CN103801324B - Precipitated iron Catalysts and its preparation method used for Fischer-Tropsch synthesis - Google Patents
Precipitated iron Catalysts and its preparation method used for Fischer-Tropsch synthesis Download PDFInfo
- Publication number
- CN103801324B CN103801324B CN201410069772.0A CN201410069772A CN103801324B CN 103801324 B CN103801324 B CN 103801324B CN 201410069772 A CN201410069772 A CN 201410069772A CN 103801324 B CN103801324 B CN 103801324B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- precipitation
- slurry
- fischer
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The invention discloses a kind of precipitated iron Catalysts and its preparation method 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 parts2. By each component and proportioning in catalyst are optimized, 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 C5+Selective high, byproduct CH4With waste CO2Selectively 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 economy, easy, can quantity-produced microspheroidal precipitation ferrimanganic titanium system fischer-tropsch synthetic catalyst.
Description
Technical field
The present invention relates to Fischer-Tropsch synthesis technical field, in particular to a kind of precipitated iron catalyst used for Fischer-Tropsch synthesis and preparation thereofMethod.
Background technology
Fischer-Tropsch is synthetic is with synthesis gas (CO+H2) be raw material, this reaction raw materials synthesis gas can be obtained by conversion of natural gas or coal gasification,The synthetic indirect liquid of coal taking paraffin hydrocarbon as main liquid fuel under catalyst (being mainly iron-based and cobalt-based) and appropriate reaction conditionOne of change technology. This technology is gained the name because of its initial development people Germanization scholar's F. Fischer and general the executing of H. Toro, and Fischer-Tropsch is closedBecome or F-T synthetic technology. Fischer-tropsch synthetic catalyst is mainly divided into iron-based and cobalt-base catalyst, wherein ferrum-based catalyst sulfur resistanceGood, 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 realizeProduction ways by coal to liquid fuel, this technology is applicable to the few oily energy resource structure present situation of Chinese many coals very much, and therefore Fischer-Tropsch closesThe exploitation of one-tenth 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. ForImprove 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. mentioned one contain Fe, Cu, K,The skeletal iron catalyst of Mn and surplus Al, this catalyst is that Fe, Cu, Mn, Al metal powder are heated to molten condition,Mix rear quenching, then with alkali dissolution of metals Al, with the alcoholic solution dipping of potassium, obtain the catalyst before activation, this catalystThere is higher synthesis gas activity of conversion selective with preferably middle cut. But skeletal iron catalyst condition harshness not only while preparing,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 alsoHeight, economy is not as precipitated iron catalyst; And the catalytic activity of skeletal iron catalyst, olefine selective and stability are all to some extentShortcoming, also exists the defect of undercapacity, finally causes the preparation energy consumption of this catalyst high, cost is high, less economical, nothingMethod meets 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, the catalysis used for Fischer-Tropsch synthesis of this precipitated ironAgent good sphericity, specific area are 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, urgedIn agent, each component comprises by weight: the Fe of 100 parts, the Mn of 0.3～20 part, the Ti of 0.1～15 part, 0.2～10 partCu, and the SiO of the K of 0.3～10 part and 3～40 parts2。
Further, in catalyst, each component comprises by weight: the Fe of 100 parts, the Mn of 0.5～15 part, 0.5～12 partTi, the Cu of 0.5～10 part, and the SiO of the K of 0.3～8 part and 3.5～30 parts2。
Further, in catalyst Fe with Fe2O3Form exist, Mn exists with the form of MnO, Cu is with the shape of CuOFormula exists, and the specific area of catalyst is 140～250m2/g。
According to a further aspect in the invention, provide the preparation method of a kind of precipitated iron catalyst used for Fischer-Tropsch synthesis, comprised following stepRapid: (1) is dissolved in the soluble metallic salt of Fe, Mn, Ti, Cu in deionized water, obtains metal salt solution, metal salt solutionThe weight ratio of middle metallic element is Fe:Mn:Ti:Cu=100:0.3～20:0.1～15:0.2～10, and the concentration of Fe ion is0.3～2.5mol/L; (2) by metal salt solution and precipitant solution precipitation reaction, be precipitated slurry, will precipitate slurries filtration,Washing, obtains 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:SiO2For the catalyst slurry of 100:0.3～10:3～40; And (4) are dry by catalyst slurryDry, 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, and in catalyst slurry, the weight ratio of each component is Fe:K:SiO2=100:0.3～8:3.5～30。
Further, in step (2), in precipitation reaction process, metal salt solution mixes with precipitant solution stream, precipitation reactionObtain precipitation slurry.
Further, in the preparation method of catalyst used for Fischer-Tropsch synthesis: step in (2) exists metal salt solution and precipitant solutionAt 40 DEG C～85 DEG C, precipitation, is precipitated slurry, and the pH that adjusts precipitation slurry is 5～10; To precipitate slurry at 30 DEG C～80 DEG CLeave standstill aging 0～6h, filter, wash, obtain co-precipitation filter cake; In step (3), in co-precipitation filter cake, add containing potassium solubilitySalt, Ludox and/or containing after potassium Ludox, the making beating that adds water, the pH of adjustment catalyst slurry is 4.5～9; Will in step (4)Catalyst slurry is dry in spray dryer, and spray-dired hot-wind inlet place temperature is 210 DEG C～330 DEG C, wind exhausting outlet place temperatureDegree is 92 DEG C～120 DEG C; Sintering temperature in step (4) is 280～550 DEG C, and roasting time is 2.5～10h; The ratio of catalystSurface area is 140～250m2/g。
Further, in step (2), first metal salt solution and precipitant solution are preheated to respectively to 40 DEG C～85 DEG C, then are total toBe to carry out precipitation reaction in the deionized water of 40～85 DEG C with flowing into temperature, the time of precipitation reaction is 5～70min.
Further, precipitant solution be ammonium carbonate, sodium carbonate, potash, saleratus, NaOH, potassium hydroxide orThe deionized water solution of ammoniacal liquor, the concentration of precipitant solution is 0.3～2mol/L, is preferably 0.5～1.5mol/L.
Further, in step (3) containing potassium soluble-salt be in potash, saleratus, potassium nitrate one or more go fromThe sub-aqueous solution; Ludox and containing SiO in potassium Ludox2Weight content be 5～50%.
Apply technical scheme of the present invention, by each component and proportioning in catalyst are in optimized selection, make final precipitationIron catalyst has good sphericity, higher abrasion intensity, high-specific surface area. In addition, preparation process condition temperature of the present inventionWith, CO conversion ratio and reactivity are higher, long chain hydrocarbon C5+Selective high, byproduct CH4With waste CO2Selectively low,Hydrocarbon product distributes rationally, and in end product, methane and carbon dioxide content is low, is applicable to industrialized oil from Fischer-Tropsch synthesis, closesBecome the production of wax. This preparation technology's flow process economy, easy, can quantity-produced microspheroidal synthetic the urging of precipitation ferrimanganic titanium system Fischer-TropschAgent.
Brief description of the drawings
The Figure of description that forms the application's a part is used to provide a further understanding of the present invention, schematic reality of the present inventionExecute example and explanation thereof for explaining the present invention, do 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.
Detailed description of the invention
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 precipitationIron 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, 0.1～15Part Ti, the Cu of 0.2～10 part, and the SiO of the K of 0.3～10 part and 3～40 parts2. Preferably, the each component in catalystComprise 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 0.3～8The K of part and the SiO of 3.5～30 parts2。
Be in optimized selection by the component to catalyst and proportioning, make final precipitated iron catalyst have good sphericity,Higher abrasion intensity and specific area. In addition, process conditions gentleness of the present invention, CO conversion ratio and reactivity are higher, longChain hydrocarbon C5+Selective high, byproduct CH4With waste CO2Selectively low, hydrocarbon product distribute rationally, first in end productAlkane and carbon dioxide content are low, are 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. SiO2Add raisingThe abrasion intensity of catalyst, reduced rate of wear, make precipitated iron catalyst be more suitable for the application in paste state bed reactor.And simultaneously, collaborative being added on of metal element Ti and metallic element Fe, Mn, Cu, K improved the specific area of catalyst and dividesWhen divergence, 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 and urgeThe stability of agent, thus efficiently carrying out of Fischer-Tropsch building-up process ensured.
In catalyst used for Fischer-Tropsch synthesis provided by the present invention, metallic element can exist in a variety of forms, as with simple substance, carbonizationThe form of thing, nitride or oxide exists. Wherein be preferably with the form of oxide and exist. Metallic element forms with oxideThe mode existing, can improve the catalytic activity of catalyst, and the preparation of metal oxide is relatively easy, is conducive to reduce catalysisThe production cost of agent. Wherein, in catalyst Fe with Fe2O3Form exist, Mn exists with the form of MnO, Cu is with CuOForm exist.
Its granularity of catalyst provided by the present invention and specific area can reach the level of existing catalyst, are even better than existing urgingAgent. Preferably, the specific area of the prepared catalyst of the present invention is 140～250m2/ g. In this catalyst due to Fe3O4SurelyThe reorganization that the physical arrangement that the existence of earnest phase has weakened catalyst in the synthetic reduction reaction of Fischer-Tropsch causes because of its chemical phase transformation andDivide, increased the long-term run stability of catalyst, the agent structure of catalyst is 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 metal element Ti withThe collaborative interpolation of metallic element Fe, Mn, Cu, K and Si, has improved specific area, decentralization, the abrasion intensity of catalystAnd stability, the specific area of catalyst is controlled in above-mentioned scope, be conducive to the absorption of course of reaction Raw gas, fromAnd effectively improve the catalytic activity of catalyst, ensure synthetic efficiently the carrying out of Fischer-Tropsch.
According to a further aspect in the invention, provide a kind of method of preparing above-mentioned microspheroidal precipitated iron catalyst, comprised following stepRapid: (1) is dissolved in the soluble metallic salt of Fe, Mn, Ti, Cu in deionized water, obtains metal salt solution, metal salt solutionThe weight ratio of middle metallic element is Fe:Mn:Ti:Cu=100:0.3～20:0.1～15:0.2～10, and the concentration of Fe ion is0.3～2.5mol/L; (2) by metal salt solution and precipitant solution precipitation reaction, be precipitated slurry, will precipitate slurries filtration,Washing, obtains 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:SiO2For the catalyst slurry of 100:0.3～10:3～40; And (4) are dry by catalyst slurryDry, 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, and these precipitation method are by adjusting raw materialRatio and batch mixing step, make formed catalyst select at sphericity, specific area, pore volume, catalytic activity and productThe aspects such as property have better advantage, and while being applied to Fischer-Tropsch compound probability, CO conversion ratio is high, CH4And CO2Selectively low, longChain hydrocarbon C5+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, FeThe concentration of ion is 0.5～2.2mol/L, and in catalyst slurry, the weight ratio of each component is Fe:K:SiO2=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 grass of metalHydrochlorate, if its in deionized water, have good dissolubility just can, particularly, the raw material of Fe is preferably Fe (NO3)3；MnRaw material be preferably Mn (NO3)2; The raw material of Ti is preferably titanium potassium oxalate (K2TiO(C2O4)2); The raw material of Cu is preferably Cu (NO3)2Or CuCl2。
In preparation method provided by the present invention, in step (2), precipitant solution includes but not limited to ammonium carbonate, sodium carbonate, carbonA kind of deionized water solution in acid potassium, saleratus, NaOH, potassium hydroxide and ammoniacal liquor, is preferably ammonium carbonate or carbonic acidSodium, 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 intoIn metal salt solution, produce precipitation, or metal salt solution is slowly flowed in precipitant solution and produces and precipitate. Wherein be preferably alsoPrecipitation reaction is carried out in stream mixing. More preferably, in step (2), first metal salt solution and precipitant solution are preheated to respectively40 DEG C～80 DEG C, then be to carry out precipitation reaction in the deionized water of 40～80 DEG C by its common temperature that flows into, wherein precipitation reaction timeBetween be 5～70min. Under the condition stirring, carry out precipitation reaction, until precipitation reaction a period of time makes solution reach precipitation pHCan 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 ferric ion heavy simultaneouslyThe inhomogeneous Fe that can not get stablizing forms sediment2O3Situation occur. The present invention is chosen under the state of preheating and carries out and flow mixing, especially commonWith flowing in the deionized water of preheating, can ensure to react and carry out in stable temperature conditions, make the crystal phase structure of catalyst moreAdd completely, performance is more stable, because parallel-flow precipitation can be produced continuously, has greatly improved production efficiency, while shortening reactionBetween.
A preferred embodiment of the invention is at 40 DEG C～85 DEG C in step (2) by metal salt solution and precipitant solutionLower precipitation, is precipitated slurry, and the pH that adjusts precipitation slurry is 5～10; To precipitate slurry leaves standstill aging at 30 DEG C～80 DEG C0～6h, filters, washs, and obtains co-precipitation filter cake; In co-precipitation filter cake, add containing potassium soluble-salt, Ludox and/or contain potassiumAfter Ludox, the making beating that adds water, the pH that adjusts catalyst slurry is 4.5～9; Catalyst slurry is dry in spray dryer,Spray-dired hot-wind inlet place temperature is 210 DEG C～330 DEG C, and wind exhausting outlet place temperature is 92 DEG C～120 DEG C; Roasting in step S4Burning temperature is 280～550 DEG C, and roasting time is 2.5～10h; The specific area of catalyst is 140～250m2/g。
Leave standstill aging step and contribute to obtain all even stable Fe3O4Crystalline phase particle, and then obtained stability and preferably activePrecipitated iron catalyst. The salt-mixture precipitation slurry obtaining is carried out to separating for several times and washing, obtain filtrate and filter cake, control filter cakeIn the content of free state water 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 is not limited to this, also can adopt oneA little conventional acid and/or alkali are adjusted, but the acid of these routines and/or alkali are more responsive, make mixing salt solution in precipitation processPH amplitude of variation larger, be difficult for control, therefore, the present invention preferably adopts sodium carbonate and ammonium carbonate to carry out as precipitant solutionAccurately adjust lentamente, be finally precipitated slurry. Although the present invention has added precipitating reagent, the foreign ion forming can beIn follow-up calcination steps, remove totally, also there is 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, the making beating 5 that adds water～50min, obtains catalyst slurry. Containing potassium soluble-salt be preferably in potash, saleratus and potassium nitrate one or moreDeionized water solution; Ludox and containing SiO in potassium Ludox2Weight content be 5～50%; Containing SiO in potassium Ludox2：K2OMass ratio be 1.2:1～4:1. Ludox of the present invention and containing potassium Ludox be business Ludox, add containing potassium siliconAfter colloidal sol, can no longer add other solution containing potassium ion, this is because the potassium Ludox that contains adding provides SiO on the one hand2，Potassium element in precipitated iron catalyst is provided on the other hand. Adopt SiO2The weight content Ludox that is 5～50% and containing potassium siliconColloidal sol can either ensure the content of silicon in final catalyst, again can be because of SiO2The higher system viscosity that makes of content is too large, and impact is mixedThe uniformity of closing. Except controlling Ludox and containing SiO in potassium Ludox2Content outside, the preferably content of foreign ion in LudoxBe controlled at below 0.1%, can not affect like this activity of final catalyst. After adding Ludox, high-speed stirred is even, obtains catalysisAgent slurries.
For the viscosity of catalyst slurry is controlled within the scope of 500cP～5000cP so that next step is dry, according to the present inventionA kind of exemplary embodiment, adjusting the solid content of catalyst slurry is 7%～35%.
In preparation method provided by the invention, control by the proportion to each raw material, thereby improved urging of catalystChange active. In addition, also the concrete technology in each preparation process is optimized, particularly, by controlling precipitation processIn precipitation temperature, precipitation pH and sedimentation time make catalyst there is more complete structure and crystalline phase; By controlling sintering temperatureMake catalyst there is more excellent reducing property and catalytic performance with roasting time, meanwhile, improve sintering temperature and can promote hydrocarbonClass product is to the skew of heavy hydrocarbon direction, thus the distribution of adjustment product.
Precipitated iron catalyst used for Fischer-Tropsch synthesis for extensive continuous industrial production prepared by the present invention and traditional precipitated iron are urgedAgent is compared, and has the advantage that good sphericity and surface smoothness are high, and particle diameter is that the yield rate of 2～180 μ m reaches more than 88%,Rate of wear is lower than 5%/h, and the catalyst after roasting has higher specific area, up to 140～250m2/ g, pore volume is0.4～0.65cm3/ g. Compared with existing other precipitated iron catalyst, specific area and the particle size catalyst in above-mentioned scopeThere is 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.
Embodiment 1
Take nine water ferric nitrate 40.4kg, manganese nitrate (Mn (NO3)2·4H2O) 3.43kg, copper nitrate (Cu (NO3)2·3H2O）0.8kg、Oxalic acid dihydrate titanium potassium (K2TiO(C2O4)2·2H2O) 2.43kg, adds deionized water dissolving, is made into Fe concentration 2.0mol/L metalSalting liquid, is preheated to 70 DEG C. Get sodium carbonate 19kg, add deionized water dissolving, be configured to the sodium carbonate that concentration is 1.0mol/LPrecipitant solution, is preheated to 70 DEG C.
Metal salt solution and precipitant solution are also flowed into and filled in the reaction beaker of 70 DEG C of deionized waters of 300mL, keep temperatureBe 70 DEG C and stir state under carry out precipitation reaction. Be controlled at 6.0 ± 0.3 o'clock until pH, finish to stir, wherein when precipitation reactionBetween be 5min, be precipitated slurry. To precipitate slurry aging 0.5h at 80 DEG C, filtration, washed twice obtain co-precipitation filter cake.
By even the co-precipitation filter cake stirring to pulp that adds water, and add SiO2Weight content is that 5% Ludox and concentration are 0.9mol/LPotash mixed liquor, obtain catalyst slurry, adjust the pH to 7.0 of catalyst slurry, stir 20min, filter and make filterFe, K, SiO in cake2Gross weight than for Fe:K:SiO2＝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 sprayingIn drying machine, spraying is dried, and spraying drying condition is that hot-wind inlet place temperature is 280 DEG C, 102 DEG C of wind exhausting outlet place temperature, atomizationRotating speed 10000rpm, completes charging and moulding in 50 minutes, spray dried catalyst in Muffle furnace in 550 DEG C 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, 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：SiO2＝100：6.8：5.9：3.8：3：15。
Embodiment 2
Take nine water ferric nitrate 40.4kg, manganese nitrate (Mn (NO3)2·4H2O) 0.8kg, copper nitrate (Cu (NO3)2·3H2O）1.1kg，Oxalic acid dihydrate titanium potassium (K2TiO(C2O4)2·2H2O) 1.0kg, adds deionized water dissolving, and the concentration that is made into Fe is 2.2mol/LMetal salt solution, is preheated to 60 DEG C. Take ammonium carbonate solid 35kg, add deionized water dissolving, being mixed with concentration is 0.7mol/LAmmonium carbonate precipitant solution, be preheated to 35 DEG C.
Metal salt solution and precipitant solution are also flowed into and filled in the reaction beaker of 40 DEG C of deionized waters of 25kg, maintain the temperature at40 DEG C and stir state under carry out precipitation reaction, be precipitated slurry, the precipitation reaction time is 70 minutes, adjust precipitation slurryPH to 8.5 ± 0.3, aging 3.5h at 60 DEG C, filter, washing obtain co-precipitation filter cake three times.
By even the co-precipitation filter cake stirring to pulp that adds water, and add SiO2Weight content is that 50% Ludox and concentration are 1.8mol/LPotassium nitrate, obtain catalyst slurry, adjust the pH to 6.0 of catalyst slurry, stir 20min, filter make Fe in filter cake,K、SiO2Gross weight than for Fe:K:SiO2＝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 sprayingIn drying machine, spraying is dried, and spraying drying condition is that hot-wind inlet place temperature is 320 DEG C, 92 DEG C of wind exhausting outlet place temperature, atomizationRotating speed 8000rpm, completes charging and moulding in 50 minutes, and the dried catalyst of spraying, at 460 DEG C of roasting 5h, obtains finished product, noteFor 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 shapeShape 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：SiO2＝100：3.1：2.4：5.2：1.5：8。
Embodiment 3
Take nine water ferric nitrate 40.4kg, manganese nitrate (Mn (NO3)2·4H2O) 1.3kg, copper nitrate (Cu (NO3)2·3H2O）0.7kg，Oxalic acid dihydrate titanium potassium (K2TiO(C2O4)2·2H2O) 0.38kg, adds deionized water dissolving, and the concentration that is made into Fe is 1.6mol/LMetal salt solution, is preheated to 80 DEG C. Weighing sodium carbonate 28kg, adds deionized water dissolving, and being mixed with concentration is 2.0mol/L'sPrecipitant solution, is preheated to 80 DEG C.
Metal salt solution and precipitant solution are also flowed into and filled in the reaction beaker of 80 DEG C of deionized waters of 35kg, maintain the temperature at80 DEG C, under the state stirring, carry out precipitation reaction, be precipitated slurry, adjust pH to 7.5 ± 0.3 of precipitation slurry, not oldChange is directly filtered, washing obtains co-precipitation filter cake three times.
By even the co-precipitation filter cake stirring to pulp that adds water, and add SiO2Weight content is that 28% Ludox and concentration are 1mol/LPotassium nitrate, obtain catalyst slurry, adjust the pH to 9.0 of catalyst slurry, stir 12min, filter make Fe in filter cake,K、SiO2Gross weight than for Fe:K:SiO2＝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 sprayingIn drying machine, spraying is dried, and spraying drying condition is that hot-wind inlet place temperature is 260 DEG C, 115 DEG C of wind exhausting outlet place temperature, atomizationRotating speed 8000rpm, completes charging and moulding in 50 minutes, and the dried catalyst of spraying, at 500 DEG C of roasting 4h, obtains finished product, noteFor 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 shapeShape 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：SiO2＝100：5.1：0.9：3.3.：5：25。
Embodiment 4
Take nine water ferric nitrate 40.4kg, manganese nitrate (Mn (NO3)2·4H2O) 1.52kg, copper nitrate (Cu (NO3)2·3H2O）0.5kg，Oxalic acid dihydrate titanium potassium (K2TiO(C2O4)2·2H2O) 1.14kg, adds deionized water dissolving, and the concentration that is made into Fe is 0.5mol/LMetal salt solution, is preheated to 80 DEG C. Weighing sodium carbonate 20kg, adds deionized water dissolving, and being mixed with concentration is 1.5mol/L'sPrecipitant solution, is preheated to 50 DEG C.
Precipitant solution is joined to precipitation reaction in mixed salt solution, maintain the temperature at 80 DEG C, be precipitated slurry, adjustPH to 6.0 ± 0.3 of whole precipitation slurry, 50 DEG C 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 SiO2Weight content be 30% containing potassium Ludox, obtain catalysisAgent slurries, the pH to 5.0 of adjustment catalyst slurry, stirs 22min, filters and makes Fe in filter cake, K, SiO2Gross weightThan being Fe:K:SiO2＝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 sprayingIn drying machine, spraying is dried, and spraying drying condition is that hot-wind inlet place temperature is 210 DEG C, 120 DEG C of wind exhausting outlet place temperature, atomizationRotating speed 8000rpm, completes charging and moulding in 50 minutes, and the dried catalyst of spraying, at 280 DEG C of roasting 10h, obtains finished product, noteFor 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, shapeNot 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：SiO2＝100：6：2.8：2.3.：4：12。
Embodiment 5
Take nine water ferric nitrate 40.4kg, manganese nitrate (Mn (NO3)2·4H2O) 2.0kg, copper nitrate (Cu (NO3)2·3H2O）0.954kg，Oxalic acid dihydrate titanium potassium (K2TiO(C2O4)2·2H2O) 4.64kg, adds deionized water dissolving, and the concentration that is made into Fe is 2.3mol/LMetal salt solution, is preheated to 40 DEG C. Take potash 23kg, add deionized water dissolving, being mixed with concentration is 1.8mol/L'sSodium carbonate precipitant solution, is preheated to 40 DEG C.
Metal salt solution and precipitant solution are also flowed into and filled in the reaction beaker of 40 DEG C of deionized waters of 25kg, maintain the temperature at40 DEG C, under the state stirring, carry out precipitation reaction, be precipitated slurry, the precipitation reaction time is 37 minutes, adjusts precipitation slurryPH to 7.0 ± 0.3 of material, aging 3.5h at 60 DEG C, filtration, washing obtain co-precipitation filter cake three times.
By even the co-precipitation filter cake stirring to pulp that adds water, and add SiO2Weight content is that 20% Ludox and concentration are 2.5mol/LSolution of potassium carbonate, obtain catalyst slurry, adjust the pH to 5.5 of catalyst slurry, stir 30min, filter and make filter cakeMiddle Fe, K, SiO2Gross weight than for Fe:K:SiO2＝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 sprayingIn drying machine, spraying is dried, and spraying drying condition is that hot-wind inlet place temperature is 300 DEG C, 102 DEG C of wind exhausting outlet place temperature, atomizationRotating speed 9000rpm, completes charging and moulding in 50 minutes, and the dried catalyst of spraying, at 520 DEG C of roasting 4.5h, obtains finished product, noteFor 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：SiO2＝100：7.9：11.2：4.5：2.5：22。
Embodiment 6
Take nine water ferric nitrate 40.4kg, manganese nitrate (Mn (NO3)2·4H2O) 0.12kg, copper nitrate (Cu (NO3)2·3H2O）0.1kg，Oxalic acid dihydrate titanium potassium (K2TiO(C2O4)2·2H2O) 0.2kg, adds deionized water dissolving, and the concentration that is made into Fe is 0.5mol/LMetal salt solution, is preheated to 60 DEG C. Take saleratus 38kg, add deionized water dissolving, being mixed with concentration is 0.5mol/LSodium carbonate precipitant solution, be preheated to 60 DEG C.
Metal salt solution and precipitant solution are also flowed into and filled in the reaction beaker of 60 DEG C of deionized waters of 30g, wherein slaineThe flow velocity of solution is 4L/min, maintains the temperature at 60 DEG C, under the state stirring, carries out precipitation reaction, is precipitated slurry, adjustsPH to 10.0 ± 0.3 of whole precipitation slurry, aging 6h at 60 DEG C, 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 that 30% Ludox and concentration areThe potassium nitrate solution of 2.5mol/L, obtains catalyst slurry, adjusts the pH to 9 of catalyst slurry, stirs 30min, and filtration makesObtain Fe, K, SiO in filter cake2Gross weight than for Fe:K:SiO2＝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 dryIn dry machine, spraying is dried, and spraying drying condition is that hot-wind inlet place temperature is 330 DEG C, 92 DEG C of wind exhausting outlet place temperature, and atomization turnsSpeed 9000rpm, completes charging and moulding in 50 minutes, and the dried catalyst of spraying, at 280 DEG C of roasting 4.5h, obtains finished product, is designated asCatalyst 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：SiO2＝100：0.5：0.5：0.5：0.3：3.5。
Embodiment 7
Take nine water ferric nitrate 40.4kg, manganese nitrate (Mn (NO3)2·4H2O) 3.75kg, copper nitrate (Cu (NO3)2·3H2O）2kg，Oxalic acid dihydrate titanium potassium (K2TiO(C2O4)2·2H2O) 4.8kg, adds deionized water dissolving, and the concentration that is made into Fe is 0.3mol/LMetal salt solution, is preheated to 85 DEG C. Take saleratus 15kg, add deionized water dissolving, being mixed with concentration is 0.5mol/LPrecipitant solution, be preheated to 85 DEG C.
Metal salt solution and precipitant solution are also flowed into and filled in the reaction beaker of 85 DEG C of deionized waters of 30g, maintain the temperature at85 DEG C, under the state stirring, carry out precipitation reaction, the precipitation reaction time is 50 minutes, is precipitated slurry, adjusts precipitation slurryPH to 5.0 ± 0.3 of material, aging 6h at 85 DEG C, filtration, washing obtain co-precipitation filter cake three times.
By even the co-precipitation filter cake stirring to pulp that adds water, and add SiO2Weight content is that 30% Ludox and concentration are 0.8mol/LPotassium nitrate solution, obtain catalyst slurry, adjust the pH to 4.5 of catalyst slurry, stir 30min, filter and make filter cakeMiddle Fe, K, SiO2Gross weight than for Fe:K:SiO2＝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 sprayingIn drying machine, spraying is dried, and spraying drying condition is that hot-wind inlet place temperature is 330 DEG C, 92 DEG C of wind exhausting outlet place temperature, atomizationRotating speed 9000rpm, completes charging and moulding in 50 minutes, and the dried catalyst of spraying, at 280 DEG C of roasting 4.5h, obtains finished product, noteFor 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：SiO2＝100：15：12：10：8：30。
Embodiment 8
Take nine water ferric nitrate 40.4kg, manganese nitrate (Mn (NO3)2·4H2O) 0.08kg, copper nitrate (Cu (NO3)2·3H2O）0.05kg, titanyl sulfate (TiOSO4) 0.02kg adds deionized water dissolving, the concentration that is made into Fe is 0.3mol/L slaineSolution, is preheated to 85 DEG C. Take sodium acid carbonate 18kg, add deionized water dissolving, be mixed with the precipitation that concentration is 0.5mol/LAgent solution, is preheated to 85 DEG C.
Metal salt solution and precipitant solution are also flowed into and filled in the reaction beaker of 85 DEG C of deionized waters of 30g, maintain the temperature at85 DEG C, under the state stirring, carry out precipitation reaction, be precipitated slurry, wherein the precipitation reaction time is 20 minutes, it is heavy to adjustPH to 6.0 ± 0.3 of shallow lake slurry, aging 6h at 85 DEG C, filtration, washing obtain co-precipitation filter cake three times.
By even the co-precipitation filter cake stirring to pulp that adds water, and add SiO2Weight content is that 28% Ludox and concentration are 0.8mol/LPotassium nitrate solution, obtain catalyst slurry, adjust the pH to 5.0 of catalyst slurry, stir 30min, filter and make filter cakeMiddle Fe, K, SiO2Gross weight than for Fe:K:SiO2＝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 sprayingIn drying machine, spraying is dried, and spraying drying condition is that hot-wind inlet place temperature is 270 DEG C, 106 DEG C of wind exhausting outlet place temperature, atomizationRotating speed 9000rpm, completes charging and moulding in 50 minutes, and the dried catalyst of spraying, at 415 DEG C of roasting 2.5h, obtains finished product, noteFor 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：SiO2＝100：0.3：0.1：0.2：0.3：3。
Embodiment 9
Take nine water ferric nitrate 40.4kg, manganese nitrate (Mn (NO3)2·4H2O) 5kg, copper nitrate (Cu (NO3)2·3H2O）2.1kg，Oxalic acid dihydrate titanium potassium (K2TiO(C2O4)2·2H2O) 6.2kg, adds deionized water dissolving, and the concentration that is made into Fe is 0.3mol/LMetal salt solution, is preheated to 85 DEG C. Take sodium acid carbonate 18kg, add deionized water dissolving, being mixed with concentration is 0.5mol/LPrecipitant solution, be preheated to 85 DEG C.
Metal salt solution and precipitant solution are also flowed into and filled in the reaction beaker of 85 DEG C of deionized waters of 30g, maintain the temperature at85 DEG C, under the state stirring, carry out precipitation reaction, be precipitated slurry, wherein the precipitation reaction time is 20 minutes, it is heavy to adjustPH to 6.0 ± 0.3 of shallow lake slurry, aging 6h at 85 DEG C, filtration, washing obtain co-precipitation filter cake three times.
By even the co-precipitation filter cake stirring to pulp that adds water, and add SiO2Weight content is that 28% Ludox and concentration are 0.8mol/LPotassium nitrate solution, obtain catalyst slurry, adjust the pH to 5.0 of catalyst slurry, stir 30min, filter and make filter cakeMiddle Fe, K, SiO2Gross weight than for Fe:K:SiO2＝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 sprayingIn drying machine, spraying is dried, and spraying drying condition is that hot-wind inlet place temperature is 270 DEG C, 106 DEG C of wind exhausting outlet place temperature, atomizationRotating speed 9000rpm, completes charging and moulding in 50 minutes, and the dried catalyst of spraying, at 415 DEG C of roasting 2.5h, obtains finished product, noteFor 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：SiO2＝100：20：15：10：10：40。
Comparative example 1
Take nine water ferric nitrate 40.4kg, manganese nitrate (Mn (NO3)2·4H2O) 5.9kg, copper nitrate (Cu (NO3)2·3H2O）2.6kg, oxalic acid dihydrate titanium potassium (K2TiO(C2O4)2·2H2O) 7.5kg, adds deionized water dissolving, and the concentration that is made into Fe is 0.3mol/LMetal salt solution, is preheated to 85 DEG C. Take sodium acid carbonate 18kg, add deionized water dissolving, being mixed with concentration is 0.5mol/LPrecipitant solution, be preheated to 85 DEG C.
Metal salt solution and precipitant solution are also flowed into and filled in the reaction beaker of 85 DEG C of deionized waters of 30g, maintain the temperature at85 DEG C, under the state stirring, carry out precipitation reaction, be precipitated slurry, wherein the precipitation reaction time is 20 minutes, it is heavy to adjustPH to 6.0 ± 0.3 of shallow lake slurry, aging 6h at 85 DEG C, filtration, washing obtain co-precipitation filter cake three times.
By even the co-precipitation filter cake stirring to pulp that adds water, and add SiO2Weight content is that 28% Ludox and concentration are 0.8mol/LPotassium nitrate solution, obtain catalyst slurry, adjust the pH to 5.0 of catalyst slurry, stir 30min, filter and make filter cakeMiddle Fe, K, SiO2Gross weight than for Fe:K:SiO2＝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 sprayingIn drying machine, spraying is dried, and spraying drying condition is that hot-wind inlet place temperature is 270 DEG C, 106 DEG C of wind exhausting outlet place temperature, atomizationRotating speed 9000rpm, completes charging and moulding in 50 minutes, and the dried catalyst of spraying, at 415 DEG C of roasting 2.5h, obtains finished product, shouldCatalyst 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：SiO2＝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 grainDegree instrument determination method is measured the size distribution of microspheroidal precipitated iron catalyst, employing low-temperature nitrogen adsorption method mensuration precipitated iron catalystBET specific area and pore volume.
Adopt standard A STMD5757-95 air gunite to measure the rate of wear of precipitated iron catalyst, put by standard volume catalystEnter in air injection tube, 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, weigh before and after test certain particle diameter withThe quality of upper catalyst, calculates rate of wear. Rate of wear=(rear standard grain of the quality-test of the above catalyst of standard particle diameter before testThe quality of the above catalyst in footpath)/quality/testing time of the above catalyst of standard particle diameter before testing.
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, and the grain of the precipitated iron catalyst of preparing in embodiment 1～9Degree distributes and concentrates, and specific area is large, pore volume is moderate, and intensity is high, has good attrition resistance. Especially catalyst 1,2,3With 5 there is best performance, be applicable to the connection of gasoline, diesel oil and high-quality paraffin in the Fischer-Tropsch compound probability of extensive oar state bedSymphysis is produced.
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 prepareReally, the evaluation test of Fischer-Tropsch synthesis is carried out on fixed bed reactors, gets the catalysis in embodiment 1～9 and comparative example 1Agent, grain diameter is 30～150 μ m, H at 250 DEG C2/ CO=1.5, unstripped gas speed is 3000 ± 20mL/gcal/h, reaction pressurePower 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 Table3。
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, the catalyst 1～9 that adopts preparation technology of the present invention to obtainIn precipitated iron catalyst can both move for a long time, wherein the conversion ratio of CO is higher, all approach or exceed 80%, carbon monoxideBe converted into carbon dioxide selectively all below 27.5%, show that the catalytic activity of this catalyst is very high; The methane choosing of catalystSelecting property all below 4%, C5+Selectively reach more than 80% lower carbon number hydrocarbons (C2～C4) in olefine selective all higher than 55%, lowCarbon olefin relative amount is high. In addition, from catalyst of the present invention through the response data of 400 hours and the response data pair of 50 hoursThan finding out, both differ minimum, and data, almost without declining, illustrate that catalyst provided by the present invention has good stablizingProperty.
Than the catalyst of its components by weight, each components by weight is Fe:Mn:Ti:Cu:K=100:0.5～15:The catalyst of 0.5～12:0.5～10:0.3～8:3.5～30 has higher catalytic activity, selective and stability; ThanDirectly by a kind of method of carrying out precipitation reaction in another that flows in metal salt solution and precipitant solution, by after preheatingMetal salt solution mixes with precipitant solution stream, the method for precipitation reaction is more conducive to improve catalytic activity, the selection of catalystProperty and stability. Therefore, precipitated iron catalyst provided by the present invention is to have higher activity and good selective, is onePlant the high economy catalyst that is applicable to producing 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, strongSpend highly, during for fischer-tropsch reaction, there is good selective and stability, be suitable for industrialized oil from Fischer-Tropsch synthesis, synthetic waxProduce;
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, canTo 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 those skilled in the art, the present invention can have various modifications and variations. Within the spirit and principles in the present invention all, any amendment of doing, etc.With replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (6)
1. 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, obtains metal salt solution, described goldThe weight ratio that belongs to metallic element in salting liquid is Fe:Mn:Ti:Cu=100:0.3～20:0.1～15:0.2～10, the concentration of Fe ionBe 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, obtains 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,To Fe:K:SiO2The weight ratio catalyst slurry that is 100:0.3～10:3～40; And
(4) described catalyst slurry is dry, roasting, obtains described precipitated iron catalyst used for Fischer-Tropsch synthesis;
In described step (2), first described metal salt solution and described precipitant solution are preheated to respectively to 40～85 DEG C, then by itThe common temperature that flows into is to carry out described precipitation reaction in the deionized water of 40～85 DEG C, and the time of described precipitation reaction is 5～70min.
2. preparation method according to claim 1, is characterized in that, in described metal salt solution, the weight ratio of each component is 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, described catalystIn slurries, the weight ratio of each component is Fe:K:SiO2＝100:0.3～8:3.5～30。
3. preparation method according to claim 1, 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 DEG C～85 DEG C, obtain instituteState precipitation slurry, the pH that adjusts described precipitation slurry is 5～10; Described precipitation slurry is left standstill aging at 30 DEG C～80 DEG C0～6h, filters, washs, and obtains 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 temperatureDegree is 210 DEG C～330 DEG C, and wind exhausting outlet place temperature is 92 DEG C～120 DEG C;
Sintering temperature in described step (4) is 280～550 DEG C, and roasting time is 2.5～10h; The ratio table of described catalystArea is 140～250m2/g。
4. preparation method according to claim 1, is characterized in that, described precipitant solution is ammonium carbonate, sodium carbonate, carbonic acidThe deionized water solution of potassium, saleratus, NaOH, potassium hydroxide or ammoniacal liquor, the concentration of described precipitant solution is0.3～2mol/L。
5. preparation method according to claim 4, is characterized in that, the concentration of described precipitant solution is 0.5～1.5mol/L.
6. preparation method according to claim 1, is characterized in that, described in step (3) containing potassium soluble-salt be potash,In saleratus, potassium nitrate one or more; Described Ludox and described containing SiO in potassium Ludox2Weight content be5～50％。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410069772.0A CN103801324B (en) | 2014-02-27 | 2014-02-27 | Precipitated iron Catalysts and its preparation method used for Fischer-Tropsch synthesis |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410069772.0A CN103801324B (en) | 2014-02-27 | 2014-02-27 | Precipitated iron Catalysts and its preparation method used for Fischer-Tropsch synthesis |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103801324A CN103801324A (en) | 2014-05-21 |
| CN103801324B true CN103801324B (en) | 2016-05-25 |
Family
ID=50698996
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410069772.0A Active CN103801324B (en) | 2014-02-27 | 2014-02-27 | Precipitated iron Catalysts and its preparation method used for Fischer-Tropsch synthesis |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103801324B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN104707620B (en) * | 2015-03-16 | 2017-08-01 | 中科合成油技术有限公司 | A kind of fischer-tropsch synthetic catalyst and preparation method and application |
| 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 |
| 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 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101298046A (en) * | 2008-05-05 | 2008-11-05 | 神华集团有限责任公司 | Iron catalyst containing titanium deposition for catalyzing Fischer-Tropsch synthesis reaction and method for producing the same |
| CN102658143A (en) * | 2012-04-06 | 2012-09-12 | 神华集团有限责任公司 | Preparation method of Fischer-Tropsch synthesis precipitated iron catalyst |
-
2014
- 2014-02-27 CN CN201410069772.0A patent/CN103801324B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101298046A (en) * | 2008-05-05 | 2008-11-05 | 神华集团有限责任公司 | Iron catalyst containing titanium deposition for catalyzing Fischer-Tropsch synthesis reaction and method for producing the same |
| CN102658143A (en) * | 2012-04-06 | 2012-09-12 | 神华集团有限责任公司 | Preparation method of Fischer-Tropsch synthesis precipitated iron catalyst |
Non-Patent Citations (2)
| Title |
|---|
| Cu、K助剂对FeMn/SiO2催化费托合成的影响;张成华等;《物理化学学报》;20061130;第22卷(第11期);文章第1311页右栏第1段 * |
| 费托合成沉淀铁催化剂性能的研究进展;范洋波等;《浙江化工》;20091031;第40卷(第10期);文章第20页左栏第3-4段 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103801324A (en) | 2014-05-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106031871B (en) | A kind of CO2Hydrogenation takes ferrum-based catalyst and its preparation and the application of low-carbon alkene | |
| CN103801324B (en) | Precipitated iron Catalysts and its preparation method used for Fischer-Tropsch synthesis | |
| CN102658143B (en) | Preparation method of Fischer-Tropsch synthesis precipitated iron catalyst | |
| CN101829580B (en) | Fischer-Tropsch synthetic catalyst, preparation method and application thereof | |
| CN104549296B (en) | Microspheroidal synthesis gas directly prepares catalyst of low-carbon alkene and preparation method thereof | |
| CN105363464B (en) | Catalyst of synthesis gas light hydrocarbon directly processed and preparation method thereof | |
| CN106607037B (en) | GTO catalyst for fluid bed and preparation method thereof | |
| CN103933989B (en) | For the synthesis of the Catalysts and its preparation method of low-carbon alkene | |
| CN105363458B (en) | Synthesize catalyst of light hydrocarbon and preparation method thereof | |
| CN105363463B (en) | Catalyst of synthesis gas light hydrocarbon and preparation method thereof | |
| CN102371162B (en) | High stability iron / manganese catalyst for fluidized bed Fischer-Tropsch synthesis and preparation method thereof | |
| CN105435803B (en) | Catalyst of microspheroidal synthesis of gas produced low-carbon hydrocarbon and preparation method thereof | |
| CN104107699B (en) | Ferrum-based catalyst for synthesizing low-carbon alkene and preparation method thereof | |
| CN103801307B (en) | Precipitated iron catalyst used for Fischer-Tropsch synthesis and preparation method thereof | |
| CN109647426A (en) | The ferrum-based catalyst of the direct producing light olefins of synthesis gas | |
| CN102039135A (en) | Fe-based fluidized bed catalyst for Fischer-Tropsch synthesis and preparation method thereof | |
| CN103657678B (en) | Microspheroidal iron-base fischer-tropsch synthesis catalyst, preparation method and application thereof | |
| CN111167470B (en) | Catalyst for preparing olefin from synthesis gas, preparation method thereof and application of catalyst in olefin production | |
| CN103801329B (en) | Microspheric catalyst for preparing oils and paraffin from synthesis gas and preparation method thereof | |
| CN109225235A (en) | High-efficiency abrasion-proof syrup state bed Fischer Tropsch synthesis iron base catalyst and its preparation method and application | |
| CN109651034A (en) | The method of one-step method from syngas production low-carbon alkene | |
| CN103657676B (en) | Microspherical Fischer-Tropsch catalyst and its preparation method and application | |
| CN109647412A (en) | Synthesis gas directly produces the ferrum-based catalyst of low-carbon alkene | |
| CN103521232A (en) | Micro spherical iron-based Fischer-Tropsch synthesis catalyst and preparation method thereof | |
| CN105597776A (en) | Catalyst for Fischer-Tropsch synthesis and preparing method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |