CN103801324A - Precipitated iron catalyst for Fischer-Tropsch synthesis and preparation method thereof - Google Patents
Precipitated iron catalyst for Fischer-Tropsch synthesis and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a precipitated iron catalyst for Fischer-Tropsch synthesis and a preparation method thereof. The catalyst comprises the following components in parts by weight: 100 parts of Fe, 0.3-20 parts of Mn, 0.1-15 parts of Ti, 0.2-10 parts of Cu, 0.3-10 parts of K and 3-40 parts of SiO2. By optimizing the components in the catalyst and ratios, the final precipitated iron catalyst has good degree of sphericity, higher abrasion strength and high specific surface area. Besides, the preparation process has the advantages of mild conditions, higher CO conversion rate and reaction activity, high long chain hydrocarbon C<5+> selectivity, low byproduct CH4 and waste product CO2 selectivity, reasonable hydrocarbon product distribution and low contents of methane and carbon dioxide in the final product, is suitable for industrial production of oil products and wax obtained by virtue of Fischer-Tropsch synthesis, is economical, simple and convenient and can be used for continuously producing a microspheric precipitated iron manganese-titanium system catalyst for Fischer-Tropsch synthesis.
Description
Technical field
The present invention relates to Fischer-Tropsch synthesis technical field, in particular to a kind of precipitated iron Catalysts and its preparation method used for Fischer-Tropsch synthesis.
Background technology
Fischer-Tropsch is synthetic is with synthesis gas (CO+H
2) be raw material, this reaction raw materials synthesis gas can be obtained by conversion of natural gas or coal gasification, one of synthetic ICL for Indirect Coal Liquefaction technology take paraffin hydrocarbon as main liquid fuel under catalyst (being mainly iron-based and cobalt-based) and appropriate reaction condition.This technology is gained the name because of its initial development people Germanization scholar's F. Fischer and general the executing of H. Toro, i.e. synthetic the or F-T synthetic technology of Fischer-Tropsch.Fischer-tropsch synthetic catalyst is mainly divided into iron-based and cobalt-base catalyst, and wherein ferrum-based catalyst sulfur resistance is good, and activity of conversion is high, is specially adapted to coal based synthetic gas Fischer-Tropsch synthetic.Utilize the Fischer-Tropsch synthesis of coal based synthetic gas to realize the production ways to liquid fuel by coal, this technology is applicable to the few oily energy resource structure present situation of Chinese many coals very much, and therefore the exploitation of Fischer-Tropsch synthetic technology is significant to Chinese energy.
Fischer-Tropsch synthesis device can react with fixed bed, fluid bed or slurry state bed, wherein starches state bed technique advantage larger.In order to improve the transformation efficiency of synthesis gas, improve the selective of product, the development of new catalyst is being carried out all the time.
In iron manganese catalyst, the patent CN1495148A of Hydrocarbon Technology Co. of the U.S. has mentioned the skeletal iron catalyst of a kind of Fe of containing, Cu, K, Mn and surplus Al, this catalyst is that Fe, Cu, Mn, Al metal powder are heated to molten condition, mix rear quenching, again with alkali dissolution of metals Al, with the alcoholic solution dipping of potassium, the catalyst before being activated, this catalyst has higher synthesis gas activity of conversion and preferably middle cut is selective.But skeletal iron catalyst condition harshness not only while preparing is as high in temperature conditions, need to, by METAL HEATING PROCESS to high-temperature molten-state, in the time of washing, use again the alcoholic solution of potassium, cost is also higher, and economy is not as precipitated iron catalyst; And the catalytic activity of skeletal iron catalyst, olefine selective and stability are all short of to some extent, also exist the defect of undercapacity, finally cause the preparation energy consumption of this catalyst high, cost is high, less economical, cannot meet the requirement of industrialization FT catalyst-assembly.
Summary of the invention
The present invention aims to provide a kind of precipitated iron Catalysts and its preparation method used for Fischer-Tropsch synthesis, and this precipitated iron catalyst spherical degree used for Fischer-Tropsch synthesis is good, specific area is large, selectively good, intensity and active high of product component.
To achieve these goals, according to an aspect of the present invention, provide a kind of precipitated iron catalyst used for Fischer-Tropsch synthesis, in catalyst, each component comprises by weight: the Fe of 100 parts, the Mn of 0.3～20 part, the Ti of 0.1～15 part, the Cu of 0.2～10 part, and the SiO of the K of 0.3～10 part and 3～40 parts
2.
Further, in catalyst, each component comprises by weight: the Fe of 100 parts, the Mn of 0.5～15 part, the Ti of 0.5～12 part, the Cu of 0.5～10 part, and the SiO of the K of 0.3～8 part and 3.5～30 parts
2.
Further, in catalyst Fe with Fe
2o
3form exist, Mn exists with the form of MnO, Cu exists with the form of CuO, the specific area of catalyst is 140～250m
2/ g.
According to a further aspect in the invention, the preparation method of a kind of precipitated iron catalyst used for Fischer-Tropsch synthesis is provided, comprise the following steps: (1) is dissolved in the soluble metallic salt of Fe, Mn, Ti, Cu in deionized water, obtain metal salt solution, in metal salt solution, the weight ratio of metallic element is Fe:Mn:Ti:Cu=100:0.3～20:0.1～15:0.2～10, and the concentration of Fe ion is 0.3～2.5mol/L; (2) by metal salt solution and precipitant solution precipitation reaction, be precipitated slurry, will precipitate slurries filtration, washing, obtain co-precipitation filter cake; (3) in co-precipitation filter cake, add containing potassium soluble-salt, Ludox and/or contain potassium Ludox, the making beating that adds water, obtains Fe:K:SiO
2for the catalyst slurry of 100:0.3～10:3～40; And (4) are dry by catalyst slurry, roasting, is precipitated iron catalyst used for Fischer-Tropsch synthesis.
Further, in metal salt solution the weight ratio of each component be Fe:Mn:Ti:Cu=100:0.5～15:0.5～12:0.5～10, the concentration of Fe ion is 0.5～2.2mol/L, in catalyst slurry, the weight ratio of each component is Fe:K:SiO
2=100:0.3～8:3.5～30.
Further, in step (2), in precipitation reaction process, metal salt solution mixes with precipitant solution stream, and precipitation reaction obtains precipitation slurry.
Further, in the preparation method of catalyst used for Fischer-Tropsch synthesis: in step (2), metal salt solution and precipitant solution are precipitated at 40 ℃～85 ℃, be precipitated slurry, the pH that adjusts precipitation slurry is 5～10; To precipitate slurry and at 30 ℃～80 ℃, leave standstill aging 0～6h, and filter, wash, obtain co-precipitation filter cake; In step (3), in co-precipitation filter cake, add containing potassium soluble-salt, Ludox and/or contain after potassium Ludox, the making beating that adds water, the pH that adjusts catalyst slurry is 4.5～9; In step (4), catalyst slurry is dry in spray dryer, spray-dired hot-wind inlet place temperature is 210 ℃～330 ℃, and wind exhausting outlet place temperature is 92 ℃～120 ℃; Sintering temperature in step (4) is 280～550 ℃, and roasting time is 2.5～10h; The specific area of catalyst is 140～250m
2/ g.
Further, in step (2), first metal salt solution and precipitant solution are preheated to respectively to 40 ℃～85 ℃, then are to carry out precipitation reaction in the deionized water of 40～85 ℃ by its common temperature that flows into, the time of precipitation reaction is 5～70min.
Further, precipitant solution is the deionized water solution of ammonium carbonate, sodium carbonate, potash, saleratus, NaOH, potassium hydroxide or ammoniacal liquor, and the concentration of precipitant solution is 0.3～2mol/L, is preferably 0.5～1.5mol/L.
Further, in step (3), be one or more deionized water solution in potash, saleratus, potassium nitrate containing potassium soluble-salt; Ludox and containing SiO in potassium Ludox
2weight content be 5～50%.
Apply technical scheme of the present invention, by each component and proportioning in catalyst are in optimized selection, make final precipitated iron catalyst there is good sphericity, higher abrasion intensity, high-specific surface area.In addition, preparation process condition gentleness of the present invention, CO conversion ratio and reactivity are higher, long chain hydrocarbon C
5+selective high, byproduct CH
4with waste CO
2selectively low, hydrocarbon product distribute rationally, in end product, methane and carbon dioxide content is low, is applicable to the production of industrialized oil from Fischer-Tropsch synthesis, synthetic wax.This preparation technology's flow process economy, easy, can quantity-produced microspheroidal precipitation ferrimanganic titanium system fischer-tropsch synthetic catalyst.
Accompanying drawing explanation
The Figure of description that forms the application's a part is used to provide a further understanding of the present invention, and schematic description and description of the present invention is used for explaining the present invention, does not form inappropriate limitation of the present invention.In the accompanying drawings:
Fig. 1 shows according to the scanning electron microscope (SEM) photograph of the microspheroidal precipitated iron catalyst of a kind of exemplary embodiments of the present invention;
Fig. 2 shows according to the scanning electron microscope (SEM) photograph of the microspheroidal precipitated iron catalyst of another kind of exemplary embodiments of the present invention;
Fig. 3 shows according to the scanning electron microscope (SEM) photograph of the microspheroidal precipitated iron catalyst of another exemplary embodiments of the present invention; And
Fig. 4 shows according to the scanning electron microscope (SEM) photograph of the microspheroidal precipitated iron catalyst of another exemplary embodiments of the present invention.
The specific embodiment
It should be noted that, in the situation that not conflicting, the feature in embodiment and embodiment in the application can combine mutually.Describe below with reference to the accompanying drawings and in conjunction with the embodiments the present invention in detail.
The problems such as the activity that existing skeletal iron catalyst exists is low in order to solve, poor selectivity, the invention provides a kind of precipitated iron catalyst used for Fischer-Tropsch synthesis, in this catalyst, each component comprises by weight: the Fe of 100 parts, the Mn of 0.3～20 part, the Ti of 0.1～15 part, the Cu of 0.2～10 part, and the SiO of the K of 0.3～10 part and 3～40 parts
2.Preferably, the each component in catalyst comprises by weight: the Fe of 100 parts, the Mn of 0.5～15 part, the Ti of 0.5～12 part, the Cu of 0.5～10 part, and the SiO of the K of 0.3～8 part and 3.5～30 parts
2.
Be in optimized selection by the component to catalyst and proportioning, make final precipitated iron catalyst there is good sphericity, higher abrasion intensity and specific area.In addition, process conditions gentleness of the present invention, CO conversion ratio and reactivity are higher, long chain hydrocarbon C
5+selective high, byproduct CH
4with waste CO
2selectively low, hydrocarbon product distribute rationally, in end product, methane and carbon dioxide content is low, is applicable to the production of industrialized oil from Fischer-Tropsch synthesis, synthetic wax.This preparation technology's flow process economy, easy, can quantity-produced microspheroidal precipitation ferrimanganic titanium system fischer-tropsch synthetic catalyst,
In catalyst used for Fischer-Tropsch synthesis provided by the present invention, Ti element add the activated centre that is conducive to dispersed catalyst, improve olefine selective and the catalytic activity of catalyst, and can improve stability and the intensity of catalyst.SiO
2add the abrasion intensity that has improved catalyst, reduced rate of wear, make precipitated iron catalyst be more suitable for the application in paste state bed reactor.And simultaneously, metal element Ti and metallic element Fe, Mn, Cu, K collaborative is added on when improving the specific area of catalyst and decentralization, can also improve conversion ratio and the selectivity of light olefin of the synthetic middle carbon monoxide of Fischer-Tropsch, more be conducive to improve the stability of catalyst, thereby guarantee efficiently carrying out of Fischer-Tropsch building-up process.
In catalyst used for Fischer-Tropsch synthesis provided by the present invention, metallic element can exist in a variety of forms, as existed with the form of simple substance, carbide, nitride or oxide.Wherein be preferably with the form of oxide and exist.Metallic element forms the mode existing with oxide, can improve the catalytic activity of catalyst, and the preparation of metal oxide is relatively easy, is conducive to reduce the production cost of catalyst.Wherein, in catalyst Fe with Fe
2o
3form exist, Mn exists with the form of MnO, Cu exists with the form of CuO.
Its granularity of catalyst provided by the present invention and specific area can reach the level of existing catalyst, are even better than existing catalyst.Preferably, the specific area of the prepared catalyst of the present invention is 140～250m
2/ g.In this catalyst due to Fe
3o
4the existence of resistate phase has weakened reorganization and the division that the physical arrangement of catalyst in the synthetic reduction reaction of Fischer-Tropsch causes because of its chemical phase transformation, increase the long-term run stability of catalyst, the agent structure of catalyst has been played a part to carrier and active balancing each other; The existence of Si element has increased physical stability and the mechanical strength of catalyst, has improved abrasion intensity.By the collaborative interpolation of metal element Ti and metallic element Fe, Mn, Cu, K and Si, specific area, decentralization, abrasion intensity and the stability of catalyst are improved, the specific area of catalyst is controlled in above-mentioned scope, be conducive to the absorption of course of reaction Raw gas, thereby effectively improve the catalytic activity of catalyst, guarantee synthetic efficiently the carrying out of Fischer-Tropsch.
According to a further aspect in the invention, a kind of method of preparing above-mentioned microspheroidal precipitated iron catalyst is provided, comprise the following steps: (1) is dissolved in the soluble metallic salt of Fe, Mn, Ti, Cu in deionized water, obtain metal salt solution, in metal salt solution, the weight ratio of metallic element is Fe:Mn:Ti:Cu=100:0.3～20:0.1～15:0.2～10, and the concentration of Fe ion is 0.3～2.5mol/L; (2) by metal salt solution and precipitant solution precipitation reaction, be precipitated slurry, will precipitate slurries filtration, washing, obtain co-precipitation filter cake; (3) in co-precipitation filter cake, add containing potassium soluble-salt, Ludox and/or contain potassium Ludox, the making beating that adds water, obtains Fe:K:SiO
2for the catalyst slurry of 100:0.3～10:3～40; And (4) are dry by catalyst slurry, roasting, is precipitated iron catalyst used for Fischer-Tropsch synthesis.
This catalyst used for Fischer-Tropsch synthesis provided by the present invention has adopted the precipitation method to be prepared, these precipitation method are by adjusting material rate and batch mixing step, make formed catalyst there is better advantage at aspects such as sphericity, specific area, pore volume, catalytic activity and product selectivity, while being applied to Fischer-Tropsch compound probability, CO conversion ratio is high, CH
4and CO
2selectively low, long chain hydrocarbon C
5+selective height and hydrocarbon product distribute more reasonable.
Preferably, in metal salt solution, the weight ratio of each component is Fe:Mn:Ti:Cu=100:0.5～15:0.5～12:0.5～10, and the concentration of Fe ion is 0.5～2.2mol/L, and in catalyst slurry, the weight ratio of each component is Fe:K:SiO
2=100:0.3～8:3.5～30.
In preparation method provided by the present invention, soluble metallic salt includes, but are not limited to nitrate, sulfate and the oxalates of metal, if its in deionized water, have good dissolubility just can, particularly, the raw material of Fe is preferably Fe (NO
3)
3; The raw material of Mn is preferably Mn (NO
3)
2; The raw material of Ti is preferably titanium potassium oxalate (K
2tiO (C
2o
4)
2); The raw material of Cu is preferably Cu (NO
3)
2or CuCl
2.
In preparation method provided by the present invention, in step (2), precipitant solution includes but not limited to deionized water solution a kind of in ammonium carbonate, sodium carbonate, potash, saleratus, NaOH, potassium hydroxide and ammoniacal liquor, be preferably ammonium carbonate or sodium carbonate, the concentration of precipitant solution is 0.3～2mol/L, is preferably 0.5～1.5mol/L.
When precipitation reaction, concrete intermediate processing can be and flow to mix and carry out precipitation reaction, or precipitant solution is slowly flowed into and in metal salt solution, produces precipitation, or metal salt solution is slowly flowed into and in precipitant solution, produces precipitation.Wherein be preferably and flow to mix and carry out precipitation reaction.More preferably, in step (2), first metal salt solution and precipitant solution are preheated to respectively to 40 ℃～80 ℃, then are to carry out precipitation reaction in the deionized water of 40～80 ℃ by its common temperature that flows into, wherein the time of precipitation reaction is 5～70min.Under the condition stirring, carry out precipitation reaction, until precipitation reaction a period of time, making solution reach precipitation pH can finish.
Adopt the mode mixed precipitation of parallel-flow precipitation make soluble metallic salt and precipitant mix more even, react more complete, can make catalyst there is larger specific area, thereby improve the catalytic activity of catalyst, avoid that ferric ions precipitation is inhomogeneous can not get stablizing Fe simultaneously
2o
3situation occur.The present invention is chosen in and under the state of preheating, carries out and flow mixing, especially jointly flow in the deionized water of preheating, can guarantee to react and carry out in stable temperature conditions, make the crystal phase structure of catalyst more complete, performance is more stable, because parallel-flow precipitation can be produced continuously, production efficiency, Reaction time shorten are greatly improved.
A preferred embodiment of the invention, is that metal salt solution and precipitant solution are precipitated at 40 ℃～85 ℃ in step (2), is precipitated slurry, and the pH that adjusts precipitation slurry is 5～10; To precipitate slurry and at 30 ℃～80 ℃, leave standstill aging 0～6h, and filter, wash, obtain co-precipitation filter cake; In co-precipitation filter cake, add containing potassium soluble-salt, Ludox and/or contain after potassium Ludox, the making beating that adds water, the pH that adjusts catalyst slurry is 4.5～9; Catalyst slurry is dry in spray dryer, and spray-dired hot-wind inlet place temperature is 210 ℃～330 ℃, and wind exhausting outlet place temperature is 92 ℃～120 ℃; Sintering temperature in step S4 is 280～550 ℃, and roasting time is 2.5～10h; The specific area of catalyst is 140～250m
2/ g.
Leave standstill aging step and contribute to obtain all even stable Fe
3o
4crystalline phase particle, and then obtained stability and active precipitated iron catalyst preferably.The salt-mixture precipitation slurry obtaining is carried out to separating for several times and washing, obtain filtrate and filter cake, control the content of the free state water in filter cake between 50～95%, the impurity ion content such as electrical conductivity and acid group are (<1000 μ S) in allowed band.
The present invention preferably adopts pH to 5～10 of precipitant solution adjustment precipitation slurry, but be not limited to this, also can adopt the acid of some routines and/or alkali to adjust, but acid and/or the alkali of these routines are more responsive, make the pH amplitude of variation of mixing salt solution in precipitation process larger, be difficult for controlling, therefore, the present invention preferably adopts sodium carbonate and ammonium carbonate accurately to adjust lentamente as precipitant solution, is finally precipitated slurry.Although the present invention has added precipitating reagent, the foreign ion forming can be removed totally in follow-up calcination steps, also has advantage with low cost.
The present invention adds containing potassium soluble-salt, Ludox and/or contains potassium Ludox in the co-precipitation filter cake obtaining, and the making beating 5～50min that adds water, obtains catalyst slurry.Be preferably one or more the deionized water solution in potash, saleratus and potassium nitrate containing potassium soluble-salt; Ludox and containing SiO in potassium Ludox
2weight content be 5～50%; Containing SiO in potassium Ludox
2: K
2the mass ratio of O is 1.2:1～4:1.Ludox of the present invention and be business Ludox containing potassium Ludox, adds containing can no longer adding other solution containing potassium ion after potassium Ludox, this be because add provide on the one hand SiO containing potassium Ludox
2, the potassium element in precipitated iron catalyst is provided on the other hand.Adopt SiO
2the weight content Ludox that is 5～50% and can either guarantee the content of silicon in final catalyst containing potassium Ludox, again can be because of SiO
2the higher system viscosity that makes of content is too large, the uniformity that impact mixes.Except controlling Ludox and containing SiO in potassium Ludox
2content outside, preferably in Ludox, the content of foreign ion is controlled at below 0.1%, can not affect like this activity of final catalyst.After adding Ludox, high-speed stirred is even, obtains catalyst slurry.
For the viscosity of catalyst slurry is controlled within the scope of 500cP～5000cP, so that next step is dry, according to a kind of exemplary embodiment of the present invention, the solid content of adjusting catalyst slurry is 7%～35%.
In preparation method provided by the invention, control by the proportion to each raw material, thereby improved the catalytic activity of catalyst.In addition, also the concrete technology in each preparation process is optimized, particularly, makes catalyst there is more complete structure and crystalline phase by precipitation temperature, precipitation pH and the sedimentation time controlled in precipitation process; Make catalyst there is more excellent reducing property and catalytic performance by controlling sintering temperature and roasting time, meanwhile, improve sintering temperature and can promote hydrocarbon product to the skew of heavy hydrocarbon direction, thereby adjust the distribution of product.
Precipitated iron catalyst used for Fischer-Tropsch synthesis for extensive continuous industrial production prepared by the present invention is compared with traditional precipitated iron catalyst, there is the advantage that good sphericity and surface smoothness are high, particle diameter is that the yield rate of 2～180 μ m reaches more than 88%, rate of wear is lower than 5%/h, catalyst after roasting has higher specific area, up to 140～250m
2/ g, pore volume is 0.4～0.65cm
3/ g.Compared with existing other precipitated iron catalyst, specific area and the particle size catalyst in above-mentioned scope has good activity and chemical physical stability, can be applicable to preferably gas-liquid-solid phase reaction device.
Further illustrate beneficial effect of the present invention below in conjunction with specific embodiment.
Take nine water ferric nitrate 40.4kg, manganese nitrate (Mn (NO
3)
24H
2o) 3.43kg, copper nitrate (Cu (NO
3)
23H
2o) 0.8kg, oxalic acid dihydrate titanium potassium (K
2tiO (C
2o
4)
22H
2o) 2.43kg, adds deionized water dissolving, is made into Fe concentration 2.0mol/L metal salt solution, is preheated to 70 ℃.Get sodium carbonate 19kg, add deionized water dissolving, being configured to concentration is the sodium carbonate precipitant solution of 1.0mol/L, is preheated to 70 ℃.
By metal salt solution and precipitant solution and flow into and fill in the reaction beaker of 70 ℃ of deionized waters of 300mL, keeping temperature is to carry out precipitation reaction under 70 ℃ and the state that stirs.Be controlled at 6.0 ± 0.3 o'clock until pH, finish to stir, wherein the precipitation reaction time is 5min, is precipitated slurry.To precipitate slurry aging 0.5h at 80 ℃, filtration, washed twice obtain co-precipitation filter cake.
By even the co-precipitation filter cake stirring to pulp that adds water, and add SiO
2weight content is the potash mixed liquor that 5% Ludox and concentration are 0.9mol/L, obtains catalyst slurry, adjusts the pH to 7.0 of catalyst slurry, stirs 20min, filters and makes Fe in filter cake, K, SiO
2gross weight than for Fe:K:SiO
2=100:3:15.
In filter cake, add pure water making beating, the solid content of adjusting catalyst slurry is 28wt%.Catalyst slurry is sent into spraying in spray dryer to be dried, spraying drying condition is that hot-wind inlet place temperature is 280 ℃, 102 ℃ of wind exhausting outlet place temperature, atomization rotating speed 10000rpm, within 50 minutes, complete charging and moulding, spray dried catalyst in Muffle furnace in 550 ℃ of roasting 2.5h, obtain finished product, be designated as catalyst 1.The ESEM of catalyst 1 is shown in Fig. 1, and as can be seen from Figure 1 this catalyst spherical degree is high, without burr, and shape ideal, granularity is moderate.
ICP(inductively coupled plasma spectrum generator) analysis result shows that the weight ratio of each component in catalyst 1 consists of Fe:Mn:Ti:Cu:K:SiO
2=100:6.8:5.9:3.8:3:15.
Embodiment 2
Take nine water ferric nitrate 40.4kg, manganese nitrate (Mn (NO
3)
24H
2o) 0.8kg, copper nitrate (Cu (NO
3)
23H
2o) 1.1kg, oxalic acid dihydrate titanium potassium (K
2tiO (C
2o
4)
22H
2o) 1.0kg, adds deionized water dissolving, and the concentration that is made into Fe is 2.2mol/L metal salt solution, is preheated to 60 ℃.Take ammonium carbonate solid 35kg, add deionized water dissolving, being mixed with concentration is the ammonium carbonate precipitant solution of 0.7mol/L, is preheated to 35 ℃.
Metal salt solution and precipitant solution are also flowed into and filled in the reaction beaker of 40 ℃ of deionized waters of 25kg, maintain the temperature at 40 ℃ and stir state under carry out precipitation reaction, be precipitated slurry, the precipitation reaction time is 70 minutes, adjust pH to 8.5 ± 0.3 of precipitation slurry, aging 3.5h at 60 ℃, filtration, washing obtain co-precipitation filter cake three times.
By even the co-precipitation filter cake stirring to pulp that adds water, and add SiO
2weight content is the potassium nitrate that 50% Ludox and concentration are 1.8mol/L, obtains catalyst slurry, adjusts the pH to 6.0 of catalyst slurry, stirs 20min, filters and makes Fe in filter cake, K, SiO
2gross weight than for Fe:K:SiO
2=100:1.5:8.
In filter cake, add pure water making beating, the solid content of adjusting catalyst slurry is 18wt%.Catalyst slurry is sent into spraying in spray dryer to be dried, spraying drying condition is that hot-wind inlet place temperature is 320 ℃, 92 ℃ of wind exhausting outlet place temperature, atomization rotating speed 8000rpm, within 50 minutes, complete charging and moulding, spray dried catalyst at 460 ℃ of roasting 5h, obtain finished product, be designated as catalyst 2.The ESEM of catalyst 2 is shown in Fig. 2, and as can be seen from Figure 2 this catalyst spherical degree is high, without burr, and shape ideal, granularity is moderate.
ICP(inductively coupled plasma spectrum generator) analysis result shows that the weight ratio of each component in catalyst 2 consists of Fe:Mn:Ti:Cu:K:SiO
2=100:3.1:2.4:5.2:1.5:8.
Embodiment 3
Take nine water ferric nitrate 40.4kg, manganese nitrate (Mn (NO
3)
24H
2o) 1.3kg, copper nitrate (Cu (NO
3)
23H
2o) 0.7kg, oxalic acid dihydrate titanium potassium (K
2tiO (C
2o
4)
22H
2o) 0.38kg, adds deionized water dissolving, and the concentration that is made into Fe is 1.6mol/L metal salt solution, is preheated to 80 ℃.Weighing sodium carbonate 28kg, adds deionized water dissolving, is mixed with the precipitant solution that concentration is 2.0mol/L, is preheated to 80 ℃.
Metal salt solution and precipitant solution are also flowed into and filled in the reaction beaker of 80 ℃ of deionized waters of 35kg, maintain the temperature at 80 ℃, under the state stirring, carry out precipitation reaction, be precipitated slurry, adjust pH to 7.5 ± 0.3 of precipitation slurry, not aging direct filtration, washing obtain co-precipitation filter cake three times.
By even the co-precipitation filter cake stirring to pulp that adds water, and add SiO
2weight content is the potassium nitrate that 28% Ludox and concentration are 1mol/L, obtains catalyst slurry, adjusts the pH to 9.0 of catalyst slurry, stirs 12min, filters and makes Fe in filter cake, K, SiO
2gross weight than for Fe:K:SiO
2=100:5:25.
In filter cake, add pure water making beating, the solid content of adjusting catalyst slurry is 30wt%.Catalyst slurry is sent into spraying in spray dryer to be dried, spraying drying condition is that hot-wind inlet place temperature is 260 ℃, 115 ℃ of wind exhausting outlet place temperature, atomization rotating speed 8000rpm, within 50 minutes, complete charging and moulding, spray dried catalyst at 500 ℃ of roasting 4h, obtain finished product, be designated as catalyst 3.The ESEM of catalyst 3 is shown in Fig. 3, and as can be seen from Figure 3 this catalyst spherical degree is high, without burr, and shape ideal, granularity is moderate.
ICP(inductively coupled plasma spectrum generator) analysis result shows that the weight ratio of each component in catalyst 3 consists of Fe:Mn:Ti:Cu:K:SiO
2=100:5.1:0.9:3.3.:5:25.
Embodiment 4
Take nine water ferric nitrate 40.4kg, manganese nitrate (Mn (NO
3)
24H
2o) 1.52kg, copper nitrate (Cu (NO
3)
23H
2o) 0.5kg, oxalic acid dihydrate titanium potassium (K
2tiO (C
2o
4)
22H
2o) 1.14kg, adds deionized water dissolving, and the concentration that is made into Fe is 0.5mol/L metal salt solution, is preheated to 80 ℃.Weighing sodium carbonate 20kg, adds deionized water dissolving, is mixed with the precipitant solution that concentration is 1.5mol/L, is preheated to 50 ℃.
Precipitant solution is joined to precipitation reaction in mixed salt solution, maintains the temperature at 80 ℃, be precipitated slurry, adjust pH to 6.0 ± 0.3 of precipitation slurry, 50 ℃ aging 2.5 hours, filter, washing obtains co-precipitation filter cake.
By even the co-precipitation filter cake stirring to pulp that adds water, and add SiO
2weight content be 30% containing potassium Ludox, obtain catalyst slurry, adjust the pH to 5.0 of catalyst slurry, stir 22min, filter and make Fe in filter cake, K, SiO
2gross weight than for Fe:K:SiO
2=100:4:12.
In filter cake, add pure water making beating, the solid content of adjusting catalyst slurry is 33wt%.Catalyst slurry is sent into spraying in spray dryer to be dried, spraying drying condition is that hot-wind inlet place temperature is 210 ℃, 120 ℃ of wind exhausting outlet place temperature, atomization rotating speed 8000rpm, within 50 minutes, complete charging and moulding, spray dried catalyst at 280 ℃ of roasting 10h, obtain finished product, be designated as catalyst 4.The ESEM of catalyst 4 is shown in Fig. 4, and as can be seen from Figure 4 this catalyst spherical degree is relatively poor, and shape is not very desirable.
ICP(inductively coupled plasma spectrum generator) analysis result shows that the weight ratio of each component in catalyst 3 consists of Fe:Mn:Ti:Cu:K:SiO
2=100:6:2.8:2.3.:4:12.
Embodiment 5
Take nine water ferric nitrate 40.4kg, manganese nitrate (Mn (NO
3)
24H
2o) 2.0kg, copper nitrate (Cu (NO
3)
23H
2o) 0.954kg, oxalic acid dihydrate titanium potassium (K
2tiO (C
2o
4)
22H
2o) 4.64kg, adds deionized water dissolving, and the concentration that is made into Fe is 2.3mol/L metal salt solution, is preheated to 40 ℃.Take potash 23kg, add deionized water dissolving, being mixed with concentration is the sodium carbonate precipitant solution of 1.8mol/L, is preheated to 40 ℃.
Metal salt solution and precipitant solution are also flowed into and filled in the reaction beaker of 40 ℃ of deionized waters of 25kg, maintain the temperature at 40 ℃, under the state stirring, carry out precipitation reaction, be precipitated slurry, the precipitation reaction time is 37 minutes, adjust pH to 7.0 ± 0.3 of precipitation slurry, aging 3.5h at 60 ℃, filtration, washing obtain co-precipitation filter cake three times.
By even the co-precipitation filter cake stirring to pulp that adds water, and add SiO
2weight content is the solution of potassium carbonate that 20% Ludox and concentration are 2.5mol/L, obtains catalyst slurry, adjusts the pH to 5.5 of catalyst slurry, stirs 30min, filters and makes Fe in filter cake, K, SiO
2gross weight than for Fe:K:SiO
2=100:2.5:22.
In filter cake, add pure water making beating, the solid content of adjusting catalyst slurry is 25wt%.Catalyst slurry is sent into spraying in spray dryer to be dried, spraying drying condition is that hot-wind inlet place temperature is 300 ℃, 102 ℃ of wind exhausting outlet place temperature, atomization rotating speed 9000rpm, within 50 minutes, complete charging and moulding, spray dried catalyst at 520 ℃ of roasting 4.5h, obtain finished product, be designated as catalyst 5.
ICP(inductively coupled plasma spectrum generator) analysis result shows that the weight ratio of each component in catalyst 5 consists of Fe:Mn:Ti:Cu:K:SiO
2=100:7.9:11.2:4.5:2.5:22.
Embodiment 6
Take nine water ferric nitrate 40.4kg, manganese nitrate (Mn (NO
3)
24H
2o) 0.12kg, copper nitrate (Cu (NO
3)
23H
2o) 0.1kg, oxalic acid dihydrate titanium potassium (K
2tiO (C
2o
4)
22H
2o) 0.2kg, adds deionized water dissolving, and the concentration that is made into Fe is 0.5mol/L metal salt solution, is preheated to 60 ℃.Take saleratus 38kg, add deionized water dissolving, being mixed with concentration is the sodium carbonate precipitant solution of 0.5mol/L, is preheated to 60 ℃.
Metal salt solution and precipitant solution are also flowed into and filled in the reaction beaker of 60 ℃ of deionized waters of 30g, wherein the flow velocity of metal salt solution is 4L/min, maintain the temperature at 60 ℃, under the state stirring, carry out precipitation reaction, be precipitated slurry, adjust pH to 10.0 ± 0.3 of precipitation slurry, aging 6h at 60 ℃, filtration, washing obtain co-precipitation filter cake three times.
By even the co-precipitation filter cake stirring to pulp that adds water, and to add SiO2 weight content be the potassium nitrate solution that 30% Ludox and concentration are 2.5mol/L, obtain catalyst slurry, adjust the pH to 9 of catalyst slurry, stir 30min, filter and make Fe in filter cake, K, SiO
2gross weight than for Fe:K:SiO
2=100:0.3:3.5.
In filter cake, add pure water making beating, the solid content of adjusting catalyst slurry is 7wt%.Catalyst slurry is sent into spraying in spray dryer to be dried, spraying drying condition is that hot-wind inlet place temperature is 330 ℃, 92 ℃ of wind exhausting outlet place temperature, atomization rotating speed 9000rpm, within 50 minutes, complete charging and moulding, spray dried catalyst at 280 ℃ of roasting 4.5h, obtain finished product, be designated as catalyst 6.
ICP(inductively coupled plasma spectrum generator) analysis result shows that the weight ratio of each component in catalyst 6 consists of Fe:Mn:Ti:Cu:K:SiO
2=100:0.5:0.5:0.5:0.3:3.5.
Embodiment 7
Take nine water ferric nitrate 40.4kg, manganese nitrate (Mn (NO
3)
24H
2o) 3.75kg, copper nitrate (Cu (NO
3)
23H
2o) 2kg, oxalic acid dihydrate titanium potassium (K
2tiO (C
2o
4)
22H
2o) 4.8kg, adds deionized water dissolving, and the concentration that is made into Fe is 0.3mol/L metal salt solution, is preheated to 85 ℃.Take saleratus 15kg, add deionized water dissolving, be mixed with the precipitant solution that concentration is 0.5mol/L, be preheated to 85 ℃.
Metal salt solution and precipitant solution are also flowed into and filled in the reaction beaker of 85 ℃ of deionized waters of 30g, maintain the temperature at 85 ℃, under the state stirring, carry out precipitation reaction, the precipitation reaction time is 50 minutes, be precipitated slurry, adjust pH to 5.0 ± 0.3 of precipitation slurry, aging 6h at 85 ℃, filtration, washing obtain co-precipitation filter cake three times.
By even the co-precipitation filter cake stirring to pulp that adds water, and add SiO
2weight content is the potassium nitrate solution that 30% Ludox and concentration are 0.8mol/L, obtains catalyst slurry, adjusts the pH to 4.5 of catalyst slurry, stirs 30min, filters and makes Fe in filter cake, K, SiO
2gross weight than for Fe:K:SiO
2=100:8:30.
In filter cake, add pure water making beating, the solid content of adjusting catalyst slurry is 35wt%.Catalyst slurry is sent into spraying in spray dryer to be dried, spraying drying condition is that hot-wind inlet place temperature is 330 ℃, 92 ℃ of wind exhausting outlet place temperature, atomization rotating speed 9000rpm, within 50 minutes, complete charging and moulding, spray dried catalyst at 280 ℃ of roasting 4.5h, obtain finished product, be designated as catalyst 7.
ICP(inductively coupled plasma spectrum generator) analysis result shows that the weight ratio of each component in catalyst 6 consists of Fe:Mn:Ti:Cu:K:SiO
2=100:15:12:10:8:30.
Embodiment 8
Take nine water ferric nitrate 40.4kg, manganese nitrate (Mn (NO
3)
24H
2o) 0.08kg, copper nitrate (Cu (NO
3)
23H
2o) 0.05kg, titanyl sulfate (TiOSO
4) 0.02kg adds deionized water dissolving, the concentration that is made into Fe is 0.3mol/L metal salt solution, is preheated to 85 ℃.Take sodium acid carbonate 18kg, add deionized water dissolving, be mixed with the precipitant solution that concentration is 0.5mol/L, be preheated to 85 ℃.
Metal salt solution and precipitant solution are also flowed into and filled in the reaction beaker of 85 ℃ of deionized waters of 30g, maintain the temperature at 85 ℃, under the state stirring, carry out precipitation reaction, be precipitated slurry, wherein the precipitation reaction time is 20 minutes, adjust pH to 6.0 ± 0.3 of precipitation slurry, aging 6h at 85 ℃, filtration, washing obtain co-precipitation filter cake three times.
By even the co-precipitation filter cake stirring to pulp that adds water, and add SiO
2weight content is the potassium nitrate solution that 28% Ludox and concentration are 0.8mol/L, obtains catalyst slurry, adjusts the pH to 5.0 of catalyst slurry, stirs 30min, filters and makes Fe in filter cake, K, SiO
2gross weight than for Fe:K:SiO
2=100:0.3:3.
In filter cake, add pure water making beating, the solid content of adjusting catalyst slurry is 21wt%.Catalyst slurry is sent into spraying in spray dryer to be dried, spraying drying condition is that hot-wind inlet place temperature is 270 ℃, 106 ℃ of wind exhausting outlet place temperature, atomization rotating speed 9000rpm, within 50 minutes, complete charging and moulding, spray dried catalyst at 415 ℃ of roasting 2.5h, obtain finished product, be designated as catalyst 8.
ICP(inductively coupled plasma spectrum generator) analysis result shows that the weight ratio of each component in catalyst 8 consists of Fe:Mn:Ti:Cu:K:SiO
2=100:0.3:0.1:0.2:0.3:3.
Embodiment 9
Take nine water ferric nitrate 40.4kg, manganese nitrate (Mn (NO
3)
24H
2o) 5kg, copper nitrate (Cu (NO
3)
23H
2o) 2.1kg, oxalic acid dihydrate titanium potassium (K
2tiO (C
2o
4)
22H
2o) 6.2kg, adds deionized water dissolving, and the concentration that is made into Fe is 0.3mol/L metal salt solution, is preheated to 85 ℃.Take sodium acid carbonate 18kg, add deionized water dissolving, be mixed with the precipitant solution that concentration is 0.5mol/L, be preheated to 85 ℃.
Metal salt solution and precipitant solution are also flowed into and filled in the reaction beaker of 85 ℃ of deionized waters of 30g, maintain the temperature at 85 ℃, under the state stirring, carry out precipitation reaction, be precipitated slurry, wherein the precipitation reaction time is 20 minutes, adjust pH to 6.0 ± 0.3 of precipitation slurry, aging 6h at 85 ℃, filtration, washing obtain co-precipitation filter cake three times.
By even the co-precipitation filter cake stirring to pulp that adds water, and add SiO
2weight content is the potassium nitrate solution that 28% Ludox and concentration are 0.8mol/L, obtains catalyst slurry, adjusts the pH to 5.0 of catalyst slurry, stirs 30min, filters and makes Fe in filter cake, K, SiO
2gross weight than for Fe:K:SiO
2=100:10:40.
In filter cake, add pure water making beating, the solid content of adjusting catalyst slurry is 21wt%.Catalyst slurry is sent into spraying in spray dryer to be dried, spraying drying condition is that hot-wind inlet place temperature is 270 ℃, 106 ℃ of wind exhausting outlet place temperature, atomization rotating speed 9000rpm, within 50 minutes, complete charging and moulding, spray dried catalyst at 415 ℃ of roasting 2.5h, obtain finished product, be designated as catalyst 9.
ICP(inductively coupled plasma spectrum generator) analysis result shows that the weight ratio of each component in catalyst 9 consists of Fe:Mn:Ti:Cu:K:SiO
2=100:20:15:10:10:40.
Comparative example 1
Take nine water ferric nitrate 40.4kg, manganese nitrate (Mn (NO
3)
24H
2o) 5.9kg, copper nitrate (Cu (NO
3)
23H
2o) 2.6kg, oxalic acid dihydrate titanium potassium (K
2tiO (C
2o
4)
22H
2o) 7.5kg, adds deionized water dissolving, and the concentration that is made into Fe is 0.3mol/L metal salt solution, is preheated to 85 ℃.Take sodium acid carbonate 18kg, add deionized water dissolving, be mixed with the precipitant solution that concentration is 0.5mol/L, be preheated to 85 ℃.
Metal salt solution and precipitant solution are also flowed into and filled in the reaction beaker of 85 ℃ of deionized waters of 30g, maintain the temperature at 85 ℃, under the state stirring, carry out precipitation reaction, be precipitated slurry, wherein the precipitation reaction time is 20 minutes, adjust pH to 6.0 ± 0.3 of precipitation slurry, aging 6h at 85 ℃, filtration, washing obtain co-precipitation filter cake three times.
By even the co-precipitation filter cake stirring to pulp that adds water, and add SiO
2weight content is the potassium nitrate solution that 28% Ludox and concentration are 0.8mol/L, obtains catalyst slurry, adjusts the pH to 5.0 of catalyst slurry, stirs 30min, filters and makes Fe in filter cake, K, SiO
2gross weight than for Fe:K:SiO
2=100:0.1:2.
In filter cake, add pure water making beating, the solid content of adjusting catalyst slurry is 21wt%.Catalyst slurry is sent into spraying in spray dryer to be dried, spraying drying condition is that hot-wind inlet place temperature is 270 ℃, 106 ℃ of wind exhausting outlet place temperature, atomization rotating speed 9000rpm, within 50 minutes, complete charging and moulding, spray dried catalyst at 415 ℃ of roasting 2.5h, obtain finished product, this catalyst is designated as 1b.
ICP(inductively coupled plasma spectrum generator) analysis result shows that the weight ratio of each component in catalyst 1b consists of Fe:Mn:Ti:Cu:K:SiO
2=100:23:18:12:0.1:2.
The precipitated iron catalyst of preparing in embodiment 1～9 and comparative example 1 is carried out to performance test.Wherein, adopt laser particle analyzer determination method to measure the size distribution of microspheroidal precipitated iron catalyst, adopt low-temperature nitrogen adsorption method to measure BET specific area and the pore volume of precipitated iron catalyst.
Adopt standard A STMD5757-95 air gunite to measure the rate of wear of precipitated iron catalyst, put into air injection tube by standard volume catalyst, impact microspheroidal precipitated iron catalyst with high-voltage high-speed air stream, make between catalyst granules and particle, mutual frictional impact between catalyst granules and metallic walls, the fine powder grinding off is taken away by air-flow, weighs the quality of the certain above catalyst of particle diameter in test front and back, calculates rate of wear.Quality/the testing time of the above catalyst of standard particle diameter before rate of wear=(quality of the rear above catalyst of standard particle diameter of the quality-test of the above catalyst of standard particle diameter before test)/test.
Wherein in embodiment 1～9 and comparative example 1 performance test of catalyst in table 1.
The performance indications of table 1. precipitated iron catalyst
Data from table 1 can find out, compared with comparative example 1, the size distribution of the precipitated iron catalyst of preparing in embodiment 1～9 is concentrated, and specific area is large, pore volume is moderate, and intensity is high, has good attrition resistance.Especially catalyst 1,2,3 and 5 has best performance, the Joint Production of gasoline, diesel oil and high-quality paraffin in the Fischer-Tropsch compound probability of applicable extensive oar state bed.
In the time being applied to Fischer-Tropsch synthesis, there is good effect in order to further illustrate the catalyst that adopts method of the present invention to prepare, the evaluation test of Fischer-Tropsch synthesis is carried out on fixed bed reactors, get the catalyst in embodiment 1～9 and comparative example 1, grain diameter is 30～150 μ m, H at 250 ℃
2/ CO=1.5, unstripped gas speed is 3000 ± 20mL/gcal/h, reaction pressure 1.6MPa.Wherein the reaction time be the evaluation result of 50 hours in table 2, the reaction time is that the evaluation result of 450 hours is in table 3.
The Fischer-Tropsch fixed bed evaluation result of table 2. precipitated iron catalyst
Table 3
From table 2 and table 3, can find out, compared with catalyst 1b, adopt the precipitated iron catalyst in the catalyst 1～9 that preparation technology of the present invention obtains to move for a long time, wherein the conversion ratio of CO is higher, all approach or exceed 80%, carbon monoxide be converted into carbon dioxide selectively all below 27.5%, show that the catalytic activity of this catalyst is very high; The methane selectively of catalyst all below 4%, C
5+selectively reach more than 80% lower carbon number hydrocarbons (C
2～C
4) middle olefine selective is all higher than 55%, low-carbon alkene relative amount is high.In addition, can find out through the response data of 400 hours and the response data contrast of 50 hours from catalyst of the present invention, both differ minimum, and data almost, without declining, illustrate that catalyst provided by the present invention has good stability.
Than the catalyst of its components by weight, the catalyst that each components by weight is Fe:Mn:Ti:Cu:K=100:0.5～15:0.5～12:0.5～10:0.3～8:3.5～30 has higher catalytic activity, selective and stability; Than directly by a kind of method of carrying out precipitation reaction in another that flows in metal salt solution and precipitant solution, by the metal salt solution after preheating with precipitant solution and flow mix, the method for precipitation reaction is more conducive to improve the catalytic activity of catalyst, selectively and stability.Therefore, precipitated iron catalyst provided by the present invention is to have higher activity and good selective, is the high economy catalyst of a kind of applicable production Fischer-Tropsch-artificial oil and wax.
To sum up, precipitated iron catalyst provided by the present invention and preparation method thereof has the following advantages:
1) the ferrimanganic titanium copper potassium silicon formula precipitated iron catalyst good sphericity that this provides, any surface finish, specific area is large, and intensity is high, has good selective and stability during for fischer-tropsch reaction, is suitable for the production of industrialized oil from Fischer-Tropsch synthesis, synthetic wax;
2) this preparation method's operating process is short, raw material preparation condition require low, except calcination steps needs high temperature without high-temperature and high-pressure conditions, mild condition, simple and easy to do;
3) dry continuously shaped to spray, be conducive to improve the production efficiency of catalyst used for Fischer-Tropsch synthesis, reduce manufacturing cost, can adapt to the extensive continuous industrial production of catalyst.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for a person skilled in the art, the present invention can have various modifications and variations.Within the spirit and principles in the present invention all, any modification of doing, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (10)
1. a precipitated iron catalyst used for Fischer-Tropsch synthesis, is characterized in that, in described catalyst, each component comprises by weight: the Fe of 100 parts, the Mn of 0.3～20 part, the Ti of 0.1～15 part, the Cu of 0.2～10 part, and the SiO of the K of 0.3～10 part and 3～40 parts
2.
2. catalyst according to claim 1, is characterized in that, in described catalyst, each component comprises by weight: the Fe of 100 parts, the Mn of 0.5～15 part, the Ti of 0.5～12 part, the Cu of 0.5～10 part, and the SiO of the K of 0.3～8 part and 3.5～30 parts
2.
3. catalyst according to claim 1 and 2, is characterized in that, in described catalyst, Fe is with Fe
2o
3form exist, Mn exists with the form of MnO, Cu exists with the form of CuO, the specific area of described catalyst is 140～250m
2/ g.
4. a preparation method for precipitated iron catalyst used for Fischer-Tropsch synthesis, is characterized in that, comprises the following steps:
(1) soluble metallic salt of Fe, Mn, Ti, Cu is dissolved in deionized water, obtain metal salt solution, in described metal salt solution, the weight ratio of metallic element is Fe:Mn:Ti:Cu=100:0.3～20:0.1～15:0.2～10, and the concentration of Fe ion is 0.3～2.5mol/L;
(2) by described metal salt solution and precipitant solution precipitation reaction, be precipitated slurry, by described precipitation slurries filtration, washing, obtain co-precipitation filter cake;
(3) in described co-precipitation filter cake, add containing potassium soluble-salt, Ludox and/or contain potassium Ludox, the making beating that adds water, obtains Fe:K:SiO
2for the catalyst slurry of 100:0.3～10:3～40; And
(4) described catalyst slurry is dry, roasting, obtains described precipitated iron catalyst used for Fischer-Tropsch synthesis.
5. preparation method according to claim 4, it is characterized in that, in described metal salt solution the weight ratio of each component be Fe:Mn:Ti:Cu=100:0.5～15:0.5～12:0.5～10, the concentration of described Fe ion is 0.5～2.2mol/L, and in described catalyst slurry, the weight ratio of each component is Fe:K:SiO
2=100:0.3～8:3.5～30.
6. according to the preparation method described in claim 4 or 5, it is characterized in that, described in described step (2), in precipitation reaction process, described metal salt solution mixes with described precipitant solution stream, and precipitation reaction obtains described precipitation slurry.
7. method according to claim 4, is characterized in that, in the preparation method of described catalyst used for Fischer-Tropsch synthesis:
In described step (2), described metal salt solution and described precipitant solution are precipitated at 40 ℃～85 ℃, obtain described precipitation slurry, the pH that adjusts described precipitation slurry is 5～10; Described precipitation slurry is left standstill at 30 ℃～80 ℃ to aging 0～6h, filter, wash, obtain described co-precipitation filter cake;
In described step (3), in described co-precipitation filter cake, add containing potassium soluble-salt, Ludox and/or contain after potassium Ludox, the making beating that adds water, the pH that adjusts described catalyst slurry is 4.5～9;
In described step (4), described catalyst slurry is dry in spray dryer, spray-dired hot-wind inlet place temperature is 210 ℃～330 ℃, and wind exhausting outlet place temperature is 92 ℃～120 ℃;
Sintering temperature in described step (4) is 280～550 ℃, and roasting time is 2.5～10h; The specific area of described catalyst is 140～250m
2/ g.
8. method according to claim 7, it is characterized in that, in described step (2), first described metal salt solution and described precipitant solution are preheated to respectively to 40～85 ℃, be to carry out described precipitation reaction in the deionized water of 40～85 ℃ by its common temperature that flows into again, the time of described precipitation reaction is 5～70min.
9. preparation method according to claim 4, it is characterized in that, described precipitant solution is the deionized water solution of ammonium carbonate, sodium carbonate, potash, saleratus, NaOH, potassium hydroxide or ammoniacal liquor, the concentration of described precipitant solution is 0.3～2mol/L, is preferably 0.5～1.5mol/L.
10. preparation method according to claim 4, is characterized in that, described in step (3), is one or more deionized water solution in potash, saleratus, potassium nitrate containing potassium soluble-salt; Described Ludox and described containing SiO in potassium Ludox
2weight content be 5～50%.
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| CN105688926A (en) * | 2014-11-24 | 2016-06-22 | 神华集团有限责任公司 | Fischer-tropsch iron-based catalyst high in low carbon olefin yield, and preparation method thereof |
| CN108654654A (en) * | 2017-04-01 | 2018-10-16 | 神华集团有限责任公司 | Precipitated iron fischer-tropsch catalysts and its preparation method and application |
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| CN105688926B (en) * | 2014-11-24 | 2020-08-21 | 国家能源投资集团有限责任公司 | Fischer-Tropsch iron-based catalyst for producing more low-carbon olefins and preparation method thereof |
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| CN105597776A (en) * | 2016-02-22 | 2016-05-25 | 神华集团有限责任公司 | Catalyst for Fischer-Tropsch synthesis and preparing method thereof |
| CN108654654A (en) * | 2017-04-01 | 2018-10-16 | 神华集团有限责任公司 | Precipitated iron fischer-tropsch catalysts and its preparation method and application |
| CN108654654B (en) * | 2017-04-01 | 2021-09-03 | 国家能源投资集团有限责任公司 | Precipitated iron Fischer-Tropsch catalyst and preparation method and application thereof |
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