WO2009011590A1 - Chemically activated carbon and methods for preparing same - Google Patents
Chemically activated carbon and methods for preparing same Download PDFInfo
- Publication number
- WO2009011590A1 WO2009011590A1 PCT/NL2008/050497 NL2008050497W WO2009011590A1 WO 2009011590 A1 WO2009011590 A1 WO 2009011590A1 NL 2008050497 W NL2008050497 W NL 2008050497W WO 2009011590 A1 WO2009011590 A1 WO 2009011590A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- activated carbon
- particles
- phosphoric acid
- comminuted
- binder
- Prior art date
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 176
- 238000000034 method Methods 0.000 title claims abstract description 44
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 64
- 239000002245 particle Substances 0.000 claims abstract description 49
- 239000002023 wood Substances 0.000 claims abstract description 35
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 29
- 239000011230 binding agent Substances 0.000 claims abstract description 29
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 26
- 239000005418 vegetable material Substances 0.000 claims abstract description 24
- 239000011257 shell material Substances 0.000 claims abstract description 13
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims abstract description 12
- 235000005074 zinc chloride Nutrition 0.000 claims abstract description 6
- 239000011592 zinc chloride Substances 0.000 claims abstract description 6
- 235000011007 phosphoric acid Nutrition 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 25
- 230000004913 activation Effects 0.000 claims description 23
- 239000000126 substance Substances 0.000 claims description 21
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- 230000003213 activating effect Effects 0.000 claims description 10
- 238000003763 carbonization Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000008188 pellet Substances 0.000 claims description 9
- 239000004575 stone Substances 0.000 claims description 9
- 240000007817 Olea europaea Species 0.000 claims description 6
- 229920005610 lignin Polymers 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000007858 starting material Substances 0.000 claims description 6
- 239000001273 butane Substances 0.000 claims description 5
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 5
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 5
- 244000060011 Cocos nucifera Species 0.000 claims description 4
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 4
- 235000013399 edible fruits Nutrition 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 244000144725 Amygdalus communis Species 0.000 claims description 2
- 235000011437 Amygdalus communis Nutrition 0.000 claims description 2
- 235000020224 almond Nutrition 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000000470 constituent Substances 0.000 claims description 2
- 235000014571 nuts Nutrition 0.000 claims description 2
- 239000000463 material Substances 0.000 description 23
- 238000001994 activation Methods 0.000 description 21
- 238000001179 sorption measurement Methods 0.000 description 21
- 239000007789 gas Substances 0.000 description 19
- 239000011148 porous material Substances 0.000 description 17
- 239000002994 raw material Substances 0.000 description 17
- 238000001125 extrusion Methods 0.000 description 16
- 238000004519 manufacturing process Methods 0.000 description 15
- 230000007423 decrease Effects 0.000 description 11
- 239000012071 phase Substances 0.000 description 11
- 230000000740 bleeding effect Effects 0.000 description 9
- 238000003795 desorption Methods 0.000 description 9
- 235000013312 flour Nutrition 0.000 description 9
- 238000011084 recovery Methods 0.000 description 8
- 230000032683 aging Effects 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 7
- 239000000446 fuel Substances 0.000 description 7
- 230000000274 adsorptive effect Effects 0.000 description 6
- 238000000746 purification Methods 0.000 description 6
- 238000007493 shaping process Methods 0.000 description 6
- 239000003463 adsorbent Substances 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 241000196324 Embryophyta Species 0.000 description 4
- 239000002828 fuel tank Substances 0.000 description 4
- 239000006101 laboratory sample Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 235000013311 vegetables Nutrition 0.000 description 4
- 229920001732 Lignosulfonate Polymers 0.000 description 3
- 239000004117 Lignosulphonate Substances 0.000 description 3
- 239000002156 adsorbate Substances 0.000 description 3
- 230000033228 biological regulation Effects 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003502 gasoline Substances 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 235000019357 lignosulphonate Nutrition 0.000 description 3
- 238000010926 purge Methods 0.000 description 3
- 239000011122 softwood Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000011121 hardwood Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 239000011800 void material Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 241000609240 Ambelania acida Species 0.000 description 1
- 241000512259 Ascophyllum nodosum Species 0.000 description 1
- 241001481828 Glyptocephalus cynoglossus Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 241000533293 Sesbania emerus Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003466 anti-cipated effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 239000010905 bagasse Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003077 lignite Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000003415 peat Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000011833 salt mixture Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- -1 soft and hard coals Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 230000035900 sweating Effects 0.000 description 1
- 239000011269 tar Substances 0.000 description 1
- 239000011299 tars and pitches Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
-
- 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
- C01B32/342—Preparation characterised by non-gaseous activating 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
-
- 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
- C01B32/354—After-treatment
- C01B32/384—Granulation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/10—Inorganic adsorbents
- B01D2253/102—Carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2259/00—Type of treatment
- B01D2259/45—Gas separation or purification devices adapted for specific applications
- B01D2259/4516—Gas separation or purification devices adapted for specific applications for fuel vapour recovery systems
-
- 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
- C01B32/342—Preparation characterised by non-gaseous activating agents
- C01B32/348—Metallic compounds
-
- 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
- C01B32/354—After-treatment
- C01B32/382—Making shaped products, e.g. fibres, spheres, membranes or foam
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
- F02M—SUPPLYING COMBUSTION ENGINES IN GENERAL WITH COMBUSTIBLE MIXTURES OR CONSTITUENTS THEREOF
- F02M25/00—Engine-pertinent apparatus for adding non-fuel substances or small quantities of secondary fuel to combustion-air, main fuel or fuel-air mixture
- F02M25/08—Engine-pertinent apparatus for adding non-fuel substances or small quantities of secondary fuel to combustion-air, main fuel or fuel-air mixture adding fuel vapours drawn from engine fuel reservoir
- F02M25/0854—Details of the absorption canister
Definitions
- the present invention relates to activated carbon and methods for preparing the same.
- this invention relates to new carbons useful in vapor adsorption and methods for their production. More particularly, this invention relates to activated carbon derived from carbonaceous material prepared by shaping and chemical activation to produce carbon of high density, low pressure drop, high hardness, low attrition and high activity.
- Activated carbon is a microcrystalline, non-graphitic form of carbon which has been processed to increase internal porosity. Activated carbons are characterized by a large specific surface area typically in the range of 400 to 2500 m 2 /g, which permits its industrial use in the purification of liquids and gases by the adsorption of gases and vapors from gases and of dissolved or dispersed substances from liquids. Commercial grades of activated carbon are designated as either gas- phase or liquid-phase adsorbents. Liquid-phase carbons generally may be powdered, granular, or shaped and gas-phase, vapor-adsorbent carbons are hard granules or hard, relatively dust-free shaped pellets.
- Activated carbon is widely used in industry in the purification of liquids and gases.
- a gas which is to be purified is passed through a bed of granular activated carbon.
- molecules of impurities in the gas are adsorbed onto the surface of the activated carbon.
- Activated carbon is also used in industry for the storage and recovery of valuable components. For example a gas with a valuable component is passed through a bed of granular activated carbon. As the bed has been saturated the adsorbed component is recovered by desorption using a carrier gas passing counter current through the activated carbon bed or by lowering the pressure.
- the available surface area of activated carbon is dependent on its pore volume. Since the surface area per unit volume decreases as individual pore size increases, large surface area is maximized by maximizing the number of pores of very small dimensions and/or minimizing the number of pores of very large dimensions.
- Pore sizes are defined by the International Union of Pure and Applied Chemistry as micropores (pore width ⁇ 2 nm), mesopores (pore width 2-50 nm), and macropores (pore width>50 nm). Micropores and mesopores contribute to the adsorptive capacity of the activated carbon; whereas, the macropores reduce the density and can be detrimental to the adsorbant effectiveness of the activated carbon, on a carbon volume basis.
- the adsorption capacity and rate of adsorption depend to a large extent upon the internal surface area and pore size distribution in relation to the dimensions of the adsorbate to remove. For purification the adsorption capacity and the adsorption rate must be as high as possible.
- Conventional chemically activated lignocellulose -based carbons generally exhibit more mesoporosity than steani activated carbon.
- steam (so gas) activated carbon generally exhibit more microporosity.
- the rate of desorption of an activated carbon depends to a large extent upon the internal surface area and pore size distribution.
- an optimal adsorption capacity is achieved by maximizing the number of pores with dimensions just large enough to enclose the adsorbate molecules to be removed.
- An optimal fit between the adsorbate dimension and the pores dimension increases not only the adsoption capacity, it also increases the physical adsorption forces, preventing desorption.
- the optimal pores size distribution is a compromise between pores giving a high initial adsorption capacity and pores giving a low rest adsorption with as a consequence a high desorption capacity.
- butane is used as model component and the carbon is specified on butane working capacity (BWC).
- BWC butane working capacity
- the pressure drop, the hardness and the attrition is of importance, next to the optimal pores size distribution.
- the pressure drop should be as low as possible.
- the pressure drop decreases as the particle sizes increase.
- the rate of adsorption and the rate of desorption decrease as the particle size increases. If a high adsorption and desorption rate is desirable, a compromise is necessary.
- a high hardness and a low attrition is necessary to prevent deterioration of the carbon adsorbent during a many years stay in a filter , especially in recovery applications.
- Shaped carbons as extrudates can be produced with an optimal diameter and a high hardness and low attrition
- Commercial activated carbon has generally been made from material of plant origin, such as wood (hardwood and softwood), corncobs, kelp, coffee beans, rice hulls, fruit pits, nutshells, e.g. from coconut, and wastes such as bagasse and lignin.
- Activated carbon also has been made from peat, lignite, soft and hard coals, tars and pitches, asphalt, petroleum residues, and carbon black. Activation of the raw material is accomplished by one of two distinct processes: 1) chemical activation, or (2) gas activation.
- Chemical activation typically is carried out commercially by impregnation of the carbonaceous material precursor with a chemical activation agent, and the blend is heated to a temperature of 350°C-700°C. Chemical activation agents reduce the formation of tar and other by-products, thereby increasing yield.
- Chemically activated carbon by virtue of its raw materials and manufacturing process, tends to be of low density with a highly developed mesopore structure, optionally combined with a high developed large micropores structure.
- a highly developed mesopore structure For gas phase recovery processes a high adsorption capacity combined with a fast desorption rate and high desorption capacity is important, for which a highly developed large micropore structure is required.
- activated carbons are in granular shape for gas phase processes.
- the highly developed micropore structure is a desirable feature, whereas the low density is a disadvantage of any granular form of chemically activated carbon.
- the pore structure of the carbon with its inherent surface area is of paramount importance in determining the effectiveness of the activated carbon as an adsorbent.
- the density is also an important feature of the effectiveness of the adsorbent, as the application of granular activated carbon is invariably in the form of a static bed of fixed volumetric size.
- the normal method used to determine the efficiency of a granular activated carbon for purification is the weight of material it can adsorb, per unit volume of activated carbon up to breakthrough. For recovery it is important " to determine the weight of material it can desorb per unit volume of activated carbon.
- This test is normally carried out by placing a volume of activated carbon in a standard U-tube and passing a vapor through the activated carbon bed optionally followed by desorbing the adsorbed material. The carbon is weighed before and after this process and the difference provides the weight of substance adsorbed or desorbed by the carbon.
- the raw material normally used in the production of chemically activated carbon is a carbonaceous vegetable material such as wood which has been milled to about 2-5 mm particle size.
- the activated carbon when produced is usually ground into a powder form for use in liquid purification.
- the activated carbon can also be broken (for example 10*35 mesh) or the activated carbon can be shaped into pellets of various sizes, optionally using a binder before or after activation. Shaped carbons and especially extrudates show a low pressure drop, a high hardness and low attrition
- US 4,677,086 the binding of activated carbon in extrudates using an inorganic binder has been described. In the described method a separate step is necessary for producing extrudates.
- Activated carbons produced in this way have been limited in BWC.
- EP-A 557 208 also a chemical activation process of a granular material has been described using wood as starting material. According to this process, wood powder is mixed with phosphoric acid.. After mixing plasticizing takes place during heating to the activation temperature. By regulation the temperature profile, further plasticizing takes place.
- This document describes methods to handle and to use the plasticization to increase the performance of the product (higher BWC; butane working capacity).
- the plasticisation is carried out in a separate step. After the plasticization the material is shaped for example by spheronizing or by extrusion. For extrusion the plasticized material is milled. The material must be "soft" enough for shaping as extrusion. After shaping the material is activated.
- an activatable binder is added before extrusion and activation to produce an activated carbon with enhanced hardness and physical integrity.
- EP-A 423 967 a process to produce activated carbon directly by chemically activation of a shaped granular material containing a high lignin vegetable raw material is described. According to this process milled vegetable raw material, such as olive stone powder is mixed with phosphoric acid, shaped by extrusion, dried and activated.
- the prior art gas-phase carbons described in EP-A 423 967 is produced according to a limited step processes making the production process for these carbons less expensive.
- the blended material After mixing of the raw material with phosphoric acid, the blended material is shaped, directly followed by drying and activation.
- the shape of extrudates have to stay intact during all the process steps after extrusion and not sweat phosphoric acid, sticking the particles together forming big lumps, which are difficult to activate. Big lumps are not suited for gas phases processes because a decrease of kinetics, caused by the low external surface area of the particles and by a large void fraction, causing a low density and leakage flows as a consequence of the irregular shape. This phenomenon makes it difficult to use wood in these processes.
- the invention is based on the surprising finding that the use of a combination of on the one hand wood particles and on the other hand a young vegetable material, such as shells and kernels, result in a synergistic improvement of a number of the properties of the activated carbon.
- the invention is characterized by a chemically activated carbon, based on a combination of wood particles and comminuted carbonaceous vegetable material selected from kernel or shell material, in a weight ratio of between 10-90 to 90-10, preferably between 15-85 and 90-10, further optionally containing a binder, said carbon having been chemically activated using phosphoric acid or zinc chloride .
- the binder is preferably present in a concentration of up to 35 wt. %, based on the weight of said combination of wood particles and comminuted carbonaceous vegetable material plus binder. If present, the concentration preferably is at least 5 wt. %, based on the weight of said combination of wood particles and comminuted carbonaceous vegetable material plus binder.
- the invention is characterized by the process of producing this chemically activated carbon.
- This process for producing a chemically activated carbon comprises the steps of: providing a starting material in the form of a mixture of wood particles and comminuted carbonaceous vegetable material from kernel material and comminuted carbonaceous vegetable material from shell material and optionally a binder; mixing said starting material with a chemical activating agent, selected from phosphoric acid and zinc chloride, to impregnate the particles with the chemical activating agent; pelletising (shaping) said mixture comprising the chemical activating agent to form pellets; subjecting said pellets to a heat treatment, comprising heating the pellets to remove water and other volatile constituents present to consolidate the granular nature; and carbonising the treated particles, preferably at a temperature from about 350 to about 700 0 C, in particular from about 400 to about 650 0 C. No separate heat pre-treatment plasticization step before shaping is necessary.
- the weight ratio wood particles to comminuted carbonaceous vegetable material usually is between 10-90 to 90-10.
- the concentration of the binder usually is up to 35 wt.% based on total weight before activation, preferably 5-35 wt.%.
- an activatable binder such as lignin or lignin compounds.
- Such method for preparing activated carbon according to the invention is in particular suitable for preparing activated carbon according to the invention.
- the invention is directed to the use of an activated carbon as defined above or produced in accordance with the invention, in an evaporative loss control device.
- the invention provides a way to obtain chemically activated carbon in a simple way, using wood as a raw material combined with a comminuted carbonaceous vegetable material or a binder, whilst maintaining a good-working capacity, and improving shape stability (low tendency of the pellets to stick together) compared to a comparable process wherein activated carbon is prepared from only wood material.
- the combined use of wood particles and comminuted carbonaceous vegetable material or binder even results in an improved activated carbon, more in particular in respect to the adsorptive properties, such as working capacity and processing into final particles for use in various processes, more in particular in devices to reduce vapor emission from vehicles (evaporative loss control devices).
- the use of a combination of wood particles and comminuted carbonaceous vegetable material, plus optionally binder may even provide a synergistic effect with respect to the working capacity.
- the increase of the amount of wood particles in the mixture with comminuted kernel or stone material results in a large improvement of the properties, which improvement is maintained over the whole range of the ratio in the mixture.
- a further advantage resides in the increased flexibility in the selection of the starting materials, which makes it possible, while retaining the good product properties, to select the cheapest combination of materials, depending on the market situation.
- An important property of the activated carbon of invention is the measure of bleeding and ageing, which is determined on the basis of the butane retentivity.
- the value thereof is preferably below 7.5 g/100g, as determined in accordance with ASTM D5228.
- the raw materials used in the production of chemically activated carbon of the invention are on the one hand wood.
- the wood particles are selected from wood chips, saw dust and wood flour.
- nut shell, fruit stone and kernel, and in particular, olive stone, almond shell and coconut shell are especially useful as the second component of the mixture.
- These materials are also preferably used in comminuted form, as chips or flour.
- the particle size of the wood and other particles can be selected within wide ranges.
- the particle size of the comminuted vegetable materials may be characterized by at most 5 weight % having a size of less than 1 ⁇ m and at least 95 weight % having a size of less than 750 ⁇ m. More in particular at most 5 weight % may have a size of less than 1 ⁇ m and at least 95 weight % has a size of less than 500 ⁇ m.
- the particle size of the wood particles materials may be characterized by at most 5 weight % having a size of less than 1 ⁇ m and at least 95 weight % having a size of less than 750 ⁇ m. More in particular at most 5 weight % may have a size of less than 1 ⁇ m and at least 95 weight % has a size of less than ⁇ OO ⁇ m.
- mixture particles sizes are preferably chosen to provide a high density and good processing properties, in particular with respect to low shrink by plasticization.
- the particles are mixed with the chemical activating agent, preferably as an aqueous solution.
- This agent is based on phosphoric acid or zinc chloride, preferably phosphoric acid.
- the preferred phosphoric acid is a 50-86% aqueous ortho phosphoric acid, for instance a 60-80 % aqueous ortho phosphoric acid.
- the chemical activation agent does not contain lithium-salts.
- the chemical activating agent is added to the combination of wood particles and comminuted carbonaceous vegetable material in a weight ratio of between 1:1 and 3:1 respectively and preferably a ratio of between 1.5:1 and 2.2:1.
- the mixture preferably consists only of the wood particles, comminuted carbonaceous vegetable material selected from kernel or shell material, in a weight ratio of between 10-90 to 90-10, binder, chemical activating agent, water and optional binder.
- the mixture is shaped especially by extrusion to get hard, processable extrudates with diameters between 1.5 and 5 mm.
- the mixture is then preferably heated to plasticise the wood material within the extrudates whereas the vegetable material act as a template preventing sweating.
- This heating is preferable to a final temperature of between 100 and 200 0 C, in particular for a duration of between 10 and 50 minutes.
- the material plasticises and dries.
- it is carbonised at a temperature suitable for this, such as a temperature between 350 and 700 0 C.
- the activated carbon according to the present invention is very hard with a low attrition and with a low pressure drop
- the activated carbon according to the present invention is especially suited for use in adsorptive processes, more in particular those processes wherein a high adsorptive capacity has to be obtained within a relatively small volume. Due to the higher capacity per volume, the material can be used to improve adsorptive processes.
- VTVE vegetable raw material
- WM wood raw material
- PA aqueous phosphoric acid
- Bleeding and ageing have a relation with the retentivity. Bleeding is mentioned as an important property for fulfilling LEVII requirements for automobiles.
- Ageing is the decrease in working capacity (WC) in time for carbons applied in a filter in a car during a large number of parking /driving cycles.
- WC working capacity
- a high retentivity predicts a high bleeding and a fast ageing
- the results show a numerous decrease in retentivity for the OSF/SWF mixtures compared to 100% OSF- carbon. A higher content of SWF in the OSF/SWF mixture raises the effect on
- WF laboratory samples with different types of. WF have been produced according to the recipe given in example 1. As WF has been used SWF, HWF and WWF. . The sets have been produced with different batches OSF and SWF, with different OSFAWF ratio's and with pure PA or with recovered PA. In table 3 the results thereof have been given for BWC and retentivity . Next to SWF also HWF and WWF can be used to replace OSF.
- the run is continued by replacing 25% of the OSF by soft wood flour (SWF) So the OSF having a particle size range 5 wt.% ⁇ 10 ⁇ m and 95wt.% ⁇ 300 ⁇ m was mixed with 25 %soft SWF having a particle size range 5wt.% ⁇ 10 ⁇ m and 95wt.% ⁇ 300 ⁇ m.
- a 65 % aqueous plant phosphoric acid solution was added in a ratio of 1:2 and the mixture was blended, followed by extrusion.
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- Combustion & Propulsion (AREA)
- Mechanical Engineering (AREA)
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- Supplying Secondary Fuel Or The Like To Fuel, Air Or Fuel-Air Mixtures (AREA)
Abstract
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JP2010516946A JP5773647B2 (en) | 2007-07-19 | 2008-07-18 | Chemical activated carbon and method for its preparation |
CN2008800253224A CN101790491B (en) | 2007-07-19 | 2008-07-18 | Chemically activated carbon and methods for preparing same |
KR1020157020042A KR20150090277A (en) | 2007-07-19 | 2008-07-18 | Chemically activated carbon and methods for preparing same |
US12/669,225 US8759253B2 (en) | 2007-07-19 | 2008-07-18 | Chemically activated carbon and methods for preparing same |
MX2010000761A MX2010000761A (en) | 2007-07-19 | 2008-07-18 | Chemically activated carbon and methods for preparing same. |
BRPI0814272-6A BRPI0814272B1 (en) | 2007-07-19 | 2008-07-18 | PROCESS FOR PRODUCTION OF A CHEMICALLY ACTIVATED CARBON AND USE OF A ACTIVATED CARBON |
ES08779043.2T ES2620420T3 (en) | 2007-07-19 | 2008-07-18 | Process for the preparation of chemically activated carbon |
EP08779043.2A EP2183186B1 (en) | 2007-07-19 | 2008-07-18 | Method for preparing chemically activated carbon |
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EP (1) | EP2183186B1 (en) |
JP (1) | JP5773647B2 (en) |
KR (2) | KR20100074107A (en) |
CN (1) | CN101790491B (en) |
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- 2008-07-18 MX MX2010000761A patent/MX2010000761A/en active IP Right Grant
- 2008-07-18 KR KR1020107003542A patent/KR20100074107A/en active Search and Examination
- 2008-07-18 US US12/669,225 patent/US8759253B2/en active Active
- 2008-07-18 JP JP2010516946A patent/JP5773647B2/en active Active
- 2008-07-18 CN CN2008800253224A patent/CN101790491B/en active Active
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JP2011530153A (en) * | 2008-08-05 | 2011-12-15 | ダウ グローバル テクノロジーズ エルエルシー | Lithium metal phosphate / carbon nanocomposites as cathode active materials for rechargeable lithium batteries |
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CN110577217A (en) * | 2019-10-16 | 2019-12-17 | 中国矿业大学 | Honeycomb porous carbon, preparation method thereof and electrode plate of supercapacitor |
Also Published As
Publication number | Publication date |
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KR20100074107A (en) | 2010-07-01 |
BRPI0814272B1 (en) | 2019-02-19 |
CN101790491A (en) | 2010-07-28 |
US20100298134A1 (en) | 2010-11-25 |
EP2183186B1 (en) | 2017-02-15 |
MX2010000761A (en) | 2010-08-02 |
CN101790491B (en) | 2013-03-13 |
US8759253B2 (en) | 2014-06-24 |
EP2183186A1 (en) | 2010-05-12 |
JP5773647B2 (en) | 2015-09-02 |
JP2010533638A (en) | 2010-10-28 |
KR20150090277A (en) | 2015-08-05 |
ES2620420T3 (en) | 2017-06-28 |
BRPI0814272A2 (en) | 2015-02-03 |
PL2183186T3 (en) | 2017-07-31 |
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