CN108722439B - Catalyst containing assistant alpha-aluminum oxide loaded bimetallic oxide and preparation method thereof - Google Patents
Catalyst containing assistant alpha-aluminum oxide loaded bimetallic oxide and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an alpha-Al containing auxiliary agent for high-efficiency conversion of synthesis gas2O3A preparation method of loaded bimetallic oxide nano-particles. The high-temperature cracking method is utilized for the first time to prepare the bimetallic oxide nano-particles and load the bimetallic oxide nano-particles to alpha-Al2O3The carrier is added with K auxiliary agent and/or S auxiliary agent and then applied to a reaction system for directly preparing low-carbon olefin from synthesis gas, the preparation process of the catalyst is divided into three steps, the first step is to prepare bimetallic nano-particles by using a high-temperature cracking method, and the second step is to load the bimetallic nano-particles to alpha-Al2O3And (3) a carrier. This process allows the bimetallic oxide nanoparticle size to be related only to the pyrolysis process, and not to the loading. And thirdly, doping an auxiliary agent. The invention has the beneficial effects that: the catalyst with different particle sizes and different loading amounts can be prepared according to the use requirement, and then the K auxiliary agent and/or the S auxiliary agent are doped. The catalyst prepared by the method has the advantages of high selectivity, long service life, low preparation cost and relatively simple process.
Description
Technical Field
The invention relates to synthesis gas (CO/H)2) In particular to alpha-Al containing auxiliary agent for high-efficiency conversion of synthesis gas2O3A catalyst loaded with bimetallic oxide and a preparation method thereof.
Background
The synthesis gas can be used for preparing various chemical raw materials such as methane, low-carbon olefin, low-carbon alkane, gasoline, diesel oil and the like and liquid fuel, is an important chemical raw material gas, is mainly derived from petroleum cracking, and depends heavily on petroleum resources. However, the current energy structure situation of China is 'lean oil, little gas and relatively rich coal', the dependence of oil in China on the outside is over 50% of the internationally recognized safety warning line since 2008, and over 60% in 2013, so that the energy safety of China is seriously threatened. Therefore, the research on the related technology of the high-efficiency conversion of the non-petroleum route synthetic gas with coal as the source accords with the excessive dependence of China on imported petroleum resources.
The high-efficiency conversion of the synthesis gas is to convert CO and H2Directly synthesizing hydrocarbon under the action of catalyst by using raw material as raw material, and its reaction equation is (2n +1) H2+n CO→CnH2n+2+n H2O；2n H2+n CO→CnH2n+n H2O; accompanied by a water-vapor shift reaction H2O+CO→CO2+H2. The product composition is complex and is distributed in Anderson-Schulz-Flory (ASF). According to the distribution of ASF model products, the synthesis gas conversion products are difficult to be concentrated to a certain carbon number, and the active component sintering and lower mechanical strength caused by the conversion of the catalyst active phase, surface carbon and high temperature also become the bottleneck of industrialization.
At present, the conversion process of the synthesis gas is mainly used for synthesizing oil products and low-carbon olefins, and the catalyst mainly comprises Co, Fe, Ru, Ni and the like, wherein the Co and Fe catalysts have good reaction performance and low price, and are beneficial to large-scale application in industrial production. In contrast, the Fe-based catalyst has a wide process operation range, and can be adjusted according to the reaction temperature and pressureSelectively produce olefin, aromatic hydrocarbon and oxygen-containing compound. alpha-Al2O3Because the surface inertia of the carrier is beneficial to the reduction and carbonization of the Fe component, the carrier is a good carrier for preparing low-carbon olefin by using the synthesis gas.
The traditional supported Fe-based catalyst mostly adopts an impregnation method to load active components, and the method is easy to cause the active components and a carrier to generate stronger interaction in the high-temperature roasting process of the active components, thereby reducing the activity and stability of the catalyst. On the other hand, at high Fe loading, the obtained particle size is also large, which is not beneficial to the improvement of the conversion rate and the generation of low-carbon olefin. There is therefore a need to design more efficient supported catalysts and methods for their preparation.
Disclosure of Invention
The invention aims to overcome the technical defects in the prior art and provide alpha-Al containing auxiliary agent for high-efficiency conversion of synthesis gas2O3A preparation method of loaded bimetallic oxide nano-particles. The first time, the high temperature cracking method is utilized to prepare the bimetal oxide (the molecular formula is shown as MFe)2O4) Nanoparticles and loading thereof to alpha-Al2O3Carrier, addition of K adjuvant (K)2CO3) And/or S auxiliary (FeSO)4·7H2O) and then applied to a reaction system for directly preparing low-carbon olefin by synthesis gas, wherein the preparation process of the catalyst is divided into three steps, the first step is to prepare bimetallic nano-particles by using a high-temperature cracking method, and the second step is to load the bimetallic nano-particles to alpha-Al2O3And (3) a carrier. This process allows the bimetallic oxide nanoparticle size to be related only to the pyrolysis process, and not to the loading. And thirdly, doping an auxiliary agent. The catalyst with different particle sizes and different loading amounts can be prepared according to the use requirement, and then the K auxiliary agent and/or the S auxiliary agent are doped. The catalyst prepared by the method has the advantages of high selectivity, long service life, low preparation cost and relatively simple process.
The technical scheme adopted for realizing the purpose of the invention is as follows:
alpha-Al containing auxiliary agent of the invention2O3The catalyst loaded with bimetallic oxide, wherein the carrier is 70-99 wt% of the weight of the catalystThe bimetallic oxide nano-particles and the auxiliary agent together account for 1 wt% -30 wt% of the weight of the catalyst, the bimetallic is metal iron and metal M, and the molar ratio of M to iron is 1: (1-10), the auxiliary agent is K2CO3And/or FeSO4·7H2O, wherein K2CO3The mass ratio of the catalyst to the catalyst is (0.005-0.05):1, or FeSO4·7H2The mass ratio of O to the catalyst is (0.001-0.01):1, or K2CO3、FeSO4·7H2The mass ratio of O to the catalyst is (0.005-0.05): (0001-0.01): 1, the catalyst contains Fe3O4A crystalline phase, the particle size of the bimetallic oxide nanoparticles is 5-20nm, the activity of the catalyst is not reduced within 60h, and the catalyst is prepared according to the following steps:
s1: dissolving a mixture of iron oleate and oleic acid M and oleic acid in a high-boiling-point solvent, wherein the mass ratio of the mixture of iron oleate and oleic acid M to oleic acid is (5-50): 1; degassing with inert gas for 30-60 min; heating to 280-340 deg.C at a temperature rising rate of 3-5 deg.C/min, maintaining for 10-60min, and naturally cooling to room temperature, wherein M is Zn, Co, Mn, Ni, Mg, Cu, Ce, Zr or V;
s2: adding ethanol for precipitation, and performing centrifugal separation; dispersing in hexane, precipitating with ethanol, centrifuging, and diluting to constant volume with cyclohexane in a volumetric flask to make the total content of iron and metal M1-3 mg/mL to obtain cyclohexane solution of bimetallic oxide nanoparticles;
s3: taking a certain amount of prepared cyclohexane solution containing bimetallic oxide nano particles and a carrier alpha-Al2O3Mixing, wherein the cyclohexane solution is mixed with alpha-Al2O3The mass ratio of the carrier is (10-100): 1mL/g, stirring at room temperature for 12-36h, spin-drying by using a rotary evaporator, and then roasting at the temperature of 300 ℃ and 500 ℃ for 2-6h under air blowing to obtain alpha-Al2O3A catalyst supporting a bimetallic oxide.
S4: weighing K2CO3And/or FeSO4·7H2Dissolving O in deionized water, stirring, and adding alpha-Al obtained from S32O3A catalyst that supports a bi-metal oxide,stirring for 12-36h at room temperature, spin-drying by using a rotary evaporator, drying at 120 ℃ for 6-12h at 100-2O3A catalyst supporting a bimetallic oxide.
Preferably, the mass ratio of the mixture of the ferric oleate-the oleic acid M and the oleic acid in S1 is adjusted to obtain the same loading amount and different particle sizes of the bimetallic oxide loaded on the alpha-Al2O3A catalyst on a support.
Preferably, the carrier accounts for 90-95 wt% of the catalyst, and the active component bimetal oxide and the auxiliary agent together account for preferably 5-10 wt% of the catalyst.
Preferably, the metal M is magnesium metal and the bimetallic oxide is magnesium iron oxide, wherein the molar ratio of magnesium to iron is 0.27: 2.73.
preferably, the metal M is manganese metal, and the bimetallic oxide is ferromanganese oxide, wherein the particle size of the ferromanganese oxide nanoparticles is 9.2-11.6 nm.
In another aspect of the invention, a method of making alpha-Al2O3A method of loading a bimetallic oxide catalyst, characterized by: the method comprises the following steps:
s1: dissolving a mixture of iron oleate and oleic acid M and oleic acid in a high-boiling-point solvent, wherein the mass ratio of a compound of iron oleate and oleic acid M to oleic acid is (5-50): 1; degassing with inert gas for 30-60 min; heating to 280-340 deg.C at a temperature rising rate of 3-5 deg.C/min, maintaining for 10-60min, and naturally cooling to room temperature, wherein M is Zn, Co, Mn, Ni, Mg, Cu, Ce, Zr or V;
s2: adding ethanol for precipitation, and performing centrifugal separation; dispersing in hexane, precipitating with ethanol, centrifuging, and diluting to constant volume with cyclohexane in a volumetric flask to make total content of iron and M1-3 mg/Ml to obtain cyclohexane solution of bimetallic oxide nanoparticles;
s3: taking a certain amount of prepared cyclohexane solution containing bimetallic oxide nano particles and a carrier alpha-Al2O3Mixing, wherein the cyclohexane solution is mixed with alpha-Al2O3The mass ratio of the carrier is (10-1)00): 1mL/g, stirring at room temperature for 12-36h, spin-drying by using a rotary evaporator, and then roasting at the temperature of 300 ℃ and 500 ℃ for 2-6h under air blowing to obtain alpha-Al2O3A catalyst supporting a bimetallic oxide.
S4: weighing K2CO3And/or FeSO4·7H2Dissolving O in deionized water, stirring, and adding alpha-Al obtained from S32O3Fe load3O4The catalyst is stirred for 12-36h at room temperature, is dried by a rotary evaporator at the temperature of 100-120 ℃ for 6-12h, and is roasted for 2-6h at the temperature of 300-500 ℃ under air blowing, and finally the alpha-Al doped with the K and/or S auxiliary agent is obtained2O3A catalyst supporting a bimetallic oxide.
Preferably, the iron oleate-oleic acid M complex in S1 is prepared by the following steps:
1): preparing a mixed solvent by taking ethanol, deionized water and hexane in a volume ratio of 20:16:35, and weighing FeCl3、MClnAnd dissolving sodium oleate in the mixed solvent to obtain a mixed solution, wherein: FeCl3、MClnThe molar ratio of the mixture of (a) to the sodium oleate is 1: 3;
2): heating the mixed solution in the step 1) to 58-70 ℃, keeping the temperature for 3-5h, washing with water after the reaction is finished, separating by using a separating funnel, taking supernatant, repeatedly washing, and distilling under reduced pressure to remove excessive solvent to obtain the mixture of the iron oleate and the oleic acid M.
Preferably, the high-boiling solvent in step S1 is octadecene or trioctylamine.
Preferably, the inert gas used in step S1 is nitrogen, argon or helium.
Preferably, the rotation speed of the centrifugal separation in the step S2 is 9500rpm, and the time is 10 min.
In another aspect of the invention, α -Al2O3Use of a catalyst supporting a bimetallic oxide for the preparation of hydrocarbons from synthesis gas.
Preferably, the reaction for preparing hydrocarbon compound by using synthesis gas is carried out at the ratio of gas flow rate to the amount of catalyst of 10000-60000mL·g-1·h-1Under the condition that the reduction condition is normal pressure H2The flow rate is 30-180 mL/min-1The temperature is 350-450 ℃, and the raw material feeding molar ratio n (H)2CO is 1-2), the reaction temperature is 300-350 ℃, the reaction pressure is 0.5-2.5MPa, and the reaction synthesis is realized under the existence of a catalyst.
Compared with the prior art, the invention has the beneficial effects that:
the active component is more dispersed and stable, the particle size of the active component can be accurately regulated and controlled, and the active component is independent of the loading amount of the active component. The activity and stability of the catalyst can be effectively improved by regulating and controlling the particle size of the active component. The catalyst prepared by the method has the advantages of high selectivity, long service life, no reduction of activity within 60 hours, low preparation cost and relatively simple process.
Drawings
FIG. 1 is a bimetallic oxide supported on alpha-Al2O3TEM image of the catalyst.
FIG. 2 is a bimetallic oxide supported on alpha-Al2O3XRD pattern of catalyst.
Detailed Description
The invention is described in further detail below with reference to the figures and specific examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Examples 1 to 3
Preparation of Zn doped with K, S adjuvant and having different zinc contentsmFenO4/α-Al2O3Catalyst:
the method comprises the following steps: the mixture was mixed (80mL ethanol, 64mL deionized water, 140mL hexane) and 5.90g FeCl was weighed out separately3、0.50g ZnCl2And 36.5g of sodium oleate (example 1), 5.41g of FeCl3、0.91g ZnCl2And 36.5g of sodium oleate (example 2), 4.99g of FeCl3、1.26g ZnCl2And 36.5g of sodium oleate (example 3) were added to the mixture; heating the mixed solution to 60 ℃, keeping the temperature for 4 hours, washing the mixed solution by using 100mL of water after the reaction is finished, separating the mixed solution by using a separating funnel, taking supernatant,washing is repeated for five times, and excess solvent is removed by reduced pressure distillation to obtain an iron oleate-zinc oleate mixture;
step two: 36g of the resulting iron oleate-zinc oleate mixture and 5.7g of oleic acid were dissolved in 100g of octadecene; firstly using N2Degassing for 30 min; heating to 340 deg.C at a rate of 3.3 deg.C/min, maintaining for 30min (after a series of reactions, the initial transparent solution becomes turbid and brown), and naturally cooling to room temperature; adding 250mL of ethanol for precipitation, and performing centrifugal separation (9500rpm, 10 min); dispersing in 100mL hexane, precipitating with 250mL ethanol, centrifuging (9500rpm, 10min), and adding cyclohexane to the volume in a 500mL volumetric flask; 150mL of prepared cyclohexane solution containing ferroferric oxide and 4g of alpha-Al2O3Mixing the carriers, stirring for 24h at room temperature, spin-drying by using a rotary evaporator, and roasting for 4h at 350 ℃ under air purging to finally obtain Zn with different zinc contentsmFenO4/α-Al2O3A catalyst.
Step three: respectively weighing 0.0089g K2CO3And 0.0022g FeSO4·7H2Dissolving O in 50mL of deionized water, stirring uniformly, and adding 1g of Zn obtained abovemFenO4/α-Al2O3Stirring for 12h at room temperature, spin-drying by using a rotary evaporator, drying at 120 ℃ overnight, and then roasting for 2h at 500 ℃ under air purging to finally obtain K, S-doped auxiliary ZnmFenO4/α-Al2O3A catalyst.
Example 1 Zn obtained in step two0.27Fe2.73O4The size of the nanoparticles is 12nm, Zn0.27Fe2.73O4Shown in FIG. 1b, Zn0.27Fe2.73O4/α-Al2O3The TEM spectrum of (A) is shown in FIG. 1 a. It can be seen that Zn0.27Fe2.73O4Good dispersibility before loading, uniform particle size, Zn0.27Fe2.73O4Loaded on alpha-Al2O3The dispersibility of the particles is still kept good, and the size distribution of the nano particles is very uniform. In the process of addingAfter adding K additive and S additive, Zn0.27Fe2.73O4/α-Al2O3The particle dispersibility of (2) is still kept good, the particle dispersibility is still kept good, and the size distribution of the nano particles is still uniform.
Example 2 Zn obtained in step two0.5Fe2.5O4The size of the nanoparticles is 14.3nm, Zn0.5Fe2.5O4The TEM spectrum of (A) is shown in FIG. 1d, Zn0.5Fe2.5O4/α-Al2O3The TEM spectrum of the compound is shown in FIG. 1 c; zn0.5Fe2.5O4The particle dispersibility remains good before and after loading, and the nanoparticle size distribution is very uniform. Zn0.5Fe2.5O4/α-Al2O3After the K additive and the S additive are added, the particle dispersibility still keeps good, and the size distribution of the nano particles is still uniform.
Example 3 Zn obtained in step two0.69Fe2.31O4The size of the nanoparticles is 14.1nm, Zn0.69Fe2.31O4The TEM spectrum of (A) is shown in FIG. 1f, Zn0.69Fe2.31O4/α-Al2O3The TEM spectrum of (A) is shown in FIG. 1e, Zn of examples 1-3mFenO4/α-Al2O3The XRD spectrum of the compound is shown in figure 2. Zn0.69Fe2.31O4The particle dispersibility remains good before and after loading, and the nanoparticle size distribution is very uniform. Zn0.69Fe2.31O4/α-Al2O3After the K additive and the S additive are added, the particle dispersibility is still good, and the size distribution of the nano particles is still uniform.
Wherein: the TEM employed a Tecnai G2F20 field emission electron microscope from FEI, the Netherlands. A Schottky type field emission gun is used as an electron source, the point resolution and the line resolution of the instrument are 0.248nm and 0.102nm, the acceleration voltage is 200kV, and the maximum amplification factor is 19 ten thousand times. The sample preparation process comprises the following steps: carefully grinding the sample in an agate mortar, taking a small amount of the ground sample, dispersing the ground sample in absolute ethyl alcohol, dispersing the ground sample by ultrasonic oscillation, and dripping the ground sample on a copper net attached with a carbon film for naturally drying;
XRD was characterized using a RigakuD/Max-2500X-ray diffractometer (Japan science Inc.) with the following operating parameters: cu Kalpha is used as a ray source (lambda is 0.154nm), the working voltage is 40kV, the working current is 200mA, the scanning range is 10-90 degrees, and the scanning speed is 8 degrees/min.
The dried catalyst powder pellets were sieved to 40 to 60 mesh, the catalyst obtained in example 1 to 3 was weighed and loaded in an amount of 0.2g, and the catalyst activity was evaluated in a pressurized micro-reaction system. The reactants were introduced at 45mL/min CO and 45mL/minH2And internal standard gas 10mL/min Ar at 340 deg.C and 1.0Mpa, and the ratio of reaction gas flow rate to catalyst amount is 27000 mL-g-1·h-1The reaction was carried out and the product was analyzed by gas chromatography. The resulting reaction properties are shown in table 1. Wherein: FTY represents the moles of iron per second converted to CO per unit mass, O/P (2-4) represents C2～C4The ratio of alkene to alkane in the compound.
TABLE 1 Zn doped with K and S adjuvants of different Zn contentsmFenO4/α-Al2O3High efficiency conversion reaction result of catalyst synthesis gas
Wherein: FTY represents the moles of iron per second converted to CO per unit mass, O/P (2-4) represents C2～C4The ratio of alkene to alkane in the compound.
Wherein: 0.5K-0.05S-Zn0.27Fe2.73O4/α-Al2O3The meaning of (A) is: with alpha-Al2O3Is loaded with Zn as a carrier0.27Fe2.73O4And K, S co-agent, Zn0.27Fe2.73O4Wherein the molar ratio of Zn to Fe is 0.27: 2.73, the mass fraction of K in the catalyst was 0.5%, and the mass fraction of S in the catalyst was 0.05%.
[ examples 4 to 9 ]
Under other experimental conditions and experimentsIn the case of the same embodiment 1, the raw material in the first step is changed to 5.90g of FeCl which is respectively weighed3、0.865g CoCl2·6H2O and 36.5g sodium oleate (example 4), 5.90g FeCl3、0.50g CeCl3·7H2O and 36.5g of sodium oleate (example 5), 5.90g of FeCl3、0.847g ZrCl4And 36.5g of sodium oleate (example 6), 5.90g of FeCl3、0.49g CuCl2And 36.5g of sodium oleate (example 7), 5.90g of FeCl3、0.35g MgCl2And 36.5g of sodium oleate (example 8), 5.90g of FeCl3、0.57g VCl3And 36.5g of sodium oleate (example 9), to give M doped with different metals0.27Fe2.73O4/α-Al2O3Catalysts, the products obtained in examples 4 to 9 were respectively: 0.5K-0.05S-Co0.27Fe2.73O4/α-Al2O3，0.5K-0.05S-Ce0.27Fe2.73O4/α-Al2O3，0.5K-0.05S-Zr0.27Fe2.73O4/α-Al2O3，0.5K-0.05S-Cu0.27Fe2.73O4/α-Al2O3，0.5K-0.05S-Mg0.27Fe2.73O4/α-Al2O3，0.5K-0.05S-V0.27Fe2.73O4/α-Al2O3. M obtained in examples 4 to 90.27Fe2.73O4The TEM spectrum of the compound is shown in figure 1g-1l, and the XRD spectrum is shown in figure 2.
The dried catalyst powder pellets were sieved to 40 to 60 mesh, the catalyst obtained in examples 4 to 9 was weighed and loaded in an amount of 0.2g, and the catalyst activity was evaluated in a pressurized micro-reaction system. The reactants were introduced at 45mL/min CO and 45mL/minH2And internal standard gas 10mL/min Ar at 340 deg.C and 1.0Mpa, and the ratio of reaction gas flow rate to catalyst amount is 27000 mL-g-1·h-1The reaction was carried out and the product was analyzed by gas chromatography. The resulting reaction properties are shown in table 2.
TABLE 2M doped with different metals of K and S promoters0.27Fe2.73O4/α-Al2O3High efficiency conversion reaction result of catalyst synthesis gas
[ examples 10 to 13 ]
Under the condition that other experimental conditions are completely the same as those of the example 1, the raw materials in the step one are changed into the method of respectively weighing 4.32g of FeCl3、1.68g MnCl2And 36.5g of sodium oleate, the solvent was changed to trioctylamine, the oleic acid content in step two was changed to 2.4g (example 10), 3.0g (example 11), 3.4g (example 12), 5.7g (example 13), giving MnFe in different particle sizes2O4/α-Al2O3Catalysts, the catalysts obtained in examples 10 to 13, were each MnFe2O4(9.2)/α-Al2O3，MnFe2O4(11.6)/α-Al2O3，MnFe2O4(13.6)/α-Al2O3，MnFe2O4(16.3)/α-Al2O3. The TEM spectra and XRD spectra of the catalysts obtained in examples 10 to 13 are shown in FIGS. 1m to p and 2, respectively.
The dried catalyst powder pellets were sieved to 40 to 60 mesh, the catalyst obtained in example 10 to 13 was weighed out at a loading of 0.2g, and the catalyst activity was evaluated in a pressurized micro-reaction system. The reactants were introduced at 45mL/min CO and 45mL/minH2And internal standard gas 10mL/min Ar at 340 deg.C and 1.0Mpa, and the ratio of reaction gas flow rate to catalyst amount is 27000 mL-g-1·h-1The reaction was carried out and the product was analyzed by gas chromatography. The resulting reaction properties are shown in table 3.
TABLE 3 MnFe doped with K and S promoters of different particle sizes2O4/α-Al2O3High efficiency conversion reaction result of catalyst synthesis gas
Wherein:0.5K-0.05S-MnFe2O4(9.2)/α-Al2O3the particle size of the ferromanganese bimetallic oxide is 9.2 nm.
As can be seen from FIG. 1, MFe prepared by pyrolysis2O4The nanoparticle size distribution is very uniform (within 10%). The nano particles with uniform size distribution are loaded on a carrier, and the K and S addition agents are still well dispersed.
As can be seen from FIG. 2, the K and S promoter-added catalysts obtained from different particle sizes and metal doping both contain mainly Fe3O4The crystalline phase, mainly Fe, being obtained by conventional impregnation and precipitation methods2O3Crystalline phase of Fe3O4Crystal phase ratio of Fe2O3The crystal phase is more easily reduced and carbonized, resulting in higher activity.
Comparative example 1
The traditional dipping method is adopted to prepare Fe2O3/α-Al2O3A catalyst. The process is as follows: 3.2g of ferric ammonium citrate (NH) are weighed4)3Fe(C6H5O7)2Dissolved in 100mL of deionized water. 4.0g of alpha-Al was added2O3Stirring for 24h, spin-drying with a rotary evaporator at 120 deg.C overnight, and calcining at 500 deg.C for 4h (5 deg.C/min) under air purge to obtain 10 Fe/alpha-Al2O3Catalyst (wherein the mass fraction of Fe element is 10%).
Adding auxiliary agents K and S on the catalyst, and weighing 0.0089g K2CO3And 0.0022g FeSO4·7H2Dissolving O in 50mL of deionized water, stirring uniformly, adding 1g of iron-based loaded alpha-Al of comparative example 12O3Stirring the catalyst for 12h at room temperature, carrying out spin drying by using a rotary evaporator, drying at 120 ℃ overnight, and then roasting at 500 ℃ for 2h under air purging to finally obtain K, S-doped auxiliary agent-containing 0.5K-0.05S-Fe with different particle sizes2O3/α-Al2O3The catalyst performance was evaluated under the reaction conditions of example 14. FTY is 277X 10-6molCO gFe -1s-1The activity is far lower than that of examples 4-5, and the catalyst has obvious deactivation phenomenon in 30 h.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (9)
1. alpha-Al containing auxiliary agent2O3A bimetallic oxide supported catalyst characterized by: the carrier accounts for 70-99 wt% of the weight of the catalyst, the bimetallic oxide nanoparticles and the auxiliary agent account for 1-30 wt% of the weight of the catalyst, the bimetallic is metallic iron and metal M, and the molar ratio of M to iron is 1: (1-10), the auxiliary agent is K2CO3And/or FeSO4·7H2O, wherein K2CO3The mass ratio of the catalyst to the catalyst is (0.005-0.05):1, or FeSO4·7H2The mass ratio of O to the catalyst is (0.001-0.01):1, or K2CO3、FeSO4·7H2The mass ratio of O to the catalyst is (0.005-0.05): (0001-0.01): 1, the catalyst contains Fe3O4A crystalline phase, the particle size of the bimetallic oxide nanoparticles is 5-20nm, the activity of the catalyst is not reduced within 60h, and the catalyst is prepared according to the following steps:
s1: dissolving a mixture of iron oleate and oleic acid M and oleic acid in a high-boiling-point solvent, wherein the mass ratio of the mixture of iron oleate and oleic acid M to oleic acid is (5-50): 1; degassing with inert gas for 30-60 min; heating to 280-340 deg.C at a temperature rising rate of 3-5 deg.C/min, maintaining for 10-60min, and naturally cooling to room temperature, wherein M is Zn, Co, Mn, Ni, Mg, Cu, Ce, Zr or V;
s2: adding ethanol for precipitation, and performing centrifugal separation; dispersing in hexane, precipitating with ethanol, centrifuging, and diluting to constant volume with cyclohexane in a volumetric flask to make the total content of iron and M1-3 mg/mL to obtain cyclohexane solution of bimetallic oxide nanoparticles;
s3: taking a certain amount of prepared cyclohexane solution containing bimetallic oxide nano particles and a carrier alpha-Al2O3Mixing, wherein the volume fraction of the cyclohexane solution is equal to that of the alpha-Al2O3The ratio of the mass parts of the carrier is (10-100): 1, wherein the unit of volume fraction is mL, the unit of mass fraction is g, stirring for 12-36h at room temperature, carrying out spin drying by using a rotary evaporator, and then roasting for 2-6h at the temperature of 500 ℃ under the air purging to obtain alpha-Al2O3A catalyst supporting a bimetallic oxide;
s4: weighing K2CO3And/or FeSO4·7H2Dissolving O in deionized water, stirring, and adding alpha-Al obtained from S32O3Stirring the catalyst loaded with the bimetallic oxide for 12-36h at room temperature, spin-drying by using a rotary evaporator, drying at the temperature of 100-120 ℃ for 6-12h, and then roasting at the temperature of 300-500 ℃ for 2-6h under air blowing to finally obtain the alpha-Al doped with the K and/or S auxiliary agent2O3A catalyst supporting a bimetallic oxide;
by adjusting the mass ratio of the mixture of the ferric oleate and the oleic acid M to the oleic acid in S1, the method can obtain the method for loading the bimetallic oxides with the same loading amount and different particle sizes to the alpha-Al by using the auxiliary agent2O3A catalyst on a support.
2. alpha-Al containing auxiliary according to claim 12O3A bimetallic oxide supported catalyst characterized by: the metal M is metal magnesium, the bimetallic oxide is magnesium iron oxide, and the molar ratio of magnesium to iron is 0.27: 2.73.
3. preparation of alpha-Al containing auxiliary agent2O3A method of loading a bimetallic oxide catalyst, characterized by: the method comprises the following steps:
s1: dissolving an iron oleate-oleic acid M compound and oleic acid in a high-boiling-point solvent, wherein the mass ratio of the iron oleate-oleic acid M compound to the oleic acid (5-50): 1; degassing with inert gas for 30-60 min; heating to 280-340 deg.C at a temperature rising rate of 3-5 deg.C/min, maintaining for 10-60min, and naturally cooling to room temperature, wherein M is Zn, Co, Mn, Ni, Mg, Cu, Ce, Zr or V;
s2: adding ethanol for precipitation, and performing centrifugal separation; dispersing in hexane, precipitating with ethanol, centrifuging, and diluting to constant volume with cyclohexane in a volumetric flask to make the total content of iron and M1-3 mg/mL to obtain cyclohexane solution of bimetallic oxide nanoparticles;
s3: taking a certain amount of prepared cyclohexane solution containing bimetallic oxide nano particles and a carrier alpha-Al2O3Mixing, wherein the volume fraction of the cyclohexane solution is equal to that of the alpha-Al2O3The ratio of the mass parts of the carrier is (10-100): 1, wherein the unit of volume fraction is mL, the unit of mass fraction is g, stirring for 12-36h at room temperature, carrying out spin drying by using a rotary evaporator, and then roasting for 2-6h at the temperature of 500 ℃ under the air purging to obtain alpha-Al2O3A catalyst supporting a bimetallic oxide.
S4: weighing K2CO3And/or FeSO4·7H2Dissolving O in deionized water, stirring, and adding alpha-Al obtained from S32O3Stirring the catalyst loaded with the bimetallic oxide for 12-36h at room temperature, spin-drying by using a rotary evaporator, drying at the temperature of 100-120 ℃ for 6-12h, and then roasting at the temperature of 300-500 ℃ for 2-6h under air blowing to finally obtain the alpha-Al doped with the K and/or S auxiliary agent2O3A catalyst supporting a bimetallic oxide.
4. The method for preparing alpha-Al containing additive according to claim 32O3A method of loading a bimetallic oxide catalyst, characterized by: the iron oleate-oleic acid M complex in S1 is prepared by the following steps:
1): preparing a mixed solvent by taking ethanol, deionized water and hexane in a volume ratio of 20:16:35, and weighing FeCl3Dissolving M chloride and sodium oleate in a mixed solvent to obtain a mixed solution, wherein: FeCl3The molar ratio of the mixture of M chloride to sodium oleate is 1: 3;
2): heating the mixed solution in the step 1) to 58-70 ℃, keeping the temperature for 3-5h, washing with water after the reaction is finished, separating by using a separating funnel, taking supernatant, repeatedly washing, and distilling under reduced pressure to remove excessive solvent to obtain the mixture of the iron oleate and the oleic acid M.
5. The method for preparing alpha-Al containing additive according to claim 32O3A method of loading a bimetallic oxide catalyst, characterized by: the high-boiling solvent in the step S1 is octadecene or trioctylamine.
6. The method for preparing alpha-Al containing additive according to claim 32O3A method of loading a bimetallic oxide catalyst, characterized by: the inert gas used in step S1 is nitrogen, argon or helium.
7. The method for preparing alpha-Al containing additive according to claim 32O3A method of loading a bimetallic oxide catalyst, characterized by: the rotation speed of the centrifugal separation in the step S2 is 9500rpm, and the time is 10 min.
8. alpha-Al containing additives according to claim 12O3Use of a catalyst supporting a bimetallic oxide for the preparation of hydrocarbons from synthesis gas.
9. alpha-Al containing auxiliary according to claim 82O3The application of the catalyst loaded with the bimetallic oxide in preparing hydrocarbon compounds by using synthesis gas is characterized in that: the ratio of the gas flow rate to the catalyst dosage in the reaction is 10000-60000 mL-g-1·h-1Under the condition that the reduction condition is normal pressure H2The flow rate is 30-180 mL/min-1The temperature is 350-450 ℃, and the raw material feeding molar ratio is H2CO ═ 1-2: 1, the reaction temperature is 300-350 ℃, the reaction pressure is 0.5-2.5MPa and the reaction synthesis is realized under the existence of a catalyst.
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