CN108262044B - Preparation method of Fischer-Tropsch synthesis catalyst and prepared Fischer-Tropsch synthesis catalyst - Google Patents
Preparation method of Fischer-Tropsch synthesis catalyst and prepared Fischer-Tropsch synthesis catalyst Download PDFInfo
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
- C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
- C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
- C10G2/332—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals of the iron-group
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
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Abstract
The invention relates to a preparation method of a Fischer-Tropsch synthesis catalyst and the prepared Fischer-Tropsch synthesis catalyst, and the method comprises the following steps: a. adding a VIII group metal salt solution into a first mixed solution comprising a carrier, a first solvent and ammonia water under stirring for reaction, and then filtering and drying to obtain a catalyst intermediate; wherein the carrier is diamond-shaped nano gamma-Al2O3The adding speed of the VIII group metal salt solution is 0.01-1 ml/(min 200 g of the first mixed solution); b. and roasting the obtained catalyst intermediate to obtain the Fischer-Tropsch synthesis catalyst. The Fischer-Tropsch synthesis catalyst prepared by the method has high initial CO conversion rate and steady-state CO conversion rate, and C5 +The selectivity of hydrocarbon, olefin and diesel oil is good.
Description
Technical Field
The invention relates to the technical field of Fischer-Tropsch synthesis catalysts, in particular to a preparation method of a Fischer-Tropsch synthesis catalyst and the prepared Fischer-Tropsch synthesis catalyst.
Background
The fischer-tropsch synthesis (FTS), also known as fischer-tropsch synthesis, has evolved over the last hundred years since its discovery in 1923. The commonly used fischer-tropsch catalysts include iron-based catalysts and cobalt-based catalysts, among which the cobalt-based catalysts are widely used in the fischer-tropsch synthesis industry due to their advantages of high selectivity for long-chain hydrocarbons, high deactivation resistance, and low water gas shift reaction (WGS) activity. The active component of the cobalt-based catalyst is metallic cobalt, and usually, the cobalt-based catalyst is pre-reduced to activate the catalyst before reaction. If the cobalt-based catalyst contains unreduced cobalt oxide species, the CO conversion of the fischer-tropsch reaction is reduced, CH4The selectivity is increased. The reduction degree of the cobalt-based catalyst and the form of the reduced metal cobalt have great influence on the catalytic performance of the catalyst in the Fischer-Tropsch synthesis reaction. The cobalt-based catalyst has many factors affecting the reduction degree and dispersion degree of cobalt species, such as preparation method, carrier type and structure, auxiliary agent, reduction condition, etc. The reduction degree of cobalt species in the cobalt-based catalyst and the dispersion degree of metal cobalt can be improved, so that the number of active sites of the metal cobalt on the surface of the catalyst can be greatly increased, and the gold in the cobalt-based catalyst is greatly improvedThe cobalt atom utilization rate is adopted to reduce the cost of the catalyst. In order to increase the dispersion degree of the active metal in the catalyst, oxide carriers having a certain interaction with the active metal, such as alumina, titania, silica, etc., are often selected. However, increased dispersion of the active metals of the catalyst generally leads to enhanced interaction between the active metals and the support, resulting in difficulty in reducing the active metals. Therefore, when the catalytic performance of the catalyst is examined, both the degree of reduction and the degree of dispersion of the active metal are considered.
Because of its good mechanical and chemical strength and high cobalt species dispersion, alumina-supported cobalt-based catalysts are commonly used in fischer-tropsch synthesis reactions. However, there is a strong interaction between alumina and cobalt species, which makes it difficult to reduce the cobalt species in the catalyst. In view of the mutually restrictive factors of the degree of reduction and the degree of dispersion, many studies have reported that the degree of reduction and the degree of dispersion of cobalt species are balanced by changing the properties of the carrier alumina, such as changing the parameters of the pore structure, the specific surface area, the surface properties and the like of the alumina. The reduction degree and the dispersity of the cobalt species are improved by changing the preparation method of the catalyst, adding a proper auxiliary agent and the like.
Similarly, the iron-based catalyst also has the above-mentioned problem of the cobalt-based catalyst, and it is required to improve the degree of dispersion and reduction of iron on the surface of the catalyst. In addition, the prior art has the defects of complicated Fischer-Tropsch catalyst synthesis steps, low catalytic activity and the like.
Disclosure of Invention
The invention aims to provide a preparation method of a Fischer-Tropsch synthesis catalyst and the prepared Fischer-Tropsch synthesis catalyst5 +The selectivity of hydrocarbon, olefin and diesel oil is good.
In order to achieve the above object, the present invention provides a method for preparing a fischer-tropsch synthesis catalyst, which comprises a, adding a group VIII metal salt solution to a first mixed solution comprising a carrier, a first solvent and aqueous ammonia under stirring for reaction, then filtering and drying,obtaining a catalyst intermediate; wherein the VIII group metal salt solution is an iron salt solution and/or a cobalt salt solution, the concentration of the VIII group metal salt solution is 0.001-0.1 mol/L, the pH value of the first mixed solution is 7.0-8.0, and the carrier is diamond-shaped nano gamma-Al2O3The weight ratio of the carrier to the first solvent on a dry basis is 1: (10-500), wherein the addition rate of the group VIII metal salt solution is 0.01-1 ml/(min 200 g of the first mixed solution), and the first solvent comprises water and/or ethanol; b. roasting the obtained catalyst intermediate to obtain a Fischer-Tropsch synthesis catalyst; wherein the content of the VIII group metal in the Fischer-Tropsch synthesis catalyst is 5-20 wt% based on the dry weight of the Fischer-Tropsch synthesis catalyst.
Optionally, the group VIII metal salt solution is added at a rate of 0.05 to 0.1 ml/(min · 200 g of the first mixed solution).
Optionally, the reaction in the step a is carried out at a temperature of 10-50 ℃ for 12-24 hours under a stirring state.
Optionally, the drying temperature in the step a is 50-120 ℃, and the drying time is 12-48 hours; in the step b, the roasting temperature is 200-500 ℃, and the roasting time is 1-48 hours.
Optionally, the group VIII metal salt is at least one selected from the group consisting of cobalt chloride, cobalt nitrate, ferric chloride and ferric nitrate.
Optionally, the rhombohedral-shaped nano gamma-Al2O3The preparation steps comprise: (1) mixing alkoxy aluminum, a second solvent and organic acid to obtain a second mixed solution with the pH value of 4-7; wherein the second solvent is at least one selected from deionized water, ethanol and isopropanol, and the weight ratio of the aluminum isopropoxide to the second solvent is 1: (10-200); (2) carrying out hydrothermal crystallization on the obtained second mixed solution with the pH value of 4-7, and filtering to obtain a crystallization product; (3) drying and roasting the obtained crystallized product to obtain the diamond-shaped nano gamma-Al2O3。
Optionally, the rhombohedral-shaped nano gamma-Al2O3The preparation steps further comprise: and (2) stirring the second mixed solution with the pH value of 4-7 obtained in the step (1) at the temperature of 60-90 ℃ for 2-10 hours, and then performing hydrothermal crystallization.
Optionally, the temperature of the hydrothermal crystallization in the step (2) is 150-250 ℃, and the time is 1-48 hours.
Optionally, in the step (3), the drying temperature is 50-200 ℃ and the drying time is 1-48 hours; the roasting temperature is 200-1000 ℃, and the roasting time is 1-12 hours.
Optionally, the rhombohedral-shaped nano gamma-Al2O3The length of the glass is 80-120 nm, and the width of the glass is 60-120 nm.
The invention also provides a Fischer-Tropsch synthesis catalyst prepared by the method.
The invention makes VIII metal salt and ammonia water precipitant slowly precipitant on the surface of gamma-alumina carrier, which can improve the dispersion degree, reduction degree and active site number of VIII metal on the carrier surface, further improve the initial conversion rate, steady state conversion rate and C of Fischer-Tropsch synthesis catalyst CO5 +Hydrocarbon, olefin and diesel selectivity.
In addition, the gamma-alumina carrier is in a rhombic sheet shape, the main exposed crystal face on the surface of the gamma-alumina carrier is a (110) crystal face, and the metal precipitate can form a mesostructured catalyst on the exposed crystal face so as to increase the structural action between the carrier and the metal and further improve the dispersion degree and the reduction degree of the metal on the surface of the carrier.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 shows rhombohedral nano-gamma-Al prepared in example 1 of the present invention2O3(a) Fischer-Tropsch Synthesis catalyst (c) prepared in example 1 and Fischer-Tropsch Synthesis catalyst (c) prepared in comparative example 1XRD pattern of the synthetic catalyst (b).
FIG. 2 shows rhombohedral nano-gamma-Al prepared in example 1 of the present invention2O3Transmission Electron Microscopy (HRTEM).
FIG. 3 is a transmission electron micrograph (HRTEM) of a Fischer-Tropsch synthesis catalyst prepared in comparative example 1 of the present invention.
FIG. 4 is a transmission electron micrograph (HRTEM) of a Fischer-Tropsch synthesis catalyst prepared in example 1 of the present invention.
Detailed Description
The following detailed description of embodiments of the invention refers to the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The invention provides a preparation method of a Fischer-Tropsch synthesis catalyst, which comprises a, adding a VIII group metal salt solution into a first mixed solution comprising a carrier, a first solvent and ammonia water under stirring for reaction, and then filtering and drying to obtain a catalyst intermediate; wherein the group VIII metal salt solution is an iron salt solution and/or a cobalt salt solution, the concentration of the group VIII metal salt solution is 0.001-0.1 mol/L, preferably 0.001-0.07 mol/L, more preferably 0.001-0.004 mol/L or more preferably 0.05-0.07 mol/L, the pH value of the first mixed solution is 7.0-8.0, and the carrier is rhombic nano gamma-Al2O3The weight ratio of the carrier to the first solvent on a dry basis is 1: (10-500), preferably 1: (20-400), more preferably 1: (200-300), the adding speed of the group VIII metal salt solution is 0.01-1 ml/(min 200 g of the first mixed solution), the first solvent comprises water and/or ethanol, and the volume ratio is preferably 1: (0.5-1) water and ethanol, more preferably water, wherein the ammonia water preferably accounts for 20-28 wt%; b. roasting the obtained catalyst intermediate to obtain a Fischer-Tropsch synthesis catalyst; wherein, the content of the VIII group metal in the Fischer-Tropsch synthesis catalyst is 5 to 20 weight percent, preferably 12 to 18 weight percent based on the dry weight of the Fischer-Tropsch synthesis catalyst.
The inventor of the invention surprisingly found that the precipitation of the VIII group metal into the rhombohedral nano gamma-Al is controlled2O3The exposed crystal face of the catalyst can improve the dispersion degree, the reduction degree and the number of active sites of the VIII group metal on the surface of the carrier, thereby improving the initial conversion rate, the steady-state conversion rate and the C of the Fischer-Tropsch synthesis catalyst CO5 +Hydrocarbon selectivity.
According to the invention, the VIII group metal salt is slowly precipitated on the rhombohedral nano gamma-Al2O3The addition method of the group VIII metal salt solution of the present invention is not limited, and for example, the group VIII metal salt solution may be poured or pumped, as long as the addition rate of the group VIII metal salt solution satisfies 0.01 to 1 ml/(min · 200 g of the first mixed solution), preferably satisfies 0.05 to 0.1 ml/(min · 200 g of the first mixed solution), and more preferably 0.05 to 0.6 ml/(min · 200 g of the first mixed solution). Preferably, the group VIII metal salt is added at a rate of (1X 10)-5～1)×10-3Mol/(min 200 g of the first mixed solution), preferably (1X 10)-3～1×10-2)×10-3Mols/(min. 200 g of the first mixture).
According to the invention, the group VIII metal salt precipitates immediately when added to the alkaline liquid, but the reaction takes a certain time to complete, for example, the reaction is continued for a certain time under stirring, preferably, the reaction temperature is 10-50 ℃ and the reaction time is 12-24 hours. The reaction time is calculated from the time when the addition of the group VIII metal salt solution is completed.
According to the present invention, drying and roasting are well known to those skilled in the art, and are helpful for combining the metal and the carrier and converting the metal precipitate into oxide from hydroxide, so as to facilitate the subsequent reduction, for example, the drying temperature in step a may be 50 to 120 ℃, and the time may be 12 to 48 hours; the roasting temperature in the step b can be 200-500 ℃, preferably 250-450 ℃, the time can be 1-48 hours, preferably 2-12 hours, and the roasting is preferably carried out in a static air atmosphere.
The type of the group VIII metal salt is not particularly limited in the present invention as long as it is soluble in water or other solvents, and for example, the group VIII metal salt may be at least one selected from the group consisting of cobalt chloride, cobalt nitrate, ferric chloride and ferric nitrate.
The nano-structure material has the advantages of large specific surface area, more interface atoms, high atomic diffusion coefficient of an interface region, preferred crystal plane orientation and high chemical activity, and therefore, the nano-structure material has been internationally researched and developed as a fourth-generation catalyst. The high activity and excellent selectivity of the nanoparticle catalyst have attracted the attention of catalytic workers. The invention provides diamond-shaped nano gamma-Al2O3Can be purchased commercially or made by self, as long as the shape of the material meets the diamond shape. According to the crystal structure analysis of cubic system aluminum oxide (JCPDS-1-1303), the rhombohedral nano gamma-Al2O3The externally exposed crystal plane is mainly (110) crystal plane (C)>70 percent) of the crystal surface, the main characteristic of the outer surface presents the (110) crystal surface characteristic, and the metal precipitate is directionally deposited on the gamma-Al through regulating and controlling the crystallization process of the metal ions2O3A mesostructured catalyst is formed on the external exposed crystal face of the nanocrystal, and the structure (such as growth direction, unit cell parameters and the like) of an active component can be obviously regulated and controlled, so that the catalytic performance of the catalyst can be regulated and controlled.
Rhombus-shaped nano gamma-Al2O3The specific preparation steps of (a) may include: (1) mixing alkoxy aluminum, a second solvent and organic acid to obtain a second mixed solution with the pH value of 4-7; wherein the second solvent is at least one selected from deionized water, ethanol and isopropanol, preferably isopropanol, and the weight ratio of the aluminum isopropoxide to the second solvent is 1: (10-200); (2) carrying out hydrothermal crystallization on the obtained second mixed solution with the pH value of 4-7, preferably 4.5-6, and filtering to obtain a crystallization product; (3) drying and roasting the obtained crystallized product to obtain the diamond-shaped nano gamma-Al2O3. The aluminum alkoxide is preferably aluminum isopropoxide, and the organic acid is preferably acetic acid.
The mixture of the aluminum alkoxide and the organic acid may generate a precipitate, and for the subsequent crystallization reaction, the mixed solution may be aged for a period of time to form a small seed crystal, for example, the second mixed solution with a pH value of 4 to 7 obtained in step (1) is stirred at 60 to 90 ℃ for 2 to 10 hours, and then the hydrothermal crystallization is performed.
Hydrothermal crystallization is well known to those skilled in the art and is used for producing alumina crystals, for example, the temperature of the hydrothermal crystallization in step (2) is 150 to 250 ℃, preferably 160 to 220 ℃, and the time is 1 to 48 hours, preferably 12 to 40 hours.
The product obtained by hydrothermal crystallization is generally boehmite or pseudo-boehmite with poor crystallinity, has high water content and is difficult to directly precipitate metal, so that the product needs to be dried and roasted to form gamma-Al2O3. The drying and baking are well known to those skilled in the art, for example, the drying temperature is 50 to 200 ℃ and the drying time is 1 to 48 hours; the roasting temperature is 200-1000 ℃, and the roasting time is 1-12 hours.
The rhombus is not a rhombus in strict geometric sense but a rhombus-like shape, and forms a regular parallelogram shape, and the rhombus-shaped nano gamma-Al2O3The length of (a) can be 80-120 nm, the width can be 60-120 nm, and the length and the width respectively refer to a longer diagonal line and a shorter diagonal line of the rhombus.
The invention also provides a Fischer-Tropsch synthesis catalyst prepared by the method.
The invention is further illustrated by the following examples, but is not to be construed as being limited thereto.
The XRD pattern detected by the embodiment of the invention is measured by using an advanced D8X-ray powder diffractometer manufactured by Brucker company, and the specific measurement parameters are as follows: CuK alpha is used as a ray source; the tube voltage is 40KV, and the tube current is 30 mA; the number of scanning steps is 0.0167 deg., and the wide angle range is 10-80 deg.. The crystalline phases of the various materials were confirmed against the standard XRD spectra card of the international union of powder diffraction standards (JCPDS). Co is calculated from the equation of Xiele3O4Crystal grain diameter of (2):
wherein d is the average grain diameter of the metal; lambda-wavelength of X-rays
B-half-peak width of characteristic diffraction peak.
The transmission electron microscope image detected by the embodiment of the invention is measured by a Tecnai G220 type transmission electron microscope instrument produced by FEI company in the Netherlands, and the specific measurement parameters are the microscopic appearances of the observed carrier and the catalyst. The sample preparation method is as follows: and dispersing the powder sample in absolute ethyl alcohol for 2min by ultrasonic dispersion, sucking a small amount of solution by a capillary tube, dipping the solution on a copper net with a carbon film attached to the surface, and putting the copper net into a transmission electron microscope for TEM test after the absolute ethyl alcohol is dried.
The metal dispersion degree testing method of the catalyst provided by the embodiment of the invention comprises the following steps: h is carried out on an AMI-200 catalyst multifunctional characterizer of Zeton-Altamira company in the United states2TPD (Hydrogen Temperature Programmed Desorption) and oxygen titration experiments. From H2-calculating the dispersion and grain diameter of Co from TPD measurements; the reduction degree of Co was calculated from the oxygen titration measurement results. H2TPD testing procedure is as follows: loading 0.12g of catalyst into a U-shaped quartz reaction tube filled with quartz wool, heating the catalyst to 450 ℃ from room temperature in a pure hydrogen flow with the flow rate of 30mL/min at the heating rate of 10 ℃/min, keeping the temperature for 10 hours, and pre-reducing a catalyst sample; then, the temperature is reduced to 100 ℃, and argon with the flow rate of 10mL/min is introduced for purging for 1 h; and starting a temperature programmed desorption process, heating to 400 ℃ at a speed of 10 ℃/min in argon flow at a flow rate of 30mL/min, keeping for 2h, and desorbing the hydrogen chemically adsorbed on the catalyst. TCD records hydrogen signals, and the hydrogen chemisorption amount is calculated by TPD area integration in a pulse volume calibration mode.
And after the hydrogen temperature programmed desorption is finished, carrying out an oxygen titration experiment. Helium (25mL/min) was purged through the catalyst and then a certain amount of oxygen was pulsed at 450 ℃. And the TCD detects an oxygen signal, and oxygen consumption for complete oxidation of the catalyst is obtained after the total number of consumed oxygen pulses is calculated, so that the reduction degree of the catalyst is obtained.
The specific calculation method of the dispersion degree and the reduction degree is as follows:
suppose H2The chemisorption on the Co atoms is carried out as Co: H ═ 1:1, the dispersion (D) then being:
the specific activity of the catalyst in the embodiment of the invention is measured by a heterogeneous catalysis micro-reaction device method.
The specific activity in the catalyst of the present invention is defined as: the number of CO molecules converted per unit time per unit specific surface area of the catalyst.
The calculation formula of the initial conversion rate of CO and the steady-state conversion rate of CO in the embodiment of the invention is as follows:
initial CO conversion ═ amount of inlet CO (mol) -amount of initial outlet CO (mol) ]/amount of inlet CO (mol);
steady state conversion of CO ═ amount of inlet CO (mol) -amount of steady state outlet CO (mol) ]/amount of inlet CO (mol);
the hydrocarbon selectivity refers to the mole percentage of each hydrocarbon in the product, and the diesel refers to the product with the distillation range of 200-340 ℃.
Example 1
Adding 5g of aluminum isopropoxide into 500mL of deionized water, adding a few drops of acetic acid to adjust the pH value to 5, stirring for 8h at 80 ℃, then transferring into a hydrothermal reaction kettle, and carrying out hydrothermal crystallization reaction for 24h in a 200 ℃ oven. Then taking out the crystallized product, centrifugally separating, washing three times by using deionized water, drying for 8 hours at 50 ℃ to obtain a catalyst intermediate, roasting the catalyst intermediate for 4 hours at 600 ℃ to obtain the rhombic flaky gamma-Al with regular appearance2O3The XRD pattern of the nanocrystal is shown in figure 1, and the transmission electron micrograph is shown in figure 2.
The prepared rhombohedral lamellar gamma-Al2O3Adding 0.816g of nanocrystal into a conical flask, adding 200mL of deionized water and 2.4mL of ammonia water (27 wt%), stirring, adjusting the pH value to 7.5, then weighing 0.712g of cobalt nitrate hexahydrate,dissolving with 40mL of deionized water, pumping the cobalt nitrate solution into a conical flask at the speed of 0.05 mL/min, centrifugally separating, drying in an oven at 100 ℃ for 24h, and roasting at 350 ℃ for 6h to obtain the Fischer-Tropsch synthesis catalyst, which is recorded as Co/Al2O3NS-D, XRD pattern shown in FIG. 1, transmission electron micrograph shown in FIG. 4, metal dispersity 39.4%, and specific activity 34.67X 1020S-1。
0.5 g of prepared Fischer-Tropsch synthesis catalyst Co/Al is taken2O3And (3) uniformly mixing NS-D and 5g of 40-mesh quartz sand, adding the mixture into a Fischer-Tropsch synthesis fixed bed reaction device, introducing hydrogen and carbon monoxide, heating and pressurizing to react at the reaction temperature of 200 ℃ and the reaction pressure of 1MPa, wherein the reaction results are shown in Table 1.
Comparative example 1
Diamond flake gamma-Al prepared in example 12O3Using nanocrystalline as a carrier, using cobalt nitrate as a cobalt source, preparing the catalyst by adopting a full pore impregnation method on the basis of the weight content of metal cobalt in the catalyst of 15 weight percent, drying the catalyst in an oven at 100 ℃ for 24 hours, roasting the dried catalyst at 350 ℃ for 6 hours to obtain the Fischer-Tropsch synthesis catalyst, and marking the catalyst as 15 percent Co/Al2O3NS-I, XRD pattern shown in FIG. 1, transmission electron micrograph shown in FIG. 3, metal dispersity 29.4%, and specific activity 10.88X 1020S-1。
The procedure of example 1 was followed using a catalyst of 15% Co/Al2O3The Fischer-Tropsch synthesis reaction was carried out with-NS-I, and the reaction results are shown in Table 1.
Comparative example 2
In the commercial gamma-Al2O3Taking cobalt nitrate as a cobalt source (trade mark of Z600200, purchased from Sasol company, the morphology of which is irregular), preparing the catalyst by adopting a full pore impregnation method on the basis of 15 wt% of metallic cobalt in the catalyst, drying the catalyst in an oven at 100 ℃ for 24 hours, and roasting the catalyst at 350 ℃ for 6 hours to obtain the Fischer-Tropsch synthesis catalyst, which is marked as 15% Co/Al2O3-C-I, metal dispersity 9.2%, specific activity 6.4X 1020S-1。
The procedure of example 1 was followed using a catalyst of 15% Co/Al2O3-C-I toThe Fischer-Tropsch synthesis reaction results are shown in Table 1.
As can be seen from FIG. 1, the support prepared in example 1 of the present invention was γ -Al2O3And after the catalyst is loaded with metal, the catalyst also keeps gamma-Al all the time2O3The characteristic peak of the crystal is strong, and the crystal crystallinity is high.
As can be seen from FIG. 2, according to the crystal structure analysis of cubic aluminum oxide (JCPDS-1-1303),. gamma. -Al2O3The externally exposed crystal plane is mainly (110) crystal plane (C)>70%), the outer surface is characterized primarily by (110) crystal planes.
As can be seen from FIGS. 3-4, the morphology of the supported metal catalyst is changed compared with the carrier, but the length is between 80 and 120 nanometers, the width is between 60 and 120 nanometers, and the black area on the surface of the catalyst is supported cobalt.
As can be seen from Table 1, the Fischer-Tropsch synthesis catalyst prepared by the method of the present invention has high initial conversion rate and steady-state conversion rate of CO, and C5 +The selectivity of hydrocarbon, olefin and diesel oil is good.
TABLE 1
Claims (10)
1. A method of preparing a fischer-tropsch synthesis catalyst, the method comprising:
a. adding a VIII group metal salt solution into a first mixed solution comprising a carrier, a first solvent and ammonia water under stirring for reaction, and then filtering and drying to obtain a catalyst intermediate; wherein the VIII group metal salt solution is an iron salt solution and/or a cobalt salt solution, the concentration of the VIII group metal salt solution is 0.001-0.1 mol/L, the pH value of the first mixed solution is 7.0-8.0, and the carrier is diamond-shaped nano gamma-Al2O3The weight ratio of the carrier to the first solvent on a dry basis is 1: (10 to 500), wherein the group VIII metal salt solution is added at a rate of 0.01 to 1 ml/(min. 200 g of the first mixed solution)The first solvent comprises water and/or ethanol; the reaction in the step a is carried out at the temperature of 10-50 ℃ for 12-24 hours under the stirring state;
b. roasting the obtained catalyst intermediate to obtain a Fischer-Tropsch synthesis catalyst; wherein the content of the VIII group metal in the Fischer-Tropsch synthesis catalyst is 5-20 wt% based on the dry weight of the Fischer-Tropsch synthesis catalyst.
2. The method according to claim 1, wherein the group VIII metal salt solution is added at a rate of 0.05 to 0.1 ml/(min 200 g of the first mixed solution).
3. The method according to claim 1, wherein the drying in step a is carried out at a temperature of 50 to 120 ℃ for 12 to 48 hours; in the step b, the roasting temperature is 200-500 ℃, and the roasting time is 1-48 hours.
4. The method according to claim 1, wherein the group VIII metal salt is at least one selected from the group consisting of cobalt chloride, cobalt nitrate, ferric chloride and ferric nitrate.
5. The method according to claim 1, wherein the rhombohedral-shaped nano-gamma-Al2O3The preparation steps comprise:
(1) mixing aluminum isopropoxide, a second solvent and organic acid to obtain a second mixed solution with the pH value of 4-7; wherein the second solvent is at least one selected from deionized water, ethanol and isopropanol, and the weight ratio of the aluminum isopropoxide to the second solvent is 1: (10-200);
(2) carrying out hydrothermal crystallization on the obtained second mixed solution with the pH value of 4-7, and filtering to obtain a crystallization product;
(3) drying and roasting the obtained crystallized product to obtain the diamond-shaped nano gamma-Al2O3。
6. The method of claim 5, whereinThe rhombohedral nano gamma-Al2O3The preparation steps further comprise: and (2) stirring the second mixed solution with the pH value of 4-7 obtained in the step (1) at the temperature of 60-90 ℃ for 2-10 hours, and then performing hydrothermal crystallization.
7. The method according to claim 5, wherein the temperature of the hydrothermal crystallization in the step (2) is 150 to 250 ℃ for 1 to 48 hours.
8. The method according to claim 5, wherein in the step (3), the drying temperature is 50-200 ℃ and the drying time is 1-48 hours; the roasting temperature is 200-1000 ℃, and the roasting time is 1-12 hours.
9. The method according to claim 1, wherein the rhombohedral-shaped nano-gamma-Al2O3The length of the glass is 80-120 nm, and the width of the glass is 60-120 nm.
10. A fischer-tropsch synthesis catalyst prepared by the process of any one of claims 1 to 9.
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