CN106807438A - A kind of ferrum-based catalyst and preparation method thereof - Google Patents
A kind of ferrum-based catalyst and preparation method thereof Download PDFInfo
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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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/46—Iron group metals or copper
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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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
- B01J29/14—Iron group metals or copper
- B01J29/146—Y-type faujasite
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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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/65—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively
- B01J29/66—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively containing iron group metals, noble metals or copper
- B01J29/68—Iron group metals or copper
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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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/76—Iron group metals or copper
- B01J29/7615—Zeolite Beta
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
- C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
- C10G2/334—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 molecular sieve catalysts
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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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
Abstract
The present invention relates to technical field of catalytic chemistry, there is provided a kind of ferrum-based catalyst and preparation method thereof, including：Molecular sieve and silica are added into iron salt solutions, suspension is obtained after stirring, solvent is evaporated, then dried in an oven, obtain solid, be calcined, obtain ferrum-based catalyst., using metallic iron and molecular sieve as the active component of catalyst, molecular sieve bore diameter is smaller, is unfavorable for the diffusion of reacting gas and product for the present invention；Silica as catalyst dispersant, the effect with dispersed metal iron and molecular sieve, while playing support effect；The addition of silica avoids the phenomenon of hot-spot, improves the selectivity of catalyst.The present invention prepare for Fischer-Tropsch synthesis catalyst, it is very high in 10 16 hydrocarbon fraction selectivity for carbon number, and the content of isoparaffin improves, it is adaptable to as Aviation Fuel, the cost of investment and operating cost of device to be effectively reduced.
Description
Technical field
The present invention relates to technical field of catalytic chemistry, more particularly to a kind of ferrum-based catalyst and preparation method thereof.
Background technology
The energy is the basis that modern society depends on for existence and development, and the supply capacity of clean fuel is related to national economy
Sustainable development, is one of basis of national strategy safety guarantee.F- T synthesis (Fischer-Tropsch Synthesis,
Abbreviation FTS) it is through synthesis gas (H by coal, natural gas and biomass2+ CO) it is converted into not by catalysts such as iron-based, cobalt-baseds
The high-quality clean fuel liquid and the practicable techniques of high valuable chemicals of sulfur-bearing, nitrogen and aromatic hydrocarbons, are to solve petroleum resources
Worsening shortages and the effective way for avoiding environmental pollution.Ferrum-based catalyst is most common catalyst in F- T synthesis, and price is low
Honest and clean, extensively, methane selectively is low for reserves, and with olefine selective higher.Meanwhile, the water gas shift reation of ferrum-based catalyst
Excellent, can readjust prices H2/ CO ratios can with high selectivity synthesize Aviation Fuel through appropriate modification.
Aviation Fuel is not only the important fuel of engine engine, also has very in the field such as solvent and chemicals synthesis
Important application, the world is consumed more than 75000m3/ d (LIU G, YAN B, CHEN G.Technical review on jet
fuel production.Renew.Sust.Energ.Rev.,2013,25:59-70), its main component is C8-C18 scopes
Normal hydrocarbon, isohydrocarbon, cycloalkane and aromatic hydrocarbon composition.But the primary product of F- T synthesis is linear paraffin, is met
Anderson-Schulz-Flory (ASF) is distributed, and synthetic product is mainly the COMPLEX MIXED of the linear paraffin composition of C1-C50+
Thing, heavier hydrocarbon products need secondary operation.
At present, researcher is typically had long chain alkane through further cracking modification and hydroisomerizing by two step process
There is the intermediate oil of excellent combustion performance.But this process is remained high due to complex process, production cost, to a certain extent
Constrain the extensive use that coal base F- T synthesis prepare clean fuel liquid technology.Therefore, under the conditions of primary reformer, development of new
Catalyst realizes that controlled syntheses Aviation Fuel has very important significance.
The content of the invention
Present invention solves the technical problem that being to provide a kind of ferrum-based catalyst and preparation method thereof, the ferrum-based catalyst pair
Aviation Fuel cut selectivity is higher.
In view of this, the invention provides a kind of ferrum-based catalyst, by weight percentage, consist of the following composition：
Metallic iron 10-40%；
Silica 1 0-20%；
Molecule screen over-size.
Preferably, the molecular sieve is one or more in ZSM-35, ZSM-5, Y type molecular sieve, Beta.
Preferably, the silica alumina ratio 10-50 of the molecular sieve：1.
Accordingly, the preparation method that the ferrum-based catalyst described in a kind of above-mentioned technical proposal is also provided of the invention, including with
Lower step：Molecular sieve and silica are added into iron salt solutions, suspension is obtained after stirring；By the solvent in the suspension
It is evaporated, then dries in an oven, obtains solid；The solid is calcined in air atmosphere, sintering temperature is 400-600
DEG C, obtain ferrum-based catalyst.
Preferably, the mass concentration of the iron salt solutions is 10-40%.
Preferably, the molysite in the iron salt solutions is selected from one or more in iron chloride, ferric nitrate, ferric acetate.
Preferably, the solvent in the iron salt solutions is selected from water, ethanol, normal propyl alcohol, isopropanol, n-butanol, isobutanol
One or more.
Preferably, in the step of obtaining suspension, mixing time is 1-10h.
Preferably, in the step of obtaining solid, drying temperature is 80-120 DEG C, and drying time is 5-24h.
Preferably, in the step of obtaining ferrum-based catalyst, roasting time is 3-10h.
The invention provides a kind of ferrum-based catalyst and preparation method thereof, comprise the following steps：By molecular sieve and silica
Add into iron salt solutions, suspension is obtained after stirring；Solvent in the suspension is evaporated, is then dried in an oven,
Obtain solid；The solid is calcined in air atmosphere, sintering temperature is 400-600 DEG C, obtains ferrum-based catalyst.With it is existing
Technology is compared, and the present invention, because molecular sieve bore diameter is smaller, is unfavorable for using metallic iron and molecular sieve as the active component of catalyst
The diffusion of reacting gas and product；Silica as catalyst dispersant, the effect with dispersed metal iron and molecular sieve,
Play support effect simultaneously；The addition of silica avoids the phenomenon of hot-spot, can also avoid the side reaction under high temperature,
Improve the selectivity of catalyst.The present invention prepare for Fischer-Tropsch synthesis catalyst, for carbon number in 10-16
Hydrocarbon gasoline cut selectivity it is very high, and isoparaffin content improve, it is adaptable to as Aviation Fuel；Do not deposited in product
In carbon number wax product high, this can save the devices such as follow-up paraffin catalytic pyrolysis, and reduce line clogging
The problems such as, so as to be effectively reduced the cost of investment and operating cost of device.Additionally, preparation method is simple of the present invention, cost
It is cheap, adapt to large-scale industrial production.
Specific embodiment
For a further understanding of the present invention, the preferred embodiment of the invention is described with reference to embodiment, but
It should be appreciated that these descriptions are simply to further illustrate the features and advantages of the present invention, rather than to the claims in the present invention
Limitation.
The embodiment of the invention discloses a kind of ferrum-based catalyst, by weight percentage, consist of the following composition：
Metallic iron 10%-40%；
Silica 1 0%-20%；
Molecule screen over-size.
The present invention is using metallic iron and molecular sieve as the active component of catalyst, and content is higher, and the catalysis for playing key is made
With.Because molecular sieve bore diameter is smaller, be unfavorable for the diffusion of reacting gas and product, silica as catalyst dispersant,
Effect with dispersed metal iron and molecular sieve, while playing support effect.
Catalyst prepared by the present invention is used for Fischer-Tropsch synthesis, and the reaction is exothermic reaction, the addition meeting of silica
The phenomenon of hot-spot is avoided, the side reaction under high temperature can also be avoided, improve the selectivity of catalyst.
Selected molecular sieve carrier of the invention is preferably with BET specific surface area in 100-500m2The micro porous molecular sieve of/g range is
Main, larger BET specific surface area is beneficial to raising catalytic performance；And research has shown that, silica alumina ratio is higher in molecular sieve carrier, and its is resistance to
Hot acid resistance is better, therefore the present invention is sieved using the acid Series Molecules compared with high silica alumina ratio.The molecular sieve is preferably ZSM-
35th, one or more in ZSM-5, Y type molecular sieve, Beta；The silica alumina ratio of described molecular sieve carrier is preferably 10-50：1,
More preferably 10-30：1, more preferably 15：1.Preferably, the silica aperture is preferably sized to 5-50nm, more preferably
5-30nm, more preferably 10nm.
Accordingly, the present invention also provides a kind of preparation method of ferrum-based catalyst, comprises the following steps：By molecular sieve and oxygen
SiClx is added into iron salt solutions, and suspension is obtained after stirring；Solvent in the suspension is evaporated, is then done in an oven
It is dry, obtain solid；The solid is calcined in air atmosphere, sintering temperature is 400-600 DEG C, obtains ferrum-based catalyst.
Preferably, the iron salt solutions are preferably the aqueous solution or alcoholic solution of molysite, in the iron salt solutions
Solvent is selected from one or more in water, ethanol, normal propyl alcohol, isopropanol, n-butanol, isobutanol.In order to improve going back for metallic iron
Former degree, the molysite in the iron salt solutions is selected from one or more in iron chloride, ferric nitrate, ferric acetate；The iron salt solutions
Mass concentration be 10%-40%.In the step of obtaining suspension, mixing time is preferably 1-10h, more preferably 3-10h, more
Preferably 5-10h.
The present invention is using metallic iron and molecular sieve as the active component of catalyst, and content is higher, and the catalysis for playing key is made
With.Because molecular sieve bore diameter is smaller, be unfavorable for the diffusion of reacting gas and product, silica as catalyst dispersant,
Play dispersed metal iron and molecular sieve, while playing support effect.
Catalyst prepared by the present invention is used for Fischer-Tropsch synthesis, and the reaction is exothermic reaction, the addition meeting of silica
The phenomenon of hot-spot is avoided, the side reaction under high temperature can also be avoided, improve the selectivity of catalyst.
Selected molecular sieve carrier of the invention is preferably with BET specific surface area in 100-500m2The micro porous molecular sieve of/g range is
Main, larger BET specific surface area is beneficial to raising catalytic performance；Research has shown that, silica alumina ratio is higher in molecular sieve carrier, and its is heat-resisting
Acid resistance is better, therefore the present invention is sieved using the acid Series Molecules compared with high silica alumina ratio.The molecular sieve be preferably ZSM-35,
One or more in ZSM-5, Y type molecular sieve, Beta；The silica alumina ratio of described molecular sieve carrier is preferably 10-50：1, it is more excellent
Elect 10-30 as：1, more preferably 15：1.Preferably, the silica aperture is preferably sized to 5-50nm, more preferably 5-
30nm, more preferably 10nm.
In the step of obtaining solid, drying temperature is preferably 80-120 DEG C, more preferably 100-120 DEG C；Drying time is excellent
Elect 5-24h, more preferably 6-20h as.
In the step of obtaining ferrum-based catalyst, roasting time is preferably 3-10h, more preferably 5-10h；Sintering temperature is preferred
It is 500-600 DEG C, more preferably 550-600 DEG C.
Synthesis gas beam system Aviation Fuel ferrum-based catalyst prepared by the present invention, but the catalyst is before for F- T synthesis
Activation of catalyst need to be made by reduction in hydrogen, its catalytic performance so can be just given full play to.The invention also discloses the conjunction
Into the preparation method of gas beam system Aviation Fuel catalyst, using simple infusion process by cobalt salt and auxiliary element be impregnated into without
On the molecular sieve carrier of any treatment, preparation method is simple is with low cost.The Fischer-Tropsch synthesis catalyst for preparing, it is right
In carbon number 10-16 hydrocarbon gasoline cut selectivity it is very high, and isoparaffin content improve；Do not exist in product
Carbon number wax product high, this can save the devices such as follow-up paraffin catalytic pyrolysis, and reduce line clogging etc.
Problem, so as to be effectively reduced the cost of investment and operating cost of device.The present invention prepare catalyst can normal pressure and compared with
Carried out at low temperature, be environmentally friendly, it is that one kind can that energy-saving and emission-reduction are also achieved while environmental protection is realized
The method for adapting to large-scale industrial production.
Ferrum-based catalyst prepared by the present invention, reduction makes catalysis during the catalyst needs by hydrogen before for F- T synthesis
Agent is activated, and so can just give full play to its catalytic performance.
For a further understanding of the present invention, the technical scheme that the present invention is provided is carried out specifically with reference to embodiment
Bright, protection scope of the present invention is not limited by the following examples.
The raw material and chemical reagent that the embodiment of the present invention is used are purchased in market.
Embodiment 1
10Fe/20SiO2The preparation of -70ZSM-35 catalyst：
Weigh in Fe(NO3)39H2O 8.04g addition 50mL deionized waters, ultrasonic dissolution obtains iron nitrate solution.Weigh sial
Than ZSM-35 molecular sieve 7.78g and silica 2.22g (aperture 10nm) for 15, in the above-mentioned iron nitrate solution of addition, in room
Temperature stirring 4h.Then the solvent in above-mentioned suspension is evaporated, the solid after being evaporated is put into 120 DEG C of oven drying 6h.After drying
Solid be heated to being calcined 5h under 550 DEG C, air atmosphere with the heating rate of 2 DEG C/min in Muffle furnace, obtain iron-based catalysis
Agent 10Fe/20SiO2The content of -70ZSM-35, wherein iron is the 10% of catalyst carrier weight.
Embodiment 2
10Fe/20SiO2The preparation of -70ZSM-5 catalyst：
Weigh in Fe(NO3)39H2O 8.04g addition 50mL deionized waters, ultrasonic dissolution obtains iron nitrate solution.Weigh sial
Than ZSM-5 molecular sieve 7.78g and silica 2.22g (aperture 10nm) for 25, in the above-mentioned iron nitrate solution of addition, in room temperature
Stirring 4h.Then the solvent in above-mentioned suspension is evaporated, the solid after being evaporated is put into 120 DEG C of oven drying 6h.It is dried
Solid is heated to being calcined 5h under 550 DEG C, air atmosphere in Muffle furnace with the heating rate of 2 DEG C/min, obtains ferrum-based catalyst
10Fe/20SiO2The content of -70ZSM-5, wherein iron is the 10% of catalyst carrier weight.
Embodiment 3
10Fe/20SiO2The preparation of -70Y catalyst：
Weigh in Fe(NO3)39H2O 8.04g addition 50mL deionized waters, ultrasonic dissolution obtains iron nitrate solution.Weigh sial
Than Y molecular sieve 7.78g and silica 2.22g for 25, add in above-mentioned iron nitrate solution, 4h is stirred at room temperature.Then steam
The solvent in above-mentioned suspension is done, the solid after being evaporated is put into 120 DEG C of oven drying 6h.Dried solid is in Muffle furnace
It is heated to being calcined 5h under 550 DEG C, air atmosphere with the heating rate of 2 DEG C/min, obtains ferrum-based catalyst 10Fe/20SiO2-
The content of 70Y, wherein iron is the 10% of catalyst carrier weight.
Embodiment 4
10Fe/20SiO2The preparation of -70Beta catalyst：
Weigh in Fe(NO3)39H2O 8.04g addition 50mL deionized waters, ultrasonic dissolution obtains iron nitrate solution.Weigh sial
Than Beta molecular sieves 7.78g and silica 2.22g for 25, add in above-mentioned iron nitrate solution, 4h is stirred at room temperature.Then
The solvent in above-mentioned suspension is evaporated, the solid after being evaporated is put into 120 DEG C of oven drying 6h.Dried solid is in Muffle furnace
In be heated to being calcined 5h under 550 DEG C, air atmosphere with the heating rate of 2 DEG C/min, obtain ferrum-based catalyst 10Fe/20SiO2-
The content of 70Beta, wherein iron is the 10% of catalyst carrier weight.
Embodiment 5
20Fe/20SiO2The preparation of -60ZSM-35 catalyst：
Weigh in Fe(NO3)39H2O 18.09g addition 50mL deionized waters, ultrasonic dissolution obtains iron nitrate solution.Weigh silicon
Aluminum ratio is 15 ZSM-35 molecular sieve 7.5g and silica 2.5g (aperture 10nm), in the above-mentioned iron nitrate solution of addition, in room
Temperature stirring 4h.Then the solvent in above-mentioned suspension is evaporated, the solid after being evaporated is put into 120 DEG C of oven drying 6h.After drying
Solid be heated to being calcined 5h under 550 DEG C, air atmosphere with the heating rate of 2 DEG C/min in Muffle furnace, obtain iron-based catalysis
Agent 20Fe/20SiO2The content of -60ZSM-35, wherein iron is the 20% of catalyst carrier weight.
Embodiment 6
30Fe/20SiO2The preparation of -50ZSM-35 catalyst：
Weigh in Fe(NO3)39H2O 31g addition 100mL deionized waters, ultrasonic dissolution obtains iron nitrate solution.Weigh sial
Than ZSM-35 molecular sieve 7.15g and silica 2.85g (aperture 10nm) for 15, in the above-mentioned iron nitrate solution of addition, in room
Temperature stirring 4h.Then the solvent in above-mentioned suspension is evaporated, the solid after being evaporated is put into 120 DEG C of oven drying 6h.After drying
Solid be heated to being calcined 5h under 550 DEG C, air atmosphere with the heating rate of 2 DEG C/min in Muffle furnace, obtain iron-based catalysis
Agent 30Fe/20SiO2The content of -50ZSM-35, wherein iron is the 30% of catalyst carrier weight.
Embodiment 7
20Fe/20SiO2The preparation of -40ZSM-35-20Y catalyst：
Weigh in Fe(NO3)39H2O 8.04g addition 50mL deionized waters, ultrasonic dissolution obtains iron nitrate solution.Weigh sial
Than the ZSM-35 molecular sieve 5g for 15, the Y molecular sieve 2.5g and silica 2.5g (aperture 10nm) that silica alumina ratio is 25, in addition
State in iron nitrate solution, 4h is stirred at room temperature.Then the solvent in above-mentioned suspension is evaporated, the solid after being evaporated is put into 120 DEG C
Oven drying 6h.Dried solid is heated to 550 DEG C, under air atmosphere in Muffle furnace with the heating rate of 2 DEG C/min
Roasting 5h, obtains ferrum-based catalyst 20Fe/20SiO2The content of -40ZSM-35-20Y, wherein iron is catalyst carrier weight
20%.
Comparative example 1
20Fe/80SiO2The preparation of catalyst：
Weigh in Fe(NO3)39H2O 18.09g addition 50mL deionized waters, ultrasonic dissolution obtains iron nitrate solution.Claim dioxy
SiClx 10g (aperture 10nm), adds in above-mentioned iron nitrate solution, and 4h is stirred at room temperature.Then it is evaporated molten in above-mentioned suspension
Agent, the solid after being evaporated is put into 120 DEG C of oven drying 6h.Dried solid is in Muffle furnace with the intensification speed of 2 DEG C/min
Rate is heated to being calcined 5h under 550 DEG C, air atmosphere, obtains ferrum-based catalyst 20Fe/80SiO2, the wherein content of iron is catalyst
The 20% of vehicle weight.
Comparative example 2
The preparation of 20Fe/80ZSM-35 catalyst：
Weigh in Fe(NO3)39H2O 18.09g addition 50mL deionized waters, ultrasonic dissolution obtains iron nitrate solution.Weigh silicon
Aluminum ratio is 25 ZSM-5 molecular sieve 10g, is added in above-mentioned iron nitrate solution, and 4h is stirred at room temperature.Then it is evaporated above-mentioned suspension
In solvent, the solid after being evaporated is put into 120 DEG C of oven drying 6h.Dried solid is in Muffle furnace with 2 DEG C/min's
Heating rate is heated to being calcined 5h under 550 DEG C, air atmosphere, obtains ferrum-based catalyst 20Fe/80ZSM-35, the wherein content of iron
It is the 20% of catalyst carrier weight.
Catalyst performance is tested
The catalyst that embodiment 1-7 and comparative example 1-2 are prepared is carried out after hydrogen reducing in fixed bed reactors
Synthesis gas beam system Aviation Fuel active testing.Test condition is：Reaction temperature is 250-300 DEG C；Reaction pressure is 2MPa；Close
It is 1000h into gas air speed-1；The volume ratio of hydrogen and carbon monoxide is 2.Each reaction operating mode continues at least 10h, liquids and gases
Product gas chromatographic analysis, as a result as shown in table 1.
The performance test results of catalyst prepared by the embodiment of the present invention of table 1 and comparative example
The explanation of above example is only intended to help and understands the method for the present invention and its core concept.It should be pointed out that right
For those skilled in the art, under the premise without departing from the principles of the invention, the present invention can also be carried out
Some improvement and modification, these are improved and modification is also fallen into the protection domain of the claims in the present invention.
Claims (10)
1. a kind of ferrum-based catalyst, it is characterised in that by weight percentage, consist of the following composition：
Metallic iron 10-40%；
Silica 1 0-20%；
Molecule screen over-size.
2. ferrum-based catalyst according to claim 1, it is characterised in that the molecular sieve is ZSM-35, ZSM-5, Y type point
Son sieve, one or more in Beta.
3. ferrum-based catalyst according to claim 1, it is characterised in that the silica alumina ratio 10-50 of the molecular sieve：1.
4. the preparation method of the ferrum-based catalyst described in a kind of claim 1-3 any one, it is characterised in that including following step
Suddenly：
Molecular sieve and silica are added into iron salt solutions, suspension is obtained after stirring；
Solvent in the suspension is evaporated, is then dried in an oven, obtain solid；
The solid is calcined in air atmosphere, sintering temperature is 400-600 DEG C, obtains ferrum-based catalyst.
5. preparation method according to claim 4, it is characterised in that the mass concentration of the iron salt solutions is 10-40%.
6. preparation method according to claim 4, it is characterised in that the molysite in the iron salt solutions be selected from iron chloride,
One or more in ferric nitrate, ferric acetate.
7. preparation method according to claim 4, it is characterised in that the solvent in the iron salt solutions be selected from water, ethanol,
One or more in normal propyl alcohol, isopropanol, n-butanol, isobutanol.
8. preparation method according to claim 4, it is characterised in that in the step of obtaining suspension, mixing time is 1-
10h。
9. preparation method according to claim 4, it is characterised in that in the step of obtaining solid, drying temperature is 80-
120 DEG C, drying time is 5-24h.
10. preparation method according to claim 4, it is characterised in that in the step of obtaining ferrum-based catalyst, roasting time
It is 3-10h.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109939725A (en) * | 2019-03-15 | 2019-06-28 | 武汉科技大学 | A kind of synthesis gas directly converts the catalyst and preparation method thereof of isoparaffin processed |
| CN109939725B (en) * | 2019-03-15 | 2021-12-14 | 武汉科技大学 | Catalyst for preparing isoparaffin by directly converting synthesis gas and preparation method thereof |
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