CN103480407A - Iron-based catalyst auxiliary as well as preparation method and application thereof - Google Patents
Iron-based catalyst auxiliary as well as preparation method and application thereof Download PDFInfo
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- CN103480407A CN103480407A CN201310450370.0A CN201310450370A CN103480407A CN 103480407 A CN103480407 A CN 103480407A CN 201310450370 A CN201310450370 A CN 201310450370A CN 103480407 A CN103480407 A CN 103480407A
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Abstract
The invention provides an iron-based catalyst auxiliary as well as a preparation method and an application thereof. The auxiliary comprises the components in percentage by weight as follows: 25%-60% of molecular sieves, 1%-20% of ferric oxide and 25%-75% of N-doped carbon nano tubes, wherein nitrogen content of the carbon nano tubes is 1 wt% to 30 wt%; ferric oxide and N-doped carbon nano tubes are loaded on the molecular sieves; and Fe-N-C centers are formed between at least a part of ferric oxide and at least a part of carbon nano tubes in the iron-based catalyst auxiliary. According to the iron-based catalyst auxiliary, the carbon nano tubes and ferric oxide are highly dispersed on the molecular sieves to generate more stable active centers; ferric oxide and nitrogen are tightly combined to support walls of the carbon nano tubes stably and form Fe-N-C centers with the carbon nano tubes, so that the hydrogenation capacity of iron is improved; the carbon nano tubes have very high strength, so that activity exertion of Fe can be effectively maintained; and the N-doped carbon nano tubes facilitate reduction of acidity of the auxiliary, and oil molecules can be effectively prevented from being excessively degraded.
Description
Technical field
The present invention relates to the catalyst preparation field, in particular to a kind of Fe-series catalyst auxiliary agent and its preparation method and application.Background technology
DCL/Direct coal liquefaction is under the condition of HTHP, by means of the effect of hydrogen supply dissolvent and catalyst, makes hydrogen enter the molecular structure of coal and derivative thereof, thereby coal is converted into to the clean coal technology of product liquid.DCL/Direct coal liquefaction is complicated physics, chemical process, and its influence factor is numerous, mainly comprises: the kind of coal and character, reactor character, catalyst, solvent, reaction temperature and time, atmosphere etc.Wherein, because the activity and selectivity of catalyst greatly affects reaction rate, conversion ratio, oily productive rate, gas yield and the hydrogen consumption of coal liquefaction, thereby exploitation and the design catalytic activity is high, selectively good and cheap catalyst is the focus of DCL/Direct coal liquefaction research always.
Catalyst for coal liquefaction can be divided into three major types: the first kind is oil hydrofinishing class catalyst, as cobalt (Co), molybdenum (Mo), nickel (Ni) catalyst that is reactive metal; Equations of The Second Kind is metal halide catalyst, as ZnCl
2, SnCl
2deng; The 3rd class is Fe-series catalyst, comprises the natural crystal of iron content, the industrial residu of iron content and the compound (as oxide, sulfide and the hydroxide of iron) of various pure state iron.Result of study shows, the catalytic activity of oil Hydrobon catalyst is higher, but this metalloid catalyst price comparison costliness is difficult to reclaim and regeneration in the Coal liquefaction system; Metal halide catalyst belongs to acidic catalyst, and cracking ability is strong, but the equipment of coal liquification device is had to stronger corrosiveness, has not now used this class catalyst; The Fe-series catalyst activity is moderate, has higher cost performance, once uses and need not reclaim, and this class catalyst claims again abandoning property catalyst, is emphasis and the direction of coal direct liquefaction catalyst research.
A large amount of research has all been done to Fe-series catalyst by research institution both at home and abroad for many years, comprises the natural crystal of iron content, the industrial residu of iron content and the compound (as oxide, sulfide and the hydroxide etc. of iron) of various pure state iron.The brown coal liquefaction process of Japan adopts limonite as catalyst for coal liquefaction, has obtained Expected Results, in German coal liquefaction craft, has adopted aluminium making residue, claims again red mud as catalyst.Yet while using the ore class as the Fe-series catalyst of representative, though the ultra-fine grinding of ore can improve active, but the ultra-fine grinding meeting brings larger power consumption, increased the coal liquefaction cost, because the larger real density of iron ore makes it, in course of conveying and in reactor, all easily deposit in addition, the coal supply liquefaction process brings hidden danger.And the abandoning property catalyst that red mud is representative, addition is large, has increased the load of reactor, simultaneously in the Separation of Solid and Liquid process of decompression distillation because too much catalyst adds, the oil mass of taking out of from residue also can increase, and has reduced the integral body oil yield in the coal liquefaction process.
Therefore, according to the characteristics of coal liquefaction, usually adopt at present the higher Fe-series catalyst of cost performance, this type of catalyst changes into Fe in course of reaction under hydrogen sulfide and atmosphere of hydrogen
1-xs, it is considered to the form of expression of iron catalyst usually, as U.S. HTI company has developed artificial synthetic high dispersive iron catalyst (GelCat
tM), addition is 0.5wt%; And " 863 effective catalyst " that Shenhua Group and China Coal Research Institute are developed jointly is the synthetic hydrated ferric oxide FeOOH of ferrous sulfate and ammonia precipitation process, addition is 1wt%, has realized at present industrialization, has obtained good effect.
Although, can be by several different methods as increased the dispersiveness of catalyst, reduce catalyst grain size, avoid the activity of the measure raising Fe-series catalysts such as catalyst particle Second Aggregation, reduce the use amount of catalyst, and then improve the conversion ratio of coal and the productive rate of liquefaction oil, but itself hydrogenation activity of Fe-series catalyst relatively a little less than, there is certain limitation in deep conversion to coal, therefore, if according to the research mode of prior art, Fe-series catalyst itself is improved and can not obtain positive effect.
Summary of the invention
The present invention aims to provide a kind of Fe-series catalyst auxiliary agent and its preparation method and application, to solve the relatively weak problem of itself hydrogenation activity of Fe-series catalyst in prior art.
To achieve these goals, according to an aspect of the present invention, provide a kind of Fe-series catalyst auxiliary agent, this Fe-series catalyst auxiliary agent comprises that weight percentage is: 25～60% molecular sieve; 1～20% iron oxide; And the CNT of 25～75% nitrogen doping, the nitrogen content in CNT is 1～30wt%; Wherein, iron oxide and nitrogen doping carbon nanotube loaded on molecular sieve, and there is the Fe-N-C center between iron oxide and at least part of CNT at least partly in the Fe-series catalyst auxiliary agent.
Further, in above-mentioned Fe-series catalyst auxiliary agent, the molecular sieve weight content is 25～50%, the iron oxide weight content is 5～15%, the CNT weight content of nitrogen doping is 35～65wt%, and the nitrogen content in CNT is 10～30wt%.
Further, the multi-walled carbon nano-tubes that above-mentioned CNT is Bamboo-shaped, the caliber of multi-walled carbon nano-tubes is 20～70nm, joint length is 8～80nm.
Further, above-mentioned molecular sieve is mesopore molecular sieve or micro porous molecular sieve, preferably SAPO-5 molecular sieve, SAPO-11 molecular sieve, SAPO-31 molecular sieve, SAPO-36 molecular sieve, SBA-15 molecular sieve or NaY molecular sieve.
According to a further aspect in the invention, a kind of preparation method of Fe-series catalyst auxiliary agent is provided, this preparation method comprises: the iron in iron salt solutions is loaded on the roasting molecular sieve, form load molecular sieve, wherein, the mass ratio of iron salt solutions and roasting molecular sieve is 0.5:1～4.5:1, and in iron salt solutions, the weight percentage of Fe is 1～10%; Step S2 is reacted liquid organic amine and load molecular sieve under 650～1000 ℃, obtains the Fe-series catalyst auxiliary agent, and wherein, the consumption of liquid organic amine is 10～40ml/g load molecular sieve.
Further, above-mentioned steps S2 comprises: by liquid organic amine, make liquid organic amine be carried and form organic amine steam by carrier gas carrier gas; Under 650～1000 ℃, pass into organic amine steam to load molecular sieve, and keep 0.5～5h, obtain the Fe-series catalyst auxiliary agent.
Further, above-mentioned carrier gas is selected from a kind of in nitrogen and inert gas.
Further, above-mentioned carrier gas also comprises ammonia, and in carrier gas, the volumn concentration of ammonia is below 20%.
Further, above-mentioned organic amine is selected from one or more in the group that hexa, ethylenediamine, ethamine, propylamine, diethylamine, triethylamine form.
Further, above-mentioned steps S1 comprises: iron salt solutions is mixed with the roasting molecular sieve, form mixture, the mass ratio of iron salt solutions and roasting molecular sieve is 1:1～4:1; Mixture is carried out under 100～150 ℃ to drying, obtain solid-state dry; Solid-state dry, at 500～850 ℃ of lower roasting 2～8h, is obtained to load molecular sieve.
Further, above-mentioned iron salt solutions mixes and comprises with the roasting molecular sieve: under stirring condition, iron salt solutions is dropwise joined in the roasting molecular sieve, form mixture.
Further, above-mentioned iron salt solutions is iron nitrate solution, ferrum sulfuricum oxydatum solutum or copperas solution.
Further, above-mentioned roasting molecular sieve is the molecular sieve at 500～850 ℃ of lower roasting 2～8h.
Further, above-mentioned preparation method also comprises the process more than 100 orders that load molecular sieve is ground between step S1 and step S2.
Further, above-mentioned molecular sieve is mesopore molecular sieve or micro porous molecular sieve, preferably SAPO-5 molecular sieve, SAPO-11 molecular sieve, SAPO-31 molecular sieve, SAPO-36 molecular sieve, SBA-15 molecular sieve or NaY molecular sieve.
According to another aspect of the invention, provide a kind of above-mentioned application of Fe-series catalyst auxiliary agent in coal liquefaction.
Apply technical scheme of the present invention, the CNT that comprises the molecular sieve of rational proportion in the Fe-series catalyst auxiliary agent simultaneously and load on iron oxide and nitrogen doping on molecular sieve, CNT and iron oxide high degree of dispersion on molecular sieve, thus more multistable fixed activated centre generated on molecular sieve; The iron oxide of high degree of dispersion, with the combine closely tube wall of stable support CNT of nitrogen, and and CNT between form the Fe-N-C center, make the hydrogenation ability of iron get a promotion, almost be equivalent to the hydrogenation ability of the noble metals such as Ni, Mo; And CNT itself has high intensity, at the catalytic process meso-hole structure, be difficult for caving in, therefore can effectively maintain the activity performance of active component Fe; Simultaneously, the CNT of nitrogen doping contributes to reduce the acidity of auxiliary agent, can effectively avoid the little molecule byproduct of the too deteriorated generation of oil product molecule in being applied to Coal liquefaction; Further, this Fe-series catalyst auxiliary agent has the characteristic of the bigger serface of molecular sieve and CNT, and then has optimized the catalytic activity of Fe-series catalyst auxiliary agent.Coordinate other Fe-series catalysts to use catalyst promoter of the present invention, can effectively regulate the hydrogenation effect of coal liquefaction system, and then improve the conversion ratio of coal and the yield of liquefaction oil, promote DCL/Direct coal liquefaction efficiency.
The accompanying drawing explanation
The Figure of description that forms the application's a part is used to provide a further understanding of the present invention, and schematic description and description of the present invention the present invention does not form inappropriate limitation of the present invention for explaining.In the accompanying drawings:
Fig. 1 shows the SEM Electronic Speculum figure according to the catalyst promoter of embodiments of the invention 1;
Fig. 2 shows the SEM Electronic Speculum figure according to the catalyst promoter of embodiments of the invention 5; And
Fig. 3 shows the SEM Electronic Speculum figure according to the catalyst promoter of embodiments of the invention 8.
The specific embodiment
It should be noted that, in the situation that do not conflict, embodiment and the feature in 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 application is in order to solve the relatively weak problem of itself hydrogenation activity of Fe-series catalyst, taked to improve in different and prior art the method for Fe-series catalyst itself, a kind of Fe-series catalyst auxiliary agent and preparation method thereof has been proposed, this Fe-series catalyst auxiliary agent and Fe-series catalyst are used in conjunction with, have obviously improved the hydrogenation activity of Fe-series catalyst.Therefore in a kind of typical embodiment of the present invention, a kind of Fe-series catalyst auxiliary agent is provided, above-mentioned Fe-series catalyst auxiliary agent comprises the CNT of the nitrogen doping of molecular sieve that weight percentage is 25～60%, 1～20% iron oxide and 25～75%, and the nitrogen content in CNT is 1～30wt%; Wherein, described iron oxide and nitrogen doping carbon nanotube loaded on described molecular sieve, and there is the Fe-N-C center between iron oxide and at least part of CNT at least partly in the Fe-series catalyst auxiliary agent.
The CNT that comprises the molecular sieve of rational proportion in Fe-series catalyst auxiliary agent of the present invention simultaneously and load on iron oxide and nitrogen doping on molecular sieve, CNT and iron oxide high degree of dispersion on molecular sieve is conducive to Fe-series catalyst and generates more multistable fixed activated centre on molecular sieve when being used in conjunction with Fe-series catalyst; The iron oxide of high degree of dispersion, with the combine closely tube wall of stable support CNT of nitrogen, and and CNT between form the Fe-N-C center, make the hydrogenation ability of iron get a promotion, almost be equivalent to the hydrogenation ability of the noble metals such as Ni, Mo; And CNT itself has high intensity, at the catalytic process meso-hole structure, be difficult for caving in, therefore can effectively maintain the activity performance of active component Fe; Simultaneously, the CNT of nitrogen doping contributes to reduce the acidity of auxiliary agent, can effectively avoid the little molecule byproduct of the too deteriorated generation of oil product molecule in being applied to Coal liquefaction; Further, this Fe-series catalyst auxiliary agent has the characteristic of the bigger serface of molecular sieve and CNT, and then has optimized the catalytic activity of Fe-series catalyst auxiliary agent.Coordinate Fe-series catalyst to use catalyst promoter of the present invention, can effectively regulate the hydrogenation effect of coal liquefaction system, and then improve the conversion ratio of coal and the yield of liquefaction oil, promote DCL/Direct coal liquefaction efficiency.
In a kind of preferred embodiment of the present invention, in above-mentioned Fe-series catalyst auxiliary agent, the molecular sieve weight content is 25～50%, the iron oxide weight content is 5～15%, the CNT weight content of nitrogen doping is 35～65%, and the nitrogen content in CNT is 10～30wt%.This embodiment has optimized the proportioning of CNT, iron oxide and the nitrogen of Fe-series catalyst auxiliary agent, has therefore further improved the catalytic activity of this Fe-series catalyst auxiliary agent in Coal liquefaction.
The multi-walled carbon nano-tubes that CNT in Fe-series catalyst of the present invention is Bamboo-shaped, the caliber of multi-walled carbon nano-tubes is 20～70nm, joint length is 8～80nm.The wall of CNT is many walls, has strengthened the intensity of CNT, and then has improved the intensity of catalyst promoter; And the caliber of CNT is 20～70nm, joint length is 8～80nm, makes CNT have larger specific area on the one hand, more is conducive on the other hand the distribution of CNT on molecular sieve.
Can be used for molecular sieve of the present invention is mesopore molecular sieve or micro porous molecular sieve.In a preferred embodiment, preferred above-mentioned molecular sieve is SAPO-5 molecular sieve, SAPO-11 molecular sieve, SAPO-31 molecular sieve, SAPO-36 molecular sieve, SBA-15 molecular sieve or NaY molecular sieve.
In the another kind of typical embodiment of the present invention, a kind of preparation method of Fe-series catalyst auxiliary agent is provided, this preparation method comprises: the iron in iron salt solutions is loaded on the roasting molecular sieve, form load molecular sieve, wherein, the mass ratio of iron salt solutions and roasting molecular sieve is 0.5:1～4.5:1, and in iron salt solutions, the weight percentage of Fe is 1～10%; Step S2 is reacted liquid organic amine and load molecular sieve under 650～1000 ℃, obtains the Fe-series catalyst auxiliary agent, and wherein, the consumption of liquid organic amine is 10～40ml/g load molecular sieve.
Above-mentioned embodiment can adopt the molecular sieve carried heteroatomic method that the application commonly uses that iron is loaded on the roasting molecular sieve and forms load molecular sieve, and then under 650～1000 ℃, make load molecular sieve and organic amine react to form nitrogenous CNT, due to the ferro element of load on molecular sieve can the catalyzed carbon nanotube formation, therefore further improved formation speed and the quality of CNT; And, when forming CNT, the carbon in organic amine steam, nitrogen element and ferro element have formed the Fe-N-C center, have strengthened the intensity of Fe-series catalyst auxiliary agent when for the Fe-series catalyst auxiliary agent, having increased new high activity center.And, the present invention is by controlling the amount ratio of organic amine and molecular sieve, obtain the Fe-series catalyst auxiliary agent of the content of carbon nanotubes of suitable nitrogen doping, having of the nitrogen-doped nanometer pipe of high-intensity Optimum Contents is beneficial to catalytic activity and the intensity that improves resulting Fe-series catalyst auxiliary agent.
And in above-mentioned embodiment, difference due to iron salt dissolved degree and roasting molecular sieve absorption of water, the mass ratio of iron salt solutions and roasting molecular sieve is controlled to 0.5:1～4.5:1, and in the control iron salt solutions, the weight percentage of Fe is 1～10%, thereby the enough and uniform Fe of load on the roasting molecular sieve have been guaranteed; In order further to optimize load capacity and the load quality of Fe, preferably in iron salt solutions, the weight percentage of Fe is 3～6%.
In another preferred embodiment of the present invention, above-mentioned preparation method's step S2 by liquid organic amine, makes liquid organic amine be carried and form organic amine steam by carrier gas carrier gas; Under 650～1000 ℃, pass into organic amine steam to load molecular sieve, and keep 0.5～5h, obtain the Fe-series catalyst auxiliary agent.
Utilize carrier gas to pass through liquid organic amine, make organic amine be entrained in carrier gas and be dispersed in carrier gas and form organic amine steam, be conducive to more disperse, form more efficiently CNT on load molecular sieve, wherein the reaction time is not limited in 5h, proper extension in 0.5～5h is conducive to the generation of more CNTs, but the growth of overlong time CNT is not obvious, therefore, the application preferably keeps 0.5～5h.
Carrier gas of the present invention is selected from a kind of in nitrogen and inert gas.Utilize nitrogen or the inert gas that chemical reactivity is lower can the formation of CNT not to be had a negative impact as carrier gas.
In another preferred embodiment of the present invention, above-mentioned carrier gas also comprises ammonia, and in carrier gas, the volumn concentration of ammonia is below 20%.Mix certain ammonia in carrier gas, can regulate neatly the nitrogen content in the CNT of nitrogen doping, and then obtain catalytic activity Fe-series catalyst auxiliary agent easy to control in size.
Organic amine of the present invention is selected from one or more in the group that hexa, ethylenediamine, ethamine, propylamine, diethylamine, triethylamine form.Therefore above-mentioned organic amine major part can be used as the template of Zeolite synthesis, can not have a negative impact to the performance of load molecular sieve, and be that liquid can synthetic raw material be used as CNT more easily.
In another preferred embodiment of the present invention, above-mentioned preparation method's step S1 comprises: iron salt solutions is mixed with the roasting molecular sieve, and the mass ratio of iron salt solutions and roasting molecular sieve is 1:1～4:1, forms mixture; Mixture is carried out under 100～150 ℃ to drying, obtain solid-state dry; Solid-state dry, at 500～850 ℃ of lower roasting 2～8h, is obtained to load molecular sieve.
In the above-mentioned preferred embodiment of the present invention, dry run under the mixture of molysite and roasting molecular sieve is passed through to 100～150 ℃, the binding ability of strengthening iron and roasting molecular sieve, and, above-mentioned dipping and dry process can be carried out in gradation, those skilled in the art can select dipping and dry number of times according to the water imbibition of amount, dissolubility and the applied roasting molecular sieve of adopted molysite etc., and the water absorption of or roasting molecular sieve larger than the amount of iron salt solutions as configured hour can suitably increase dipping and dry number of times; And, at roasting process, the iron in molecular sieve in part silicon, aluminium and load is reset, thus the stability of the iron of the intensity of the load molecular sieve after the iron of further having strengthened load and institute's load.
In a preferred embodiment of the present invention, above-mentioned iron salt solutions mixes and comprises with the roasting molecular sieve: under stirring condition, iron salt solutions is dropwise joined in the roasting molecular sieve, form mixture.Adopt in this embodiment the mode splashed into to add molysite, and stir the roasting molecular sieve when dripping, make the roasting molecular sieve fully mix with molysite, and then guaranteed the uniformity that Fe disperses on the roasting molecular sieve.
Can be used for iron salt solutions of the present invention is iron nitrate solution, ferrum sulfuricum oxydatum solutum or copperas solution.Preferred iron nitrate solution.
Roasting molecular sieve of the present invention is the molecular sieve at 500～850 ℃ of lower roasting 2～8h.Through 500～850 ℃ of lower roasting 2～8h, make the skeleton structure of molecular sieve more firm in molecular sieve.
In another preferred embodiment of the present invention, above-mentioned preparation method also comprises the process more than 100 orders that load molecular sieve is ground between step S1 and step S2.In order further to optimize the uniformity that CNT distributes on load molecular sieve, preferably adopt more than above-described embodiment is ground to 100 orders by load molecular sieve.
Can be used for molecular sieve of the present invention is mesopore molecular sieve or micro porous molecular sieve.In a preferred embodiment, preferred above-mentioned molecular sieve is SAPO-5 molecular sieve, SAPO-11 molecular sieve, SAPO-31 molecular sieve, SAPO-36 molecular sieve, SBA-15 molecular sieve or NaY molecular sieve.
In another typical embodiment of the present invention, provide the application of a kind of above-mentioned Fe-series catalyst auxiliary agent in coal liquefaction.Because Fe-series catalyst auxiliary agent of the present invention has more Fe-N-C activated centre, thereby can effectively strengthen the hydrogenation activity of catalyst; In addition, because CNT has high intensity, therefore at the Coal liquefaction central hole structure, be not easy to cave in, and then can effectively maintain the active dispersion formed of catalyst promoter, extended the service life of catalyst; Simultaneously, the CNT of nitrogen doping can reduce the acidity of Fe-series catalyst auxiliary agent, can effectively avoid the little molecule byproduct of the too deteriorated one-tenth of oil product molecule in Coal liquefaction, coordinate Fe-series catalyst to use catalyst promoter of the present invention, can effectively regulate the hydrogenation effect of coal liquefaction system, and then increase the conversion ratio of coal and the yield of liquefaction oil, promote DCL/Direct coal liquefaction efficiency.
Below with reference to embodiment and Comparative Examples, further illustrate beneficial effect of the present invention.
Embodiment 1
Take 10.1g Fe (NO)
39H
2o is dissolved in 20g distilled water, then is impregnated on the SBA-15 sieve sample of 10g after 600 ℃ of roasting 3h.Below porphyrize to 150 μ m, put into 600 ℃ of roasting 6h of Muffle furnace after 100 ℃ of oven dry 12h, obtain the Fe/SBA-15 catalyst.The Fe/SBA-15 catalyst is packed in little porcelain boat, be heated to 800 ℃, adjusting nitrogen is flow velocity 200mlmin
-1, entering into diethylamine air-blowing bottle, the gaseous mixture after bubbling enters into tube furnace, (the 200ml diethylamine is put in the air-blowing bottle in the water bath with thermostatic control of 55.5 ℃ in advance), constant temperature keeps 2h, naturally cooling, obtain the Fe/CNx composite of black, the catalyst promoter that this composite is embodiment 1.
Embodiment 2
Take 10.1g Fe (NO)
39H
2o is dissolved in 20g distilled water, then is impregnated on the SBA-15 sieve sample of 10g after 600 ℃ of roasting 3h.Below porphyrize to 150 μ m, put into 600 ℃ of roasting 6h of Muffle furnace after 100 ℃ of oven dry 12h, obtain the Fe/SBA-15 catalyst.The Fe/SBA-15 catalyst is packed in little porcelain boat, be heated to 800 ℃, adjust nitrogen flow rate 200mlmin
-1, entering into triethylamine air-blowing bottle, the gaseous mixture after bubbling enters into tube furnace, (the 200ml triethylamine is put in the air-blowing bottle in the water bath with thermostatic control of 89.5 ℃ in advance), constant temperature keeps 2h, naturally cooling, obtain the Fe/CNx composite of black, the catalyst promoter that this composite is embodiment 2.
Embodiment 3
Take 10.1g Fe (NO)
39H
2o is dissolved in 20g distilled water, then is impregnated on the SBA-15 sieve sample of 10g after 600 ℃ of roasting 3h.Below porphyrize to 150 μ m, put into 600 ℃ of roasting 6h of Muffle furnace after 100 ℃ of oven dry 12h, obtain the Fe/SBA-15 catalyst.The Fe/SBA-15 catalyst is packed in little porcelain boat, and little porcelain boat is put into the tube furnace flat-temperature zone, is heated to 800 ℃, then adjusts 190mlmin
-1the nitrogen of flow velocity and 10mLmin
-1after converging, the ammonia of flow velocity enters into triethylamine air-blowing bottle, gaseous mixture after bubbling enters into tube furnace, (the 200ml triethylamine is put in the air-blowing bottle of water bath with thermostatic control of 89.5 ℃ in advance), constant temperature keeps 2h, naturally cooling, obtain the Fe/CNx composite of black, the catalyst promoter that this composite is embodiment 3.
Embodiment 4
Take 20.2g Fe (NO)
39H
2o is dissolved in 20g distilled water, then is impregnated on the NaY sieve sample of 10g after 600 ℃ of roasting 3h.Below porphyrize to 150 μ m, put into 600 ℃ of roasting 6h of Muffle furnace after 100 ℃ of oven dry 12h, obtain the Fe/NaY catalyst.The Fe/NaY catalyst is packed in little porcelain boat, be heated to 800 ℃, adjust nitrogen flow rate 200mlmin
-1, entering into diethylamine air-blowing bottle, the gaseous mixture after bubbling enters into tube furnace, (the 200ml diethylamine is put in the air-blowing bottle in the water bath with thermostatic control of 55.5 ℃ in advance), constant temperature keeps 2h, naturally cooling, obtain the Fe/CNx composite of black, the catalyst promoter that this composite is embodiment 4.
Embodiment 5
Take 5.05g Fe (NO)
39H
2o is dissolved in 20g distilled water, then is impregnated on the NaY sieve sample of 10g after 600 ℃ of roasting 3h.Below porphyrize to 150 μ m, put into 600 ℃ of roasting 6h of Muffle furnace after 100 ℃ of oven dry 12h, obtain the Fe/NaY catalyst.The Fe/NaY catalyst is packed in little porcelain boat, be heated to 800 ℃, adjust nitrogen flow rate 200mlmin
-1, entering into diethylamine air-blowing bottle, the gaseous mixture after bubbling enters into tube furnace, (the 200ml diethylamine is put in the air-blowing bottle in the water bath with thermostatic control of 55.5 ℃ in advance), constant temperature keeps 2h, naturally cooling, obtain the Fe/CNx composite of black, the catalyst promoter that this composite is embodiment 5.
Embodiment 6
Take 2.12g Fe
2(SO
4)
39H
2o is dissolved in 10g distilled water, then is impregnated on the SAPO-5 sieve sample of 10g after 500 ℃ of roasting 8h.Below porphyrize to 150 μ m, put into 600 ℃ of roasting 6h of Muffle furnace after 150 ℃ of oven dry 5h, obtain the Fe/SAPO-5 catalyst.The Fe/SAPO-5 catalyst is packed in little porcelain boat, be heated to 1000 ℃, adjust nitrogen flow rate 100mlmin
-1enter into ethylenediamine air-blowing bottle, gaseous mixture after bubbling enters into tube furnace, (the 100ml ethylenediamine is put in the air-blowing bottle in the water bath with thermostatic control of 55.5 ℃ in advance), constant temperature keeps 0.5h, naturally cooling, obtain the Fe/CNx composite of black, the catalyst promoter that this composite is embodiment 6.
Embodiment 7
Take 12.16g FeSO
47H
2o is dissolved in 20g distilled water, then is impregnated on the SAPO-5 sieve sample of 10g after 500 ℃ of roasting 8h.Below porphyrize to 150 μ m, put into 850 ℃ of roasting 2h of Muffle furnace after 150 ℃ of oven dry 5h, obtain the Fe/SAPO-5 catalyst.The Fe/SAPO-5 catalyst being packed in little porcelain boat, be heated to 700 ℃, is 300mlmin by flow velocity
-1nitrogen and flow velocity be 100mlmin
-1after converging, the ammonia of flow velocity enters into ethylenediamine air-blowing bottle, gaseous mixture after bubbling enters into tube furnace, (the 400ml ethylenediamine is put in the air-blowing bottle in the water bath with thermostatic control of 55.5 ℃ in advance), constant temperature keeps 5h, naturally cooling, obtain the Fe/CNx composite of black, the catalyst promoter that this composite is embodiment 7.
Embodiment 8
Take 4.92g Fe
2(SO
4)
39H
2o is dissolved in 20g distilled water, then is impregnated on the SAPO-5 sieve sample of 10g after 600 ℃ of roasting 6h.Below porphyrize to 150 μ m, put into 700 ℃ of roasting 4h of Muffle furnace after 150 ℃ of oven dry 5h, obtain the Fe/SAPO-5 catalyst.The Fe/SAPO-5 catalyst being packed in little porcelain boat, be heated to 800 ℃, is 270mlmin by flow velocity
-1nitrogen and flow velocity be 30mlmin
-1after converging, the ammonia of flow velocity enters into diethylamine air-blowing bottle, gaseous mixture after bubbling enters into tube furnace, (the 300ml diethylamine is put in the air-blowing bottle in the water bath with thermostatic control of 55.5 ℃ in advance), constant temperature keeps 6h, naturally cooling, obtain the Fe/CNx composite of black, the catalyst promoter that this composite is embodiment 8.
Embodiment 9
Take 5.56g FeSO
47H
2o is dissolved in 20g distilled water, then is impregnated on the SBA-15 sieve sample of 10g after 600 ℃ of roasting 6h.Below porphyrize to 150 μ m, put into 700 ℃ of roasting 4h of Muffle furnace after 150 ℃ of oven dry 5h, obtain the Fe/SBA-15 catalyst.The Fe/SBA-15 catalyst being packed in little porcelain boat, be heated to 800 ℃, is 255mlmin by flow velocity
-1nitrogen and flow velocity be 45mlmin
-1after converging, the ammonia of flow velocity enters into diethylamine air-blowing bottle, gaseous mixture after bubbling enters into tube furnace, (the 300ml diethylamine is put in the air-blowing bottle in the water bath with thermostatic control of 55.5 ℃ in advance), constant temperature keeps 5h, naturally cooling, obtain the Fe/CNx composite of black, the catalyst promoter that this composite is embodiment 9.
Comparative Examples 1
Take 10.1g Fe (NO)
39H
2o is dissolved in 20g distilled water, then is impregnated on the SBA-15 sieve sample of 10g after 600 ℃ of roasting 3h.Below porphyrize to 150 μ m, put into 600 ℃ of roasting 6h of Muffle furnace after 100 ℃ of oven dry 12h, obtain the Fe/SBA-15 catalyst, the catalyst promoter that this composite is Comparative Examples 1.
Comparative Examples 2
Take 10.1g Fe (NO)
39H
2o is dissolved in 20g distilled water, then is impregnated on the SBA-15 sieve sample of 10g after 600 ℃ of roasting 3h.Below porphyrize to 150 μ m, put into 600 ℃ of roasting 6h of Muffle furnace after 100 ℃ of oven dry 12h, obtain the Fe/SBA-15 catalyst.The Fe/SBA-15 catalyst is packed in little porcelain boat, be heated to 500 ℃, adjusting nitrogen is flow velocity 200mlmin
-1, entering into diethylamine air-blowing bottle, the gaseous mixture after bubbling enters into tube furnace, (the 200ml diethylamine is put in the air-blowing bottle in the water bath with thermostatic control of 55.5 ℃ in advance), constant temperature keeps 2h, naturally cooling, obtain the Fe/CNx composite of black, the catalyst promoter that this composite is Comparative Examples 2.
Comparative Examples 3
Take 10.1g Fe (NO) 39H2O and be dissolved in 40g distilled water, then be impregnated on the SBA-15 sieve sample of 10g after 600 ℃ of roasting 3h.Below porphyrize to 150 μ m, put into 600 ℃ of roasting 6h of Muffle furnace after 100 ℃ of oven dry 12h, obtain the Fe/SBA-15 catalyst.The Fe/SBA-15 catalyst is packed in little porcelain boat, be heated to 800 ℃, adjusting nitrogen is flow velocity 200mlmin-1, enter into diethylamine air-blowing bottle, the gaseous mixture after bubbling enters into tube furnace, (the 200ml diethylamine is put in the air-blowing bottle in the water bath with thermostatic control of 55.5 ℃ in advance), constant temperature keeps 4h, naturally cooling, obtain the Fe/CNx composite of black, the catalyst promoter that this composite is Comparative Examples 3.
In above-described embodiment 1 to 9 and Comparative Examples 1 to 3, the catalyst aid of preparation all takes a morsel and adopts firing method elemental microanalysis method test N/C mol ratio, adopt its shape characteristic of SEM electron microscopic observation, adopt TEM electron microscopic observation CNT diameter, concrete outcome is in Table 1, and wherein the SEM Electronic Speculum test result of the catalyst promoter of embodiment 1, embodiment 5 and embodiment 8 is shown in Fig. 1 to Fig. 3; The catalyst promoter prepared in above-described embodiment 1 to 9 and Comparative Examples 1 to 3 takes respectively 0.10g to be added in the autoclave Coal liquefaction, carries out the Performance of Hydrogenation Liquefaction of Coal test, the results are shown in Table 3, and Coal liquefaction performance test condition is as described below:
Each catalyst promoter 0.10g in accurate weighing above-described embodiment, add in 500mL autoclave Coal liquefaction as auxiliary agent respectively.Testing coal sample used is the Xinjiang Heishan coal, and Industrial Analysis and elementary analysis are in Table 2, and the addition of dry coal is 50g, and solvent is naphthane, and quantity of solvent is 75g, adds croci 2.15g as catalyst, adds 1.72g sulphur powder.Autoclave reacts cold hydrogen first pressing 10MPa, 450 ℃ of constant temperature 1h, react complete cooling fast, get the gas sample and survey gas composition, collect reacted liquid-solid phase, respectively by n-hexane and oxolane Soxhlet extraction 48h, by extracting residue ashing, obtain the data such as coal conversion ratio, oily yield, gas productive rate, pitch productive rate, specifically in Table 3.
Table 1
Table 2
Table 3
| The reaction numbering | The conversion ratio of coal (%) | Liquefaction oil productive rate (%) | Gas productive rate (%) | Pitch productive rate (%) |
| Without auxiliary agent | 88.21 | 44.28 | 8.59 | 28.69 |
| Embodiment 1 | 90.17 | 45.43 | 8.32 | 26.86 |
| Embodiment 2 | 88.98 | 44.93 | 8.52 | 28.11 |
| Embodiment 3 | 90.66 | 46.26 | 8.34 | 26.61 |
| Embodiment 4 | 90.81 | 46.38 | 8.30 | 26.35 |
| Embodiment 5 | 89.25 | 45.12 | 8.50 | 27.22 |
| Embodiment 6 | 89.58 | 44.69 | 8.42 | 27.91 |
| Embodiment 7 | 91.21 | 46.78 | 8.55 | 25.35 |
| Embodiment 8 | 90.46 | 46.01 | 8.44 | 26.61 |
| Embodiment 9 | 91.11 | 47.12 | 8.48 | 24.73 |
| Comparative Examples 1 | 88.31 | 44.65 | 8.49 | 28.18 |
| Comparative Examples 2 | 88.59 | 44.75 | 8.68 | 27.98 |
| Comparative Examples 3 | 89.93 | 44.96 | 8.50 | 27.61 |
Data by table 1 can be found out, different molecular sieve used in embodiment, different organic amine atmosphere and different dipping iron amount can be prepared nitrogen-doped carbon nanometer pipe composite Fe/CNx, the productive rate of the composite of just preparing, nitrogen doping, CNT external diameter are slightly had any different, but the content of the CNT obtained in as Comparative Examples 2 when changing the CNT synthesis temperature is few, almost can't detect; The CNT obtained as Comparative Examples 3 when increasing the consumption of iron salt solutions generates yield reducation, and in CNT, the nitrogen doping also can reduce.Data by table 3 can be found out, composite prepared in different condition by embodiment 1 to 9 adds in Coal liquefaction as auxiliary agent, all than the Coal liquefaction performance of the auxiliary agent of Comparative Examples 1 to 3 preparation, all increase, in the conversion ratio that has improved coal and liquefaction oil productive rate, do not increase the gas productive rate, effectively improved DCL/Direct coal liquefaction efficiency.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for a person skilled in the art, the present invention can have various modifications and variations.Within the spirit and principles in the present invention all, any modification of doing, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (16)
1. a Fe-series catalyst auxiliary agent, is characterized in that, described Fe-series catalyst auxiliary agent comprises that weight percentage is:
25～60% molecular sieve;
1～20% iron oxide; And
The CNT of 25～75% nitrogen doping, the nitrogen content in described CNT is 1～30wt%;
Wherein, described iron oxide and nitrogen doping carbon nanotube loaded on described molecular sieve, and there is the Fe-N-C center between at least part of described iron oxide and at least part of described CNT in described Fe-series catalyst auxiliary agent.
2. Fe-series catalyst auxiliary agent according to claim 1, it is characterized in that, molecular sieve weight content described in described Fe-series catalyst auxiliary agent is 25～50%, described iron oxide weight content is 5～15%, the CNT weight content of described nitrogen doping is 35～65%, and the nitrogen content in described CNT is 10～30wt%.
3. Fe-series catalyst auxiliary agent according to claim 1 and 2, is characterized in that, the multi-walled carbon nano-tubes that described CNT is Bamboo-shaped, and the caliber of described multi-walled carbon nano-tubes is 20～70nm, joint length is 8～80nm.
4. Fe-series catalyst auxiliary agent according to claim 1 and 2, it is characterized in that, described molecular sieve is mesopore molecular sieve or micro porous molecular sieve, preferably SAPO-5 molecular sieve, SAPO-11 molecular sieve, SAPO-31 molecular sieve, SAPO-36 molecular sieve, SBA-15 molecular sieve or NaY molecular sieve.
5. the preparation method of a Fe-series catalyst auxiliary agent, is characterized in that, described preparation method comprises:
Step S1, load on the iron in iron salt solutions on the roasting molecular sieve, forms load molecular sieve, and wherein, the mass ratio of described iron salt solutions and described roasting molecular sieve is 0.5:1～4.5:1, and in described iron salt solutions, the weight percentage of Fe is 1～10%;
Step S2 is reacted liquid organic amine and described load molecular sieve under 650～1000 ℃, obtains described Fe-series catalyst auxiliary agent, and wherein, the consumption of described liquid organic amine is 10～40ml/g load molecular sieve.
6. preparation method according to claim 5, is characterized in that, described step S2 comprises:
By described liquid organic amine, make described liquid organic amine be carried and form described organic amine steam by described carrier gas carrier gas;
Under 650～1000 ℃, pass into described organic amine steam to described load molecular sieve, and keep 0.5～5h, obtain described Fe-series catalyst auxiliary agent.
7. preparation method according to claim 6, is characterized in that, described carrier gas is selected from a kind of in nitrogen and inert gas.
8. preparation method according to claim 7, is characterized in that, described carrier gas also comprises ammonia, and described in described carrier gas, the volumn concentration of ammonia is below 20%.
9. preparation method according to claim 6, is characterized in that, described organic amine is selected from one or more in the group that hexa, ethylenediamine, ethamine, propylamine, diethylamine, triethylamine form.
10. preparation method according to claim 5, is characterized in that, described step S1 comprises:
Described iron salt solutions is mixed with described roasting molecular sieve, form mixture, the mass ratio of described iron salt solutions and described roasting molecular sieve is 1:1～4:1;
Described mixture is carried out under 100～150 ℃ to drying, obtain solid-state dry;
Described solid-state dry, at 500～850 ℃ of lower roasting 2～8h, is obtained to described load molecular sieve.
11. preparation method according to claim 10, is characterized in that, described iron salt solutions mixes and comprises with described roasting molecular sieve: under stirring condition, described iron salt solutions is dropwise joined in described roasting molecular sieve, form described mixture.
12. preparation method according to claim 5, is characterized in that, described iron salt solutions is iron nitrate solution, ferrum sulfuricum oxydatum solutum or copperas solution.
13. according to the described preparation method of any one in claim 5 to 12, it is characterized in that, described roasting molecular sieve is the molecular sieve at 500～850 ℃ of lower roasting 2～8h.
14. according to the described preparation method of any one in claim 5 to 12, it is characterized in that, described preparation method also comprises described load molecular sieve is ground to the process more than 100 orders between described step S1 and described step S2.
15. according to the described preparation method of any one in claim 5 to 12, it is characterized in that, described molecular sieve is mesopore molecular sieve or micro porous molecular sieve, preferably SAPO-5 molecular sieve, SAPO-11 molecular sieve, SAPO-31 molecular sieve, SAPO-36 molecular sieve, SBA-15 molecular sieve or NaY molecular sieve.
16. the application of the described Fe-series catalyst auxiliary agent of any one in coal liquefaction in a claim 1 to 4.
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| CN104084227A (en) * | 2014-06-26 | 2014-10-08 | 上海第二工业大学 | Direct coal liquefaction catalytic additive, preparation method and application of direct coal liquefaction catalytic additive |
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