CA1082673A - Method of making activated carbon - Google Patents
Method of making activated carbonInfo
- Publication number
- CA1082673A CA1082673A CA256,143A CA256143A CA1082673A CA 1082673 A CA1082673 A CA 1082673A CA 256143 A CA256143 A CA 256143A CA 1082673 A CA1082673 A CA 1082673A
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- CA
- Canada
- Prior art keywords
- fine particles
- carbonaceous
- activated carbon
- carbonaceous fine
- slurry
- Prior art date
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- 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
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- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
TITLE
A METHOD OF MAKING ACTIVATED CARBON
ABSTRACT OF THE DISCLOSURE
Activated carbon is made by forming a slurry of carbonaceous and non-carbonaceous fine particles, preferably finely divided non-caking coal, in a suspension liquid, preferably water. A liquid lyophobic to the suspension liquid and the non-carbonaceous fine particles and lyophilic to the carbonaceous fine particles, which is preferably carbonizable, is added to the slurry; and the resulting mixture agitated to preferentially agglomerate the carbonaceous fine particles while the non-carbonaceous fine particles remain substantially unagglomerated in the slurry. The agglomerated fine particles of carbonaceous material are thereafter separated from the mixture, and carbonized and activated, preferably by heating to greater than about 450°C. and preferably greater than 500°C. in the presence of steam, to form activated carbon.
A METHOD OF MAKING ACTIVATED CARBON
ABSTRACT OF THE DISCLOSURE
Activated carbon is made by forming a slurry of carbonaceous and non-carbonaceous fine particles, preferably finely divided non-caking coal, in a suspension liquid, preferably water. A liquid lyophobic to the suspension liquid and the non-carbonaceous fine particles and lyophilic to the carbonaceous fine particles, which is preferably carbonizable, is added to the slurry; and the resulting mixture agitated to preferentially agglomerate the carbonaceous fine particles while the non-carbonaceous fine particles remain substantially unagglomerated in the slurry. The agglomerated fine particles of carbonaceous material are thereafter separated from the mixture, and carbonized and activated, preferably by heating to greater than about 450°C. and preferably greater than 500°C. in the presence of steam, to form activated carbon.
Description
1~82673 FIELD OF THE INVENTION
The present invention relates to the making of activated carbon of high surface area, high carbonaceous content and uniform granule size and packing.
BAC~GROUND OF THE INVENTION
Activated carbon is an amorphous form of carbon which is specially treated to produce a very large surface area, ranging generally from 300 and 2,000 m2/g. This large surface area means that the internal pore structure has been very highly developed. It is this structure that provides ac~ivated carbon with the ability to absorb gases and vapors from gases, an~ dissolved or dispersed substances from liquids. Activated carbons remove colors, odors and unwanted flavors from gases and so~utions by absorbing the undesired impurities on their surfaces. Activated carbon appears commercially in two forms:
light fluffy powders generally used for decolorizing, and hard, dense granules or pellets generally used for vapor adsorption.
Almost any carbonaceous material of either anlmal, vegatable or mineral origin can bè made into activated carbon when properly treated. Activated carbon has been prepared from the blood, flesh and bones of animals; it has been made of
The present invention relates to the making of activated carbon of high surface area, high carbonaceous content and uniform granule size and packing.
BAC~GROUND OF THE INVENTION
Activated carbon is an amorphous form of carbon which is specially treated to produce a very large surface area, ranging generally from 300 and 2,000 m2/g. This large surface area means that the internal pore structure has been very highly developed. It is this structure that provides ac~ivated carbon with the ability to absorb gases and vapors from gases, an~ dissolved or dispersed substances from liquids. Activated carbons remove colors, odors and unwanted flavors from gases and so~utions by absorbing the undesired impurities on their surfaces. Activated carbon appears commercially in two forms:
light fluffy powders generally used for decolorizing, and hard, dense granules or pellets generally used for vapor adsorption.
Almost any carbonaceous material of either anlmal, vegatable or mineral origin can bè made into activated carbon when properly treated. Activated carbon has been prepared from the blood, flesh and bones of animals; it has been made of
2~ vegetable materials including hardwoods, softwoods, corncobs, k~lp, coffee beans? rice hulls, fruit pits, nut shells (particularly peanu~ shells), bagasse and lignin; and it haQ been made of minerals including peat, lignite, soft and hard coalq, tars and pitches, asphalt, petroleum residues, and carbon blacks. However, for economic ,- . ~.
2.
. ~ `, ' ~ .
! ' ~LOi3Z673 reasons, bones, wood, peat, lignite and paper mill waste (lignin) are most generally used for the manufacture of powdered carbons, and cocoanut shells, coal, peat and petroleum residues are usèd for granular carbons.
Regardless of the raw material or the form of the product, activated carbon generally is made by one of two basic methods: chemical or gas activation. Chemical activation depends on the action of inorganic chemicals, e.g. zinc chloride or phosphoric acid, present naturally or added to the raw material to degrade or dehydrate the organic molecules during carbonization or calcination. Gas activation depends on selective oxidation of the carbonaceous matter with air at low temperature, or steam, carbon dioxide, flue gas, chlorine or similar gases or vapors a~ high temperature.` The oxidation is usually preceded by a primary carbonization of the raw material.
The adsorbing power of an activated carbon varies direct-ly with (i) the carbon purity of the activated material, and ~ii) the surface area per unit of weight of the activated material.
The higher the purity and the greater the bulk of a unit weight of activated carbon, the greater the adsorbing power. Granular carbons also require consideration of the resistance to flow of fluid or gas through a unit weight of the activated carbon. A `
gr~nular activated carbon is provided in a packed bed, and the gas or liquid to be purified is passed through the packed bed. The more gas or liquid that can be passed through a unit weight of the activated carbon in a given time, and the more uniformly the :
~:)82~i73 gas or liquid can pass through the activated carbon, the greater is the adsorbing power of the activated carbon. Also consideration of granular carbons is that the granules have sufficient green and finished strength to permit automated processing through drying, carbonizing and activating furnaces and ormation of the activated carbon bed.
Accordingly, methods for making activated carbon are directed to (i) decreasing the non-carbonaceous content, (ii) increasing the surface area per unit weight, and (iii) providing more uniformly sized and packed and spherically shaped granular carbon. For example, coal and lignite (e.g. brown coal) have been found to ~rovide more pure activated carbon if first treated with hydrochloric acid to remove ash and then carbonized to remove the chlorinated hydrocarbons, e.g. United States Patent No. 2,040,931 and Ind. Eng. Chem. 38, 7, 745 (1946).
Similarly, coal has been processed to increase the surface area per unit of weight, e.g. United States Patent No. 3,483,134, and processed with coal tar, coke-oven and wood pitch to form 8pherical granules of essentially uniform size, e.g. United ~0 States Patent No. 3,533,961.
The present invention provides a simplified method of making an improved activated carbon fro~ materials such as coal.
It inexpensively provides activated carbons with high carbon content and high surface area per unit weight, and with unifQrm granulaF size and packing as well as generally spberical shape.
' " , . ' , ~ ' .
~ O ~ ~ 6 ~ 3 SUMMARY OF THE INVENTION
A method is provi~ed for making at low cost, activated carbon and particularly granular activated carbon, having high carbon content and high surface area per unit of weight. The method also enables granules of activated carbon to be made of more uniform, controlled size and packing, and granules of generally spherical shape.
The method commences by dispersing of carbonaceous and non-carbonaceous fine particles, such as coal and ash fine particles, in a suspension liquid, preferably water, to orm a slurry. The slurry may be preferably formed by co~linuting carbonaceous material, such as coal from a mine, in suitable comminution apparatus and mixing the comminuted carbonaceous and non-carbonaceous fine par~icles with water.
Alternatively, the slurry may be preferably the waste from other processing such as aqueous underflow from a con~entional coal washing plant, or slurried sediment and refuse from a settling pond of a coal washing plant. In an~ case, where coal is used, ie is of a non-caking kind as known to coke makers.
` The slurry has added to it an àgglomerating liquid lyo-phobic to water and the non-carbonaceous ine particles and ; ~`
lyophilic to the carbonacèous ine particles to form a mixture.
The agglomerating llquid is preferably a hydrocarbon that can be volatilized and/or carbonized along with the carbonaceous ine particles as hereinafter described, ha~ing an initial boil-ing poin~ greater than about 65C. and preferably greater than 150C. The mixture is then agitated to preferentially agglomerate the carbonaceous fine particles, while leaving the -.
.' ' ' 5. ~-.; ~ . .
, ~ O ~ Z 67 3 non-carbonaceous ~ine particles substantially unagglomerated in the mixture. Thereafter, the ag~lomerated carbonaceous fine particles are separated from the mixture. The size and packing (density) o~ the agglomeràtes have substantial uniformity, and the size can be controlled by the composition and percentage of the liquid and the degree and duration of the agitation.
The separated agglomerates of carbonaceous fine particles are then carbonized and activated preferably in a conventional furnace to form ac~ivated carbon. Typically carbonizing and activation is performed in the same furnace, with the activation preceded by primary carbonization of the separated agglomerates. The carbonized and activating is pre-ferably performed by heating,the agglomerates of.carbonaceo~s fine p~rtLcles to above about 450C. and preferably above 500C.
in the presence of steam. Alternatively, the agglomerates may be activated by selective oxidation with carbon dioxide, flue gas, chlorine, or similar gases or vapors at high temperature or by selective oxidation with air at low temperature. ..
` The size, packing (denQity3 and shape of the activated carbon granules are.closely controlled by controlling the agglomeration of carbonaceous, fine particles in the mixture of agglomerating and suspension liquids, and carbonaceous and non-carbonaceous fine particles. Specifically, the size and den~ity of the agglomera~es is,controlled by thè composition and additions o`f the agglomerating.liquid and rapidity and duration of agitation of the mixture. The shape of the agglomerates is generally spherical, and the agglomerates are generally uniform in size by reason of the operation of agglomeration process.
, .
.. , ~ .
1~826'73 Other details, objects and advantages of the present invention will become apparent as the following descrip~ion of the presently preferred embodiments thereof and the presently preferred methods of practicing the same proceeds.
BRIEF DESCRIPTION QF THE DRAWINGS
In the accompanying drawings, the presently preferred embodiments-of the invention and the presently preferred :.
methods of practicing the invention are shown, in which:
Figure 1 is a schematic illu$trating various methods, ., of making activated carbon in accordance with the present.
invention; and Figure 2 is a schematic illustrating the operation of apparatus utilized in the performance of examples .in accordance ;``
with the present invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring specifically ~o Figure 1, ac~iva~ed carbon is made in accordance with the present invention by first dispersing carbonaceous and non-carbonaceous fine particles, ~-preferably from a carbonaceous material`, in, a suspension liquid , to form a slurry. "Fine particles" are small particles pre- . , ferably of less than .600 millimeter (28 mesh Tyler) .in size and typically leSQ than ~200 millimeter ~65 mes.h Tyler) in : size. "Carbonaceous material" is any availabLe raw ma~eriaL.rich in carbon that when~ finely divided in~o fine par~icles contains fine particles o.f non-carbonaceous material as well as - , - .. .
':
., .- . ............................. ...
- . . . . -~(~8Z673 carbonaceous material. Materials particularly suitable are lignite, bituminous eoai, anthracite eoal, earbon blaek and eoke-oven and wood pitches having a softening point above 80 C, with bituminous and anthraeite coal being most preferred.
The earbonaceous material is most desirably an an-thraeite or bi-tumin-ous coal of the non-eaking kind from a mine, where the carbonaceous fine parti-eles are eoal and the non-earbonaeeous fine particles are ash. "Ash" fine par-tieles are small particles of materials such as clay and slate that generally appear as ash rather than vola-tiles on complete burning of the coal. "Non-eaking eoal" is known to eoke makers as determined by the semi-quantitive Gieseler Plastometer Test ~ASTM D 1812-69) or the Free-Swelling Index (ASTM D 720-67).
The slurry may be formed in various alternative ways from such mined, non-eaking coal. For example, partieulate eoal 10 may be conveyed directly ~ram a mine to a eomminuting means 11. Comminuting means 11 may be any suitable e~mmereially available eomminuting means, such as a ball mill. Preferably eomminuting means 11 is selected to provide fine particles of uniform size.
During grinding in comminuting means 11, water or other suspension liquid is added to disperse coal and ash fine particles to form slurry 13. Slurry 13 eontains preferably about 5 to 40 percent and most desirably about 20 to 25 ~0 pereent solids of earbonaceous and non-carbonaceous fine particles.
Alternatively, slurry 13 may be underflow 14 from a conventional coal washer, whieh typically has a relative low solids content of about 5 to 15 pereent solids in water. Underflow 14 may be mixed with refuse slurry 15 of eoal and ash fine partieles of relatively high solids eontent, i.e. at least ~bout 50 pereent solids, formed by dispersing the sediment of an existing s~ttling pond adjaeent the eoal washing plant in water. The mixing of underflow 14 and refusé slurry 15 of about 5 to 40 percent and most typically 20 to 25 pereent solids of eoal and ash fine particles.
8.
~ . .. : ~ .
Slurry 13 is processed in agitator apparatus 16 to preferentially agglomerate the carbonaceous (e.,g. coal) fine particles, while the non-carbonaceous (e.g. ash) fine particles remain substan~ially unagglomerated and dispersed in the slurry.
Added eo slurry 13 at the inlet to agita~or apparatus 16 is agglo-merating liquid 17, which is lyophobic to the suspension liquid (e.g. water) and to non-carbonaceous fine particles and lyophilic carbonaceous to form a mixture. "Lyophilic" as herein used means that, in a disperse system, there is a marked affinity (wettability) between a disperse component and the dispersion medium and/or another disperse component. Some examples are gLue and water, rubber and benzene. "Lyophobic" as used herein means that in a disperse system, there is substantially no affinity (wettability) between the disperse component and the dispersion medium and/or another disperse component.
Examples are colloidal "solutions"of metals.
Agglomerating liquid 17 is preerably a hydrocarbon liquid that can ~e carbonized along with the carbonaceous fine particles as hereinafter described. Materials particularly ` 20 suitable for agglomerating liquid 17 are hydrocarbons having an initial boiling point greater than about 65C. , ,~
and preferably greater than 150C. Specifically suitable are light oil, light fuel oil, hea~y fuel oil, and kerosene. Also 8uitable are creosote, ~iltered anthracene oil, hydrogena~ed .
filtered anthracene oil, lubricat,ing oil such`aQ SAE 20, and chlorinated biphenyls. Heavy hydrocarbon materials such as a - heavy crude petroleum, oil shale crude or coal tar may be utilized in certain instances! but these heavier hydrocarbons are not preferred. Heavy hydrocarbon liquids typically contain .
g .
~ ~ 8 2 67 3 molecular groups lyophilic to non-carbonaceous ~ine particles as well as carbonaceous fine particles and, therefore, do not provide the degree of separation of carbonaceous fine particles from non-carbonaceous fine particles preferred in the present method. In addition, such heavy hydrocarbon liquids often need to be heated to provide sufficient fluidity for the operation of the present invention.
Agglomerating liquid 17 is selected and added in measured amounts to control the agglomeration of carbonaceous fine particles as hereinafter described. Preferably, liquid 17 is addad in amounts of about 2 to 10 percent by weight and mo~t desirably between 3 and 7 by weight of the total solids in slurry 13 for high recovery, e.g. 88-98 percent weight, and greater amounts up to and exceeding 30 percent by weight may in some instances be utilized; however, such lesser and greater amounts are not preferred because sufficient agglomeration and binding of coal fine par~icles is not provided, on the one hand, and a waste of highly refined petroleum or coal tar derivative results, on the other hand.
Mixture of slurry 13 and agglomera~ing liquid 17 are mixed and agitated in agitator apparatus 16. Agitator apparatus 16 may be any suitable àgitating apparatus such as a modified turbine,` disc or conè impeller mixer. Preferably, however, agit~tOr apparatus 16 is a tank equipped with a motor driven propell~r 18 extending to the bottom portion of the tank as a Pre~ier Mill. ;
During agitation in agitator apparatus 16, the . 10.
~L082673 carbonaceous fine particles are preferentially wetted by agglomerating liquid 17, which is preferably immiscible to water, and the carbonaceous fine particles agglomerated into coarser particulate. The size of the agglomera~es is primarily controlled by the composition and the percentage of liquid 17 added to ~lurry 13, and lS controlled to provide the desired size and density for the granules of activated carbon. For the preferred percentage of 2 to 10 percent by weight, the agglomerates typically have sizes of from about 1 to 2 millimeters.
The time required to effect agglomeration is generally dependent upon the degree of turbulence or agitation, with the shorter ~gglomeration time being associated with the higher agitation -~peed. The degree and duration of the agitation in apparatus 16 is also controlled to provide the desired size and packing (density) of the agglomerates.
The carbonaceous agglomerat-es, being impregnated and having adsorbed on the surfaces thereof liquid 17, which is generally less dense than the suspension liquid, will tend to float to the top of the mixture. Agglomerated first mixture 19 is thus removed from the top of agitator apparatus 16 to a separator 20, where the carbonaceous agglomerates are separated from the suspension liquids and unagglomerated non-carbonac`eous fine particles by size and/or density. Preferably, separator 20 is a sieve bend of an appropriate mesh size, e.g. 100 or 200 mesh Tyler, such as that manufactured by authority from DSN NV
Vedernaldse Staatsmijnen. Alternatively, other size separators such as sn elutriator, cyclone or splral separator, which i9 '' , . ':
"''` ' ' .
, ' ', "
- ` 11. ' - ~
' . .` .: - . .: .. ~ . `
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~C~8Z6~73 commercially available, may be u~ilized. Alternatively, the carbonaceous agglomerates may be also separated in a float-sink tank where the carbonaceous agglomerates, which tend to float, are skimmed off by a rotating paddle through an overflow, while the water and unagglomerated non-carbonaceous fine particles, ~hich ~end to sink, are removed from the bottom o~ the tank as slurry 21 containing the non-carbonaceous fine particles and substantially free of carbonaceous fine particles and agglomerating liquid.
At this stage, separated carbonaceous agglomerates 22, which generally contain about 7 to 12 percent moisture, may be processed (not shown) by pelletizing into larger particulate. The agglomeratès may be pelletized to generally uniorm particle sizes of 0.05 to 0.75 inch in diameter by feeding the agglomerates to pelletizing disc or tumbler along with a binder liquid to form a second mixture and agitate said mixture. Alternatively, the agglomerates may be agitated, extruded or otherwise molded into pellets upon addition of a binder liquid to form said second mixture.
Binder liquids particularly suitable for this purpose are heavy hydrocarbons such as coke-oven coal tar, oil shale crude, petroleum crude or hèavy fuel oil such as Bunker C, which is pre~erably heated to, for example, 100C to increase fluidity.
The requirement for the binder liquid is that it be capable Of carbonizing and producing coherent pellets or granules in which the aggomerates are bonded together with sufficient strength to permit me~hanized pFocessing and handling without ~ ~
:::
12.
` ` ` ' ~82673 subs~antial crumbling. In this connection, it may be desirable that the product be subsequently oven dried at, e.g.
100C , to bond the binder to and within the agglomerates. An accelerator is also pref~erably included in the binder liquid to hasten bonding of the binder in shorter times and/or at lower temperatures.
Whether pelletized or not, separated carbonaceous agglome~ates 22 are circulated via a pipeline or the like to furnàce 23. In furnace 23 the carbonaceous agglomerates 21 are carbonized by heating to at least about hS0C. and preferably above 500C., and typically below about 900C.
Toward the end o the carbonizing cycle, carbonaceous . .
agglomerate~ are also pre~erably activated in furnace 23 by addition of steam 24. Alternatively, although not most preferred, carbon dioxide, flue gas, chlorine or similar gases or vapors may be utilized at high temperature or air at low temperature to selectively ox~dize and activate the carbonaceous agglomerates.
On completion of the carbonizing and activating cycles, .
`activated carbon 25 is removed from furnace 23 as a finished.
product. Activated.carbon 25 is a granular composit~on o~
Qubstantially uniform size an~ packing (density) and essentially spherical configuration. The size and packing of the !
granules can be controlled with relative precision by selection .
o the agglomerating liquid and control o~ ~he relativè amount (or percentage) of agglomerating liquid by weigh~ to the total solids content of the slurry that is used. The size and packing of the granules are also controlled to .a lesser extent by the rapidity and duration to which the mixture is agitated in the..
, ' ' ~' .
13. : -.
- .,. ~
~ , , ~LC382~73 agitation apparatus. Preferably, the various parameters are controlled so that the agglomerates are between .150 millimeter (~00 mesh Tyler) and 1.20 millimeter tl4 mesh Tyler) in size, which generally requires that the agglomerating liquid be between 2 and 10 percent by weight of the total solids content in the slurry and having an.~initial boiling point greater than The ~ollowing non-limiting specific examples are given illustrating performance of the present method for making activated carbon, EXAMPLE I
An aqueous coal slurry was formed from crushed non-coking coal having a particle size of less than .150 millimeter (100 mesh Tyler) and water. The slurry had a content of 10 to 40/O by weight of solids to water. .The coal slurry was mixed~
with a carbonaceous (hydrocarbon) liquid in the form of a heavy fuel oil. The quantity.of carbonaceous,liquid utilized was between 6 and 25% by weight of the solids in the slurry with which the liquid was mixed. The mixture was maintainèd at 100F.
while agitated within an apparatus as shown in Figure 2 of the 20 . drawings.
The coal slurry was lntroduced to the bottom oE a cylindrical tank 31 of agitator.apparatus 30 by way of inlet 32, while carbonàceous liquid 33 was introduced by way of inlet :
34. The resulting mixture is subjected to the agitating action.
of scrapper blades 35 and agitator blades 36 connected to ~
rotating shaft 37, which is'driven by power means (not shown). '.
' 1~. ' :, -- . .~ . .. : . . . ... .
~8Z673 Also connected to shaft 37 is inner cylindrical housing 38, which is provided to channel the mixture helically through the agitator apparatus 30.
Accordingly, coal slurry 29 is continuously fed into the bottom of housing 31 and subjected to rapid agitation as it flows upwardly between the inner rotating cylindrical housing 38 and the outer cylindrical housing 31.
As a result of the lyophilic action of the agglomerated liquid 33 and the agi~a~ion in the mixture, agglomerates 39 are formed within apparatus 30. The ~g~lomerates 3~ overflow from -the agitating apparatus 30 at the top over screened outlet ~0.
10 At outlet 40, the agglomerates 39 flow over screen 41 of appropriate mesh to provide for separation of the agglomerates from the water and non-carbonaceous (ash) fine particles. The agglomerates 39 are 1/16 to 1/4 inch in si.~e as they come into screen 41. The water and non-carbonaceous fine p~rticles pass through the screen 41 and are discharged through funnel 42.
Agglomerates of increased size and hardness as compared to the fines in the coal slurry were obtained by use of agitator apparatus 30. Also, the non-carbonaceous (ash) content of the agglomerates was reduced as compared to the content of the coal slurry entering the apparatus The results of this processing are shown in TABLE I below.
TABLE I
Percentage of Solids by Weight Sample oAsh Content of Ash Content of Carbonaceous Liquid Con-Coal Slurry Coal Slurry Agglomerates tent of Agglomerates 1 12.1 7.7 13.6 2 10.4 4.7 19.4
2.
. ~ `, ' ~ .
! ' ~LOi3Z673 reasons, bones, wood, peat, lignite and paper mill waste (lignin) are most generally used for the manufacture of powdered carbons, and cocoanut shells, coal, peat and petroleum residues are usèd for granular carbons.
Regardless of the raw material or the form of the product, activated carbon generally is made by one of two basic methods: chemical or gas activation. Chemical activation depends on the action of inorganic chemicals, e.g. zinc chloride or phosphoric acid, present naturally or added to the raw material to degrade or dehydrate the organic molecules during carbonization or calcination. Gas activation depends on selective oxidation of the carbonaceous matter with air at low temperature, or steam, carbon dioxide, flue gas, chlorine or similar gases or vapors a~ high temperature.` The oxidation is usually preceded by a primary carbonization of the raw material.
The adsorbing power of an activated carbon varies direct-ly with (i) the carbon purity of the activated material, and ~ii) the surface area per unit of weight of the activated material.
The higher the purity and the greater the bulk of a unit weight of activated carbon, the greater the adsorbing power. Granular carbons also require consideration of the resistance to flow of fluid or gas through a unit weight of the activated carbon. A `
gr~nular activated carbon is provided in a packed bed, and the gas or liquid to be purified is passed through the packed bed. The more gas or liquid that can be passed through a unit weight of the activated carbon in a given time, and the more uniformly the :
~:)82~i73 gas or liquid can pass through the activated carbon, the greater is the adsorbing power of the activated carbon. Also consideration of granular carbons is that the granules have sufficient green and finished strength to permit automated processing through drying, carbonizing and activating furnaces and ormation of the activated carbon bed.
Accordingly, methods for making activated carbon are directed to (i) decreasing the non-carbonaceous content, (ii) increasing the surface area per unit weight, and (iii) providing more uniformly sized and packed and spherically shaped granular carbon. For example, coal and lignite (e.g. brown coal) have been found to ~rovide more pure activated carbon if first treated with hydrochloric acid to remove ash and then carbonized to remove the chlorinated hydrocarbons, e.g. United States Patent No. 2,040,931 and Ind. Eng. Chem. 38, 7, 745 (1946).
Similarly, coal has been processed to increase the surface area per unit of weight, e.g. United States Patent No. 3,483,134, and processed with coal tar, coke-oven and wood pitch to form 8pherical granules of essentially uniform size, e.g. United ~0 States Patent No. 3,533,961.
The present invention provides a simplified method of making an improved activated carbon fro~ materials such as coal.
It inexpensively provides activated carbons with high carbon content and high surface area per unit weight, and with unifQrm granulaF size and packing as well as generally spberical shape.
' " , . ' , ~ ' .
~ O ~ ~ 6 ~ 3 SUMMARY OF THE INVENTION
A method is provi~ed for making at low cost, activated carbon and particularly granular activated carbon, having high carbon content and high surface area per unit of weight. The method also enables granules of activated carbon to be made of more uniform, controlled size and packing, and granules of generally spherical shape.
The method commences by dispersing of carbonaceous and non-carbonaceous fine particles, such as coal and ash fine particles, in a suspension liquid, preferably water, to orm a slurry. The slurry may be preferably formed by co~linuting carbonaceous material, such as coal from a mine, in suitable comminution apparatus and mixing the comminuted carbonaceous and non-carbonaceous fine par~icles with water.
Alternatively, the slurry may be preferably the waste from other processing such as aqueous underflow from a con~entional coal washing plant, or slurried sediment and refuse from a settling pond of a coal washing plant. In an~ case, where coal is used, ie is of a non-caking kind as known to coke makers.
` The slurry has added to it an àgglomerating liquid lyo-phobic to water and the non-carbonaceous ine particles and ; ~`
lyophilic to the carbonacèous ine particles to form a mixture.
The agglomerating llquid is preferably a hydrocarbon that can be volatilized and/or carbonized along with the carbonaceous ine particles as hereinafter described, ha~ing an initial boil-ing poin~ greater than about 65C. and preferably greater than 150C. The mixture is then agitated to preferentially agglomerate the carbonaceous fine particles, while leaving the -.
.' ' ' 5. ~-.; ~ . .
, ~ O ~ Z 67 3 non-carbonaceous ~ine particles substantially unagglomerated in the mixture. Thereafter, the ag~lomerated carbonaceous fine particles are separated from the mixture. The size and packing (density) o~ the agglomeràtes have substantial uniformity, and the size can be controlled by the composition and percentage of the liquid and the degree and duration of the agitation.
The separated agglomerates of carbonaceous fine particles are then carbonized and activated preferably in a conventional furnace to form ac~ivated carbon. Typically carbonizing and activation is performed in the same furnace, with the activation preceded by primary carbonization of the separated agglomerates. The carbonized and activating is pre-ferably performed by heating,the agglomerates of.carbonaceo~s fine p~rtLcles to above about 450C. and preferably above 500C.
in the presence of steam. Alternatively, the agglomerates may be activated by selective oxidation with carbon dioxide, flue gas, chlorine, or similar gases or vapors at high temperature or by selective oxidation with air at low temperature. ..
` The size, packing (denQity3 and shape of the activated carbon granules are.closely controlled by controlling the agglomeration of carbonaceous, fine particles in the mixture of agglomerating and suspension liquids, and carbonaceous and non-carbonaceous fine particles. Specifically, the size and den~ity of the agglomera~es is,controlled by thè composition and additions o`f the agglomerating.liquid and rapidity and duration of agitation of the mixture. The shape of the agglomerates is generally spherical, and the agglomerates are generally uniform in size by reason of the operation of agglomeration process.
, .
.. , ~ .
1~826'73 Other details, objects and advantages of the present invention will become apparent as the following descrip~ion of the presently preferred embodiments thereof and the presently preferred methods of practicing the same proceeds.
BRIEF DESCRIPTION QF THE DRAWINGS
In the accompanying drawings, the presently preferred embodiments-of the invention and the presently preferred :.
methods of practicing the invention are shown, in which:
Figure 1 is a schematic illu$trating various methods, ., of making activated carbon in accordance with the present.
invention; and Figure 2 is a schematic illustrating the operation of apparatus utilized in the performance of examples .in accordance ;``
with the present invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring specifically ~o Figure 1, ac~iva~ed carbon is made in accordance with the present invention by first dispersing carbonaceous and non-carbonaceous fine particles, ~-preferably from a carbonaceous material`, in, a suspension liquid , to form a slurry. "Fine particles" are small particles pre- . , ferably of less than .600 millimeter (28 mesh Tyler) .in size and typically leSQ than ~200 millimeter ~65 mes.h Tyler) in : size. "Carbonaceous material" is any availabLe raw ma~eriaL.rich in carbon that when~ finely divided in~o fine par~icles contains fine particles o.f non-carbonaceous material as well as - , - .. .
':
., .- . ............................. ...
- . . . . -~(~8Z673 carbonaceous material. Materials particularly suitable are lignite, bituminous eoai, anthracite eoal, earbon blaek and eoke-oven and wood pitches having a softening point above 80 C, with bituminous and anthraeite coal being most preferred.
The earbonaceous material is most desirably an an-thraeite or bi-tumin-ous coal of the non-eaking kind from a mine, where the carbonaceous fine parti-eles are eoal and the non-earbonaeeous fine particles are ash. "Ash" fine par-tieles are small particles of materials such as clay and slate that generally appear as ash rather than vola-tiles on complete burning of the coal. "Non-eaking eoal" is known to eoke makers as determined by the semi-quantitive Gieseler Plastometer Test ~ASTM D 1812-69) or the Free-Swelling Index (ASTM D 720-67).
The slurry may be formed in various alternative ways from such mined, non-eaking coal. For example, partieulate eoal 10 may be conveyed directly ~ram a mine to a eomminuting means 11. Comminuting means 11 may be any suitable e~mmereially available eomminuting means, such as a ball mill. Preferably eomminuting means 11 is selected to provide fine particles of uniform size.
During grinding in comminuting means 11, water or other suspension liquid is added to disperse coal and ash fine particles to form slurry 13. Slurry 13 eontains preferably about 5 to 40 percent and most desirably about 20 to 25 ~0 pereent solids of earbonaceous and non-carbonaceous fine particles.
Alternatively, slurry 13 may be underflow 14 from a conventional coal washer, whieh typically has a relative low solids content of about 5 to 15 pereent solids in water. Underflow 14 may be mixed with refuse slurry 15 of eoal and ash fine partieles of relatively high solids eontent, i.e. at least ~bout 50 pereent solids, formed by dispersing the sediment of an existing s~ttling pond adjaeent the eoal washing plant in water. The mixing of underflow 14 and refusé slurry 15 of about 5 to 40 percent and most typically 20 to 25 pereent solids of eoal and ash fine particles.
8.
~ . .. : ~ .
Slurry 13 is processed in agitator apparatus 16 to preferentially agglomerate the carbonaceous (e.,g. coal) fine particles, while the non-carbonaceous (e.g. ash) fine particles remain substan~ially unagglomerated and dispersed in the slurry.
Added eo slurry 13 at the inlet to agita~or apparatus 16 is agglo-merating liquid 17, which is lyophobic to the suspension liquid (e.g. water) and to non-carbonaceous fine particles and lyophilic carbonaceous to form a mixture. "Lyophilic" as herein used means that, in a disperse system, there is a marked affinity (wettability) between a disperse component and the dispersion medium and/or another disperse component. Some examples are gLue and water, rubber and benzene. "Lyophobic" as used herein means that in a disperse system, there is substantially no affinity (wettability) between the disperse component and the dispersion medium and/or another disperse component.
Examples are colloidal "solutions"of metals.
Agglomerating liquid 17 is preerably a hydrocarbon liquid that can ~e carbonized along with the carbonaceous fine particles as hereinafter described. Materials particularly ` 20 suitable for agglomerating liquid 17 are hydrocarbons having an initial boiling point greater than about 65C. , ,~
and preferably greater than 150C. Specifically suitable are light oil, light fuel oil, hea~y fuel oil, and kerosene. Also 8uitable are creosote, ~iltered anthracene oil, hydrogena~ed .
filtered anthracene oil, lubricat,ing oil such`aQ SAE 20, and chlorinated biphenyls. Heavy hydrocarbon materials such as a - heavy crude petroleum, oil shale crude or coal tar may be utilized in certain instances! but these heavier hydrocarbons are not preferred. Heavy hydrocarbon liquids typically contain .
g .
~ ~ 8 2 67 3 molecular groups lyophilic to non-carbonaceous ~ine particles as well as carbonaceous fine particles and, therefore, do not provide the degree of separation of carbonaceous fine particles from non-carbonaceous fine particles preferred in the present method. In addition, such heavy hydrocarbon liquids often need to be heated to provide sufficient fluidity for the operation of the present invention.
Agglomerating liquid 17 is selected and added in measured amounts to control the agglomeration of carbonaceous fine particles as hereinafter described. Preferably, liquid 17 is addad in amounts of about 2 to 10 percent by weight and mo~t desirably between 3 and 7 by weight of the total solids in slurry 13 for high recovery, e.g. 88-98 percent weight, and greater amounts up to and exceeding 30 percent by weight may in some instances be utilized; however, such lesser and greater amounts are not preferred because sufficient agglomeration and binding of coal fine par~icles is not provided, on the one hand, and a waste of highly refined petroleum or coal tar derivative results, on the other hand.
Mixture of slurry 13 and agglomera~ing liquid 17 are mixed and agitated in agitator apparatus 16. Agitator apparatus 16 may be any suitable àgitating apparatus such as a modified turbine,` disc or conè impeller mixer. Preferably, however, agit~tOr apparatus 16 is a tank equipped with a motor driven propell~r 18 extending to the bottom portion of the tank as a Pre~ier Mill. ;
During agitation in agitator apparatus 16, the . 10.
~L082673 carbonaceous fine particles are preferentially wetted by agglomerating liquid 17, which is preferably immiscible to water, and the carbonaceous fine particles agglomerated into coarser particulate. The size of the agglomera~es is primarily controlled by the composition and the percentage of liquid 17 added to ~lurry 13, and lS controlled to provide the desired size and density for the granules of activated carbon. For the preferred percentage of 2 to 10 percent by weight, the agglomerates typically have sizes of from about 1 to 2 millimeters.
The time required to effect agglomeration is generally dependent upon the degree of turbulence or agitation, with the shorter ~gglomeration time being associated with the higher agitation -~peed. The degree and duration of the agitation in apparatus 16 is also controlled to provide the desired size and packing (density) of the agglomerates.
The carbonaceous agglomerat-es, being impregnated and having adsorbed on the surfaces thereof liquid 17, which is generally less dense than the suspension liquid, will tend to float to the top of the mixture. Agglomerated first mixture 19 is thus removed from the top of agitator apparatus 16 to a separator 20, where the carbonaceous agglomerates are separated from the suspension liquids and unagglomerated non-carbonac`eous fine particles by size and/or density. Preferably, separator 20 is a sieve bend of an appropriate mesh size, e.g. 100 or 200 mesh Tyler, such as that manufactured by authority from DSN NV
Vedernaldse Staatsmijnen. Alternatively, other size separators such as sn elutriator, cyclone or splral separator, which i9 '' , . ':
"''` ' ' .
, ' ', "
- ` 11. ' - ~
' . .` .: - . .: .. ~ . `
` ~
~C~8Z6~73 commercially available, may be u~ilized. Alternatively, the carbonaceous agglomerates may be also separated in a float-sink tank where the carbonaceous agglomerates, which tend to float, are skimmed off by a rotating paddle through an overflow, while the water and unagglomerated non-carbonaceous fine particles, ~hich ~end to sink, are removed from the bottom o~ the tank as slurry 21 containing the non-carbonaceous fine particles and substantially free of carbonaceous fine particles and agglomerating liquid.
At this stage, separated carbonaceous agglomerates 22, which generally contain about 7 to 12 percent moisture, may be processed (not shown) by pelletizing into larger particulate. The agglomeratès may be pelletized to generally uniorm particle sizes of 0.05 to 0.75 inch in diameter by feeding the agglomerates to pelletizing disc or tumbler along with a binder liquid to form a second mixture and agitate said mixture. Alternatively, the agglomerates may be agitated, extruded or otherwise molded into pellets upon addition of a binder liquid to form said second mixture.
Binder liquids particularly suitable for this purpose are heavy hydrocarbons such as coke-oven coal tar, oil shale crude, petroleum crude or hèavy fuel oil such as Bunker C, which is pre~erably heated to, for example, 100C to increase fluidity.
The requirement for the binder liquid is that it be capable Of carbonizing and producing coherent pellets or granules in which the aggomerates are bonded together with sufficient strength to permit me~hanized pFocessing and handling without ~ ~
:::
12.
` ` ` ' ~82673 subs~antial crumbling. In this connection, it may be desirable that the product be subsequently oven dried at, e.g.
100C , to bond the binder to and within the agglomerates. An accelerator is also pref~erably included in the binder liquid to hasten bonding of the binder in shorter times and/or at lower temperatures.
Whether pelletized or not, separated carbonaceous agglome~ates 22 are circulated via a pipeline or the like to furnàce 23. In furnace 23 the carbonaceous agglomerates 21 are carbonized by heating to at least about hS0C. and preferably above 500C., and typically below about 900C.
Toward the end o the carbonizing cycle, carbonaceous . .
agglomerate~ are also pre~erably activated in furnace 23 by addition of steam 24. Alternatively, although not most preferred, carbon dioxide, flue gas, chlorine or similar gases or vapors may be utilized at high temperature or air at low temperature to selectively ox~dize and activate the carbonaceous agglomerates.
On completion of the carbonizing and activating cycles, .
`activated carbon 25 is removed from furnace 23 as a finished.
product. Activated.carbon 25 is a granular composit~on o~
Qubstantially uniform size an~ packing (density) and essentially spherical configuration. The size and packing of the !
granules can be controlled with relative precision by selection .
o the agglomerating liquid and control o~ ~he relativè amount (or percentage) of agglomerating liquid by weigh~ to the total solids content of the slurry that is used. The size and packing of the granules are also controlled to .a lesser extent by the rapidity and duration to which the mixture is agitated in the..
, ' ' ~' .
13. : -.
- .,. ~
~ , , ~LC382~73 agitation apparatus. Preferably, the various parameters are controlled so that the agglomerates are between .150 millimeter (~00 mesh Tyler) and 1.20 millimeter tl4 mesh Tyler) in size, which generally requires that the agglomerating liquid be between 2 and 10 percent by weight of the total solids content in the slurry and having an.~initial boiling point greater than The ~ollowing non-limiting specific examples are given illustrating performance of the present method for making activated carbon, EXAMPLE I
An aqueous coal slurry was formed from crushed non-coking coal having a particle size of less than .150 millimeter (100 mesh Tyler) and water. The slurry had a content of 10 to 40/O by weight of solids to water. .The coal slurry was mixed~
with a carbonaceous (hydrocarbon) liquid in the form of a heavy fuel oil. The quantity.of carbonaceous,liquid utilized was between 6 and 25% by weight of the solids in the slurry with which the liquid was mixed. The mixture was maintainèd at 100F.
while agitated within an apparatus as shown in Figure 2 of the 20 . drawings.
The coal slurry was lntroduced to the bottom oE a cylindrical tank 31 of agitator.apparatus 30 by way of inlet 32, while carbonàceous liquid 33 was introduced by way of inlet :
34. The resulting mixture is subjected to the agitating action.
of scrapper blades 35 and agitator blades 36 connected to ~
rotating shaft 37, which is'driven by power means (not shown). '.
' 1~. ' :, -- . .~ . .. : . . . ... .
~8Z673 Also connected to shaft 37 is inner cylindrical housing 38, which is provided to channel the mixture helically through the agitator apparatus 30.
Accordingly, coal slurry 29 is continuously fed into the bottom of housing 31 and subjected to rapid agitation as it flows upwardly between the inner rotating cylindrical housing 38 and the outer cylindrical housing 31.
As a result of the lyophilic action of the agglomerated liquid 33 and the agi~a~ion in the mixture, agglomerates 39 are formed within apparatus 30. The ~g~lomerates 3~ overflow from -the agitating apparatus 30 at the top over screened outlet ~0.
10 At outlet 40, the agglomerates 39 flow over screen 41 of appropriate mesh to provide for separation of the agglomerates from the water and non-carbonaceous (ash) fine particles. The agglomerates 39 are 1/16 to 1/4 inch in si.~e as they come into screen 41. The water and non-carbonaceous fine p~rticles pass through the screen 41 and are discharged through funnel 42.
Agglomerates of increased size and hardness as compared to the fines in the coal slurry were obtained by use of agitator apparatus 30. Also, the non-carbonaceous (ash) content of the agglomerates was reduced as compared to the content of the coal slurry entering the apparatus The results of this processing are shown in TABLE I below.
TABLE I
Percentage of Solids by Weight Sample oAsh Content of Ash Content of Carbonaceous Liquid Con-Coal Slurry Coal Slurry Agglomerates tent of Agglomerates 1 12.1 7.7 13.6 2 10.4 4.7 19.4
3 21.8 4.7 17.2
4 32.6 5.6 15.0 15. :
, ' ~ ,: ,; , : : , .. .
~ Z 67 ~
The agglomerates as above formed are then placed in an electric furnace and heated to 500C. until the agglomerates become dull red in color. Thereafter, steam is introduced into the ~urnace, and the heating continued at 500C. to compensate or the cooling effect of the steam. The separa~ed agglomerates are ~hus carbonized and the agglomerate~ activated in furnace 43. Agglomerating liquid 33 is volitilized in the process.
Activated carbon 45 in granular form is subsequently removed rom urnace 43.
EXAMPLE II
Coal slurry 29 was again introduced to apparatus 30 as above described while maintaining an operating temperature of room temperature rather than 100F. as used in connection with Example I. The agglomerating liquid 33 was changed by adding a light solvent to the heavy fuel oil to lower the viscosity of the liquids sufficient for operation at room temperature. The quantity of light solvent added was 10 to 15% by weight of the undiluted fuel oil used.
The mixing and agitation steps were perfor~ed in the same way as described in connection with Example I. And the ~0 carbonizing and activating steps in furnace 43 were performed as described in connection with Example I. The resulting activated carbon 45 again had a granular size of substantially uniform packing (hardness) and particle size, and had a high carbon content ~about 9~ percent) and internal surface area estimated to be about 3500 square feet per gram.
.
. .
. , --. - .
10826~3 . .
While the preferred embodiments of the invention have been specifically described, it is distinctly understood that ehe invention may be otherwise variously embodied and used within the scope of the ollowing claims.
` 17. ~ ~ :
-.,, ~ . . . . .
, ' ~ ,: ,; , : : , .. .
~ Z 67 ~
The agglomerates as above formed are then placed in an electric furnace and heated to 500C. until the agglomerates become dull red in color. Thereafter, steam is introduced into the ~urnace, and the heating continued at 500C. to compensate or the cooling effect of the steam. The separa~ed agglomerates are ~hus carbonized and the agglomerate~ activated in furnace 43. Agglomerating liquid 33 is volitilized in the process.
Activated carbon 45 in granular form is subsequently removed rom urnace 43.
EXAMPLE II
Coal slurry 29 was again introduced to apparatus 30 as above described while maintaining an operating temperature of room temperature rather than 100F. as used in connection with Example I. The agglomerating liquid 33 was changed by adding a light solvent to the heavy fuel oil to lower the viscosity of the liquids sufficient for operation at room temperature. The quantity of light solvent added was 10 to 15% by weight of the undiluted fuel oil used.
The mixing and agitation steps were perfor~ed in the same way as described in connection with Example I. And the ~0 carbonizing and activating steps in furnace 43 were performed as described in connection with Example I. The resulting activated carbon 45 again had a granular size of substantially uniform packing (hardness) and particle size, and had a high carbon content ~about 9~ percent) and internal surface area estimated to be about 3500 square feet per gram.
.
. .
. , --. - .
10826~3 . .
While the preferred embodiments of the invention have been specifically described, it is distinctly understood that ehe invention may be otherwise variously embodied and used within the scope of the ollowing claims.
` 17. ~ ~ :
-.,, ~ . . . . .
Claims (7)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A method of making activated carbon comprising the steps of:
A. dispersing carbonaceous and non-carbonaceous fine particles in a suspension liquid to form a slurry;
B. adding to the slurry a liquid lyophobic to the suspension liquid and the non-carbonaceous fine particles and lyophilic to the carbonaceous fine particles to form a mixture;
C. agitating the mixture to preferentially agglomerate said carbonaceous fine particles while the non-carbonaceous fine particles remains substantially unagglomerated in the mixture;
D. separating the agglomerated carbonaceous fine particles from the mixture;
E. carbonizing the separated agglomerated carbonaceous material; and F, activating the separated agglomerated carbonaceous material to form activated carbon.
A. dispersing carbonaceous and non-carbonaceous fine particles in a suspension liquid to form a slurry;
B. adding to the slurry a liquid lyophobic to the suspension liquid and the non-carbonaceous fine particles and lyophilic to the carbonaceous fine particles to form a mixture;
C. agitating the mixture to preferentially agglomerate said carbonaceous fine particles while the non-carbonaceous fine particles remains substantially unagglomerated in the mixture;
D. separating the agglomerated carbonaceous fine particles from the mixture;
E. carbonizing the separated agglomerated carbonaceous material; and F, activating the separated agglomerated carbonaceous material to form activated carbon.
2. A method of making activated carbon as set forth in claim 1 wherein:
steps E and F are performed at least partially concurrently by use of gas activation.
steps E and F are performed at least partially concurrently by use of gas activation.
3. A method of making activated carbon as set forth in claim 2 wherein:
steps E and F are performed by heating the separated agglomerated carbonaceous fine particles to at least 450°C.
in the presence of steam.
18.
steps E and F are performed by heating the separated agglomerated carbonaceous fine particles to at least 450°C.
in the presence of steam.
18.
4. A method of making activated carbon as set forth in claim 1 wherein:
the carbonaceous fine particles are coal and the non-carbonaceous fine particles are ash processed from non-caking coal.
the carbonaceous fine particles are coal and the non-carbonaceous fine particles are ash processed from non-caking coal.
5. A method of making activated carbon as set forth in claim 4 wherein:
steps E and F are performed at least partially concurrently by use of gas activation.
steps E and F are performed at least partially concurrently by use of gas activation.
6. A method of making activated carbon as set forth in claim 5 wherein:
steps E and F are performed by heating the separated agglomerated carbonaceous fine particles to at least 500°C.
in the presence of steam.
steps E and F are performed by heating the separated agglomerated carbonaceous fine particles to at least 500°C.
in the presence of steam.
7. A method of making activated carbon or set forth in Claim 1 wherein:
after separation the agglomerated carbonaceous fine particles and prior to carbonizing and activating, a carboniza-ble binder liquid is added to the agglomerates to form a second mixture and the second mixture agitated to pelletize the agglomerated carbonaceous fine particles.
19.
after separation the agglomerated carbonaceous fine particles and prior to carbonizing and activating, a carboniza-ble binder liquid is added to the agglomerates to form a second mixture and the second mixture agitated to pelletize the agglomerated carbonaceous fine particles.
19.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US59276275A | 1975-07-03 | 1975-07-03 | |
| US592,762 | 1975-07-03 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1082673A true CA1082673A (en) | 1980-07-29 |
Family
ID=24371963
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA256,143A Expired CA1082673A (en) | 1975-07-03 | 1976-07-02 | Method of making activated carbon |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPS595524B2 (en) |
| CA (1) | CA1082673A (en) |
| DE (1) | DE2629798C3 (en) |
| FR (1) | FR2316191A1 (en) |
| GB (1) | GB1504819A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4338943C2 (en) * | 1993-11-15 | 1997-07-10 | Basf Ag | Process for the production of carbon granules |
| JP5087550B2 (en) * | 2006-10-12 | 2012-12-05 | 株式会社キャタラー | Activated carbon, canister and intake system filter using the same, and method for producing the activated carbon |
| CN104401990A (en) * | 2014-10-27 | 2015-03-11 | 宁夏宝塔石化科技实业发展有限公司 | Preparation method for activated carbon special for mercury removal of flue gas |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1968845A (en) * | 1930-12-04 | 1934-08-07 | Jacque C Morrell | Process for producing activated carbon |
| US2008144A (en) * | 1932-07-22 | 1935-07-16 | Jacque C Morrell | Structural adsorptive carbon and process of making the same |
| FR777364A (en) * | 1934-08-06 | 1935-02-18 | Structural activated carbon and process for making it | |
| US3901823A (en) * | 1971-11-18 | 1975-08-26 | Westvaco Corp | Agglomerating activated carbon |
-
1976
- 1976-07-02 FR FR7620389A patent/FR2316191A1/en active Granted
- 1976-07-02 DE DE2629798A patent/DE2629798C3/en not_active Expired
- 1976-07-02 CA CA256,143A patent/CA1082673A/en not_active Expired
- 1976-07-02 GB GB27724/76A patent/GB1504819A/en not_active Expired
- 1976-07-03 JP JP51079393A patent/JPS595524B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS595524B2 (en) | 1984-02-06 |
| FR2316191B1 (en) | 1981-12-18 |
| DE2629798C3 (en) | 1980-09-04 |
| DE2629798B2 (en) | 1980-01-03 |
| JPS527893A (en) | 1977-01-21 |
| FR2316191A1 (en) | 1977-01-28 |
| DE2629798A1 (en) | 1977-01-20 |
| GB1504819A (en) | 1978-03-22 |
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