CN103480407B - Fe-series catalyst auxiliary agent and its preparation method and application - Google Patents

Fe-series catalyst auxiliary agent and its preparation method and application Download PDF

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CN103480407B
CN103480407B CN201310450370.0A CN201310450370A CN103480407B CN 103480407 B CN103480407 B CN 103480407B CN 201310450370 A CN201310450370 A CN 201310450370A CN 103480407 B CN103480407 B CN 103480407B
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molecular sieve
auxiliary agent
cnt
roasting
series catalyst
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CN103480407A (en
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谢晶
王利军
李克健
李永伦
章序文
袁明
高山松
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China Shenhua Coal to Liquid Chemical Co Ltd
Shenhua Group Corp Ltd
Shanghai Research Institute of China Shenhua Coal to Liquid Chemical Co Ltd
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China Shenhua Coal to Liquid Chemical Co Ltd
Shenhua Group Corp Ltd
Shanghai Research Institute of China Shenhua Coal to Liquid Chemical Co Ltd
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Abstract

The invention provides a kind of Fe-series catalyst auxiliary agent and its preparation method and application.This auxiliary agent comprises weight percentage: the molecular sieve of 25 ~ 60%, the CNT of the iron oxide of 1 ~ 20% and the N doping of 25 ~ 75%, and the nitrogen content in CNT is 1 ~ 30wt%; Wherein, iron oxide and N doping over a molecular sieve carbon nanotube loaded, and at least part of iron oxide and between CNT, there is Fe-N-C center at least partly in Fe-series catalyst auxiliary agent.In this auxiliary agent, CNT and iron oxide high degree of dispersion are over a molecular sieve, generate more multistable fixed activated centre; Iron oxide and nitrogen are combined closely stable support CNT tube wall, and form Fe-N-C center with CNT, improve the hydrogenation capability of iron; CNT has high intensity, effectively can maintain the activation plays of Fe; The CNT of N doping contributes to reducing auxiliary agent acidity, can effectively avoid oil product molecule too deteriorated.

Description

Fe-series catalyst auxiliary agent and its preparation method and application
Technical field
The present invention relates to field of catalyst preparation, 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, thus coal is converted into 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, activity and selectivity due to catalyst greatly affects the reaction rate of coal liquefaction, conversion ratio, oily productive rate, gas yield and hydrogen consumption, thus develops and design the focus that high, the selective good and cheap catalyst of catalytic activity is 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 active metal; Equations of The Second Kind is metal halide catalyst, as ZnCl 2, SnCl 2deng; 3rd class is Fe-series catalyst, comprises the compound (as the oxide of iron, sulfide and hydroxide) of the natural crystal of iron content, the industrial residu of iron content and various pure state iron.Result of study shows, the catalytic activity of oil Hydrobon catalyst is higher, but this kind of metallic catalyst price comparison is expensive, is difficult to reclaim and regeneration in Coal liquefaction system; Metal halide catalyst belongs to acidic catalyst, and cracking ability is strong, but has stronger corrosiveness to the equipment of coal liquification device, does not now use this kind of catalyst; Fe-series catalyst activity is moderate, has higher cost performance, and once use and need not reclaim, this kind of catalyst, also known as abandoning property catalyst, is emphasis and the direction of coal direct liquefaction catalyst research.
Both at home and abroad large quantifier elimination has all done to Fe-series catalyst in research institution for many years, comprises the compound (as the oxide of iron, sulfide and hydroxide etc.) of the natural crystal of iron content, the industrial residu of iron content and various pure state iron.The brown coal liquefaction technique of Japan adopts limonite as catalyst for coal liquefaction, achieves Expected Results, have employed aluminium making residue, also known as red mud as catalyst in German coal liquefaction craft.But when using ore class Fe-series catalyst representatively, though the ultra-fine grinding of ore can improve activity, but ultra-fine grinding can bring larger power consumption, add coal liquefaction cost, in addition because the real density that iron ore is larger makes it all easily deposit in course of conveying and in reactor, bring hidden danger to coal liquefaction.And red mud is the abandoning property catalyst of representative, addition is large, adds 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 reduces the entirety oil yield in coal liquefaction.
Therefore, according to the feature of coal liquefaction, usually adopt the Fe-series catalyst that cost performance is higher at present, 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 HTI company of the U.S. develops the high dispersive iron catalyst (GelCat of Prof. Du Yucang tM), addition is 0.5wt%; And " 863 effective catalyst " that Shenhua Group and China Coal Research Institute are developed jointly is the hydrated ferric oxide FeOOH of ferrous sulfate and ammonia precipitation process synthesis, addition is 1wt%, has achieved industrialization at present, achieves good effect.
Although, can by multiple method as increased the dispersiveness of catalyst, reduce catalyst grain size, avoid the measures such as catalyst particle Second Aggregation to improve the activity of Fe-series catalyst, 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 is relatively weak, one definite limitation is existed to the deep conversion of coal, therefore, if research mode conventionally carries out improvement to Fe-series catalyst itself 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 problem that in prior art, itself hydrogenation activity of Fe-series catalyst is relatively weak.
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 weight percentage and is: the molecular sieve of 25 ~ 60%; The iron oxide of 1 ~ 20%; And the CNT of the N doping of 25 ~ 75%, the nitrogen content in CNT is 1 ~ 30wt%; Wherein, iron oxide and N doping over a molecular sieve carbon nanotube loaded, and at least part of iron oxide and between CNT, there is Fe-N-C center at least partly in Fe-series catalyst auxiliary agent.
Further, above-mentioned Fe-series catalyst auxiliary agent Middle molecule sieve weight content is 25 ~ 50%, iron oxide weight content is 5 ~ 15%, the carbon nanotubes content of N doping is 35 ~ 65wt%, and the nitrogen content in CNT is 10 ~ 30wt%.
Further, above-mentioned CNT is the multi-walled carbon nano-tubes of Bamboo-shaped, and the caliber of multi-walled carbon nano-tubes is 20 ~ 70nm, and joint length is 8 ~ 80nm.
Further, above-mentioned molecular sieve is mesopore molecular sieve or micro porous molecular sieve, preferred 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, provide a kind of preparation method of Fe-series catalyst auxiliary agent, this preparation method comprises: by the iron load in iron salt solutions on 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, makes liquid organic amine and load molecular sieve react at 650 ~ 1000 DEG C, obtains 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 carrier gas by liquid organic amine, liquid organic amine is carried by carrier gas and forms organic amine steam; At 650 ~ 1000 DEG C, pass into organic amine steam to load molecular sieve, and keep 0.5 ~ 5h, obtain Fe-series catalyst auxiliary agent.
Further, above-mentioned carrier gas is selected from the one 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 of hexa, ethylenediamine, ethamine, propylamine, diethylamine, triethylamine composition.
Further, above-mentioned steps S1 comprises: mixed with roasting molecular sieve by iron salt solutions, and form mixture, the mass ratio of iron salt solutions and roasting molecular sieve is 1:1 ~ 4:1; Mixture is carried out drying at 100 ~ 150 DEG C, obtains solid-state dry; By solid-state dry roasting 2 ~ 8h at 500 ~ 850 DEG C, obtain load molecular sieve.
Further, above-mentioned iron salt solutions mixes with roasting molecular sieve and comprises: under agitation, is dropwise joined by iron salt solutions in roasting molecular sieve, forms 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 of roasting 2 ~ 8h at 500 ~ 850 DEG C.
Further, above-mentioned preparation method also comprises process load molecular sieve being ground to more than 100 orders between step S1 and step S2.
Further, above-mentioned molecular sieve is mesopore molecular sieve or micro porous molecular sieve, preferred 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, a kind of above-mentioned application of Fe-series catalyst auxiliary agent in coal liquefaction is provided.
Apply technical scheme of the present invention, comprise the CNT of the molecular sieve of rational proportion and load iron oxide and N doping over a molecular sieve in Fe-series catalyst auxiliary agent simultaneously, CNT and iron oxide high degree of dispersion over a molecular sieve, thus generate more multistable fixed activated centre over a molecular sieve; The tube wall of the iron oxide of high degree of dispersion, stable support CNT of combining closely with nitrogen, and and between CNT, form Fe-N-C center, the hydrogenation capability of iron is got a promotion, is almost equivalent to the hydrogenation capability of the noble metals such as Ni, Mo; And CNT itself has high intensity, not easily cave at catalytic process meso-hole structure, therefore, it is possible to effectively maintain the activation plays of active component Fe; Meanwhile, the CNT of N doping contributes to the acidity reducing auxiliary agent, can effectively avoid the undue deterioration of oil product molecule to generate Small molecular byproduct being applied in Coal liquefaction; Further, this Fe-series catalyst auxiliary agent has the characteristic of the bigger serface of molecular sieve and CNT, and then optimizes the catalytic activity of Fe-series catalyst auxiliary agent.Coordinate other Fe-series catalysts to use catalyst promoter of the present invention, effectively can 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.
Accompanying drawing explanation
The Figure of description forming a application's part is used to provide a further understanding of the present invention, and schematic description and description of the present invention, for explaining the present invention, does not form inappropriate limitation of the present invention.In the accompanying drawings:
Fig. 1 shows the SEM Electronic Speculum figure of the catalyst promoter according to embodiments of the invention 1;
Fig. 2 shows the SEM Electronic Speculum figure of the catalyst promoter according to embodiments of the invention 5; And
Fig. 3 shows the SEM Electronic Speculum figure of the catalyst promoter according to embodiments of the invention 8.
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.Below with reference to the accompanying drawings and describe the present invention in detail in conjunction with the embodiments.
The application is in order to solve the relatively weak problem of itself hydrogenation activity of Fe-series catalyst, take the method improving Fe-series catalyst itself in different and prior art, propose a kind of Fe-series catalyst auxiliary agent and preparation method thereof, by this Fe-series catalyst auxiliary agent and Fe-series catalyst with the use of, significantly improve the hydrogenation activity of Fe-series catalyst.Therefore in a kind of typical embodiment of the present invention, provide a kind of Fe-series catalyst auxiliary agent, above-mentioned Fe-series catalyst auxiliary agent comprise weight percentage be the molecular sieve of 25 ~ 60%, the iron oxide of 1 ~ 20% and 25 ~ 75% the CNT of N doping, the nitrogen content in CNT is 1 ~ 30wt%; Wherein, described iron oxide and N doping carbon nanotube loaded on described molecular sieve, and at least part of iron oxide and between CNT, there is Fe-N-C center at least partly in Fe-series catalyst auxiliary agent.
Comprise the CNT of the molecular sieve of rational proportion and load iron oxide and N doping over a molecular sieve in Fe-series catalyst auxiliary agent of the present invention simultaneously, CNT and iron oxide high degree of dispersion over a molecular sieve, when with Fe-series catalyst with the use of time be conducive to Fe-series catalyst and generate more multistable fixed activated centre over a molecular sieve; The tube wall of the iron oxide of high degree of dispersion, stable support CNT of combining closely with nitrogen, and and between CNT, form Fe-N-C center, the hydrogenation capability of iron is got a promotion, is almost equivalent to the hydrogenation capability of the noble metals such as Ni, Mo; And CNT itself has high intensity, not easily cave at catalytic process meso-hole structure, therefore, it is possible to effectively maintain the activation plays of active component Fe; Meanwhile, the CNT of N doping contributes to the acidity reducing auxiliary agent, can effectively avoid the undue deterioration of oil product molecule to generate Small molecular byproduct being applied in Coal liquefaction; Further, this Fe-series catalyst auxiliary agent has the characteristic of the bigger serface of molecular sieve and CNT, and then optimizes the catalytic activity of Fe-series catalyst auxiliary agent.Coordinate Fe-series catalyst to use catalyst promoter of the present invention, effectively can 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, above-mentioned Fe-series catalyst auxiliary agent Middle molecule sieve weight content is 25 ~ 50%, iron oxide weight content is 5 ~ 15%, the carbon nanotubes content of N doping is 35 ~ 65%, and the nitrogen content in CNT is 10 ~ 30wt%.This embodiment optimizes the proportioning of the CNT of Fe-series catalyst auxiliary agent, iron oxide and nitrogen, therefore further increases the catalytic activity of this Fe-series catalyst auxiliary agent in Coal liquefaction.
CNT in Fe-series catalyst of the present invention is the multi-walled carbon nano-tubes of Bamboo-shaped, and the caliber of multi-walled carbon nano-tubes is 20 ~ 70nm, and joint length is 8 ~ 80nm.The wall of CNT is many walls, enhances the intensity of CNT, and then improves 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, is more conducive to CNT distribution over a molecular sieve on the other hand.
Molecular sieve used in 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, provide a kind of preparation method of Fe-series catalyst auxiliary agent, this preparation method comprises: by the iron load in iron salt solutions on 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, makes liquid organic amine and load molecular sieve react at 650 ~ 1000 DEG C, obtains Fe-series catalyst auxiliary agent, and wherein, the consumption of liquid organic amine is 10 ~ 40ml/g load molecular sieve.
Iron load is formed load molecular sieve by the molecular sieve carried heteroatomic method that above-mentioned embodiment can adopt the application to commonly use on roasting molecular sieve, and then make load molecular sieve and organic amine react at 650 ~ 1000 DEG C to form nitrogenous CNT, because the ferro element of load on molecular sieve can the formation of catalyzing carbon nanotube, therefore further improve formation speed and the quality of CNT; And while formation CNT, the carbon in organic amine steam, nitrogen element and ferro element define Fe-N-C center, for Fe-series catalyst auxiliary agent add new high activity center while enhance the intensity of Fe-series catalyst auxiliary agent.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 N doping, the nitrogen-doped nanometer pipe of the Optimum Contents of high strength have the catalytic activity and intensity that are beneficial to the Fe-series catalyst auxiliary agent that raising obtains.
And in above-mentioned embodiment, due to the difference of iron salt dissolved degree and roasting molecular sieve absorption of water, the mass ratio of iron salt solutions and roasting molecular sieve is controlled at 0.5:1 ~ 4.5:1, and the weight percentage controlling Fe in iron salt solutions is 1 ~ 10%, thus ensure that the enough and uniform Fe of load on roasting molecular sieve; In order to optimize load capacity and the load quality of Fe further, in preferred iron salt solutions, the weight percentage of Fe is 3 ~ 6%.
In another preferred embodiment of the present invention, carrier gas by liquid organic amine, makes liquid organic amine be carried by carrier gas and forms organic amine steam by the step S2 of above-mentioned preparation method; At 650 ~ 1000 DEG C, pass into organic amine steam to load molecular sieve, and keep 0.5 ~ 5h, obtain Fe-series catalyst auxiliary agent.
Carrier gas is utilized to pass through liquid organic amine, organic amine is entrained in carrier gas and is dispersed in carrier gas to form organic amine steam, be conducive to more disperseing on load molecular sieve, more efficiently forming CNT, within wherein the reaction time is not limited to 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 the one in nitrogen and inert gas.The nitrogen utilizing chemical reactivity lower or inert gas can not have a negative impact to the formation of CNT 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, the nitrogen content in the CNT of N doping can be regulated neatly, and then obtain catalytic activity Fe-series catalyst auxiliary agent easy to control in size.
Organic amine of the present invention be selected from hexa, ethylenediamine, ethamine, propylamine, diethylamine, triethylamine composition group in one or more.Above-mentioned organic amine major part as the template of Zeolite synthesis, therefore can not be able to have a negative impact to the performance of load molecular sieve, and be liquid can more easily as CNT synthesis raw material use.
In another preferred embodiment of the present invention, above-mentioned preparation method step S1 comprises: mixed with roasting molecular sieve by iron salt solutions, and the mass ratio of iron salt solutions and roasting molecular sieve is 1:1 ~ 4:1, forms mixture; Mixture is carried out drying at 100 ~ 150 DEG C, obtains solid-state dry; By solid-state dry roasting 2 ~ 8h at 500 ~ 850 DEG C, obtain load molecular sieve.
In the above-mentioned preferred embodiment of the present invention, by the mixture of molysite and roasting molecular sieve by the dry run at 100 ~ 150 DEG C, 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 the number of times of dipping and drying according to the water imbibition of the amount of adopted molysite, dissolubility and the roasting of applying molecular sieve etc., suitably can increase dipping and dry number of times time less than the amount of iron salt solutions as configured water absorption that is comparatively large or roasting molecular sieve; And at roasting process, the iron in molecular sieve in part silicon, aluminium and load is reset, thus further enhance the stability of the intensity of the load molecular sieve after load iron and the iron of institute's load.
In one preferred embodiment of the invention, above-mentioned iron salt solutions mixes with roasting molecular sieve and comprises: under agitation, is dropwise joined by iron salt solutions in roasting molecular sieve, forms mixture.Adopt the mode of instillation to add molysite in this embodiment, and stir roasting molecular sieve while dropping, roasting molecular sieve is fully mixed with molysite, and then ensure that the uniformity that Fe disperses on roasting molecular sieve.
Iron salt solutions used in 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 of roasting 2 ~ 8h at 500 ~ 850 DEG C.By molecular sieve roasting 2 ~ 8h at 500 ~ 850 DEG C, make the skeleton structure of molecular sieve more firm.
In another preferred embodiment of the present invention, above-mentioned preparation method also comprises process load molecular sieve being ground to more than 100 orders between step S1 and step S2.In order to optimize the uniformity that CNT distributes on load molecular sieve further, preferably adopt above-described embodiment that load molecular sieve is ground to more than 100 orders.
Molecular sieve used in 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, thus effectively can strengthen the hydrogenation activity of catalyst; In addition, because CNT has high intensity, be therefore not easy to cave at Coal liquefaction central hole structure, and then effectively can maintain the dispersion of catalyst promoter activity formation, extend the service life of catalyst; Simultaneously, the CNT of N doping can reduce the acidity of Fe-series catalyst auxiliary agent, the undue deterioration of oil product molecule can be effectively avoided to become Small molecular byproduct in Coal liquefaction, Fe-series catalyst is coordinated to use catalyst promoter of the present invention, effectively can 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 example, further illustrate beneficial effect of the present invention.
Embodiment 1
Take 10.1g Fe (NO) 39H 2o is dissolved in 20g distilled water, is then impregnated on the SBA-15 sieve sample of 10g after 600 DEG C of roasting 3h.To dry after 12h below porphyrize to 150 μm, put into Muffle furnace 600 DEG C of roasting 6h, obtain Fe/SBA-15 catalyst for 100 DEG C.Loaded in little porcelain boat by Fe/SBA-15 catalyst, be heated to 800 DEG C, adjustment nitrogen is flow velocity 200mlmin -1, enter into diethylamine air-blowing bottle, the gaseous mixture after bubbling enters into tube furnace, (200ml diethylamine is put in the air-blowing bottle in the water bath with thermostatic control of 55.5 DEG C in advance), constant temperature keeps 2h, naturally cools, obtain the Fe/CNx composite of black, this composite is the catalyst promoter of embodiment 1.
Embodiment 2
Take 10.1g Fe (NO) 39H 2o is dissolved in 20g distilled water, is then impregnated on the SBA-15 sieve sample of 10g after 600 DEG C of roasting 3h.To dry after 12h below porphyrize to 150 μm, put into Muffle furnace 600 DEG C of roasting 6h, obtain Fe/SBA-15 catalyst for 100 DEG C.Fe/SBA-15 catalyst is loaded in little porcelain boat, is heated to 800 DEG C, adjustment nitrogen flow rate 200mlmin -1, enter into triethylamine air-blowing bottle, the gaseous mixture after bubbling enters into tube furnace, (200ml triethylamine is put in the air-blowing bottle in the water bath with thermostatic control of 89.5 DEG C in advance), constant temperature keeps 2h, naturally cools, obtain the Fe/CNx composite of black, this composite is the catalyst promoter of embodiment 2.
Embodiment 3
Take 10.1g Fe (NO) 39H 2o is dissolved in 20g distilled water, is then impregnated on the SBA-15 sieve sample of 10g after 600 DEG C of roasting 3h.To dry after 12h below porphyrize to 150 μm, put into Muffle furnace 600 DEG C of roasting 6h, obtain Fe/SBA-15 catalyst for 100 DEG C.Loaded by Fe/SBA-15 catalyst in little porcelain boat, little porcelain boat puts into tube furnace flat-temperature zone, is heated to 800 DEG C, then adjusts 190mlmin -1the nitrogen of flow velocity and 10mLmin -1triethylamine air-blowing bottle is entered into after the ammonia of flow velocity converges, gaseous mixture after bubbling enters into tube furnace, (200ml triethylamine is put in the air-blowing bottle of the water bath with thermostatic control of 89.5 DEG C in advance), constant temperature keeps 2h, naturally cool, obtain the Fe/CNx composite of black, this composite is the catalyst promoter of embodiment 3.
Embodiment 4
Take 20.2g Fe (NO) 39H 2o is dissolved in 20g distilled water, is then impregnated on the NaY molecular sieve sample of 10g after 600 DEG C of roasting 3h.To dry after 12h below porphyrize to 150 μm, put into Muffle furnace 600 DEG C of roasting 6h, obtain Fe/NaY catalyst for 100 DEG C.Fe/NaY catalyst is loaded in little porcelain boat, is heated to 800 DEG C, adjustment nitrogen flow rate 200mlmin -1, enter into diethylamine air-blowing bottle, the gaseous mixture after bubbling enters into tube furnace, (200ml diethylamine is put in the air-blowing bottle in the water bath with thermostatic control of 55.5 DEG C in advance), constant temperature keeps 2h, naturally cools, obtain the Fe/CNx composite of black, this composite is the catalyst promoter of embodiment 4.
Embodiment 5
Take 5.05g Fe (NO) 39H 2o is dissolved in 20g distilled water, is then impregnated on the NaY molecular sieve sample of 10g after 600 DEG C of roasting 3h.To dry after 12h below porphyrize to 150 μm, put into Muffle furnace 600 DEG C of roasting 6h, obtain Fe/NaY catalyst for 100 DEG C.Fe/NaY catalyst is loaded in little porcelain boat, is heated to 800 DEG C, adjustment nitrogen flow rate 200mlmin -1, enter into diethylamine air-blowing bottle, the gaseous mixture after bubbling enters into tube furnace, (200ml diethylamine is put in the air-blowing bottle in the water bath with thermostatic control of 55.5 DEG C in advance), constant temperature keeps 2h, naturally cools, obtain the Fe/CNx composite of black, this composite is the catalyst promoter of embodiment 5.
Embodiment 6
Take 2.12g Fe 2(SO 4) 39H 2o is dissolved in 10g distilled water, is then impregnated on the SAPO-5 sieve sample of 10g after 500 DEG C of roasting 8h.To dry after 5h below porphyrize to 150 μm, put into Muffle furnace 600 DEG C of roasting 6h, obtain Fe/SAPO-5 catalyst for 150 DEG C.Fe/SAPO-5 catalyst is loaded in little porcelain boat, is heated to 1000 DEG C, adjustment nitrogen flow rate 100mlmin -1enter into ethylenediamine air-blowing bottle, gaseous mixture after bubbling enters into tube furnace, (100ml ethylenediamine is put in the air-blowing bottle in the water bath with thermostatic control of 55.5 DEG C in advance), constant temperature keeps 0.5h, naturally cool, obtain the Fe/CNx composite of black, this composite is the catalyst promoter of embodiment 6.
Embodiment 7
Take 12.16g FeSO 47H 2o is dissolved in 20g distilled water, is then impregnated on the SAPO-5 sieve sample of 10g after 500 DEG C of roasting 8h.To dry after 5h below porphyrize to 150 μm, put into Muffle furnace 850 DEG C of roasting 2h, obtain Fe/SAPO-5 catalyst for 150 DEG C.Being loaded in little porcelain boat by Fe/SAPO-5 catalyst, be heated to 700 DEG C, is 300mlmin by flow velocity -1nitrogen and flow velocity be 100mlmin -1ethylenediamine air-blowing bottle is entered into after the ammonia of flow velocity converges, gaseous mixture after bubbling enters into tube furnace, (400ml ethylenediamine is put in the air-blowing bottle in the water bath with thermostatic control of 55.5 DEG C in advance), constant temperature keeps 5h, naturally cool, obtain the Fe/CNx composite of black, this composite is the catalyst promoter of embodiment 7.
Embodiment 8
Take 4.92g Fe 2(SO 4) 39H 2o is dissolved in 20g distilled water, is then impregnated on the SAPO-5 sieve sample of 10g after 600 DEG C of roasting 6h.To dry after 5h below porphyrize to 150 μm, put into Muffle furnace 700 DEG C of roasting 4h, obtain Fe/SAPO-5 catalyst for 150 DEG C.Being loaded in little porcelain boat by Fe/SAPO-5 catalyst, be heated to 800 DEG C, is 270mlmin by flow velocity -1nitrogen and flow velocity be 30mlmin -1diethylamine air-blowing bottle is entered into after the ammonia of flow velocity converges, gaseous mixture after bubbling enters into tube furnace, (300ml diethylamine is put in the air-blowing bottle in the water bath with thermostatic control of 55.5 DEG C in advance), constant temperature keeps 6h, naturally cool, obtain the Fe/CNx composite of black, this composite is the catalyst promoter of embodiment 8.
Embodiment 9
Take 5.56g FeSO 47H 2o is dissolved in 20g distilled water, is then impregnated on the SBA-15 sieve sample of 10g after 600 DEG C of roasting 6h.To dry after 5h below porphyrize to 150 μm, put into Muffle furnace 700 DEG C of roasting 4h, obtain Fe/SBA-15 catalyst for 150 DEG C.Being loaded in little porcelain boat by Fe/SBA-15 catalyst, be heated to 800 DEG C, is 255mlmin by flow velocity -1nitrogen and flow velocity be 45mlmin -1diethylamine air-blowing bottle is entered into after the ammonia of flow velocity converges, gaseous mixture after bubbling enters into tube furnace, (300ml diethylamine is put in the air-blowing bottle in the water bath with thermostatic control of 55.5 DEG C in advance), constant temperature keeps 5h, naturally cool, obtain the Fe/CNx composite of black, this composite is the catalyst promoter of embodiment 9.
Comparative example 1
Take 10.1g Fe (NO) 39H 2o is dissolved in 20g distilled water, is then impregnated on the SBA-15 sieve sample of 10g after 600 DEG C of roasting 3h.To dry after 12h below porphyrize to 150 μm for 100 DEG C, put into Muffle furnace 600 DEG C of roasting 6h, obtain Fe/SBA-15 catalyst, this composite is the catalyst promoter of comparative example 1.
Comparative example 2
Take 10.1g Fe (NO) 39H 2o is dissolved in 20g distilled water, is then impregnated on the SBA-15 sieve sample of 10g after 600 DEG C of roasting 3h.To dry after 12h below porphyrize to 150 μm, put into Muffle furnace 600 DEG C of roasting 6h, obtain Fe/SBA-15 catalyst for 100 DEG C.Loaded in little porcelain boat by Fe/SBA-15 catalyst, be heated to 500 DEG C, adjustment nitrogen is flow velocity 200mlmin -1, enter into diethylamine air-blowing bottle, the gaseous mixture after bubbling enters into tube furnace, (200ml diethylamine is put in the air-blowing bottle in the water bath with thermostatic control of 55.5 DEG C in advance), constant temperature keeps 2h, naturally cools, obtain the Fe/CNx composite of black, this composite is the catalyst promoter of comparative example 2.
Comparative example 3
Taking 10.1g Fe (NO) 39H2O is dissolved in 40g distilled water, is then impregnated on the SBA-15 sieve sample of 10g after 600 DEG C of roasting 3h.To dry after 12h below porphyrize to 150 μm, put into Muffle furnace 600 DEG C of roasting 6h, obtain Fe/SBA-15 catalyst for 100 DEG C.Fe/SBA-15 catalyst is loaded in little porcelain boat, be heated to 800 DEG C, adjustment nitrogen is flow velocity 200mlmin-1, enter into diethylamine air-blowing bottle, the gaseous mixture after bubbling enters into tube furnace, (200ml diethylamine is put in the air-blowing bottle in the water bath with thermostatic control of 55.5 DEG C in advance), constant temperature keeps 4h, naturally cool, obtain the Fe/CNx composite of black, this composite is the catalyst promoter of comparative example 3.
In above-described embodiment 1 to 9 and comparative example 1 to 3, the catalyst aid of preparation all takes a morsel and adopts combustion method elemental microanalysis method test N/C mol ratio, adopt its shape characteristic of SEM electron microscopic observation, adopt TEM electron microscopic observation carbon nanotube 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; In above-described embodiment 1 to 9 and comparative example 1 to 3, the catalyst promoter of preparation takes 0.10g respectively and adds in autoclave Coal liquefaction, and carry out Performance of Hydrogenation Liquefaction of Coal test, the results are shown in Table 3, Coal liquefaction performance test conditions is as described below:
Each catalyst promoter 0.10g in accurate weighing above-described embodiment, adds in 500mL autoclave Coal liquefaction respectively as auxiliary agent.Testing coal sample used is 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 DEG C of constant temperature 1h, react complete quick cooling, get 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
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 example 1 88.31 44.65 8.49 28.18
Comparative example 2 88.59 44.75 8.68 27.98
Comparative example 3 89.93 44.96 8.50 27.61
As can be seen from the data of table 1, different molecular sieve used in embodiment, different organic amine atmosphere and different dipping iron can prepare nitrogen-doped carbon nanometer pipe composite Fe/CNx, the productive rate of the composite just prepared, N doping amount, CNT external diameter are slightly distinguished, but when changing CNT synthesis temperature as comparative example 2 in the content of CNT that obtains few, almost cannot detect; The CNT obtained as comparative example 3 when increasing the consumption of iron salt solutions generates output to be reduced, and in CNT, N doping amount also can reduce.As can be seen from the data of table 3, the composite that embodiment 1 to 9 is prepared in different condition adds in Coal liquefaction as auxiliary agent, all all increase than the Coal liquefaction performance of the auxiliary agent of comparative example 1 to 3 preparation, while the conversion ratio that improve coal and liquefaction oil productive rate, do not increase gas productive rate, effectively improve 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 amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.

Claims (17)

1. a Fe-series catalyst auxiliary agent, is characterized in that, described Fe-series catalyst auxiliary agent comprises weight percentage and is:
The molecular sieve of 25 ~ 50%;
The iron oxide of 5 ~ 15%; And
The CNT of the N doping of 35 ~ 65%, the nitrogen content in described CNT is 10 ~ 30wt%;
Wherein, described iron oxide and N doping carbon nanotube loaded on described molecular sieve, and between at least part of described iron oxide and at least part of described CNT, there is Fe-N-C center in described Fe-series catalyst auxiliary agent.
2. Fe-series catalyst auxiliary agent according to claim 1, is characterized in that, described CNT is the multi-walled carbon nano-tubes of Bamboo-shaped, and the caliber of described multi-walled carbon nano-tubes is 20 ~ 70nm, and joint length is 8 ~ 80nm.
3. Fe-series catalyst auxiliary agent according to claim 1, is characterized in that, described molecular sieve is mesopore molecular sieve or micro porous molecular sieve.
4. Fe-series catalyst auxiliary agent according to claim 3, is characterized in that, described 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.
5. a preparation method for Fe-series catalyst auxiliary agent, is characterized in that, described preparation method comprises:
Step S1, by the iron load in iron salt solutions on roasting molecular sieve, form load molecular sieve, 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, makes liquid organic amine and described load molecular sieve react at 650 ~ 1000 DEG C, 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 carrier gas by described liquid organic amine, described liquid organic amine is carried by described carrier gas and forms described organic amine steam;
At 650 ~ 1000 DEG C, 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 the one 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 be selected from hexa, ethylenediamine, ethamine, propylamine, diethylamine, triethylamine composition group in one or more.
10. preparation method according to claim 5, is characterized in that, described step S1 comprises:
Mixed with described roasting molecular sieve by described iron salt solutions, 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 drying at 100 ~ 150 DEG C, obtains solid-state dry;
By described solid-state dry roasting 2 ~ 8h at 500 ~ 850 DEG C, obtain described load molecular sieve.
11. preparation methods according to claim 10, is characterized in that, described iron salt solutions mixes with described roasting molecular sieve and comprises: under agitation, is dropwise joined in described roasting molecular sieve by described iron salt solutions, forms described mixture.
12. preparation methods according to claim 5, is characterized in that, described iron salt solutions is iron nitrate solution, ferrum sulfuricum oxydatum solutum or copperas solution.
13. preparation methods according to any one of claim 5 to 12, it is characterized in that, described roasting molecular sieve is the molecular sieve of roasting 2 ~ 8h at 500 ~ 850 DEG C.
14. preparation methods according to any one of claim 5 to 12, it is characterized in that, described preparation method also comprises the process described load molecular sieve being ground to more than 100 orders between described step S1 and described step S2.
15. preparation methods according to any one of claim 5 to 12, it is characterized in that, described molecular sieve is mesopore molecular sieve or micro porous molecular sieve.
16. preparation methods according to claim 15, is characterized in that, described 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.
The application of Fe-series catalyst auxiliary agent in coal liquefaction according to any one of 17. 1 kinds of Claims 1-4.
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