EP1235744A1 - Activated carbons and method for obtaining same from a partly mesophase and partly mesogenic pitch - Google Patents
Activated carbons and method for obtaining same from a partly mesophase and partly mesogenic pitchInfo
- Publication number
- EP1235744A1 EP1235744A1 EP00981431A EP00981431A EP1235744A1 EP 1235744 A1 EP1235744 A1 EP 1235744A1 EP 00981431 A EP00981431 A EP 00981431A EP 00981431 A EP00981431 A EP 00981431A EP 1235744 A1 EP1235744 A1 EP 1235744A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- pitch
- approximately
- partially
- resins
- activated carbon
- 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.)
- Withdrawn
Links
- 238000000034 method Methods 0.000 title claims abstract description 41
- 239000011340 mesogenic pitch Substances 0.000 title abstract description 4
- 239000011295 pitch Substances 0.000 claims abstract description 69
- 239000011347 resin Substances 0.000 claims abstract description 62
- 229920005989 resin Polymers 0.000 claims abstract description 62
- 238000003763 carbonization Methods 0.000 claims abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 113
- 229910052799 carbon Inorganic materials 0.000 claims description 31
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 30
- 230000004913 activation Effects 0.000 claims description 22
- 230000008569 process Effects 0.000 claims description 18
- 239000007789 gas Substances 0.000 claims description 16
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 14
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000002243 precursor Substances 0.000 claims description 10
- 238000000605 extraction Methods 0.000 claims description 8
- 230000005587 bubbling Effects 0.000 claims description 7
- 239000001569 carbon dioxide Substances 0.000 claims description 7
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 230000001681 protective effect Effects 0.000 claims description 6
- 238000003860 storage Methods 0.000 claims description 6
- 238000005470 impregnation Methods 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 230000000721 bacterilogical effect Effects 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000011084 recovery Methods 0.000 claims description 4
- 230000002285 radioactive effect Effects 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- 239000011300 coal pitch Substances 0.000 claims description 2
- 230000018044 dehydration Effects 0.000 claims description 2
- 238000006297 dehydration reaction Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 230000002045 lasting effect Effects 0.000 claims description 2
- 239000012528 membrane Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 230000003213 activating effect Effects 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 description 14
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 239000011148 porous material Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- 229940072033 potash Drugs 0.000 description 9
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 9
- 235000015320 potassium carbonate Nutrition 0.000 description 9
- 238000001179 sorption measurement Methods 0.000 description 9
- 238000011282 treatment Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 6
- 239000003570 air Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000003245 coal Substances 0.000 description 4
- 230000035800 maturation Effects 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 238000013019 agitation Methods 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 239000012080 ambient air Substances 0.000 description 1
- 238000007707 calorimetry Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000010981 drying operation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000011301 petroleum pitch Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- -1 tire Substances 0.000 description 1
- 238000007158 vacuum pyrolysis Methods 0.000 description 1
- 238000013022 venting Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
- B01J20/28071—Pore volume, e.g. total pore volume, mesopore volume, micropore volume being less than 0.5 ml/g
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D5/00—Composition of materials for coverings or clothing affording protection against harmful chemical agents
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
- B01J20/28073—Pore volume, e.g. total pore volume, mesopore volume, micropore volume being in the range 0.5-1.0 ml/g
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28078—Pore diameter
- B01J20/2808—Pore diameter being less than 2 nm, i.e. micropores or nanopores
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28078—Pore diameter
- B01J20/28083—Pore diameter being in the range 2-50 nm, i.e. mesopores
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/318—Preparation characterised by the starting materials
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/318—Preparation characterised by the starting materials
- C01B32/33—Preparation characterised by the starting materials from distillation residues of coal or petroleum; from petroleum acid sludge
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
- F17C11/00—Use of gas-solvents or gas-sorbents in vessels
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/20—Capture or disposal of greenhouse gases of methane
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
Definitions
- the present invention relates to active carbon.
- microporous structure which determines the adsorption properties defined by two main parameters which are:
- the pores are classified into three categories, according to their sizes:
- microporous volume is generally desired to be the greatest, although each of the applications calls upon active carbon whose characteristics differ.
- active carbon For the storage of gas, preference will be given to active carbon with a high microporous volume, having large micropore sizes and a low level of mesopores since the gas is stored in the latter in the gaseous phase.
- the inventors therefore set out to find new methods for synthesizing active carbon, in order to obtain products having particular properties, in these applications.
- the present invention therefore relates to a process for obtaining active charcoals from a partially mesophase and partially mesogenous pitch containing less than about 40%, and preferably less than 30%, of ⁇ -type resins, more approximately 40%, and preferably more than 50%, of ⁇ -type resins and between approximately 5 and 30% of ⁇ -type resins, comprising the activation of such a pitch, possibly preceded by its charring.
- ⁇ resins is meant resins insoluble in toluene and in quinoline, by resins of ⁇ type resins insoluble in toluene but soluble in quinoline and by resins of type ⁇ resins soluble in toluene and in quinoline.
- the percentages (%) of the different resins are expressed relative to the total weight of all the resins.
- the present invention more particularly relates to a process for obtaining active carbon from a partially mesophase and partially mesogenous pitch containing less than about 40%, and preferably less than 30%, of ⁇ type resins, more d '' approximately 40%, and preferably more than 50%, of ⁇ -type resins and between approximately 5 and 30% of ⁇ -type resins comprising the following steps:
- the present invention further relates to a process for obtaining active carbon from a partially mesophase and partially mesogenous pitch containing less than about 40%, and preferably less than 30%, of ⁇ -type resins, more '' approximately 40%, and preferably more than 50%, of ⁇ -type resins and between approximately 5 and 30% of ⁇ -type resins comprising the following steps:
- the partially mesophase and partially mesogenous pitch contains between approximately 1 0 and 35% of ⁇ type resins, between approximately 50 and 70% of ⁇ type resins and between approximately 1 0 and 25 % of ⁇ type resins.
- Another object of the present invention is a process for obtaining active carbon from a partially mesophase and partially mesogenous pitch containing approximately 25 and 40%, and preferably between 30 and 35%, of ⁇ -type resins, between approximately 40 and 60%, and preferably between 45 and 55%, of ⁇ -type resins and between approximately 15 and 30%, and preferably between 20 and 30% of ⁇ -type resins comprising the following steps:
- the partially mesophase and partially mesogenous pitch is obtained by selective extraction, ⁇ -type resins not polymerized in toluene, from a pitch containing such resins. It is then a polyaromatic fraction.
- the partially mesophase and partially mesogenated pitch is obtained by distillation of the unpolymerized ⁇ resins, from a pitch containing such resins.
- the partially mesophase and partially mesogenated pitch is obtained by bubbling air within a pitch containing ⁇ -type resins.
- the driving pitches. to partially mesophase and partially mesogenous pitch may be petroleum, coal, tire, wood, vacuum pyrolysis, or other waste. They may however be any other pitch, or other chemical material having an aromatic potential, allowing active carbon to be obtained which meets the needs expressed above.
- the present invention also relates to a partially mesophase and partially mesogenous pitch containing between approximately 25 and 40%, and preferably between 30 and 35%, of ⁇ -type resins, between approximately 40 and 60%, and preferentially between 45 and 55 %, of ⁇ -type resins and between approximately 15 and 30%, and preferably between 20 and 30% of ⁇ -type resins.
- Such activated carbon can be characterized in that at least
- 80%, and preferably 90% of the micropores have, a size between approximately 0, 10 and 0.60 nm, preferably. between approximately 0.25 and 0.55 nm. and a microporous volume of between approximately 0.10 and 0.30 cm 3 / g, and preferably between 0.15 and 0.25 cm 3 / g.
- This type of activated carbon has a door effect.
- Another activated carbon according to the present invention is characterized in that at least 80%, and preferably 90%, of the micropores have a size of between approximately 0.4 and 0.8 nm, preferably between approximately 0.55 and 0, 65 nm, and a microporous volume of between approximately 0.10 and 0.30 cm 3 / g, and preferably between 0.15 and 0.25 cm 3 / g.
- Yet another activated carbon is that characterized in that at least 80%, and preferably 90% of the micropores have a size of between about 0.5 and 0.9 nm and a microporous volume of between about 0.4 and 0.6 cm 3 / g.
- coals can be used as molecular sieves, and generally in filtration or separation operations.
- Also other objects of the present invention are filtration membranes and separation columns containing such coals or coals obtained by one of the methods according to the present invention.
- U na urter activated carbon according to the invention is that characterized in that at least 80%, and preferably 90%, of the micropores have a size of between approximately 0.5 and 3 nm, preferably between approximately 0.7 and 2.7 nm, and a microporous volume greater than approximately 0.8 cm 3 / g, and preferably greater than approximately 1.2 cm 3 / g. It can be used for gas storage.
- the present invention also relates to a gas storage element or a cold production element, in particular by solid / gas sorption, containing at least one activated carbon of this type, or obtained by a process according to the present invention.
- any of the active carbons according to the invention may be included as a constituent of protective materials with respect to gases containing radioactive, bacteriological - or deleterious chemical substances, such as the materials used for the manufacture of protective clothing.
- “NBC” protection Nuclear, Bacteriological and Chemical protection
- these different functions could be combined by incorporating into these protective materials at least two of the active carbons according to the invention.
- the invention also relates to a protective material with respect to gases containing radioactive, bacteriological or chemical substances comprising at least one activated carbon according to the invention.
- Figure 1 schematically summarizes the steps of the process for preparing active carbon by activation with water vapor.
- FIG. 2 illustrates the porosity of an activated carbon obtained by activation by steam.
- FIG. 3 schematically summarizes the steps of the process for the preparation of active carbon by activation with carbon dioxide.
- Figure 4 illustrates the porosity of an activated carbon obtained by activation with carbon dioxide.
- FIG. 5 schematically summarizes the steps of the process for preparing active carbon by activation with potash.
- FIG. 6 illustrates the porosity of an activated carbon obtained by activation with potassium hydroxide for an impregnation rate of 1/1 having a pore size of 0.7 nm and a microporous volume of 0.5 cm 3 / g.
- the precursor used here is an untreated coal pitch of composition ⁇ 1 1% ⁇ 16% ⁇ 73% and a softening point of
- a mature pitch is - thus obtained and has a density greater than the starting pitch (1.33 g / cm 3 ) following a loss of mass during the heat treatment of 5% by mass.
- the aromatic fraction is then isolated by selective extraction of the non-polymerized ⁇ resins in toluene.
- 1 00 g rammes of mature pitch, ground and sieved into particles of size less than 200 ⁇ m, are mixed with 20 liters of toluene, then filtered under vacuum. After rinsing with alcohol, the extraction residue is dried under vacuum. All extraction, filtration and drying operations are carried out at room temperature. The extraction residue obtained then has a composition ⁇ 32% ⁇ 52% ⁇ 1 6%. The overall yield from this operation is 25%.
- the extraction residue thus obtained is then heated in a tubular oven at 2 ° C / min in air (0.5 l / min) until a temperature of 280 ° C and left at this temperature for 30 minutes in order to favor oxidation reactions contributing to the crosslinking of polyaromatic molecules and obtaining an infusible material.
- the infusible material thus obtained is then carbonized under nitrogen (0.5 l / min) at 2 ° C / min up to a temperature of 900 ° C.
- the mass loss during the stabilization and carbonization stages is 20%.
- the opening and development of micropores in the carbonisate obtained by operations (1), (2) and (3) are carried out in a tubular furnace at 800 ° C. using a nitrogen gas stream ( 0.1 l / min) saturated with water vapor by bubbling in a distilled water bath thermostatically controlled at 63 ° C for a period varying from 3 to 12 hours allowing active carbon to be obtained in the rate range d '' wear from 30% to 60%.
- Figure 1 shows the steps of this process.
- the materials obtained have adsorbable volumes Wo ranging from 0.25 cm 3 / g to 0.60 cm 3 / g corresponding respectively to micropore sizes from 0.60 nm to 1.50 nm. Thus, for an activation period of 2 hours, a wear rate of 1 3% is obtained.
- the activated carbon has a homogeneously distributed pore size around 0.6 nm, as illustrated in FIG. 2 and a microporous volume of 0.2 cm 3 / g. Such activated carbon can be used as a mole
- Example 1 The procedure presented in Example 1 was repeated with the exception of the activation procedure which is carried out at 900 ° C. under a stream of carbon dioxide (0.5 l / min) during a period allowing the obtaining with a wear rate of less than 1 5% by mass.
- the activated carbon thus obtained has a microporous volume of 0.20 cm 3 / g and a porosity essentially composed of micropores of size between 0.3 nm and 0.5 nm. This type of door-effect microporosity gives this activated carbon a very high selectivity with respect to various adsorbates.
- FIG. 5 summarizes the steps in this process.
- Such an activated carbon impregnated under conditions respecting a mass ratio of 1: 1 between the precursor ex-pitch and the potash, conducted after a mass loss of 15%, to an activated carbon whose microporosity is centered on 0, 6 nm, as illustrated in FIG. 6, and of microporous volume Wo 0.5 cm 3 / g.
- the high adsorption capacity is approximately twice that of activated carbon with a similar microporous structure.
- the pitch obtained contains at this stage of the process 4% of ⁇ resins, 23.7% of ⁇ resins and 72.3% of ⁇ resins.
- This heat treatment is, from the point of view of the modification of the pitch composition, equivalent to the treatment of Example 1 (400 ° C. 5 hours), there is thus a possibility of choice between a heat treatment process with tray or a process with a thermal ramp alone.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- General Chemical & Material Sciences (AREA)
- Toxicology (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Business, Economics & Management (AREA)
- Emergency Management (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Carbon And Carbon Compounds (AREA)
- Treatment Of Liquids With Adsorbents In General (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Separation Of Gases By Adsorption (AREA)
Abstract
The invention concerns activated carbons. It further concerns a method for obtaining said activated carbons from a partly mesophased and partly mesogenic pitch. It concerns a method for obtaining activated carbons from a partly mesophase and partly mesogenic pitch containing less than about 40 % of type alpha resins, more than about 40 % of type beta resins and between about 5 and 30 % of type gamma resins by activating said pitch preceded by its optional carbonization.
Description
Ch a rb ons actifs et leu r procédé d 'obtention à pa rti r d' u n brai partiel lement mésophasé et parti e llement mésogéné Active ch a rb ons and their process to obtain a partially mesophase and partially mesogenous pitch
La présente invention est relative à des charbons actifs.The present invention relates to active carbon.
Elle a en outre pour objet un procédé d'obtention de ces charbons actifs à partir d'un brai partiellement mésophasé et partiellement mésogéné. La production et i'usage de charbons actifs n'a cessé de progresser au cours des vingt dernières années, d u fait notamment des problèmes liés à l'environnement. Les principaux domaines d'application concernent actuellement:It further relates to a process for obtaining these active carbon from a partially mesophase and partially mesogenous pitch. The production and use of activated carbon has grown steadily over the past twenty years, in particular due to environmental problems. The main areas of application currently concern:
- la séparation et la purification de mélanges de gaz dans l'industrie chimique et pétrolière,- separation and purification of gas mixtures in the chemical and petroleum industry,
- le traitement de l'air,- air treatment,
- le traitement de l'eau, et- water treatment, and
- le stockage d u méthane ou d'autres gaz.- storage of methane or other gases.
D'autres domaines sont intéressés, notamment celui de la production de froid par adsorption/désorption de CO2 ou NH3 par exemple.Other fields are interested, in particular that of the production of cold by adsorption / desorption of CO 2 or NH 3 for example.
Pour chacun de ces domaines, à l'exception d u traitement de l'eau, les possibilités de développement et d'amélioration son conditionnées par l'obtention de charbons actifs à texture microporeuse contrôlée et à faible coût de revient.For each of these areas, with the exception of water treatment, the possibilities for development and improvement are conditioned by obtaining active carbon with controlled microporous texture and at low cost price.
C'est en effet la structure microporeuse qui détermine les propriétés d'adsorption définies par deux paramètres principaux qui sont:It is indeed the microporous structure which determines the adsorption properties defined by two main parameters which are:
- la taille des pores, - le volume microporeux qui détermine la capacité maximale d'adsorption dans les micropores, et- the size of the pores, - the microporous volume which determines the maximum adsorption capacity in the micropores, and
- le volume, total adsorbé qui détermine la capacité maximale d'adsorption dans la totalité des pores et la surface.- the volume, total adsorbed which determines the maximum adsorption capacity in all of the pores and the surface.
Les pores sont classés en trois catégories, en fonction de leurs tailles:The pores are classified into three categories, according to their sizes:
- les micropores ayant une taille comprise entre 0 à 2 nm,- micropores having a size between 0 to 2 nm,
- les mésop'ores ayant une taille comprise entre 2 à 50. nm .et- mesop ' ores having a size between 2 to 50. nm .et
- les macropores ayant une taille supérieure à 50nm
Le volume microporeux est généralement souhaité le plus important, bien que chacu ne des applications fasse appel à des charbons actifs dont les caractéristiques diffèrent.- macropores having a size greater than 50nm The microporous volume is generally desired to be the greatest, although each of the applications calls upon active carbon whose characteristics differ.
La séparation de mélanges gazeux et le traitement de l'air nécessitent des charbons actifs dont la taille de micropores est déterminée par le taille des molécules d u gaz à séparer. On recherche donc des charbons actifs à porosité la plus homogène possible et à volume microporeux élevé.The separation of gas mixtures and the treatment of air require active carbon, the size of micropores of which is determined by the size of the gas molecules to be separated. We are therefore looking for active carbon with the most homogeneous porosity possible and a high microporous volume.
Pour le stockage de gaz, on privilégiera les charbons actifs à fort volume microporeux, présentant des tailles de micropores élevées et un taux de mésopores faible puisque le gaz est stocké dans ces derniers en phase gazeuse.For the storage of gas, preference will be given to active carbon with a high microporous volume, having large micropore sizes and a low level of mesopores since the gas is stored in the latter in the gaseous phase.
Enfin pour la production de froid , il a été montré que l'amélioration des performances des machines passe par l'obtention de charbon actif dont la taille des micropores varie suivant la température de froid désirée. Le coefficient de performance de la machine dépend très fortement de l'homogénéité de la porosité et du volume microporeux qui doit être le plus élevé possible. En conclusion quel que soit le domaine d'application , le besoin de charbons actifs à porosité contrôlée et homogène et à forte capacité d'adsorption conditionne l'amélioration des procédés.Finally, for the production of cold, it has been shown that improving the performance of the machines requires obtaining activated carbon, the size of the micropores of which varies according to the desired cold temperature. The coefficient of performance of the machine very strongly depends on the homogeneity of the porosity and the microporous volume which must be as high as possible. In conclusion, whatever the field of application, the need for active carbon with controlled and homogeneous porosity and with high adsorption capacity conditions the improvement of the processes.
U ne étude des possibilités offertes par les fabricants montre que les besoins sont loin d'être couverts actuellement. A titre d'exemple des prod uits utilisés pour le stockage des gaz sont ceux pouvant être obtenus par le procédé décrit dans le brevet US- 4.082.694. Ce procédé comprend une étape de traitement d'u n prod uit carboné, tel que des résidus de charbon ou de pétrole, par de la potasse, suivie d'une activation du produit en résultant par chauffage jusqu'à une température comprise entre 704°C (1 300°F) et 982°C (1 800° F). Dans ce brevet, les résidus de charbon ou de pétrole ne sont pas traités , et contiennent donc une proportion très importante de résines de type α, définies comme étant insolubles dans le toluène et la quinoléine et constituées d'une fraction aromatique organisée.
DAGUERRE et al . (1997, Carbon'87, 23ème Conférence biennale sur le carbone, 156-1 57) décrivent la préparation de charbons actifs en utilisant des fractions définies d 'un brai de pétrole dénommé A240. Après un traitement thermique, le brai est fractionné à l'aide de toluène. Deux fractions dénommées EP 1 et EP2, définies par leur solubilité dans le toluène et dans la quinoléine sont particulièrement obtenues. Ces fractions sont ensuite préoxydées à 280°C puis carbonisées à 1000° C avant d'être activées dans un flux de gaz carbonique à 900°C . Le taux d'usure (burn-off) des charbons actifs ainsi obtenus est compris entre 10% et 60%. Les charbons issus des deux fractions EP 1 et EP2 avec des taux d'usure variables, sont caractérisés par la mesure de leu r volume de micropores et la dimension moyenne des pores. II ressort de cette revue succincte de l'état de la technique que les produits obtenus ne présentent pas de propriétés optimales pour les applications mentionnées ci-dessus.A study of the possibilities offered by the manufacturers shows that the needs are far from being covered at present. By way of example of the products used for the storage of gases are those obtainable by the process described in patent US-4,082,694. This process includes a step of treating a carbonaceous product, such as coal or petroleum residues, with potash, followed by activation of the resulting product by heating to a temperature between 704 °. C (1,300 ° F) and 982 ° C (1,800 ° F). In this patent, coal or petroleum residues are not treated, and therefore contain a very large proportion of α-type resins, defined as being insoluble in toluene and quinoline and consisting of an organized aromatic fraction. DAGUERRE et al. (1997, Carbon'87, 23rd Biennial Carbon Conference, 156-1 57) describe the preparation of active carbon using defined fractions of a petroleum pitch called A240. After a heat treatment, the pitch is fractionated using toluene. Two fractions called EP 1 and EP2, defined by their solubility in toluene and in quinoline are particularly obtained. These fractions are then preoxidized at 280 ° C and then carbonized at 1000 ° C before being activated in a flow of carbon dioxide at 900 ° C. The rate of wear (burn-off) of the activated carbon thus obtained is between 10% and 60%. The coals from the two fractions EP 1 and EP2 with variable wear rates are characterized by the measurement of their volume of micropores and the average size of the pores. It emerges from this brief review of the state of the art that the products obtained do not have optimal properties for the applications mentioned above.
Les inventeurs se sont donc attachés à trouver de nouveaux procédés de synthèse de charbons actifs, afin d'obtenir des produits présentant des propriétés particulières, dans ces applications.The inventors therefore set out to find new methods for synthesizing active carbon, in order to obtain products having particular properties, in these applications.
La présente invention a donc pour objet un procédé d'obtention de charbons actifs à partir d'une brai partiellement mésophasé et partiellement mésogéné contenant moins d'environ 40%, et preferentiellement moins de 30%, de résines de type α , plus d'environ 40% , et preferentiellement plus de 50%, de résines de type β et entre environ 5 et 30% de résines de type γ, comprenant l'activation d'un tel brai, éventuellement précédée par sa carbonisation. On entend pa r résines de type α les résines insolubles dans le toluène et dans la quinoléine, par résines de type β les résines insolubles dans lé toluène mais solubles dans la quinoléine et par résines de type γ les résines solubles dans le toluène et dans la quinoléine.
Pour la présente invention , les pourcentages (%) des différentes résines sont exprimés par rapport au poids total de l'ensemble des résines.The present invention therefore relates to a process for obtaining active charcoals from a partially mesophase and partially mesogenous pitch containing less than about 40%, and preferably less than 30%, of α-type resins, more approximately 40%, and preferably more than 50%, of β-type resins and between approximately 5 and 30% of γ-type resins, comprising the activation of such a pitch, possibly preceded by its charring. By α resins is meant resins insoluble in toluene and in quinoline, by resins of β type resins insoluble in toluene but soluble in quinoline and by resins of type γ resins soluble in toluene and in quinoline. For the present invention, the percentages (%) of the different resins are expressed relative to the total weight of all the resins.
La présente invention a plus particulièrement pour objet u n procédé d'obtention de charbons actifs à partir d'une brai partiellement mésophasé et partiellement mésogéné contenant moins d'environ 40%, et preferentiellement moins de 30%, de résines de type α, plus d'environ 40%, et preferentiellement plus de 50% , de résines de type β et entre environ 5 et 30% de résines de type γ comprenant les étapes suivantes:The present invention more particularly relates to a process for obtaining active carbon from a partially mesophase and partially mesogenous pitch containing less than about 40%, and preferably less than 30%, of α type resins, more d '' approximately 40%, and preferably more than 50%, of β-type resins and between approximately 5 and 30% of γ-type resins comprising the following steps:
- mise en suspension du brai dans une solution de potasse pour imprégnation, jusqu'à l'obtention d'un précurseur imprégné,- suspending the pitch in a potash solution for impregnation, until an impregnated precursor is obtained,
- déshydratation du précurseur imprégné,- dehydration of the impregnated precursor,
- chauffage d u précurseur imprégné à une température comprise entre environ 300°C et 1000°C,- heating of the impregnated precursor to a temperature between approximately 300 ° C and 1000 ° C,
- lavage et séchage du charbon actif résultant.- washing and drying the resulting activated carbon.
La présente invention est en outre relative à un procédé d'obtention de charbons actifs à partir d'une brai partiellement mésophasé et partiellement mésogéné contenant moins d'environ 40% , et preferentiellement moins de 30%, de résines de type α, plus d'environ 40%, et preferentiellement plus de 50%, de résines de type β et entre environ 5 et 30% de résines de type γ comprenant les étapes suivantes:The present invention further relates to a process for obtaining active carbon from a partially mesophase and partially mesogenous pitch containing less than about 40%, and preferably less than 30%, of α-type resins, more '' approximately 40%, and preferably more than 50%, of β-type resins and between approximately 5 and 30% of γ-type resins comprising the following steps:
- pré-oxydation d u brai à une température comprise entre 250 et 350°C ,- pre-oxidation of pitch at a temperature between 250 and 350 ° C,
- carbonisation en atmosphère inerte à une température comprise entre environ 800 et 1000°C ,- carbonization in an inert atmosphere at a temperature between about 800 and 1000 ° C,
- activation par un courant d' un gaz inerte, tel que de l'azote, saturé en vapeur d'eau, et - récupération d u charbon actif.- activation by a current of an inert gas, such as nitrogen, saturated with water vapor, and - recovery of active carbon.
Selon un mode de mise en œuvre préférentiel de ces procédés le brai partiellement mésophasé et partiellement mésogéné contient entre environ 1 0 et 35% de résines de type α, entre environ 50 et 70% de résines de type β et entre environ 1 0 et 25% de résines de type γ.
U n autre objet de la présente invention est un procédé d'obtention de charbons actifs à partir d'une brai partiellement mésophasé et partiellement mésogéné contenant environ 25 et 40%, et preferentiellement entre 30 et 35%, de résines de type α, entre environ 40 et 60% ,et preferentiellement entre 45 et 55% , de résines de type β et entre environ 1 5 et 30%, et preferentiellement entre 20 et 30% de résines de type γ comprenant les étapes suivantes:According to a preferred embodiment of these methods, the partially mesophase and partially mesogenous pitch contains between approximately 1 0 and 35% of α type resins, between approximately 50 and 70% of β type resins and between approximately 1 0 and 25 % of γ type resins. Another object of the present invention is a process for obtaining active carbon from a partially mesophase and partially mesogenous pitch containing approximately 25 and 40%, and preferably between 30 and 35%, of α-type resins, between approximately 40 and 60%, and preferably between 45 and 55%, of β-type resins and between approximately 15 and 30%, and preferably between 20 and 30% of γ-type resins comprising the following steps:
- oxydation du brai à une température comprise entre 200 et 400°C durant entre 10 min et 1 heure ,- pitch oxidation at a temperature between 200 and 400 ° C lasting between 10 min and 1 hour,
- carbonisation sous atmosphère inerte, jusqu'à atteindre une température comprise entre 800 et 1 000°C ,- carbonization under an inert atmosphere, until a temperature between 800 and 1000 ° C is reached,
- activation dans un courant de dioxyde de carbone à une température comprise entre environ 800 et 1000°C,et - récupération du charbon actif.- activation in a stream of carbon dioxide at a temperature between about 800 and 1000 ° C, and - recovery of the activated carbon.
Selon un mode de mise en œuvre particulier de ces procédés, le brai partiellement mésophasé et partiellement mésogéné est obtenu par extraction sélective, des résines de type γ non polymérisées dans le toluène, à partir d'un brai contenant de telles résines. Il s'agit alors d 'une fraction polyaromatique.According to a particular implementation of these methods, the partially mesophase and partially mesogenous pitch is obtained by selective extraction, γ-type resins not polymerized in toluene, from a pitch containing such resins. It is then a polyaromatic fraction.
Selon un autre mode de mise en œuvre de ces procédés le brai partiellement mésophasé et partiellement mésogéné est obtenu par distillation des résines γ non polymérisées, à partir d'u n brai contenant de telles résines. Selon encore un autre mode de mise en oeuvre de l'invention le brai partiellement mésophasé et partiellement mésogéné est obtenu par bullage d'air au sein d'un brai contenant des résines de type γ.According to another embodiment of these methods, the partially mesophase and partially mesogenated pitch is obtained by distillation of the unpolymerized γ resins, from a pitch containing such resins. According to yet another embodiment of the invention, the partially mesophase and partially mesogenated pitch is obtained by bubbling air within a pitch containing γ-type resins.
Les brais conduisant. à des brais partiellement mésophasé et partiellement mésogéné peuvent être des brais de pétrole, de houille, de pneus , de bois, de pyrolyse sous vide, ou encore de déchets divers. Ils peuvent être néanmoins tout autre brai, ou autre matière chimique ayant un potentiel aromatique, permettant l'obtention des charbons actifs répondant aux besoins exprimés ci- dessus.
La présente invention est en outre relative à un brai partiellement mésophasé et partiellement mésogéné contenant entre environ 25 et 40%, et preferentiellement entre 30 et 35%, de résines de type α, entre environ 40 et 60% ,et preferentiellement entre 45 et 55%, de résines de type β et entre environ 15 et 30%, et preferentiellement entre 20 et 30% de résines de type γ.The driving pitches. to partially mesophase and partially mesogenous pitch may be petroleum, coal, tire, wood, vacuum pyrolysis, or other waste. They may however be any other pitch, or other chemical material having an aromatic potential, allowing active carbon to be obtained which meets the needs expressed above. The present invention also relates to a partially mesophase and partially mesogenous pitch containing between approximately 25 and 40%, and preferably between 30 and 35%, of α-type resins, between approximately 40 and 60%, and preferentially between 45 and 55 %, of β-type resins and between approximately 15 and 30%, and preferably between 20 and 30% of γ-type resins.
Les procédés selon la présente invention permettent d'obtenir divers charbons actifs présentant des propriétés intéressantes dans les applications mentionnées ci-dessus. Un tel charbon actif peut être caractérisé en ce qu'au moinsThe methods according to the present invention make it possible to obtain various active carbons having advantageous properties in the applications mentioned above. Such activated carbon can be characterized in that at least
80% ,et preferentiellement 90% des micropores présentent, une taille comprise entre environ 0, 10 et 0,60 nm, preferentiellement . entre environ 0,25 et 0,55 nm.et un volume microporeux compris entre environ 0, 10 et 0,30 cm3/g,et preferentiellement entre 0, 15 et 0 ,25 cm3/g . Ce type de charbon actif présente un effet de porte.80%, and preferably 90% of the micropores have, a size between approximately 0, 10 and 0.60 nm, preferably. between approximately 0.25 and 0.55 nm. and a microporous volume of between approximately 0.10 and 0.30 cm 3 / g, and preferably between 0.15 and 0.25 cm 3 / g. This type of activated carbon has a door effect.
Un autre charbon actif selon la présente invention est caractérisé en ce qu'au moins 80% ,et preferentiellement 90%, des micropores présentent une taille comprise entre environ 0 ,4 et 0,8 nm , preferentiellement entre environ 0, 55 et 0,65 nm , et un volume microporeux compris entre environ 0, 10 et 0, 30 cm3/g ,et preferentiellement entre 0, 1 5 et 0,25 cm3/g.Another activated carbon according to the present invention is characterized in that at least 80%, and preferably 90%, of the micropores have a size of between approximately 0.4 and 0.8 nm, preferably between approximately 0.55 and 0, 65 nm, and a microporous volume of between approximately 0.10 and 0.30 cm 3 / g, and preferably between 0.15 and 0.25 cm 3 / g.
Encore un autre charbon actif est celui caractérisé en ce qu'au moi ns 80%, et preferentiellement 90% des micropores présentent u ne taille comprise entre environ 0, 5 et 0,9 nm et un vol ume microporeux compris entre environ 0,4 et 0,6 cm3/g .Yet another activated carbon is that characterized in that at least 80%, and preferably 90% of the micropores have a size of between about 0.5 and 0.9 nm and a microporous volume of between about 0.4 and 0.6 cm 3 / g.
Ces trois charbons peuvent être utilisés comme tamis moléculaire , et de manière générale dans des opérations de filtration ou de séparation .These three coals can be used as molecular sieves, and generally in filtration or separation operations.
Aussi d'autres objets de la présente invention sont des membranes de filtration et des colonnes de séparation contenant de tels charbons ou des charbons obtenus par l'u n des procédés selon la présente invention .Also other objects of the present invention are filtration membranes and separation columns containing such coals or coals obtained by one of the methods according to the present invention.
U n a utre charbon actif selon l'invention est celui caractérisé en ce qu'au moins 80% ,et preferentiellement 90 %, des micropores présentent une taille comprise entre environ 0 ,5 et 3 nm ,
preferentiellement entre environ 0, 7 et 2,7 nm, et un volume microporeux supérieur à environ 0, 8 cm3/g ,et preferentiellement supérieur à environ 1 ,2 cm3/g . I l peut être utilisé pour le stockage de gaz. La présente invention est encore relative à un élément de stockage de gaz ou un élément de production de froid , en particulier par sorption solide/gaz, contenant au moins un charbon actif de ce type, ou obtenu par un procédé selon la présente invention . L'un quelconque des charbons actifs selon l'invention peut être inclus en tant que constituant de matériaux protecteurs vis-à- vis de gaz contenant des substances radioactives, bactériologiques - ou chimiques délétères , tels que les matériaux utilisés pour la fabrication de tenues de protection dites « NBC «(protection N ucléaire, Bactériologique et Chimique), en particulier dans les mousses imprégnées pour tenues N BC. Selon le type de charbon actif selon l'invention choisi, on obtiendra soit une adsorption par affinité sélective du charbon actif vis-à-vis d'un gaz ou d'une molécule déterminée, soit une grande capacité d'adsorption de d ivers composés.U na urter activated carbon according to the invention is that characterized in that at least 80%, and preferably 90%, of the micropores have a size of between approximately 0.5 and 3 nm, preferably between approximately 0.7 and 2.7 nm, and a microporous volume greater than approximately 0.8 cm 3 / g, and preferably greater than approximately 1.2 cm 3 / g. It can be used for gas storage. The present invention also relates to a gas storage element or a cold production element, in particular by solid / gas sorption, containing at least one activated carbon of this type, or obtained by a process according to the present invention. Any of the active carbons according to the invention may be included as a constituent of protective materials with respect to gases containing radioactive, bacteriological - or deleterious chemical substances, such as the materials used for the manufacture of protective clothing. “NBC” protection (Nuclear, Bacteriological and Chemical protection), in particular in impregnated foams for N BC outfits. According to the type of activated carbon according to the invention chosen, one will obtain either an adsorption by selective affinity of the activated carbon with respect to a gas or a determined molecule, or a great capacity of adsorption of various compounds .
Selon un mode de réalisation particulier, ces différentes fonctions pourraient être combinées en incorporant à ces matériaux de protection au moins deux des charbons actifs selon l'invention. L'invention concerne, aussi u n matériau protecteur vis-à-vis de gaz contenant des substances radioactives, bactériologiq ues ou chimiques comprenant au moins un charbon actif selon l'invention.According to a particular embodiment, these different functions could be combined by incorporating into these protective materials at least two of the active carbons according to the invention. The invention also relates to a protective material with respect to gases containing radioactive, bacteriological or chemical substances comprising at least one activated carbon according to the invention.
La présente invention est illustrée, sans pou r autant être limitée par les exemples qui suivent.The present invention is illustrated, without being able to be limited by the following examples.
La figure 1 résume schématiquement les étapes du procédé de préparation de charbons actifs par activation par de la vapeur d'eau.Figure 1 schematically summarizes the steps of the process for preparing active carbon by activation with water vapor.
La fig ure 2 illustre la porosité d'un charbon actif obtenu par activation par de la vapeur d'eau.
La figure 3 résume schématiquement les étapes du procédé de préparation de charbons actifs par activation par d u dioxyde de carbone.Fig ure 2 illustrates the porosity of an activated carbon obtained by activation by steam. FIG. 3 schematically summarizes the steps of the process for the preparation of active carbon by activation with carbon dioxide.
La figure 4 illustre la porosité d'un charbon actif obtenu par activation par du dioxyde de carbone.Figure 4 illustrates the porosity of an activated carbon obtained by activation with carbon dioxide.
La figure 5 résume schématiquement les étapes du procédé de préparation de charbons actifs par activation par de la potasse.FIG. 5 schematically summarizes the steps of the process for preparing active carbon by activation with potash.
La figure 6 illustre la porosité d'un charbon actif obtenu par activation par de la potasse pour u n taux d'imprégnation de 1 /1 présentant une taille de pore de 0,7 nm et u n volume microporeux de 0.5 cm3/g.FIG. 6 illustrates the porosity of an activated carbon obtained by activation with potassium hydroxide for an impregnation rate of 1/1 having a pore size of 0.7 nm and a microporous volume of 0.5 cm 3 / g.
EXEMPLE 1EXAMPLE 1
Production de charbons actifs par activation par de la vapeur d 'eauActivated carbon production by activation with steam
(1 ) Préparation d'un brai mature adapté à la production de charbons actifs(1) Preparation of a mature pitch suitable for the production of active carbon
Le précurseu r utilisé ici est un brai de houille non traité de composition α 1 1 % β 16% γ 73% et un point de ramollissement deThe precursor used here is an untreated coal pitch of composition α 1 1% β 16% γ 73% and a softening point of
1 10°C et une densité de 1 ,308 g/cm3. 500 grammes de brai sont placés dans un réacteur Pyrex de 1 litre et chauffés sous atmosphère inerte (0, 5 I/min) à 2°C/min jusqu'à une température de1 10 ° C and a density of 1.308 g / cm 3 . 500 grams of pitch are placed in a 1 liter Pyrex reactor and heated under an inert atmosphere (0.5 I / min) at 2 ° C / min to a temperature of
400°C. Après 5 heures de maturation à cette température, le brai est refroidi à température ambiante. U ne agitation cisaillante400 ° C. After 5 hours of maturation at this temperature, the pitch is cooled to room temperature. Shear agitation
(turbine rushton 4 pales avec 4 contre-pales) est maintenue à une vitesse de 500 tours/min du rant toute la période de fluidité du brai.(4-blade rushton turbine with 4 counter-blades) is maintained at a speed of 500 rpm of the rant throughout the period of fluidity of the pitch.
Un brai mature est - ainsi obtenu et présente une densité supérieure au brai de départ ( 1 ,33 g/cm3) consécutive à une perte de masse durant le traitement thermique de 5% en masse.A mature pitch is - thus obtained and has a density greater than the starting pitch (1.33 g / cm 3 ) following a loss of mass during the heat treatment of 5% by mass.
L'évolution de la composition due aux réactions chimiques de polymérisation cond uit à u ne composition 1 5% β26% γ59% . Le rendement massique global de cette opération est d e 95% .
(2) Concentration pa r extraction de la fraction polyaromatiq ueThe evolution of the composition due to the chemical polymerization reactions leads to a composition 1 5% β26% γ59%. The overall mass yield of this operation is 95%. (2) Concentration by extraction of the polyaromatic fraction
La fraction aromatique est alors isolée par extraction sélective des résines γ non-polymérisées dans le toluène . 1 00 g rammes de brai mature broyé et tamisé en particules de taille inférieure à 200 μm sont mélangés à 20 litres de toluène, puis filtrés sous vide. Après rinçage à l'alcool, le résidu d'extraction est séché sous vide. Toutes les opérations d'extraction, filtration et séchage sont réalisées à température ambiante. Le résidu d'extraction obtenu présente alors une composition α32% β52% γ1 6%. Le rendement global de cette opération est de 25%.The aromatic fraction is then isolated by selective extraction of the non-polymerized γ resins in toluene. 1 00 g rammes of mature pitch, ground and sieved into particles of size less than 200 μm, are mixed with 20 liters of toluene, then filtered under vacuum. After rinsing with alcohol, the extraction residue is dried under vacuum. All extraction, filtration and drying operations are carried out at room temperature. The extraction residue obtained then has a composition α32% β52% γ1 6%. The overall yield from this operation is 25%.
(3) Préoxydation et carbonisation(3) Preoxidation and carbonization
Le résidu d'extraction ainsi obtenu est ensuite chauffé dans un four tubulaire à 2°C/min sous air (0,5 l/min) j usqu'à une température de 280°C et laissé à cette température durant 30 minutes afin de favoriser les réactions d'oxydation contribuant à la réticulation des molécules polyaromatiques et à l'obtention d'u n matériau infusible. Le matériau infusible ainsi obtenu est alors carbonisé sous azote (0, 5 l/min) à 2°C/min jusqu'à une température de 900°C. La perte de masse lors des étapes de stabilisation et de carbonisation est de 20%.The extraction residue thus obtained is then heated in a tubular oven at 2 ° C / min in air (0.5 l / min) until a temperature of 280 ° C and left at this temperature for 30 minutes in order to favor oxidation reactions contributing to the crosslinking of polyaromatic molecules and obtaining an infusible material. The infusible material thus obtained is then carbonized under nitrogen (0.5 l / min) at 2 ° C / min up to a temperature of 900 ° C. The mass loss during the stabilization and carbonization stages is 20%.
(4) Préparation d u charbon actif par activation(4) Preparation of activated carbon by activation
L'ouverture et le développement de micropores dans le carbonisât obtenu par les opérations (1 ), (2) et (3) sont réalisés d ans un four tubulaire à 800°C à l'aide d'un courant gazeux d'azote (0, 1 l/min) saturé en vapeur d'eau pa r bullage dans un bain d'eau distillée thermostatée à 63°C durant une période variant de 3 à 12 heures permettant l'obtention de charbons actifs dans la gamme de taux d'usure de 30% à 60%. La figure 1 représente les étapes de ce procédé..
Les matériaux obtenus présentent des volumes adsorbables Wo allant de 0,25 cm3/g à 0, 60 cm3/g correspondant respectivement à des tailles de micropores de 0,60 nm à 1 , 50 nm . Ainsi pour une d urée d'activation de 2 heures on obtient un taux d'usure de 1 3%. Le charbon actif présente une taille de pores distrib uée de manière homogène autour de 0,6 nm , comme l'illustre la figure 2 et un volume microporeux de 0,2 cm3/g . U n tel charbon actif peut être utilisé comme tamis moléculaire.The opening and development of micropores in the carbonisate obtained by operations (1), (2) and (3) are carried out in a tubular furnace at 800 ° C. using a nitrogen gas stream ( 0.1 l / min) saturated with water vapor by bubbling in a distilled water bath thermostatically controlled at 63 ° C for a period varying from 3 to 12 hours allowing active carbon to be obtained in the rate range d '' wear from 30% to 60%. Figure 1 shows the steps of this process. The materials obtained have adsorbable volumes Wo ranging from 0.25 cm 3 / g to 0.60 cm 3 / g corresponding respectively to micropore sizes from 0.60 nm to 1.50 nm. Thus, for an activation period of 2 hours, a wear rate of 1 3% is obtained. The activated carbon has a homogeneously distributed pore size around 0.6 nm, as illustrated in FIG. 2 and a microporous volume of 0.2 cm 3 / g. Such activated carbon can be used as a molecular sieve.
L'obtention de charbons actifs fortement activés (80% de taux d'usure) cond uit à des charbons actifs de volumes microporeux supérieu rs à 0,8 cm3/g et de taille de pores de l'ordre de 2 à 3 nm .Obtaining highly activated active carbon (80% wear rate) leads to active carbon with microporous volumes greater than 0.8 cm 3 / g and pore size of the order of 2 to 3 nm .
EXEMPLE 2EXAMPLE 2
Production d e charbons actifs par activation par d u dioxyde de carboneActivated carbon production by activation with carbon dioxide
La procéd ure présentée dans l'exemple 1 a été répétée à l'exception de la procédure d'activation qui est réalisée à 900°C sous courant de dioxyde de carbone (0, 5 l/min) durant une période permettant l'obtention de taux d'usure inférieur à 1 5% en masse.The procedure presented in Example 1 was repeated with the exception of the activation procedure which is carried out at 900 ° C. under a stream of carbon dioxide (0.5 l / min) during a period allowing the obtaining with a wear rate of less than 1 5% by mass.
La figure 3 résume schématiq uement ce procédé.Figure 3 summarizes schematically this process.
Le charbon actif ainsi obtenu possède un volume microporeux de 0 ,20 cm3/g et une porosité essentiellement composée de micropores de taille comprise entre 0, 3 nm et 0, 5 nm . Ce type de microporosité dite à effet-de-porte confère à ce charbon actif une très forte sélectivité vis-à-vis de divers adsorbats.The activated carbon thus obtained has a microporous volume of 0.20 cm 3 / g and a porosity essentially composed of micropores of size between 0.3 nm and 0.5 nm. This type of door-effect microporosity gives this activated carbon a very high selectivity with respect to various adsorbates.
La mise en évidence d' une telle propriété est réalisée par la technique de calorimétrie d'immersion dans divers liquides organiques de dimension moléculaire comprise entre 0,33 et 1 , 5 nm .The demonstration of such a property is carried out by the technique of calorimetry of immersion in various organic liquids of molecular size between 0.33 and 1.5 nm.
La d istribution de la taille des pores est illustrée par la figure 4.
EXEMPLE 3The pore size distribution is illustrated in Figure 4. EXAMPLE 3
Production de charbons actifs de porosité homogène, à faible taille de pores et forte capacité d'adsorption par traitement par de la potasseProduction of active carbon with homogeneous porosity, small pore size and high adsorption capacity by treatment with potash
Les procédures (1 ) et (2) de préparation d'un précurseur ex- brai concentré en molécules polyaromatiques présentées dans l'exemple 1 ont été répétées et le précurseur obtenu est mis en suspension dans une solution normale de potasse. Ce mélange s'effectue en présence d'un agent tensio-actif afin de faciliter la mise en suspension des particules de brai qui sont à l'origine hyd rophobes. Ce mélange est déshydraté sous agitation d u rant 2 à 3 heures et le brai imprégné obtenu est chauffé à 800°C sous flux d'azote (0, 5 l/min) avec une vitesse de chauffe de 10°C/min dans une cellule en nickel. Après deux heures de traitement à cette température, le charbon actif obtenu est refroidi et mis en suspension dans l'eau en évitant tout contact avec l'air ambiant (une mise à l'air provoque une combustion spontanée du réactif). Le charbon actif est alors, filtré et rincé à l'eau jusqu'à obtention d'un filtrat de pH neutre.The procedures (1) and (2) for the preparation of a precursor exhumed concentrated in polyaromatic molecules presented in example 1 were repeated and the precursor obtained is suspended in a normal potash solution. This mixture is carried out in the presence of a surfactant in order to facilitate the suspension of the pitch particles which are originally hydrophobic. This mixture is dehydrated with stirring of the rant for 2 to 3 hours and the impregnated pitch obtained is heated to 800 ° C. under a flow of nitrogen (0.5 l / min) with a heating rate of 10 ° C./min in a cell. nickel. After two hours of treatment at this temperature, the activated carbon obtained is cooled and suspended in water, avoiding any contact with ambient air (venting causes spontaneous combustion of the reagent). The activated carbon is then filtered and rinsed with water until a filtrate of neutral pH is obtained.
La figure 5 résume les étapes de ce procédé. Un tel charbon actif imprégné dans des conditions respectant u ne proportion massique de 1 : 1 entre le précurseur ex-brai et la potasse, cond uit après une perte de masse de 15% , à un charbon actif dont la microporosité est centrée sur 0,6 nm, comme l'illustre la figure 6, et de volume microporeux Wo=0, 5 cm3/g. Il convient de remarquer la forte capacité d'adsorption qui est environ le double de celle des charbons actifs de structure microporeuse semblable.Figure 5 summarizes the steps in this process. Such an activated carbon impregnated under conditions respecting a mass ratio of 1: 1 between the precursor ex-pitch and the potash, conduced after a mass loss of 15%, to an activated carbon whose microporosity is centered on 0, 6 nm, as illustrated in FIG. 6, and of microporous volume Wo = 0.5 cm 3 / g. It should be noted that the high adsorption capacity is approximately twice that of activated carbon with a similar microporous structure.
L'augmentation des proportions massiques d'imprég nation jusqu'à des taux d'imprégnation de potasse de 1 :4 ou plus, permet d 'obtenir des charbons actifs dont le volume microporeux est s upérieur à 1 ,3 cm3/g et des tailles de pores voisines de 2 nm.
EXEMPLE 4The increase in the mass proportions of impregnation up to potash impregnation rates of 1: 4 or more makes it possible to obtain active charcoals whose microporous volume is greater than 1.3 cm 3 / g and pore sizes close to 2 nm. EXAMPLE 4
Prod u ction de cha rbon actif à partir d'un brai d istillé traité par de la potasseProd u ction of active carbon from a distilled pitch treated with potash
U n brai de houille de composition initiale γ=84,5% , β = 1 3 , 5 % et α= 1 , 9% (insolubles à la quinoléine primaires) , a été soumis dans un premier temps à un traitement thermique (2°C/min) sous atmosphère inerte (flux d'azote 0, 5 l/min) à 470°C sans plateau de maturation . Ce traitement permet d'augmenter le taux initial de résines β sans pour autant développer trop de résines α. Le brai obtenu contient à ce stade du procédé 4% de résines α, 23,7% de résines β et 72 ,3% de résines γ.A pitch of coal of initial composition γ = 84.5%, β = 13.5% and α = 1.9% (insoluble in primary quinoline), was first subjected to a heat treatment (2 ° C / min) under an inert atmosphere (nitrogen flow 0.5 l / min) at 470 ° C without a maturation stage. This treatment increases the initial rate of β resins without developing too many α resins. The pitch obtained contains at this stage of the process 4% of α resins, 23.7% of β resins and 72.3% of γ resins.
Ce traitement thermique est, du point de vue de la modification de la composition du brai, équivalent au traitement de l'exemple 1 (400°C 5 heures), il existe ainsi une possibilité de choix entre un procédé de traitement thermique avec plateau ou un procédé avec rampe thermique seule.This heat treatment is, from the point of view of the modification of the pitch composition, equivalent to the treatment of Example 1 (400 ° C. 5 hours), there is thus a possibility of choice between a heat treatment process with tray or a process with a thermal ramp alone.
Le brai modifié est ensuite distillé sous pression réduite dans le but d'éliminer les résines γ, 125 grammes de brai modifié sont introduits dans un réacteur de 500 millilitres et chauffés jusqu'à 380°C à une vitesse de 10°C/min . Après obtention d'un brai parfaitement fluide (vers 180°C dans notre cas), un vide dynamique (1 0 mmHg) assu ré par une trompe à vide est créé dans le réacteur. Les matières volatiles sont entraînées vers un condenseur par le biais d'une cond uite thermostatée à 250°C. Durant toute la d istillation , le brai est soumis à une agitation (mobile pompant à 4 pales inclinées, 300 tours/min) afin d'homogénéiser sa composition . On obtient un brai mésogénique de composition α= 14% β=62% γ=24% et de densité d = 1 ,344cm3/g . Le rendement global des étapes de traitement thermique et de distillation est alors de 60%.The modified pitch is then distilled under reduced pressure in order to remove the γ resins, 125 grams of modified pitch are introduced into a 500 milliliter reactor and heated to 380 ° C at a speed of 10 ° C / min. After obtaining a perfectly fluid pitch (around 180 ° C in our case), a dynamic vacuum (10 mmHg) ensured by a vacuum pump is created in the reactor. The volatile matter is entrained towards a condenser by means of a conduit thermostated at 250 ° C. During the whole distillation, the pitch is subjected to agitation (mobile pumping with 4 inclined blades, 300 revolutions / min) in order to homogenize its composition. We obtain a mesogenic pitch of composition α = 14% β = 62% γ = 24% and density d = 1.344 cm 3 / g. The overall yield of the heat treatment and distillation steps is then 60%.
L'activation de ce brai par la procédure présentée dans l'exemple 3 , conduit à l'obtention de charbons actifs identiques aux matériaux obtenus par activation d'un brai extrait. Leurs propriétés sont présentées dans le tableau ci-après.
EXEMPLE 5The activation of this pitch by the procedure presented in Example 3, leads to the production of active carbon identical to the materials obtained by activation of an extracted pitch. Their properties are presented in the table below. EXAMPLE 5
Prod uction de charbon actif à partir d'un brai oxydé par bul lage traité pa r de la potasseProd uction of activated carbon from an oxidized pitch by bubbling treated by potash
500 grammes de brai , identique à celui de l'exemple 4, ont été broyés et introduits dans un réacteur de 1 litre en inox. Le brai est chauffé à 300°C à une vitesse de chauffe de 2°C/min et mature à cette température pendant une durée de 5 heures. Le bullage d'air (0 , 5 l/min) au sein du brai est assuré par un bulleur en inox fritte soudé à la base du réacteur tandis qu'une agitation mécanique, assurée par une turbine rushton à 4 pales associées à un ensemble de 4 contre-pales , garantit une répartition homogène du gaz réactif au sein du brai. Enfin, un thermocouple immergé, relié à un régulateur, permet de contrôler la température de maturation à + 1 °C.500 grams of pitch, identical to that of Example 4, were ground and introduced into a 1 liter stainless steel reactor. The pitch is heated to 300 ° C at a heating rate of 2 ° C / min and mature at this temperature for a period of 5 hours. Air bubbling (0.5 l / min) within the pitch is ensured by a sintered stainless steel bubbler welded to the base of the reactor while mechanical agitation is ensured by a 4-blade rushton turbine associated with an assembly. of 4 counter-blades, guarantees a homogeneous distribution of the reactive gas within the pitch. Finally, an immersed thermocouple, connected to a regulator, allows the maturation temperature to be controlled at + 1 ° C.
L'agitation du brai et le bullage réactif débutent dès l'obtention d'un brai parfaitement liquéfié, c'est-à-dire à partir de 180°C . Après maturation , l'agitation et le bullage sont arrêtés et le brai est refroid i jusq u'à température ambiante sous une atmosphère inerte. Le brai est ensuite broyé. Sa composition en résines est de 23, 1 % de résines α, 59,0% de résines β et 17,9% de résines γ. Sa densité est de 1 , 32 cm3/g . Elle est par comparaison plus faible que celle des produits présentés dans les exemples 1 et 4 obtenus par des traitements thermiques à plus haute température. Le rendement global est 75%.The stirring of the pitch and the reactive bubbling begin as soon as a perfectly liquefied pitch is obtained, that is to say from 180 ° C. After maturation, stirring and bubbling are stopped and the pitch is cooled to room temperature under an inert atmosphere. The pitch is then ground. Its resin composition is 23.1% of α resins, 59.0% of β resins and 17.9% of γ resins. Its density is 1.32 cm 3 / g. It is by comparison lower than that of the products presented in Examples 1 and 4 obtained by heat treatments at higher temperature. The overall yield is 75%.
L'activation de ce brai par la procédure présentée dans l'exemple 3 conduit à l'obtention de charbons actifs identiques à ceux obtenus par activation d'un brai extrait.The activation of this pitch by the procedure presented in Example 3 leads to the production of active carbons identical to those obtained by activation of an extracted pitch.
Leurs propriétés sont présentées dans le tableau ci-après.
Tablea u : Caractéristiques des charbons actifs des exemples 4 et 5Their properties are presented in the table below. Table u: Characteristics of the active carbon of Examples 4 and 5
Wo: Volume microporeux en cm /g Lo: Taille moyenne des pores en nm
Wo: Microporous volume in cm / g Lo: Average pore size in nm
Claims
1 . Procédé d'obtention de charbons actifs à partir d'un brai partiellement mésophasé et partiellement mésogéné contenant moins d'environ 40% de résines de type α, plus d'environ 40% de résines de type β et entre environ 5 et 30% de résines de type γ par activation d udit brai éventuellement précédée par sa carbonisation .1. Process for obtaining active carbon from a partially mesophase and partially mesogenous pitch containing less than approximately 40% of α-type resins, more than 40% of β-type resins and between approximately 5 and 30% of γ type resins by activation of said pitch possibly preceded by its carbonization.
2. Procédé selon la revendication 1 comprenant les étapes suivantes: - mise en suspension du brai partiellement mésophasé et partiellement mésogéné dans une solution de potasse pour imprégnation jusqu'à l'obtention d'un précurseur imprégné,2. Method according to claim 1 comprising the following steps: - suspending the partially mesophase and partially mesogenated pitch in a potassium hydroxide solution for impregnation until an impregnated precursor is obtained,
- déshydratation du précurseur imprégné,- dehydration of the impregnated precursor,
- chauffage du précurseur imprégné à une température comprise entre environ 300°C et 1000°C, etheating the impregnated precursor to a temperature between approximately 300 ° C. and 1000 ° C., and
- lavage et séchage d u charbon actif résultant.- washing and drying of the resulting activated carbon.
3. Procédé selon la revendication 1 comprenant les étapes suivantes: pré-oxydation du brai partiellement mésophasé et partiellement mésogéné à une température comprise entre 250 et 350°C ,3. Method according to claim 1 comprising the following steps: pre-oxidation of partially mesophase and partially mesogenated pitch at a temperature between 250 and 350 ° C,
- carbonisation en atmosphère inerte à une température comprise entre environ 800 et 1000°C ,- carbonization in an inert atmosphere at a temperature between about 800 and 1000 ° C,
- activation par un courant d'un gaz inerte saturé en vapeur d'eau, et- activation by a current of an inert gas saturated with water vapor, and
- récupération du charbon actif .- recovery of activated carbon.
4. Procédé selon l'une des revendications 1 à 3 caractérisé en ce que le brai partiellement mésophasé et partiellement mésogéné contient entre environ 10 et 35% de résines de type α, entre environ 50 et 70% de résines de type β et entre environ 1 0 et 25% de résines de type γ.4. Method according to one of claims 1 to 3 characterized in that the partially mesophase and partially mesogenous pitch contains between approximately 10 and 35% of α-type resins, between approximately 50 and 70% of β-type resins and between approximately 1 0 and 25% of γ type resins.
5. Procédé d'obtention de charbons actifs selon la revendication 1 caractérisé en ce que le brai partiellement mésophasé et partiellement mésogéné contient environ 25 et 40% de résines de type α, entre environ 40 et 60% de résines de type β et entre environ 15 et 30% de résines de type γ et en ce qu'il comprend les étapes suivantes:5. Method for obtaining active carbon according to claim 1 characterized in that the partially mesophase and partially mesogenous pitch contains about 25 and 40% of α type resins, between about 40 and 60% of type resins β and between approximately 15 and 30% of γ type resins and in that it comprises the following stages:
- oxydation d u brai à une température comp rise entre 200 et 400°C durant entre 1 0 min et 1 heure , - carbonisation sous atmosphère inerte, jusqu'à atteindre une températu re comprise entre 800 et 1000°C- oxidation of the pitch at a temperature between 200 and 400 ° C lasting between 1 0 min and 1 hour, - carbonization under an inert atmosphere, until a temperature between 800 and 1000 ° C is reached
- activation dans un courant de d ioxyde de carbone à une température comprise entre environ 800 et 1000°C,etactivation in a stream of carbon dioxide at a temperature between approximately 800 and 1000 ° C., and
- récupération du charbon actif. - recovery of activated carbon.
6. Procédé selon l'une des revendications 1 à 5 caractérisé en ce que le brai partiellement mésophasé et partiellement mésogéné est obtenu par extraction sélective, des résines de type , γ non polymérisées dans le toluène, à partir d'un brai contenant de telles résines. 6. Method according to one of claims 1 to 5 characterized in that the partially mesophase and partially mesogenous pitch is obtained by selective extraction, resins of type, γ not polymerized in toluene, from a pitch containing such resins.
7. Procédé selon l'une des revendications 1 à 5 caractérisé en ce que le brai partiellement mésophasé et partiellement mésogéné est obtenu par distillation des résines γ non polymérisées, à partir d'un brai contenant de telles résines.7. Method according to one of claims 1 to 5 characterized in that the partially mesophase and partially mesogenated pitch is obtained by distillation of the unpolymerized γ resins, from a pitch containing such resins.
8. Procédé selon l'une des revendications 1 à 5 caractérisé en ce que le brai partiellement mésophasé et partiellement mésogéné est obtenu par bullage d'air au sein d'un brai contenant des résines γ non polymérisées.8. Method according to one of claims 1 to 5 characterized in that the partially mesophase and partially mesogenous pitch is obtained by bubbling air within a pitch containing unpolymerized γ resins.
9 Procédé selon l'une des revendications 1 à 8 caractérisé en ce que le brai est un brai de houille. 9 Method according to one of claims 1 to 8 characterized in that the pitch is a coal pitch.
1 0. Brai partiellement mésophasé et partiellement mésogéné caractérisé en ce qu'il contient entre environ 25 et 40% de résines de type α, entre environ 40 et 60% de résines de type β et entre environ 15 et 30% de résines de type γ.1 0. Partially mesophase and partially mesogenous pitch characterized in that it contains between approximately 25 and 40% of α type resins, between approximately 40 and 60% of β type resins and between approximately 15 and 30% of type resins γ.
1 1 . Charbon actif caractérisé en ce qu'au moins 80% des micropores présentent une' taille comprise entre environ 0, 10 et1 1. Activated carbon wherein at least 80% of the micropores have a 'size of between about 0, 10 and
0,60 nm et un volume microporeux compris entre environ 0, 1 0 et 0,30 cm3/g .0.60 nm and a microporous volume of between approximately 0.10 and 0.30 cm 3 / g.
12. Charbon actif caractérisé en ce qu'au moins 80% des micropores présentent une taille comprise entre environ 0 ,4 et 0 , 8 nm et u n volume microporeux compris entre environ 0, 10 et 0, 30 cm3/g .12. Activated carbon characterized in that at least 80% of the micropores have a size of between approximately 0.4 and 0.8 nm and a microporous volume of between approximately 0.10 and 0.30 cm 3 / g.
13. Charbon actif caractérisé en ce qu'au moins 80% des micropores présentent une taille comprise entre environ 0, 5 et 0, 9 nm et un volume microporeux compris entre environ 0,4 et 0,6 cm3/g.13. Activated carbon characterized in that at least 80% of the micropores have a size of between approximately 0.5 and 0.9 nm and a microporous volume of between approximately 0.4 and 0.6 cm 3 / g.
14. Charbon actif caractérisé en ce qu'au moins 80% des micropores présentent une taille comprise entre environ 0,5 et 3 nm et un volume microporeux supérieur à environ 0, 8 cm3/g . 14. Activated carbon, characterized in that at least 80% of the micropores have a size of between approximately 0.5 and 3 nm and a microporous volume greater than approximately 0.8 cm 3 / g.
15. Membrane de filtration caractérisée en ce que elle comprend du charbon actif selon l'une des revendications 1 1 , 12 et15. filtration membrane characterized in that it comprises activated carbon according to one of claims 1 1, 12 and
1 3.1 3.
16. Colonne de séparation caractérisée en ce qu'elle contient d u charbon actif selon l'une des revendications 1 1 , 12 et 1 3. 16. Separation column characterized in that it contains active carbon according to one of claims 1 1, 12 and 1 3.
17. Elément de stockage de gaz caractérisé en ce qu'il contient du charbon actif selon la revendication 14.17. A gas storage element characterized in that it contains activated carbon according to claim 14.
1 8. Equipement de production de froid caractérisé en ce qu'il contient du charbon actif selon la revendication 14.1 8. Equipment for producing cold, characterized in that it contains activated carbon according to claim 14.
19. Matériau protecteur vis-à-vis de gaz contenant des substances radioactives, bactériologiques ou chimiques, ledit matériau protecteur comprenant au moins un charbon actif selon l'une des revendications 1 1 à 14. 19. Protective material vis-à-vis gases containing radioactive, bacteriological or chemical substances, said protective material comprising at least one activated carbon according to one of claims 1 1 to 14.
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FR9914607A FR2801297B1 (en) | 1999-11-19 | 1999-11-19 | ACTIVE CARBONS AND THEIR PROCESS FOR OBTAINING A PARTIALLY MESOPHASE AND PARTIALLY MESOGENIC PIT |
PCT/FR2000/003204 WO2001036326A1 (en) | 1999-11-19 | 2000-11-17 | Activated carbons and method for obtaining same from a partly mesophase and partly mesogenic pitch |
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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 |
CN110028067B (en) * | 2019-04-19 | 2021-05-28 | 广东煤基碳材料研究有限公司 | Super-capacitor activated carbon and preparation method thereof |
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GB1298938A (en) * | 1968-12-24 | 1972-12-06 | Lancashire Tar Distillers Ltd | Active carbon |
GB1444732A (en) * | 1973-09-04 | 1976-08-04 | Shell Int Research | Production of active carbon |
FR2467177A1 (en) * | 1979-10-09 | 1981-04-17 | British Petroleum Co | Active carbon prodn. - using petroleum pitch |
US4431623A (en) * | 1981-06-09 | 1984-02-14 | The British Petroleum Company P.L.C. | Process for the production of carbon fibres from petroleum pitch |
EP0087749B1 (en) * | 1982-02-23 | 1986-05-07 | Mitsubishi Oil Company, Limited | Pitch as a raw material for making carbon fibers and process for producing the same |
JPS58145782A (en) * | 1982-02-23 | 1983-08-30 | Mitsubishi Oil Co Ltd | Preparation of pitch |
JPS5982417A (en) * | 1982-11-04 | 1984-05-12 | Mitsubishi Oil Co Ltd | Pitch for raw material of carbon fiber and its preparation |
US4518482A (en) * | 1982-07-19 | 1985-05-21 | E. I. Du Pont De Nemours And Company | Pitch for direct spinning into carbon fibers derived from a coal distillate feedstock |
US4806227A (en) * | 1984-04-06 | 1989-02-21 | The Dow Chemical Company | Carbon black inhibition of pitch polymerization |
JPH0280315A (en) * | 1988-09-17 | 1990-03-20 | Osaka Gas Co Ltd | Granulated active carbon |
DE3938581A1 (en) * | 1989-11-21 | 1991-05-23 | Ruiter Ernest De | Air supply for gas-mask from protective suit - interior also incorporating aerosol protection |
DE69231789T2 (en) * | 1991-06-19 | 2001-09-20 | Morinobu Endo | Pitch-based activated carbon fiber |
JPH05209322A (en) * | 1991-06-19 | 1993-08-20 | Morinobu Endo | Pitch-based active carbon yarn |
DE4310110A1 (en) * | 1992-07-07 | 1994-01-13 | Kaercher Gmbh & Co Alfred | Multi-layer, textile, gas-permeable filter material against chemical pollutants |
JP2735491B2 (en) * | 1993-10-25 | 1998-04-02 | ウェストヴァコ コーポレイション | Microporous activated carbon and its production method |
JP2993343B2 (en) | 1993-12-28 | 1999-12-20 | 日本電気株式会社 | Polarizing electrode and method of manufacturing the same |
JPH0873863A (en) * | 1994-09-09 | 1996-03-19 | Petoca:Kk | Nitrogen-containing isotropic pitch |
US5605618A (en) * | 1994-09-09 | 1997-02-25 | Petoca, Ltd. | Process for preparing nitrogen-containing isotropic pitch and nitrogen-containing isotropic pitch |
JPH11267244A (en) * | 1998-03-23 | 1999-10-05 | Toyobo Co Ltd | Protective clothing material for toxic gas |
-
1999
- 1999-11-19 FR FR9914607A patent/FR2801297B1/en not_active Expired - Fee Related
-
2000
- 2000-11-17 CA CA002392026A patent/CA2392026A1/en not_active Abandoned
- 2000-11-17 US US10/130,485 patent/US7105083B1/en not_active Expired - Fee Related
- 2000-11-17 EP EP00981431A patent/EP1235744A1/en not_active Withdrawn
- 2000-11-17 AU AU18683/01A patent/AU1868301A/en not_active Abandoned
- 2000-11-17 JP JP2001538284A patent/JP2003514741A/en active Pending
- 2000-11-17 WO PCT/FR2000/003204 patent/WO2001036326A1/en active Application Filing
Non-Patent Citations (1)
Title |
---|
See references of WO0136326A1 * |
Also Published As
Publication number | Publication date |
---|---|
JP2003514741A (en) | 2003-04-22 |
CA2392026A1 (en) | 2001-05-25 |
FR2801297A1 (en) | 2001-05-25 |
FR2801297B1 (en) | 2002-02-01 |
US7105083B1 (en) | 2006-09-12 |
AU1868301A (en) | 2001-05-30 |
WO2001036326A1 (en) | 2001-05-25 |
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