United States Patent [191 [11] E Re.

31,093
Tolles et a1. [45] Reissued Nov, 30, 1982

[54] PROCESS FOR MAKING ACTIVATED 1,505,496 8/1924 Rohde ..... .. .... .. 252/425

CARBON WITH CONTROL OF METAL ION 1,520,437 12/1924 Pipkin ..... .. 252/447
CONCENTRATION IN PHOSPHORIC ACID 1,520,801 l2/ 1924 Bonnard 252/425
1,619,649 3/1927 Bonnard .. 252/425
[75] Inventors: Edward D. Tolles, Charleston, SC; 1,788,466 l/193l Lourens .... .. 252/423
Robert L. Stallings, Cary, NC; 2,008,145 7/1935 Morrell . . .. . . _ . . .. 252/421

Charles E. Miller, Mt. Pleasant, SC. 2,441,125 5/1948 Berl . . ... . . . ... . . . . . . . . .. 252/425

2,835,343 5/1958 Wolff et al. .... .. 252/447

[73] Assignee: Westvaco Corporation, New York, 3,066,099 11/1962 Mohun ...................... .. 252/445
N.Y. 3,168,485 2/1965 Knobloch et a1. .. 252/444
3,479,300 ll/ 1969 Riven et a1. ......... .. 252/430
[21] Appl. No: 270,371 3,492,244 1/1970 Fujiwara et al. . 252/425
[22] Filed: Jun. 4, 1981 3,764,561 10/1973 Nishino et a]. ...... ..
3,835,064 9/1974 Shinomiya et a1. .... .. 252/423
3,923,689 12/1975 Boughten etal. .. . . . . . . .. 252/444
Related US. Patent Documents 3,950,267 4/ 1976 Arakawa et a1. ... . . . . . . .. 252/445

Reissue of: 4,075,282 2/ 1978 Storp et a1. ....................... .. 252/444

[64] Patent No: 4,155,878 Primary Examiner-P. E. Konopka
Issued: May 22, 1979
Appl. No.: 904,696 Attorney, Agent, or FirmTerry B. McDaniel; Richard
L. Schmalz
lFiled: May 10, 1978
[51] lint. 1131.3 ..................... .. C01B 31/12; B011 20/20; [5 7] ABSTRACT
B01J 21/18 A process for improvement of wood-base active carbon
[52] US. Cl. ................................... .. 252/423; 252/425 made in the presence of phosphoric acid is disclosed
[58] liieid of Search .............. .. 252/423, 425, 445, 447 herein. The improvement comprises controlling the
[56] References Cited amount of dissolved salts of the group sodium, potas
sium, calcium and magnesium in the process acid to
U.S, PATENT DOCUMENTS
provide a metal ion concentration from 0.5% to 2.0%
29,560 8/1860 Belton ............................... .. 252/425 by weight. The controlled addition of these metal salts
252/425 improves the adsorptivity for fuel vapors and the decol
1,286,187
1,250,228 11/1918
12/1917 Mumford
Rule et a1. ...... .. ..
.. 252/425
1,383,755 7/1921 Punnett et a]. 252/425
orizing activity of the carbon.
1,438,113 12/1922 Hudson ......... .. 252/423
1,502,592 7/1924 Sauer ................................. .. 252/425 6 Claims, No Drawings
 Re. 31,093
1 2
PROCESS FOR MAKING ACTIVATED CARBON DETAILED DESCRIPTION OF THE
WITH CONTROL OF METAL ION INVENTION
CONCENTRATION IN PHOSPHORIC ACID In the production of activating carbon, a suitable
granulated cellulosic source material such as sawdust,
Matter enclosed in heavy brackets [ ] appears in the ground wood, pulp or bark is saturated with phosphoric
original patent but forms no part of this reissue speci?ca acid and simultaneously carbonized and activated at
tion; matter printed in italics indicates the additions made 800 F. to l,300 F., preferably 1,000 F. to 1,050 E,
by reissue. for approximately 15 minutes to 1 hour in an activation
furnace to drive off volatiles.
BACKGROUND OF THE INVENTION Following furnace activation, the activated carbon
containing residual phosphoric acid is washed with
(1) Field of the Invention water to remove this acid and the carbon product is
The present invention relates to a process for improv subsequently dried.
ing the properties of wood-base carbon activated in the 15 The wash water is retained and evaporatively con
presence of phosphoric acid. More particularly, this centrated for acid recovery and recycle. This acid
invention relates to controlling the amount of certain carries with it certain metal ions extracted from the
metal salts dissolved in the process acid. wood; and with repeated use, metal concentrations
(2) Description of the Prior Art gradually increase in this acid.
In the production of activated carbon from wood, 20 In the activation of sawdust at an optimum tempera
sawdust is mixed with various chemical agents, carbon ture of about 1,000 F., the phosphoric acid probably
ized and often subsequently activated by gas reactions. serves to protect against cracking or disproportionation
Wood-base carbons have been used for decolorizing by of cellulosic or other components of the wood which
contacting solutions with the activated carbon. One 25 would produce small molecular groups tending to evap
orate as vapors or tars. As carbonization proceeds
such example appears in U.S. Pat. No. 1,383,755 under these conditions, the wood material undergoes
wherein alkali metal sulfates were added to sawdust and structural changes ultimately resulting in a high-porous
other materials to assist in activation. Another use for
activated carbon.
carbons is in the gas phase for adsorption of hydrocar It was found that the adsorption properties of the
bon vapor. An example of this type of carbon is de 30 activated product are highly dependent upon the con
scribed in U.S. Pat. No. 3,764,561. centration of dissolved Na+,K+,Mg++, and Ca++ in
These and other patents have sought to improve one the process acid. For example, as the concentration of
adsorbing property or another using varied techniques these ions increases from 0% to at least 4% of the acid
including the application of metal salts. The use of such weight, the adsorptivity for fuel vapors as measured by
metals is generally characterized by large proportions 35 the Butane Working Capacity (BWC) test monotoni
of salt relative to the wood, high temperatures (around cally decreases. Also, as the metal ion content increases
1,800 E), and frequently contact with oxidizing gases from 0% to about 23%, (relative to the acid) the decol
at l,500-l,800 F. orizing ability increases as measured by the Decoloriz
Activated carbon can also be made from wood by ing Index (D1) or Molasses Value (MV) test. As the
carbonizing it in the presence of phosphoric acid at concentration increases above this level, the decoloriz
temperatures around 800-l,300 F. It has now been
ing ability then decreases. The presence of these metal
ions in the process acid can be the result of accumula
found that by controlling the amount of certain dis tive extraction from the wood itself or can be due to
solved metals in this process acid during heat treatment, intentional addition of acid soluble metal salts.
activated carbons having desirable decolorizing ability 45 Thus, a product showing satisfactory performance by
and desirable gas adsorbing ability, or both, may be both BWC and DI tests may be obtained by controlling
obtained. the metal ion content in the process acid at concentra
It is, therefore, the general object of this invention to tions between 0.5% and 2% relative to the acid. This is
provide a process for improving the decolorizing ability equivalent to about 0.35-l.4% relative to sawdust.
and the gas adsorbing ability of wood-base activated 50 Experiments have shown that the carbon product
carbon produced in the presence of phosphoric acid. using pure phosphoric acid has a very high BWC.
Another object of this invention is to provide an This is determined by a test which measures the amount
improved process for producing wood-base activated of butane which can be purged from carbon with air
carbon by controlling the amount of dissolved metal under certain flow conditions after the carbon is
salt in the process acid during activation. 55 presaturated with this vapor. This property is related to
Other objects, features, and advantages will be evi performance in fuel evaporation control. It is likely that
dent from the following detailed description of the good performance in this test results from the develop
invention. ment of pores which are of optimum size for adsorption
and desorption of butane under the test conditions.
SUMMARY OF THE INVENTION When even small amounts of such metal ions as
It has been found that controlling the amount of dis Na+,K+,Ca+, and Mg++ are present, the resultant
carbon shows poorer BWC. It is suspected that the
solved metal salts from the group consisting of sodium, metal ions catalyzed oxidation of the carbon material
potassium, magnesium, calcium and mixtures thereof in under the process conditions and enlarge the pores
the process acid to provide a metal ion concentration 65 beyond the optimum size.
between 0.5% and 2.0%, preferably 0.6% to 1.0%, by It is also believed that the decolorizing ability of the
weight of acid improved the adsorbing activity for both carbon increases because of this pore enlargement. Ac
decolorizing and gas phase adsorption.v cording to this concept, the optimum pore size for liq
 Re. 31,093
3 4
uid decolorization is larger than that for vapor phase While the invention has been described and illus
BWC. This size is thought to be promoted under the trated herein by references to various speci?c materials,
process conditions by metal ion concentration of about procedures and examples, it is understood that the in
23%. At higher concentrations, the optimum is ex vention is not restricted to the particular materials,
ceeded; and D1 or MV is observed to decrease. combinations of materials, and procedures selected for
The presence or absence of residual metals in the that purpose. Numerous variations of such details can
carbon product is not believed to affect adsorption be employed, as will be appreciated by those skilled in
signi?cantly. For the most part, these metals are re the art.
tained in the acid which is washed off. The importance What is claimed is: '
of the metal is thought to lie in the effect of its ions on 0 1. In a process for producing wood-base active car
the activation mechanism. bon by the steps of treating a wood material with phos
In summary, it is believed that pore size development phoric acid at a temperature between 800 F. and 1,300
and associated adsorption properties are sensitive to the F. and recovering and recycling the phosphoric acid
presence of critical amounts of the metal ions during wherein the wood material contains one or more salts
carbonization/activation of wood by the action of phos selected from the group consisting of sodium, potas
phoric acid at temperatures between 800 F. and l,300 sium, calcium and magnesium salts and mixtures
F. Therefore, the adsorption properties related to BWC thereof, the improvement comprising maintaining the
and DI can be controlled by controlling the amount of concentration in the phosphoric acid of metal ions from
these metals present during activation. the group consisting of sodium, potassium, calcium and
In order to more clearly illustrate the present inven magnesium between 0.5% and 2.0% by weight of the
tion, the following example is set forth: acid.
2. The process according to claim 1 wherein the
EXAMPLE activating temperature is between l,000 F. and 1,050
Sawdust at 42% moisture content was mixed with P.
phosphoric acid at an acid to sawdust ratio of 1.4:1. The 3. The process according to claim 1 wherein sawdust
amount of potassium ions in the phosphoric acid was is the starting material for said wood-base carbon.
measured by a Model 330 Perkin-Elmer Atomic Ad 4. The process according to claim 1 wherein the
sorption Spectrophotometer. The activating tempera [metal ion concentration in the phosphoric acid is main
ture was l,050 F. at a residence time of 45 minutes. The tained between [1.0% and 1.5%] 0.6% and 1.0% .
purpose of this run was to see if the DI could be in 30 5. The process according to claim 1 wherein said
creased while still maintaining BWC above 9.0. It was metal ion is sodium.
found that when the concentration of potassium ion was 6. The process according to claim 1 wherein said
maintained between 0.5% and 2.0% that the BWC re metal ion is potassium.
R * ll 11 *
mained above 9 and the DI was between 14 and 32.5.
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