CN106582890A - Carrier of Fischer-Tropsch synthesis catalyst, preparation method thereof, Fischer-Tropsch synthesis catalyst and preparation method thereof - Google Patents
Carrier of Fischer-Tropsch synthesis catalyst, preparation method thereof, Fischer-Tropsch synthesis catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a carrier of a Fischer-Tropsch synthesis catalyst, a preparation method thereof, a Fischer-Tropsch synthesis catalyst and a preparation method thereof. The preparation method of the Fischer-Tropsch synthesis catalyst includes: under a roasting condition, subjecting an inorganic carrier and ammonia-containing gas to first contact, and then conducting second contact with inert gas. The carrier of the Fischer-Tropsch synthesis catalyst provided by the invention can have smaller grain size cobalt oxide crystal when used for acquiring the Fischer-Tropsch synthesis catalyst, thus greatly improving the dispersion of active component cobalt on the Fischer-Tropsch synthesis catalyst, and can improve the activity and selectivity of the catalyst in Fischer-Tropsch synthesis when used for Fischer-Tropsch synthesis.
Description
Technical field
The present invention relates to a kind of carrier of fischer-tropsch synthetic catalyst and preparation method thereof, and it is a kind of including the load
The Fischer-Tropsch synthesis cobalt-based catalyst of body, and the preparation method of Fischer-Tropsch synthesis cobalt-based catalyst.
Background technology
With the increasingly depleted and in poor quality of petroleum resources, unconventional day in current world wide, will be developed
Right gas (shale gas, combustible ice and coal bed gas etc.), then the automobile-used of clean environment firendly is obtained by GTL routes
Trend of the fuel as future development.
In GTL routes, Fischer-Tropsch synthesis (abbreviation F-T synthesizes, Fiscber-Tropscb synthesis) is
Crucial step.Fiscber-Tropscb synthesis are that one kind will be obtained by raw materials such as coal and natural gass under certain condition
Synthesis gas (hydrogen and CO) be converted into transport fuel and chemical products Technology.But take-
Support synthesis haves the shortcomings that products distribution is wide in range, and how to obtain heavy hydrocarbon to greatest extent is restriction expense
The wide variety of key factor of support synthetic technology.Therefore, research can obtain heavy hydrocarbon with high selectivity
Fischer-Tropsch catalyst tool is of great significance.
For the cobalt-base catalyst used in Fiscber-Tropscb synthesis, most crucial problem is：Catalyst exists
How the generation of methane, how modulation product wide in range ASF are suppressed under the premise of high activity and stability
Distribution is regulated and controled with realizing product structure, and obtains intermediate oil as far as possible.
CN1454714A discloses a kind of preparation method of Co based Fischer-Tropsch synthesis catalyst.The method is with necessarily
The ammonia spirit of concentration is aging at room temperature to silica-gel carrier, then drying carries out surface at 100-150 DEG C
It is modified, then again cobalt salt solution is added in surface-modified silica-gel carrier, dipping, aging, Jing
It is dried, roasting obtains catalyst.
CN101224430A discloses a kind of hydrophobic organic modification of Co group Fischer-Tropsch synthesized catalyst.The catalysis
The preparation method of agent is (1) by cobalt nitrate and noble metal nitrate or muriatic aqueous impregnation porous
Silica gel, obtains sample；(2) sample is added in organic solvent with the organosilan for providing hydrophobic group
It is heated to reflux, respectively with toluene and acetone extraction, then is vacuum dried the cobalt-base catalyst for obtaining hydrophobically modified.
The content of the invention
It is an object of the invention to how to obtain particle size on cobalt-base catalyst used for Fischer-Tropsch synthesis close
Suitable cobalt, so that cobalt has more preferable dispersion, so as to improve activity and choosing of the catalyst in F- T synthesis
Selecting property, there is provided a kind of carrier of fischer-tropsch synthetic catalyst and preparation method thereof and fischer-tropsch synthetic catalyst and
Its preparation method.
To achieve these goals, the present invention provides a kind of preparation side of the carrier of fischer-tropsch synthetic catalyst
Method, the method include：Under roasting condition, inorganic carrier and the gas containing ammonia are carried out into first and is connect
Touch, then the second contact is carried out with noble gases again.
Present invention also offers the carrier of fischer-tropsch synthetic catalyst obtained in method provided by the present invention.
Present invention also offers a kind of fischer-tropsch synthetic catalyst, the fischer-tropsch synthetic catalyst includes that the present invention is carried
For fischer-tropsch synthetic catalyst carrier, and the cobalt being supported on the carrier of the fischer-tropsch synthetic catalyst
Element and precious metal element；During the precious metal element is group viii b element and VIIB races element
At least one in addition to cobalt element.
Present invention also offers a kind of preparation method of fischer-tropsch synthetic catalyst, including：(1) by the present invention
The method of offer is obtained the carrier of fischer-tropsch synthetic catalyst；(2) cobalt element and your gold are introduced to the carrier
Category element, drying, roasting and optional reduction are obtained fischer-tropsch synthetic catalyst；Wherein, it is described expensive
Metallic element is at least one in group viii b element and VIIB races element in addition to cobalt element.
Method of the present invention by inorganic carrier is carried out in the presence of ammonia and noble gases roasting successively,
The carrier of fischer-tropsch synthetic catalyst is prepared for, further obtained cobalt-base catalyst can have the carrier
Particle size is less and suitable cobalt (is easy to oxidation so as to be difficult direct measurement as as-reduced metal is unstable
The size of cobalt, by measuring the crystallite dimension of cobalt oxide to estimate the size of cobalt in the present invention), improve
Dispersibility of the cobalt in cobalt-base catalyst.When carrying out Fischer-Tropsch synthesis using the cobalt-base catalyst, can
Improve activity and selectivity of the catalyst in F- T synthesis.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Specific embodiment
Hereinafter the specific embodiment of the present invention is described in detail.It should be appreciated that this place is retouched
The specific embodiment stated is merely to illustrate and explains the present invention, is not limited to the present invention.
The present invention provides a kind of preparation method of the carrier of fischer-tropsch synthetic catalyst, and the method includes：In roasting
Under the conditions of burning, inorganic carrier and the gas containing ammonia are carried out into the first contact, then again with noble gases
Carry out the second contact.
In the cobalt-base catalyst for F- T synthesis, during oxidation state cobalt is considered as the activity for generate methane
The heart, reduction-state cobalt are considered as the active center for generating long chain hydrocarbons.It is theoretical according to this, increase reduction-state cobalt
Quantity, you can obtain the fischer-tropsch synthetic catalyst of high heavy hydrocarbon yield.But the present inventor notes
Anticipate and arrive, be not that suitable reduction-state cobalt is easily obtained on carrier.Because existing between metal and carrier
Interact, part cobalt is on the one hand made with Co2+In the form of, strong interaction is formed with carrier, compared with
Difficult reduction.Therefore, if reducing metal and carrier interphase interaction, more reduction-state cobalts can be obtained,
So as to improve selectivity of catalyst.But on the other hand if cobalt is excessively weak with carrier interphase interaction,
Cobalt can be caused not good in the dispersion of carrier surface, so as to cause the utilization rate of active component cobalt not high and shadow
Ring the stability of catalyst.The present inventor's research finds, if by carrier in high-temperature roasting condition
Lower first Jing ammonia gas are processed, then with inert gas treatment, then the modified support for obtaining is further applied
When preparing cobalt-base catalyst, the catalyst for obtaining can, particle diameter more preferable with the dispersion on carrier surface
The less reduction-state cobalt of yardstick.Thus apply for the present invention.
According to the present invention, under roasting condition, the inorganic carrier and the gas containing ammonia pass through
Contact can react with the hydroxyl on the inorganic carrier surface, obtain surface hydroxyl it is appropriate without airborne
Body, so as to contribute to obtaining the cobalt-base catalyst with less crystallite dimension cobalt oxide crystallite.Further
Control contact consumption and speed of the gas containing ammonia with inorganic carrier, can be more beneficial for being had
The scattered fischer-tropsch synthetic catalyst of more preferable cobalt.Under preferable case, relative to the inorganic carrier of 10g, ammonia
The consumption of gas is 1-10mL/min, more preferably 3-8mL/min, is still more preferably 5-8mL/min
(such as 6mL/min).Gas volume in the present invention is the volume of standard atmosphere pressure.
The present inventor also has found under study for action, the inorganic carrier Jing after the process that the first contact is obtained
Ammonia if do not removed the absorption that may be remained, brings final fischer-tropsch synthetic catalyst into, and Fischer-Tropsch will be affected to close
Into reaction effect, therefore take will carry out the inorganic carrier after the first contact yet further with indifferent gas
Body carries out the second contact, to remove the ammonia on inorganic carrier.
According to the present invention, the gas containing ammonia is the mixed gas of ammonia and noble gases, for
Consider to obtain the carrier of preferable fischer-tropsch synthetic catalyst, the concentration of the ammonia in gas gas containing ammonia
Can be 1-20 volumes %, preferably 5-10 volumes %, more preferably 5-8 volumes %.Noble gases can
With at least one in nitrogen, helium and neon.
According to the present invention, the roasting condition can help ammonia and the inorganic carrier is modified, preferably
In the case of, the temperature of the roasting is 200-500 DEG C, and preferable temperature is 250-400 DEG C；The roasting
Time is 0.5-4h, and the preferred time is 1-3h.Here, the roasting condition is also first contact and the
The condition of two contacts.
It is according to the present invention, in order to obtain the carrier of the more excellent fischer-tropsch synthetic catalyst of performance, excellent
Selection of land, the method be additionally included in it is described first contact before, by the inorganic carrier the rate of heat addition be 1-20
DEG C/h, the temperature of the roasting is heated under conditions of preferably 1-10 DEG C/h, and removes the nothing
It is passed through the gas containing ammonia after oxygen around airborne body again.
According to the present invention, first contact can be in the device that can provide roasting condition with the second contact
In carry out, such as Muffle furnace etc..For environmental protection consideration, it is also possible to carry out in chemical adsorption instrument.This
It is bright that to this, there is no particular limitation.
The present invention can be to the inorganic carrier without special restriction, it is preferable that the inorganic carrier is oxygen
Change at least one in aluminum, silicon oxide, zirconium oxide, titanium oxide, silica gel, activated carbon and carborundum, more
Preferably aluminium oxide and/or silica gel.
Present invention also offers the carrier of fischer-tropsch synthetic catalyst obtained in method provided by the present invention.
Preferably, the carrier of the fischer-tropsch synthetic catalyst is modified aluminas or modified silica-gel.
Present invention also offers a kind of fischer-tropsch synthetic catalyst, the fischer-tropsch synthetic catalyst includes that the present invention is carried
For fischer-tropsch synthetic catalyst carrier, and the cobalt being supported on the carrier of the fischer-tropsch synthetic catalyst
Element and precious metal element；During the precious metal element is group viii b element and VIIB races element
At least one in addition to cobalt element.
Preferably, the precious metal element is at least one in platinum, palladium, ruthenium and rhenium.
It should be noted that the cobalt that contains of fischer-tropsch synthetic catalyst and precious metal element, in sale and transport
During, can be in the form of oxidation state；When Fischer-Tropsch synthesis are carried out, with the shape of reduction-state
Formula is present.
In accordance with the present invention it is preferred that, cobalt element is by the supported on carriers in the fischer-tropsch synthetic catalyst
Cobalt oxide, then cobalt oxide reduction is obtained, the crystallite dimension of the cobalt oxide is 10-11nm.In Fischer-Tropsch
On the carrier of synthetic catalyst, the cobalt oxide with less crystallite dimension, can carry out reduction treatment work
After change, obtain disperseing more preferable metallic cobalt active center, the expense higher so as to obtain dispersion and reduction degree
Support is cobalt group catalyst synthesized, improves activity and selectivity of the catalyst in Fischer-Tropsch synthesis.
, according to the invention it is preferred in the case of, on the basis of the gross weight of the fischer-tropsch synthetic catalyst, institute
The content for stating the carrier of fischer-tropsch synthetic catalyst is 50-90 weight %, and the content of cobalt element is 5-40 weight
%, the content of precious metal element is 0.01-2 weight %.
The content of cobalt element, precious metal element in fischer-tropsch synthetic catalyst can be by XRF instruments half
Quantitative Analysis are obtained.
Present invention also offers a kind of preparation method of fischer-tropsch synthetic catalyst, including：(1) by the present invention
The method of offer is obtained the carrier of fischer-tropsch synthetic catalyst；(2) cobalt element and your gold are introduced to the carrier
Category element, drying, roasting and optional reduction are obtained fischer-tropsch synthetic catalyst；Wherein, it is described expensive
Metallic element is at least one in group viii b element and VIIB races element in addition to cobalt element.
According to the present invention, in step (2), the method that can pass through dipping introduces cobalt to the carrier
Element and precious metal element.It is specifically as follows：Before the precursor containing cobalt element and precious metal element
The carrier of fischer-tropsch synthetic catalyst described in the solution impregnation of body.The precursor of cobalt described in the solution and
The concentration of the precursor of precious metal additive can be 1.2-2.69g/mL.
In the present invention, the precursor of the cobalt element is cobalt salt, such as cobalt nitrate；The precious metal element
Salt of the precursor for precious metal additive, such as nitrate or chloride of described precious metal additive, Ke Yiwei
Nitric acid rhenium, ruthenic chloride, the acid of chlorine palladium and chloroplatinic acid.
In step (2), the drying can be by dipping after the fischer-tropsch synthetic catalyst load
Body is dried 2-4h at 80 DEG C -150 DEG C.The roasting can make the cobalt unit in fischer-tropsch synthetic catalyst precursor
The precursor of the precursor and precious metal element of element is changed into oxide form presence.The roasting can
Think roasting 2-5h, the roasting preferably at 250 DEG C -350 DEG C at 250 DEG C -500 DEG C by dried product
2.5-3.5h is burnt, fischer-tropsch synthetic catalyst precursor is obtained.
In step (2), fischer-tropsch synthetic catalyst precursor can be used to sell and transport.When carry out
During F- T synthesis, fischer-tropsch synthetic catalyst precursor is reduced, make cobalt element and exist with reduction-state.Institute
State and be also originally intended to turn the cobalt element and precious metal element of oxide form in fischer-tropsch synthetic catalyst precursor
It is changed into the cobalt and noble metal of reduction-state.It is preferred that the reduction is in presence of hydrogen, reduction pressure is
0.1-1MPa, reduction temperature are 350-450 DEG C, and the recovery time is 4-6h.
In the present invention, in the preparation method of above-mentioned fischer-tropsch synthetic catalyst, before fischer-tropsch synthetic catalyst
Body carries out reduction can be carried out after fischer-tropsch synthetic catalyst precursor is obtained immediately, it is also possible to close Fischer-Tropsch
Load into catalyst precarsor reduced before F- T synthesis being carried out in Fischer-Tropsch synthesis device online.Due to
Preparing, transporting, be easily oxidized using the metal of pre reduction state, be unfavorable for commercial Application, preferably first make
Standby fischer-tropsch synthetic catalyst precursor, then by the fischer-tropsch synthetic catalyst precursor in Fischer-Tropsch synthesis device
Line is reduced.
In the method for preparing fischer-tropsch synthetic catalyst, before the carrier of fischer-tropsch synthetic catalyst, cobalt element
Body, the inventory of the precursor of precious metal element cause each component in the fischer-tropsch synthetic catalyst for obtaining
Composition is as it was previously stated, will not be described here.
According to the present invention, above-mentioned fischer-tropsch synthetic catalyst can be used for conduct in various Fischer-Tropsch synthesis and urge
Agent is used, and it (is such as 2 by mol ratio for example to catalyze and synthesize gas：1 hydrogen and carbon monoxide composition)
Prepare the hydro carbons (C of more than C55 +Hydro carbons).
Hereinafter will be described the present invention by embodiment.
In following examples and comparative example：
Synthesis gas is made up of the carbon monoxide of the hydrogen and 33.3mol% of 66.6mol%；
CO conversion ratios are：
V in formula1、V2The volume that response system gas is flowed into and out in certain time period is represented respectively；
C1,CO、C2,COIn representing unstripped gas and tail gas respectively, correspondence CO molar concentrations (are analyzed by on-line chromatograph
To).XCORepresent the conversion ratio of CO.
The selectivity of Fischer-Tropsch synthesis can be counted based on the volume and composition of raw material and gas-phase product
Calculate, it is assumed that reaction raw materials and gaseous product are ideal gases, then can define following physical quantity (T first1、
P1Indicate entry into the temperature and pressure of gas；T2、P2Represent the temperature and pressure of exhaust gas)：
Wherein, into the molal quantity of response system CO：Participate in reaction CO's
Molal quantity：ncon=ntotal·XCO,
The molal quantity (molal quantity for pressing C is calculated) of each material in tail gas：
CO2：
CH4：
C4 -：
C5 +The selectivity of hydro carbons：
CH4Selectivity：
CO2Selectivity：
The crystallite dimension of the cobalt oxide crystallite loaded on fischer-tropsch synthetic catalyst is by public purchased from Brooker
The XRD instrument of department's D8ADVANCE ECO powder diffractometer models carries out XRD signs and obtains.
The content of cobalt element, precious metal element in fischer-tropsch synthetic catalyst is by embodiment and comparative example
The inventory of each raw material is calculated.
Embodiment 1
The present embodiment is used for the carrier and fischer-tropsch synthetic catalyst of the fischer-tropsch synthetic catalyst for illustrating the present invention
The preparation method of catalyst.
Take aluminium oxide (the German SASOL companies PURAL-Scca trades mark, the specific surface area 190 of 100g
m2/ g) be placed in Muffle furnace, after vacuumizing by the gas containing ammonia (ammonia level be 4 volumes %,
Carrier gas is nitrogen) Muffle furnace is passed through with the speed of 50mL/min, and aluminium oxide is roasted at 400 DEG C
2.5h is burnt, pure nitrogen gas is then passed to and aluminium oxide is continued into roasting 2h, obtain modified aluminas.
By the Re of 0.3g2O7With the Co (NO of 36.23g3)2·6H2O is made into 25mL solution, impregnates 20g
Above-mentioned modified aluminas, stand 12h, after 120 DEG C of dryings, the roasting at 400 DEG C obtains catalyst
Precursor.Catalyst precarsor is carried out into XRD determining, the crystallite dimension for measuring cobalt oxide is 10.2nm.
In fixed bed reactor (12 × 1000mm), the 40-60 purposes of filling 2mL are above-mentioned urges
Agent precursor, carries out temperature programmed reduction in pure hydrogen, and reduction pressure is normal pressure, reduction temperature is 400
DEG C, the recovery time be 5h, obtain fischer-tropsch synthetic catalyst.
Synthesis gas (H is passed through in reactor2+ CO) Fischer-Tropsch synthesis are carried out, reaction pressure is
2.5MPa, reaction temperature are 210 DEG C, H2The volume ratio of/CO is the air inlet air speed (GHSV) of 2, synthesis gas
For 2000h-1, reaction result is shown in Table 1.
Embodiment 2
The present embodiment is used for the carrier and fischer-tropsch synthetic catalyst of the fischer-tropsch synthetic catalyst for illustrating the present invention
The preparation method of catalyst.
Take commercial silica gel (Qingdao Haiyang chemical industry, specific surface area 520m of 100g2/ g) it is placed in Muffle furnace,
By the gas containing ammonia (ammonia level be 4 volumes %, carrier gas is nitrogen) with 50 after vacuumizing
The speed of mL/min is passed through Muffle furnace, and silica gel roasting 4h is then passed to pure nitrogen gas at 600 DEG C
Silica gel is continued into roasting 2h, modified silica-gel is obtained.
By the RuCl of 0.57g3With the Co (NO of 27.73g3)2·6H2O is made into 18mL solution, dipping
The above-mentioned modified silica-gel of 20g, stands 12h, and after 120 DEG C of dryings, the roasting at 400 DEG C is catalyzed
Agent precursor.Catalyst precarsor is carried out into XRD determining, the crystallite dimension for measuring cobalt oxide is 10.5nm.
In fixed bed reactor (12 × 1000mm), the 40-60 purposes of filling 2mL are above-mentioned
Catalyst precarsor, carries out temperature programmed reduction in pure hydrogen, and reduction pressure is normal pressure, reduction temperature is
400 DEG C, the recovery time be 5h, obtain fischer-tropsch synthetic catalyst.
Synthesis gas (H is passed through in reactor2+ CO) Fischer-Tropsch synthesis are carried out, reaction pressure is
2.5MPa, reaction temperature are 210 DEG C, H2The volume ratio of/CO is the air inlet air speed (GHSV) of 2, synthesis gas
For 2000h-1, reaction result is shown in Table 1.
Embodiment 3
The present embodiment is used for the carrier and fischer-tropsch synthetic catalyst of the fischer-tropsch synthetic catalyst for illustrating the present invention
The preparation method of catalyst.
Take aluminium oxide (the German SASOL companies PURAL-Scca trades mark, the specific surface area of 20g
190m2/ g) it is placed in Muffle furnace, after vacuumizing, by the gas containing ammonia, (ammonia level is 6 bodies
Product %, carrier gas is nitrogen) Muffle furnace is passed through with the speed of 50mL/min, and by oxygen at 500 DEG C
Change aluminum roasting 3h, then pass to pure nitrogen gas and aluminium oxide is continued into roasting 2h, obtain modified aluminas.
By the Mo (NO of 0.72g3)3·5H2Co (the NO of O and 20.14g3)2·6H2O is made into 16mL
Solution, impregnates the modified aluminas of 20g, stands 12h, after 120 DEG C of dryings, the roasting at 400 DEG C,
Obtain catalyst precarsor.Catalyst precarsor is carried out into XRD determining, the crystallite dimension for measuring cobalt oxide is
10.4nm.The 40-60 purposes of filling 2mL in fixed bed reactor (12 × 1000mm)
Above-mentioned catalyst precarsor, carries out temperature programmed reduction in pure hydrogen, and reduction pressure is normal pressure, reduction temperature
It is 5h to spend for 400 DEG C, recovery time, obtains fischer-tropsch synthetic catalyst.
Synthesis gas (H is passed through in reactor2+ CO) F-T synthesis reaction is carried out, reaction pressure is
2.5MPa, reaction temperature are 210 DEG C, H2The volume ratio of/CO is the air inlet air speed (GHSV) of 2, synthesis gas
For 2000h-1, reaction result is shown in Table 1.
Embodiment 4
The present embodiment is used for the carrier and fischer-tropsch synthetic catalyst of the fischer-tropsch synthetic catalyst for illustrating the present invention
The preparation method of catalyst.
Take aluminium oxide (the German SASOL companies PURAL-Scca trades mark, the specific surface area of 20g
190m2/ g) it is placed in Muffle furnace, after vacuumizing, by the gas containing ammonia, (ammonia level is 3 bodies
Product %, carrier gas is nitrogen) Muffle furnace is passed through with the speed of 50mL/min, and by oxygen at 700 DEG C
Change aluminum roasting 3h, then pass to pure nitrogen gas and aluminium oxide is continued into roasting 2h, obtain modified aluminas.
By the Pd (NH of 0.24g4)2Cl2With the Co (NO of 20.23g3)2·6H2O is made into 20mL solution,
The above-mentioned modified aluminas of dipping 20g, stand 12h, and after 120 DEG C of dryings, the roasting at 400 DEG C is obtained
To catalyst precarsor.Catalyst precarsor is carried out into XRD determining, the crystallite dimension for measuring cobalt oxide is 10.9
nm。
In fixed bed reactor (12 × 1000mm), the 40-60 purposes of filling 2mL are above-mentioned
Catalyst precarsor, carries out temperature programmed reduction in pure hydrogen, and reduction pressure is normal pressure, reduction temperature is
400 DEG C, the recovery time be 5h, obtain fischer-tropsch synthetic catalyst.
Synthesis gas (H is passed through in reactor2+ CO) Fischer-Tropsch synthesis are carried out, reaction pressure is
2.5MPa, reaction temperature are 210 DEG C, H2The volume ratio of/CO is the air inlet air speed (GHSV) of 2, synthesis gas
For 2000h-1, reaction result is shown in Table 1.
Comparative example 1
The ammonia spirit that the concentration of 20mL is 10 weight % is added into the commercial silica gel (Qing Daohai of 20g
Foreignize work, specific surface area 350m2/ g), aging 6h, 120 DEG C are dried 24h, after 800 DEG C of roastings, obtain
Process silica gel.
By the Re of 0.4g2O7With the Co (NO of 40.23g3)2·6H2O is made into 20mL solution, impregnates 20g
Above-mentioned process silica gel, stands 12h, after 120 DEG C of dryings, the roasting 3h at 400 DEG C, before obtaining catalyst
Body.Catalyst precarsor is carried out into XRD determining, the crystallite dimension for measuring cobalt oxide is 12.0nm.
In fixed bed reactor (12 × 1000mm), the 40-60 purposes of filling 2mL are above-mentioned urges
Agent precursor, carries out temperature programmed reduction in pure hydrogen, and reduction pressure is normal pressure, reduction temperature is 400
DEG C, the recovery time be 5h, obtain fischer-tropsch synthetic catalyst.
Synthesis gas (H is passed through in reactor2+ CO) Fischer-Tropsch synthesis are carried out, reaction pressure is
2.5MPa, reaction temperature are 210 DEG C, H2The volume ratio of/CO is the air inlet air speed (GHSV) of 2, synthesis gas
For 2000h-1, reaction result is shown in Table 1.
Comparative example 2
By commercial silica gel (Qingdao Haiyang chemical industry, specific surface area 600m of 100g2/ g) roast at 800 DEG C
3h is burnt, obtains processing silica gel.
By the H of 0.37g2PtCl6·6H2Co (the NO of O and 8.10g3)2·6H2O is made into 10mL solution,
The above-mentioned process silica gel of dipping 20g, stands 12h, and after 120 DEG C of dryings, the roasting at 400 DEG C is obtained
Catalyst precarsor.Catalyst precarsor is carried out into XRD determining, the crystallite dimension for measuring cobalt oxide is 14.1
nm。
In fixed bed reactor (12 × 1000mm), the 40-60 purposes of filling 2mL are above-mentioned
Catalyst precarsor, carries out temperature programmed reduction in pure hydrogen, and reduction pressure is normal pressure, reduction temperature is
400 DEG C, the recovery time be 5h, obtain fischer-tropsch synthetic catalyst.
Synthesis gas (H is passed through in reactor2+ CO) Fischer-Tropsch synthesis are carried out, reaction pressure is
2.5MPa, reaction temperature are 210 DEG C, H2The volume ratio of/CO is the air inlet air speed (GHSV) of 2, synthesis gas
For 2000h-1, reaction result is shown in Table 1.
Comparative example 3
By commercial silica gel (Qingdao Haiyang chemical industry, specific surface area 260m of 100g2/ g) it is put in Muffle furnace
The roasting 2h at 500 DEG C, therebetween by containing the CO that concentration is 5 volumes %2Gas (carrier gas is nitrogen
Gas) Muffle furnace is passed through, then pass to pure nitrogen gas and silica gel is continued into roasting 2h, obtain processing silica gel.
By the H of 0.37g2PtCl6·6H2Co (the NO of O and 8.10g3)2·6H2O is made into 16mL solution,
The above-mentioned process silica gel of dipping 20g, stands 12h, and after 120 DEG C of dryings, the roasting at 400 DEG C is obtained
Catalyst precarsor.Catalyst precarsor is carried out into XRD determining, the crystallite dimension for measuring cobalt oxide is 13.6
nm。
In fixed bed reactor (12 × 1000mm), the 40-60 purposes of filling 2mL are above-mentioned
Catalyst precarsor, carries out temperature programmed reduction in pure hydrogen, and reduction pressure is normal pressure, reduction temperature is
400 DEG C, the recovery time be 5h, obtain fischer-tropsch synthetic catalyst.
Synthesis gas (H is passed through in reactor2+ CO) Fischer-Tropsch synthesis are carried out, reaction pressure is
2.5MPa, reaction temperature are 210 DEG C, H2The volume ratio of/CO is the air inlet air speed (GHSV) of 2, synthesis gas
For 2000h-1, reaction result is shown in Table 1.
Comparative example 4
The ammonia spirit that the concentration of 20mL is 4 weight % is added into 20g aluminium oxidies (German SASOL
Company's PURAL-Scca trades mark, specific surface area 190m2/ g), aging 6h, after 120 DEG C are dried 24h,
Obtain processing alumina support.
By the Re of 0.3g2O7With the Co (NO of 36.23g3)2·6H2O is made into 25mL solution, impregnates 20g
Above-mentioned modified aluminas, stand 12h, after 120 DEG C of dryings, the roasting at 400 DEG C obtains catalyst
Precursor.Catalyst precarsor is carried out into XRD determining, the crystallite dimension for measuring cobalt oxide is 12.2nm.
In fixed bed reactor (12 × 1000mm), the 40-60 purposes of filling 2mL are above-mentioned urges
Agent precursor, carries out temperature programmed reduction in pure hydrogen, and reduction pressure is normal pressure, reduction temperature is 400
DEG C, the recovery time be 5h, obtain fischer-tropsch synthetic catalyst.
Synthesis gas (H is passed through in reactor2+ CO) Fischer-Tropsch synthesis are carried out, reaction pressure is
2.5MPa, reaction temperature are 210 DEG C, H2The volume ratio of/CO is the air inlet air speed (GHSV) of 2, synthesis gas
For 2000h-1, reaction result is shown in Table 1.
Table 1
| Embodiment | XCO(%) | SC5+(%) | SCH4(%) | SCO2(%) |
| Embodiment 1 | 61.59 | 89.62 | 4.85 | 0.49 |
| Embodiment 2 | 57.85 | 87.52 | 6.87 | 0.76 |
| Embodiment 3 | 56.43 | 84.26 | 9.84 | 0.56 |
| Embodiment 4 | 58.64 | 88.28 | 5.64 | 0.51 |
| Comparative example 1 | 55.83 | 83.75 | 6.54 | 0.61 |
| Comparative example 2 | 41.65 | 80.23 | 9.51 | 0.62 |
| Comparative example 3 | 28.36 | 75.26 | 15.72 | 0.68 |
| Comparative example 4 | 56.23 | 86.21 | 5.94 | 0.78 |
The preparation provided using the present invention can be seen that by the result of embodiment, comparative example and table 1
The carrier of the fischer-tropsch synthetic catalyst that method is obtained, further makes the present invention and proposes workshop section's F- T synthesis catalysis
During agent, the crystallite dimension of the cobalt oxide of Jing XRD determining load is 10-11nm, and is adopted in comparative example
When additive method prepares carrier, such as with ammonia or the carrier of Sour gas disposal, then when loading cobalt element,
The crystallite dimension of cobalt oxide is all higher than 12nm.It is anticipated that in the fischer-tropsch synthetic catalyst of present invention offer
The cobalt of the reduction-state for obtaining has more preferable dispersibility, and then when under equal conditions carrying out F- T synthesis,
The catalyst performance is substantially superior to the catalyst in comparative example, has higher CO conversion ratios and Geng Gao
C5+Selectivity.
Claims (10)
1. a kind of preparation method of the carrier of fischer-tropsch synthetic catalyst, the method include：In roasting condition
Under, inorganic carrier and the gas containing ammonia are carried out into the first contact, the is then carried out again with noble gases
Two contacts.
2. method according to claim 1, wherein, the gas containing ammonia be ammonia and
The mixed gas of noble gases, the concentration of the ammonia in gas gas containing ammonia is 1-20 volumes %, excellent
Elect 5-10 volumes % as.
3. method according to claim 2, wherein, relative to the inorganic carrier of 10g, ammonia
Consumption be 1-10mL/min, preferably 3-8mL/min.
4. the method according to any one in claim 1-3, wherein, the temperature of the roasting
For 200-500 DEG C, the time of the roasting is 0.5-4h.
5. the method according to any one in claim 1-4, wherein, the inorganic carrier is
At least one in aluminium oxide, silicon oxide, zirconium oxide, titanium oxide, silica gel, activated carbon and carborundum,
Preferably aluminium oxide and/or silica gel.
6. fischer-tropsch synthetic catalyst obtained in a kind of method by described in any one in claim 1-5
Carrier.
7. a kind of fischer-tropsch synthetic catalyst, the fischer-tropsch synthetic catalyst include the expense described in claim 6
The carrier of Tropsch synthesis catalyst, and the cobalt element being supported on the carrier of the fischer-tropsch synthetic catalyst and
Precious metal element；The precious metal element is first to remove cobalt in group viii b element and VIIB races element
At least one outside element.
8. fischer-tropsch synthetic catalyst according to claim 7, wherein, cobalt element is by described
The supported on carriers cobalt oxide of fischer-tropsch synthetic catalyst, then cobalt oxide reduction is obtained, the cobalt oxide
Crystallite dimension is 10-11nm.
9. the fischer-tropsch synthetic catalyst according to claim 7 or 8, wherein, closed with the Fischer-Tropsch
Into on the basis of the gross weight of catalyst, the content of the carrier of the fischer-tropsch synthetic catalyst is 75-90 weight
%, the content of cobalt element is 5-40 weight %, and the content of precious metal element is 0.01-2 weight %.
10. a kind of preparation method of fischer-tropsch synthetic catalyst, including：
(1) method by described in any one in claim 1-5 is obtained the load of fischer-tropsch synthetic catalyst
Body；
(2) cobalt element and precious metal element are introduced to the carrier, drying, roasting and it is optional also
Original, is obtained fischer-tropsch synthetic catalyst；
Wherein, the precious metal element is to remove cobalt element in group viii b element and VIIB races element
Outer at least one.
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