CN104785272A - Iron-based catalyst and preparation method thereof - Google Patents
Iron-based catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention provides an iron-based catalyst and a preparation method thereof. The iron-based catalyst comprises a first active constituent, a second active constituent and a catalyst carrier, wherein the first active constituent comprises FeOOH; the second active constituent comprises an active element-containing compound; the active element is one or more of element Ni, element Co, element Mo and element W; the iron-based catalyst simultaneously contains the first active constituent and the second active constituent, namely when FeOOH is used as a main catalyst, the compound containing one or more of element Ni, element Co, element Mo and element W is used as an auxiliary catalyst. The two active constituents are introduced into the iron-based catalyst, so that the iron-based catalyst is higher in catalytic activity; meanwhile, the two active constituents are wide in source and relatively low in cost, so that the production cost of the iron-based catalyst is beneficial to be lowered, and the iron-based catalyst is more suitable for industrial production and application.
Description
Technical field
The present invention relates to DCL/Direct coal liquefaction field, in particular to a kind of Fe-series catalyst and preparation method thereof.
Background technology
China in 2009 has exceeded 50%, 2013 for the first time to crude oil import interdependency and has reached 57.4%, and crude oil import total amount reaches 2.8 hundred million tons.Although the Chinese government clearly proposes during 12, externally deposited according to degree by oil and control within 61%, domestic crude oil production increasess slowly, and demand gap continues to amplify, and crude oil external dependence degree inevitably continues lifting.Crude oil external dependence degree improves constantly, and means that Chinese society is produced and the situation of energy security will be more severe.Make full use of the advantage of coal resources in China, Speeding up development and apply clean coal technology, greatly develop coal liquefaction industrialization, ensure that Chinese energy safety is the most real beyond doubt, most important one is selected.It is one of important channel of coal cleaning conversion and efficiency utilization that liquid fuel is produced in DCL/Direct coal liquefaction.
DCL/Direct coal liquefaction coal is first worn into coal dust and solvent (petroleum distillate) is made into coal, then under the effect of high temperature, high pressure and catalyst directly and hydrogen generation hydrocracking reaction, make coal directly change into liquid oil.In DCL/Direct coal liquefaction process, catalyst effectively can promote pyrolysis and the hydrogenation of coal, improves the productive rate and oil quality that generate oil.Through the research of last 100 years, the catalyst of DCL/Direct coal liquefaction mainly contains three individual system, and one is Fe-series catalyst, comprises the native iron ore of various sulfur-bearing, the iron sulfide of synthesis, the compound of the ferriferous oxide of synthesis and the hydroxide of iron and iron content; Two is Ni, Mo series catalysts, and comprise the various oxide containing Ni or Mo, sulfide, containing salt and the organic complex of Ni or Mo; Three is fused chlorides of Zn, Sn etc.Fe-series catalyst relative low price, wide material sources, have good effect in Coal liquefaction, and do not need to reclaim, and cost performance is high, and therefore investigation and application is the most extensive.Ni, Mo series catalysts belongs to traditional oil hydrogenation catalyst, and research is comparatively ripe, has more superior hydrogenation efficiency in Coal liquefaction, product quality is also better, but catalyst price is more expensive, generally load can only uses, have a definite limitation to the selection of reaction system; If heavy industrialization application, need to consider the investment of catalyst recovery system, and due to the minimizing of stock number, catalyst cost has the risk continuing to rise.The fused chloride of Zn, Sn etc. plays the catalytic cleavage C-C key effect of the friedel-crafts reaction type with acid catalysis function, and Zn, Sn itself also have hydrogenation, therefore coal liquefaction efficiency is very high, directly can produce the high gasoline products of octane number, but chloride has serious corrosiveness to equipment, limit large-scale application at present.
Although Fe-series catalyst cost performance is high, because the activity of Fe-series catalyst own is not high, by improving the certain coal conversion ratio of addition guarantee and oily production rate.But in order to realize smooth deslagging, too much catalyst can not be added again.The activity of visible raising Fe-series catalyst is the effective means solving addition and obtain contradiction between oil product amount, and the activity improving Fe-series catalyst has two paths: one is change preparation technology, synthesizes ultra-fine high dispersive or highly active catalyst; Another carries out modification to Fe-series catalyst, improves the catalytic activity of catalyst itself.
Eklund and Hager etc. can be 3 ~ 13nm spherical carbide particle from pentacarbonyl carbon and ethylene making average particle size range by laser pyrolysis technology, better performances (P C Eklund during the iron carbon particle catalysis bituminous coal prepared by the method, J M Stencel, X X Bi, R A Keogh, F J Derbyshire.Ultrafine iron catalysts for coal dissolution.ACS Fuel Chem.Prepr.1991,36 (2): 551-559.).Andrew etc. by decomposing FeCl in hydrogen-oxygen flame
3steam, has prepared the iron particle that average grain diameter is about 50nm, and this nano particle has high liquefying activity.In addition, this type of iron particle can keep its size and shape (M Andrew in presulfurization and coal liquefaction, H Charcosset, P Chiche, G Djega-Mariadassou, J P Joly, S Pregemain.Preparation of Catlyst III (Eds.Poncelet and Grange), Elsevier Science Publishers, 1983,675-682.).Linehan etc. have prepared small iron oxide particles by reversed phase micelle and rapid pyrolysis method, and particle diameter is little of 1nm, and BET specific surface area reaches 150m
2about/g, and particle diameter and pattern (the J C Linehan of particle is regulated by changing reaction condition, R M Bean, D W Matson, J L Fulton, A E Crump.New synthetic methods for theproduction of ultra-fine coal liquefaction catalysts.ACS Fuel Chem.Prepr.1992,37 (1): 488-496).To have utilized aerosol processing and microcapsules technology to prepare respectively ultra-fine and nanometer sulfuration Fe-series catalyst for Sharma etc., and investigated the impact of preparation condition on catalytic performance, result shows that the total conversion of prepared catalyst and selective being obtained for significantly improve.(R KSharma, A H Stiller, D B Dadyburjor.Effect of Preparation Conditions on the Characterization andActivity of Aerosol-Generated Ferric Sulfide-Based Catalysts for Direct Coal Liquefaction.Energy & Fuels.1996, 10 (3): 757-765.) the ultra-fine Fe-series catalyst prepared by said method has very high coal liquefaction active, but cost of material is too high, preparation technology or device therefor complexity, all be unfavorable for saving cost and large-scale development application.
The synthesis of hydroxy ferric oxide catalysts such as Koyama, find that catalyst is by the molecular γ of tiny initial state grain-FeOOH, there is high dispersive performance, its oily yield is higher than other Fe-series catalyst (T Koyama, et al.Studies on brown coalliquefaction. (19) .Effect of iron catalyst properties on liquefaction activity.Sekitan Kagaku koigiHappyo Ronbunshu.1993,30:201-204.).It take coal dust as the high-dispersion iron catalyst of the coal Direct Hydrogenation liquefaction of load that patent CN03153377.9 and patent CN200410091152.3 discloses a kind of.This catalyst is made up of three parts such as active component, carrier coal and water impurity, and active component is γ-FeOOH, and carrier is liquefaction coal itself.The type catalyst is cheap, and due to adopt liquefaction coal dust as carrier, while achieving high dispersive again can with coal dust close contact, therefore, it is possible to significantly improve coal liquefaction efficiency.But this method is only improve from the physical dispersion angle of catalyst, rely on polymolecularity to improve coal liquefaction efficiency, and the activity of Fe-series catalyst self is not greatly improved.
Existence in view of the above problems, is necessary to prepare the lower and Fe-series catalyst that auto-catalytic activity is higher of a kind of cost.
Summary of the invention
Main purpose of the present invention is to provide a kind of Fe-series catalyst and preparation method thereof, to solve the problem that in prior art, Fe-series catalyst auto-catalytic activity is lower or cost is high.
To achieve these goals, according to an aspect of the present invention, provide a kind of Fe-series catalyst, this Fe-series catalyst comprises the first active component, the second active component and catalyst carrier; Wherein, the first active component comprises FeOOH; Second active component comprises the compound containing active element, and active element is one or more in element Ni, Elements C o, elements Mo and element W.
Further, in Fe element, the first active component accounts for 3 ~ 30% of Fe-series catalyst weight, preferably accounts for 4.0 ~ 20.0%; In active element, the second active component accounts for 0.01 ~ 1% of Fe-series catalyst weight, preferably accounts for 0.02 ~ 0.8%.
Further, the weight ratio of active element and Fe element is 0.1 ~ 10%..
Further, catalyst carrier accounts for 30 ~ 90% of Fe-series catalyst weight, preferably accounts for 60 ~ 85%.
Further, the particle diameter of catalyst carrier is less than 200 μm.
Further, catalyst carrier is selected from one or more in coal dust, active carbon and CNT.
Further, weight percentage, Fe-series catalyst also comprises the water of 2 ~ 10%.
According to a further aspect in the invention, provide a kind of preparation method of above-mentioned Fe-series catalyst, this preparation method comprises the following steps: adsorb the first active component and the second active component on a catalyst support; Wherein, the first active component comprises FeOOH; Second active component comprises the compound containing active element, and active element is one or more in element Ni, Elements C o, elements Mo and element W.
Further, the step of adsorbing the first active component and the second active component on a catalyst support comprises: S1, and preparation is adsorbed with the catalyst carrier of the first active component; And S2, the soluble-salt and water that contain active element are mixed to form mixed liquor, mixed liquor are attached in the catalyst carrier being adsorbed with the first active component, dry, obtain Fe-series catalyst.
Further, step S1 is further comprising the steps of: S11, ferrous soluble-salt, catalyst carrier is mixed with water, obtains the first slurries; S12, mixes the first alkali compounds with water, obtains the first alkaline solution; And S13, the first slurries and the first alkaline solution are reacted, filters, obtain the catalyst carrier being adsorbed with the first active component.
Further, the step of adsorbing the first active component and the second active component on a catalyst support comprises: A1, by ferrous soluble-salt, mixes with water containing the soluble-salt of active element, catalyst carrier, forms the second slurries; A2, mixes the second alkali compounds with water, obtains the second alkaline solution; And A3, the second slurries and the second alkaline solution are reacted, filters, obtain Fe-series catalyst.
Further, nickeliferous soluble-salt is selected from, containing molybdenum soluble-salt, containing one or more in the group of cobalt soluble-salt and tungstenic soluble-salt composition containing the soluble-salt of active element; Wherein, nickeliferous soluble-salt is selected from one or more in the group of nickel nitrate, nickelous sulfate and nickel chloride composition; Ammonium molybdate and/or ammonium thiomolybdate is selected from containing molybdenum soluble-salt; Containing cobalt soluble-salt be selected from cobalt nitrate, cobaltous sulfate and cobalt chloride composition group in one or more; Tungstenic soluble-salt be selected from ammonium metatungstate, sodium tungstate and phosphotungstic acid composition group in one or more.
Further, ferrous soluble-salt is selected from one or more in the group of ferrous sulfate, frerrous chloride and ferrous carbonate composition; First alkali compounds and the second alkali compounds be separately selected from sodium carbonate, ammoniacal liquor and NaOH composition group in one or more; Preferably, the first alkali compounds and the second alkali compounds are separately selected from sodium carbonate or ammoniacal liquor.
Apply technical scheme of the present invention, in Fe-series catalyst, introduce two kinds of active components, effectively can improve Fe-series catalyst self hydrogenation activity in DCL/Direct coal liquefaction process, thus can more effectively improve coal liquefaction efficiency.Meanwhile, above-mentioned two active component wide material sources, cost are lower, make the production cost of this Fe-series catalyst provided by the present invention lower, are more suitable for industrialization large-scale production and application.
Detailed description of the invention
It should be noted that, when not conflicting, the embodiment in the application and the feature in embodiment can combine mutually.The present invention is described in detail below in conjunction with embodiment.
As described by background technology, there is the problem that auto-catalytic activity is lower or cost is high in existing Fe-series catalyst.In order to solve the problem, the invention provides a kind of Fe-series catalyst, this Fe-series catalyst comprises the first active component, the second active component and catalyst carrier; Wherein, the first active component comprises FeOOH; Second active component comprises the compound containing active element, active element include but not limited in element Ni, Elements C o, elements Mo and element W one or more.
Fe-series catalyst provided by the invention is simultaneously containing the first active component and the second active component, namely while using FeOOH as major catalyst, further using containing one or more compound in element Ni, Elements C o, elements Mo and element W as cocatalyst.In Fe-series catalyst, introduce this two kinds of active components, effectively can improve Fe-series catalyst self hydrogenation activity in DCL/Direct coal liquefaction process.Self higher catalytic activity makes this Fe-series catalyst of the present invention can more effectively improve coal liquefaction efficiency.Meanwhile, above-mentioned two active component wide material sources, cost are lower, make the production cost of this Fe-series catalyst provided by the present invention lower, are more suitable for industrialization large-scale production and application.
In above-mentioned Fe-series catalyst, as long as comprise above-mentioned first active component and the second active component simultaneously, higher auto-catalytic activity can be had.In a preferred embodiment, in Fe element, the first active component accounts for 3 ~ 30% of Fe-series catalyst weight, preferably accounts for 4.0 ~ 20.0%; In active element, the second active component accounts for 0.01 ~ 1% of Fe-series catalyst weight, preferably accounts for 0.02 ~ 0.8%.The content of above-mentioned two kinds of active components is controlled in above-mentioned scope, is conducive to the auto-catalytic activity improving catalyst further.
In above-mentioned Fe-series catalyst, as long as the first active component in Fe-series catalyst and the second active component are added according to said ratio, just can improve the catalytic activity of catalyst.In a preferred embodiment, the weight ratio of active element and Fe element is 0.1 ~ 10%.The weight ratio of two kinds of active components in catalyst is controlled in above-mentioned scope, the synergy of two kinds of active components can be played further, thus improve the auto-catalytic activity of Fe-series catalyst further.
In above-mentioned Fe-series catalyst, those skilled in the art can the concrete content of selective catalysis agent carrier.In a preferred embodiment, catalyst carrier accounts for 30 ~ 90% of Fe-series catalyst weight, preferably accounts for 60 ~ 85%.Percentage catalyst carrier being accounted for above-mentioned Fe-series catalyst gross weight controls in above-mentioned scope, and the active component being conducive to making Fe-series catalyst more fully load, on carrier, thus to be dispersed in reaction system more fully.Which improve the contact effect of catalyst and reactant, be conducive to the catalytic activity improving catalyst further.
In above-mentioned Fe-series catalyst, those skilled in the art can select the concrete particle diameter of catalyst carrier in above-mentioned catalyst.In one preferably embodiment, the particle diameter of catalyst carrier is less than 200 μm.This can divided active component further, is conducive to the reunion prevented between active component.And in coal liquefaction, improve catalyst activity further, with fast reaction speed, reach better coal liquefaction effect.
In above-mentioned Fe-series catalyst, carrier conventional when the catalyst carrier of employing can be Kaolinite Preparation of Catalyst.In a preferred embodiment, catalyst carrier includes but not limited to coal dust, active carbon or CNT.By catalyst cupport on carrier, disperseed by coal dust with carrier close contact, in Coal liquefaction process, catalyst can with coal fast reaction nearby, facilitate catalyst pyrolysis and the hydrogenation of large coal molecule, be conducive to the raising of coal liquefaction efficiency.Preferably, the carrier of above-mentioned catalyst is coal dust.
Fe-series catalyst of the present invention in the preparation, often introducing portion water in the catalyst.In a preferred embodiment, weight percentage, Fe-series catalyst also comprises the water of 2 ~ 10%.These water may exist with the form of free state or the crystallization water, but these water can not have a negative impact to the activity of catalyst.
Another aspect of the present invention additionally provides a kind of preparation method of above-mentioned Fe-series catalyst, and this preparation method comprises the following steps: adsorb the first active component and the second active component on a catalyst support; Wherein, the first active component comprises FeOOH; Second active component comprises the compound containing active element, active element include but not limited in element Ni, Elements C o, elements Mo and element W one or more.
Contain the first active component and the second active component by the Fe-series catalyst that said method is obtained simultaneously, namely while using FeOOH as major catalyst, further using containing one or more compound in element Ni, Elements C o, elements Mo and element W as cocatalyst.In Fe-series catalyst, introduce this two kinds of active components, effectively can improve Fe-series catalyst self hydrogenation activity in DCL/Direct coal liquefaction process.Meanwhile, above-mentioned two active component wide material sources, cost are lower, make the production cost of this Fe-series catalyst provided by the present invention lower, are more suitable for industrialization large-scale production and application.
In above-mentioned preparation method, by the technical scheme that the first active component and the second active ingredient adsorption to carrier can adopt this area conventional.In one preferably embodiment, the step of adsorbing the first active component and the second active component on a catalyst support comprises: S1, and preparation is adsorbed with the catalyst carrier of the first active component; And S2, the soluble-salt and water that contain active element are mixed to form mixed liquor, mixed liquor are attached in the catalyst carrier being adsorbed with the first active component, dry, obtain Fe-series catalyst.
In the present invention, and " soluble-salt and the water containing active element is mixed to form mixed liquor be attached to be adsorbed with the first active component catalyst carrier on " adhering mode that this area can be adopted conventional, as sprayed or dropping etc.
First prepare the catalyst carrier containing the first active component (FeOOH), then the soluble salt solutions containing the second active element is attached in catalyst carrier with the form of spray or dropping.Not there is chemical reaction in the above-mentioned soluble salt solutions containing the second active element, but is attached in the catalyst carrier containing the first active component with the form of corresponding soluble-salt, obtained required Fe-series catalyst.
According to above-mentioned instruction of the present invention, those skilled in the art can select the concrete operation method in step S1.In a preferred embodiment, step S1 is further comprising the steps of: S11, ferrous soluble-salt, catalyst carrier is mixed with water, obtains the first slurries; S12, mixes the first alkali compounds with water, obtains the first alkaline solution; And S13, the first slurries and the first alkaline solution are reacted, filters, obtain the catalyst carrier being adsorbed with the first active component.
In said process, first prepare the ferrous soluble-salt aqueous solution and preparation the first alkaline aqueous solution, then by above-mentioned two kinds of solution mixing.Ferrous ion and hydroxide ion react and generate ferrous hydroxide and precipitate, and then pass into oxygen, and ferrous hydroxide oxidation reaction occurs under being deposited in the effect of oxygen and generates FeOOH, i.e. the first active component.
In above-mentioned preparation method, those skilled in the art can also adopt another kind of by the first active component and the second active ingredient adsorption to the technical scheme on carrier.In another kind preferably embodiment, the step of adsorbing the first active component and the second active component on a catalyst support comprises: A1, by ferrous soluble-salt, mixes with water containing the soluble-salt of active element, catalyst carrier, forms the second slurries; A2, mixes the second alkali compounds with water, obtains the second alkaline solution; And A3, the second slurries and the second alkaline solution are reacted, filters, obtain Fe-series catalyst.
To comprise containing element Ni, Elements C o, elements Mo and element W containing in the soluble-salt of active element simultaneously, above-mentioned preparation process is described.In above-mentioned preparation method, first prepare simultaneously containing ferrous soluble-salt and the second slurries and the second alkaline aqueous solution that contain active element soluble-salt, then mixed with the second alkaline solution by the second slurries, ferrous ion, cobalt ions and nickel react with hydroxide ion to generate respectively and precipitate (Fe (OH)
2, Co (OH)
2with Ni (OH)
2); Pass into oxygen, under the effect of oxygen, only have Fe (OH)
2under the effect of oxygen, there is oxidation reaction, generate FeOOH, i.e. the first active component, and the second active component is respectively with Co (OH)
2, Ni (OH)
2, containing molybdenum soluble-salt and tungstenic soluble-salt form attachment on a catalyst support, obtained required Fe-series catalyst.
It should be noted that, in the real process of Kaolinite Preparation of Catalyst, a part in nickel compound containing and/or cobalt compound also can first adopt second method to be attached in catalyst carrier by those skilled in the art, then another part nickel compound containing and/or cobalt compound are being dissolved in the water, are adopting the mode of spray or dropping to be adsorbed onto on carrier.
In above-mentioned preparation method, those skilled in the art can select the kind of the soluble-salt containing active element.In one preferably embodiment, the soluble-salt containing active element includes but not limited to nickeliferous soluble-salt, containing molybdenum soluble-salt, containing one or more in cobalt soluble-salt and tungstenic soluble-salt; Wherein, nickeliferous soluble-salt includes but not limited to one or more in nickel nitrate, nickelous sulfate and nickel chloride; Ammonium molybdate and/or ammonium thiomolybdate is included but not limited to containing molybdenum soluble-salt; Cobalt nitrate is included but not limited to, one or more in cobaltous sulfate and cobalt chloride containing cobalt soluble-salt; Tungstenic soluble-salt includes but not limited to ammonium metatungstate, sodium tungstate and phosphotungstic acid. in one or more.Above-mentioned soluble-salt all has higher solubility, and stable chemical nature.Above-claimed cpd is adopted to be conducive to improving catalytic performance and the stability of catalyst.
In above-mentioned preparation method, those skilled in the art can select the kind of ferrous soluble-salt and the first alkali compounds and the second alkali compounds.In one preferably embodiment, ferrous soluble-salt includes but not limited to ferrous sulfate and/or frerrous chloride; First alkali compounds and the second alkali compounds be separately selected from sodium carbonate, ammoniacal liquor and NaOH one or more; Preferably, the first alkali compounds and the second alkali compounds are separately selected from sodium carbonate or ammoniacal liquor.Above-mentioned ferrous soluble-salt and alkali compounds have higher solubility, and raw material is easy to get, and are more suitable for industrialization large-scale production and application.
Beneficial effect of the present invention is further illustrated below in conjunction with embodiment.
Embodiment 1
Take 49.64gFeSO
47H
2o joins in 500g deionized water, after abundant stirring and dissolving, adds 100g dry pulverized coal, forms the copperas solution containing coal dust; The ammonia spirit of preparation 500g2%.Above-mentioned copperas solution containing coal dust and ammonia spirit are flow to material and make ferrous precipitation reaction to occur, and pass into air simultaneously and be oxidized, the reaction time is 60 minutes, and period controls ammoniacal liquor charging rate well to maintain reacting liquid pH value for 8.0; Controlling reaction temperature is 60 DEG C, the FeOOH slurries of rear generation coal dust load are reacted, these slurries are proceeded to centrifugation, acquisition filter cake adds deionized water and carries out making beating washing, carry out-centrifuge cycle of pulling an oar again, until record filtrate electrical conductivity when being less than 500 μ s/cm, the filter cake after washing is put into 80 DEG C of nitrogen drying casees dry 18 hours, by below solid porphyrize to 200 μm after drying, obtain the FeOOH powder of coal dust load.
Take 0.37g (NH
4)
6mo
7o
244H
2o is dissolved in 20g deionized water and forms molybdenum salting liquid, it is evenly added dropwise in above-mentioned powder, stirs, afterwards the powder that impregnated of molybdenum to be positioned in 80 DEG C of nitrogen drying casees dry 18 hours, be ground to after drying within 200um, obtain the Fe-series catalyst containing molybdenum.
Embodiment 2
This example is identical with embodiment 1, first prepares the FeOOH of powder load, then takes 1.34gNiSO
46H
2o is dissolved in 20g deionized water and forms nickel salt solution, it is evenly added dropwise in above-mentioned powder, stirs, afterwards the powder that impregnated of nickel to be positioned in 80 DEG C of nitrogen drying casees dry 18 hours, be ground to after drying within 200um, obtain nickeliferous Fe-series catalyst.
Embodiment 3
This example is identical with embodiment 1, first prepares the FeOOH of powder load, then takes 0.95gCoSO
47H
2o is dissolved in 20g deionized water and forms cobalt salt solution, it is evenly added dropwise in above-mentioned powder, stirs, afterwards the powder that impregnated of nickel to be positioned in 80 DEG C of nitrogen drying casees dry 18 hours, be ground to after drying within 200um, obtain the Fe-series catalyst containing cobalt, be set to 3# catalyst.
Embodiment 4
This example is identical with embodiment 1, first prepares the FeOOH of powder load, then takes 0.44g (NH
4)
6h
2w
12o
40.
xh
2o is dissolved in 20g deionized water and forms tungsten salt solution, it is evenly added dropwise in above-mentioned powder, stirs, afterwards the powder that impregnated of nickel to be positioned in 80 DEG C of nitrogen drying casees dry 18 hours, be ground to after drying within 200um, obtain the Fe-series catalyst of tungstenic.
Embodiment 5
Take 49.64gFeSO
47H
2o, 0.99gNi (NO
3)
26H
2o joins in 500g deionized water, after abundant stirring and dissolving, adds 150g dry pulverized coal, is formed containing the ferrous iron of coal dust and the mixed solution of nickel; The ammonia spirit of preparation 500g1.8%.Flow to material by above-mentioned make ferrous precipitation reaction to occur containing the ferrous iron of coal dust and the mixed solution of nickel and ammonia spirit, pass into air simultaneously and be oxidized, the reaction time is 100 minutes, and period controls ammoniacal liquor charging rate well to maintain reacting liquid pH value for 7.5; Controlling reaction temperature is 25 DEG C, the nickeliferous of rear generation coal dust load and FeOOH slurries are reacted, these slurries are proceeded to centrifugation, acquisition filter cake adds deionized water and carries out making beating washing, carry out-centrifuge cycle of pulling an oar again, until record filtrate electrical conductivity when being less than 500 μ s/cm, the filter cake after washing is put into 100 DEG C of nitrogen drying casees dry 16 hours, by below solid porphyrize to 200 μm after drying, obtain the powder of the nickeliferous of coal dust load and FeOOH.
Take 0.37g (NH
4)
6mo
7o
244H
2o is dissolved in 20g deionized water and forms molybdenum salting liquid, it is evenly added dropwise in above-mentioned powder, stirs, afterwards the powder that impregnated of molybdenum to be positioned in 100 DEG C of nitrogen drying casees dry 16 hours, be ground to after drying within 200um, obtain the Fe-series catalyst containing molybdenum and nickel.
Embodiment 6
Take 49.64gFeSO
47H
2o, 0.95gCoSO
47H
2o joins in 500g deionized water, after abundant stirring and dissolving, adds 80g dry pulverized coal, forms the mixed solution containing the ferrous iron of coal dust, nickel, cobalt; The ammonia spirit of preparation 500g1.8%.Flow to material by above-mentioned make ferrous precipitation reaction to occur containing the ferrous iron of coal dust, the mixed solution of cobalt and ammonia spirit, pass into air simultaneously and be oxidized, the reaction time is 160 minutes, and period controls ammoniacal liquor charging rate well to maintain reacting liquid pH value for 8.5; Controlling reaction temperature is 65 DEG C, that has reacted the load of rear generation coal dust contains cobalt, FeOOH slurries, these slurries are proceeded to centrifugation, acquisition filter cake adds deionized water and carries out making beating washing, carry out-centrifuge cycle of pulling an oar again, until record filtrate electrical conductivity when being less than 500 μ s/cm, the filter cake after washing is put into 60 DEG C of nitrogen drying casees dry 32 hours, by below solid porphyrize to 200 μm after drying, obtain the powder containing cobalt and FeOOH of coal dust load.
Take 0.37g (NH
4)
6mo
7o
244H
2o and 0.95gCoSO
47H
2o is dissolved in the solution forming molybdenum salt and cobalt salt in 20g deionized water, it is evenly added dropwise in above-mentioned powder, stir, afterwards the powder that impregnated of molybdenum and cobalt to be positioned in 60 DEG C of nitrogen drying casees dry 32 hours, be ground to after drying within 200um, obtain the Fe-series catalyst containing molybdenum and cobalt.
Embodiment 7
Take 49.64gFeSO
47H
2o, 0.45gNi (NO
3)
26H
2o, 0.48gCoSO
47H
2o joins in 500g deionized water, after abundant stirring and dissolving, adds 40g dry pulverized coal, forms the mixed solution containing the ferrous iron of coal dust, nickel, cobalt; The ammonia spirit of preparation 500g1.8%.The mixed solution of above-mentioned ferrous iron containing coal dust, nickel, cobalt and ammonia spirit are flow to material and make ferrous precipitation reaction to occur, and pass into air simultaneously and be oxidized, the reaction time is 160 minutes, and period controls ammoniacal liquor charging rate well to maintain reacting liquid pH value for 8.5; Controlling reaction temperature is 65 DEG C, nickeliferous, cobalt, the FeOOH slurries of the load of rear generation coal dust are reacted, these slurries are proceeded to centrifugation, acquisition filter cake adds deionized water and carries out making beating washing, carry out-centrifuge cycle of pulling an oar again, until record filtrate electrical conductivity when being less than 500 μ s/cm, the filter cake after washing is put into 60 DEG C of nitrogen drying casees dry 32 hours, by below solid porphyrize to 200 μm after drying, obtain the powder of nickeliferous, cobalt, the FeOOH of coal dust load.
Take 0.18g (NH
4)
6mo
7o
244H
2o and 0.45gNi (NO
3)
26H
2o, 0.48gCoSO
47H
2o is dissolved in the solution forming molybdenum salt and cobalt salt in 20g deionized water, it is evenly added dropwise in above-mentioned powder, stir, afterwards the powder that impregnated of molybdenum and cobalt to be positioned in 60 DEG C of nitrogen drying casees dry 32 hours, be ground to after drying within 200um, obtain the Fe-series catalyst containing molybdenum and cobalt.
Embodiment 8
Take 49.64gFeSO
47H
2o joins in 500g deionized water, forms sulfur acid ferrous iron solution after abundant stirring and dissolving; The ammonia spirit of preparation 500g2%.Above-mentioned copperas solution containing coal dust and ammonia spirit are flow to material and make ferrous precipitation reaction to occur, and pass into air simultaneously and be oxidized, the reaction time is 60 minutes, and period controls ammoniacal liquor charging rate well to maintain reacting liquid pH value for 8.0; Controlling reaction temperature is 60 DEG C, rear generation FeOOH slurries are reacted, 40g dry pulverized coal is added in this slurry, stir, FeOOH is fully mixed with coal dust, again these slurries are proceeded to centrifugation, acquisition filter cake adds deionized water and carries out making beating washing, carry out-centrifuge cycle of pulling an oar again, until record filtrate electrical conductivity when being less than 500 μ s/cm, filter cake after washing is put into 80 DEG C of nitrogen drying casees dry 18 hours, by below solid porphyrize to 200 μm after drying, obtain the FeOOH powder of coal dust load.
Take 0.18g (NH
4)
6mo
7o
244H
2o, 0.45gNi (NO
3)
26H
2o, 0.48gCoSO
47H
2o and 0.14g (NH
4) 6H
2w
12o
40.XH
2o is dissolved in 20g deionized water and forms molybdenum salting liquid, it is evenly added dropwise in above-mentioned powder, stirs, afterwards the powder that impregnated of molybdenum to be positioned in 80 DEG C of nitrogen drying casees dry 18 hours, be ground to after drying within 200um, obtain the Fe-series catalyst containing molybdenum, nickel, cobalt, tungsten.
Embodiment 9
Take 34.10gFeCl
24H
2o joins in 500g deionized water, forms chloride containing ferrous iron solution after abundant stirring and dissolving; The sodium carbonate liquor of preparation 300g10% concentration.Above-mentioned copperas solution containing coal dust and aqueous sodium carbonate are flow to material and make ferrous precipitation reaction to occur, and pass into air simultaneously and be oxidized, the reaction time is 60 minutes, and period controls the charging rate of sodium carbonate liquor well to maintain reacting liquid pH value for 6.5; Controlling reaction temperature is 50 DEG C, rear generation FeOOH slurries are reacted, 100g dry pulverized coal is added in this slurry, stir, FeOOH is fully mixed with coal dust, again these slurries are proceeded to centrifugation, acquisition filter cake adds deionized water and carries out making beating washing, carry out-centrifuge cycle of pulling an oar again, until record filtrate electrical conductivity when being less than 500 μ s/cm, filter cake after washing is put into 70 DEG C of nitrogen drying casees dry 24 hours, by below solid porphyrize to 200 μm after drying, obtain the FeOOH powder of coal dust load.
Take 0.45gNi (NO
3)
26H
2o, 0.48gCoSO
47H
2o is dissolved in 20g deionized water and forms molybdenum salting liquid, it is evenly added dropwise in above-mentioned powder, stirs, afterwards the powder that impregnated of nickel and cobalt to be positioned in 70 DEG C of nitrogen drying casees dry 24 hours, be ground to after drying within 200um, obtain Fe-series catalyst that is nickeliferous, cobalt.
Embodiment 10
Take 165.48gFeSO
47H
2o joins in 1000g deionized water, after abundant stirring and dissolving, adds 100g dry pulverized coal, forms the copperas solution containing coal dust; The ammonia spirit of preparation 2000g2%.Above-mentioned copperas solution containing coal dust and ammonia spirit are flow to material and make ferrous precipitation reaction to occur, and pass into air simultaneously and be oxidized, the reaction time is 60 minutes, and period controls ammonia spirit charging rate well to maintain reacting liquid pH value for 8.0; Controlling reaction temperature is 60 DEG C, the FeOOH slurries of rear generation coal dust load are reacted, these slurries are proceeded to centrifugation, acquisition filter cake adds deionized water and carries out making beating washing, carry out-centrifuge cycle of pulling an oar again, until record filtrate electrical conductivity when being less than 500 μ s/cm, the filter cake after washing is put into 80 DEG C of nitrogen drying casees dry 18 hours, by below solid porphyrize to 200 μm after drying, obtain the FeOOH powder of coal dust load.
Take 0.12g (NH
4)
6mo
7o
244H
2o is dissolved in 20g deionized water and forms molybdenum salting liquid, it is evenly added dropwise in above-mentioned powder, stirs, afterwards the powder that impregnated of molybdenum to be positioned in 80 DEG C of nitrogen drying casees dry 18 hours, be ground to after drying within 200um, obtain the Fe-series catalyst containing molybdenum.
Embodiment 11
Take 23.36gFeSO
47H
2o joins in 500g deionized water, after abundant stirring and dissolving, adds 100g active carbon, forms the copperas solution containing coal dust; The ammonia spirit of preparation 500g2%.Above-mentioned copperas solution containing coal dust and ammonia spirit are flow to material and make ferrous precipitation reaction to occur, and pass into air simultaneously and be oxidized, the reaction time is 60 minutes, and period controls ammonia spirit charging rate well to maintain reacting liquid pH value for 8.0; Controlling reaction temperature is 60 DEG C, the FeOOH slurries of rear generation coal dust load are reacted, these slurries are proceeded to centrifugation, acquisition filter cake adds deionized water and carries out making beating washing, carry out-centrifuge cycle of pulling an oar again, until record filtrate electrical conductivity when being less than 500 μ s/cm, the filter cake after washing is put into 80 DEG C of nitrogen drying casees dry 18 hours, by below solid porphyrize to 200 μm after drying, obtain the FeOOH powder of coal dust load.
Take 0.13g (NH
4)
6mo
7o
244H
2o is dissolved in 20g deionized water and forms molybdenum salting liquid, it is evenly added dropwise in above-mentioned powder, stirs, afterwards the powder that impregnated of molybdenum to be positioned in 80 DEG C of nitrogen drying casees dry 18 hours, be ground to after drying within 200um, obtain the Fe-series catalyst containing molybdenum.
Embodiment 12
Take 62.05gFeSO
47H
2o joins in 500g deionized water, after abundant stirring and dissolving, adds 100g dry pulverized coal, forms the copperas solution containing coal dust; The ammonia spirit of preparation 500g2%.Above-mentioned copperas solution containing coal dust and ammonia spirit are flow to material and make ferrous precipitation reaction to occur, and pass into air simultaneously and be oxidized, the reaction time is 60 minutes, and period controls ammonia spirit charging rate well to maintain reacting liquid pH value for 8.0; Controlling reaction temperature is 60 DEG C, the FeOOH slurries of rear generation coal dust load are reacted, these slurries are proceeded to centrifugation, acquisition filter cake adds deionized water and carries out making beating washing, carry out-centrifuge cycle of pulling an oar again, until record filtrate electrical conductivity when being less than 500 μ s/cm, the filter cake after washing is put into 80 DEG C of nitrogen drying casees dry 18 hours, by below solid porphyrize to 200 μm after drying, obtain the FeOOH powder of coal dust load.
Take 2.3g (NH
4)
6mo
7o
244H
2o is dissolved in 20g deionized water and forms molybdenum salting liquid, it is evenly added dropwise in above-mentioned powder, stirs, afterwards the powder that impregnated of molybdenum to be positioned in 80 DEG C of nitrogen drying casees dry 18 hours, be ground to after drying within 200um, obtain the Fe-series catalyst containing molybdenum.
Embodiment 13
Take 297.86gFeSO
47H
2o joins in 1000g deionized water, after abundant stirring and dissolving, adds 100g dry pulverized coal, forms the copperas solution containing coal dust; The ammonia spirit of preparation 3000g2%.Above-mentioned copperas solution containing coal dust and ammonia spirit are flow to material and make ferrous precipitation reaction to occur, and pass into air simultaneously and be oxidized, the reaction time is 60 minutes, and period controls ammonia spirit charging rate well to maintain reacting liquid pH value for 8.0; Controlling reaction temperature is 60 DEG C, the FeOOH slurries of rear generation coal dust load are reacted, these slurries are proceeded to centrifugation, acquisition filter cake adds deionized water and carries out making beating washing, carry out-centrifuge cycle of pulling an oar again, until record filtrate electrical conductivity when being less than 500 μ s/cm, the filter cake after washing is put into 80 DEG C of nitrogen drying casees dry 18 hours, by below solid porphyrize to 200 μm after drying, obtain the FeOOH powder of coal dust load.
Take 0.07g (NH
4)
6mo
7o
244H
2o is dissolved in 20g deionized water and forms molybdenum salting liquid, it is evenly added dropwise in above-mentioned powder, stirs, afterwards the powder that impregnated of molybdenum to be positioned in 80 DEG C of nitrogen drying casees dry 18 hours, be ground to after drying within 200um, obtain the Fe-series catalyst containing molybdenum.
Embodiment 14
Take 114.56gFeSO
47H
2o joins in 1000g deionized water, after abundant stirring and dissolving, adds 100g dry pulverized coal, forms the copperas solution containing coal dust; The ammonia spirit of preparation 1000g2%.Above-mentioned copperas solution containing coal dust and ammonia spirit are flow to material and make ferrous precipitation reaction to occur, and pass into air simultaneously and be oxidized, the reaction time is 60 minutes, and period controls ammonia spirit charging rate well to maintain reacting liquid pH value for 8.0; Controlling reaction temperature is 60 DEG C, the FeOOH slurries of rear generation coal dust load are reacted, these slurries are proceeded to centrifugation, acquisition filter cake adds deionized water and carries out making beating washing, carry out-centrifuge cycle of pulling an oar again, until record filtrate electrical conductivity when being less than 500 μ s/cm, the filter cake after washing is put into 80 DEG C of nitrogen drying casees dry 18 hours, by below solid porphyrize to 200 μm after drying, obtain the FeOOH powder of coal dust load.
Take 0.85g (NH
4)
6mo
7o
244H
2o is dissolved in 20g deionized water and forms molybdenum salting liquid, it is evenly added dropwise in above-mentioned powder, stirs, afterwards the powder that impregnated of molybdenum to be positioned in 80 DEG C of nitrogen drying casees dry 18 hours, be ground to after drying within 200um, obtain the Fe-series catalyst containing molybdenum.
Embodiment 15
Take 16.55gFeSO
47H
2o joins in 500g deionized water, after abundant stirring and dissolving, adds 100g dry pulverized coal, forms the copperas solution containing coal dust; The sodium hydroxide solution of preparation 500g2%.Above-mentioned copperas solution containing coal dust and sodium hydroxide solution are flow to material and make ferrous precipitation reaction to occur, pass into air to be oxidized simultaneously, reaction time is 60 minutes, and period controls sodium hydrate aqueous solution charging rate well to maintain reacting liquid pH value for 8.0; Controlling reaction temperature is 60 DEG C, the FeOOH slurries of rear generation coal dust load are reacted, these slurries are proceeded to centrifugation, acquisition filter cake adds deionized water and carries out making beating washing, carry out-centrifuge cycle of pulling an oar again, until record filtrate electrical conductivity when being less than 500 μ s/cm, the filter cake after washing is put into 80 DEG C of nitrogen drying casees dry 18 hours, by below solid porphyrize to 200 μm after drying, obtain the FeOOH powder of coal dust load.
Take 0.27g (NH
4)
6mo
7o
244H
2o is dissolved in 20g deionized water and forms molybdenum salting liquid, it is evenly added dropwise in above-mentioned powder, stirs, afterwards the powder that impregnated of molybdenum to be positioned in 80 DEG C of nitrogen drying casees dry 18 hours, be ground to after drying within 200um, obtain the Fe-series catalyst containing molybdenum.
Embodiment 16
Take 579.17gFeSO
47H
2o joins in 2000g deionized water, after abundant stirring and dissolving, adds 100g active carbon, forms the copperas solution containing coal dust; The ammonia spirit of preparation 5000g2%.Above-mentioned copperas solution containing coal dust and ammonia spirit are flow to material and make ferrous precipitation reaction to occur, and pass into air simultaneously and be oxidized, the reaction time is 60 minutes, and period controls ammonia spirit charging rate well to maintain reacting liquid pH value for 8.0; Controlling reaction temperature is 60 DEG C, the FeOOH slurries of rear generation coal dust load are reacted, these slurries are proceeded to centrifugation, acquisition filter cake adds deionized water and carries out making beating washing, carry out-centrifuge cycle of pulling an oar again, until record filtrate electrical conductivity when being less than 500 μ s/cm, the filter cake after washing is put into 80 DEG C of nitrogen drying casees dry 18 hours, by below solid porphyrize to 200 μm after drying, obtain the FeOOH powder of coal dust load.
Take 6.13g (NH
4)
6mo
7o
244H
2o is dissolved in 50g deionized water and forms molybdenum salting liquid, it is evenly added dropwise in above-mentioned powder, stirs, afterwards the powder that impregnated of molybdenum to be positioned in 80 DEG C of nitrogen drying casees dry 18 hours, be ground to after drying within 200um, obtain the Fe-series catalyst containing molybdenum.
Comparative example 1
Take 49.64gFeSO
47H
2o joins in 500g deionized water, after abundant stirring and dissolving, adds 100g dry pulverized coal, forms the copperas solution containing coal dust; The ammonia spirit of preparation 500g2%.Above-mentioned copperas solution containing coal dust and ammonia spirit are flow to material and make ferrous precipitation reaction to occur, and pass into air simultaneously and be oxidized, the reaction time is 60 minutes, and period controls ammoniacal liquor charging rate well to maintain reacting liquid pH value for 8.0; Controlling reaction temperature is 60 DEG C, the FeOOH slurries of rear generation coal dust load are reacted, these slurries are proceeded to centrifugation, acquisition filter cake adds deionized water and carries out making beating washing, carry out-centrifuge cycle of pulling an oar again, until record filtrate electrical conductivity when being less than 500 μ s/cm, the filter cake after washing is put into 80 DEG C of nitrogen drying casees dry 18 hours, after dry drying, namely the powder below solid porphyrize to 150 μm is obtained comparative catalyst, be designated as 10# catalyst.
In embodiment 1 to 16 and comparative example 1, the composition of the catalyst of preparation is in table 1;
Performance test: take a certain amount of catalyst respectively and carry out coal liquefaction autoclave test.Coal liquefaction performance test process is as follows:
A certain amount of catalyst of accurate weighing, adds in 500mL autoclave Coal liquefaction.Test coal sample used, Industrial Analysis and results of elemental analyses are in table 2, and the addition of coal dust is 30g; With coal liquefaction recycle oil for solvent, solvent adding amount is 45g, and it is 1:100 that the catalyst measurement criteria added is Fe/ dry coal weight ratio, adds 0.34g sulphur powder.
Autoclave reacts cold hydrogen first pressing 10MPa, 450 DEG C of constant temperature 1h, react complete quick cooling, get gas sample and survey its composition, collect reacted liquid-solid phase, respectively by n-hexane and oxolane Soxhlet extraction 48h, by extracting residue ashing, calculate data such as obtaining coal conversion ratio, oily yield, gas productive rate, pitch productive rate, specifically in table 3.
The composition of table 1 catalyst
The Industrial Analysis of table 2 coal and elementary analysis
The coal liquefaction experimental result of table 3 catalyst
From above description, can find out, the above embodiments of the present invention achieve following technique effect: as can be seen from the data recorded in table 3, compared to comparative example 1, adopt catalyst provided by the invention, in coal liquefaction application, the conversion ratio of coal and liquefaction oil productive rate are all improved, particularly oily yield castering action is obvious, illustrates that catalyst hydrogenation activity in Coal liquefaction that invention provides is higher thus.
In Fe-series catalyst, introduce two kinds of active components, effectively can improve Fe-series catalyst self hydrogenation activity in DCL/Direct coal liquefaction process.Meanwhile, above-mentioned two active component wide material sources, cost are lower, make the production cost of this Fe-series catalyst provided by the present invention lower, are more suitable for industrialization large-scale production and application.
These are 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 amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (13)
1. a Fe-series catalyst, is characterized in that, described Fe-series catalyst comprises the first active component, the second active component and catalyst carrier; Wherein, described first active component comprises FeOOH; Described second active component comprises the compound containing active element, and described active element is one or more in element Ni, Elements C o, elements Mo and element W.
2. Fe-series catalyst according to claim 1, is characterized in that, in Fe element, described first active component accounts for 3 ~ 30% of described Fe-series catalyst weight, preferably accounts for 4.0 ~ 20.0%; In described active element, described second active component accounts for 0.01 ~ 1% of described Fe-series catalyst weight, preferably accounts for 0.02 ~ 0.8%.
3. Fe-series catalyst according to claim 2, is characterized in that, the weight ratio of described active element and Fe element is 0.1 ~ 10%.
4. Fe-series catalyst according to any one of claim 1 to 3, is characterized in that, described catalyst carrier accounts for 30 ~ 90% of described Fe-series catalyst weight, preferably accounts for 60 ~ 85%.
5. Fe-series catalyst according to claim 4, is characterized in that, the particle diameter of described catalyst carrier is less than 200 μm.
6. Fe-series catalyst according to claim 5, is characterized in that, described catalyst carrier be selected from coal dust, active carbon and CNT one or more.
7. Fe-series catalyst according to claim 1, is characterized in that, weight percentage, and described Fe-series catalyst also comprises the water of 2 ~ 10%.
8. a preparation method for the Fe-series catalyst according to any one of claim 1 to 7, is characterized in that, described preparation method comprises the following steps:
Adsorb the first active component and the second active component on a catalyst support;
Wherein, described first active component comprises FeOOH; Described second active component comprises the compound containing active element, and described active element is one or more in element Ni, Elements C o, elements Mo and element W.
9. preparation method according to claim 8, is characterized in that, the step that described catalyst carrier is adsorbed described first active component and described second active component comprises:
S1, preparation is adsorbed with the described catalyst carrier of described first active component; And
S2, is mixed to form mixed liquor by the soluble-salt and water that contain described active element, is attached to by described mixed liquor in the described catalyst carrier being adsorbed with described first active component, dry, obtains described Fe-series catalyst.
10. preparation method according to claim 9, is characterized in that, described step S1 is further comprising the steps of:
S11, mixes ferrous soluble-salt, described catalyst carrier with water, obtains the first slurries;
S12, mixes the first alkali compounds with water, obtains the first alkaline solution; And
Described first slurries and described first alkaline solution are reacted by S13, filter, obtain the described catalyst carrier being adsorbed with described first active component.
11. preparation methods according to claim 8, is characterized in that, the step that described catalyst carrier is adsorbed described first active component and described second active component comprises:
A1, by ferrous soluble-salt, mixes with water containing the soluble-salt of described active element, described catalyst carrier, forms the second slurries;
A2, mixes the second alkali compounds with water, obtains the second alkaline solution; And
Described second slurries and described second alkaline solution are reacted by A3, filter, obtain described Fe-series catalyst.
12. preparation methods according to claim 9 or 11, is characterized in that, the described soluble-salt containing active element is selected from nickeliferous soluble-salt, containing molybdenum soluble-salt, containing one or more in the group of cobalt soluble-salt and tungstenic soluble-salt composition; Wherein,
Described nickeliferous soluble-salt be selected from nickel nitrate, nickelous sulfate and nickel chloride composition group in one or more;
The described molybdenum soluble-salt that contains is selected from ammonium molybdate and/or ammonium thiomolybdate;
Described containing cobalt soluble-salt be selected from cobalt nitrate, cobaltous sulfate and cobalt chloride composition group in one or more;
Described tungstenic soluble-salt is selected from ammonium metatungstate, sodium tungstate and phosphotungstic acid. one or more in the group of composition.
13. preparation methods according to claim 10 or 11, is characterized in that,
Described ferrous soluble-salt is selected from ferrous sulfate and/or frerrous chloride; Described first alkali compounds and described second alkali compounds be separately selected from sodium carbonate, ammoniacal liquor and NaOH composition group in one or more; Preferably, described first alkali compounds and described second alkali compounds are separately selected from sodium carbonate or ammoniacal liquor.
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| CN106000413A (en) * | 2016-06-15 | 2016-10-12 | 河南大学 | Method for preparing molybdenum doped akaganeite nanoparticles |
| CN108579778A (en) * | 2018-03-19 | 2018-09-28 | 煤炭科学技术研究院有限公司 | A kind of carbon nanotube is the hydrogenation catalyst and the preparation method and application thereof of carrier |
| CN109647535A (en) * | 2018-12-28 | 2019-04-19 | 中国船舶重工集团公司第七八研究所 | A kind of loaded ferrum-based catalyst of coal |
| CN111876189A (en) * | 2020-07-21 | 2020-11-03 | 中国神华煤制油化工有限公司 | Method for two-stage catalytic direct liquefaction of coal and application thereof |
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