CN1244395C - Preparation of coal based carbon film - Google Patents
Preparation of coal based carbon film Download PDFInfo
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- CN1244395C CN1244395C CN 03134197 CN03134197A CN1244395C CN 1244395 C CN1244395 C CN 1244395C CN 03134197 CN03134197 CN 03134197 CN 03134197 A CN03134197 A CN 03134197A CN 1244395 C CN1244395 C CN 1244395C
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- coal
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- carbon membrane
- binding agent
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- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The present invention belongs to the technical field of new materials, which relates to a preparation method for a carbon film, particularly to a preparation method for a coal-based carbon film. The present invention is characterized in that coal with low price is used as a raw material; by changing the grain size of coal powder, the sort and the addition amount of plastering agents and charing conditions, carbon films which have different average pore diameters, different pore diameter distribution, high mechanical strength, numerous pore structures and good separation performance and are used for meeting different separation purposes can be prepared. The present invention solves the problems of high cost, poor mechanical strength, complicated technology and the like for carbon film preparation, provides a preparation method for separation carbon films with low cost, simple production technology, easy industrialization and high strength, and can be widely used for preparing carbon films for different separation purposes.
Description
Technical field
The invention belongs to new material technology field, a kind of preparation method of carbon membrane particularly relates to the preparation method of coal-based carbon film.
Background technology
Over nearly 30 years, carbon membrane has caused numerous scientific research personnel's great attention as a kind of novel separation membrane, and this has mainly due to carbon membrane: (1) Heat stability is good.Carbon membrane can used under up to 400 ℃ temperature under the situation of aerobic, at the high temperature that can stand under the situation of anaerobic more than 800 ℃; (2) chemical stability is good.Can under the environment of organic steam or solvent, non-oxidizing acid or alkali existence, use; (3) aperture is controlled.Same raw materials can be used for the different carbon membranes that separate purpose by selecting different conditions to prepare; (4) long service life of carbon membrane and renewable; (5) energy consumption is low.Compare with traditional separation process such as rectifying, absorption, carbon membrane separates and does not need undergoing phase transition, and separation process carries out at normal temperatures, need not heat separation of material.
About the existing many relevant reports of the technology of preparing of carbon membrane.Hatori makes non-support plate carbon membrane with phase inversion casting film-forming on smooth glass plate after drying, the charing.Yet in order to reach certain separation, film must be thin as far as possible, thereby this dull and stereotyped carbon membrane is usually more crisp, easily split, bad mechanical strength, in processing and operation difficulty greatly (Carbon, 1992,30:303-304).US5089135 discloses and has a kind ofly prepared hollow fiber carbon membrane with the hollow-fibre membrane charing, although this carbon membrane has good separating property, yet its mechanical strength is still very poor, range of application is very restricted, and, doughnut is difficult to carry out large-scale industrial production with film tool form, and this has limited the process of industrialization of carbon membrane largely.
Summary of the invention
The purpose of this invention is to provide that a kind of cost is low, production technology is simple, be easy to the preparation method that industrialized high strength is separated carbon membrane, problems such as the carbon membrane preparation cost is higher to solve, bad mechanical strength, complex process.
Technical scheme of the present invention is:
(1) refinement of feed coal.With the coal of various degrees of metamorphism as: brown coal, bituminous coal and anthracite etc. are feed coal, at first adopt disintegrating apparatus that coal dust is broken to about 200 orders, mix with water and quartz sand then and be incorporated in thinning processing in the sand mill, can control coal sample size in processing procedure between 5～40 μ m according to the difference of milling time, milling time is chosen in 12～48 hours usually.After the taking-up, can store for future use after handling through filter sand, precipitation, oven dry.Wherein the sand mill rotating speed is 1000～1400 rev/mins, and coal dust, quartz sand, water three's mass ratio is about 10: 9: 7.
(2) under the normal temperature coal dust and binding agent are put into blender, binding agent then requires to have stronger cohesive force and plasticity to a certain degree, common optional coal tar, carboxymethyl cellulose, 403 glue, phenolic resins, poly furfuryl alcohol, furane resins, acrylonitrile-styrol copolymer with and with the high molecular polymers such as graft copolymer of polybutadiene rubber as binding agent, the addition of binding agent is 20%～70% of a mixture gross mass, after mixing, again mixed material is put into forming press, the control briquetting pressure is between 2～6Mpa, it is even to make it extrude quality, straight and ganoid former film, according to the mould difference of selecting, the former film of extruding can be tubulose (single channel and multichannel), various ways such as tabular.
(3) at room temperature former film being carried out drying handles.Must guarantee that volatile component evenly vapors away in the former film when dry, otherwise former film distortion back has a strong impact on generation to its performance, thereby drying condition elects under the normal temperature usually and dry on screen cloth as, be 5～24 hours drying time, wherein preferred 10～15 hours.
(4) dried former film is put into temperature programming control retort, under inert gas shielding, carried out just preparing required separation carbon membrane after charing is handled with certain heating rate.Wherein inert gas is selected wherein a kind of such as nitrogen, argon gas usually for use, and heating rate generally is controlled at 1～6 ℃/min, and the whole temperature of charing is chosen as 600～1000 ℃ usually, and under this temperature constant temperature 30～120min.
Effect of the present invention and benefit are:
(1) with feed coal be the carbon membrane of persursor material preparation not only production cost is low, but also have higher porosity and flux, pore structure is even, mechanical strength is high.
(2) average pore size of carbon membrane and pore-size distribution are easy to control.Can prepare the carbon membranes that are used for different separation purposes by the granularity that changes coal dust, kind, addition and the carbonization condition of binding agent.
(3) Zhi Bei carbon membrane porosity height, mechanical strength is big, and smooth surface is intact, and can be as the supporter of compound carbon membrane.
The specific embodiment
Below be described in detail the specific embodiment of the present invention and embodiment.
Embodiment 1
Adopt complete disintegrating apparatus that coal dust is broken to about 200 orders, then with water and quartz sand mixing water mill, control sand mill rotating speed is 1200 rev/mins, and coal dust, quartz sand, water three's mass ratio is about 10: 9: 7.Ground 12 hours, the particle mean size of measuring coal dust this moment is about 20 μ m.Taking by weighing 80g coal dust and 40g coal tar respectively puts into blender and mixes; then; put into forming press; squeeze out the tubulose carbon membrane during for 4MPa in briquetting pressure; after being allowed to condition under the room temperature dry 10 hours, put into retort, under argon shield; heating rate with 3 ℃/min rises to 900 ℃ and constant temperature 30min, treats that it is cooled to just can take out below 100 ℃.Through test, the average pore size of carbon membrane is 100nm, and porosity is 44%, at 20 ℃, and N under the 0.2Mp
2Permeation flux is 9.891 * 10
-5Cm
3.cm/ (cm
2.s.cmHg).
Embodiment 2
Adopt complete disintegrating apparatus that coal dust is broken to about 200 orders, then with water and quartz sand mixing water mill, control sand mill rotating speed is 1200 rev/mins, and coal dust, quartz sand, water three's mass ratio is about 10: 9: 7.Ground 24 hours, the particle mean size of measuring coal dust this moment is about 10 μ m.Taking by weighing 80g coal dust and 55g carboxymethyl cellulose binding agent respectively puts into blender and mixes; then; put into forming press; squeeze out the tubulose carbon membrane during for 4MPa in briquetting pressure; after being allowed to condition under the room temperature dry 10 hours, put into retort, under argon shield; heating rate with 3 ℃/min rises to 900 ℃ and constant temperature 30min, treats that it is cooled to just can take out below 100 ℃.Through test, the average pore size of carbon membrane is 60nm, and porosity is 40%, at 20 ℃, and N under the 0.2Mp
2Permeation flux is 1.507 * 10
-5Cm
3.cm/ (cm
2.s.cmHg).
Claims (3)
1. the preparation method of a carbon membrane, be to be raw material with the coal, the addition of the granularity by changing coal dust, the kind of binding agent, binding agent and carbonization condition preparation have different average pore diameters and pore-size distribution be used for satisfy the different mechanical strength height that separate purpose, pore structure prosperity, carbon membrane that separating property is good, it is characterized in that:
(1) earlier feed coal is crushed to 200 orders, then it is mixed with water and quartz sand and put into sand mill and carry out thinning processing, milling time is 12～48 hours; The sand mill rotating speed is 1000～1400 rev/mins, coal dust: quartz sand: the mass ratio of water is 10: 9: 7;
(2) will handle through step (1) under the normal temperature and obtain coal dust with binding agent is put into blender, and after mixing, again mixed material be put into make-up machine, adjustment moulding pressure extrusion becomes former film, makes even, the straight and smooth surface of its quality; The addition of binding agent accounts for 20%～70% of mixture gross mass; Pressure is 2～6MPa during moulding; The former film that squeezes out through make-up machine is single channel tubulose or multichannel tubulose or tabular;
(3) dried former film is put into temperature programming control retort, under inert gas shielding, carried out just preparing required separation carbon membrane after charing is handled with certain heating rate; Inert gas is nitrogen or argon gas, and heating rate is controlled at 1～6 ℃/min; The whole temperature of charing is 600～1000 ℃; Constant temperature 30～120min under this temperature.
2. according to the described a kind of carbon membrane preparation method of claim 1, it is characterized in that feed coal is brown coal, bituminous coal or anthracite.
3. according to the described a kind of carbon membrane preparation method of claim 1, it is characterized in that binding agent is coal tar, carboxymethyl cellulose, 403 glue, phenolic resins, poly furfuryl alcohol, furane resins, acrylonitritrile-styrene resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03134197 CN1244395C (en) | 2003-08-30 | 2003-08-30 | Preparation of coal based carbon film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03134197 CN1244395C (en) | 2003-08-30 | 2003-08-30 | Preparation of coal based carbon film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1490076A CN1490076A (en) | 2004-04-21 |
| CN1244395C true CN1244395C (en) | 2006-03-08 |
Family
ID=34154411
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 03134197 Expired - Fee Related CN1244395C (en) | 2003-08-30 | 2003-08-30 | Preparation of coal based carbon film |
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| CN (1) | CN1244395C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100384722C (en) * | 2005-12-28 | 2008-04-30 | 大连理工大学 | Process for preparing nano hybrid carbon film |
| CN102527257B (en) * | 2011-12-31 | 2013-11-06 | 大连理工大学 | Preparation method of conductive carbon membrane |
| CN103272490B (en) * | 2013-06-07 | 2016-01-06 | 大连理工大学 | A kind of fiber reinforcement flat carbon film and preparation method thereof |
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2003
- 2003-08-30 CN CN 03134197 patent/CN1244395C/en not_active Expired - Fee Related
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| CN1490076A (en) | 2004-04-21 |
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Granted publication date: 20060308 Termination date: 20170830 |