CN104148106B - Synthesis gas produces catalyst of low-carbon alkene and preparation method thereof - Google Patents

Abstract

The present invention relates to a kind of synthesis gas and produce catalyst and preparation method thereof of low-carbon alkene, mainly solve in prior art the problem that CO conversion ratio and selectivity of light olefin in preparation of low carbon olefines by synthetic gas reaction are relatively low.The present invention uses catalyst to be made up of complex carrier and active component, wherein complex carrier is made up of alpha-aluminium oxide and ZSM 5 molecular sieve, the silica alumina ratio of ZSM 5 is 40～200, load active component on complex carrier, and active component contains with the following compositions of atomic ratio measuring chemical formula: Fe₁₀₀A_aB_bC_cOx, wherein A is to obtain at least one in transition metal Cu, Mn, and B is to obtain at least one in group of the lanthanides La, Ce, and C is at least one in alkali metal K, Cs；Wherein complex carrier weight is the 20～80% of catalyst weight；In terms of complex carrier percentage by weight, alpha-aluminium oxide is the technical scheme of 20%～the 99% of complex carrier weight, preferably solves this problem, can be used for synthesis gas and produces the commercial production of low-carbon alkene.

Description

Synthesis gas produces catalyst of low-carbon alkene and preparation method thereof

Technical field

The present invention relates to a kind of synthesis gas catalyst producing low-carbon alkene and preparation method thereof.

Background technology

Low-carbon alkene refers to that carbon number is less than or equal to the alkene of 4.Low-carbon alkene right and wrong with ethylene, propylene as representative The most important basic organic chemical industry raw material, along with the quick 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 the petrochemical industry route that lighter hydrocarbons (ethane, Petroleum, light diesel fuel) crack, due to The day by day shortage of Global Oil resource and the long-term run at high level of crude oil price, development low-carbon alkene industry relies solely on petroleum light hydrocarbon Can run into an increasing raw material difficult problem, low-carbon alkene production technology and raw material for the tube cracking furnace technique of 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, anti-by F-T synthesis Should directly prepare the carbon number process of low-carbon alkene less than or equal to 4, this technique without as indirect method technique from conjunction Become gas through methanol or dimethyl ether, prepare alkene, simplification of flowsheet further, greatly reduce investment.Petroleum resources are short at home Lacking, it is current that external dependence degree is more and more higher, international oil price constantly rises violently, selects synthesis gas producing olefinic hydrocarbons technique can widen former material Material source, can will be based on high cost raw material with crude oil, natural gas, coal and recyclable materials for raw material production synthesis gas Replacement scheme is provided in terms of the steam cracking technology of Petroleum.Chinese abundant coal resources and the coal price of relative moderate The good market opportunity is provided for Development of Coal oil refining and application preparation of low carbon olefines by synthetic gas technique.And enrich at Natural Gas In China Oil gas field near, if Gas Prices is cheap, also be application preparation of low carbon olefines by synthetic gas technique fabulous opportunity.If energy Utilize coal and the natural gas resource of China's abundant, by gas making producing synthesis gas (carbon monoxide and the gaseous mixture of hydrogen), send out The substitute energy source for petroleum technology of exhibition 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 technique functions comes from traditional Fischer-Tropsch synthesis, traditional Fischer-Tropsch synthetic Carbon number distribution defer to ASF distribution, 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%.It is the biggest that chain increases probability α value, and the selectivity of product heavy hydrocarbon is more Greatly.Once α value determines, and the selectivity of whole synthetic product determines that, chain increase probability α value depend on catalyst form, Granularity and reaction condition etc..In recent years, it has been found that due to alhpa olefin on a catalyst adsorb the alkene secondary counter caused again Should, products distribution deviates from preferable ASF distribution.F-T synthesis is a kind of strong exothermal reaction, and substantial amounts of reaction heat will promote catalyst Carbon deposit reaction is easier to generate methane and low-carbon alkanes, causes selectivity of light olefin significantly to decline；Secondly, complicated power It is unfavorable that factor also causes to selectivity synthesis low-carbon alkene；The ASF distribution of Fischer-Tropsch synthetic limits synthesizing low-carbon alkene Selectivity.The catalyst of F-T synthesis gas producing light olefins is mainly ferrum catalyst series, directly makes to improve synthesis gas Take the selectivity of low-carbon alkene, fischer-tropsch synthetic catalyst can be carried out physics and chemical modification, as utilized molecular sieve suitable Pore passage structure, beneficially low-carbon alkene diffuse out metal active centres, the secondary response of suppression low-carbon alkene in time；Improve gold Belong to ion dispersibility, also have preferable olefine selective；Support-metal strong interaction changes can also improve low-carbon alkene choosing Selecting property；Adding suitable transition metal, can strengthen the bond energy of active component and carbon, suppression methane generates, and improves low-carbon alkene Selectivity；Adding electronics accelerating auxiliaries, promote CO chemisorbed heat to increase, adsorbance also increases, and hydrogen adsorptive capacity reduces, result Selectivity of light olefin increases；Eliminate catalyst acid center, the secondary response of low-carbon alkene can be suppressed, improve its selectivity. By the Support effect of catalyst carrier and some transition metal promoter of interpolation and alkali metal promoter, can obviously improve catalyst performance Can, develop the fischer-tropsch synthetic catalyst of the novel high-activity height selectivity producing light olefins with product non-ASF distribution.

The bifunctional catalyst of fischer-tropsch synthetic catalyst and molecular sieve component composition can improve tradition Fischer-Tropsch as one Catalyst directional selectivity is poor, breaks through the effective ways that ASF limits, by synthesis gas high-activity high-selectivity be converted into desired Product.ZSM-5 molecular sieve is the effective active component of hydrocarbon catalytic cracking preparing low carbon olefin hydrocarbon, and ZSM-5 molecular sieve has MFI structure, belongs to mesoporous molecular sieve, and due to the architectural characteristic of himself, ZSM-5 can make the straight chain in gasoline fraction and short-chain branch alkane Hydrocarbon carries out cracking and isomerization in its lattice, generates low-carbon alkene, thus increases the productivity of low-carbon alkene.Owing to ZSM-5 divides Sub-sieve itself has stronger acid catalysis function can promote the secondary response of low-carbon alkene, causes selectivity of light olefin very poor. Ion exchange or solid-state diffusion decomposition method can be used, carry out introducing Na or K in ZSM-5 molecular sieve duct at alkali modification Reason, reduces it acid, to suppress low-carbon alkene secondary response on ZSM-5 acid centre.

Synthesis gas is directly produced low-carbon alkene by F-T synthesis, it has also become the study hotspot of fischer-tropsch synthetic catalyst exploitation One of.In patent CN1083415A disclosed in Dalian Chemiclophysics Inst., Chinese Academy of Sciences, with Group IIA alkali metal oxides such as MgO Or ferrum-Mn catalyst system that silica-rich zeolite molecular sieve (or phosphorus aluminum zeolite) supports, make auxiliary agent with highly basic K or Cs ion, closing Becoming gas reaction for preparing light olefins pressure is 1.0 ~ 5.0MPa, and at reaction temperature 300 ~ 400 DEG C, (CO turns can to obtain higher activity Rate 90%) and selectivity (selectivity of light olefin 66%).But this catalyst preparation process is complicated, particularly carrier zeolite molecules The preparation molding process cost of sieve is higher, is unfavorable for industrialized production.The patent that Beijing University of Chemical Technology is declared In CN01144691.9, use laser pyrolysis processes to combine solid state reaction combination technique and be prepared for Fe₃The Fe base nanometer that C is main is urged Agent is applied to preparation of low carbon olefines by synthetic gas, and achieves good catalytic effect, owing to needs use laser pyrolysis technology, system Standby technics comparing is loaded down with trivial details, and raw material uses Fe (CO)₅, catalyst cost is the highest, industrialization difficulty.Beijing University of Chemical Technology is declared In patent CN03109585.2, employing vacuum impregnation technology is prepared the Fe/ activated-carbon catalyst that manganese, copper, zinc silicon, potassium etc. are auxiliary agent and is used Reacting in preparation of low carbon olefines by synthetic gas, under conditions of circulating without unstripped gas, CO conversion ratio 96%, low-carbon alkene is at nytron Selectivity 68% in thing.Iron salt and auxiliary agent manganese salt that the preparation of this catalyst uses are more expensive and less soluble ferric oxalate and second Acid manganese, simultaneously with ethanol as solvent, the most inevitable cost of material increasing catalyst preparation process and running cost.For entering one Step reduces the cost of catalyst, and in its patent CN200710063301.9, catalyst uses common medicine and reagent to prepare, The iron salt used is ferric nitrate, and manganese salt is manganese nitrate, and potassium salt is potassium carbonate, and activated carbon is coconut husk charcoal, can must flow by catalyst Carrying out high-temperature roasting and Passivation Treatment under nitrogen protection, need special installation, preparation process is complicated, relatively costly.And above-mentioned urge Agent CO conversion ratio in fixed bed reaction and selectivity of light olefin are the most relatively low.

Summary of the invention

The technical problem to be solved is in prior art during preparation of low carbon olefines by synthetic gas, and CO conversion ratio is relatively Low, that in product, selectivity of light olefin is relatively low problem, it is provided that a kind of synthesis gas produces the catalyst of low-carbon alkene, this catalyst There is CO conversion ratio high, the advantage that selectivity of light olefin is high.

In order to solve above-mentioned technical problem, the technical solution used in the present invention is as follows: a kind of synthesis gas produces low-carbon alkene Catalyst, catalyst is made up of complex carrier and active component, and wherein complex carrier is by Alpha-alumina and ZSM-5 molecular sieve group Becoming, the silica alumina ratio of ZSM-5 is 40～200, load active component on complex carrier, and active component contains with atomic ratio measuring chemistry The following compositions of formula: Fe₁₀₀A_aB_bC_cOx

Wherein A is to obtain at least one in transition metal Cu, Mn,

B is to obtain at least one in group of the lanthanides La, Ce,

C is at least one in alkali metal K, Cs.

The span of a is 2.0～40.0；

The span of b is 2.0～35.0；

The span of c is 2.0～35.0；

X is to meet in catalyst the oxygen atom sum needed for each element valence；

Wherein complex carrier weight is the 20～80% of catalyst weight；In terms of complex carrier percentage by weight, Alpha-alumina For complex carrier weight 20%～99%.

In technique scheme, in terms of catalyst weight percent, the preferred scope of complex carrier weight is catalyst weight The 30～70% of amount；In terms of complex carrier percentage by weight, preferred scope is complex carrier weight the 30% of Alpha-alumina weight ～80%；In terms of complex carrier percentage by weight, preferred scope is complex carrier weight 40%～the 60% of Alpha-alumina weight； In complex carrier, the optimization range of the silica alumina ratio of ZSM-5 molecular sieve is 100～150, and the prioritization scheme of active component A is manganese；Live The prioritization scheme of property component B is lanthanum；The prioritization scheme of active component C is potassium.

In technique scheme, a kind of synthesis gas produces the preparation method of the catalyst of low-carbon alkene, comprises the following steps:

(1) by Alpha-alumina and ZSM-5 molecular sieve powder mix homogeneously, after tabletting, complex carrier is prepared in crushing and screening molding H

(2) by iron salt, transition metal mantoquita or manganese salt, lanthanide series lanthanum salt or cerium salt, and alkali metal potassium salt or cesium salt, Soluble in water make mixed solution I；

(3) under the conditions of vacuum 1-80 kPa, above-mentioned mixed solution I be impregnated in the compound of forming in (2) step On carrier H catalyst precarsor J；

(4) by catalyst precarsor J, 450-750 DEG C of roasting 0.5-4.5 hour, obtains required catalyst after drying.

Catalyst prepared by the present invention is for F-T synthesis reaction for preparing light olefins, with H₂It is former with the synthesis gas of CO composition Material, H₂Being 1 ~ 3 with the mol ratio of CO, be 250 ~ 400 DEG C in reaction temperature, reaction pressure is 1.0 ~ 3.0Mpa, feed gas volume Air speed is 500 ~ 2500h^-1Condition and range in, unstripped gas contacts with fixed bde catalyst, generates main containing C₂-C₄Low carbene Hydrocarbon.

The inventive method uses vacuum impregnation technology to prepare catalyst, and active component and auxiliary agent high uniformity can be made to be scattered in Carrier surface, increases the quantity of the active sites being exposed to carrier surface, improves the conversion ratio of CO.

The inventive method uses lanthanide series La, Ce of introducing in the catalyst and alkali metal K, Cs to help as catalyst Agent, can strengthen catalyst activity component and the interaction strength of carrier with the electron valence state of modulation active component Fe, thus has It is beneficial to improve the selectivity of light olefin of catalyst.

On the one hand the inventive method uses Alpha-alumina and the difunctional complex carrier of ZSM-5 molecular sieve mixing, can be in order to Produce low-carbon alkene with iron-base fischer-tropsch synthesis catalyst high-activity high-selectivity on Alpha-alumina, on the other hand utilize complex carrier The splitting action of middle ZSM-5 molecular sieve, the long chain hydrocarbon catalytic pyrolysis generated by fischer-tropsch reaction, improves low-carbon alkene further and selects Property.Because ZSM-5 molecular sieve has MFI structure, belonging to mesoporous molecular sieve, due to the architectural characteristic of himself, ZSM-5 can make gasoline Straight chain and short-chain branch alkane in fraction carry out cracking and isomerization in its lattice, generate low-carbon alkene, thus increase low-carbon (LC) The productivity of alkene.

The method using the present invention, at H₂Being 1.2 with the mol ratio of CO, be 340 DEG C in reaction temperature, reaction pressure is 1.2Mpa, feed gas volume air speed is 1000h^-1Under conditions of, CO conversion ratio, up to 99.6%, improves 3.6% than prior art；Low Carbon olefin selectivity in Hydrocarbon, up to 74.0%, improves 6.0% than prior art.Achieve preferable technology effect Really.Use complex carrier to achieve unforeseeable technique effect, compare and be used alone Alpha-alumina or ZSM-5 molecular sieve, urge The activity and selectivity of agent all improves more than 15%.

Below by embodiment, the invention will be further elaborated.

Detailed description of the invention

The present invention is described further for the following examples, and protection scope of the present invention is not by these embodiments Restriction.

[embodiment 1]

By 60.0g Alpha-alumina and 40.0g ZSM-5 molecular sieve (silica alumina ratio 100) powder mix homogeneously, tabletting is sieved into 60-80 mesh prepares complex carrier H；134.9g Fe(NO3)39H2O, the manganese nitrate solution of 35.6g 50%, 14.5g six are hydrated Lanthanum (III) nitrate and 1.7g potassium nitrate, be dissolved in 35.0g water and make mixed solution I；Under conditions of vacuum 80kPa, by above-mentioned Mixed solution I impregnated on the complex carrier H that 60.0 g have prepared to obtain catalyst precarsor J；The catalyst precarsor J impregnated exists It is dried under the conditions of 110 DEG C, then carries out roasting, sintering temperature 450 DEG C, roasting time 2h, obtain producing low-carbon (LC) for synthesis gas The catalyst of alkene.In catalyst, active component is respectively 40% and 60% with the weight of complex carrier, and in complex carrier, ZSM-5 divides Son sieve and the weight ratio of Alpha-alumina, and the composition formula of active component atomic ratio is as follows:

40%Fe₁₀₀Mn₃₀La₁₀K₅O_x+ 60%(40% ZSM-5+60% α-Al₂O₃).

Obtained catalyst carries out the experimental result of synthesis gas production low-carbon alkene under certain reaction condition and is listed in table 1。

[embodiment 2]

By 99.0g Alpha-alumina and 1.0g ZSM-5 molecular sieve (silica alumina ratio 100) powder mix homogeneously, tabletting is sieved into 60-80 mesh prepares complex carrier H；134.9g Fe(NO3)39H2O, the manganese nitrate solution of 35.6g 50%, 14.5g six are hydrated Lanthanum (III) nitrate and 1.7g potassium nitrate, be dissolved in 35.0g water and make mixed solution I；Under conditions of vacuum 80kPa, by above-mentioned Mixed solution I impregnated on the complex carrier H that 60.0 g have prepared to obtain catalyst precarsor J；The catalyst precarsor J impregnated exists It is dried under the conditions of 110 DEG C, then carries out roasting, sintering temperature 450 DEG C, roasting time 2h, obtain producing low-carbon (LC) for synthesis gas The catalyst of alkene.In catalyst, active component is respectively 40% and 60% with the weight of complex carrier, and in complex carrier, ZSM-5 divides Son sieve and the weight ratio of Alpha-alumina, and the composition formula of active component atomic ratio is as follows:

40%Fe₁₀₀Mn₃₀La₁₀K₅O_x+ 60%(1% ZSM-5+99% α-Al₂O₃).

Obtained catalyst carries out the experimental result of synthesis gas production low-carbon alkene under certain reaction condition and is listed in table 1。

[embodiment 3]

By 20.0g Alpha-alumina and 80.0g ZSM-5 molecular sieve (silica alumina ratio 100) powder mix homogeneously, tabletting is sieved into 60-80 mesh prepares complex carrier H；134.9g Fe(NO3)39H2O, the manganese nitrate solution of 35.6g 50%, 14.5g six are hydrated Lanthanum (III) nitrate and 1.7g potassium nitrate, be dissolved in 35.0g water and make mixed solution I；Under conditions of vacuum 80kPa, by above-mentioned Mixed solution I impregnated on the complex carrier H that 60.0 g have prepared to obtain catalyst precarsor J；The catalyst precarsor J impregnated exists It is dried under the conditions of 110 DEG C, then carries out roasting, sintering temperature 450 DEG C, roasting time 2h, obtain producing low-carbon (LC) for synthesis gas The catalyst of alkene.In catalyst, active component is respectively 40% and 60% with the weight of complex carrier, and in complex carrier, ZSM-5 divides Son sieve and the weight ratio of Alpha-alumina, and the composition formula of active component atomic ratio is as follows:

40%Fe₁₀₀Mn₃₀La₁₀K₅O_x+ 60%(80% ZSM-5+20% α-Al₂O₃).

Obtained catalyst carries out the experimental result of synthesis gas production low-carbon alkene under certain reaction condition and is listed in table 1。

[embodiment 4]

By 40.0g Alpha-alumina and 60.0g ZSM-5 molecular sieve (silica alumina ratio 150) powder mix homogeneously, tabletting is sieved into 60-80 mesh prepares complex carrier H；By 80.4g Fe(NO3)39H2O, 19.2g Gerhardite, 17.3g six nitric hydrate Cerium and 2.0g potassium nitrate, be dissolved in 30.0g water and make mixed solution I；Under conditions of vacuum 10kPa, by above-mentioned mixing Solution I impregnated on the complex carrier H that 70.0 g have prepared to obtain catalyst precarsor J；The catalyst precarsor J impregnated is 110 It is dried under the conditions of DEG C, then carries out roasting, sintering temperature 550 DEG C, roasting time 3h, obtain producing low-carbon alkene for synthesis gas Catalyst.In catalyst, active component is respectively 30% and 70% with the weight of complex carrier, ZSM-5 molecular sieve in complex carrier With the weight ratio of Alpha-alumina, and the composition formula of active component atomic ratio is as follows:

30%Fe₁₀₀Cu₄₀Ce₂₀K₁₀O_x+ 70%(60% ZSM-5+40% α-Al₂O₃).

Obtained catalyst carries out the experimental result of synthesis gas production low-carbon alkene under certain reaction condition and is listed in table 1。

[embodiment 5]

By 80.0g Alpha-alumina and 20.0g ZSM-5 molecular sieve (silica alumina ratio 150) powder mix homogeneously, tabletting is sieved into 60-80 mesh prepares complex carrier H；121.1g Fe(NO3)39H2O, the manganese nitrate solution of 21.5g 50%, 39.0g six are hydrated Cerous nitrate and 8.8g cesium nitrate, be dissolved in 35.0g water and make mixed solution I；Under conditions of vacuum 80kPa, by above-mentioned Mixed solution I impregnated on the complex carrier H that 50.0 g have prepared to obtain catalyst precarsor J；The catalyst precarsor J impregnated exists It is dried under the conditions of 110 DEG C, then carries out roasting, sintering temperature 650 DEG C, roasting time 4h, obtain producing low-carbon (LC) for synthesis gas The catalyst of alkene.In catalyst, active component is respectively 50% and 50% with the weight of complex carrier, and in complex carrier, ZSM-5 divides Son sieve and the weight ratio of Alpha-alumina, and the composition formula of active component atomic ratio is as follows:

50%Fe₁₀₀Mn₂₀Ce₃₀Cs₁₅O_x+ 50%(20% ZSM-5+80% α-Al₂O₃).

Obtained catalyst carries out the experimental result of synthesis gas production low-carbon alkene under certain reaction condition and is listed in table 1。

[embodiment 6]

By 90.0g Alpha-alumina and 10.0g ZSM-5 molecular sieve (silica alumina ratio 150) powder mix homogeneously, tabletting is sieved into 60-80 mesh prepares complex carrier H；By 140.1g Fe(NO3)39H2O, 8.4g Gerhardite, 39.0g six nitric hydrate Lanthanum and 8.8g cesium nitrate, be dissolved in 35.0g water and make mixed solution I；Under conditions of vacuum 10kPa, by above-mentioned mixing Solution I impregnated on the complex carrier H that 40.0 g have prepared to obtain catalyst precarsor J；The catalyst precarsor J impregnated is 110 It is dried under the conditions of DEG C, then carries out roasting, sintering temperature 750 DEG C, roasting time 1h, obtain producing low-carbon alkene for synthesis gas Catalyst.In catalyst, active component is respectively 60% and 40% with the weight of complex carrier, ZSM-5 molecular sieve in complex carrier With the weight ratio of Alpha-alumina, and the composition formula of active component atomic ratio is as follows:

60%Fe₁₀₀Cu₁₀La₃₅Cs₂₀O_x+ 40%(10% ZSM-5+90% α-Al₂O₃).

Obtained catalyst carries out the experimental result of synthesis gas production low-carbon alkene under certain reaction condition and is listed in table 1。

[embodiment 7]

By 90.0g Alpha-alumina and 10.0g ZSM-5 molecular sieve (silica alumina ratio 150) powder mix homogeneously, tabletting is sieved into 60-80 mesh prepares complex carrier H；211.3g Fe(NO3)39H2O, the manganese nitrate solution of 9.4g 50%, 11.3g six are hydrated Lanthanum (III) nitrate and 30.6g cesium nitrate, be dissolved in 40.0g water and make mixed solution I；Under conditions of vacuum 80kPa, by upper State mixed solution I and impregnated on the complex carrier H that 30.0 g have prepared to obtain catalyst precarsor J；The catalyst precarsor J impregnated It is dried under the conditions of 110 DEG C, then carries out roasting, sintering temperature 550 DEG C, roasting time 2h, obtain producing low for synthesis gas The catalyst of carbon olefin.In catalyst, active component is respectively 70% and 30% with the weight of complex carrier, ZSM-5 in complex carrier Molecular sieve and the weight ratio of Alpha-alumina, and the composition formula of active component atomic ratio is as follows:

70%Fe₁₀₀Mn₅La₅Cs₃₀O_x+ 30%(80% ZSM-5+20% α-Al₂O₃).

Obtained catalyst carries out the experimental result of synthesis gas production low-carbon alkene under certain reaction condition and is listed in table 1。

[embodiment 8]

By 99.0g Alpha-alumina and 1.0g ZSM-5 molecular sieve (silica alumina ratio 150) powder mix homogeneously, tabletting is sieved into 60-80 mesh prepares complex carrier H；By 55.7g Fe(NO3)39H2O, 8.3g Gerhardite, 14.9g six nitric hydrate Lanthanum and 1.4g potassium nitrate, be dissolved in 30.0g water and make mixed solution I；Under conditions of vacuum 80kPa, by above-mentioned mixing Solution I impregnated on the complex carrier H that 80.0 g have prepared to obtain catalyst precarsor J；The catalyst precarsor J impregnated is 110 It is dried under the conditions of DEG C, then carries out roasting, sintering temperature 550 DEG C, roasting time 2h, obtain producing low-carbon alkene for synthesis gas Catalyst.In catalyst, active component is respectively 20% and 80% with the weight of complex carrier, ZSM-5 molecular sieve in complex carrier With the weight ratio of Alpha-alumina, and the composition formula of active component atomic ratio is as follows:

20%Fe₁₀₀Cu₂₅La₂₅K₁₀O_x+ 80%(1% ZSM-5+99% α-Al₂O₃).

Obtained catalyst carries out the experimental result of synthesis gas production low-carbon alkene under certain reaction condition and is listed in table 1。

[embodiment 9]

By 50.0g Alpha-alumina and 50.0g ZSM-5 molecular sieve (silica alumina ratio 100) powder mix homogeneously, tabletting is sieved into 60-80 mesh prepares complex carrier H；119.2g Fe(NO3)39H2O, the manganese nitrate solution of 21.1g 50%, 25.6g six are hydrated Cerous nitrate and 4.5g potassium nitrate, be dissolved in 35.0g water and make mixed solution I；Under conditions of vacuum 80kPa, by above-mentioned Mixed solution I impregnated on the complex carrier H that 60.0 g have prepared to obtain catalyst precarsor J；The catalyst precarsor J impregnated exists It is dried under the conditions of 110 DEG C, then carries out roasting, sintering temperature 450 DEG C, roasting time 3h, obtain producing low-carbon (LC) for synthesis gas The catalyst of alkene.In catalyst, active component is respectively 40% and 60% with the weight of complex carrier, and in complex carrier, ZSM-5 divides Son sieve and the weight ratio of Alpha-alumina, and the composition formula of active component atomic ratio is as follows:

40%Fe₁₀₀Mn₂₀Ce₂₀K₁₅O_x+ 60%(50% ZSM-5+50% α-Al₂O₃).

Obtained catalyst carries out the experimental result of synthesis gas production low-carbon alkene under certain reaction condition and is listed in table 1。

[embodiment 10]

By 70.0g Alpha-alumina and 30.0g ZSM-5 molecular sieve (silica alumina ratio 100) powder mix homogeneously, tabletting is sieved into 60-80 mesh prepares complex carrier H；By 132.7g Fe(NO3)39H2O, 23.8g Gerhardite, 28.5g six nitric hydrate Cerium and 6.4g cesium nitrate, be dissolved in 40.0g water and make mixed solution I；Under conditions of vacuum 80kPa, by above-mentioned mixing Solution I impregnated on the complex carrier H that 50.0g has prepared to obtain catalyst precarsor J；The catalyst precarsor J impregnated is at 110 DEG C Under the conditions of be dried, then carry out roasting, sintering temperature 450 DEG C, roasting time 3h, obtain producing low-carbon alkene for synthesis gas Catalyst.In catalyst, the weight of active component and complex carrier is respectively 50% and 50%, in complex carrier ZSM-5 molecular sieve and The weight ratio of Alpha-alumina, and the composition formula of active component atomic ratio is as follows:

50%Fe₁₀₀Cu₃₀Ce₂₀Cs₁₀O_x+ 50%(30% ZSM-5+70% α-Al₂O₃).

Obtained catalyst carries out the experimental result of synthesis gas production low-carbon alkene under certain reaction condition and is listed in table 1。

[comparative example 1]

100.0g alpha-alumina powder tabletting is sieved into 60-80 mesh and prepares alpha-alumina supports H；By 134.9g nine Nitric hydrate ferrum, the manganese nitrate solution of 35.6g 50%, 14.5g lanthanum nitrate hexahydrate and 1.7g potassium nitrate, be dissolved in 35.0g water In make mixed solution I；Under conditions of vacuum 80kPa, above-mentioned mixed solution I be impregnated in α that 60.0 g have prepared- On alumina support H catalyst precarsor J；The catalyst precarsor J impregnated is dried under the conditions of 110 DEG C, then carries out roasting, Sintering temperature 450 DEG C, roasting time 2h, obtain producing the catalyst of low-carbon alkene for synthesis gas.Active component in catalyst It is respectively 40% and 60% with the weight of alpha-alumina supports, and the composition formula of active component atomic ratio is as follows:

40%Fe₁₀₀Mn₃₀La₁₀K₅O_x+ 60% α-Al₂O₃。

Obtained catalyst carries out the experimental result of synthesis gas production low-carbon alkene under certain reaction condition and is listed in table 1。

[comparative example 2]

100.0g ZSM-5 molecular sieve (silica alumina ratio 100) pressed powder is sieved into 60-80 mesh and prepares ZSM-5 molecular sieve Carrier H；By 134.9g Fe(NO3)39H2O, the manganese nitrate solution of 35.6g 50%, 14.5g lanthanum nitrate hexahydrate and 1.7g nitre Acid potassium, is dissolved in 35.0g water and makes mixed solution I；Under conditions of vacuum 80kPa, above-mentioned mixed solution I be impregnated in On the ZSM-5 molecular sieve carrier H that 60.0 g have prepared catalyst precarsor J；The catalyst precarsor J impregnated is at 110 DEG C of bars It is dried under part, then carries out roasting, sintering temperature 450 DEG C, roasting time 2h, obtain producing urging of low-carbon alkene for synthesis gas Agent.In catalyst, active component is respectively 40% and 60%, and active component atomic ratio with the weight of ZSM-5 molecular sieve carrier Composition formula as follows:

40%Fe₁₀₀Mn₃₀La₁₀K₅O_x+ 60%ZSM-5.

Obtained catalyst carries out the experimental result of synthesis gas production low-carbon alkene under certain reaction condition and is listed in table 1。

[comparative example 3]

By 10.0g Alpha-alumina and 90.0g ZSM-5 molecular sieve (silica alumina ratio 100) powder mix homogeneously, tabletting is sieved into 60-80 mesh prepares complex carrier H；134.9g Fe(NO3)39H2O, the manganese nitrate solution of 35.6g 50%, 14.5g six are hydrated Lanthanum (III) nitrate and 1.7g potassium nitrate, be dissolved in 35.0g water and make mixed solution I；Under conditions of vacuum 80kPa, by above-mentioned Mixed solution I impregnated on the complex carrier H that 60.0 g have prepared to obtain catalyst precarsor J；The catalyst precarsor J impregnated exists It is dried under the conditions of 110 DEG C, then carries out roasting, sintering temperature 450 DEG C, roasting time 2h, obtain producing low-carbon (LC) for synthesis gas The catalyst of alkene.In catalyst, active component is respectively 40% and 60% with the weight of complex carrier, and in complex carrier, ZSM-5 divides Son sieve and the weight ratio of Alpha-alumina, and the composition formula of active component atomic ratio is as follows:

40%Fe₁₀₀Mn₃₀La₁₀K₅O_x+ 60%(90% ZSM-5+10% α-Al₂O₃).

Obtained catalyst carries out the experimental result of synthesis gas production low-carbon alkene under certain reaction condition and is listed in table 1。

Above-described embodiment with the reducing condition of comparative example is:

Temperature 450 DEG C

Pressure normal pressure

Loaded catalyst 3 ml

Catalyst loading 1000 hours^-1

Reducing gases H₂

8 hours recovery times

Reaction condition is:

8 millimeters of fixed bed reactors of φ

Reaction temperature 340 DEG C

Reaction pressure 1.2MPa

Loaded catalyst 3 ml

Catalyst loading 1000 hours^-1

Proportioning raw materials (mole) H₂/ CO=1.2/1

The evaluation result of table 1 embodiment catalyst

Claims (9)

1. synthesis gas produces a catalyst for low-carbon alkene, and catalyst is made up of complex carrier and active component, is wherein combined Carrier is made up of Alpha-alumina and ZSM-5 molecular sieve, and the silica alumina ratio of ZSM-5 is 40～200, supported active group on complex carrier Point, active component contains with the following compositions of atomic ratio measuring chemical formula: Fe₁₀₀A_aB_bC_cOx

Wherein A is to obtain at least one in transition metal Cu, Mn,

B is to obtain at least one in group of the lanthanides La, Ce,

C is at least one in alkali metal K, Cs；

The span of a is 2.0～40.0；

The span of b is 2.0～35.0；

The span of c is 2.0～35.0；

X is to meet in catalyst the oxygen atom sum needed for each element valence；

Wherein complex carrier weight is the 20～80% of catalyst weight；In terms of complex carrier percentage by weight, Alpha-alumina is multiple Close the 20%～99% of vehicle weight.

Synthesis gas the most according to claim 1 produces the catalyst of low-carbon alkene, it is characterised in that with catalyst weight hundred Proportion by subtraction meter, complex carrier weight is the 30～70% of catalyst weight.

Synthesis gas the most according to claim 1 produces the catalyst of low-carbon alkene, it is characterised in that with complex carrier weight Percentages, Alpha-alumina weight is the 30%～80% of complex carrier weight.

Synthesis gas the most according to claim 3 produces the catalyst of low-carbon alkene, it is characterised in that with complex carrier weight Percentages, Alpha-alumina weight is the 40%～60% of complex carrier weight.

Synthesis gas the most according to claim 1 produces the catalyst of low-carbon alkene, it is characterised in that the silicon of ZSM-5 molecular sieve Aluminum ratio is 100～150.

Synthesis gas the most according to claim 1 produces the catalyst of low-carbon alkene, it is characterised in that described active component A For manganese.

Synthesis gas the most according to claim 1 produces the catalyst of low-carbon alkene, it is characterised in that described active component B For lanthanum.

Synthesis gas the most according to claim 1 produces the catalyst of low-carbon alkene, it is characterised in that described active component C For potassium.

9. the preparation method of the catalyst of synthesis gas production low-carbon alkene described in claim 1, comprises the following steps:

(1) by Alpha-alumina and ZSM-5 molecular sieve powder mix homogeneously, after tabletting, complex carrier H is prepared in crushing and screening molding；

(2) by iron salt, transition metal mantoquita or manganese salt, lanthanide series lanthanum salt or cerium salt, and alkali metal potassium salt or cesium salt, it is dissolved in Water is made mixed solution I；

(3) under the conditions of vacuum 1-80 kPa, above-mentioned mixed solution I be impregnated in the complex carrier H of forming in (2) step Go up to obtain catalyst precarsor J；

(4) by catalyst precarsor J, 450-750 DEG C of roasting 0.5-4.5 hour, obtains required catalyst after drying.