CN104549352A - Catalyst for producing low carbon olefin from synthesis gas and use method of catalyst - Google Patents
Catalyst for producing low carbon olefin from synthesis gas and use method of catalyst Download PDFInfo
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Abstract
The invention relates to a catalyst for producing low carbon olefin from synthesis gas and a use method of the catalyst for producing the low carbon olefin from the synthesis gas. According to the catalyst and the use method, the problems of low CO conversion rate and low carbon olefin selectivity in reaction for preparing low carbon olefin from the synthesis gas in the prior art are mainly solved. The catalyst for producing low carbon olefin from the synthesis gas comprises the following components in percentage by weight: (a) 5%-50% of an iron element or oxides of the iron element, (b) 4%-20% of at least one element selected from manganese and zirconium or oxides of the element, (c) 1%-10% of a bismuth element or oxides of the bismuth element and (d) 25%-90% of a carrier, wherein the carrier comprises the following components in parts by weight: (1) 15-40 parts of alpha-aluminum oxide, (2) 1-45 parts of calcium oxide, (3) 1-5 parts of titanium dioxide and (4) 1-20 parts of potassium oxide. According to the technical scheme, the problems are well solved; the catalyst can be applied to the industrial production for producing low carbon olefin from the synthesis gas by virtue of a fixed bed.
Description
Technical field
The present invention relates to catalyst and using method thereof that a kind of synthesis gas produces low-carbon alkene.
Background technology
Low-carbon alkene refers to that carbon number is less than or equal to the alkene of 4.The low-carbon alkene being representative with ethene, propylene is very important basic organic chemical industry raw material, and along with the quick 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, due to day by day shortage and the long-term run at high level of crude oil price of Global Oil resource, development low-carbon alkene industrial only dependence petroleum light hydrocarbon is that the tube cracking furnace technique of raw material can run into an increasing raw material difficult problem, and low-carbon alkene production technology and raw material must diversification.The direct preparing low-carbon olefins of one-step method from syngas is exactly that carbon monoxide and hydrogen are under catalyst action, by Fischer-Tropsch synthesis directly obtained carbon number be less than or equal to the process of the low-carbon alkene of 4, this technique without the need to as indirect method technique from synthesis gas through methanol or dimethyl ether, prepare alkene further, simplification of flowsheet, greatly reduces investment.Petroleum resources shortage at home, it is current that external dependence degree is more and more higher, international oil price constantly rises violently, synthesis gas producing olefinic hydrocarbons technique is selected to widen raw material sources, will with crude oil, natural gas, coal and recyclable materials for synthesis gas be produced by raw material, can for providing replacement scheme based on the steam cracking technology aspect of high cost raw material as naphtha.The coal price of the coal resources that China is abundant and relative moderate is that Development of Coal oil refining and application preparation of low carbon olefines by synthetic gas technique provide 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 energy problem of solution China.
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 defers to ASF distribution, and it is selective that each hydro carbons all has theoretical maximum, as C
2-C
4the selective of cut is up to 57%, gasoline fraction (C
5-C
11) be selectively up to 48%.Chain growth probability α value is larger, product heavy hydrocarbon selective larger.Once α value determines, the selective of whole synthetic product just determines, and chain growth probability α value depends on catalyst composition, granularity and reaction condition etc.In recent years, it is found that due to alhpa olefin on a catalyst adsorb the alkene secondary response caused again, product distribution deviates from desirable ASF and distributes.F-T synthesis is a kind of strong exothermal reaction, and a large amount of reaction heat will impel catalyst carbon deposit to react more easily generation methane and low-carbon alkanes, cause selectivity of light olefin significantly to decline; Secondly, it is unfavorable that complicated kinetic factor also causes to selectivity synthesis low-carbon alkene; The ASF distribution of Fischer-Tropsch synthetic limits the selective of synthesizing low-carbon alkene.The catalyst mainly iron catalyst series of F-T synthesis gas producing light olefins, in order to improve the selective of the direct preparing low-carbon olefins of synthesis gas, physics and chemistry modification can be carried out to fischer-tropsch synthetic catalyst, as the pore passage structure utilizing molecular sieve suitable, be conducive to low-carbon alkene to spread in time and leave metal active centres, 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 generation, raising 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, the secondary response of low-carbon alkene can be suppressed, improve that it is selective.By Support effect and some transition metal promoter of interpolation and the alkali metal promoter of catalyst carrier, obviously can improve catalyst performance, develop the fischer-tropsch synthetic catalyst of the novel high-activity high selectivity producing light olefins with the non-ASF distribution of product.
One-step method from syngas directly produces low-carbon alkene, has become one of study hotspot of fischer-tropsch synthetic catalyst exploitation.In patent CN1083415A disclosed in Dalian Chemiclophysics Inst., Chinese Academy of Sciences, by iron-Mn catalyst system that the IIA race alkali metal oxides such as MgO or silica-rich zeolite molecular sieve (or phosphorus aluminium zeolite) support, auxiliary agent is made with highly basic K or Cs ion, be 1.0 ~ 5.0MPa in preparation of low carbon olefines by synthetic gas reaction pressure, at reaction temperature 300 ~ 400 DEG C, higher activity (CO conversion ratio 90%) and selective (selectivity of light olefin 66%) can be obtained.But this catalyst preparation process is complicated, and particularly the shaping process cost of the preparation of carrier zeolite molecular sieve is higher, is unfavorable for suitability for industrialized production.In the number of patent application 01144691.9 that Beijing University of Chemical Technology declares, laser pyrolysis processes is adopted to prepare in conjunction with solid phase reaction combination technique with Fe
3c is that main Fe base nano-catalyst is applied to preparation of low carbon olefines by synthetic gas, and achieves good catalytic effect, and because needs use 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 ZL03109585.2 that Beijing University of Chemical Technology declares, vacuum impregnation technology is adopted to prepare the Fe/ activated-carbon catalyst for auxiliary agent such as manganese, copper, zinc silicon, potassium for the synthesis of gas reaction for preparing light olefins, under the condition circulated without unstripped gas, CO conversion ratio 96%, low-carbon alkene in hydrocarbon selective 68%.The molysite that this catalyst preparing uses and auxiliary agent manganese salt are more expensive and more insoluble ferric oxalate and manganese acetate, simultaneously with ethanol as solvent, and just inevitable cost of material and the running cost increasing catalyst preparation process.For reducing the cost of catalyst further; in its number of patent application 200710063301.9; 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 carry out high-temperature roasting and Passivation Treatment by catalyst, need special installation under flowing nitrogen protection; preparation process is complicated, and cost is higher.And the CO conversion ratio of above-mentioned catalyst in fixed bed reaction and selectivity of light olefin all lower.
Summary of the invention
Technical problem to be solved by this invention is that in prior art, synthesis gas produces the problem that in low-carbon alkene technology, in CO low conversion rate and product, selectivity of light olefin is low, the catalyst providing a kind of new synthesis gas to produce low-carbon alkene and using method thereof, when this catalyst is used for the reaction of fixed bed preparation of low carbon olefines by synthetic gas, there is the advantage that in CO conversion ratio height and product, selectivity of light olefin is high.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of catalyst producing low-carbon alkene for the synthesis of gas, comprises following component by weight percentage:
A) 5 ~ 50% ferro element or its oxide;
B) 4 ~ 20% be selected from least one element in manganese and zirconium or its oxide;
C) 1 ~ 10% bismuth element or its oxide;
D) carrier of 25 ~ 90%, in vehicle weight number, comprises following component (1) 15 ~ 40 part of Alpha-alumina; (2) 1 ~ 45 parts of calcium oxide; (3) 1 ~ 5 parts of titanium dioxide; (4) 1 ~ 20 parts of potassium oxides.
In technique scheme, in catalyst, the oxide of iron is di-iron trioxide, and in catalyst weight percent, the preferable range of content is 10 ~ 40%; In catalyst, the oxide of manganese and zirconium is respectively manganese oxide and zirconia, and in catalyst weight percent, the preferable range of content is 10 ~ 20%; The oxide of the bismuth described in catalyst is bismuth oxide, and in catalyst weight percent, the preferable range of content is 1 ~ 5%.
In technique scheme, composite oxide carrier is prepared by Alpha-alumina, powdered whiting, titanium dioxide and potash high temperature sintering, and calculate with vehicle weight number, the preferable range of Alpha-alumina content is 20 ~ 40 parts; The preferable range of calcium oxide content is 10 ~ 40 parts; The preferable range of content of titanium dioxide is 3 ~ 5 parts; The preferable range of potassium oxide content is 1 ~ 10 part.
In technique scheme, synthesis gas used produces the preparation method of light olefins catalyst, comprises the following steps:
(1) after the mixed-powder of Alpha-alumina, powdered whiting and titanium dioxide being carried out ball milling mixing, obtained compound G is stand-by;
(2) add in deionized water by potash, until completely dissolved, add in above-mentioned compound G and carry out kneaded and formed and dry, after drying, after high temperature sintering, cooling, crushing and screening prepares composite oxide carrier H;
(3) by molysite, manganese salt or zirconates and bismuth salt, in water-soluble deionized water, mixed solution I is made;
(4) under vacuum 1 ~ 80 kPa condition, above-mentioned mixed solution I to be impregnated on the composite oxide carrier H of forming in step (2) to obtain catalyst precarsor J;
(5) required catalyst is obtained by after catalyst precarsor J drying, roasting.
In technique scheme, the preferable range of high temperature sintering temperature is 1100 ~ 1600 DEG C, more preferably the scope of high temperature sintering temperature is 1200 ~ 1400 DEG C, the preferable range of sintering time is 1 ~ 6 hour, more preferably the scope of sintering time is 2 ~ 4 hours, the preferable range of the sintering temperature in step (5) is 450 ~ 750 DEG C, and the preferable range of roasting time is 1.0 ~ 4.5 hours.
Synthesis gas produces a method for low-carbon alkene, take synthesis gas as raw material, H
2be 1 ~ 3 with the mol ratio of CO, be 250 ~ 400 DEG C in reaction temperature, reaction pressure is 1.0 ~ 3.0Mpa, and feed gas volume air speed is 500 ~ 5000h
-1condition under, unstripped gas and described catalyst exposure react and generate containing C
2~ C
4alkene.
The catalyst that the inventive method adopts is prepared by vacuum impregnation technology, and active component and auxiliary agent high uniformity can be made to be scattered in complex sintered Oxide-supports, increases the quantity being exposed to the active sites of carrier surface, improves the conversion ratio of CO.
Transient metal Mn or Zr is introduced as catalyst promoter in the catalyst that the inventive method adopts, can the electron valence state of modulation active component Fe, particularly introduce main group metal Bi, not only can modulation active component electron valence state, and strengthen the interaction strength of catalyst activity component and carrier, thus be conducive to the selectivity of light olefin improving catalyst.
Add calcium oxide and potassium oxide in the catalyst complex carrier that the inventive method adopts, not only significantly reduce catalyst surface acid, improve selectivity of light olefin, and improve anti-carbon effect, reduce area carbon and generate; Appropriate titanium dioxide is introduced in carrier, shaping as stabilizing agent high temperature sintering together with Alpha-alumina, improve mechanical strength and the heat endurance of catalyst while keeping carrier loose structure.
The reaction condition that synthesis gas produces low-carbon alkene is as follows: with H
2with CO composition synthesis gas be raw material, H
2be 1 ~ 3 with the mol ratio of CO, be 250 ~ 400 DEG C in reaction temperature, reaction pressure is 1.0 ~ 3.0Mpa, and feed gas volume air speed is 500 ~ 5000h
-1condition under, unstripped gas and above-mentioned catalyst exposure, achieve good technique effect: CO conversion ratio can reach 99.8%, than prior art improve 3.8%; Selective in hydrocarbon of low-carbon alkene reaches 75.9%, improves 7.9%, the results are shown in subordinate list in more detail than prior art.
The present invention is described further for the following examples, and protection scope of the present invention is not by the restriction of these embodiments.
Detailed description of the invention
[embodiment 1]
Take 45.0 grams of Alpha-alumina (Al
2o
3) powder and 40.1 grams of powdered whiting (CaCO
3) powder and 3.4 grams of titanium dioxide (TiO
2) powder mixes, in ball mill, mixed 1 hour of mill, makes compound G stand-by; Take 11.5 grams of potash (K
2cO
3), add 30 ml deionized waters, until completely dissolved, add in the mixed compound G of above-mentioned mill, carry out kneading extruded; At the temperature of 1300 DEG C, sinter 2 hours after oven dry, make complex carrier, after cooling, crushing and screening becomes 60 ~ 80 orders to prepare composite oxide carrier H; By 101.2 grams of Fe(NO3)39H2Os, the manganese nitrate solution of 25.2 gram 50%, 10.4 gram of five nitric hydrate bismuth, be dissolved in 35.0 grams of deionized waters and make mixed solution I; Under the condition of vacuum 80kPa, above-mentioned mixed solution I to be impregnated on 70.0 grams of composite oxide carrier H prepared to obtain catalyst precarsor J; The catalyst precarsor J flooded is dry under 110 DEG C of conditions, then carries out roasting, sintering temperature 600 DEG C, roasting time 2h, namely obtains the catalyst that required synthesis gas produces low-carbon alkene.Obtained catalyst, comprises following component: 20% Fe
2o
3, 5% MnO, 5% Bi
2o
3, 40% α-Al
2o
3, 20% CaO, 3% TiO
2, 7% K
2o; Obtained catalyst carries out synthesis gas under certain condition and produces low-carbon alkene reaction, and experimental result lists in table 1.
[embodiment 2]
Take 63.1 grams of Alpha-alumina (Al
2o
3) powder and 8.0 grams of powdered whiting (CaCO
3) powder and 9.0 grams of titanium dioxide (TiO
2) powder mixes, in ball mill, mixed 1 hour of mill, makes compound G stand-by; Take 19.8 grams of potash (K
2cO
3), add 30 ml deionized waters, until completely dissolved, add in the mixed compound G of above-mentioned mill, carry out kneading extruded; At the temperature of 1300 DEG C, sinter 2 hours after oven dry, make complex carrier, after cooling, crushing and screening becomes 60 ~ 80 orders to prepare composite oxide carrier H; By 253.0 grams of Fe(NO3)39H2Os, the manganese nitrate solution of 100.9 gram 50%, 10.4 gram of five nitric hydrate bismuth, be dissolved in 35.0 grams of deionized waters and make mixed solution I; Under the condition of vacuum 80kPa, above-mentioned mixed solution I to be impregnated on 25.0 grams of composite oxide carrier H prepared to obtain catalyst precarsor J; The catalyst precarsor J flooded is dry under 110 DEG C of conditions, then carries out roasting, sintering temperature 600 DEG C, roasting time 2h, namely obtains the catalyst that required synthesis gas produces low-carbon alkene.Obtained catalyst, comprises following component: 50% Fe
2o
3, 20% MnO, 5% Bi
2o
3, 17.5% α-Al
2o
3, 1.25% CaO, 2.5% TiO
2, 3.75% K
2o; Obtained catalyst carries out synthesis gas under certain condition and produces low-carbon alkene reaction, and experimental result lists in table 1.
[embodiment 3]
Take 18.6 grams of Alpha-alumina (Al
2o
3) powder and 59.9 grams of powdered whiting (CaCO
3) powder and 0.7 gram of titanium dioxide (TiO
2) powder mixes, in ball mill, mixed 1 hour of mill, makes compound G stand-by; Take 20.8 grams of potash (K
2cO
3), add 30 ml deionized waters, until completely dissolved, add in the mixed compound G of above-mentioned mill, carry out kneading extruded; At the temperature of 1300 DEG C, sinter 2 hours after oven dry, make complex carrier, after cooling, crushing and screening becomes 60 ~ 80 orders to prepare composite oxide carrier H; By 25.3 grams of Fe(NO3)39H2Os, the manganese nitrate solution of 20.2 gram 50%, 2.1 gram of five nitric hydrate bismuth, be dissolved in 35.0 grams of deionized waters and make mixed solution I; Under the condition of vacuum 80kPa, above-mentioned mixed solution I to be impregnated on 90.0 grams of composite oxide carrier H prepared to obtain catalyst precarsor J; The catalyst precarsor J flooded is dry under 110 DEG C of conditions, then carries out roasting, sintering temperature 600 DEG C, roasting time 2h, namely obtains the catalyst that required synthesis gas produces low-carbon alkene.Obtained catalyst, comprises following component: 5% Fe
2o
3, 4% MnO, 1% Bi
2o
3, 25% α-Al
2o
3, 45% CaO, 1% TiO
2, 19% K
2o; Obtained catalyst carries out synthesis gas under certain condition and produces low-carbon alkene reaction, and experimental result lists in table 1.
[embodiment 4]
Take 24.0 grams of Alpha-alumina (Al
2o
3) powder and 73.6 grams of powdered whiting (CaCO
3) powder and 1.0 grams of titanium dioxide (TiO
2) powder mixes, in ball mill, mixed 1 hour of mill, makes compound G stand-by; Take 1.4 grams of potash (K
2cO
3), add 30 ml deionized waters, until completely dissolved, add in the mixed compound G of above-mentioned mill, carry out kneading extruded; At the temperature of 1300 DEG C, sinter 2 hours after oven dry, make complex carrier, after cooling, crushing and screening becomes 60 ~ 80 orders to prepare composite oxide carrier H; By 50.5 grams of Fe(NO3)39H2Os, the manganese nitrate solution of 50.5 gram 50%, 20.8 gram of five nitric hydrate bismuth, be dissolved in 35.0 grams of deionized waters and make mixed solution I; Under the condition of vacuum 80kPa, above-mentioned mixed solution I to be impregnated on 70.0 grams of composite oxide carrier H prepared to obtain catalyst precarsor J; The catalyst precarsor J flooded is dry under 110 DEG C of conditions, then carries out roasting, sintering temperature 600 DEG C, roasting time 2h, namely obtains the catalyst that required synthesis gas produces low-carbon alkene.Obtained catalyst, comprises following component: 10% Fe
2o
3, 10% MnO, 10% Bi
2o
3, 25% α-Al
2o
3, 43% CaO, 1% TiO
2, 1% K
2o; Obtained catalyst carries out synthesis gas under certain condition and produces low-carbon alkene reaction, and experimental result lists in table 1.
[embodiment 5]
Take 34.8 grams of Alpha-alumina (Al
2o
3) powder and 31.0 grams of powdered whiting (CaCO
3) powder and 8.7 grams of titanium dioxide (TiO
2) powder mixes, in ball mill, mixed 1 hour of mill, makes compound G stand-by; Take 25.5 grams of potash (K
2cO
3), add 30 ml deionized waters, until completely dissolved, add in the mixed compound G of above-mentioned mill, carry out kneading extruded; At the temperature of 1300 DEG C, sinter 2 hours after oven dry, make complex carrier, after cooling, crushing and screening becomes 60 ~ 80 orders to prepare composite oxide carrier H; By 202.4 grams of Fe(NO3)39H2Os, the manganese nitrate solution of 50.5 gram 50%, 10.4 gram of five nitric hydrate bismuth, be dissolved in 35.0 grams of deionized waters and make mixed solution I; Under the condition of vacuum 80kPa, above-mentioned mixed solution I to be impregnated on 45.0 grams of composite oxide carrier H prepared to obtain catalyst precarsor J; The catalyst precarsor J flooded is dry under 110 DEG C of conditions, then carries out roasting, sintering temperature 600 DEG C, roasting time 2h, namely obtains the catalyst that required synthesis gas produces low-carbon alkene.Obtained catalyst, comprises following component: 40% Fe
2o
3, 10% MnO, 5% Bi
2o
3, 20% α-Al
2o
3, 10% CaO, 5% TiO
2, 10% K
2o; Obtained catalyst carries out synthesis gas under certain condition and produces low-carbon alkene reaction, and experimental result lists in table 1.
[embodiment 6]
Take 23.8 grams of Alpha-alumina (Al
2o
3) powder and 73.7 grams of powdered whiting (CaCO
3) powder and 1.0 grams of titanium dioxide (TiO
2) powder mixes, in ball mill, mixed 1 hour of mill, makes compound G stand-by; Take 1.5 grams of potash (K
2cO
3), add 30 ml deionized waters, until completely dissolved, add in the mixed compound G of above-mentioned mill, carry out kneading extruded; At the temperature of 1300 DEG C, sinter 2 hours after oven dry, make complex carrier, after cooling, crushing and screening becomes 60 ~ 80 orders to prepare composite oxide carrier H; By 50.6 grams of Fe(NO3)39H2Os, the manganese nitrate solution of 100.9 gram 50%, 10.4 gram of five nitric hydrate bismuth, be dissolved in 35.0 grams of deionized waters and make mixed solution I; Under the condition of vacuum 80kPa, above-mentioned mixed solution I to be impregnated on 65.0 grams of composite oxide carrier H prepared to obtain catalyst precarsor J; The catalyst precarsor J flooded is dry under 110 DEG C of conditions, then carries out roasting, sintering temperature 600 DEG C, roasting time 2h, namely obtains the catalyst that required synthesis gas produces low-carbon alkene.Obtained catalyst, comprises following component: 10% Fe
2o
3, 20% MnO, 5% Bi
2o
3, 23% α-Al
2o
3, 40% CaO, 1% TiO
2, 1% K
2o; Obtained catalyst carries out synthesis gas under certain condition and produces low-carbon alkene reaction, and experimental result lists in table 1.
[embodiment 7]
Take 45.0 grams of Alpha-alumina (Al
2o
3) powder and 40.1 grams of powdered whiting (CaCO
3) powder and 3.4 grams of titanium dioxide (TiO
2) powder mixes, in ball mill, mixed 1 hour of mill, makes compound G stand-by; Take 11.5 grams of potash (K
2cO
3), add 30 ml deionized waters, until completely dissolved, add in the mixed compound G of above-mentioned mill, carry out kneading extruded; At the temperature of 1300 DEG C, sinter 2 hours after oven dry, make complex carrier, after cooling, crushing and screening becomes 60 ~ 80 orders to prepare composite oxide carrier H; By 101.2 grams of Fe(NO3)39H2Os, 17.4 gram of five nitric hydrate zirconium, 10.4 gram of five nitric hydrate bismuth, be dissolved in 35.0 grams of deionized waters and make mixed solution I; Under the condition of vacuum 80kPa, above-mentioned mixed solution I to be impregnated on 70.0 grams of composite oxide carrier H prepared to obtain catalyst precarsor J; The catalyst precarsor J flooded is dry under 110 DEG C of conditions, then carries out roasting, sintering temperature 600 DEG C, roasting time 2h, namely obtains the catalyst that required synthesis gas produces low-carbon alkene.Obtained catalyst, comprises following component: 20% Fe
2o
3, 5% ZrO
2, 5% Bi
2o
3, 40% α-Al
2o
3, 20% CaO, 3% TiO
2, 7% K
2o; Obtained catalyst carries out synthesis gas under certain condition and produces low-carbon alkene reaction, and experimental result lists in table 1.
[embodiment 8]
Take 45.0 grams of Alpha-alumina (Al
2o
3) powder and 40.1 grams of powdered whiting (CaCO
3) powder and 3.4 grams of titanium dioxide (TiO
2) powder mixes, in ball mill, mixed 1 hour of mill, makes compound G stand-by; Take 11.5 grams of potash (K
2cO
3), add 30 ml deionized waters, until completely dissolved, add in the mixed compound G of above-mentioned mill, carry out kneading extruded; At the temperature of 1300 DEG C, sinter 2 hours after oven dry, make complex carrier, after cooling, crushing and screening becomes 60 ~ 80 orders to prepare composite oxide carrier H; By 25.3 grams of Fe(NO3)39H2Os, 69.7 gram of five nitric hydrate zirconium, 10.4 gram of five nitric hydrate bismuth, be dissolved in 35.0 grams of deionized waters and make mixed solution I; Under the condition of vacuum 80kPa, above-mentioned mixed solution I to be impregnated on 70.0 grams of composite oxide carrier H prepared to obtain catalyst precarsor J; The catalyst precarsor J flooded is dry under 110 DEG C of conditions, then carries out roasting, sintering temperature 600 DEG C, roasting time 2h, namely obtains the catalyst that required synthesis gas produces low-carbon alkene.Obtained catalyst, comprises following component: 5% Fe
2o
3, 20% ZrO
2, 5% Bi
2o
3, 40% α-Al
2o
3, 20% CaO, 3% TiO
2, 7% K
2o; Obtained catalyst carries out synthesis gas under certain condition and produces low-carbon alkene reaction, and experimental result lists in table 1.
[embodiment 9]
Take 45.0 grams of Alpha-alumina (Al
2o
3) powder and 40.1 grams of powdered whiting (CaCO
3) powder and 3.4 grams of titanium dioxide (TiO
2) powder mixes, in ball mill, mixed 1 hour of mill, makes compound G stand-by; Take 11.5 grams of potash (K
2cO
3), add 30 ml deionized waters, until completely dissolved, add in the mixed compound G of above-mentioned mill, carry out kneading extruded; At the temperature of 1300 DEG C, sinter 2 hours after oven dry, make complex carrier, after cooling, crushing and screening becomes 60 ~ 80 orders to prepare composite oxide carrier H; By 75.9 grams of Fe(NO3)39H2Os, 34.8 gram of five nitric hydrate zirconium, 10.4 gram of five nitric hydrate bismuth, be dissolved in 35.0 grams of deionized waters and make mixed solution I; Under the condition of vacuum 80kPa, above-mentioned mixed solution I to be impregnated on 70.0 grams of composite oxide carrier H prepared to obtain catalyst precarsor J; The catalyst precarsor J flooded is dry under 110 DEG C of conditions, then carries out roasting, sintering temperature 600 DEG C, roasting time 2h, namely obtains the catalyst that required synthesis gas produces low-carbon alkene.Obtained catalyst, comprises following component: 15% Fe
2o
3, 10% ZrO
2, 5% Bi
2o
3, 40% α-Al
2o
3, 20% CaO, 3% TiO
2, 7% K
2o; Obtained catalyst carries out synthesis gas under certain condition and produces low-carbon alkene reaction, and experimental result lists in table 1.
[embodiment 10]
Take 45.0 grams of Alpha-alumina (Al
2o
3) powder and 40.1 grams of powdered whiting (CaCO
3) powder and 3.4 grams of titanium dioxide (TiO
2) powder mixes, in ball mill, mixed 1 hour of mill, makes compound G stand-by; Take 11.5 grams of potash (K
2cO
3), add 30 ml deionized waters, until completely dissolved, add in the mixed compound G of above-mentioned mill, carry out kneading extruded; At the temperature of 1100 DEG C, sinter 6 hours after oven dry, make complex carrier, after cooling, crushing and screening becomes 60 ~ 80 orders to prepare composite oxide carrier H; By 101.2 grams of Fe(NO3)39H2Os, the manganese nitrate solution of 25.2 gram 50%, 10.4 gram of five nitric hydrate bismuth, be dissolved in 35.0 grams of deionized waters and make mixed solution I; Under the condition of vacuum 80kPa, above-mentioned mixed solution I to be impregnated on 70.0 grams of composite oxide carrier H prepared to obtain catalyst precarsor J; The catalyst precarsor J flooded is dry under 110 DEG C of conditions, then carries out roasting, sintering temperature 600 DEG C, roasting time 2h, namely obtains the catalyst that required synthesis gas produces low-carbon alkene.Obtained catalyst, comprises following component: 20% Fe
2o
3, 5% MnO, 5% Bi
2o
3, 40% α-Al
2o
3, 20% CaO, 3% TiO
2, 7% K
2o; Obtained catalyst carries out synthesis gas under certain condition and produces low-carbon alkene reaction, and experimental result lists in table 1.
[embodiment 11]
Take 45.0 grams of Alpha-alumina (Al
2o
3) powder and 40.1 grams of powdered whiting (CaCO
3) powder and 3.4 grams of titanium dioxide (TiO
2) powder mixes, in ball mill, mixed 1 hour of mill, makes compound G stand-by; Take 11.5 grams of potash (K
2cO
3), add 30 ml deionized waters, until completely dissolved, add in the mixed compound G of above-mentioned mill, carry out kneading extruded; At the temperature of 1600 DEG C, sinter 1 hour after oven dry, make complex carrier, after cooling, crushing and screening becomes 60 ~ 80 orders to prepare composite oxide carrier H; By 101.2 grams of Fe(NO3)39H2Os, the manganese nitrate solution of 25.2 gram 50%, 8.3 gram of five nitric hydrate bismuth, 1.6 grams of magnesium nitrate hexahydrates, be dissolved in 35.0 grams of deionized waters and make mixed solution I; Under the condition of vacuum 80kPa, above-mentioned mixed solution I to be impregnated on 70.0 grams of composite oxide carrier H prepared to obtain catalyst precarsor J; The catalyst precarsor J flooded is dry under 110 DEG C of conditions, then carries out roasting, sintering temperature 600 DEG C, roasting time 2h, namely obtains the catalyst that required synthesis gas produces low-carbon alkene.Obtained catalyst, comprises following component: 20% Fe
2o
3, 5% MnO, 4% Bi
2o
3, 1% MgO, 40% α-Al
2o
3, 20% CaO, 3% TiO
2, 7% K
2o; Obtained catalyst carries out synthesis gas under certain condition and produces low-carbon alkene reaction, and experimental result lists in table 1.
[embodiment 12]
The catalyst that Example 1 is obtained, other are constant, only change reaction condition, and carry out preparation of low carbon olefines by synthetic gas, experimental result lists in table 2.
[comparative example 1]
Take 45.0 grams of Alpha-alumina (Al
2o
3) powder and 40.1 grams of powdered whiting (CaCO
3) powder and 3.4 grams of titanium dioxide (TiO
2) powder mixes, in ball mill, mixed 1 hour of mill, makes compound G stand-by; Take 11.5 grams of potash (K
2cO
3), add 30 ml deionized waters, until completely dissolved, add in the mixed compound G of above-mentioned mill, carry out kneading extruded; At the temperature of 1300 DEG C, sinter 2 hours after oven dry, make complex carrier, after cooling, crushing and screening becomes 60 ~ 80 orders to prepare composite oxide carrier H; By 101.2 grams of Fe(NO3)39H2Os, the manganese nitrate solution of 50.5 gram 50%, be dissolved in 35.0 grams of deionized waters and make mixed solution I; Under the condition of vacuum 80kPa, above-mentioned mixed solution I to be impregnated on 70.0 grams of composite oxide carrier H prepared to obtain catalyst precarsor J; The catalyst precarsor J flooded is dry under 110 DEG C of conditions, then carries out roasting, sintering temperature 600 DEG C, roasting time 2h, namely obtains the catalyst that required synthesis gas produces low-carbon alkene.Obtained catalyst, comprises following component: 20% Fe
2o
3, 10% MnO, 40% α-Al
2o
3, 20% CaO, 3% TiO
2, 7% K
2o; Obtained catalyst carries out synthesis gas under certain condition and produces low-carbon alkene reaction, and experimental result lists in table 1.
[comparative example 2]
Take 45.0 grams of Alpha-alumina (Al
2o
3) powder and 40.1 grams of powdered whiting (CaCO
3) powder and 3.4 grams of titanium dioxide (TiO
2) powder mixes, in ball mill, mixed 1 hour of mill, makes compound G stand-by; Take 11.5 grams of potash (K
2cO
3), add 30 ml deionized waters, until completely dissolved, add in the mixed compound G of above-mentioned mill, carry out kneading extruded; At the temperature of 1300 DEG C, sinter 2 hours after oven dry, make complex carrier, after cooling, crushing and screening becomes 60 ~ 80 orders to prepare composite oxide carrier H; By 50.6 grams of Fe(NO3)39H2Os, the manganese nitrate solution of 25.2 gram 50%, 31.2 gram of five nitric hydrate bismuth, be dissolved in 35.0 grams of deionized waters and make mixed solution I; Under the condition of vacuum 80kPa, above-mentioned mixed solution I to be impregnated on 70.0 grams of composite oxide carrier H prepared to obtain catalyst precarsor J; The catalyst precarsor J flooded is dry under 110 DEG C of conditions, then carries out roasting, sintering temperature 600 DEG C, roasting time 2h, namely obtains the catalyst that required synthesis gas produces low-carbon alkene.Obtained catalyst, comprises following component: 10% Fe
2o
3, 5% MnO, 15% Bi
2o
3, 40% α-Al
2o
3, 20% CaO, 3% TiO
2, 7% K
2o; Obtained catalyst carries out synthesis gas under certain condition and produces low-carbon alkene reaction, and experimental result lists in table 1.
[comparative example 3]
Take 44.3 grams of Alpha-alumina (Al
2o
3) powder and 39.5 grams of powdered whiting (CaCO
3) powder mixes, in ball mill, mixed 1 hour of mill, makes compound G stand-by; Take 16.2 grams of potash (K
2cO
3), add 30 ml deionized waters, until completely dissolved, add in the mixed compound G of above-mentioned mill, carry out kneading extruded; At the temperature of 1300 DEG C, sinter 2 hours after oven dry, make complex carrier, after cooling, crushing and screening becomes 60 ~ 80 orders to prepare composite oxide carrier H; By 30.4 grams of Fe(NO3)39H2Os, the manganese nitrate solution of 7.6 gram 50%, 3.1 gram of five nitric hydrate bismuth, be dissolved in 35.0 grams of deionized waters and make mixed solution I; Under the condition of vacuum 80kPa, above-mentioned mixed solution I to be impregnated on 70.0 grams of composite oxide carrier H prepared to obtain catalyst precarsor J; The catalyst precarsor J flooded is dry under 110 DEG C of conditions, then carries out roasting, sintering temperature 600 DEG C, roasting time 2h, namely obtains the catalyst that required synthesis gas produces low-carbon alkene.Obtained catalyst, comprises following component: 20% Fe
2o
3, 5% MnO, 5% Bi
2o
3, 40% α-Al
2o
3, 20% CaO, 10% K
2o; Obtained catalyst carries out synthesis gas under certain condition and produces low-carbon alkene reaction, and experimental result lists in table 1.
[comparative example 4]
Take 47.6 grams of Alpha-alumina (Al
2o
3) powder and 31.8 grams of powdered whiting (CaCO
3) powder and 11.9 grams of titanium dioxide (TiO
2) powder mixes, in ball mill, mixed 1 hour of mill, makes compound G stand-by; Take 8.7 grams of potash (K
2cO
3), add 30 ml deionized waters, until completely dissolved, add in the mixed compound G of above-mentioned mill, carry out kneading extruded; At the temperature of 1300 DEG C, sinter 2 hours after oven dry, make complex carrier, after cooling, crushing and screening becomes 60 ~ 80 orders to prepare composite oxide carrier H; By 30.4 grams of Fe(NO3)39H2Os, the manganese nitrate solution of 7.6 gram 50%, 3.1 gram of five nitric hydrate bismuth, be dissolved in 35.0 grams of deionized waters and make mixed solution I; Under the condition of vacuum 80kPa, above-mentioned mixed solution I to be impregnated on 70.0 grams of composite oxide carrier H prepared to obtain catalyst precarsor J; The catalyst precarsor J flooded is dry under 110 DEG C of conditions, then carries out roasting, sintering temperature 600 DEG C, roasting time 2h, namely obtains the catalyst that required synthesis gas produces low-carbon alkene.Obtained catalyst, comprises following component: 20% Fe
2o
3, 5% MnO, 5% Bi
2o
3, 40% α-Al
2o
3, 15% CaO, 10% TiO
2, 5% K
2o; Obtained catalyst carries out synthesis gas under certain condition and produces low-carbon alkene reaction, and experimental result lists in table 1.
The reducing condition of above-described embodiment and comparative example is:
Temperature 450 DEG C
Pressure normal pressure
Loaded catalyst 3 ml
Catalyst loading 1000 hours
-1
Reducing gases H
2
8 hours recovery times
Reaction condition is:
φ 8 millimeters of fixed bed reactors
Reaction temperature 340 DEG C
Reaction pressure 1.7MPa
Loaded catalyst 3 ml
Catalyst loading 1000 hours
-1
Pulp furnish (mole) H
2/ CO=1.6/1
Table 1
Table 2
* the appreciation condition of change compared with the condition described in table 1.
Claims (10)
1. produce a catalyst for low-carbon alkene for the synthesis of gas, comprise following component by weight percentage:
A) 5 ~ 50% ferro element or its oxide;
B) 4 ~ 20% be selected from least one element in manganese and zirconium or its oxide;
C) 1 ~ 10% bismuth element or its oxide;
D) carrier of 25 ~ 90%, in vehicle weight number, comprises following component (1) 15 ~ 40 part of Alpha-alumina; (2) 1 ~ 45 parts of calcium oxide; (3) 1 ~ 5 parts of titanium dioxide; (4) 1 ~ 20 parts of potassium oxides.
2. the catalyst producing low-carbon alkene for the synthesis of gas according to claim 1, it is characterized in that the oxide of iron in described catalyst is di-iron trioxide, in catalyst weight percent, content is 10 ~ 40%.
3. the catalyst producing low-carbon alkene for the synthesis of gas according to claim 1, it is characterized in that the oxide of manganese and zirconium in described catalyst is respectively manganese oxide and zirconia, in catalyst weight percent, content is 10 ~ 20%.
4. the catalyst producing low-carbon alkene for the synthesis of gas according to claim 1, it is characterized in that the oxide of the bismuth described in described catalyst is bismuth oxide, in catalyst weight percent, content is 1 ~ 5%.
5. the catalyst producing low-carbon alkene for the synthesis of gas according to claim 1, it is characterized in that described Alpha-alumina is in vehicle weight number, content is 20 ~ 40 parts.
6. the catalyst producing low-carbon alkene for the synthesis of gas according to claim 1, it is characterized in that described calcium oxide is in vehicle weight number, content is 10 ~ 40 parts.
7. the catalyst producing low-carbon alkene for the synthesis of gas according to claim 1, it is characterized in that described titanium dioxide is in vehicle weight number, content is 3 ~ 5 parts.
8. the catalyst producing low-carbon alkene for the synthesis of gas according to claim 1, it is characterized in that described potassium oxide is in vehicle weight number, content is 1 ~ 10 part.
9. the catalyst producing low-carbon alkene for the synthesis of gas according to claim 1, it is characterized in that described carrier is prepared by Alpha-alumina, powdered whiting, titanium dioxide and potash high temperature sintering, sintering temperature is 1100 ~ 1600 DEG C, and sintering time is 1 ~ 6 hour.
10. synthesis gas produces a method for low-carbon alkene, take synthesis gas as raw material, H
2be 1 ~ 3 with the mol ratio of CO, be 250 ~ 400 DEG C in reaction temperature, reaction pressure is 1.0 ~ 3.0Mpa, and feed gas volume air speed is 500 ~ 5000h
-1condition under, unstripped gas and the catalyst exposure described in any one of claim 1 ~ 9 react and generate containing C
2~ C
4alkene.
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| CN107597131A (en) * | 2017-09-08 | 2018-01-19 | 鄂尔多斯职业学院 | Catalyst for synthesizing low-carbon alkene |
| CN109651033A (en) * | 2017-10-10 | 2019-04-19 | 中国石油化工股份有限公司 | The method of fixed bed preparing low-carbon olefins |
| CN109651029A (en) * | 2017-10-10 | 2019-04-19 | 中国石油化工股份有限公司 | The catalyst of fixed bed production low-carbon alkene |
| CN109651028A (en) * | 2017-10-10 | 2019-04-19 | 中国石油化工股份有限公司 | The method of fixed bed production low-carbon alkene |
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| KR20110116009A (en) * | 2008-12-08 | 2011-10-24 | 사솔 테크날러지 (프로프라이어터리) 리미티드 | Olefin selective ft catalyst composition and preparation thereof |
| CN101757925B (en) * | 2009-12-31 | 2012-01-18 | 浙江工业大学 | Fused iron catalyst for producing light olefins from syngas and preparation method and application thereof |
| CN103212399B (en) * | 2013-04-19 | 2015-07-01 | 宁夏大学 | Preparation method and application for low carbon olefin zirconium-based catalyst through synthesis gas |
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| CN107597131A (en) * | 2017-09-08 | 2018-01-19 | 鄂尔多斯职业学院 | Catalyst for synthesizing low-carbon alkene |
| CN109651033A (en) * | 2017-10-10 | 2019-04-19 | 中国石油化工股份有限公司 | The method of fixed bed preparing low-carbon olefins |
| CN109651029A (en) * | 2017-10-10 | 2019-04-19 | 中国石油化工股份有限公司 | The catalyst of fixed bed production low-carbon alkene |
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| CN109651028B (en) * | 2017-10-10 | 2021-10-01 | 中国石油化工股份有限公司 | Method for producing low-carbon olefin by fixed bed |
| CN109651029B (en) * | 2017-10-10 | 2021-10-01 | 中国石油化工股份有限公司 | Catalyst for producing low-carbon olefin by fixed bed |
| CN112642437A (en) * | 2019-10-12 | 2021-04-13 | 中国石油化工股份有限公司 | Catalyst for preparing low-carbon olefin from synthesis gas and preparation method and application thereof |
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