CN108262044A - The preparation method of fischer-tropsch synthetic catalyst and prepared fischer-tropsch synthetic catalyst - Google Patents
The preparation method of fischer-tropsch synthetic catalyst and prepared fischer-tropsch synthetic catalyst Download PDFInfo
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- CN108262044A CN108262044A CN201611265150.0A CN201611265150A CN108262044A CN 108262044 A CN108262044 A CN 108262044A CN 201611265150 A CN201611265150 A CN 201611265150A CN 108262044 A CN108262044 A CN 108262044A
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
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- C—CHEMISTRY; METALLURGY
- 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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- C—CHEMISTRY; METALLURGY
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
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Abstract
Preparation method and prepared fischer-tropsch synthetic catalyst, this method the present invention relates to a kind of fischer-tropsch synthetic catalyst include：A, group VIII metal salt solution is added under stiring in the first mixed liquor including carrier, the first solvent and ammonium hydroxide and reacted, be then filtered and dry, obtain catalyst intermediate；Wherein, the carrier is diamond shaped nanometer γ Al2O3, the addition speed of the group VIII metal salt solution for 0.01~1 milliliter/(200 gram of first mixed liquor of minute)；B, gained catalyst intermediate is roasted, obtains fischer-tropsch synthetic catalyst.The fischer-tropsch synthetic catalyst CO initial conversions and steady state conversion prepared using the method for the present invention is high, C5 +Hydro carbons, alkene and diesel oil are selectively good.
Description
Technical field
The present invention relates to fischer-tropsch synthetic catalyst technical fields, and in particular, to a kind of preparation of fischer-tropsch synthetic catalyst
Method and prepared fischer-tropsch synthetic catalyst.
Background technology
Fiscber-Tropscb synthesis (FTS or for F- T synthesis) is since nineteen twenty-three is found, the development after last 100 years.It is common
Fischer-Tropsch catalyst have ferrum-based catalyst and cobalt-base catalyst, wherein cobalt-base catalyst is due to having higher long chain hydrocarbons
The advantages such as selectivity, higher resistance to deactivation ability and relatively low water gas shift reaction active (WGS), so being widely used
In Fiscber-Tropscb synthesis industrialization.Active component in cobalt-base catalyst is metallic cobalt, it is generally the case that cobalt-base catalyst is anti-
It will carry out activated catalyst by prereduction before answering.If cause in cobalt-base catalyst containing unreduced cobalt oxide species
The CO conversion ratios of F-T synthesis reaction reduce, CH4Selectivity raising.Metallic cobalt after the reduction degree of cobalt-base catalyst and reduction
Form has significant impact to the F-T synthesis reaction catalytic performance of catalyst.The reduction degree of cobalt species in cobalt-base catalyst and
The influence factor of dispersion degree has very much, such as preparation method, carrier and structure, auxiliary agent, reducing condition etc..Cobalt-based is improved to urge
The dispersion degree of the reduction degree of cobalt species and metallic cobalt can greatly increase the active sites points of catalyst surface metallic cobalt in agent
Mesh, so as to greatly improve the atom utilization of metallic cobalt in cobalt-base catalyst to reduce the cost of catalyst.In order to make catalysis
Active metal dispersion degree higher in agent usually selects the oxide carrier for having certain interaction with active metal, such as three
Al 2 O, titanium dioxide, silica etc..However, the active metal dispersion degree raising of catalyst would generally make active metal
Interaction between carrier is strengthened, and active metal is caused to be difficult to be reduced.So when investigating the catalytic performance of catalyst both
Dispersion degree will also be seen by seeing the reduction degree of active metal.
Since the cobalt-base catalyst of alundum (Al2O3) load has good mechanical strength and chemical stability, higher cobalt
Species dispersion degree, so this catalyst is usually used in F-T synthesis reaction.But alundum (Al2O3) is with cobalt species that there are stronger
Interaction, causes cobalt species in catalyst to be difficult to be reduced.The factor that this conditions each other for reduction degree and dispersion degree, has
Many research reports balance the reduction degree of cobalt species and dispersion degree by changing the property of carrier alundum, such as change three
The parameters such as pore structure, specific surface area, the surface nature of Al 2 O.Also by preparation method, the addition conjunction for changing catalyst
Suitable auxiliary agent etc. improves the reduction degree of cobalt species and dispersion degree.
Similarly, there is also the problem of above-mentioned cobalt-base catalyst, need to improve iron in catalyst surface for ferrum-based catalyst
Dispersion degree and reduction degree.In addition, the shortcomings of fischer-tropsch catalysts synthesis step is cumbersome, catalytic activity is not high exists in the prior art.
Invention content
The object of the present invention is to provide a kind of preparation methods of fischer-tropsch synthetic catalyst and prepared F- T synthesis to be catalyzed
Agent, the fischer-tropsch synthetic catalyst CO initial conversions prepared using the method for the present invention and steady state conversion are high, C5 +Hydro carbons, alkene and
Diesel oil is selectively good.
To achieve these goals, the present invention provides a kind of preparation method of fischer-tropsch synthetic catalyst, this method include a,
Group VIII metal salt solution is added under stiring in the first mixed liquor including carrier, the first solvent and ammonium hydroxide and is carried out instead
Should, it is then filtered and dries, obtain catalyst intermediate；Wherein, the group VIII metal salt solution is iron salt solutions
And/or cobalt salt solution, a concentration of 0.001~0.1 mol/L of the group VIII metal salt solution, first mixed liquor
PH value for 7.0~8.0, the carrier is diamond shaped nanometer γ-Al2O3, with the carrier of dry basis and described first
The weight ratio of solvent is 1：(10~500), the addition speed of the group VIII metal salt solution for 0.01~1 milliliter/(point
200 gram of first mixed liquor of clock), first solvent includes water and/or ethyl alcohol；B, gained catalyst intermediate is roasted
It burns, obtains fischer-tropsch synthetic catalyst；Wherein, on the basis of the dry weight of the fischer-tropsch synthetic catalyst, the F- T synthesis
The content of group VIII metal is 5~20 weight % in catalyst.
Optionally, the addition speed of the group VIII metal salt solution is 0.05~0.1 milliliter/(minute 200 grams the
One mixed liquor).
Optionally, the temperature reacted described in step a is 10~50 DEG C, and the time is 12~24 hours, and the reaction is being stirred
It mixes and is carried out under state.
Optionally, temperature dry described in step a is 50~120 DEG C, and the time is 12~48 hours；Described in step b
The temperature of roasting is 200~500 DEG C, and the time is 1~48 hour.
Optionally, the group VIII metal salt is at least one in cobalt chloride, cobalt nitrate, iron chloride and ferric nitrate
Kind.
Optionally, the diamond shaped nanometer γ-Al2O3Preparation process include：(1) by aluminum alkoxide, the second solvent and have
Machine acid mixes, and obtains the second mixed liquor that pH value is 4~7；Wherein, second solvent is selected from deionized water, ethyl alcohol and different
The weight ratio of at least one of propyl alcohol, the aluminium isopropoxide and second solvent is 1：(10~200)；(2) by gained pH
The second mixed liquor being worth for 4~7 carries out hydrothermal crystallizing, and crystallization product is obtained after filtering；(3) gained crystallization product is dried
And roasting, obtain the diamond shaped nanometer γ-Al2O3。
Optionally, the diamond shaped nanometer γ-Al2O3Preparation process further include：By resulting ph in step (1) for 4~
After 7 the second mixed liquor stirs 2~10 hours at 60~90 DEG C, then carry out the hydrothermal crystallizing.
Optionally, the temperature of hydrothermal crystallizing described in step (2) is 150~250 DEG C, and the time is 1~48 hour.
Optionally, in step (3), the temperature of the drying is 50~200 DEG C, and the time is 1~48 hour；The temperature of roasting
It is 200~1000 DEG C to spend, and the time is 1~12 hour.
Optionally, the diamond shaped nanometer γ-Al2O3Length for 80~120 nanometers, width is 60~120 nanometers.
The present invention also provides the fischer-tropsch synthetic catalysts prepared by a kind of method provided by the present invention.
The present invention by group VIII metal salt and the slow precipitating reagent of ammonia precipitation process agent on gamma-aluminium oxide carrier surface, can
Dispersion degree, reduction degree and number of active sites of the group VIII metal in carrier surface are improved, and then improves F- T synthesis catalysis
Agent CO initial conversions, steady state conversion and C5 +Hydro carbons, alkene and diesel oil selectivity.
In addition, the gamma-aluminium oxide carrier of the present invention is diamond platy, the main exposed crystal face on surface is (110) crystal face,
Metal precipitates can form mesoscopic structure catalyst on the exposure crystal face, to increase the work of the structure between carrier and metal
With, and then dispersion degree and reduction degree of the metal in carrier surface can be further improved.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Description of the drawings
Attached drawing is to be used to provide further understanding of the present invention, and a part for constitution instruction, with following tool
Body embodiment is used to explain the present invention, but be not construed as limiting the invention together.In the accompanying drawings：
Fig. 1 is the diamond shaped nanometer γ-Al prepared by the embodiment of the present invention 12O3(a), F- T synthesis prepared by embodiment 1
The XRD diagram of fischer-tropsch synthetic catalyst (b) prepared by catalyst (c) and comparative example 1.
Fig. 2 is the diamond shaped nanometer γ-Al prepared by the embodiment of the present invention 12O3Transmission electron microscope picture (HRTEM).
Fig. 3 is the transmission electron microscope picture (HRTEM) of fischer-tropsch synthetic catalyst prepared by comparative example 1 of the present invention.
Fig. 4 is the transmission electron microscope picture (HRTEM) of fischer-tropsch synthetic catalyst prepared by the embodiment of the present invention 1.
Specific embodiment
The specific embodiment of the present invention is described in detail below in conjunction with attached drawing.It should be understood that this place is retouched
The specific embodiment stated is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The present invention provides a kind of preparation method of fischer-tropsch synthetic catalyst, and this method includes a, group VIII metal salt is molten
Liquid, which is added under stiring in the first mixed liquor including carrier, the first solvent and ammonium hydroxide, to be reacted, and is then filtered and is done
It is dry, obtain catalyst intermediate；Wherein, the group VIII metal salt solution is iron salt solutions and/or cobalt salt solution, described the
A concentration of 0.001~0.1 mol/L of group VIII metal salting liquid, preferably 0.001~0.07 mol/L, further preferably
For 0.001~0.004 mol/L or further preferably 0.05~0.07 mol/L, the pH value of first mixed liquor is
7.0~8.0, the carrier is diamond shaped nanometer γ-Al2O3, with the carrier of dry basis and the weight of first solvent
Amount is than being 1：(10~500), preferably 1：(20-400), further preferably 1：(200~300), the group VIII metal
The addition speed of salting liquid for 0.01~1 milliliter/(200 gram of first mixed liquor of minute), first solvent include water and/or
Ethyl alcohol, preferably volume ratio are 1：The water of (0.5-1) and the mixed liquor of ethyl alcohol, more preferably water, the weight fraction of the ammonium hydroxide
Preferably 20~28 weight %；B, gained catalyst intermediate is roasted, obtains fischer-tropsch synthetic catalyst；Wherein, with institute
On the basis of the dry weight for stating fischer-tropsch synthetic catalyst, in the fischer-tropsch synthetic catalyst content of group VIII metal for 5~
20 weight %, preferably 12~18 weight %.
Inventor has been surprisingly found that, controls group VIII precipitated metal to diamond shaped nanometer γ-Al2O3Exposure it is brilliant
On face, dispersion degree, reduction degree and number of active sites of the group VIII metal in carrier surface can be improved, and then improve Fischer-Tropsch
Synthetic catalyst CO initial conversions, steady state conversion and C5 +Hydrocarbon selective.
According to the present invention, group VIII metal salt is slowly deposited in diamond shaped nanometer γ-Al2O3Surface helps to improve
The dispersion degree of group VIII metal, there is no limit, such as can be for feed postition of the present invention to group VIII metal salt solution
It pours into or is pumped into, as long as 0.01~1 milliliter of the addition speed satisfaction of group VIII metal salt solution/(200 gram first of minute is mixed
Close liquid), preferably satisfy 0.05~0.1 milliliter/(200 gram of first mixed liquor of minute), further preferred 0.05~0.6 milliliter/
(200 gram of first mixed liquor of minute).Preferably, the addition speed of the group VIII metal salt is (1 × 10-5~1)
×10-3Mole/(200 gram of first mixed liquor of minute), preferably (1 × 10-3~1 × 10-2)×10-3Mole/(minute 200
Gram the first mixed liquor).
According to the present invention, group VIII metal salt can generate precipitation immediately in akaline liquid is added to, but the reaction
It needs to continue for some time, it could the reaction was complete, such as the reaction was continued a period of time under stirring, it is preferable that described anti-
The temperature answered is 10~50 DEG C, and the time is 12~24 hours.It should be noted that the reaction time is molten from group VIII metal salt
Liquid addition starts to calculate after finishing.
According to the present invention, dry and roasting is well-known to those skilled in the art, is contributed to metal and carrier
With reference to, and metal precipitates is made to be converted into oxide by hydroxide, in favor of the progress of sequential reduction, for example, institute in step a
It can be 50~120 DEG C to state dry temperature, and the time can be 12~48 hours；The temperature roasted described in step b can be
200~500 DEG C, preferably 250~450 DEG C, the time can be 1~48 hour, preferably 2~12 hours, preferably empty in static state
It is carried out in gas atmosphere.
The present invention limits the type of group VIII metal salt there is no specific, as long as water or other solvents can be dissolved in i.e.
Can, for example, the group VIII metal salt can be selected from least one of cobalt chloride, cobalt nitrate, iron chloride and ferric nitrate.
Nano structural material is with large specific surface area, interface atoms are more, interface zone atomic diffusivity is high, and has and select
Excellent high preferred orientation and very high chemism, thus, in the world research and development are carried out as forth generation catalyst.It receives
Rice corpuscles catalyst has the attention of high activity and excellent the selectivity person that caused catalyst operation.Diamond shape provided by the invention
Shape nanometer γ-Al2O3It can be commercially available or makes by oneself, as long as its pattern meets diamond shaped.It is aoxidized according to cubic system
The crystal structure analysis of aluminium (JCPDS-1-1303), diamond shaped nanometer γ-Al2O3Outer exposed crystal face predominantly (110) crystal face (>
70%), (110) crystal face feature is presented in outer surface main feature, by regulating and controlling the crystallization process of metal ion, by metal precipitates
Orientated deposition is in γ-Al2O3On nanocrystalline outer exposed crystal face, a kind of mesoscopic structure catalyst is formed, it can notable regulation activity
The structure (such as direction of growth, cell parameter etc.) of component, so as to regulate and control its catalytic performance.
A kind of diamond shaped nanometer γ-Al2O3Specific preparation process can include：(1) by aluminum alkoxide, the second solvent and
Organic acid mixes, and obtains the second mixed liquor that pH value is 4~7；Wherein, second solvent be selected from deionized water, ethyl alcohol and
The weight ratio of at least one of isopropanol, preferably isopropanol, the aluminium isopropoxide and second solvent is 1：(10~
200)；(2) the second mixed liquor that resulting ph is 4~7, preferably 4.5~6 is subjected to hydrothermal crystallizing, crystallization is obtained after filtering
Product；(3) gained crystallization product is dried and roasted, obtain the diamond shaped nanometer γ-Al2O3.The aluminum alkoxide is excellent
Aluminium isopropoxide is selected as, the organic acid is preferably acetic acid.
Precipitation can be generated after aluminum alkoxide and organic acid mixing, it, can be by mixed liquor for the progress of follow-up crystallization
Carry out aging for a period of time, to form small crystal seed, for example, by resulting ph in step (1) be 4~7 the second mixed liquor 60
After being stirred 2~10 hours at~90 DEG C, then carry out the hydrothermal crystallizing.
Hydrothermal crystallizing is well-known to those skilled in the art, for producing alpha-alumina crystals, for example, institute in step (2)
The temperature for stating hydrothermal crystallizing is 150~250 DEG C, and preferably 160~220 DEG C, the time is 1~48 hour, and preferably 12~40 is small
When.
Hydrothermal crystallizing products therefrom is generally the poor boehmite or boehmite of crystallinity, and water content is higher, difficult
With Direct precipitation metal, it is therefore desirable to be dried and roasted to form γ-Al2O3.The drying and roasting are this field skills
Known to art personnel, for example, the temperature of the drying is 50~200 DEG C, the time is 1~48 hour；The temperature of roasting is 200
~1000 DEG C, the time is 1~12 hour.
Heretofore described diamond shaped and the diamond shape of non-critical geometric meaning shape, but class diamond shape are formed more regular
Parallelogram shape, the diamond shaped nanometer γ-Al2O3Length can be 80~120 nanometers, width can be 60~
120 nanometers, which respectively refers to the longer diagonal of diamond shape and shorter diagonal.
The present invention also provides the fischer-tropsch synthetic catalysts prepared by a kind of method provided by the present invention.
It is further illustrated the present invention below by embodiment, but the present invention is not therefore subject to any restriction.
The XRD diagram that the embodiment of the present invention is detected uses the Advance D8 type X-rays produced using Brucker companies
Powder diffractometer instrument is measured, and specific location parameter is：CuK α are used as radiographic source；Tube voltage 40KV, tube current 30mA；
It is 0.0167 ° to scan step number, and big angular region is 10-80 °.The standard x RD spectrogram cards of the international powder diffraction standard association meeting of control
(JCPDS) confirm the crystalline phase of various substances.By following Scherrer equation calculation Co3O4Crystal grain diameter：
Wherein, the average crystal grain diameter of d-metal；The wavelength of λ-X rayB-characteristic diffraction peak
Half-peak breadth.
The transmission electron microscope picture that the embodiment of the present invention is detected is transmitted using the Tecnai G220 types of Dutch FEI Co.'s production
Electron microscopy instrument is measured, and specific location parameter is the microscopic appearance for observing carrier and catalyst.Sample preparation methods
It is as follows：Powder sample is dispersed in absolute ethyl alcohol after ultrasonic disperse 2min, is dipped in a small amount of solution of capillary absorption attached to surface
Have on the copper mesh of carbon film, after absolute ethyl alcohol dries, copper mesh is put into transmission electron microscope, carry out TEM tests.
The metal dispersity test method of catalyst of the embodiment of the present invention is as follows：The Zeton-Altamira companies in the U.S.
H is carried out on the multi-functional characterization instrument of AMI-200 type catalyst2-TPD(Hydrogen Temperature Programmed
Desorption) with oxygen titration experiments.By H2- TPD measurement results calculate the dispersion degree and crystal grain diameter for obtaining Co；It is titrated by oxygen
Measurement result calculates the reduction degree for obtaining Co.H2- TPD testing procedures are as follows：The loading of 0.12g catalyst is taken to be lined with the U- of silica wool
In type crystal reaction tube, flow be 30mL/min flow of pure hydrogen in the heating rate of 10 DEG C/min from room temperature to
10h is kept after 450 DEG C, prereduction is carried out to catalyst sample；Then 100 DEG C are cooled to, is passed through the argon that flow velocity is 10mL/min
1h is swept in air-blowing；Subsequent start-up temperature programmed desorption is warming up to 400 DEG C in argon gas stream of the flow velocity for 30mL/min with 10 DEG C/min
After keep 2h, the hydrogen of chemisorbed in desorption catalyzing agent.TCD records hydrogen signal, and hydrogen chemisorption amount is by pulse volume
Calibrating mode carries out TPD area integral calculating.
After the completion for the treatment of hydrogen temperature programmed desorption, oxygen titration experiments are carried out.First it is passed through helium (25mL/min) purging catalysis
Agent, then in 450 DEG C of a certain amount of oxygen of pulse.TCD detects oxygen signal, is catalyzed after calculating consumption pulse of oxygen sum
The oxygen demand of agent complete oxidation, so as to obtain the reduction degree of catalyst.
The circular of dispersion degree and reduction degree is as follows：
Assuming that H2Chemisorbed on Co atoms is by Co:H=1:1 carries out, then dispersion degree (D) is：
The specific activity of catalyst of the embodiment of the present invention is measured using heterogeneous catalysis micro-reaction device method.
Specific activity in the present invention in catalyst is defined as：The unit interval converts in unit catalyst specific surface area CO points
Subnumber.
CO initial conversions and the calculation formula of CO steady state conversions are in the embodiment of the present invention：
CO initial conversions=[import CO amounts (mol)-initial outlet CO amounts (mol)]/import CO amounts (mol)；
CO steady state conversions=[import CO amounts (mol)-steady state outlet CO amounts (mol)]/import CO amounts (mol)；
Hydrocarbon selective refers to the molar percentage of each hydro carbons in product, and diesel oil refers to the production that boiling range is 200~340 DEG C
Product.
Embodiment 1
Aluminium isopropoxide 5g is added in 500mL deionized waters, adds a few drop second acid for adjusting pH for 5,80 DEG C of stirring 8h, then
It is transferred in hydrothermal reaction kettle, carrying out hydrothermal crystallizing in 200 DEG C of baking ovens reacts 24 hours.Then crystallization product is taken out, centrifuged
Separation, adopts and is washed with deionized three times, and 50 DEG C of dry 8h obtain catalyst intermediate, by catalyst intermediate in 600 DEG C of roastings
4h is burnt to get to the diamond platy γ-Al of regular appearance2O3Nanocrystalline, XRD diagram is shown in Fig. 1, and transmission electron microscope picture is shown in Fig. 2.
By prepared diamond platy γ-Al2O3Nanocrystalline 0.816g is added in conical flask, then adds 200mL deionizations
Water, 2.4mL ammonium hydroxide (27 weight %), stirring, adjust pH value be 7.5, then weigh 0.712g cobalt nitrate hexahydrates, with 40mL go from
Cobalt nitrate solution is pumped into the speed of 0.05 ml/min in conical flask by sub- water dissolution, is centrifuged, in 100 DEG C of baking oven
Drying for 24 hours, then roasts 6h at 350 DEG C, obtains fischer-tropsch synthetic catalyst, is denoted as Co/Al2O3- NS-D, XRD diagram are shown in Fig. 1, transmission
Electron microscope is shown in Fig. 4, metal dispersity 39.4%, and specific activity is 34.67 × 1020S-1。
Take the fischer-tropsch synthetic catalyst Co/Al that 0.5 restraint is standby2O3- NS-D and 40 mesh quartz sands of 5g are uniformly mixed, and are added to
In F- T synthesis fixed-bed reactor, hydrogen and carbon monoxide are passed through, heating pressurizes and reacts, reaction temperature 200
DEG C, reaction pressure 1MPa, reaction result is shown in Table 1.
Comparative example 1
Diamond platy γ-the Al prepared with embodiment 12O3Nanocrystalline is carrier, and cobalt nitrate is cobalt source, with golden in catalyst
Belong to the weight content of cobalt on the basis of 15 weight %, using full hole preparation catalyst, in 100 DEG C of oven dryings for 24 hours, then
6h is roasted at 350 DEG C, obtains fischer-tropsch synthetic catalyst, is denoted as 15%Co/Al2O3- NS-I, XRD diagram are shown in Fig. 1, transmission electron microscope picture
See Fig. 3, metal dispersity 29.4%, specific activity is 10.88 × 1020S-1。
Catalyst 15%Co/Al is used according to the method for embodiment 12O3- NS-I carries out Fischer-Tropsch synthesis, reaction result
It is shown in Table 1.
Comparative example 2
With business γ-Al2O3For carrier, (commercial grades Z600200, purchased from Sasol companies, pattern is random shape
Shape), cobalt nitrate is cobalt source, by the weight content of metallic cobalt in catalyst on the basis of 15 weight %, to impregnate legal system using full hole
Standby catalyst, for 24 hours, then at 350 DEG C roasts 6h in 100 DEG C of oven dryings, obtains fischer-tropsch synthetic catalyst, be denoted as 15%Co/
Al2O3- C-I, metal dispersity 9.2%, specific activity are 6.4 × 1020S-1。
Catalyst 15%Co/Al is used according to the method for embodiment 12O3- C-I carries out Fischer-Tropsch synthesis, and reaction result is shown in
Table 1.
It will be seen from figure 1 that the carrier prepared by the embodiment of the present invention 1 is γ-Al2O3, and after the upper metal of load, catalysis
Agent is also always maintained at γ-Al2O3Characteristic peak, peak intensity is stronger, and crystal structure degree is high.
Figure it is seen that according to the crystal structure analysis of cubic system aluminium oxide (JCPDS-1-1303), γ-Al2O3
Outer exposed crystal face predominantly (110) crystal face (>70%), (110) crystal face feature is presented in outer surface main feature.
From Fig. 3-4 as can be seen that its pattern of the upper catalyst of metal of load is varied from compared with carrier, but length exists
Between 80~120 nanometers, for width between 60~120 nanometers, catalyst surface black region is the cobalt of load.
As it can be seen from table 1 the fischer-tropsch synthetic catalyst prepared using the method for the present invention, CO initial conversions and stable state
High conversion rate, C5 +Hydro carbons, alkene and diesel oil are selectively good.
Table 1
Claims (11)
1. a kind of preparation method of fischer-tropsch synthetic catalyst, this method include：
A, by group VIII metal salt solution add under stiring in the first mixed liquor including carrier, the first solvent and ammonium hydroxide into
Row reaction, is then filtered and dries, obtain catalyst intermediate；Wherein, the group VIII metal salt solution is molysite
Solution and/or cobalt salt solution, a concentration of 0.001~0.1 mol/L of the group VIII metal salt solution, described first is mixed
The pH value for closing liquid is 7.0~8.0, and the carrier is diamond shaped nanometer γ-Al2O3, with the carrier of dry basis with it is described
The weight ratio of first solvent is 1：(10~500), the addition speed of the group VIII metal salt solution for 0.01~1 milliliter/
(200 gram of first mixed liquor of minute), first solvent include water and/or ethyl alcohol；
B, gained catalyst intermediate is roasted, obtains fischer-tropsch synthetic catalyst；Wherein, with the fischer-tropsch synthetic catalyst
Dry weight on the basis of, in the fischer-tropsch synthetic catalyst content of group VIII metal be 5~20 weight %.
2. according to the method described in claim 1, wherein, the addition speed of the group VIII metal salt solution for 0.05~
0.1 milliliter/(200 gram of first mixed liquor of minute).
3. according to the method described in claim 1, wherein, the temperature reacted described in step a is 10~50 DEG C, the time for 12~
24 hours, the reaction carried out under stirring.
4. according to the method described in claim 1, wherein, dry temperature described in step a is 50~120 DEG C, the time 12
~48 hours；The temperature roasted described in step b is 200~500 DEG C, and the time is 1~48 hour.
5. according to the method described in claim 1, wherein, the group VIII metal salt is selected from cobalt chloride, cobalt nitrate, chlorination
At least one of iron and ferric nitrate.
6. according to the method described in claim 1, wherein, the diamond shaped nanometer γ-Al2O3Preparation process include：
(1) aluminum alkoxide, the second solvent and organic acid are mixed, obtains the second mixed liquor that pH value is 4~7；Wherein, described second
Solvent is selected from least one of deionized water, ethyl alcohol and isopropanol, the weight of the aluminium isopropoxide and second solvent
Than being 1：(10~200)；
(2) the second mixed liquor that resulting ph is 4~7 is subjected to hydrothermal crystallizing, crystallization product is obtained after filtering；
(3) gained crystallization product is dried and roasted, obtain the diamond shaped nanometer γ-Al2O3。
7. according to the method described in claim 6, wherein, the diamond shaped nanometer γ-Al2O3Preparation process further include：It will step
Suddenly after the second mixed liquor that resulting ph is 4~7 in (1) stirs 2~10 hours at 60~90 DEG C, then the hydro-thermal crystalline substance is carried out
Change.
8. according to the method described in claim 6, wherein, the temperature of hydrothermal crystallizing described in step (2) is 150~250 DEG C, when
Between be 1~48 hour.
9. according to the method described in claim 6, wherein, in step (3), the temperature of the drying is 50~200 DEG C, the time
It is 1~48 hour；The temperature of roasting is 200~1000 DEG C, and the time is 1~12 hour.
10. according to the method described in claim 1, wherein, the diamond shaped nanometer γ-Al2O3Length for 80~120 nanometers,
Width is 60~120 nanometers.
11. the fischer-tropsch synthetic catalyst in claim 1~10 prepared by any one method.
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