CN105688911B - A kind of preparation method of high activity ferrum-based catalyst - Google Patents
A kind of preparation method of high activity ferrum-based catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 82
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 230000000694 effects Effects 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 241000209094 Oryza Species 0.000 claims abstract description 44
- 235000007164 Oryza sativa Nutrition 0.000 claims abstract description 44
- 235000009566 rice Nutrition 0.000 claims abstract description 44
- 239000010903 husk Substances 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 41
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 22
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 15
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 14
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 14
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 14
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 claims abstract description 5
- 239000008367 deionised water Substances 0.000 claims abstract description 5
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 5
- 238000012545 processing Methods 0.000 claims abstract description 3
- 239000011573 trace mineral Substances 0.000 claims abstract description 3
- 235000013619 trace mineral Nutrition 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 238000001556 precipitation Methods 0.000 claims description 12
- 229910017086 Fe-M Inorganic materials 0.000 claims description 9
- 239000003153 chemical reaction reagent Substances 0.000 claims description 9
- 230000001376 precipitating effect Effects 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 239000002244 precipitate Substances 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 abstract description 8
- 239000010703 silicon Substances 0.000 abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052799 carbon Inorganic materials 0.000 abstract description 5
- 230000009257 reactivity Effects 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 description 21
- 239000007789 gas Substances 0.000 description 15
- 230000009467 reduction Effects 0.000 description 13
- 239000003863 metallic catalyst Substances 0.000 description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000003245 coal Substances 0.000 description 5
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 4
- 239000003502 gasoline Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 230000004044 response Effects 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- -1 C12 aliphatic hydrocarbons Chemical class 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- DQMUQFUTDWISTM-UHFFFAOYSA-N O.[O-2].[Fe+2].[Fe+2].[O-2] Chemical compound O.[O-2].[Fe+2].[Fe+2].[O-2] DQMUQFUTDWISTM-UHFFFAOYSA-N 0.000 description 1
- 229910003978 SiClx Inorganic materials 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 229910001567 cementite Inorganic materials 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 235000003642 hunger Nutrition 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- KSOKAHYVTMZFBJ-UHFFFAOYSA-N iron;methane Chemical compound C.[Fe].[Fe].[Fe] KSOKAHYVTMZFBJ-UHFFFAOYSA-N 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000012163 sequencing technique Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 230000037351 starvation Effects 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- 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
- B01J23/745—Iron
-
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
-
- 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
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/394—Metal dispersion value, e.g. percentage or fraction
-
- 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
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
Landscapes
- 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)
Abstract
A kind of preparation method of high activity ferrum-based catalyst, is related to a kind of preparation method of catalyst, and rice husk method prepares high activity Fe M/SiO2Catalyst flow path：Using intermediate processing, Fe (NO3)3·9H2O (>=99%) dissolves in deionized water, is then deposited in the duct of rice husk；After washing, filtered presoma are 10 hours dry in 120 DEG C of baking ovens, the catalyst after roasting restores 10 hours for 250 400 DEG C in synthesis gas atmosphere；Prepared Fe M/SiO2Catalyst is respectively designated as Fe M（A）/SiO2B, wherein M refer to the trace element contained in rice husk, have K, Ca, Mg etc., A to refer to the mass fraction of load Fe, this method makes full use of the elements such as the silicon, carbon and trace meter contained in rice husk, considerably improves the activity of catalyst.Catalyst prepared by this method is used for Fischer-Tropsch synthesis, shows good reactivity and splendid stability.
Description
Technical field
The present invention relates to a kind of preparation methods of catalyst, more particularly to a kind of preparation side of high activity ferrum-based catalyst
Method.
Background technology
Gasoline, appearance are transparency liquid, and main component is C4~C12 aliphatic hydrocarbons and cyclic hydrocarbon composition.Gasoline is mainly answered
For internal combustion engine and car engine.Industrial gasoline is mainly made by petroleum fractionating or heavy end cracking.Crude oil is through distilling, urging
Change cracking, thermal cracking, be hydrocracked, the processes such as catalytic reforming generate gasoline component.But with the high speed development of world economy, stone
The worsening shortages of oily resource, the rapid development of the getting worse and biomass technology of environmental pollution, F- T synthesis（Fischer-
Tropsch synthesis：By coal, natural gas, one that biomass indirect reformer is liquid fuel and high valuable chemicals
The important technical process of kind）The extensive concern of countries in the world is caused again.In conjunction with the resource of China's " rich coal, oil starvation, few gas "
Feature develops using coal as the coal chemical technology of waste petroleum-type product, implements oil and replaces strategy, is relationship China economy
The key subjects of long-term stability development and energy security, and realize the inevitable choice of national " with coal for replacing oil " strategy.But take
Ask product extremely complex, using different iron-baseds, cobalt-based or noble metal catalyst, the selective difference of liquid product is larger.
Wherein, ferrum-based catalyst is cheap, and content is big in the earth's crust, becomes the source of most important expense denitrating catalyst.
Metallic catalyst is to study earliest in solid catalyst, is most deep, while and obtaining the most widely applied
A kind of catalyst.It is most important one kind catalyst in Industrial Catalysis.By its effect classification, metallic catalyst, which can play, to be added
The effects that hydrogen, dehydrogenation, oxidation, isomerization, cyclisation.According to price category, metallic catalyst includes base metal catalysts, such as：Ni、
Cu, Co, Fe etc.；And noble metal catalyst, such as：Pt, Pd, Ru, Rh etc..Currently, the preparation method master of metallic catalyst
To include chemical method and Physical.Wherein mainly there are infusion process, coprecipitation, homogeneous precipitation method, sol-gel method in chemical method
With microemulsion method etc.；Physical has vapour deposition process, atom deposition method, sputtering method and solid-phase sequencing.It is coprecipitated in chemical method
Reaction condition is mild in method and homogeneous precipitation method preparation ground metallic catalyst preparation process, is easy to control, and equipment is thrown
Enter small, the metal particle size of preparation is uniformly dispersed controllably.And prepared catalyst activity in catalysis is reacted is higher, therefore
Extensive use in production.But during preparing metallic catalyst using coprecipitation method and homogeneous precipitation method, due to
It is widely used relatively inexpensive metal nitrate presoma, there is the largely waste water generation containing nitrate anion, the pole caused by environment
Big to influence, environment is unfriendly.Therefore, in the today implemented Green Chemistry, advocate green synthetic chemistry, exploitation is a kind of simple and practicable
, free of contamination metallic catalyst preparation method it is very necessary.
Rice husk is one layer of shell outside paddy, is by coetonium, inner glume, a few part compositions such as sterile lemma and rachilla, coetonium top
Hair with temples hairy except portion.Positive rice husk is then made of some rough prothenchyma (of wood)s, about 24~30 microns of thickness,
Rice husk is rich in cellulose, lignin, silica, wherein fat, the content of protein are relatively low, based on rice variety, area, gas
Differences, the chemical compositions such as time can be variant.
The utilization of rice husk at present includes mainly：Rice husk, which hydrolyzes, produces xylose, furfural, the utilization of silicon source and rice husk in rice husk
As energy and material power generation etc..But rice husk hydrolysis production xylose and its by-product of furfural are very more, and economic benefit value is low；Rice
Shell is only used as silicon source, and the carbon and a small amount of metal such as K, the wastes such as Na contained in rice husk is serious；Rice husk power generating is also only
The carbon in rice husk is utilized.
Invention content
The purpose of the present invention is to provide a kind of preparation method of high activity ferrum-based catalyst, this method makes full use of rice husk
In the elements such as silicon, carbon and trace meter K, Ca, Mg for containing, with the SiO generated after the silicon source roasting of rice husk2As catalyst
Carrier；With contain in rice husk elements K, Ca, Mg etc. for catalyst promoter, considerably improve catalyst activity and
Stability.
The purpose of the present invention is what is be achieved through the following technical solutions：
A kind of preparation method of high activity ferrum-based catalyst, the method includes following preparation process：
Rice husk method prepares high activity Fe-M/SiO2Catalyst flow path：Using intermediate processing, Fe (NO3)3·9H2O (≥
99%) dissolving in deionized water, is then deposited in the duct of rice husk；Precipitating reagent chooses NH respectively4OH, NaOH and
Na2CO3, 50-80 DEG C of precipitation temperature is controlled, pH value precipitates between 7-9；Wherein the quality of Fe accounts for the 1- of catalyst gross mass
60%；After washing, filtered presoma are dried 10 hours in 120 DEG C of baking ovens, 150-500 DEG C of roasting 3-5 is small in air
When, the catalyst after roasting restores 10 hours for 250-400 DEG C in synthesis gas atmosphere；Prepared Fe-M/SiO2Catalyst point
Fe-M is not named as it（A）/SiO2- B, wherein M refer to the trace element contained in rice husk, have K, Ca, Mg etc., A to refer to the matter of load Fe
Score is measured, B refers to the reduction temperature of catalyst in an inert atmosphere.
A kind of preparation method of high activity ferrum-based catalyst prepares Fe/SiO using the precipitation method2Catalyst：Fe
(NO3)3·9H2O (>=99%) dissolves in deionized water, is then deposited in SiO2In duct, the wherein quality of Fe accounts for catalyst
The 1-60% of gross mass；Using SiO2 (Cariact Q-50, Fuji Silysia Co., specific surface
area: 57 m2g-1, pore volume: 1.2 mLg-1) it is used as starting vector；First, SiO2600 DEG C under air conditions
Roasting 3 hours, purpose remove the water and other impurities of carrier surface absorption；Precipitating reagent chooses NH respectively4OH, NaOH and
Na2CO3, 50-80 DEG C of precipitation temperature is controlled, pH value precipitates between 7-9；Washing, filtered presoma in 120 DEG C of baking ovens
It after middle drying 10 hours, roasts 3-5 hours for 150-500 DEG C in air, the 250- in synthesis gas atmosphere of the catalyst after roasting
400 DEG C restore 10 hours；Prepared Fe/SiO2Catalyst is respectively designated as Fe（A）/ SiO2- B, A refer to the quality point of load Fe
Number, B refer to the reduction temperature of catalyst in an inert atmosphere.
A kind of preparation method of high activity ferrum-based catalyst prepares Fe/RHA-air catalyst using the precipitation method：
Fe (NO3)3·9H2O (>=99%) dissolves in deionized water, is then deposited in rice hull ash duct, the wherein quality of Fe accounts for
The 1-60% of catalyst gross mass；RHA-air refer to rice husk in air 500 DEG C roasting 3 hours after remaining residue, be dioxy
SiClx and trace meter oxide；Precipitating reagent chooses NH respectively4OH, NaOH and Na2CO3, control 50-80 DEG C of precipitation temperature, pH
Value precipitates between 7-9；Washing, filtered presoma in 120 DEG C of baking ovens after dry 10 hours, 150- in air
500 DEG C roast 3-5 hours, and the catalyst after roasting restores 10 hours for 250-400 DEG C in synthesis gas atmosphere；Prepared Fe/
RHA-air catalyst is respectively designated as Fe（A）/ RHA-air-B, A refer to the mass fraction of load Fe, and B refers to catalyst in indifferent gas
Reduction temperature in atmosphere.
Advantages of the present invention is with effect：
1. the present invention makes full use of the elements such as the silicon contained in rice husk, carbon and trace meter K, Ca, Mg, with the silicon of rice husk
The SiO generated after the roasting of source2Carrier as catalyst；It is helped for catalyst with the elements K that contains in rice husk, Ca, Mg etc.
Agent considerably improves the activity and stability of catalyst.The catalyst prepared using the method for this patent report, it is de- for taking
Synthetic reaction shows to show good reactivity and stability.
2. the catalyst prepared by the present invention shows higher Fe metal dispersities, smaller metal Fe particles；Rice husk
The addition of middle Si, K element considerably improve the activity and stability of catalyst.
Description of the drawings
Fig. 1 is that rice husk method prepares Fe-M/SiO2Catalyst flow path figure.
Specific implementation mode
The following describes the present invention in detail with reference to examples.
Specific example 1：
Using NaOH as precipitating reagent, it is anti-to be directly used in F- T synthesis using the different Fe load capacity catalyst of rice husk method preparation
It answers.Fischer-tropsch reaction condition is as follows：280 DEG C of reaction temperature, 1.0 MPa of pressure, 10 g of catalyst quality, reaction time
100 hours, synthesis gas formed CO/H2 = 1/1, W/F (CO + H2 + Ar) = 5 ghmol-1。
From the data in table 1 it is found that when preparing Fe base catalyst using rice husk method, when Fe load capacity is relatively low
（1wt%）, prepared catalyst activity is relatively low, and CO conversion ratios are only 12%；As the increase of Fe load capacity is from 5-40wt%, urge
The activity of agent gradually increases；But when Fe load capacity is more than 40wt%, catalyst activity declines instead.
Specific example 2：
Using NaOH as precipitating reagent, Fe load capacity prepared by rice husk method is used for 20% catalyst to be directly used in F- T synthesis anti-
It answers.Reduction temperature is 250-600 DEG C under synthesis gas environment.Fischer-tropsch reaction condition is as follows：260-300 DEG C of reaction temperature, pressure
1.0-2.5 MPa, 10 g of catalyst quality, 100 hours reaction time, synthesis gas form CO/H2 = 1/1, W/F (CO
+ H2 + Ar) = 5 ghmol-1.Table 2 is to investigate to prepare Fe-M using rice husk method（20）/ SiO2Catalyst is in different reduction temperature
Fischer-tropsch reaction activity under degree.
From the response data in table 2 it is found that using rice husk method prepare the catalyst restored under different reduction temperatures,
Its active difference is larger, when reduction temperature is relatively low（250 ℃）, catalyst activity is poor, and CO conversion ratios are only 9%, and explanation is worked as
When reduction temperature is relatively low, di-iron trioxide can not be synthesized gas and be reduced to cementite, and only small part activity is higher in other words
Ferric iron can be reduced；Reduction temperature is gradually risen from 250-350 DEG C, prepared catalyst activity is gradually mentioned, and 350
DEG C reduction when, catalyst activity is up to 66%.But when reduction temperature improves again, the reactivity of catalyst significantly reduces,
Illustrate that high temperature causes metal Fe to be sintered, grain growth.
Specific example 3：
Using NaOH as precipitating reagent, Fe load capacity prepared by rice husk method is used for 20% catalyst to be directly used in F- T synthesis anti-
It answers.Reduction temperature is 250-600 DEG C under synthesis gas environment.Fischer-tropsch reaction condition is as follows：260-300 DEG C of reaction temperature, pressure
1.0-2.5 MPa, 10 g of catalyst quality, 100 hours reaction time, synthesis gas form CO/H2 = 1/1, W/F (CO
+ H2 + Ar) = 5 ghmol-1.Table 3 is to investigate to prepare Fe-M using rice husk method（20）/ SiO2Catalyst is at different conditions
Fischer-tropsch reaction activity.
From the response data in table 3 it is found that the catalyst prepared using rice husk method, reactivity is with reaction temperature
It increases（260-300℃）And increase, increase with the increase of reaction pressure.
Specific example 4：
Using NaOH as precipitating reagent, the approximate Fe bases catalyst of content prepared using distinct methods is anti-for F- T synthesis
It answers.Fischer-tropsch reaction condition is as follows：260-300 DEG C of reaction temperature, pressure 1.0-2.5 MPa, 10 g of catalyst quality, reaction
100 hours time, synthesis gas form CO/H2 = 1/1, W/F (CO + H2 + Ar) = 5 ghmol-1.Table 4 is to investigate
Using different method for preparing catalyst on the active influence of fischer-tropsch reaction.
From the response data in table 4 it is found that the Fe/SiO prepared using conventional precipitation method2Catalyst activity is worst, only
49% CO conversion ratios, using precipitation method preparation Fe/RHA-air catalyst, its reactivity ratio's conventional precipitation method prepares catalyst
Activity it is high by about 12%, but be still below the activity that rice husk method prepares catalyst（About low 5%）.
Specific example 5：
Using NaOH as precipitating reagent, Fe load capacity prepared by rice husk method is used for 40% catalyst to be directly used in F- T synthesis anti-
It answers.Reduction temperature is 350 DEG C under synthesis gas environment.Fischer-tropsch reaction condition is as follows：300 DEG C of reaction temperature, 2.0 MPa of pressure,
20 g of catalyst quality, 2000 hours reaction time, synthesis gas form CO/H2 = 1/1, W/F (CO + H2 + Ar) =
1 ghmol-1.Table 5 is to investigate to prepare Fe-M using rice husk method（40）/ SiO2- 300 catalyst stabilities.
It is from the response data in table 5 it is found that especially good using the catalyst stability of rice husk method preparation, it reacts 2000 hours
When, catalyst is substantially without deactivation behaviours.
The above is only several embodiments of the application, not does any type of limitation to the application, although this Shen
Please disclosed as above with preferred embodiment, however not to limit the application, any person skilled in the art is not taking off
In the range of technical scheme, makes a little variation using the technology contents of the disclosure above or modification is equal to
Case study on implementation is imitated, is belonged in technical proposal scope.
Claims (1)
1. a kind of preparation method of high activity ferrum-based catalyst, which is characterized in that the method includes following preparation process：
Rice husk method prepares high activity Fe-M/SiO2Catalyst flow path：Using intermediate processing, purity is more than or equal to 99% Fe
(NO3)3·9H2O dissolves in deionized water, is then deposited in the duct of rice husk；Precipitating reagent chooses NH respectively4OH、NaOH
And Na2CO3, 50-80 DEG C of precipitation temperature is controlled, pH value precipitates between 7-9；Wherein the quality of Fe accounts for catalyst gross mass
1-60%；After washing, filtered presoma are dried 10 hours in 120 DEG C of baking ovens, 3-5 is roasted for 150-500 DEG C in air
Hour, the catalyst after roasting restores 10 hours for 250-400 DEG C in the synthesis gas atmosphere of F- T synthesis；Prepared Fe-M/
SiO2Catalyst, wherein M refer to the trace element contained in rice husk, there is K, Ca, Mg.
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| "Decolorization of Acid Red 1 by Fenton-like process using rice husk ash-based catalyst";N.K. Daud等;《Journal of Hazardous Materials》;20091201;第176卷;第939页第2.2节 * |
| "稻壳二氧化硅负载铁催化剂对苯酚双氧水羟化反应的催化活性";薄莹莹等;《常州大学学报（自然科学版）》;20120930;第24卷(第3期);第21-25页 * |
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