CN101693533A - Method for preparing nanometer carbon fiber/foam coal through taking coal liquefaction residues as raw materials - Google Patents
Method for preparing nanometer carbon fiber/foam coal through taking coal liquefaction residues as raw materials Download PDFInfo
- Publication number
- CN101693533A CN101693533A CN200910308685A CN200910308685A CN101693533A CN 101693533 A CN101693533 A CN 101693533A CN 200910308685 A CN200910308685 A CN 200910308685A CN 200910308685 A CN200910308685 A CN 200910308685A CN 101693533 A CN101693533 A CN 101693533A
- Authority
- CN
- China
- Prior art keywords
- foam
- coal
- minute
- carbon
- carbon fiber
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Carbon And Carbon Compounds (AREA)
Abstract
The method for preparing nanometer carbon fiber/foam coal through taking coal liquefaction residues as raw materials belongs to the scientific and technological field of coal materials of the scientific and technological branch of inorganic non-metallic materials. The method takes the coal liquefaction residues as the coal source of the foam coal, and compounds metallic/foam coal compound materials through the supercritical foaming method or the formwork method, and prepares the nanometer carbon fiber/foam coal compound materials through the chemical vapor deposition of organic matter. The method fully utilizes the characteristics of metallic accelerating agent containing abundant coal organic matter, iron-contained compound and the like in the coal liquefaction residues, and prepares metallic/foam coal compound materials, and the nanometer carbon fiber completely covers on the surface of the foam coal after the chemical vapor deposition. The novel nanometer carbon fiber/foam compound materials have the structural characteristics of solid foam and hollow nanometer carbon fiber. And the method is expected to be used in the fields of catalyzer and a catalyzer carrier, a fuel battery electrode material, high-effective sorbent of a fixed bed reactor and the like.
Description
Technical field
The invention belongs to inorganic non-metallic materials science technology branch carbon material science and technology field.Relating to a kind of is raw material with the coal direct liquefaction residue, adopts the supercritical foaming legal system to be equipped with Carbon foam, after chemical Vapor deposition process prepares the method for nanometer carbon fiber/foam carbon composite.
Background technology
Face today of serious oil crisis in the whole world, the rise at full speed of oil price.The China energy characteristics of resources is a rich coal resources, and oil, Sweet natural gas are poor relatively, and this has just determined that the energy structure of China must be based on coal, and the variation of essence can not take place in considerable time from now on this energy structure.In order to protect the energy and the economic security of country,, become the direction that national governments and researchist make joint efforts with the substitute of coal as oil.
Liquidation of coal is that coal is converted into liquid process by solid-state, broadly comprises the direct liquefaction and the indirect liquefaction of coal.The direct liquefaction of coal at first realizes in the U.S., Germany, Britain and Japan in 20 beginnings of the century, China since early 1980s the Direct liquefaction technology research of coal, this technology has been tending towards maturation at present.The direct liquefaction of coal is also referred to as hydrogenation liquefaction, be under the condition of high pressure hydrogen and catalyzer existence, adding hot coal (400-460 ℃) makes it that chemical transformation take place in solvent, organic macromole in the coal is converted into the liquid fuel small molecules, obtains the eco-friendly clean coal technology of liquid oil and chemical.China has classified the development of coal liquefaction technology as a strategic task of the Tenth Five-Year Plan (2001-2005) and even following medium-term and long-term energy construction.In the liquefaction process of coal, except obtaining liquid product, also produce the main by product liquefied residue that accounts for raw coal total amount 20-30%, so many level of residue has immeasurable influence to the resource utilization and the economy of liquefaction process.Therefore efficient, the utilization rationally of coal direct liquefaction residue are important problems concerning gelatin liquefaction technical development prospect.
According to the situation of the catalyzer that uses in the DCL/Direct coal liquefaction process, residue is divided into hydrothermal solution residue and catalytic liquefaction residue.The coal direct liquefaction residue is a kind of high-carbon, high ash and doctor positive material, and unconverted coal organism, inorganic mineral and the deliquescence accelerant that adds have constituted the main body of coal directly-liquefied residue in the liquefaction raw material.In general contain 50% high boiling point heavy organism (mink cell focus and asphaltene etc.) in the residue, other 50% is solid-state carbon rich material matter.At present, the approach that utilizes of coal directly-liquefied residue mainly contains the following aspects: 1. gasification hydrogen-producing, as: with liquefied residue gasification preparation synthetic gas, the synthetic gas that obtains is production H after purify and conversion etc. handled with the texaco gasification technology
2, this be coal liquefaction residue generally utilize mode; 2. coking system oil, high boiling point oils and bitumen that content in the residue is higher further are converted into retortable oil, gas and coke by pyrogenic method, to reclaim the oil in the residue, improve the yield of liquid product; 3. boiler oil, liquefied residue has higher thermal value, therefore can be used as the fuel of boiler and kiln.In addition, coal liquefaction residue has also been obtained researchist's concern as the carbon matrix precursor of the carbon material of production high added value, this has further expanded the Application Areas of coal liquefaction residue.Adopting the coal direct liquefaction residue as Qiu Jieshan seminar is carbon matrix precursor, using plasma method and arc discharge method are prepared carbon nanofiber and carbon nanotube respectively, proposed a kind of method of efficiently utilizing the coal direct liquefaction residue, realized producing the application of high value added product with coal liquefaction residue.
Although about the existing certain progress of the research of coal direct liquefaction residue character and application approach, but how effectively to utilize these valuable gelatin liquefaction wastes, make it produce bigger economic benefit and be still the challenging subject that Coal Chemical Industry scientific and technological circle pay close attention to.
Carbon foam has the developing history of four more than ten years so far as a kind of functional type raw material of wood-charcoal material.Carbon foam the earliest is that WalterFord made by pyrolysis thermosetting phenolic foam in early 1960s, is a kind of lightweight, porous, high temperature resistant, unreactiveness is corrosion-resistant, structure properties is good novel charcoal material.The preparation research of early stage Carbon foam mainly is to be raw material with the organic polymer, is subjected to the restriction of feedstock property, and the Carbon foam intensity that makes is relatively poor.For overcoming this defective, improve the mechanical property of material, widen its Application Areas, in research work subsequently, people come the structure of modulation foam carbon material by different means, be included in and add various tougheners in the preparation raw material, optimize processing parameter and attempt use different material etc., to reach the purpose of improving material property.In phase early 1990s,, the United States Air Force material laboratory realized the synthetic of greying Carbon foam but being raw material first with the mesophase pitch.Have performances such as low density, high strength, high thermal conductivity, high conductivity, fire-resistant, shock resistance through graphited Carbon foam.These performances make Carbon foam can be applied to a plurality of fields, as the solar radiation protection thermal transfer system of aircraft such as satellite, space shuttle; The shock resistance of rocket launching table top and reduction noise material; The large-scale heat exchanger of generalization factory (the especially serious occasion of acid and alkali corrosion); Blimp, racing car, racing boat, steamer etc. are the top of operation power-driven tool fast; Fire-resistant door and window such as aircraft, steamer and filtering material and biomaterial etc.In addition, Carbon foam also is considered to become a kind of new and effective fixed bed filler.People such as Stemmet, the result of study of Twigg and Richardson shows that the pressure drop of Carbon foam is well below the Ball-type packing of conventional packed bed.Because Carbon foam has higher interfacial area and makes it that important advantage be arranged aspect mass transfer.People such as Stemmet also point out, use Carbon foam and make packing material in bubble tower, have weakened the behavior of liquid phase mixed flow greatly owing to the gas flow characteristic.The interfacial area of Carbon foam is very important for mass transfer.Yet, cause its lower specific surface area (about 0.12m because Carbon foam lacks enough micropores
2Support is steady
-1Support), catalyzer can't effectively disperse in its surface.And the preparation of nanometer carbon fiber/foam carbon composite can effectively solve little this defective of Carbon foam specific surface area.In recent years, the investigator studies the method for the nanometer carbon fiber/foam charcoal growth using organic polymer or coal and make as raw material.Present preparation method normally obtains Carbon foam earlier, again at Carbon foam surface carrying metal catalyzer, after chemical gaseous phase depositing process obtains the nanometer carbon fiber/foam carbon composite.Because the charcoal material surface after pyroprocessing is a unreactiveness, lacks enough positioning of anchors with the carrying metal catalyzer, therefore, before catalyst loading, all need, to increase Carbon foam surface functional group quantity through the concentrated acid oxide treatment.This process not only makes the whole preparation process very complicated, and the use of concentrated acid inevitably produces harm to environment.In addition, because Carbon foam is at the steeping process of concentrated acid and metal salt solution subsequently, might form a small amount of bubble on the carbon matrix surface, the zone that these bubbles cover since effective carrying metal catalyzer finally cause the Carbon foam surface to have the subregion and can't cover carbon nano fiber.Cause the inhomogeneous of quality product.
Summary of the invention
For these reasons, the present invention proposes with the supercritical foaming method is technique means, is the technology of the directly synthetic metal of raw material/Carbon foam matrix material with the coal directly-liquefied residue, after chemical vapor deposition processes prepares the nanometer carbon fiber/foam carbon composite.Utilize coal directly-liquefied residue to prepare the novel charcoal material of high added value, will develop into a kind of method of efficiently utilizing coal directly-liquefied residue.The utilization of at present relevant coal directly-liquefied residue such as Qiu Jieshan seminar adopt the coal direct liquefaction residue to be carbon matrix precursor, using plasma method and arc discharge method are prepared carbon nanofiber and carbon nanotube respectively, have proposed a kind of method (Fuel.2008.87 (15-16): 3474-3476 that efficiently utilizes the coal direct liquefaction residue; Coal conversion, 2007,30 (3): 41-44) etc., the preparation of relevant nanometer carbon fiber/foam carbon composite such as Journalof Materials Chemistry.2008.18 (21): 2426-2436 and Fuel, 2009,88 (1): 46-53 etc. not having relevant coal direct liquefaction residue at present is the aspect report that carbon source prepares Carbon foam and uses it for preparation nanometer carbon fiber/foam carbon composite.
The objective of the invention is with the coal direct liquefaction residue without any processing is raw material, utilize supercritical foaming technology or template and chemical vapour deposition technique, disclose a kind of easy technology of preparing by the direct synthesis of nano carbon fiber/foam of coal liquefied residue carbon composite.
Technical scheme of the present invention: a kind of is that the concrete steps of method of feedstock production nanometer carbon fiber/foam charcoal are as follows with the coal directly-liquefied residue:
(1) take by weighing coal liquefaction residue after the grinding with supercritical foaming method or template, wherein, supercritical methanol technology is about to supercutical fluid and mixes with coal liquefaction residue, leaves standstill under its supercritical state 1-5 hour, and unexpected relief pressure makes the Carbon foam precast body; Template, it is even to be about to coal liquefaction residue and solvent, with template foam impregnation in this mixed solution 1-10 minute, after extruding, made the Carbon foam precast body at air drying 1-5 minute, 1-10g Carbon foam precast body is placed tube furnace, under air atmosphere, be warming up to 300-400 ℃ with 0.5-5 ℃/minute speed, behind the constant temperature 0.5-3h, naturally reduce to room temperature, obtain preoxidation Carbon foam precast body;
(2) the above-mentioned preoxidation Carbon foam precast body for preparing is warming up to 700-900 ℃ with 1-5 ℃/minute under rare gas element and carries out charing, be cooled to room temperature behind the constant temperature 1h naturally, obtain metal/Carbon foam matrix material;
(3) prepare the nanometer carbon fiber/foam charcoal with chemical Vapor deposition process, metal/Carbon foam matrix material is put in porcelain boat and places the Reaktionsofen flat-temperature zone, heat up under the protection of inert gas environment, when temperature rises to 400-600 ℃, switching gas is N
2/ H
2Gas mixture, sample reduction 10-60 minute, 2-20 ℃/minute is warming up to 700-900 ℃ under this atmosphere, gas switches to carbon-source gas, and after question response carried out 5-120 minute, gas switched to rare gas element, and sample shifted out reaction zone, and be cooled to room temperature, make the nanometer carbon fiber/foam charcoal.
Its supercutical fluid is selected from Skellysolve A or methyl-formiate in the described supercritical foaming method.
The template foam is polyurethane foam, melamine foamed plastic or phenolic resin foam in the described template, and solvent is tetrahydrofuran (THF) or pyridine.
The carbon source that described chemical Vapor deposition process uses is selected from methane, ethene, propylene or acetylene.
Described rare gas element is selected from nitrogen, argon gas or helium.
Characteristics of the present invention are that with the coal direct liquefaction residue be raw material, through supercritical foaming or template and follow-up chemical vapour deposition technique, and direct synthesis of nano carbon fiber/foam carbon composite.
The prepared raw material of wood-charcoal material of the present invention is characterised in that with the coal direct liquefaction residue be raw material, products obtained therefrom is the fine and close foam carbon material that evenly covers carbon nano fiber of surface coverage, the Carbon foam aperture is more even, its abscess footpath, most of holes can be between the 100-500 micron, and the Carbon foam percentage of open area can be regulated by the control foaming condition.The carbon nano fiber pipe diameter of Carbon foam surface coverage is about 100 nanometers, and size is even, and length can reach 100 microns.
Effect of the present invention and benefit are as follows:
1, the present invention is a kind of method by the directly synthetic high added value novel carbon nano-fiber of coal liquefaction residue/Carbon foam matrix material, and raw materials used is the waste of coal direct liquefaction process.Preparation process is simple, not high to equipment requirements, and parameter is controlled easily, processing ease, is easy to amplify.
2, the invention provides a kind of method by the synthetic novel carbon/carbon compound material of high added value of DCL/Direct coal liquefaction by product.The byproduct that adopts the coal direct liquefaction process has been opened up the new way of coal liquefaction residue processing and utilization as raw material, has reduced the cost of coal hydrogenation liquefaction, has enriched the content of coal liquefaction science.
3, the present invention has made full use of residual catalyst for coal liquefaction in the industrial waste coal directly-liquefied residue in preparation process, need not additionally to add catalyzer and just can obtain novel carbon/carbon compound material.
4, the nanometer carbon fiber/foam carbon composite aperture that is made by the inventive method is even, and percentage of open area is controlled, its surperficial even covering compact nanometer carbon fiber, and carbon nano fiber uniform diameter, size have cavity structure about 100nm, and length can reach 100 microns.This class matrix material has a wide range of applications in fields such as catalysis, absorption, separation, electrochemistry, fuel cells.
Embodiment
The present invention is further described below by embodiment.
Embodiment one
Take by weighing and be ground to 120 purpose coal liquefaction residue 10g and Skellysolve A 8g and pack in the porcelain crucible, place then in the autoclave, feed high pure nitrogen 2～3 times repeatedly with the emptying air, again in autoclave inflated with nitrogen to 3MPa.Be warming up to 210 ℃, be incubated 4 hours.With unexpected relief pressure of autoclave and water-cooled.Open autoclave, take out the Carbon foam precast body.The Carbon foam precast body is placed tube furnace, under the air atmosphere, be warming up to 350 ℃, be cooled to room temperature behind the constant temperature 1h, obtain oxidation Carbon foam precast body with 1 ℃/minute speed.The above-mentioned oxidation Carbon foam precast body for preparing is warming up to 700 ℃ with 2 ℃/minute carries out charing under high pure nitrogen, be cooled to room temperature behind the constant temperature 1h naturally, obtain metal/Carbon foam matrix material material.
Metal/Carbon foam matrix material is put in porcelain boat and places the Reaktionsofen flat-temperature zone.At N
2The protection environment heats up down, and when temperature rises to 600 ℃, switching gas is N
2/ H
2Gas mixture (volume ratio 1: 1, total flux 100ml/ minute), sample reduction 30 minutes.10 ℃/minute are warming up to 700 ℃ under this atmosphere, and gas switches to H
2/ C
2H
4(volume ratio 2: 1, total flux 150ml/ minute).After question response carried out 30 minutes, gas switched to N
2, and sample shifted out reaction zone, and be quickly cooled to room temperature, collect sample.
Embodiment two
Take by weighing and be ground to 80 purpose coal liquefaction residue 3g and Skellysolve A 2g and pack in the porcelain crucible, place then in the autoclave, feed high pure nitrogen 2～3 times repeatedly with the emptying air, again in autoclave inflated with nitrogen to 3MPa.Be warming up to 220 ℃, be incubated 4 hours.With the unexpected relief pressure of autoclave, place cold water to be cooled to room temperature simultaneously.Open autoclave, take out the Carbon foam precast body.The Carbon foam precast body is placed tube furnace, under the air atmosphere, be warming up to 300 ℃, be cooled to room temperature behind the constant temperature 1h, obtain oxidation Carbon foam precast body with 2 ℃/minute speed.The above-mentioned oxidation Carbon foam precast body for preparing is warming up to 700 ℃ with 2 ℃/minute carries out charing under high pure nitrogen, be cooled to room temperature behind the constant temperature 1h naturally, obtain metal/Carbon foam matrix material material.
Metal/Carbon foam matrix material is put in porcelain boat and places the Reaktionsofen flat-temperature zone.At N
2The protection environment heats up down, and when temperature rises to 600 ℃, switching gas is N
2/ H
2Gas mixture (volume ratio 1: 1, total flux 100ml/ minute), sample reduction 30 minutes.10 ℃/minute are warming up to 800 ℃ under this atmosphere, and gas switches to H
2/ C
3H
6(volume ratio 2: 1, total flux 150ml/ minute).After question response carried out 30 minutes, gas switched to N
2, and sample shifted out reaction zone, and be quickly cooled to room temperature, collect sample.
Embodiment three
Take by weighing and be ground to 60 purpose coal liquefaction residue 3g and Skellysolve A 2g and pack in the porcelain crucible, place then in the autoclave, feed high pure nitrogen 2～3 times repeatedly with the emptying air, again in autoclave inflated with nitrogen to 3MPa.Be warming up to 230 ℃, be incubated 4 hours.With the unexpected relief pressure of autoclave, place cold water to be cooled to room temperature simultaneously.Open autoclave, take out the Carbon foam precast body.The Carbon foam precast body is placed tube furnace, under the air atmosphere, be warming up to 340 ℃, be cooled to room temperature behind the constant temperature 1h, obtain oxidation Carbon foam precast body with 1 ℃/minute speed.The above-mentioned oxidation Carbon foam precast body for preparing is warming up to 700 ℃ with 2 ℃/minute carries out charing under high pure nitrogen, be cooled to room temperature behind the constant temperature 1h naturally, obtain metal/Carbon foam matrix material material.
Metal/Carbon foam matrix material is put in porcelain boat and places the Reaktionsofen flat-temperature zone.At N
2The protection environment heats up down, and when temperature rises to 600 ℃, switching gas is N
2/ H
2Gas mixture (volume ratio 1: 1, total flux 100ml/ minute), sample reduction 30 minutes.10 ℃/minute are warming up to 900 ℃ under this atmosphere, and gas switches to H
2/ C
2H
6(volume ratio 2: 1, total flux 150ml/ minute).After question response carried out 30 minutes, gas switched to N
2, and sample shifted out reaction zone, and be quickly cooled to room temperature, collect sample.
Embodiment four
Take by weighing and be ground to 40 purpose coal liquefaction residue 3g and methyl-formiate 2g and pack in the porcelain crucible, place then in the autoclave, feed high-purity argon gas 2～3 times repeatedly with the emptying air, again in autoclave applying argon gas to 6MPa.Be warming up to 230 ℃, be incubated 1 hour.With the unexpected relief pressure of autoclave, place cold water to be cooled to room temperature simultaneously.Open autoclave, take out the Carbon foam precast body.The Carbon foam precast body is placed tube furnace, under the air atmosphere, be warming up to 300 ℃, be cooled to room temperature behind the constant temperature 1h, obtain oxidation Carbon foam precast body with 0.5 ℃/minute speed.The above-mentioned oxidation Carbon foam precast body for preparing is warming up to 700 ℃ with 2 ℃/minute carries out charing under high pure nitrogen, be cooled to room temperature behind the constant temperature 1h naturally, obtain metal/Carbon foam matrix material material.
Metal/Carbon foam matrix material is put in porcelain boat and places the Reaktionsofen flat-temperature zone.Heat up under Ar protection environment, when temperature rises to 600 ℃, switching gas is N
2/ H
2Gas mixture (volume ratio 1: 1, total flux 100ml/ minute), sample reduction 30 minutes.10 ℃/minute are warming up to 800 ℃ under this atmosphere, and gas switches to H
2/ CH
4(volume ratio 2: 1, total flux 150ml/ minute).After question response carried out 120 minutes, gas switched to N
2, and sample shifted out reaction zone, and be quickly cooled to room temperature, collect sample.
Embodiment five
Take by weighing and be ground to 120 purpose coal liquefaction residue 3g and methyl-formiate 2g and pack in the porcelain crucible, place then in the autoclave, feed high-purity helium 2～3 times repeatedly, in autoclave, fill helium again to 3MPa with the emptying air.Be warming up to 230 ℃, be incubated 8 hours.With the unexpected relief pressure of autoclave, place cold water to be cooled to room temperature simultaneously.Open autoclave, take out the Carbon foam precast body.The Carbon foam precast body is placed tube furnace, under the air atmosphere, be warming up to 350 ℃, be cooled to room temperature behind the constant temperature 1h, obtain oxidation Carbon foam precast body with 1 ℃/minute speed.The above-mentioned oxidation Carbon foam precast body for preparing is warming up to 700 ℃ with 2 ℃/minute carries out charing under high pure nitrogen, be cooled to room temperature behind the constant temperature 1h naturally, obtain metal/Carbon foam matrix material material.
Metal/Carbon foam matrix material is put in porcelain boat and places the Reaktionsofen flat-temperature zone.Heat up under He protection environment, when temperature rises to 600 ℃, switching gas is N
2/ H
2Gas mixture (volume ratio 1: 1, total flux 100ml/ minute), sample reduction 30 minutes.10 ℃/minute are warming up to 800 ℃ under this atmosphere, and gas switches to H
2/ C
2H
4(volume ratio 2: 1, total flux 150ml/ minute).After question response carried out 30 minutes, gas switched to He, and sample is shifted out reaction zone, was quickly cooled to room temperature, collected sample.
Embodiment six
Take by weighing and be ground to 80 purpose coal liquefaction residue 3g and Skellysolve A 5g and pack in the porcelain crucible, place then in the autoclave, feed high pure nitrogen 2～3 times repeatedly with the emptying air, again in autoclave inflated with nitrogen to 3MPa.Be warming up to 230 ℃, be incubated 4 hours.With the unexpected relief pressure of autoclave, place cold water to be cooled to room temperature simultaneously.Open autoclave, take out the Carbon foam precast body.The Carbon foam precast body is placed tube furnace, under the air atmosphere, be warming up to 350 ℃, be cooled to room temperature behind the constant temperature 1h, obtain oxidation Carbon foam precast body with 1 ℃/minute speed.The above-mentioned oxidation Carbon foam precast body for preparing is warming up to 700 ℃ with 2 ℃/minute carries out charing under high pure nitrogen, be cooled to room temperature behind the constant temperature 1h naturally.
Metal/Carbon foam matrix material is put in porcelain boat and places the Reaktionsofen flat-temperature zone.At N
2The protection environment heats up down, and when temperature rises to 600 ℃, switching gas is N
2/ H
2Gas mixture (volume ratio 1: 1, total flux 100ml/ minute), sample reduction 30 minutes.10 ℃/minute are warming up to 800 ℃ under this atmosphere, and gas switches to H
2/ C
2H
4(volume ratio 2: 1, total flux 150ml/ minute).After question response carried out 30 minutes, gas switched to N
2, and sample shifted out reaction zone, and be quickly cooled to room temperature, collect sample, obtain the nanometer carbon fiber/foam carbon composite.
Embodiment seven
Take by weighing and be ground to 80 purpose coal liquefaction residue 3g and Skellysolve A 7g and pack in the porcelain crucible, place then in the autoclave, feed high pure nitrogen 2～3 times repeatedly with the emptying air, again in autoclave inflated with nitrogen to 3MPa.Be warming up to 230 ℃, be incubated 4 hours.With the unexpected relief pressure of autoclave, place cold water to be cooled to room temperature simultaneously.Open autoclave, take out the Carbon foam precast body.The Carbon foam precast body is placed tube furnace, under the air atmosphere, be warming up to 300 ℃, be cooled to room temperature behind the constant temperature 3h, obtain oxidation Carbon foam precast body with 0.5 ℃/minute speed.The above-mentioned oxidation Carbon foam precast body for preparing is warming up to 900 ℃ with 2 ℃/minute carries out charing under high pure nitrogen, be cooled to room temperature behind the constant temperature 1h naturally.
Metal/Carbon foam matrix material is put in porcelain boat and places the Reaktionsofen flat-temperature zone.At N
2The protection environment heats up down, and when temperature rises to 600 ℃, switching gas is N
2/ H
2Gas mixture (volume ratio 1: 1, total flux 100ml/ minute), sample reduction 60 minutes.10 ℃/minute are warming up to 800 ℃ under this atmosphere, and gas switches to H
2/ C
2H
2(volume ratio 2: 1, total flux 150ml/ minute).After question response carried out 60 minutes, gas switched to Ar, and sample is shifted out reaction zone, was quickly cooled to room temperature, collected sample, obtained the nanometer carbon fiber/foam carbon composite.
Embodiment eight
Take by weighing and be ground to 80 purpose coal liquefaction residue 3g and Skellysolve A 7g and pack in the porcelain crucible, place then in the autoclave, feed high pure nitrogen 2～3 times repeatedly with the emptying air, again in autoclave inflated with nitrogen to 3MPa.Be warming up to 230 ℃, be incubated 4 hours.With the unexpected relief pressure of autoclave, place cold water to be cooled to room temperature simultaneously.Open autoclave, take out the Carbon foam precast body.The Carbon foam precast body is placed tube furnace, under the air atmosphere, be warming up to 350 ℃, be cooled to room temperature behind the constant temperature 1h, obtain oxidation Carbon foam precast body with 0.5 ℃/minute speed.The above-mentioned oxidation Carbon foam precast body for preparing is warming up to 900 ℃ with 2 ℃/minute carries out charing under high pure nitrogen, be cooled to room temperature behind the constant temperature 1h naturally.
Metal/Carbon foam matrix material 5g is put in porcelain boat and places the Reaktionsofen flat-temperature zone.At N
2The protection environment heats up down, and when temperature rises to 400 ℃, switching gas is N
2/ H
2Gas mixture (volume ratio 1: 1, total flux 100ml/ minute), sample reduction 60 minutes.10 ℃/minute are warming up to 900 ℃ under this atmosphere, and gas switches to H
2/ C
2H
2(volume ratio 2: 1, total flux 150ml/ minute).After question response carried out 60 minutes, gas switched to N
2, and sample shifted out reaction zone, and be quickly cooled to room temperature, collect sample, obtain the nanometer carbon fiber/foam carbon composite.
Embodiment nine
Take by weighing and be ground to 80 purpose coal liquefaction residue 1g and Skellysolve A 1g and pack in the porcelain crucible, place then in the autoclave, feed high pure nitrogen 2～3 times repeatedly with the emptying air, again in autoclave inflated with nitrogen to 3MPa.Be warming up to 230 ℃, be incubated 4 hours.With the unexpected relief pressure of autoclave, place cold water to be cooled to room temperature simultaneously.Open autoclave, take out the Carbon foam precast body.The Carbon foam precast body is placed tube furnace, under the air atmosphere, be warming up to 350 ℃, be cooled to room temperature behind the constant temperature 1h, obtain oxidation Carbon foam precast body with 1 ℃/minute speed.The above-mentioned oxidation Carbon foam precast body for preparing is warming up to 700 ℃ with 2 ℃/minute carries out charing under high pure nitrogen, be cooled to room temperature behind the constant temperature 1h naturally.
Metal/Carbon foam matrix material is put in porcelain boat and places the Reaktionsofen flat-temperature zone.At N
2The protection environment heats up down, and when temperature rises to 600 ℃, switching gas is N
2/ H
2Gas mixture (volume ratio 1: 1, total flux 100ml/ minute), sample reduction 30 minutes.10 ℃/minute are warming up to 800 ℃ under this atmosphere, and gas switches to H
2/ C
2H
4(volume ratio 2: 1, total flux 150ml/ minute).After question response carried out 60 minutes, gas switched to N
2, and sample shifted out reaction zone, and be quickly cooled to room temperature, collect sample, obtain the nanometer carbon fiber/foam carbon composite
Embodiment ten
Take by weighing and be ground to 80 purpose coal liquefaction residue 10g and Skellysolve A 5g and pack in the porcelain crucible, place then in the autoclave, feed high pure nitrogen 2～3 times repeatedly with the emptying air, again in autoclave inflated with nitrogen to 6MPa.Be warming up to 230 ℃, be incubated 4 hours.With the unexpected relief pressure of autoclave, place cold water to be cooled to room temperature simultaneously.Open autoclave, take out the Carbon foam precast body.The Carbon foam precast body is placed tube furnace, under the air atmosphere, be warming up to 350 ℃, be cooled to room temperature behind the constant temperature 1h, obtain oxidation Carbon foam precast body with 1 ℃/minute speed.The above-mentioned oxidation Carbon foam precast body for preparing is warming up to 700 ℃ with 2 ℃/minute carries out charing under high pure nitrogen, be cooled to room temperature behind the constant temperature 1h naturally.
Metal/Carbon foam matrix material is put in porcelain boat and places the Reaktionsofen flat-temperature zone.At N
2The protection environment heats up down, and when temperature rises to 600 ℃, switching gas is N
2/ H
2Gas mixture (volume ratio 1: 1, total flux 100ml/ minute), sample reduction 30 minutes.10 ℃/minute are warming up to 800 ℃ under this atmosphere, and gas switches to H
2/ C
2H
4(volume ratio 2: 1, total flux 150ml/ minute).After question response carried out 5 minutes, gas switched to N
2, and sample shifted out reaction zone, and be quickly cooled to room temperature, collect sample, obtain the nanometer carbon fiber/foam carbon composite.
Embodiment 11
Take by weighing feed coal liquefied residue 10g, mix to stir forming suspension liquid with 20g tetrahydrofuran (THF) (THF).The polyurethane foam of 1cm * 1cm * 1cm size be impregnated in this suspension liquid 3 minutes, take out, fully extruding.Carbon foam after the extruding was drying at room temperature 5 minutes.This foam is placed tube furnace, under the air atmosphere, be warming up to 350 ℃, be cooled to room temperature behind the constant temperature 1h under this temperature, obtain the Carbon foam raw material of oxidative cure with 1 ℃/minute speed.The above-mentioned oxidation Carbon foam raw material that prepare are warming up to 700 ℃ with 2 ℃/minute carry out charing under high pure nitrogen, be cooled to room temperature behind the constant temperature 1h naturally.
Metal/Carbon foam matrix material 5g is put in porcelain boat and places the Reaktionsofen flat-temperature zone.At N
2The protection environment heats up down, and when temperature rises to 500 ℃, switching gas is N
2/ H
2Gas mixture air-flow (volume ratio 1: 1, total flux 100ml/ minute), sample reduction 30 minutes.10 ℃/minute are warming up to 800 ℃ under this atmosphere, and gas switches to H
2/ C
2H
4(volume ratio 2: 1, total flux 150ml/ minute).After question response carried out 30 minutes, gas switched to N
2, and sample shifted out reaction zone, and be quickly cooled to room temperature, collect sample.
Embodiment 12
Take by weighing feed coal liquefied residue 10g, mix to stir forming suspension liquid with 30g tetrahydrofuran (THF) (THF).The polyurethane foam of 1cm * 1cm * 1cm size be impregnated in this suspension liquid 3 minutes, take out, fully extruding.Carbon foam after the extruding was drying at room temperature 5 minutes.This foam is placed tube furnace, under the air atmosphere, be warming up to 350 ℃, be cooled to room temperature behind the constant temperature 1h under this temperature, obtain the Carbon foam raw material of oxidative cure with 1 ℃/minute speed.The above-mentioned oxidation Carbon foam raw material that prepare are warming up to 700 ℃ with 2 ℃/minute carry out charing under high pure nitrogen, be cooled to room temperature behind the constant temperature 1h naturally.
Metal/Carbon foam matrix material 5g is put in porcelain boat and places the Reaktionsofen flat-temperature zone.At N
2The protection environment heats up down, and when temperature rises to 500 ℃, switching gas is N
2/ H
2Gas mixture air-flow (volume ratio 1: 1, total flux 100ml/ minute), sample reduction 30 minutes.10 ℃/minute are warming up to 800 ℃ under this atmosphere, and gas switches to H
2/ C
2H
4(volume ratio 2: 1, total flux 150ml/ minute).After question response carried out 30 minutes, gas switched to N
2, and sample shifted out reaction zone, and be quickly cooled to room temperature, collect sample.
Embodiment 13
Take by weighing feed coal liquefied residue 10g, mix to stir forming suspension liquid with the 20g pyridine.The melamine foamed plastic of 1cm * 1cm * 1cm size be impregnated in this suspension liquid 5 minutes, take out, fully extruding.Carbon foam after the extruding was drying at room temperature 5 minutes.This foam is placed tube furnace, under the air atmosphere, be warming up to 400 ℃, be cooled to room temperature behind the constant temperature 0.5h under this temperature, obtain the Carbon foam raw material of oxidative cure with 5 ℃/minute speed.The above-mentioned oxidation Carbon foam raw material that prepare are warming up to 700 ℃ with 2 ℃/minute carry out charing under high pure nitrogen, be cooled to room temperature behind the constant temperature 1h naturally.
Metal/Carbon foam matrix material 5g is put in porcelain boat and places the Reaktionsofen flat-temperature zone.At N
2The protection environment heats up down, and when temperature rises to 500 ℃, switching gas is N
2/ H
2Gas mixture air-flow (volume ratio 1: 1, total flux 100ml/ minute), sample reduction 30 minutes.20 ℃/minute are warming up to 800 ℃ under this atmosphere, and gas switches to H
2/ C
2H
4(volume ratio 2: 1, total flux 150ml/ minute).After question response carried out 30 minutes, gas switched to N
2, and sample shifted out reaction zone, and be quickly cooled to room temperature, collect sample.
Embodiment 14
Take by weighing feed coal liquefied residue 10g, mix to stir forming suspension liquid with the 20g pyridine.The phenol formaldehyde foam of 1cm * 1cm * 1cm size be impregnated in this suspension liquid 10 minutes, take out, fully extruding.Carbon foam after the extruding was drying at room temperature 1 minute.This foam is placed tube furnace, under the air atmosphere, be warming up to 400 ℃, be cooled to room temperature behind the constant temperature 0.5h under this temperature, obtain the Carbon foam raw material of oxidative cure with 5 ℃/minute speed.The above-mentioned oxidation Carbon foam raw material that prepare are warming up to 700 ℃ with 2 ℃/minute carry out charing under high pure nitrogen, be cooled to room temperature behind the constant temperature 1h naturally.
Metal/Carbon foam matrix material 5g is put in porcelain boat and places the Reaktionsofen flat-temperature zone.At N
2The protection environment heats up down, and when temperature rises to 500 ℃, switching gas is N
2/ H
2Gas mixture air-flow (volume ratio 1: 1, total flux 100ml/ minute), sample reduction 30 minutes.20 ℃/minute are warming up to 800 ℃ under this atmosphere, and gas switches to H
2/ C
2H
4(volume ratio 2: 1, total flux 150ml/ minute).After question response carried out 120 minutes, gas switched to N
2, and sample shifted out reaction zone, and be quickly cooled to room temperature, collect sample.
Claims (5)
1. one kind is the method for feedstock production nanometer carbon fiber/foam charcoal with the coal directly-liquefied residue, and it is characterized in that: the concrete steps of this method are as follows:
(1) take by weighing coal liquefaction residue after the grinding with supercritical foaming method or template, wherein, supercritical methanol technology is about to supercutical fluid and mixes with coal liquefaction residue, leaves standstill under its supercritical state 1-5 hour, and unexpected relief pressure makes the Carbon foam precast body; Template, it is even to be about to coal liquefaction residue and solvent, with template foam impregnation in this mixed solution 1-10 minute, after extruding, made the Carbon foam precast body at air drying 1-5 minute, 1-10g Carbon foam precast body is placed tube furnace, under air atmosphere, be warming up to 300-400 ℃ with 0.5-5 ℃/minute speed, behind the constant temperature 0.5-3h, naturally reduce to room temperature, obtain preoxidation Carbon foam precast body;
(2) the above-mentioned preoxidation Carbon foam precast body for preparing is warming up to 700-900 ℃ with 1-5 ℃/minute under rare gas element and carries out charing, be cooled to room temperature behind the constant temperature 1h naturally, obtain metal/Carbon foam matrix material;
(3) prepare the nanometer carbon fiber/foam charcoal with chemical Vapor deposition process; metal/Carbon foam matrix material is put in porcelain boat and places the Reaktionsofen flat-temperature zone; under the protection of inert gas environment, heat up; when temperature rises to 400-600 ℃; switching gas is the N2/H2 gas mixture; gas stream sample reduction 10-60 minute; 2-20 ℃/minute is warming up to 700-900 ℃ under this atmosphere; gas switches to carbon-source gas; after question response carried out 5-120 minute, gas switched to rare gas element, and sample is shifted out reaction zone; be cooled to room temperature, make the nanometer carbon fiber/foam charcoal.
2. the preparation method of nanometer carbon fiber/foam charcoal according to claim 1 is characterized in that: its supercutical fluid is selected from Skellysolve A or methyl-formiate in the described supercritical foaming method.
3. the preparation method of nanometer carbon fiber/foam charcoal according to claim 1 is characterized in that: the template foam is polyurethane foam, melamine foamed plastic or phenolic resin foam in the described template, and solvent is tetrahydrofuran (THF) or pyridine.
4. the preparation method of nanometer carbon fiber/foam charcoal according to claim 1 is characterized in that: the carbon source that described chemical Vapor deposition process uses is selected from methane, ethene, propylene or acetylene.
5. the preparation method of nanometer carbon fiber/foam charcoal according to claim 1 is characterized in that: described rare gas element is selected from nitrogen, argon gas or helium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009103086855A CN101693533B (en) | 2009-10-23 | 2009-10-23 | Method for preparing nanometer carbon fiber/foam coal through taking coal liquefaction residues as raw materials |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009103086855A CN101693533B (en) | 2009-10-23 | 2009-10-23 | Method for preparing nanometer carbon fiber/foam coal through taking coal liquefaction residues as raw materials |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101693533A true CN101693533A (en) | 2010-04-14 |
| CN101693533B CN101693533B (en) | 2011-08-10 |
Family
ID=42092549
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009103086855A Expired - Fee Related CN101693533B (en) | 2009-10-23 | 2009-10-23 | Method for preparing nanometer carbon fiber/foam coal through taking coal liquefaction residues as raw materials |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101693533B (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102134068A (en) * | 2011-04-24 | 2011-07-27 | 大连理工大学 | Preparation method of graphitic carbon foam with high aperture ratio |
| CN102241559A (en) * | 2011-04-24 | 2011-11-16 | 大连理工大学 | Method for performing oxydehydrogenation of ethylbenzene by using carbon nanofibers loaded on surface of carbon foams as catalyst |
| CN102249214A (en) * | 2011-04-27 | 2011-11-23 | 大连理工大学 | Method for loading carbon cord on surface of carbon foam |
| CN102530916A (en) * | 2011-12-31 | 2012-07-04 | 上海大学 | Preparation method of coal-based carbon foam |
| CN103553020A (en) * | 2013-10-31 | 2014-02-05 | 湖南九华碳素高科有限公司 | Preparation method of mixed-base foamy carbon material |
| CN104591121A (en) * | 2013-10-31 | 2015-05-06 | 神华集团有限责任公司 | Super capacitor charcoal electrode material, super capacitor charcoal electrode, preparation method of material, and preparation method of electrode |
| CN106362686A (en) * | 2016-09-19 | 2017-02-01 | 天津科技大学 | Preparation method of composite material for gathering and degrading benzene series organic wastewater |
| CN106582260A (en) * | 2016-11-02 | 2017-04-26 | 广西大学 | Apparatus for purifying hydrophobic organic waste gas and purifying method therefor |
| CN106882785A (en) * | 2017-02-27 | 2017-06-23 | 天津宝坻紫荆科技有限公司 | A kind of preparation method for reclaiming quenching oil porous carbon |
| CN108557801A (en) * | 2018-06-22 | 2018-09-21 | 东北林业大学 | A kind of porous foam charcoal and preparation method thereof |
| CN108585859A (en) * | 2018-04-25 | 2018-09-28 | 国家能源投资集团有限责任公司 | Carbon/carbon composite and preparation method thereof |
| CN109437147A (en) * | 2018-10-31 | 2019-03-08 | 石狮市川大先进高分子材料研究中心 | A kind of preparation method of multifunctional C foam |
| CN114940489A (en) * | 2022-06-17 | 2022-08-26 | 太原理工大学 | Method for preparing carbon nano tube from coal liquefaction residues |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100374367C (en) * | 2003-11-07 | 2008-03-12 | 大连理工大学 | Technical method and schedule for preparation of foam carbon material used asphalt as raw material |
| US7276284B2 (en) * | 2003-12-18 | 2007-10-02 | Sgl-Carbon Ag | Carbon fiber reinforced coke from the delayed coker |
| CN100365177C (en) * | 2005-11-21 | 2008-01-30 | 大连理工大学 | Plasma method for preparing nano carbon material using coal liquefied residue as raw material |
-
2009
- 2009-10-23 CN CN2009103086855A patent/CN101693533B/en not_active Expired - Fee Related
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102241559A (en) * | 2011-04-24 | 2011-11-16 | 大连理工大学 | Method for performing oxydehydrogenation of ethylbenzene by using carbon nanofibers loaded on surface of carbon foams as catalyst |
| CN102134068A (en) * | 2011-04-24 | 2011-07-27 | 大连理工大学 | Preparation method of graphitic carbon foam with high aperture ratio |
| CN102249214A (en) * | 2011-04-27 | 2011-11-23 | 大连理工大学 | Method for loading carbon cord on surface of carbon foam |
| CN102530916A (en) * | 2011-12-31 | 2012-07-04 | 上海大学 | Preparation method of coal-based carbon foam |
| CN103553020A (en) * | 2013-10-31 | 2014-02-05 | 湖南九华碳素高科有限公司 | Preparation method of mixed-base foamy carbon material |
| CN104591121A (en) * | 2013-10-31 | 2015-05-06 | 神华集团有限责任公司 | Super capacitor charcoal electrode material, super capacitor charcoal electrode, preparation method of material, and preparation method of electrode |
| CN103553020B (en) * | 2013-10-31 | 2015-08-05 | 湖南九华碳素高科有限公司 | A kind of preparation method of mixed base foamed carbon material |
| CN104591121B (en) * | 2013-10-31 | 2017-01-04 | 神华集团有限责任公司 | A kind of ultracapacitor carbon electrode material and carbon electrode of super capacitor and preparation method thereof |
| CN106362686A (en) * | 2016-09-19 | 2017-02-01 | 天津科技大学 | Preparation method of composite material for gathering and degrading benzene series organic wastewater |
| CN106362686B (en) * | 2016-09-19 | 2018-07-31 | 天津科技大学 | A kind of preparation method of the composite material of enrichment degrading benzene object organic wastewater |
| CN106582260B (en) * | 2016-11-02 | 2023-03-17 | 海南大学 | Device and method for purifying hydrophobic organic waste gas |
| CN106582260A (en) * | 2016-11-02 | 2017-04-26 | 广西大学 | Apparatus for purifying hydrophobic organic waste gas and purifying method therefor |
| CN106882785A (en) * | 2017-02-27 | 2017-06-23 | 天津宝坻紫荆科技有限公司 | A kind of preparation method for reclaiming quenching oil porous carbon |
| CN106882785B (en) * | 2017-02-27 | 2019-05-10 | 天津宝坻紫荆科技有限公司 | A kind of preparation method recycling quenching oil porous carbon |
| CN108585859A (en) * | 2018-04-25 | 2018-09-28 | 国家能源投资集团有限责任公司 | Carbon/carbon composite and preparation method thereof |
| CN108585859B (en) * | 2018-04-25 | 2021-07-20 | 国家能源投资集团有限责任公司 | Carbon/carbon composite material and preparation method thereof |
| CN108557801A (en) * | 2018-06-22 | 2018-09-21 | 东北林业大学 | A kind of porous foam charcoal and preparation method thereof |
| CN109437147A (en) * | 2018-10-31 | 2019-03-08 | 石狮市川大先进高分子材料研究中心 | A kind of preparation method of multifunctional C foam |
| CN114940489A (en) * | 2022-06-17 | 2022-08-26 | 太原理工大学 | Method for preparing carbon nano tube from coal liquefaction residues |
| CN114940489B (en) * | 2022-06-17 | 2023-08-22 | 太原理工大学 | Method for preparing carbon nano tube from coal liquefaction residues |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101693533B (en) | 2011-08-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101693533B (en) | Method for preparing nanometer carbon fiber/foam coal through taking coal liquefaction residues as raw materials | |
| Lin et al. | Preparation of Fe-char catalyst from tank cleaning oily sludge for the catalytic cracking of oily sludge | |
| He et al. | The effects of temperature and molten salt on solar pyrolysis of lignite | |
| CN110721686B (en) | Catalytic cracking catalyst using peat carbon as carrier | |
| CN110451485B (en) | Lignin thermal reconstruction assembled carbon nanomaterial and preparation method thereof | |
| CN111250092B (en) | Preparation method and application of biomass honeycomb-shaped semicoke-loaded nickel-iron nanoparticle catalyst | |
| CN105800556B (en) | A kind of method of char gasification and methane reforming coupling technique co-producing active carbon and hydrogen | |
| Wang et al. | Catalytic toluene steam reforming using Ni supported catalyst from pyrolytic peat | |
| Du et al. | Preparation of high-activity coal char-based catalysts from high metals containing coal gangue and lignite for catalytic decomposition of biomass tar | |
| CN101376114A (en) | Method for preparing metal or metallic oxide/carbon composite material | |
| Shen | Catalytic pyrolysis of biomass with char modified by cathode materials of spent lithium-ion batteries for tar reduction and syngas production | |
| Wang et al. | Steam reforming of biomass tar model compound over two waste char-based Ni catalysts for syngas production | |
| Zhang et al. | Recent progress in melt pyrolysis: Fabrication and applications of high‐value carbon materials from abundant sources | |
| Lv et al. | Steam reforming of α-methylnaphthalene as a model compound of biomass tar over Ni-based catalyst for hydrogen-rich gas | |
| CN113318745A (en) | Preparation method of hydrogen-rich catalyst for biomass pyrolysis | |
| CN100365177C (en) | Plasma method for preparing nano carbon material using coal liquefied residue as raw material | |
| CN110205159B (en) | Method for directionally preparing high-quality oil by reforming tar and molten salt and product | |
| CN102241559A (en) | Method for performing oxydehydrogenation of ethylbenzene by using carbon nanofibers loaded on surface of carbon foams as catalyst | |
| CN114940489A (en) | Method for preparing carbon nano tube from coal liquefaction residues | |
| CN110484286B (en) | Method for preparing carbon and inhibiting tar through pyrolysis gas deposition in high-volatile coal thermal conversion process | |
| CN113426448A (en) | Preparation method and application of novel biochar-based tar cracking catalyst | |
| Wang et al. | Hydrogen production from catalytic microwave-assisted pyrolysis of corncob over transition metal (Fe, Co and Ni) modified palygorskite | |
| Tao et al. | Interface engineering of Ce/La-doped hydrochar-supported nickel catalysts for enhanced tar reforming performance at low temperature | |
| Li et al. | Catalysis co-calcination: An available and energy-saving approach to prepare metal/carbon materials with well hydrophobicity and photo-thermal conversion performance | |
| CN111377432B (en) | Method for preparing layered nano carbon material by coal solvent heat treatment |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20110810 Termination date: 20141023 |
|
| EXPY | Termination of patent right or utility model |