CN103586034B - A kind of low carbon dioxide selectivity fischer-tropsch synthetic catalyst and its preparation method and application - Google Patents
A kind of low carbon dioxide selectivity fischer-tropsch synthetic catalyst and its preparation method and application Download PDFInfo
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Abstract
The present invention discloses a kind of fischer-tropsch synthetic catalyst, and containing weight content in described catalyst is 10-80%, and the active component iron of preferred 25-60% and weight content are 10-70%, the composite metal oxide with perovskite structure of preferred 20%-60%; The complex metal formula with perovskite structure is ABO
3-y, wherein, A is alkaline-earth metal, and B is transition metal, and y is the molal quantity of the Lacking oxygen existed in composite oxides.This catalyst, while the conversion per pass improving synthesis gas, effectively can reduce CO
2selective.
Description
Technical field
The present invention relates to a kind of fischer-tropsch synthetic catalyst and its preparation method and application, relate in particular to a kind of Catalysts and its preparation method and the application that take synthesis gas as raw material and prepare liquid hydrocarbon.
Background technology
Liquid fuel is that modern society relies the blood of running, and it mainly to be produced by crude refining, processing.In recent years, owing to causing liquid fuel price continuous rise to the worry of crude supply prospect, a large amount of uses of liquid fuel simultaneously also bring serious problem of environmental pollution, and setting up continuable clean fuel liquid production method is the effective means solving above-mentioned two problems.Fischer-tropsch synthesis process refers to and coal, natural gas, living beings etc. is first converted into synthesis gas (CO and H containing carbon resource
2mixture), then synthesis gas is polymerized on a catalyst the process of gaseous state, liquid state and solid hydrocarbons, synthesis gas polymerization process is below called as Fischer-Tropsch synthesis (Fischer-Tropsch Synthesis).Liquid hydrocarbon prepared by F-T synthesis, after hydrogenation upgrading, has the character identical with the liquid fuel that petroleum refining is produced.Because the known reserves of coal, natural gas verify reserves much larger than oil, living beings are a kind of reproducible resources, therefore fischer-tropsch synthesis process can, for society provides the sufficient liquid fuel being representative with gasoline and diesel oil etc. within the longer time, be the technology of desirable production petroleum replacing fuel.
Fischer-tropsch reaction carries out on a catalyst, and the catalyst (high activity, high selectivity, high stability) with excellent properties is the technical guarantee realizing efficient fischer-tropsch synthesis process.Catalyst activity is high, can improve the specific productivity of reaction unit, and selective height can improve the utilization rate of reaction raw materials, and stability is high is conducive to the running at full capacity, the minimizing non-normal stop that maintain reaction unit.Finding in the studying for a long period of time of fischer-tropsch reaction: nickel, ruthenium, iron and cobalt have fischer-tropsch reaction activity.Nickel-base catalyst, under fischer-tropsch reaction condition, can produce too many methane, self is easy to generate volatile carbonyl nickel and run off from reactor simultaneously, is difficult to realize commercial Application.Ruthenium is the most active known fischer-tropsch reaction catalyst, but its high price and limited reserves hinder its use on industrial Fischer Tropsch Facility, and it is generally add in iron-based and cobalt-base catalyst with auxiliary agent form, improve their reactivity worth.Iron-based and cobalt-base catalyst is only had to be used successfully in F-T synthesis industry.Ferrum-based catalyst is generally divided into fused iron catalyst and precipitated iron catalyst.Fused iron catalyst is generally used for fixed bed and fluidized-bed reactor, and industry is subject to the restriction of condition in amplifying, and is difficult to realize annual megaton and generates.Precipitated iron catalyst is generally used for paste state bed reactor, and seldom a part is used for low temperature fixed bed reactors.Precipitated iron catalyst preparation technology is by the impact of many factors, and the variation a little of preparation technology, will directly affect the conversion ratio of F-T synthesis, selective, yield and product distribution etc.Adopt ferrum-based catalyst slurry reactor technology to achieve the suitability for industrialized production of F-T synthesis from Sasol company in 1993, paste state bed reactor becomes the developing direction of Fischer-Tropsch synthesis device with the moving heat, mass-transfer performance, high production capacity and low manufacturing cost etc. of excellence.
CN201210151428.7 discloses a kind of F-T synthesis precipitated iron catalyst and preparation method thereof.This catalyst comprises the component of following part by weight, and Fe: Cu: K: Me: SiO
2=100: (0.1-6): (0.5-7): (0.1-5): (2.5-27), wherein, Me is transition metal Zr and/or Y, and Fe, Cu, K and Me exist in the form of the oxide.Suitable transition metal auxiliary agent and a small amount of silica auxiliary agent are brought in the precipitation process situ reaction of this F-T synthesis precipitated iron catalyst into, and organically combine with the nano oxidized silicon bonding of follow-up introducing, the anti-wear performance of final obtained catalyst is greatly improved, chemical stability strengthens, and the problem producing fine powder when paste state bed reactor uses improves.
CN201210100391.5 discloses a kind of Fischer-Tropsch synthetic iron-based catalyst and preparation method thereof.This preparation method comprises the following steps: 1) aqueous solution of molysite, mantoquita, cobalt salt and wet chemical coprecipitation reaction are precipitated slurry; 2) by precipitate slurry after burin-in process, add water and stir, concentrated remove part moisture content; 3) potassium silicate water glass or Ludox are joined in the precipitate slurry after concentrating, stir, leave standstill 0-180 minute; 4) step 3) slurry of gained is spray-dried, after roasting, obtain Fischer-Tropsch synthetic iron-based catalyst.The preparation method of this Fischer-Tropsch synthetic iron-based catalyst, selects potash as precipitating reagent, and a kind of constituent of potassium inherently catalyst, so there is no introduce foreign ion, eliminate washing process, save great lot of water resources; Simplify preparation technology, catalyst disturbing factor in preparation process is reduced; Improve the atom utilization of catalyst preparation process raw material.
CN200910003359.3 discloses a kind of preparation method of ferrum-based catalyst containing iron, manganese, potassium, copper for F-T synthesis, and it includes following steps: the nitrate solution of alcohol acid phosphate solution or ammonium citrate solution and iron, manganese is mixed to get slurry; Then, drying, physical decomposition and calcination process are carried out to slurry; Potassium and copper auxiliary agent is added again by impregnation process; Again through roasting, compressing tablet and break process, obtain Fe-base catalyst for Fischer-Tropsch syuthesis.The catalyst using this preparation method to obtain has higher CO conversion ratio and lower CO in F-T synthesis application
2selective.
About the research of Fischer-Tropsch synthetic iron-based catalyst was never interrupted.In sum, its aspect such as catalytic activity, stability that is prepared into from ferrum-based catalyst in prior art all conducts in-depth research, and achieves larger technological progress.Although ferrum-based catalyst can have very high reactivity, research [Fuel 76 (1997) 273.] finds that the CO reacted is converted into CO with higher ratio along with CO conversion ratio raises
2instead of hydrocarbon, namely generate selective the rising along with CO conversion ratio of hydrocarbon and decline.In order to obtain higher Auditory steady-state responses, ferrum-based catalyst is considered to suitable to lower CO conversion per pass work, CO total conversion (synthesis gas utilization rate) that secondary response mode reaches high and high hydrocarbon-selective is carried out by reaction end gas circulation, but this working method adds workload and the corresponding energy consumption such as tail gas separation, gas circulation compression, and the gross efficiency limiting fischer-tropsch synthesis process improves.
Summary of the invention
For the deficiencies in the prior art, the present invention discloses a kind of fischer-tropsch synthetic catalyst and its preparation method and application.This catalyst, while the conversion per pass improving synthesis gas, effectively can reduce CO
2selective.
A kind of fischer-tropsch synthetic catalyst, containing weight content in described catalyst is 10-80%, preferred 25-60%(does not comprise the transition metal iron in composite oxides) active component iron and weight content be 10-70%, the composite metal oxide with perovskite structure of preferred 20%-60%; The complex metal formula with perovskite structure is ABO
3-y, wherein, A is alkaline-earth metal, and B is transition metal, and y is the molal quantity of the Lacking oxygen existed in composite oxides.
In fischer-tropsch synthetic catalyst of the present invention, can also be the metal promoter of 0.1-15% containing weight content, described auxiliary agent is various F-T synthesis metal promoters used in prior art, as one or more in zirconium, potassium, ruthenium, platinum, nickel, manganese, copper, zinc, chromium, vanadium, titanium, molybdenum, zirconium.
In fischer-tropsch synthetic catalyst of the present invention, described alkaline-earth metal comprises one or more in beryllium, magnesium, calcium, strontium, barium, radium.Described transition metal comprises one or more in iron, cobalt, nickel, manganese, copper, zinc, chromium, vanadium, titanium, molybdenum, zirconium.
Fischer-tropsch synthetic catalyst of the present invention, has the ABO of perovskite structure
3-ycomposite metal oxide in B be the transition metal at least comprising iron, the mol ratio of iron and all the other transition metal is not less than 3:1, is preferably not less than 4:1.
Fischer-tropsch synthetic catalyst of the present invention, described catalyst is by active component iron, the composite metal oxide BaMn with perovskite structure
1-xfe
xo
3-y(wherein, 0.85<x< 0.95) and metal promoter potassium form.The composite metal oxide of this perovskite structure can and produce to act synergistically between active component and auxiliary agent potassium and reduces CO further
2selective.
A preparation method for fischer-tropsch synthetic catalyst, comprises the preparation of the composite metal oxide with perovskite structure and active component iron and metal promoter loading process.
In the inventive method, the described preparation with the composite metal oxide of perovskite structure adopts complexometry, but is not limited to the method.Described complexometry comprises following process: first by rare earth metal and the transition metal (preferably including the transition metal of iron) of metering ratio, presoma is with complexing agent mixing wiring solution-forming and stir, then moisture evaporation is carried out, the colloidal sol of solution went from clear is transformed into the gel of thickness, final drying, roasting, the obtained composite metal oxide with perovskite structure after roasting.There is with preparation the composite metal oxide BaMn of perovskite structure
1-xfe
xo
3-y(0.85<x< 0.95) is example, specifically comprise following content: with barium nitrate, ferric nitrate, manganese nitrate for presoma, with citric acid or ethylene glycol for complexing agent, wiring solution-forming mixing and stirring, then moisture evaporation is carried out, the colloidal sol of solution went from clear is transformed into the gel of thickness, final drying, roasting, obtained BaMn after roasting
1-xfe
xo
3-y(0.85<x< 0.95) composite metal oxide.
Prepared by above-mentioned complexometry has in the composite metal oxide of perovskite structure, and complexing agent and metal ion mol ratio are 1:1 ~ 8:1, is preferably 1:1 ~ 4:1.Preparation and agitating solution, at 20 ~ 90 DEG C, carry out at being preferably 50 ~ 70 DEG C.Stir speed (S.S.) is 200 ~ 500rpm, is preferably 300 ~ 400rpm.Mixing time is 3 ~ 8 hours, is preferably 4 ~ 6 hours.Baking temperature is 60 ~ 200 DEG C, is preferably 80 ~ 150 DEG C.Drying time is 1 ~ 36 hour, is preferably 8 ~ 24 hours.Sintering temperature is 600 ~ 1000 DEG C, and roasting time is roasting 2 ~ 15 hours, is preferably roasting 3 ~ 8 hours at 700 ~ 900 DEG C.
In the inventive method, described active component and metal promoter loading process adopt infusion process, incipient impregnation or cross volume impregnation, step impregnation or total immersion stain, single-steeping or repeatedly flood.Comprise drying and roasting process after dipping, drying steps is dry 8-24 hour at 50-150 DEG C, and calcination steps is roasting 2-10 hour at 280-500 DEG C.Such as at composite metal oxide BaMn
1-xfe
xo
3-y(0.85<x< 0.95) is upper adopts equal-volume multiple maceration load active component iron and metal promoter potassium.Described active component and metal promoter also can add in the process of composite metal oxide preparing perovskite structure.
A method of reducing for fischer-tropsch synthetic catalyst, reduction temperature is 400 ~ 1000 DEG C, preferred 500-700 DEG C, and the recovery time is 1-5h, and reduction pressure is 0.5-2MPa, and reducing atmosphere is the low-carbon alkanes of hydrogen or C1-C3, preferred the latter.Adopt the fischer-tropsch synthetic catalyst of low-carbon alkanes reduction while reduction, suitable modification can be carried out to catalyst, improve the activity stability of catalyst.
Fischer-tropsch synthetic catalyst of the present invention, reduces CO in product while the conversion per pass that maintenance is high
2selective, solve CO in the on the low side and product of the ubiquitous conversion per pass of iron-base fischer-tropsch synthesis catalyst in prior art
2selective high problem.The present invention has the composite metal oxide ABO of perovskite structure
3-ypreparation process in, the change of preparation condition can have a strong impact on generation and the purity of perovskite structure.In all conditions control, choosing of sintering temperature is vital, although some catalyst composition of the prior art is more close with the present invention, because the crystalline structure of constituent content and inherence is obviously different, so do not have the performance of catalyst of the present invention.
Accompanying drawing explanation
Fig. 1 prepared by the embodiment of the present invention 1 have perovskite structure and structural formula is BaFeO
3-ythe X-ray diffractogram of composite metal oxide.
Detailed description of the invention
Further illustrate process and the effect of the inventive method below in conjunction with embodiment, but be not limited to following examples.Following weight content is all with the weighing scale of final catalyst.
Embodiment 1
Preparation contains the mixed aqueous solution of ferric nitrate and barium nitrate, is that 1.2:1 takes appropriate citric acid, in mixed aqueous solution, adds citric acid slowly by metal ion total amount mol ratio in citric acid and mixed aqueous solution, and dropping limit, limit is stirred.Stir after 5 hours, brown solution has dewatered and has become thick gel, is taken out by gel and puts in the drying box of 110 DEG C, dried overnight.Then take out dried predecessor, be placed in Muffle furnace constant temperature calcining 4 hours at 800 DEG C, obtain the composite metal oxide BaFeO with perovskite structure
3-y, adopt infusion process at composite metal oxide BaFeO
3-yupper load weight content is the auxiliary agent potassium of 10%, the active component iron of 40%, and 80 DEG C of dryings 8 hours, in 350 DEG C, roasting 4 hours obtained catalyst were designated as C-1, and evaluation result is in table 1.
Embodiment 2
The mixed aqueous solution of preparation containing calcium nitrate, manganese nitrate and barium nitrate, is that 2:1 takes appropriate citric acid by metal ion total amount mol ratio in citric acid and mixed aqueous solution, in mixed aqueous solution, adds citric acid slowly, and dropping limit, limit is stirred.Stir after 5 hours, brown solution has dewatered and has become thick gel, is taken out by gel and puts in the drying box of 110 DEG C, dried overnight.Then take out dried predecessor, be placed in Muffle furnace constant temperature calcining 6 hours at 700 DEG C, obtain the composite metal oxide CaFe with perovskite structure
0.9mn
0.1o
3-y, adopt infusion process at composite metal oxide CaFe
0.9mn
0.1o
3-yupper load weight content is the potassium of 10%, the active component iron of 40%, and 80 DEG C of dryings 8 hours, in 350 DEG C, roasting 4 hours obtained catalyst were designated as C-2, and evaluation result is in table 1.
Embodiment 3
The mixed aqueous solution of preparation containing barium nitrate, ferric nitrate and manganese nitrate, is that 2:1 takes appropriate citric acid by metal ion total amount mol ratio in citric acid and mixed aqueous solution, in mixed aqueous solution, adds citric acid slowly, and dropping limit, limit is stirred.Stir after 5 hours, brown solution has dewatered and has become thick gel, is taken out by gel and puts in the drying box of 110 DEG C, dried overnight.Then take out dried predecessor, be placed in Muffle furnace constant temperature calcining 6 hours at 700 DEG C, obtain the composite metal oxide BaFe with perovskite structure
0.9mn
0.1o
3-y, adopt infusion process at composite metal oxide BaFe
0.9mn
0.1o
3-yupper load weight content is the potassium of 10%, the active component iron of 40%, and 80 DEG C of dryings 8 hours, in 350 DEG C, roasting 4 hours obtained catalyst were designated as C-3, and evaluation result is in table 1.
Embodiment 4
The mixed aqueous solution of preparation containing barium nitrate, ferric nitrate and manganese nitrate, is that 4:1 takes appropriate citric acid by metal ion total amount mol ratio in citric acid and mixed aqueous solution, in mixed aqueous solution, adds citric acid slowly, and dropping limit, limit is stirred.Stir after 5 hours, brown solution has dewatered and has become thick gel, is taken out by gel and puts in the drying box of 110 DEG C, dried overnight.Then take out dried predecessor, be placed in Muffle furnace constant temperature calcining 8 hours at 600 DEG C, obtain the composite metal oxide BaMn with perovskite structure
0.15fe
0.85o
3-y, adopt infusion process at composite metal oxide BaMn
0.15fe
0.85o
3-yupper load weight content is the auxiliary agent potassium of 5%, the active component iron of 40%, and 80 DEG C of dryings 8 hours, roasting 4 hours obtained catalyst C-4 in 350 DEG C, evaluation result was in table 1.
Embodiment 5
The mixed aqueous solution of preparation containing manganese nitrate, calcium nitrate, is that 3:1 takes appropriate citric acid by metal ion total amount mol ratio in citric acid and mixed aqueous solution, in mixed aqueous solution, adds citric acid slowly, and dropping limit, limit is stirred.Stir after 5 hours, brown solution has dewatered and has become thick gel, is taken out by gel and puts in the drying box of 110 DEG C, dried overnight.Then take out dried predecessor, be placed in Muffle furnace constant temperature calcining 5 hours at 1000 DEG C, obtain the composite metal oxide CaMnO with perovskite structure
3-y, adopt infusion process at composite metal oxide CaMnO
3-yupper load weight content is the auxiliary agent potassium of 10%, the active component iron of 60%, and 80 DEG C of dryings 8 hours, in 350 DEG C, roasting 4 hours obtained catalyst were designated as C-5, and evaluation result is in table 1.
Comparative example 1
Conventional coprecipitation is adopted to obtain iron, calcium, the manganese composite metal oxide of non-perovskite structure, sintering temperature is 450 DEG C, then impregnation aids potassium, and obtained catalyst is designated as B1, in oxide, the weight content of barium, iron, potassium is with embodiment 5, and evaluation result is in table 1.
Carry out activity rating to catalyst prepared by above-described embodiment and comparative example, evaluation test is carried out in high pressure CSTR, using paraffin as solvent.First carry out reduction 5 hours to catalyst, reduction temperature is 650 DEG C, and wherein embodiment 4 adopts methane gas to reduce, and all the other adopt hydrogen reducing, and reduction pressure is 1.0Mpa.After reduction, catalyst is put into reactor and carry out Fischer-Tropsch synthesis, reaction actual conditions is 280 DEG C, 2000h
-1, 2.0MPa, H
2/ CO=2(mol ratio).The operation result of 200h is in table 1, and the conversion ratio of CO is conversion per pass.
Table 1 embodiment and comparative example fischer-tropsch synthetic catalyst evaluation result
Claims (11)
1. a fischer-tropsch synthetic catalyst, is characterized in that: described catalyst is by active component iron, the composite metal oxide BaMn with perovskite structure
1-xfe
xo
3-yand metal promoter potassium composition, wherein 0.85<x< 0.95; The composite metal oxide with perovskite structure containing weight content to be the active component iron of 10-80% and weight content be 10-70% in described catalyst.
2. catalyst according to claim 1, is characterized in that: the composite metal oxide with perovskite structure containing weight content to be the active component iron of 25-60% and weight content be 20%-60% in described catalyst.
3. the preparation method of the arbitrary described catalyst of claim 1 to 2, is characterized in that: comprise the preparation of the composite metal oxide with perovskite structure and active component iron and metal promoter potassium loading process.
4. method according to claim 3, it is characterized in that: with barium nitrate, ferric nitrate, manganese nitrate for presoma, with citric acid or ethylene glycol for complexing agent, wiring solution-forming mixing and stirring, then moisture evaporation is carried out, the colloidal sol of solution went from clear is transformed into the gel of thickness, final drying, roasting, obtained BaMn after roasting
1-xfe
xo
3-ycomposite metal oxide, wherein 0.85<x< 0.95.
5. method according to claim 4, is characterized in that: complexing agent and metal ion mol ratio are 1:1 ~ 8:1; Preparation and agitating solution are at 20 ~ 90 DEG C; Stir speed (S.S.) is 200 ~ 500rpm; Mixing time is 3 ~ 8 hours; Baking temperature is 60 ~ 200 DEG C; Drying time is 1 ~ 36 hour; Sintering temperature is 600 ~ 1000 DEG C, and roasting time is roasting 2 ~ 15 hours.
6. method according to claim 5, is characterized in that: complexing agent and metal ion mol ratio are 1:1 ~ 4:1; Preparation and agitating solution carry out at 50 ~ 70 DEG C; Stir speed (S.S.) is 300 ~ 400rpm; Mixing time is 4 ~ 6 hours; Baking temperature is 80 ~ 150 DEG C; Drying time is 8 ~ 24 hours; Sintering temperature is 700 ~ 900 DEG C, and roasting time is 3 ~ 8 hours.
7. the method according to right 3, is characterized in that: described active component and metal promoter loading process adopt infusion process.
8. the method according to right 7, is characterized in that: comprise drying and roasting process after dipping, and drying steps is dry 8-24 hour at 50-150 DEG C, and calcination steps is roasting 2-10 hour at 280-500 DEG C.
9. the method according to right 3, is characterized in that: at BaMn
1-xfe
xo
3-yupper employing equal-volume multiple maceration load active component iron and metal promoter potassium.
10. the method for reducing of the arbitrary described catalyst of claim 1-2, it is characterized in that: reduction temperature is 400 ~ 1000 DEG C, the recovery time is 1-5h, and reduction pressure is 0.5-2MPa, and reducing atmosphere is the low-carbon alkanes of hydrogen or C1-C3.
11. methods according to claim 10, is characterized in that: reduction temperature is 500-700 DEG C, and reducing atmosphere is the low-carbon alkanes of C1-C3.
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