CN104148106A - Catalyst for producing low-carbon olefin by using synthesis gas and preparation method of catalyst - Google Patents
Catalyst for producing low-carbon olefin by using synthesis gas and preparation method of catalyst Download PDFInfo
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Abstract
The invention relates to a catalyst for producing low-carbon olefin by using synthesis gas and a preparation method of the catalyst, and is mainly used for solving the problem of low CO conversion rate and low low-carbon olefin selectivity in reaction for preparing the low-carbon olefin by using the synthesis gas in the prior art. The catalyst consists of a composite carrier and active components, wherein the composite carrier consists of alpha-aluminium oxide and a ZSM-5 molecular sieve; the silicon-aluminium ratio of the ZSM-5 molecular sieve is 40-200; the active components are loaded on the composite carrier and comprise the following compounds with chemical formulas by atomic ratio: Fe100AaBbCcOx, A is at least one of transition metals of Cu and Mn, B is at least one of lanthanide La and Ce, and C is at least one of alkaline metals of K and Cs; the weight of the composite carrier is 20%-80% of the weight of catalyst; by weight percent of the composite carrier, the weight of alpha-aluminium oxide is 20%-99% of the weight of the composite carrier. With the adoption of the technical scheme, the problem is well solved; the catalyst can be used for industrial production of the low-carbon olefin produced by using the synthesis gas.
Description
Technical field
The present invention relates to a kind of synthesis gas and produce the Catalysts and its preparation method of low-carbon alkene.
Background technology
Low-carbon alkene refers to that carbon number is less than or equal to 4 alkene.The low-carbon alkene that ethene, propylene is representative of take is very important basic organic chemical industry raw material, and along 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 production of low-carbon alkene mainly adopts the petrochemical industry route of lighter hydrocarbons (ethane, naphtha, light diesel fuel) cracking, day by day shortage and the long-term run at high level of crude oil price due to Global Oil resource, it is that the tube cracking furnace technique of raw material can run into an increasing raw material difficult problem that development low-carbon alkene industry only relies on oil lighter hydrocarbons, and low-carbon alkene production technology and raw material must diversification.The direct preparing low-carbon olefins of one-step method from syngas is exactly that carbon monoxide and hydrogen are under catalyst action, by Fischer-Tropsch synthesis, directly make the process that carbon number is less than or equal to 4 low-carbon alkene, this technique without as indirect method technique from synthesis gas through methanol or dimethyl ether, further prepare alkene, simplification of flowsheet, greatly reduces investment.Petroleum resources shortage at home, what externally interdependency was more and more higher, international oil price constantly rises violently is current, select synthesis gas to produce olefin process and can widen raw material source, to take crude oil, natural gas, coal and recyclable materials produces synthesis gas as raw material, can be for providing replacement scheme based on expensive raw material as the steam cracking technology aspect of naphtha.Preparation of low carbon olefines by synthetic gas technique is refined oil and applied to the abundant coal resources of China with relative cheap coal price for Development of Coal provides the good market opportunity.And near the abundant oil gas field of Natural Gas In China, if Gas Prices is cheap, be also the fabulous opportunity of application preparation of low carbon olefines by synthetic gas technique.If can utilize coal and the natural gas resource of China's abundant, 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 China energy problem.
One-step method from syngas producing light olefins technique functions comes from traditional Fischer-Tropsch synthesis, and the carbon number distribution of traditional Fischer-Tropsch synthetic is deferred to ASF and distributed, and it is selective that each hydro carbons all has theoretical maximum, as C
2-C
4cut be selectively up to 57%, gasoline fraction (C
5-C
11) be selectively up to 48%.Chain growth probability α value is larger, product heavy hydrocarbon selectively larger.Once α value determined, the selective of whole synthetic product just determined, chain growth probability α value depends on catalyst composition, granularity and reaction condition etc.In recent years, it is found that due to the alkene secondary response that again absorption cause of alhpa olefin on catalyst, product distributes and deviates from desirable ASF distribution.Fischer-Tropsch is synthetic is a kind of strong exothermal reaction, and a large amount of reaction heat will impel catalyst carbon deposit reaction more easily to generate methane and low-carbon alkanes, cause selectivity of light olefin significantly to decline; Next, it is unfavorable that complicated kinetic factor causes also to selective synthetic low-carbon alkene; The ASF distribution limitation of Fischer-Tropsch synthetic synthesizing low-carbon alkene selective.The catalyst of Fischer-Tropsch preparation of low carbon olefines by synthetic gas is mainly iron catalyst series, in order to improve the selective of the direct preparing low-carbon olefins of synthesis gas, can carry out physics and chemistry modification to fischer-tropsch synthetic catalyst, as utilize the suitable pore passage structure of molecular sieve, be conducive to low-carbon alkene diffusion in time and leave metal active center, suppress the secondary response of low-carbon alkene; Improve metal ion dispersed, also have good olefine selective; Support-metal strong interaction changes also can improve selectivity of light olefin; Add suitable transition metal, can enhanced activity component and the bond energy of carbon, suppress methane and generate, improve selectivity of light olefin; Add electronics accelerating auxiliaries, impel CO chemisorbed heat to increase, adsorbance also increases, and hydrogen adsorptive capacity reduces, and result selectivity of light olefin increases; Eliminate catalyst acid center, can suppress the secondary response of low-carbon alkene, improve that it is selective.Support effect and interpolation some transition metal auxiliary agent and alkali metal promoter by catalyst carrier, can obviously improve catalyst performance, develops the fischer-tropsch synthetic catalyst of the novel high-activity high selectivity producing light olefins with the non-ASF distribution of product.
It is poor that the bifunctional catalyst that fischer-tropsch synthetic catalyst and molecular sieve component form can be used as the traditional fischer-tropsch catalysts directional selectivity of a kind of improvements, 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, ZSM-5 molecular sieve has MFI structure, belong to mesoporous molecular sieve, due to the architectural characteristic of himself, ZSM-5 can make straight chain and the short-chain branch alkane in gasoline fraction in its lattice, carry out cracking and isomerization, generate low-carbon alkene, thereby increase the productive rate of low-carbon alkene.Because ZSM-5 molecular sieve itself has the secondary response that stronger acid catalysis function can promote low-carbon alkene, cause selectivity of light olefin very poor.Can adopt ion-exchange or solid-state diffusion decomposition method, will in ZSM-5 molecular sieve duct, introduce Na or K carries out alkali modification processing, reduce its acidity, to suppress the secondary response of low-carbon alkene on ZSM-5 acid centre.
Synthesis gas is synthesized and is directly produced low-carbon alkene by Fischer-Tropsch, has become one of study hotspot of fischer-tropsch synthetic catalyst exploitation.In the disclosed patent CN1083415A of Dalian Chemiclophysics Inst., Chinese Academy of Sciences, iron-Mn catalyst system that YongMgODeng IIA family's alkali metal oxide or silica-rich zeolite molecular sieve (or phosphorus aluminium zeolite) support, with highly basic K or Cs ion, make auxiliary agent, in preparation of low carbon olefines by synthetic gas reaction pressure, be 1.0 ~ 5.0MPa, at 300 ~ 400 ℃ of reaction temperatures, can obtain higher activity (CO conversion ratio 90%) and selective (selectivity of light olefin 66%).But this catalyst preparation process is complicated, and particularly the preparation moulding process cost of carrier zeolite molecular sieve is higher, is unfavorable for suitability for industrialized production.In the patent CN01144691.9 that Beijing University of Chemical Technology declares, adopt laser pyrolysis processes to prepare with Fe in conjunction with solid phase reaction combination technique
3c is that main Fe base nano-catalyst is applied to preparation of low carbon olefines by synthetic gas, and has obtained good catalytic effect, and because needs are used laser pyrolysis technology, preparation technology is more loaded down with trivial details, and raw material adopts Fe (CO)
5, catalyst cost is very high, industrialization difficulty.In the patent CN03109585.2 that Beijing University of Chemical Technology declares, adopt vacuum impregnation technology to prepare Fe/ activated-carbon catalyst that manganese, copper, zinc silicon, potassium etc. are auxiliary agent for the synthesis of gas reaction for preparing light olefins, under the condition without unstripped gas circulation, CO conversion ratio 96%, low-carbon alkene in hydrocarbon selective 68%.Molysite and auxiliary agent manganese salt that this catalyst preparation is used are more expensive and more insoluble ferric oxalate and manganese acetate, make solvent with ethanol simultaneously, just inevitable cost of material and the running cost that increases catalyst preparation process.For further reducing the cost of catalyst; in its patent CN200710063301.9; catalyst adopts common medicine and reagent preparation, and the molysite of use is ferric nitrate, and manganese salt is manganese nitrate; sylvite is potash; active carbon is coconut husk charcoal, can must under flowing nitrogen protection, carry out high-temperature roasting and Passivation Treatment by catalyst, needs special installation; preparation process is complicated, and cost is higher.And CO conversion ratio and the selectivity of light olefin of above-mentioned catalyst in fixed bed reaction is all lower.
Summary of the invention
Technical problem to be solved by this invention is in prior art in preparation of low carbon olefines by synthetic gas process, CO conversion ratio is lower, the lower problem of selectivity of light olefin in product, provide a kind of synthesis gas to produce the catalyst of low-carbon alkene, it is high that this catalyst has CO conversion ratio, the advantage that selectivity of light olefin is high.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of synthesis gas is produced the catalyst of low-carbon alkene, catalyst is comprised of complex carrier and active component, wherein complex carrier is comprised of Alpha-alumina and ZSM-5 molecular sieve, the silica alumina ratio of ZSM-5 is 40～200, load active component on complex carrier, active component contains with the following composition of atomic ratio measuring chemical formula: Fe
100a
ab
bc
cox
Wherein A obtains at least one for being selected from transition metal Cu, Mn,
B obtains at least one for being selected from group of the lanthanides La, Ce,
C is at least one being selected from 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 meets the required oxygen atom sum of each element valence in catalyst;
Wherein complex carrier weight is catalyst weight 20～80%; With complex carrier weight percent meter, Alpha-alumina is 20%～99% of complex carrier weight.
In technique scheme, in catalyst weight percentage, the preferable range of complex carrier weight is catalyst weight 30～70%; With complex carrier weight percent meter, the preferable range of Alpha-alumina weight is 30%～80% of complex carrier weight; With complex carrier weight percent meter, the preferable range of Alpha-alumina weight is 40%～60% of complex carrier 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; The prioritization scheme of active component B is lanthanum; The prioritization scheme of active component C is potassium.
In technique scheme, a kind of synthesis gas is produced the preparation method of the catalyst of low-carbon alkene, comprises the following steps:
(1) Alpha-alumina and ZSM-5 molecular sieve powder are mixed, after compressing tablet, complex carrier H is prepared in crushing and screening moulding
(2) by molysite, transition metal mantoquita or manganese salt, lanthanide series lanthanum salt or cerium salt, and alkali metal sylvite or cesium salt, the mixed solution I of making soluble in water;
(3), under vacuum 1-80 kPa condition, the complex carrier H that above-mentioned mixed solution I be impregnated in to forming in (2) step goes up to obtain catalyst precarsor J;
(4), by catalyst precarsor J, 450-750 ℃ of roasting 0.5-4.5 hour, obtains required catalyst after drying.
Catalyst prepared by the present invention is for the synthetic reaction for preparing light olefins of Fischer-Tropsch, with H
2the synthesis gas forming with CO is raw material, H
2with the mol ratio of CO be 1 ~ 3, in reaction temperature, be 250 ~ 400 ℃, 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 C
2-C
4low-carbon alkene.
The inventive method adopts vacuum impregnation technology Kaolinite Preparation of Catalyst, can make active component and auxiliary agent height be dispersed in carrier surface, increases the quantity of the active sites that is exposed to carrier surface, improves the conversion ratio of CO.
Lanthanide series La, the Ce that the inventive method employing is introduced in catalyst and alkali metal K, Cs are as catalyst promoter, electron valence state that can modulation active component Fe, strengthen the interaction strength of catalyst activity component and carrier, thereby be conducive to improve the selectivity of light olefin of catalyst.
The difunctional complex carrier that the inventive method adopts Alpha-alumina and ZSM-5 molecular sieve to mix, can utilize on the one hand iron-base fischer-tropsch synthesis catalyst high-activity high-selectivity on Alpha-alumina to produce low-carbon alkene, utilize on the other hand the splitting action of ZSM-5 molecular sieve in complex carrier, the long chain hydrocarbon catalytic pyrolysis that fischer-tropsch reaction is generated, further improves selectivity of light olefin.Because ZSM-5 molecular sieve has MFI structure, belong to mesoporous molecular sieve, due to the architectural characteristic of himself, ZSM-5 can make straight chain and the short-chain branch alkane in gasoline fraction in its lattice, carry out cracking and isomerization, generate low-carbon alkene, thereby increase the productive rate of low-carbon alkene.
Use method of the present invention, at H
2with the mol ratio of CO be 1.2, in reaction temperature, be 340 ℃, reaction pressure is 1.2Mpa, feed gas volume air speed is 1000h
-1condition under, CO conversion ratio can reach 99.6%, than prior art, improves 3.6%; Low-carbon alkene selectively can reach 74.0% in hydrocarbon, than prior art, improves 6.0%.Obtained good technique effect.Use complex carrier to obtain unforeseeable technique effect, compare independent use Alpha-alumina or ZSM-5 molecular sieve, the activity and selectivity of catalyst all improves more than 15%.
Below by embodiment, the invention will be further elaborated.
The specific embodiment
The present invention is described further for the following examples, and protection scope of the present invention is not subject to the restriction of these embodiment.
[embodiment 1]
60.0g Alpha-alumina and 40.0g ZSM-5 molecular sieve (silica alumina ratio 100) powder are mixed, and compressing tablet is sieved into 60-80 order and prepares complex carrier H; By the manganese nitrate solution of 134.9g Fe(NO3)39H2O, 35.6g 50%, 14.5g lanthanum nitrate hexahydrate and 1.7g potassium nitrate, be dissolved in 35.0g water and make mixed solution I; Under the condition of vacuum 80kPa, above-mentioned mixed solution I be impregnated in to the upper catalyst precarsor J of obtaining of complex carrier H that 60.0 g have prepared; The catalyst precarsor J having flooded is dry under 110 ℃ of conditions, then carries out roasting, 450 ℃ of sintering temperatures, and roasting time 2h, obtains the catalyst for the synthesis of gas production low-carbon alkene.In catalyst, the weight of active component and complex carrier is respectively 40% and 60%, the weight ratio of ZSM-5 molecular sieve and Alpha-alumina in complex carrier, and the composition general formula of active component atomic ratio is as follows:
40%Fe
100Mn
30La
10K
5O
x＋60%（40%?ZSM-5+60%?α-Al
2O
3）。
Prepared catalyst carries out the experimental result of synthesis gas production low-carbon alkene and lists in table 1 under certain reaction condition.
[embodiment 2]
99.0g Alpha-alumina and 1.0g ZSM-5 molecular sieve (silica alumina ratio 100) powder are mixed, and compressing tablet is sieved into 60-80 order and prepares complex carrier H; By the manganese nitrate solution of 134.9g Fe(NO3)39H2O, 35.6g 50%, 14.5g lanthanum nitrate hexahydrate and 1.7g potassium nitrate, be dissolved in 35.0g water and make mixed solution I; Under the condition of vacuum 80kPa, above-mentioned mixed solution I be impregnated in to the upper catalyst precarsor J of obtaining of complex carrier H that 60.0 g have prepared; The catalyst precarsor J having flooded is dry under 110 ℃ of conditions, then carries out roasting, 450 ℃ of sintering temperatures, and roasting time 2h, obtains the catalyst for the synthesis of gas production low-carbon alkene.In catalyst, the weight of active component and complex carrier is respectively 40% and 60%, the weight ratio of ZSM-5 molecular sieve and Alpha-alumina in complex carrier, and the composition general formula of active component atomic ratio is as follows:
40%Fe
100Mn
30La
10K
5O
x＋60%（1%?ZSM-5+99%?α-Al
2O
3）。
Prepared catalyst carries out the experimental result of synthesis gas production low-carbon alkene and lists in table 1 under certain reaction condition.
[embodiment 3]
20.0g Alpha-alumina and 80.0g ZSM-5 molecular sieve (silica alumina ratio 100) powder are mixed, and compressing tablet is sieved into 60-80 order and prepares complex carrier H; By the manganese nitrate solution of 134.9g Fe(NO3)39H2O, 35.6g 50%, 14.5g lanthanum nitrate hexahydrate and 1.7g potassium nitrate, be dissolved in 35.0g water and make mixed solution I; Under the condition of vacuum 80kPa, above-mentioned mixed solution I be impregnated in to the upper catalyst precarsor J of obtaining of complex carrier H that 60.0 g have prepared; The catalyst precarsor J having flooded is dry under 110 ℃ of conditions, then carries out roasting, 450 ℃ of sintering temperatures, and roasting time 2h, obtains the catalyst for the synthesis of gas production low-carbon alkene.In catalyst, the weight of active component and complex carrier is respectively 40% and 60%, the weight ratio of ZSM-5 molecular sieve and Alpha-alumina in complex carrier, and the composition general formula of active component atomic ratio is as follows:
40%Fe
100Mn
30La
10K
5O
x＋60%（80%?ZSM-5+20%?α-Al
2O
3）。
Prepared catalyst carries out the experimental result of synthesis gas production low-carbon alkene and lists in table 1 under certain reaction condition.
[embodiment 4]
40.0g Alpha-alumina and 60.0g ZSM-5 molecular sieve (silica alumina ratio 150) powder are mixed, and compressing tablet is sieved into 60-80 order and prepares complex carrier H; By 80.4g Fe(NO3)39H2O, 19.2g Gerhardite, 17.3g six nitric hydrate ceriums and 2.0g potassium nitrate, be dissolved in 30.0g water and make mixed solution I; Under the condition of vacuum 10kPa, above-mentioned mixed solution I be impregnated in to the upper catalyst precarsor J of obtaining of complex carrier H that 70.0 g have prepared; The catalyst precarsor J having flooded is dry under 110 ℃ of conditions, then carries out roasting, 550 ℃ of sintering temperatures, and roasting time 3h, obtains the catalyst for the synthesis of gas production low-carbon alkene.In catalyst, the weight of active component and complex carrier is respectively 30% and 70%, the weight ratio of ZSM-5 molecular sieve and Alpha-alumina in complex carrier, and the composition general formula of active component atomic ratio is as follows:
30%Fe
100Cu
40Ce
20K
10O
x＋70%（60%?ZSM-5+40%?α-Al
2O
3）。
Prepared catalyst carries out the experimental result of synthesis gas production low-carbon alkene and lists in table 1 under certain reaction condition.
[embodiment 5]
80.0g Alpha-alumina and 20.0g ZSM-5 molecular sieve (silica alumina ratio 150) powder are mixed, and compressing tablet is sieved into 60-80 order and prepares complex carrier H; By the manganese nitrate solution of 121.1g Fe(NO3)39H2O, 21.5g 50%, 39.0g six nitric hydrate ceriums and 8.8g cesium nitrate, be dissolved in 35.0g water and make mixed solution I; Under the condition of vacuum 80kPa, above-mentioned mixed solution I be impregnated in to the upper catalyst precarsor J of obtaining of complex carrier H that 50.0 g have prepared; The catalyst precarsor J having flooded is dry under 110 ℃ of conditions, then carries out roasting, 650 ℃ of sintering temperatures, and roasting time 4h, obtains the catalyst for the synthesis of gas production low-carbon alkene.In catalyst, the weight of active component and complex carrier is respectively 50% and 50%, the weight ratio of ZSM-5 molecular sieve and Alpha-alumina in complex carrier, and the composition general formula of active component atomic ratio is as follows:
50%Fe
100Mn
20Ce
30Cs
15O
x＋50%（20%?ZSM-5+80%?α-Al
2O
3）。
Prepared catalyst carries out the experimental result of synthesis gas production low-carbon alkene and lists in table 1 under certain reaction condition.
[embodiment 6]
90.0g Alpha-alumina and 10.0g ZSM-5 molecular sieve (silica alumina ratio 150) powder are mixed, and compressing tablet is sieved into 60-80 order and prepares complex carrier H; By 140.1g Fe(NO3)39H2O, 8.4g Gerhardite, 39.0g lanthanum nitrate hexahydrate and 8.8g cesium nitrate, be dissolved in 35.0g water and make mixed solution I; Under the condition of vacuum 10kPa, above-mentioned mixed solution I be impregnated in to the upper catalyst precarsor J of obtaining of complex carrier H that 40.0 g have prepared; The catalyst precarsor J having flooded is dry under 110 ℃ of conditions, then carries out roasting, 750 ℃ of sintering temperatures, and roasting time 1h, obtains the catalyst for the synthesis of gas production low-carbon alkene.In catalyst, the weight of active component and complex carrier is respectively 60% and 40%, the weight ratio of ZSM-5 molecular sieve and Alpha-alumina in complex carrier, and the composition general formula of active component atomic ratio is as follows:
60%Fe
100Cu
10La
35Cs
20O
x＋40%（10%?ZSM-5+90%?α-Al
2O
3）。
Prepared catalyst carries out the experimental result of synthesis gas production low-carbon alkene and lists in table 1 under certain reaction condition.
[embodiment 7]
90.0g Alpha-alumina and 10.0g ZSM-5 molecular sieve (silica alumina ratio 150) powder are mixed, and compressing tablet is sieved into 60-80 order and prepares complex carrier H; By the manganese nitrate solution of 211.3g Fe(NO3)39H2O, 9.4g 50%, 11.3g lanthanum nitrate hexahydrate and 30.6g cesium nitrate, be dissolved in 40.0g water and make mixed solution I; Under the condition of vacuum 80kPa, above-mentioned mixed solution I be impregnated in to the upper catalyst precarsor J of obtaining of complex carrier H that 30.0 g have prepared; The catalyst precarsor J having flooded is dry under 110 ℃ of conditions, then carries out roasting, 550 ℃ of sintering temperatures, and roasting time 2h, obtains the catalyst for the synthesis of gas production low-carbon alkene.In catalyst, the weight of active component and complex carrier is respectively 70% and 30%, the weight ratio of ZSM-5 molecular sieve and Alpha-alumina in complex carrier, and the composition general formula of active component atomic ratio is as follows:
70%Fe
100Mn
5La
5Cs
30O
x＋30%（80%?ZSM-5+20%?α-Al
2O
3）。
Prepared catalyst carries out the experimental result of synthesis gas production low-carbon alkene and lists in table 1 under certain reaction condition.
[embodiment 8]
99.0g Alpha-alumina and 1.0g ZSM-5 molecular sieve (silica alumina ratio 150) powder are mixed, and compressing tablet is sieved into 60-80 order and prepares complex carrier H; By 55.7g Fe(NO3)39H2O, 8.3g Gerhardite, 14.9g lanthanum nitrate hexahydrate and 1.4g potassium nitrate, be dissolved in 30.0g water and make mixed solution I; Under the condition of vacuum 80kPa, above-mentioned mixed solution I be impregnated in to the upper catalyst precarsor J of obtaining of complex carrier H that 80.0 g have prepared; The catalyst precarsor J having flooded is dry under 110 ℃ of conditions, then carries out roasting, 550 ℃ of sintering temperatures, and roasting time 2h, obtains the catalyst for the synthesis of gas production low-carbon alkene.In catalyst, the weight of active component and complex carrier is respectively 20% and 80%, the weight ratio of ZSM-5 molecular sieve and Alpha-alumina in complex carrier, and the composition general formula of active component atomic ratio is as follows:
20%Fe
100Cu
25La
25K
10O
x＋80%（1%?ZSM-5+99%?α-Al
2O
3）。
Prepared catalyst carries out the experimental result of synthesis gas production low-carbon alkene and lists in table 1 under certain reaction condition.
[embodiment 9]
50.0g Alpha-alumina and 50.0g ZSM-5 molecular sieve (silica alumina ratio 100) powder are mixed, and compressing tablet is sieved into 60-80 order and prepares complex carrier H; By the manganese nitrate solution of 119.2g Fe(NO3)39H2O, 21.1g 50%, 25.6g six nitric hydrate ceriums and 4.5g potassium nitrate, be dissolved in 35.0g water and make mixed solution I; Under the condition of vacuum 80kPa, above-mentioned mixed solution I be impregnated in to the upper catalyst precarsor J of obtaining of complex carrier H that 60.0 g have prepared; The catalyst precarsor J having flooded is dry under 110 ℃ of conditions, then carries out roasting, 450 ℃ of sintering temperatures, and roasting time 3h, obtains the catalyst for the synthesis of gas production low-carbon alkene.In catalyst, the weight of active component and complex carrier is respectively 40% and 60%, the weight ratio of ZSM-5 molecular sieve and Alpha-alumina in complex carrier, and the composition general formula of active component atomic ratio is as follows:
40%Fe
100Mn
20Ce
20K
15O
x＋60%（50%?ZSM-5+50%?α-Al
2O
3）。
Prepared catalyst carries out the experimental result of synthesis gas production low-carbon alkene and lists in table 1 under certain reaction condition.
[embodiment 10]
70.0g Alpha-alumina and 30.0g ZSM-5 molecular sieve (silica alumina ratio 100) powder are mixed, and compressing tablet is sieved into 60-80 order and prepares complex carrier H; By 132.7g Fe(NO3)39H2O, 23.8g Gerhardite, 28.5g six nitric hydrate ceriums and 6.4g cesium nitrate, be dissolved in 40.0g water and make mixed solution I; Under the condition of vacuum 80kPa, above-mentioned mixed solution I be impregnated in to the upper catalyst precarsor J of obtaining of complex carrier H that 50.0g prepared; The catalyst precarsor J having flooded is dry under 110 ℃ of conditions, then carries out roasting, 450 ℃ of sintering temperatures, and roasting time 3h, obtains the catalyst for the synthesis of gas production low-carbon alkene.In catalyst, the weight of active component and complex carrier is respectively 50% and 50%, the weight ratio of ZSM-5 molecular sieve and Alpha-alumina in complex carrier, and the composition general formula of active component atomic ratio is as follows:
50%Fe
100Cu
30Ce
20Cs
10O
x＋50%（30%?ZSM-5+70%?α-Al
2O
3）。
Prepared catalyst carries out the experimental result of synthesis gas production low-carbon alkene and lists in table 1 under certain reaction condition.
[comparative example 1]
100.0g alpha-alumina powder compressing tablet is sieved into 60-80 order and prepares alpha-alumina supports H; By the manganese nitrate solution of 134.9g Fe(NO3)39H2O, 35.6g 50%, 14.5g lanthanum nitrate hexahydrate and 1.7g potassium nitrate, be dissolved in 35.0g water and make mixed solution I; Under the condition of vacuum 80kPa, above-mentioned mixed solution I be impregnated in to the upper catalyst precarsor J of obtaining of alpha-alumina supports H that 60.0 g have prepared; The catalyst precarsor J having flooded is dry under 110 ℃ of conditions, then carries out roasting, 450 ℃ of sintering temperatures, and roasting time 2h, obtains the catalyst for the synthesis of gas production low-carbon alkene.In catalyst, the weight of active component and alpha-alumina supports is respectively 40% and 60%, and the composition general formula of active component atomic ratio is as follows:
40%Fe
100Mn
30La
10K
5O
x＋60%?α-Al
2O
3。
Prepared catalyst carries out the experimental result of synthesis gas production low-carbon alkene and lists in table 1 under certain reaction condition.
[comparative example 2]
100.0g ZSM-5 molecular sieve (silica alumina ratio 100) pressed powder is sieved into 60-80 order and prepares ZSM-5 molecular sieve carrier H; By the manganese nitrate solution of 134.9g Fe(NO3)39H2O, 35.6g 50%, 14.5g lanthanum nitrate hexahydrate and 1.7g potassium nitrate, be dissolved in 35.0g water and make mixed solution I; Under the condition of vacuum 80kPa, above-mentioned mixed solution I be impregnated in to the upper catalyst precarsor J of obtaining of ZSM-5 molecular sieve carrier H that 60.0 g have prepared; The catalyst precarsor J having flooded is dry under 110 ℃ of conditions, then carries out roasting, 450 ℃ of sintering temperatures, and roasting time 2h, obtains the catalyst for the synthesis of gas production low-carbon alkene.In catalyst, the weight of active component and ZSM-5 molecular sieve carrier is respectively 40% and 60%, and the composition general formula of active component atomic ratio is as follows:
40%Fe
100Mn
30La
10K
5O
x＋60%ZSM-5。
Prepared catalyst carries out the experimental result of synthesis gas production low-carbon alkene and lists in table 1 under certain reaction condition.
[comparative example 3]
10.0g Alpha-alumina and 90.0g ZSM-5 molecular sieve (silica alumina ratio 100) powder are mixed, and compressing tablet is sieved into 60-80 order and prepares complex carrier H; By the manganese nitrate solution of 134.9g Fe(NO3)39H2O, 35.6g 50%, 14.5g lanthanum nitrate hexahydrate and 1.7g potassium nitrate, be dissolved in 35.0g water and make mixed solution I; Under the condition of vacuum 80kPa, above-mentioned mixed solution I be impregnated in to the upper catalyst precarsor J of obtaining of complex carrier H that 60.0 g have prepared; The catalyst precarsor J having flooded is dry under 110 ℃ of conditions, then carries out roasting, 450 ℃ of sintering temperatures, and roasting time 2h, obtains the catalyst for the synthesis of gas production low-carbon alkene.In catalyst, the weight of active component and complex carrier is respectively 40% and 60%, the weight ratio of ZSM-5 molecular sieve and Alpha-alumina in complex carrier, and the composition general formula of active component atomic ratio is as follows:
40%Fe
100Mn
30La
10K
5O
x＋60%（90%?ZSM-5+10%?α-Al
2O
3）。
Prepared catalyst carries out the experimental result of synthesis gas production low-carbon alkene and lists in table 1 under certain reaction condition.
The reducing condition of above-described embodiment and comparative example is:
450 ℃ of temperature
Pressure normal pressure
Loaded catalyst 3 ml
Catalyst loading 1000 hours
-1
Reducing gases H
2
8 hours recovery times
Reaction condition is:
8 millimeters of fixed bed reactors of φ
340 ℃ of reaction temperatures
Reaction pressure 1.2MPa
Loaded catalyst 3 ml
Catalyst loading 1000 hours
-1
Raw material proportioning (mole) H
2/ CO=1.2/1
The evaluation result of table 1 embodiment catalyst
Claims (9)
1. a synthesis gas is produced the catalyst of low-carbon alkene, catalyst is comprised of complex carrier and active component, wherein complex carrier is comprised of Alpha-alumina and ZSM-5 molecular sieve, the silica alumina ratio of ZSM-5 is 40～200, load active component on complex carrier, active component contains with the following composition of atomic ratio measuring chemical formula: Fe
100a
ab
bc
cox
Wherein A obtains at least one for being selected from transition metal Cu, Mn,
B obtains at least one for being selected from group of the lanthanides La, Ce,
C is at least one being selected from 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 meets the required oxygen atom sum of each element valence in catalyst;
Wherein complex carrier weight is catalyst weight 20～80%; With complex carrier weight percent meter, Alpha-alumina is 20%～99% of complex carrier weight.
2. synthesis gas according to claim 1 is produced the catalyst of low-carbon alkene, it is characterized in that in catalyst weight percentage, and complex carrier weight is catalyst weight 30～70%.
3. synthesis gas according to claim 1 is produced the catalyst of low-carbon alkene, it is characterized in that with complex carrier weight percent meter, and Alpha-alumina weight is 30%～80% of complex carrier weight.
4. synthesis gas according to claim 3 is produced the catalyst of low-carbon alkene, it is characterized in that with complex carrier weight percent meter, and Alpha-alumina weight is 40%～60% of complex carrier weight.
5. synthesis gas according to claim 1 is produced the catalyst of low-carbon alkene, and the silica alumina ratio that it is characterized in that ZSM-5 molecular sieve is 100～150.
6. synthesis gas according to claim 1 is produced the catalyst of low-carbon alkene, it is characterized in that described active component A is manganese.
7. synthesis gas according to claim 1 is produced the catalyst of low-carbon alkene, it is characterized in that described active component B is lanthanum.
8. synthesis gas according to claim 1 is produced the catalyst of low-carbon alkene, it is characterized in that described active component C is potassium.
9. the preparation method that described in claim 1, synthesis gas is produced the catalyst of low-carbon alkene, comprises the following steps:
(1) Alpha-alumina and ZSM-5 molecular sieve powder are mixed, after compressing tablet, complex carrier H is prepared in crushing and screening moulding;
(2) by molysite, transition metal mantoquita or manganese salt, lanthanide series lanthanum salt or cerium salt, and alkali metal sylvite or cesium salt, the mixed solution I of making soluble in water;
(3), under vacuum 1-80 kPa condition, the complex carrier H that above-mentioned mixed solution I be impregnated in to forming in (2) step goes up to obtain catalyst precarsor J;
(4), by catalyst precarsor J, 450-750 ℃ of roasting 0.5-4.5 hour, obtains required catalyst after drying.
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