CN105457636B - A kind of method of regulation and control metal active constituent spatial distribution in industrial egg-shell catalyst - Google Patents
A kind of method of regulation and control metal active constituent spatial distribution in industrial egg-shell catalyst Download PDFInfo
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- CN105457636B CN105457636B CN201510939257.8A CN201510939257A CN105457636B CN 105457636 B CN105457636 B CN 105457636B CN 201510939257 A CN201510939257 A CN 201510939257A CN 105457636 B CN105457636 B CN 105457636B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 120
- 102000002322 Egg Proteins Human genes 0.000 title claims abstract description 53
- 108010000912 Egg Proteins Proteins 0.000 title claims abstract description 53
- 210000003278 egg shell Anatomy 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims description 27
- 238000009826 distribution Methods 0.000 title abstract description 11
- 229910052751 metal Inorganic materials 0.000 title abstract description 8
- 239000002184 metal Substances 0.000 title abstract description 8
- 239000000470 constituent Substances 0.000 title abstract description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000002360 preparation method Methods 0.000 claims abstract description 23
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims abstract description 19
- 238000007598 dipping method Methods 0.000 claims abstract description 11
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 10
- 239000000843 powder Substances 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 239000007789 gas Substances 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 230000004913 activation Effects 0.000 claims description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 9
- 239000002243 precursor Substances 0.000 abstract description 5
- 230000008569 process Effects 0.000 description 9
- 238000010792 warming Methods 0.000 description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 5
- 238000001802 infusion Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000004375 physisorption Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000003384 imaging method Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003102 growth factor Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
- B01J35/397—Egg shell like
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
- B01J38/10—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst using elemental hydrogen
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of preparation method of catalyst, comprise the following steps：1）Prepare carrier：SiO 2 powder is mixed with Ludox and extrudes to obtain extrudate；The extrudate is calcined acquisition carrier after drying；2）Prepare cobalt nitrate solution：Prepare the cobalt nitrate solution that concentration is 1 ~ 8mol/L；3）Dipping：Precursor solution will be added in carrier, dipping removes remaining liq after terminating and obtains sample；4）By sample drying and it is calcined, obtains egg-shell catalyst.A kind of new preparation method of catalyst disclosed in this invention can spatial distribution of the Effective Regulation metal active constituent in industrial egg-shell catalyst, the catalyst activity of catalyst gets a promotion.
Description
Technical field
The invention belongs to field of catalyst preparation, and in particular to one kind regulation and control metal active constituent is catalyzed in industrial eggshell type
The method of spatial distribution in agent.
Background technology
Particle egg-shell catalyst is widely used in industry, and heat release or heat absorption are frequently accompanied by chemical reaction
Process, its hot-spot phenomenon can be reduced by egg-shell catalyst.The preparation of egg-shell catalyst is broadly divided into two kinds：Spray
Coating and infusion process.Spraying process, i.e., precursor solution is sprayed at porous carrier surface, first on egg-shell catalyst
The patent of preparation just uses this method, but operability is not strong during extensive preparation, therefore not large-scale use.Other one
Kind method is infusion process, presoma is only entered the duct outside catalyst, without being spread to catalyst core, in this method
In have the shell thickness that many parameters can all have influence on final egg-shell catalyst, these parameters include：Dip time, metal are molten
The state of carrier before liquid concentration, solution viscosity and dipping.From the point of view of industry, preparation catalyst is most square
Just, impregnation technology is safer relative to spraying process, more cost-effective, it is easier to industry amplification.But prepared by infusion process
During egg-shell catalyst, still suffer from a large amount of active components and diffused into by capillary force inside egg-shell catalyst,
And this amount of activated component is engineering noise for whole catalyst, therefore, the activity of this engineering noise how is reduced
Component so that it is a current technological difficulties that catalyst activity component, which concentrates on shell,.
Egg-shell catalyst is commonly used in Fischer-Tropsch synthesis industrial production.F- T synthesis refers to coal, natural gas
Or biomass is converted into the process of hydro carbons through synthesis gas under catalyst action.The catalyst that F- T synthesis industrially uses can
It is divided into two classes：Ferrum-based catalyst and cobalt-base catalyst, compared to ferrum-based catalyst, cobalt-base catalyst has advantages below：Height is living
Property, methane selectively are low, C5 +Selectivity is high, and water gas reaction is low etc..Therefore the Co based Fischer-Tropsch synthesis catalyst of low price is designed
With more significance.
In fixed bed reactors, because the limitation of pressure drop is, it is necessary to load large granular catalyst (diameter>1mm), but by
Long-chain olefin and alcohols can be generated in fischer-tropsch reaction, and most of liquid products are wax phase, and during the course of the reaction, wax is met
The duct of catalytic inner is filled up, reduces CO diffusion velocity, so as to reduce fischer-tropsch reaction speed and C5 +The selectivity of product,
The particle of catalyst is bigger, and suffered diffusion limitation is stronger, because diffusion rate of the hydrogen molecule in liquid wax phase is
Twice of carbon monoxide molecule diffusion rate, therefore in catalytic inner H2/ CO ratios will be apparently higher than outside, and this can select methane
The increase of selecting property, influences carbochain growth factor α.Therefore for the large granular catalyst industrially used, egg-shell catalyst can be bright
It is aobvious to reduce diffusion limitation.
When preparing egg-shell catalyst using infusion process, increase precursor concentration, regulation carrier surface tension force can succeed
Egg-shell catalyst is prepared, but can make the increase of preparation cost.
The content of the invention
In view of the above the shortcomings that prior art, it is an object of the invention to provide a kind of preparation of egg-shell catalyst
Method, for overcome in the prior art method catalytic efficiency it is low, prepare cost it is high the defects of.
In order to reach foregoing invention purpose and other purposes, the present invention is achieved by the following technical solutions：
The present invention provides a kind of preparation method of catalyst, comprises the following steps：
1) carrier is prepared：SiO 2 powder is mixed with Ludox and extrudes to obtain extrudate；The extrudate is passed through
Dry roasting obtains carrier；
2) cobalt nitrate solution is prepared：Prepare the cobalt nitrate solution that concentration is 1~8mol/L；
3) impregnate：Cobalt nitrate solution is added in carrier, dipping removes remaining liq after terminating and obtains sample；
4) by sample drying and it is calcined, obtains egg-shell catalyst.
Preferably, in step 1), the mass ratio of SiO 2 powder and Ludox is 1：(0.4~3)；The Ludox
Solid content is 35~45%.It is highly preferred that the solid content of the Ludox is 40%.
Preferably, the temperature dried described in step 1) is 60~120 DEG C, and drying time is 1~20h.
Preferably, roasting described in step 1) uses Muffle furnace or tube furnace, and programming rate is first with 1~5 DEG C/min's
Programming rate rises to 110~130 DEG C, keeps 1.5~2.5h, then rise to 300~600 with 0.5~5 DEG C/min programming rate
DEG C, keep 1~20h.
Preferably, the cobalt nitrate solution that concentration is 4~8mol/L is prepared in step 2).
Preferably, dip time is 1~10s in step 3).
It is highly preferred that dip time is 1~5s in step 3).
Preferably, the temperature dried described in step 4) is 60~120 DEG C, and drying time is 0.25~20h.
Preferably, roasting uses Muffle furnace or tube furnace in step 4), and programming rate is first with 1~5 DEG C/min heating
Speed rises to 110~130 DEG C, keeps 1.5~2.5h, then rises to 250~450 DEG C with 0.5~5 DEG C/min programming rate, protects
Hold 3~8h.
The invention also discloses a kind of catalyst, is prepared by method described above.
The invention also discloses purposes of the catalyst as described above in fixed bed fischer-tropsch reaction, and the catalyst exists
Applied to being activated before fixed bed fischer-tropsch reaction, activating also to carry out in Primordial Qi atmosphere of hydrogen, activation temperature is 350~
500 DEG C, soak time is 2~12h.
Preferably, purposes as described above, the relative pressure that the catalyst is used in fixed bed fischer-tropsch reaction react are
1.0~3.0MPa, reaction temperature are 200~300 DEG C, and mass space velocity is 500~6000mL.gcat-1.h-1, hydrogen and one oxidation
The mol ratio of carbon gas is 2.
A kind of new preparation method of catalyst disclosed in this invention, it is that a kind of Effective Regulation metal active constituent exists
The method of spatial distribution in industrial egg-shell catalyst is regulated and controled by regulating and controlling the ratio of SiO 2 powder and binding agent
The pore-size distribution of shaping carrier, when preparing egg-shell catalyst using infusion process, Effective Regulation metal active constituent is in industry
Spatial distribution in egg-shell catalyst.When carrier aperture is too small, a large amount of precursor solutions pass through capillary in dipping process
Effect enters inside shaping carrier, causes the loss of active component, simultaneously as carrier aperture is too small, is unfavorable for the expansion of product
Dissipate, therefore catalyst activity is low.Ludox ratio is reduced, carrier aperture becomes big, and capillary force dies down, a small amount of activearm
Divide and enter catalytic inner, catalyst activity increase.
The inventive method has the beneficial effect that preparation is simple, and its catalyst prepared has eggshell structure, catalyst
Be uniformly dispersed and catalytic activity is high.
Brief description of the drawings
The optical photograph that Fig. 1 is the egg-shell catalyst A and egg-shell catalyst B prepared in embodiment 1,2 and 3.
Fig. 2 is that the egg-shell catalyst A and egg-shell catalyst B prepared in Examples 1 and 2 is surveyed by nitrogen physisorption
The graph of pore diameter distribution obtained.
The X-ray diffraction spectrogram that Fig. 3 is the egg-shell catalyst A and egg-shell catalyst B prepared in Examples 1 and 2.
Fig. 4 is the X ray computer fault imaging figure of the egg-shell catalyst prepared in Examples 1 and 2.
In wherein Fig. 4, #1 layers are catalyst eggshell layer, and #2 is the silica inner core of catalyst, and #3 is in catalyst two
The Co that in-core is distributed in silica3O4Bulky grain.
Embodiment
Illustrate embodiments of the present invention below by way of specific instantiation, those skilled in the art can be by this specification
Disclosed content understands other advantages and effect of the present invention easily.The present invention can also pass through specific realities different in addition
The mode of applying is embodied or practiced, the various details in this specification can also be based on different viewpoints with application, without departing from
Various modifications or alterations are carried out under the spirit of the present invention.
Embodiment 1
The preparation of carrier：300g SiO 2 powders are uniformly mixed with 700g Ludox, are filled into banded extruder, extrusion
Machine uses 3mm circular dies.Extrudate is put into 100 DEG C of baking ovens and dries 4h, Muffle kiln roasting is placed into, to room temperature with 2
DEG C/min rises to 120 DEG C, 2h is kept, is then warming up to 500 DEG C according still further to 2 DEG C/min, 6h is kept, is taken out after being down to room temperature naturally
Carrier, sign as SiO2-A.The solid content of the Ludox is 35%.
The preparation of catalyst：Cobalt nitrate solution is configured with deionized water, its concentration is 6mol/L.Carrier is laid in core
In funnel, sand core funnel connection vavuum pump, cobalt nitrate solution is poured into funnel, vavuum pump is opened after 2s, by unnecessary presoma
Solution pumps.Dipping rear catalyst is put into 100 DEG C of baking ovens at once and dries 4h, is then transferred in Muffle furnace, to room temperature with 1
DEG C/min rises to 120 DEG C, 2h is kept, is then warming up to 250 DEG C according still further to 1 DEG C/min, 6h is kept, is taken after room temperature is down to naturally
Go out egg-shell catalyst A.
Carrier and catalyst texture property are shown in Table 1.
The optical photograph of the catalyst prepared in the present embodiment is shown in A in Fig. 1, in figure, the discrimination that can be apparent from this urge
Agent is egg-shell catalyst.The graph of pore diameter distribution measured by nitrogen physisorption of the catalyst of preparation is shown in Fig. 2.Fig. 3 is
Egg-shell catalyst A prepared by embodiment 1 X-ray diffraction spectrogram.SiO is only existed in catalyst2Diffraction maximum and Co3O4
Diffraction maximum.
Embodiment 2
The preparation of carrier：300g SiO 2 powders are uniformly mixed with 150g Ludox, are filled into banded extruder, extrusion
Machine uses 3mm circular dies.Extrudate is put into 100 DEG C of baking ovens and dries 4h, Muffle kiln roasting is placed into, to room temperature with 2
DEG C/min rises to 120 DEG C, 2h is kept, is then warming up to 500 DEG C according still further to 2 DEG C/min, 6h is kept, is taken out after being down to room temperature naturally
Carrier, sign as SiO2-B.The solid content of the Ludox is 40%.
The preparation of catalyst：Cobalt nitrate solution is configured with deionized water, its concentration is 6mol/L.Carrier is laid in core
In funnel, sand core funnel connection vavuum pump, cobalt nitrate solution is poured into funnel, vavuum pump is opened after 3 seconds, by unnecessary presoma
Solution pumps.Dipping rear catalyst is put into 100 DEG C of baking ovens at once and dries 4h, is then transferred in Muffle furnace, to room temperature with 1
DEG C/min rises to 120 DEG C, 2h is kept, is then warming up to 250 DEG C according still further to 1 DEG C/min, 6h is kept, is taken after room temperature is down to naturally
Go out egg-shell catalyst B.
Carrier and catalyst texture property are shown in Table 1.
The optical photograph of the catalyst prepared in the present embodiment is shown in B in Fig. 1, in figure, the discrimination that can be apparent from this urge
Agent is egg-shell catalyst.The graph of pore diameter distribution measured by nitrogen physisorption of the catalyst of preparation is shown in Fig. 2.Eggshell type
Catalyst A has less aperture, and egg-shell catalyst B has larger aperture.Fig. 3 is the eggshell type prepared in embodiment 2
Catalyst B X-ray diffraction spectrogram.SiO is only existed in catalyst2Diffraction maximum and Co3O4Diffraction maximum.
Fig. 4 is the X ray computer fault imaging figure of the egg-shell catalyst prepared in Examples 1 and 2, by simulation
Afterwards, the three-dimensional structure of catalyst is shown, shell-core part of catalyst is can see in figure, while can observed
The spatial distribution map of internal active metal component.#1 layers are catalyst eggshell layer, and #2 is the silica inner core of catalyst, #3
For the Co that in-core is distributed in catalyst silica3O4Bulky grain.It can be seen that in egg-shell catalyst A, Co3O4Big
Grain average grain diameter is more than 40 μm, and quantity is a lot；In core/shell-type catalyst B, Co3O4Bulky grain average grain diameter at 20 μm or so,
And quantity is significantly less than the Co in egg-shell catalyst A3O4Bulky grain.
Embodiment 3
Use carrier S iO prepared by embodiment 12- A prepares catalyst：Cobalt nitrate solution, its concentration are configured with deionized water
For 6mol/L.Carrier is laid in sand core funnel, sand core funnel connection vavuum pump, cobalt nitrate solution is poured into funnel, 15s
After open vavuum pump, unnecessary precursor solution is pumped.Dipping rear catalyst is put into 100 DEG C of baking ovens at once and dries 4h, then
It is transferred in Muffle furnace, rises to 120 DEG C with 1 DEG C/min to room temperature, keep 2h, be then warming up to 250 DEG C according still further to 1 DEG C/min,
6h is kept, catalyst C is taken out after room temperature is down to naturally.
The optical photograph of the catalyst prepared in the present embodiment is as shown in C in Fig. 1, and when dip time reaches 15s, this is urged
Eggshell type structure is not present in agent.
Embodiment 4
Take egg-shell catalyst A 2.00g to be loaded in fixed bed reactors, first reduce 8h at 400 DEG C, cut after having reduced
Unstripped gas is changed, using H2/ CO mol ratio=2:1 unstripped gas is reacted, and reaction condition is：2.0MPa, 230 DEG C,
750mL.gcat-1.h-1.Reaction result is shown in Table 2.
Embodiment 5
Take egg-shell catalyst B 2.00g to be loaded in fixed bed reactors, first reduce 8h at 400 DEG C, cut after having reduced
Unstripped gas is changed, using H2/ CO mol ratio=2:1 unstripped gas is reacted, and reaction condition is：2.0MPa, 230 DEG C,
750mL.gcat-1.h-1.Reaction result is shown in Table 2.
Embodiment 6
Take catalyst C 2.00g to be loaded in fixed bed reactors, first reduce 8h at 400 DEG C, switching raw material after having reduced
Gas, using H2/ CO mol ratio=2:1 unstripped gas is reacted, and reaction condition is：2.0MPa, 230 DEG C, 750mL.gcat- 1.h-1.Reaction result is shown in Table 2.
The embodiment carrier of table 1 and catalyst texture property
The embodiment catalyst physical and chemical performance of table 2
| Catalyst is numbered | CO conversion ratios/% | CH4Selectivity/% |
| Egg-shell catalyst A | 7.5 | 16.6 |
| Egg-shell catalyst B | 13.8 | 17.4 |
| Catalyst C | 5.6 | 19.3 |
It can be seen that the catalyst that the inventive method prepares is egg-shell catalyst from above-described embodiment, and for
Equally distributed catalyst, egg-shell catalyst has higher CO conversion ratios, while has relatively low methane selectively.And
And from table 1,2 as can be seen that reducing the content of Ludox, the specific surface area of carrier reduces, aperture increases, egg-shell catalyst
Cobaltosic oxide in kernel is reduced, the activity increase of catalyst.
Embodiment 7
The preparation of carrier：200g SiO 2 powders are uniformly mixed with 600g Ludox, are filled into banded extruder, extrusion
Machine uses 3mm circular dies.Extrudate is put into 60 DEG C of baking ovens and dries 20h, Muffle kiln roasting is placed into, to room temperature with 1
DEG C/min rises to 110 DEG C, 1.5h is kept, is then warming up to 600 DEG C according still further to 5 DEG C/min, 3h is kept, is taken after being down to room temperature naturally
Go out carrier.The solid content of the Ludox is 45%.
The preparation of catalyst：Cobalt nitrate solution is configured with deionized water, its concentration is 8mol/L.Carrier is laid in core
In funnel, sand core funnel connection vavuum pump, cobalt nitrate solution is poured into funnel, vavuum pump is opened after 3s, by unnecessary presoma
Solution pumps.Dipping rear catalyst is put into 120 DEG C of baking ovens at once and dries 20h, is then transferred in Muffle furnace, to room temperature with 5
DEG C/min rises to 130 DEG C, 2.5h is kept, is then warming up to 450 DEG C according still further to 5 DEG C/min, 8h is kept, after room temperature is down to naturally
Take out egg-shell catalyst.
Embodiment 8
The preparation of carrier：200g SiO 2 powders are uniformly mixed with 500g Ludox, are filled into banded extruder, extrusion
Machine uses 3mm circular dies.By extrudate be put into 100 DEG C of baking ovens dry 1h, place into Muffle kiln roasting, to room temperature with
0.5 DEG C/min rises to 130 DEG C, keeps 2.5h, is then warming up to 500 DEG C according still further to 4 DEG C/min, keeps 8h, is down to room temperature naturally
After take out carrier.The solid content of the Ludox is 40%.
The preparation of catalyst：Cobalt nitrate solution is configured with deionized water, its concentration is 5mol/L.Carrier is laid in core
In funnel, sand core funnel connection vavuum pump, cobalt nitrate solution is poured into funnel, vavuum pump is opened after 5s, by unnecessary presoma
Solution pumps.Dipping rear catalyst is put into 110 DEG C of baking ovens at once and dries 2.5h, is then transferred in Muffle furnace, to room temperature with 1
DEG C/min rises to 130 DEG C, 2.0h is kept, is then warming up to 600 DEG C according still further to 5 DEG C/min, 10h is kept, treats that nature is down to room temperature
After take out egg-shell catalyst.
The above-described embodiments merely illustrate the principles and effects of the present invention, not for the limitation present invention.It is any ripe
Know the personage of this technology all can carry out modifications and changes under the spirit and scope without prejudice to the present invention to above-described embodiment.Cause
This, those of ordinary skill in the art is complete without departing from disclosed spirit and institute under technological thought such as
Into all equivalent modifications or change, should by the present invention claim be covered.
Claims (9)
1. a kind of preparation method of catalyst, comprises the following steps：
1) carrier is prepared：SiO 2 powder is mixed with Ludox and extrudes to obtain extrudate；By the extrudate through drying
Roasting obtains carrier afterwards；
2) cobalt nitrate solution is prepared：Prepare the cobalt nitrate solution that concentration is 1~8mol/L；
3) impregnate：Cobalt nitrate solution is added in carrier, dipping removes remaining liq after terminating and obtains sample；
4) by sample drying and it is calcined, obtains egg-shell catalyst；
In step 1), the mass ratio of SiO 2 powder and Ludox is 1：(0.4~3)；The solid content of the Ludox is 35
~45%.
2. method as claimed in claim 1, it is characterised in that：The temperature dried described in step 1) is 60~120 DEG C, when drying
Between be 1~20h.
3. method as claimed in claim 1, it is characterised in that：Roasting uses Muffle furnace or tube furnace described in step 1), heats up
Speed rises to 110~130 DEG C for the first programming rate with 1~5 DEG C/min, keeps 1.5~2.5h, then with 0.5~5 DEG C/min's
Programming rate rises to 300~600 DEG C, keeps 1~20h.
4. method as claimed in claim 1, it is characterised in that：Dip time is 1~10s in step 3).
5. method as claimed in claim 1, it is characterised in that：The temperature dried described in step 4) is 60~120 DEG C, when drying
Between be 0.25~20h.
6. method as claimed in claim 1, it is characterised in that：Roasting uses Muffle furnace or tube furnace, programming rate in step 4)
110~130 DEG C are risen to 1~5 DEG C/min programming rate for elder generation, keeps 1.5~2.5h, then the heating with 0.5~5 DEG C/min
Speed rises to 250~450 DEG C, keeps 3~8h.
7. a kind of catalyst is prepared by any methods described of such as claim 1~6.
8. purposes of the catalyst as claimed in claim 7 in fixed bed fischer-tropsch reaction, and the catalyst is applied to fixation
Activated, activated also to carry out in Primordial Qi atmosphere of hydrogen before bed fischer-tropsch reaction, activation temperature is 350~500 DEG C, during activation
Between be 2~12h.
9. purposes as claimed in claim 8, the catalyst be used in fixed bed fischer-tropsch reaction the relative pressure that reacts for 1.0~
3.0MPa, reaction temperature are 200~300 DEG C, and mass space velocity is 500~6000mL.gcat-1.h-1, hydrogen and carbon monoxide gas
The mol ratio of body is 2.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101269329A (en) * | 2008-05-19 | 2008-09-24 | 中国科学院山西煤炭化学研究所 | Cobalt group catalyst synthesized with fischer tropsch process, production method and application thereof |
| CN104001514A (en) * | 2014-06-10 | 2014-08-27 | 中国科学院山西煤炭化学研究所 | Eggshell cobalt-based Fischer-Tropsch synthesis catalyst, and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101269329A (en) * | 2008-05-19 | 2008-09-24 | 中国科学院山西煤炭化学研究所 | Cobalt group catalyst synthesized with fischer tropsch process, production method and application thereof |
| CN104001514A (en) * | 2014-06-10 | 2014-08-27 | 中国科学院山西煤炭化学研究所 | Eggshell cobalt-based Fischer-Tropsch synthesis catalyst, and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| Eggshell catalyst in Fischer-Tropsch synthesis Intrinsic reaction kinetics;E. Peluso，et al.;《Chemical Engineering Science》;20011231;第56卷;1239-1245 * |
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