CN108043382A - A kind of preparation method based on the micro transition-metal catalyst of asphaltene high activity - Google Patents

A kind of preparation method based on the micro transition-metal catalyst of asphaltene high activity Download PDF

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Publication number
CN108043382A
CN108043382A CN201711366259.8A CN201711366259A CN108043382A CN 108043382 A CN108043382 A CN 108043382A CN 201711366259 A CN201711366259 A CN 201711366259A CN 108043382 A CN108043382 A CN 108043382A
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asphaltene
preparation
transition
metal catalyst
metal
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CN108043382B (en
Inventor
王全德
刘滋武
刘玲
康国俊
贾嘉
韩菲
轩锦锦
黄晓寒
王文鹏
魏天宇
马腾欢
单毅
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China University of Mining and Technology CUMT
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/18—Carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/745—Iron
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/86—Chromium
    • B01J23/862—Iron and chromium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/084—Decomposition of carbon-containing compounds into carbon
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10C—WORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
    • C10C3/00—Working-up pitch, asphalt, bitumen
    • C10C3/08—Working-up pitch, asphalt, bitumen by selective extraction

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Thermal Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Civil Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Structural Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Catalysts (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

A kind of preparation method based on the micro transition-metal catalyst of asphaltene high activity belongs to the preparation method of micro transition-metal catalyst.Comprise the following steps：Coal liquefaction residue and the solvent chosen are mixed, the asphaltene in coal liquefaction residue is extracted by soxhlet's extraction method；The clean alundum tube of band is placed in tube furnace, and under protective atmosphere, the temperature of alundum tube high-temperature part is increased to reaction temperature；Corundum boat with asphaltene is put into tube furnace, stops heating after a period of time, reacting furnace is cooled to room temperature under protective atmosphere；Corundum boat with transition metal chemistry product is put into tube furnace, under setting condition, heating a period of time postcooling is to room temperature, and sample is to get to the micro transition-metal catalyst of asphaltene high activity in taking-up corundum boat.Advantage：In preparation, no conventional inflammable and explosive gaseous state and liquid metal reductant are environmentally friendly and easy to operate；Content of metal is few, and catalyst preparation is at low cost；Active crystal face is more, and catalytic activity is higher.

Description

A kind of preparation method based on the micro transition-metal catalyst of asphaltene high activity
Technical field
It is particularly a kind of to be based on asphaltene high activity the present invention relates to a kind of preparation method of micro transition-metal catalyst The preparation method of micro transition-metal catalyst.
Background technology
Catalyst is a kind of change reaction rate but does not change the total standard Gibbs free energy of reaction, and the quality of itself With chemical property before the reaction after all without changed substance.In a total chemical reaction, the effect of catalyst is It reduces the reaction and required activation energy occurs, be substantially that the reaction of a difficult generation of comparison is become incidentalization Learn reaction.Compared with noble metal catalysts such as platinum, rutheniums, in catalytic field, transition-metal catalyst is because of its relatively low cost, higher Reserves and preferable catalytic activity and be subjected to great concern.Wherein a small amount of or micro transition-metal catalyst, because usually Exposed crystal face is more, and active higher and cost is cheaper, simultaneously because conventional gaseous state, the reducing loaded side of liquid reducing agent Method is difficult to the load capacity of effectively control catalyst, thus micro and ultra-low volume transition-metal catalyst becomes the research of catalytic field Hot spot.
Coal directly-liquefied residue is product after the direct catalytic hydrogenation of coal, wherein containing organic molecules such as more naphthalenes, together Shi Hanyou asphaltenes, the relatively large organic matter of preasphaltene equimolecular quantity.Yet with the factors such as technology, these organic matters one It is not developed and utilized reasonably directly, thus always as environmental pressure larger after DCL/Direct coal liquefaction.It if will wherein Asphaltene extract and the carrier as transition-metal catalyst that is carbonized, the particularly load as micro transition-metal catalyst Body will be an effective high value added utilization mode.And prepared for the design of this catalyst, it there is no report at present.
The content of the invention
The invention aims to provide a kind of preparation method based on the micro transition-metal catalyst of asphaltene high activity, Asphaltene in coal liquefaction residue is solved the problems, such as catalyst apply and widen the application of asphaltene.
The object of the present invention is achieved like this：The preparation method of micro transition-metal catalyst, comprises the following steps：
A, asphaltene is extracted using soxhlet's extraction method, coal liquefaction residue and asphaltene extractant is mixed, at 50-90 DEG C Asphaltene in coal liquefaction residue is extracted；
B, clean alundum tube is placed in tube furnace, under argon gas, nitrogen or ammonia atmosphere, by alundum tube high-temperature part Temperature be increased to reaction temperature；
C, the corundum boat with asphaltene is put into tube furnace, stops heating after 1-2h, in argon gas, nitrogen or ammonia gas Reacting furnace is cooled to room temperature under atmosphere；
D, another corundum boat with transition metal sample is put into tube furnace, under setting condition：I.e. in 900-1500 DEG C, under normal pressure and argon gas, nitrogen or ammonia atmosphere or under vacuum state, vacuum degree is 0~-0.1 during vacuum；It is cold after heating 1-6h But arrive room temperature, take out in corundum boat sample to get to the micro transition-metal catalyst of asphaltene high activity.
The asphaltene extractant is benzene, toluene and dimethylbenzene.
The asphaltene is carbon source；Argon gas, nitrogen or ammonia are protection gas；The flow velocity of the gas for 0.05~ 0.6L/min。
The reaction temperature is 900-1500 DEG C.
Affiliated metal sample is Fe, Co, Ni, V, Cr, Mn, Cu, Zn, Ti, Mo and W active transition metal.
Advantageous effect, as a result of said program, the present invention prepares active catalyst by carrier of pitch alkenyl carbon, profit The active crystal face exposed with the monatomic of trace meter or few cluster is more, and active sites are more, and then catalytic activity is high.Function model It encloses：Catalytic reaction available for related to transition-metal catalyst.Its good effect generated is mainly shown as catalytic efficiency The high, selectivity of product is good and overpotential is low etc. in electro-catalysis is applied.It solves asphaltene in coal liquefaction residue and is used as catalysis The problem of agent applies and widens the application of asphaltene, has reached the purpose of the present invention.
It has the following advantages that：The application missing of asphaltene in coal liquefaction residue is filled up, widens the application of asphaltene.
(1) in preparing, no conventional inflammable and explosive gaseous state and liquid metal reductant are environmentally friendly and easy to operate；
(2) content of metal is few, and cost of material is low；
(3) active crystal face is more, and catalytic activity is higher.
Description of the drawings：
Fig. 1 (a) is the elastic scattering electricity of the pitch alkenyl active transition metal iron catalyst obtained by the embodiment of the present invention 1 Sub- image.
Fig. 1 (b) is the elastic scattering electricity of the pitch alkenyl active transition metal iron catalyst obtained by the embodiment of the present invention 1 Sub- energy spectrum diagram.
Fig. 2 (a) is the elastic scattering electrons of pitch alkenyl active transition metal iron catalyst made from the embodiment of the present invention 2 Image.
Fig. 2 (b) is the elastic scattering electrons of pitch alkenyl active transition metal iron catalyst made from the embodiment of the present invention 2 Ferro element is distributed (Elemental mapping) figure.
Specific embodiment
The preparation method of micro transition-metal catalyst, comprises the following steps：
A, asphaltene is extracted using soxhlet's extraction method, coal liquefaction residue and asphaltene extractant is mixed, at 50-90 DEG C Asphaltene in coal liquefaction residue is extracted；
B, clean alundum tube is placed in tube furnace, under argon gas, nitrogen or ammonia atmosphere, by alundum tube high-temperature part Temperature be increased to reaction temperature；
C, the corundum boat with asphaltene is put into tube furnace, stops heating after 1-2h, in argon gas, nitrogen or ammonia gas Reacting furnace is cooled to room temperature under atmosphere；
D, another corundum boat with transition metal sample is put into tube furnace, under setting condition：I.e. in 900-1500 DEG C, under normal pressure and argon gas, nitrogen or ammonia atmosphere or under vacuum state, vacuum degree is 0~-0.1 during vacuum；It is cold after heating 1-6h But arrive room temperature, take out in corundum boat sample to get to the micro transition-metal catalyst of asphaltene high activity.
The asphaltene extractant is benzene, toluene and dimethylbenzene.
The asphaltene is carbon source；Argon gas, nitrogen or ammonia are protection gas；The flow velocity of the gas for 0.05~ 0.6L/min。
The reaction temperature is 900-1500 DEG C.
Affiliated metal sample is Fe, Co, Ni, V, Cr, Mn, Cu, Zn, Ti, Mo and W active transition metal.
Below in conjunction with the accompanying drawings to being further described to the embodiment of the present invention：
Embodiment 1:Alundum tube is put into tube furnace, under the protection for the argon inert gas that flow velocity is 0.05L/min, The temperature of alundum tube high-temperature part is increased to 900 DEG C；
Corundum boat with asphaltene is put into reacting furnace, stops heating after 1h, under ammonia atmosphere under by reacting furnace It is cooled to room temperature；
Corundum boat with transition metal siderochrome is put into tube furnace, the lower heating 1h of argon gas protection, is cooled under normal pressure After room temperature take out corundum boat in sample, the pitch alkenyl active transition metal catalyst iron obtained through power spectrum EDS analysis shows and The content of chromium is respectively 1.15 and 0.29wt.%.
Embodiment 2:Alundum tube is put into tube furnace, under the nitrogen protection that flow velocity is 0.4L/min, by alundum tube height The temperature of isothermal segment is increased to 1300 DEG C；
Corundum boat with asphaltene is put into reacting furnace, stops heating after 1h, by reacting furnace under nitrogen gas shielded It is cooled to room temperature；
Corundum boat with transition metal iron is put into tube furnace, 1h is heated under vacuum, is taken after being cooled to room temperature Go out sample in corundum boat, the content of the pitch alkenyl active transition metal catalyst iron obtained through power spectrum EDS analysis shows is 0.80wt.%.
Embodiment 3:Alundum tube is put into tube furnace, under the protection for the argon inert gas that flow velocity is 0.6L/min, The temperature of alundum tube high-temperature part is increased to 1500 DEG C；
Corundum boat with asphaltene is put into reacting furnace, stops heating after 1h, furnace cooling will be reacted under protection of argon gas But room temperature is arrived；
Corundum boat with transition metal iron is put into tube furnace, 1h is heated under vacuum, is taken after being cooled to room temperature Go out sample in corundum boat, the content of the iron obtained through power spectrum EDS analysis shows is 0.28wt.%.
Embodiment 4:Alundum tube is put into tube furnace, under the protection for the argon inert gas that flow velocity is 0.6L/min, The temperature of alundum tube high-temperature part is increased to 1500 DEG C；
Corundum boat with asphaltene is put into reacting furnace, stops heating after 1h, furnace cooling will be reacted under protection of argon gas But room temperature is arrived；
Corundum boat with transiting metal nickel is put into tube furnace, 1h is heated under vacuum, is taken after being cooled to room temperature Go out sample in corundum boat, the content of the nickel obtained through power spectrum EDS analysis shows is 0.35wt.%.
By Fig. 1 (a), Fig. 1 (b) as can be seen that prepared pitch alkenyl active transition metal catalyst contain siderochrome and The content of iron and chromium is respectively 1.15 and 0.29wt.%.
By Fig. 2 (a), Fig. 2 (b) can be seen that the more uniform distribution of micro iron in the catalyst.

Claims (5)

1. a kind of preparation method based on the micro transition-metal catalyst of asphaltene high activity, it is characterized in that：Micro transition metal The preparation method of catalyst, comprises the following steps：
A, asphaltene is extracted using soxhlet's extraction method, coal liquefaction residue and asphaltene extractant is mixed, it is right at 50-90 DEG C Asphaltene in coal liquefaction residue is extracted；
B, clean alundum tube is placed in tube furnace, under argon gas, nitrogen or ammonia atmosphere, by the temperature of alundum tube high-temperature part Degree is increased to reaction temperature；
C, the corundum boat with asphaltene is put into tube furnace, stops heating after 1-2 h, in argon gas, nitrogen or ammonia atmosphere It is lower that reacting furnace is cooled to room temperature；
D, another corundum boat with transition metal sample is put into tube furnace, under setting condition：I.e. at 900-1500 DEG C, Under normal pressure and argon gas, nitrogen or ammonia atmosphere or under vacuum state, vacuum degree is 0~-0.1 during vacuum；Heat 1-6 h postcoolings To room temperature, sample is taken out in corundum boat to get to the micro transition-metal catalyst of asphaltene high activity.
2. a kind of preparation method based on the micro transition-metal catalyst of asphaltene high activity according to claim 1, It is characterized in：The asphaltene extractant is benzene, toluene and dimethylbenzene.
3. a kind of preparation method based on the micro transition-metal catalyst of asphaltene high activity according to claim 1, It is characterized in：The asphaltene is carbon source；Argon gas, nitrogen or ammonia are protection gas；The flow velocity of the gas is 0.05~0.6 L/min。
4. a kind of preparation method based on the micro transition-metal catalyst of asphaltene high activity according to claim 1, It is characterized in：The reaction temperature is 900-1500 DEG C.
5. a kind of preparation method based on the micro transition-metal catalyst of asphaltene high activity according to claim 1, It is characterized in：Affiliated metal sample is Fe, Co, Ni, V, Cr, Mn, Cu, Zn, Ti, Mo and W active transition metal.
CN201711366259.8A 2017-12-18 2017-12-18 Preparation method of high-activity trace transition metal catalyst based on asphaltene Active CN108043382B (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101372358A (en) * 2008-10-21 2009-02-25 北京科技大学 Method for preparing tin oxide nano-wire by normal atmosphere vapor deposition
CN101962560A (en) * 2010-09-29 2011-02-02 神华集团有限责任公司 Extraction method of direct coal liquefaction residues and application of extracts
CN102733008A (en) * 2012-06-21 2012-10-17 中国科学院过程工程研究所 Method of preparing carbon fiber by using coal to directly liquefy residue-based asphalt vinyl material
CN103194254A (en) * 2013-04-27 2013-07-10 神华集团有限责任公司 Intermediate phase asphalt and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101372358A (en) * 2008-10-21 2009-02-25 北京科技大学 Method for preparing tin oxide nano-wire by normal atmosphere vapor deposition
CN101962560A (en) * 2010-09-29 2011-02-02 神华集团有限责任公司 Extraction method of direct coal liquefaction residues and application of extracts
CN102733008A (en) * 2012-06-21 2012-10-17 中国科学院过程工程研究所 Method of preparing carbon fiber by using coal to directly liquefy residue-based asphalt vinyl material
CN103194254A (en) * 2013-04-27 2013-07-10 神华集团有限责任公司 Intermediate phase asphalt and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
杨眉等: "气相沉积制备V2O5-WO3/TiO2催化剂及其脱硝性能的研究", 《动力工程学报》 *

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