In patent CN1083415A disclosed in Dalian Chemiclophysics Inst., Chinese Academy of Sciences, with the Group IIAs such as MgO alkali metal oxide or high silicon
Iron-Mn catalyst system that zeolite molecular sieve (or phosphorus aluminium zeolite) supports, 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 higher activity (CO conversion ratios
90%) it is and selective (selectivity of light olefin 66%).But the catalyst preparation process is complicated, particularly carrier zeolite molecular sieve
Preparation molding process cost it is 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, using laser pyrolysis technology, to prepare
Technics comparing is cumbersome, and raw material uses Fe (CO)5, catalyst cost is very high, and industrialization is difficult.Beijing University of Chemical Technology is declared special
In sharp ZL03109585.2, vacuum impregnation technology is used to prepare manganese, copper, zinc silicon, potassium etc. and is used for for the Fe/ activated-carbon catalysts of auxiliary agent
Preparation of low carbon olefines by synthetic gas reacts, and under conditions of no unstripped gas recycles, CO conversion ratios 96%, low-carbon alkene is in hydrocarbon
In selectivity 68%.The molysite and auxiliary agent manganese salt that the catalyst preparation uses are more expensive and less soluble ferric oxalate and acetic acid
Manganese, while with the cost of material and operating cost of ethanol as solvent, just inevitable increase catalyst preparation process.It is further
The cost of catalyst is reduced, in its number of patent application 200710063301.9, catalyst uses common drug and reagent system
It is standby, the molysite used be ferric nitrate, manganese salt is manganese nitrate, and sylvite is potassium carbonate, and activated carbon is coconut husk charcoal, can catalyst must flow
Dynamic nitrogen protection is lower to carry out high-temperature roasting and Passivation Treatment, needs special installation, preparation process is complicated, and cost is higher.It is and above-mentioned
Catalyst CO conversion ratios in the fixed bed reaction and selectivity of light olefin are relatively low.
Invention content
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
The problem of low low with selectivity of light olefin in product, carries catalyst intensity difference, the problem of thermal stability is poor under conditions of use
For a kind of new slug type preparation of low carbon olefines by synthetic gas catalyst, when which is used for fixed bed synthesizing low-carbon olefine reaction,
Have the advantages that selectivity of light olefin is high in CO high conversion rates and product.
In order to solve the above technical problems, the technical solution adopted by the present invention is as follows：A kind of slug type synthesis of gas produced low-carbon alkene
Hydrocarbon catalyst, in terms of parts by weight, including following components：
A) 10~70 parts of ferro elements or its oxide；
B) 1~10 part of cobalt element or its oxide；
C) at least one of calcium and magnesium element or its oxide are selected from for 5~20 parts；
D) at least one of silicon and zirconium element or its oxide are selected from for 5~20 parts；
E) 15~45 parts of titanium elements or its oxide；
F) 1~10 part of phosphide element or its oxide.
In above-mentioned technical proposal, the preferred embodiment of the oxide of iron is ferroso-ferric oxide (Fe3O4), the preferred scope of content
It is 30~60 parts；The preferred embodiment of the oxide of cobalt is cobalt oxide (CoO), and the preferred scope of content is 1~5 part；Calcium and magnesium
The preferred embodiment of oxide is respectively calcium oxide (CaO) and magnesia (MgO), and the preferred scope of content is 5~15 parts；Silicon and zirconium
Oxide preferred embodiment be silica (SiO2) and zirconium oxide (ZrO2), the preferred scope of content is 5~15 parts；Titanium
The preferred embodiment of oxide is respectively titanium oxide (TiO2), the preferred scope of content is 20~40 parts；The oxide of indium it is preferred
Scheme is respectively indium oxide (In2O3), the preferred scope of content is 1~5 part.
In above-mentioned technical proposal, the preparation method of the slug type preparation of low carbon olefines by synthetic gas catalyst, including following
Step：
(1) by the oxide of the oxide of iron, the oxide containing cobalt, calcic or magnesium, siliceous or zirconium oxide, titaniferous
After mill is mixed in the ball mill after oxide, the oxide containing indium and hydroxyethyl cellulose mixing, material A is obtained, obtains material
A；
(2) deionized water is added in material A, is mediated to obtain material B；
(3) material C is obtained after material B extruded mouldings are dried；
(4) by after material C high temperature sinterings, cooling crushing and screening obtains required catalyst.
In above-mentioned technical proposal, the preparation method of the slug type preparation of low carbon olefines by synthetic gas catalyst, in step (1)
Hydroxyethyl cellulose dosage is the 3~7% of all raw material gross weights, and deionized water dosage is all raw material gross weights in step (2)
The 5~15% of amount, oxide, siliceous or zirconium of all raw material gross weights for the oxide of iron, the oxide containing cobalt, calcic or magnesium
Oxide, oxide containing titanyl compound, containing indium weight and；It is 2~5 hours to grind the preferred scope done time；High temperature
The preferred scope of sintering temperature is 1200~1800 DEG C.
In above-mentioned technical proposal, the slug type preparation of low carbon olefines by synthetic gas catalyst is low for fixed bed synthesis gas system
Carbene hydrocarbon reaction, using synthesis gas as raw material, H2Molar ratio with CO is 1~3, is 250~400 DEG C in reaction temperature, reaction pressure
Power is 1.0~3.0Mpa, and feed gas volume air speed is 500~5000h-1Under conditions of, unstripped gas contacts instead with the catalyst
It should generate containing C2~C4Alkene.
The method of the present invention in catalyst activity component using introducing the second active component Co, alkaline-earth metal Ca or Mg, non-
Metal Si, transition metal Ti or Zr and main group metal In do catalyst promoter, can be with the electrovalence of modulation active component Fe
State, so as to be conducive to improve the CO conversion ratios of catalyst and the selectivity of low-carbon alkene, particularly when adding in Co and In, due to
Synergistic effect between Co and In and other active components and auxiliary agent can be released effectively the activity of catalyst, improve the conversion of CO
The selectivity of rate and low-carbon alkene achieves good technique effect.
The method of the present invention obtains high intensity height, heat using active component, co-catalysis component are uniformly mixed, through high temperature sintering
The good catalyst of stability even if being crushed in use but being unlikely to crush, can keep the stabilization of catalyst activity.
The method of the present invention, which uses to add in catalyst preparation, bonds pore creating material hydroxyethyl cellulose, due to hydroxy ethyl fiber
Element has big specific surface and abundant pore structure, it is easily made to react the abjection of the carbon dioxide of generation with oxygen at high temperature, is being urged
It is left a void in agent, increases the macroporous structure of catalyst, inside diffusional resistance is reduced.
The use condition of the catalyst is as follows：With H2Synthesis gas with CO compositions is raw material, H2With the molar 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-1's
Under the conditions of, unstripped gas is contacted with fixed bed catalyst, achieves preferable technique effect：CO conversion ratios are up to 99.8%, than existing
There is technology to improve 3.8%；Selectivity of the low-carbon alkene in hydrocarbon is improved up to 78.0% than the prior art
10.0%, more detailed result is seen attached list.It is a kind of preferable synthesis using the F- T synthesis of the catalyst under these conditions
The method of gas producing light olefins.
The present invention is described further for the following examples, and protection scope of the present invention is not by these embodiments
Limitation.
Specific embodiment
【Embodiment 1】
Weigh 40.0 grams of ferroso-ferric oxide (Fe3O4), 4.0 grams of cobalt oxides (CoO), 10.0 grams of calcium oxide (CaO), 10.0 grams
Silica (SiO2), 32.0 grams of titanium oxide (TiO2) and 4.0 grams of indium oxide (In2O3) six kinds of raw materials and based on raw material total amount
Weight percent is 5% 5 grams of hydroxyethyl cellulose, is ground in ball mill 4 hours mixed；The add weight percentage based on raw material total amount
10% 10 grams of deionized water, which is added to, grinds in mixed material, is mediated to soft shape；Kneaded material is sent into extrusion
In machine, the strip of a diameter of 5mm is made, and cuts into the column that length is 20mm, after naturally dry, is sent into drying equipment,
In 120 DEG C dry 8 hours it is spare；Dried precursor is sent into high temperature furnace, is calcined 4.0 hours in 1600 DEG C, broken after cooling
Broken 60~80 mesh that are sieved into are to get to required slug type preparation of low carbon olefines by synthetic gas catalyst.Catalyst obtained is with weight
Percentages include following components：40%Fe2O3, 4%CoO, 10%CaO, 10%SiO2, 32%TiO2, 4%In2O3；It is made
It obtains catalyst and a preparation of low carbon olefines by synthetic gas is fixed under certain reaction condition, experimental result is listed in table 1.
【Embodiment 2】
Weigh 67.5 grams of ferroso-ferric oxide (Fe3O4), 0.5 gram of cobalt oxide (CoO), 3.0 grams of calcium oxide (CaO), 3.0 gram two
Silica (SiO2), 13.0 grams of titanium oxide (TiO2) and 13.0 grams of indium oxide (In2O3) six kinds of raw materials and counted weight by raw material total amount
5 grams of the hydroxyethyl cellulose that percentage is 5% is measured, is ground in ball mill 2 hours mixed；The add weight percentage based on raw material total amount
10% 10 grams of deionized water, which is added to, grinds in mixed material, is mediated to soft shape；Kneaded material is sent into extrusion
In machine, the strip of a diameter of 5mm is made, and cuts into the column that length is 20mm, after naturally dry, is sent into drying equipment,
In 120 DEG C dry 8 hours it is spare；Dried precursor is sent into high temperature furnace, is calcined 4.0 hours in 1600 DEG C, broken after cooling
Broken 60~80 mesh that are sieved into are to get to required slug type preparation of low carbon olefines by synthetic gas catalyst.Catalyst obtained is with weight
Percentages include following components：67.5%Fe2O3, 0.5%CoO, 3%CaO, 3%SiO2, 13%TiO2, 13%In2O3；Institute
Catalyst is made, a preparation of low carbon olefines by synthetic gas is fixed under certain reaction condition, experimental result is listed in table 1.
【Embodiment 3】
Weigh 30.0 grams of ferroso-ferric oxide (Fe3O4), 5.5 grams of cobalt oxides (CoO), 22.0 grams of calcium oxide (CaO), 22.0 grams
Silica (SiO2), 20.0 grams of titanium oxide (TiO2) and 0.5 gram of indium oxide (In2O3) six kinds of raw materials and based on raw material total amount
Weight percent is 5% 5 grams of hydroxyethyl cellulose, is ground in ball mill 5 hours mixed；The add weight percentage based on raw material total amount
10% 10 grams of deionized water, which is added to, grinds in mixed material, is mediated to soft shape；Kneaded material is sent into extrusion
In machine, the strip of a diameter of 5mm is made, and cuts into the column that length is 20mm, after naturally dry, is sent into drying equipment,
In 120 DEG C dry 8 hours it is spare；Dried precursor is sent into high temperature furnace, is calcined 4.0 hours in 1600 DEG C, broken after cooling
Broken 60~80 mesh that are sieved into are to get to required slug type preparation of low carbon olefines by synthetic gas catalyst.Catalyst obtained is with weight
Percentages include following components：30%Fe2O3, 5.5%CoO, 22%CaO, 22%SiO2, 20%TiO2, 0.5%In2O3；
A preparation of low carbon olefines by synthetic gas is fixed in obtained catalyst under certain reaction condition, and experimental result is listed in table 1.
【Embodiment 4】
Weigh 8.0 grams of ferroso-ferric oxide (Fe3O4), 12.0 grams of cobalt oxides (CoO), 15.0 grams of calcium oxide (CaO), 15.0 grams
Silica (SiO2), 47.0 grams of titanium oxide (TiO2) and 3.0 grams of indium oxide (In2O3) six kinds of raw materials and based on raw material total amount
Weight percent is 5% 5 grams of hydroxyethyl cellulose, is ground in ball mill 2 hours mixed；The add weight percentage based on raw material total amount
10% 10 grams of deionized water, which is added to, grinds in mixed material, is mediated to soft shape；Kneaded material is sent into extrusion
In machine, the strip of a diameter of 5mm is made, and cuts into the column that length is 20mm, after naturally dry, is sent into drying equipment,
In 120 DEG C dry 8 hours it is spare；Dried precursor is sent into high temperature furnace, is calcined 4.0 hours in 1200 DEG C, broken after cooling
Broken 60~80 mesh that are sieved into are to get to required slug type preparation of low carbon olefines by synthetic gas catalyst.Catalyst obtained is with weight
Percentages include following components：8%Fe2O3, 12%CoO, 15%CaO, 15%SiO2, 47%TiO2, 3%In2O3；It is made
It obtains catalyst and a preparation of low carbon olefines by synthetic gas is fixed under certain reaction condition, experimental result is listed in table 1.
【Embodiment 5】
Weigh 72.0 grams of ferroso-ferric oxide (Fe3O4), 5.0 grams of cobalt oxides (CoO), 5.0 grams of calcium oxide (CaO), 5.0 gram two
Silica (SiO2), 12.0 grams of titanium oxide (TiO2) and 1.0 grams of indium oxide (In2O3) six kinds of raw materials and counted weight by raw material total amount
5 grams of the hydroxyethyl cellulose that percentage is 5% is measured, is ground in ball mill 2 hours mixed；The add weight percentage based on raw material total amount
10% 10 grams of deionized water, which is added to, grinds in mixed material, is mediated to soft shape；Kneaded material is sent into extrusion
In machine, the strip of a diameter of 5mm is made, and cuts into the column that length is 20mm, after naturally dry, is sent into drying equipment,
In 120 DEG C dry 8 hours it is spare；Dried precursor is sent into high temperature furnace, is calcined 4.0 hours in 1800 DEG C, broken after cooling
Broken 60~80 mesh that are sieved into are to get to required slug type preparation of low carbon olefines by synthetic gas catalyst.Catalyst obtained is with weight
Percentages include following components：72%Fe2O3, 5%CoO, 5%CaO, 5%SiO2, 12%TiO2, 1%In2O3；It is obtained
A preparation of low carbon olefines by synthetic gas is fixed in catalyst under certain reaction condition, and experimental result is listed in table 1.
【Embodiment 6】
Weigh 40.0 grams of ferroso-ferric oxide (Fe3O4), 5.0 grams of cobalt oxides (CoO), 5.0 grams of calcium oxide (CaO), 5.0 gram two
Silica (SiO2), 40.0 grams of titanium oxide (TiO2) and 5.0 grams of indium oxide (In2O3) six kinds of raw materials and counted weight by raw material total amount
3 grams of the hydroxyethyl cellulose that percentage is 3% is measured, is ground in ball mill 2 hours mixed；The add weight percentage based on raw material total amount
10% 10 grams of deionized water, which is added to, grinds in mixed material, is mediated to soft shape；Kneaded material is sent into extrusion
In machine, the strip of a diameter of 5mm is made, and cuts into the column that length is 20mm, after naturally dry, is sent into drying equipment,
In 120 DEG C dry 8 hours it is spare；Dried precursor is sent into high temperature furnace, is calcined 4.0 hours in 1600 DEG C, broken after cooling
Broken 60~80 mesh that are sieved into are to get to required slug type preparation of low carbon olefines by synthetic gas catalyst.Catalyst obtained is with weight
Percentages include following components：40%Fe2O3, 5%CoO, 5%CaO, 5%SiO2, 40%TiO2, 5%In2O3；It is obtained
A preparation of low carbon olefines by synthetic gas is fixed in catalyst under certain reaction condition, and experimental result is listed in table 1.
【Embodiment 7】
Weigh 44.0 grams of ferroso-ferric oxide (Fe3O4), 1.0 grams of cobalt oxides (CoO), 15.0 grams of calcium oxide (CaO), 15.0 grams
Silica (SiO2), 15.0 grams of titanium oxide (TiO2) and 10.0 grams of indium oxide (In2O3) six kinds of raw materials and based on raw material total amount
Weight percent is 7% 7 grams of hydroxyethyl cellulose, is ground in ball mill 2 hours mixed；The add weight percentage based on raw material total amount
10% 10 grams of deionized water, which is added to, grinds in mixed material, is mediated to soft shape；Kneaded material is sent into extrusion
In machine, the strip of a diameter of 5mm is made, and cuts into the column that length is 20mm, after naturally dry, is sent into drying equipment,
In 120 DEG C dry 8 hours it is spare；Dried precursor is sent into high temperature furnace, is calcined 4.0 hours in 1600 DEG C, broken after cooling
Broken 60~80 mesh that are sieved into are to get to required slug type preparation of low carbon olefines by synthetic gas catalyst.Catalyst obtained is with weight
Percentages include following components：44%Fe2O3, 1%CoO, 15%CaO, 15%SiO2, 15%TiO2, 10%In2O3；It is made
It obtains catalyst and a preparation of low carbon olefines by synthetic gas is fixed under certain reaction condition, experimental result is listed in table 1.
【Embodiment 8】
Weigh 60.0 grams of ferroso-ferric oxide (Fe3O4), 1.0 grams of cobalt oxides (CoO), 5.0 grams of calcium oxide (CaO), 5.0 gram two
Silica (SiO2), 19.0 grams of titanium oxide (TiO2) and 10.0 grams of indium oxide (In2O3) six kinds of raw materials and counted weight by raw material total amount
5 grams of the hydroxyethyl cellulose that percentage is 5% is measured, is ground in ball mill 4 hours mixed；The add weight percentage based on raw material total amount
10% 10 grams of deionized water, which is added to, grinds in mixed material, is mediated to soft shape；Kneaded material is sent into extrusion
In machine, the strip of a diameter of 5mm is made, and cuts into the column that length is 20mm, after naturally dry, is sent into drying equipment,
In 120 DEG C dry 8 hours it is spare；Dried precursor is sent into high temperature furnace, is calcined 4.0 hours in 1600 DEG C, broken after cooling
Broken 60~80 mesh that are sieved into are to get to required slug type preparation of low carbon olefines by synthetic gas catalyst.Catalyst obtained is with weight
Percentages include following components：60%Fe2O3, 1%CoO, 5%CaO, 5%SiO2, 19%TiO2, 10%In2O3；It is obtained
A preparation of low carbon olefines by synthetic gas is fixed in catalyst under certain reaction condition, and experimental result is listed in table 1.
【Embodiment 9】
Weigh 40.0 grams of ferroso-ferric oxide (Fe3O4), 4.0 grams of cobalt oxides (CoO), 10.0 grams of magnesia (MgO), 10.0 grams
Silica (SiO2), 32.0 grams of titanium oxide (TiO2) and 4.0 grams of indium oxide (In2O3) six kinds of raw materials and based on raw material total amount
Weight percent is 5% 5 grams of hydroxyethyl cellulose, is ground in ball mill 2 hours mixed；The add weight percentage based on raw material total amount
10% 10 grams of deionized water, which is added to, grinds in mixed material, is mediated to soft shape；Kneaded material is sent into extrusion
In machine, the strip of a diameter of 5mm is made, and cuts into the column that length is 20mm, after naturally dry, is sent into drying equipment,
In 120 DEG C dry 8 hours it is spare；Dried precursor is sent into high temperature furnace, is calcined 4.0 hours in 1600 DEG C, broken after cooling
Broken 60~80 mesh that are sieved into are to get to required slug type preparation of low carbon olefines by synthetic gas catalyst.Catalyst obtained is with weight
Percentages include following components：40%Fe2O3, 4%CoO, 10%MgO, 10%SiO2, 32%TiO2, 4%In2O3；It is made
It obtains catalyst and a preparation of low carbon olefines by synthetic gas is fixed under certain reaction condition, experimental result is listed in table 1.
【Embodiment 10】
Weigh 40.0 grams of ferroso-ferric oxide (Fe3O4), 4.0 grams of cobalt oxides (CoO), 10.0 grams of calcium oxide (CaO), 10.0 grams
Zirconium oxide (ZrO2), 32.0 grams of titanium oxide (TiO2) and 4.0 grams of indium oxide (In2O3) six kinds of raw materials and counted weight by raw material total amount
5 grams of the hydroxyethyl cellulose that percentage is 5% is measured, is ground in ball mill 4 hours mixed；The add weight percentage based on raw material total amount
10% 10 grams of deionized water, which is added to, grinds in mixed material, is mediated to soft shape；Kneaded material is sent into extrusion
In machine, the strip of a diameter of 5mm is made, and cuts into the column that length is 20mm, after naturally dry, is sent into drying equipment,
In 120 DEG C dry 8 hours it is spare；Dried precursor is sent into high temperature furnace, is calcined 4.0 hours in 1600 DEG C, broken after cooling
Broken 60~80 mesh that are sieved into are to get to required slug type preparation of low carbon olefines by synthetic gas catalyst.Catalyst obtained is with weight
Percentages include following components：40%Fe2O3, 4%CoO, 10%CaO, 10%ZrO2, 32%TiO2, 4%In2O3；It is made
It obtains catalyst and a preparation of low carbon olefines by synthetic gas is fixed under certain reaction condition, experimental result is listed in table 1..
【Embodiment 11】
Weigh 40.0 grams of ferroso-ferric oxide (Fe3O4), 4.0 grams of cobalt oxides (CoO), 10.0 grams of magnesia (MgO), 10.0 grams
Zirconium oxide (ZrO2), 32.0 grams of titanium oxide (TiO2) and 4.0 grams of indium oxide (In2O3) six kinds of raw materials and counted weight by raw material total amount
5 grams of the hydroxyethyl cellulose that percentage is 5% is measured, is ground in ball mill 4 hours mixed；The add weight percentage based on raw material total amount
10% 10 grams of deionized water, which is added to, grinds in mixed material, is mediated to soft shape；Kneaded material is sent into extrusion
In machine, the strip of a diameter of 5mm is made, and cuts into the column that length is 20mm, after naturally dry, is sent into drying equipment,
In 120 DEG C dry 8 hours it is spare；Dried precursor is sent into high temperature furnace, is calcined 4.0 hours in 1600 DEG C, broken after cooling
Broken 60~80 mesh that are sieved into are to get to required slug type preparation of low carbon olefines by synthetic gas catalyst.Catalyst obtained is with weight
Percentages include following components：40%Fe2O3, 4%CoO, 10%MgO, 10%ZrO2, 32%TiO2, 4%In2O3；It is made
It obtains catalyst and a preparation of low carbon olefines by synthetic gas is fixed under certain reaction condition, experimental result is listed in table 1.
【Embodiment 12】
Weigh 40.0 grams of ferroso-ferric oxide (Fe3O4), 4.0 grams of cobalt oxides (CoO), 10.0 grams of magnesia (MgO), 10.0 grams
Zirconium oxide (ZrO2), 32.0 grams of titanium oxide (TiO2), 3.8 grams of indium oxide (In2O3) and 0.2 gram of zinc oxide ZnO, seven kinds of raw materials and
Weight percent is 5% 5 grams of hydroxyethyl cellulose based on raw material total amount, is ground in ball mill 4 hours mixed；Based on raw material total amount
10 grams of the deionized water of add weight percentage 10%, which is added to, grinds in mixed material, is mediated to soft shape；Kneaded
Material is sent into banded extruder, and the strip of a diameter of 5mm is made, and cuts into the column that length is 20mm, after naturally dry, is sent into
In drying equipment, in 120 DEG C dry 8 hours it is spare；Dried precursor is sent into high temperature furnace, it is small in 1600 DEG C of calcinings 4.0
When, after cooling crushing and screening into 60~80 mesh to get to required slug type preparation of low carbon olefines by synthetic gas catalyst.It is obtained to urge
Agent by weight percentage, includes following components：40%Fe2O3, 4%CoO, 10%MgO, 10%ZrO2, 32%TiO2,
3.8%In2O3, 0.2%ZnO；A preparation of low carbon olefines by synthetic gas is fixed in obtained catalyst under certain reaction condition, real
It tests result and is listed in table 1.
【Embodiment 13】
Catalyst made from Example 1, other are constant, only change reaction condition, carry out preparation of low carbon olefines by synthetic gas, real
It tests result and is listed in table 2.
【Comparative example 1】
Weigh 40.0 grams of ferroso-ferric oxide (Fe3O4), 4.0 grams of cobalt oxides (CoO), 10.0 grams of calcium oxide (CaO), 10.0 grams
Silica (SiO2), 32.0 grams of titanium oxide (TiO2) and 4.0 grams of indium oxide (In2O3) six kinds of raw materials, mixed 4 are ground in ball mill
Hour；10 grams of the deionized water of add weight percentage 10%, which is added to, based on raw material total amount grinds in mixed material, is mediated
To soft shape；Kneaded material is sent into banded extruder, and the strip of a diameter of 5mm is made, and cuts into the column that length is 20mm
Shape after naturally dry, is sent into drying equipment, in 120 DEG C dry 8 hours it is spare；By dried precursor, it is sent into high temperature furnace
It is interior, in 1600 DEG C calcine 4.0 hours, after cooling crushing and screening into 60~80 mesh to get low to required slug type synthesis gas system
Carbene hydrocarbon catalyst.Catalyst obtained by weight percentage, includes following components：40%Fe2O3, 4%CoO, 10%CaO,
10%SiO2, 32%TiO2, 4%In2O3；A synthesis of gas produced low-carbon is fixed in obtained catalyst under certain reaction condition
Alkene, experimental result are listed in table 1.
【Comparative example 2】
Weigh 40.0 grams of ferroso-ferric oxide (Fe3O4), 4.0 grams of cobalt oxides (CoO), 10.0 grams of calcium oxide (CaO), 10.0 grams
Silica (SiO2), 32.0 grams of titanium oxide (TiO2) and 4.0 grams of indium oxide (In2O3) six kinds of raw materials and based on raw material total amount
Weight percent is 9% 9 grams of hydroxyethyl cellulose, is ground in ball mill 4 hours mixed；The add weight percentage based on raw material total amount
10 grams of the deionized water than 10%, which is added to, grinds in mixed material, is mediated to soft shape；Kneaded material, which is sent into, to be squeezed
In machine, the strip of a diameter of 5mm is made, and cuts into the column that length is 20mm, after naturally dry, is sent into drying equipment
In, in 120 DEG C dry 8 hours it is spare；Dried precursor is sent into high temperature furnace, is calcined 4.0 hours in 1600 DEG C, cooling
Afterwards crushing and screening into 60~80 mesh to get to required slug type preparation of low carbon olefines by synthetic gas catalyst.Catalyst obtained with
Weight percent meter, includes following components：40%Fe2O3, 4%CoO, 10%CaO, 10%SiO2, 32%TiO2, 4%In2O3；
A preparation of low carbon olefines by synthetic gas is fixed in obtained catalyst under certain reaction condition, and experimental result is listed in table 1.
【Comparative example 3】
Weigh 43.5 grams of ferroso-ferric oxide (Fe3O4), 4.0 grams of cobalt oxides (CoO), 10.0 grams of calcium oxide (CaO), 10.0 grams
Silica (SiO2), 32.0 grams of titanium oxide (TiO2) and 0.5 gram of indium oxide (In2O3) six kinds of raw materials and based on raw material total amount
Weight percent is 5% 5 grams of hydroxyethyl cellulose, is ground in ball mill 4 hours mixed；The add weight percentage based on raw material total amount
10% 10 grams of deionized water, which is added to, grinds in mixed material, is mediated to soft shape；Kneaded material is sent into extrusion
In machine, the strip of a diameter of 5mm is made, and cuts into the column that length is 20mm, after naturally dry, is sent into drying equipment,
In 120 DEG C dry 8 hours it is spare；Dried precursor is sent into high temperature furnace, is calcined 4.0 hours in 1600 DEG C, broken after cooling
Broken 60~80 mesh that are sieved into are to get to required slug type preparation of low carbon olefines by synthetic gas catalyst.Catalyst obtained is with weight
Percentages include following components：43.5%Fe2O3, 4%CoO, 10%CaO, 10%SiO2, 32%TiO2, 0.5%In2O3；
A preparation of low carbon olefines by synthetic gas is fixed in obtained catalyst under certain reaction condition, and experimental result is listed in table 1.
【Comparative example 4】
Weigh 32.0 grams of ferroso-ferric oxide (Fe3O4), 4.0 grams of cobalt oxides (CoO), 10.0 grams of calcium oxide (CaO), 10.0 grams
Silica (SiO2), 32.0 grams of titanium oxide (TiO2) and 12.0 grams of indium oxide (In2O3) six kinds of raw materials and based on raw material total amount
Weight percent is 5% 5 grams of hydroxyethyl cellulose, is ground in ball mill 4 hours mixed；The add weight percentage based on raw material total amount
10% 10 grams of deionized water, which is added to, grinds in mixed material, is mediated to soft shape；Kneaded material is sent into extrusion
In machine, the strip of a diameter of 5mm is made, and cuts into the column that length is 20mm, after naturally dry, is sent into drying equipment,
In 120 DEG C dry 8 hours it is spare；Dried precursor is sent into high temperature furnace, is calcined 4.0 hours in 1600 DEG C, broken after cooling
Broken 60~80 mesh that are sieved into are to get to required slug type preparation of low carbon olefines by synthetic gas catalyst.Catalyst obtained is with weight
Percentages include following components：32%Fe2O3, 4%CoO, 10%CaO, 10%SiO2, 32%TiO2, 12%In2O3；It is made
It obtains catalyst and a preparation of low carbon olefines by synthetic gas is fixed under certain reaction condition, experimental result is listed in table 1.
The reducing condition of above-described embodiment and 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
350 DEG C of reaction temperature
Reaction pressure 2.0MPa
Loaded catalyst 3ml
Catalyst loading 1000 hours-1
Raw material proportioning (mole) H2/ CO=1.5/1
Table 1
Table 2
* the evaluation condition changed compared with the condition described in table 1.
Claims (9)
1. a kind of slug type preparation of low carbon olefines by synthetic gas catalyst, in terms of parts by weight, including following components：
A) oxide of 10~70 parts of ferro elements；
B) oxide of 1~10 part of cobalt element；
C) 5~20 parts of oxides for being selected from least one of calcium and magnesium element；
D) 5~20 parts of oxides for being selected from least one of silicon and zirconium element；
E) oxide of 15~45 parts of titanium elements；
F) oxide of 1~10 part of phosphide element；
The slug type preparation of low carbon olefines by synthetic gas catalyst is made of the method including including the following steps：
(1) by the oxidation of the oxide of the oxide of iron, the oxide containing cobalt, calcic or magnesium, siliceous or zirconium oxide, titaniferous
After mill is mixed in the ball mill after object, the oxide containing indium and hydroxyethyl cellulose mixing, material A is obtained, obtains material A；Institute
The hydroxyethyl cellulose dosage stated is the 3~7% of all raw material gross weights；
(2) deionized water is added in material A, is mediated to obtain material B；
(3) material C is obtained after material B extruded mouldings are dried；
(4) by after material C high temperature sinterings, cooling crushing and screening obtains required catalyst.
2. slug type preparation of low carbon olefines by synthetic gas catalyst according to claim 1, it is characterised in that the oxygen of the iron
Compound is ferroso-ferric oxide, and content is 30~60 parts.
3. slug type preparation of low carbon olefines by synthetic gas catalyst according to claim 1, it is characterised in that the oxygen of the cobalt
Compound is cobalt oxide, and content is 1~5 part.
4. slug type preparation of low carbon olefines by synthetic gas catalyst according to claim 1, it is characterised in that the calcium and magnesium
Oxide be respectively calcium oxide and magnesia, content is 5~15 parts.
5. slug type preparation of low carbon olefines by synthetic gas catalyst according to claim 1, it is characterised in that the silicon and zirconium
Oxide be respectively silica and zirconium oxide, content is 5~15 parts.
6. slug type preparation of low carbon olefines by synthetic gas catalyst according to claim 1, it is characterised in that the oxygen of the titanium
Compound is titanium oxide, and content is 20~40 parts.
7. slug type preparation of low carbon olefines by synthetic gas catalyst according to claim 1, it is characterised in that the oxygen of the indium
Compound is indium oxide, and content is 1~5 part.
8. the preparation method of claim 1~7 any one of them slug type preparation of low carbon olefines by synthetic gas catalyst, including following
Step：
(1) by the oxidation of the oxide of the oxide of iron, the oxide containing cobalt, calcic or magnesium, siliceous or zirconium oxide, titaniferous
After mill is mixed in the ball mill after object, the oxide containing indium and hydroxyethyl cellulose mixing, material A is obtained, obtains material A；Institute
The hydroxyethyl cellulose dosage stated is the 3~7% of all raw material gross weights；
(2) deionized water is added in material A, is mediated to obtain material B；
(3) material C is obtained after material B extruded mouldings are dried；
(4) by after material C high temperature sinterings, cooling crushing and screening obtains required catalyst；The temperature of the high temperature sintering is
1200~1800 DEG C.
9. slug type preparation of low carbon olefines by synthetic gas catalyst described in claim 1 is used for one-step method from syngas producing light olefins
Reaction, using synthesis gas as raw material, H2Molar ratio with CO is 1~3, is 250~400 DEG C in reaction temperature, reaction pressure 1.0
~3.0MPa, feed gas volume air speed are 500~5000h-1Under conditions of, unstripped gas contains with catalyst haptoreaction generation
C2~C4Alkene.
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| DE2919921A1 (en) * | 1979-05-17 | 1980-11-20 | Vielstich Wolf | METHOD FOR PRODUCING GASEOUS OLEFINS FROM CARBON MONOXIDE AND CATALYSTS THEREFOR |
| CN1065026A (en) * | 1990-06-02 | 1992-10-07 | 中国科学院兰州化学物理研究所 | Preparation of ethylene by use of synthetic gas |
| EP2314557A1 (en) * | 2009-10-23 | 2011-04-27 | Netherlands Organisation for Scientific Research (Advanced Chemical Technologies for Sustainability) | Production of lower olefins from synthesis gas |
| CN102234212A (en) * | 2010-04-20 | 2011-11-09 | 中国石油化工股份有限公司 | Method for directly converting synthetic gas into low-carbon olefins |
| CN103331171A (en) * | 2013-07-08 | 2013-10-02 | 华东理工大学 | Preparation method and applications of catalyst used for preparing light olefin from synthesis gas |
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| DE2919921A1 (en) * | 1979-05-17 | 1980-11-20 | Vielstich Wolf | METHOD FOR PRODUCING GASEOUS OLEFINS FROM CARBON MONOXIDE AND CATALYSTS THEREFOR |
| CN1065026A (en) * | 1990-06-02 | 1992-10-07 | 中国科学院兰州化学物理研究所 | Preparation of ethylene by use of synthetic gas |
| EP2314557A1 (en) * | 2009-10-23 | 2011-04-27 | Netherlands Organisation for Scientific Research (Advanced Chemical Technologies for Sustainability) | Production of lower olefins from synthesis gas |
| CN102234212A (en) * | 2010-04-20 | 2011-11-09 | 中国石油化工股份有限公司 | Method for directly converting synthetic gas into low-carbon olefins |
| CN103331171A (en) * | 2013-07-08 | 2013-10-02 | 华东理工大学 | Preparation method and applications of catalyst used for preparing light olefin from synthesis gas |
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