Patented Dec. 16, 1924.

1,519,470
UNITED STATES PATENT OFFICE.
ReBERT E. WILSON, OF CAMBRIDGE, MAssACHUSETTS, AND JOSHUAC. whETZEL, or
PITTSBURGH, PENINSYLVANIA.
IIPREGNATED CARBON AND PROCESS OF MAKING SAME.
No Drawing. Application filed January 22, 1921. Serial No. 439,245.
To all whom it may concern: ordinary charcoal has but little sorbing ac
Be it known that we, RoBERT E. WILSON tion. 55
and JosHUA C. WHETZE., of Canbridge, (2) If copper oxide or copper plus silver
Massachusetts, and Pittsburgh, Pennsyl oxides or copper plus zinc oxides constitute
vania, respectively, citizens of the United the impregnating agent, the presence of such
States, have invented new and useful Im basic constituent increases the value of the
provements in Impregnated Carbons and charcoal against acid gases such as phosgene, 80
Processes of Making Same, of which the foll because of their tendency to neutralize the
lowing is a specification. HCl set free. The service time against such
0 This invention relates to the impregna gases is easily increased 50% or more.
tion of carbonaceous material, such as char (3) The third advantage might be con
coal with metallic substances. sidered a negative one in that these ma 65
Charcoal, especially that which has been terials do not decrease the true sorbent ac
activated, has found extensive use in treat tion of charcoal for the relatively inert gases
5 ing and sorbing gases. One of the problems such as chloropicrin and mustard gas, which
which has receivedi considerable attention would result with the use of other types 70
in this art involves the treatment of the of impregnating agents.
charcoal so as to increase its efficiency as a The term “impregnated carbon' as ordi
gas sorbent. It has been proposed to im narily used is carbon such as charcoal, coke.
20 pregnate the charcoal with various agents lampblack, etc., which has been treated so
to accomplish this result. There are a great as to incorporate some other substance such 75
number of impregnating materials which as a metal or oxide into the particles, or
will increase the efficiency of charcoal pieces of carbon and produce a hard, stable
against either acid gases or oxidizable gases product. Such incorporation increases the
25 but will not serve for treatment of both of
availability of the metal or oxide of the
these kinds of gases. metal for a catalytic action, on account of
Among the objects of this invention is to the large surface exposed. Activated car 80
impregnate charcoal or other carbonaceous bon is preferable for the most successful
material with certain agents and in such a impregnation with metais or metallic oxides.
30 way as to get the benefit of the action of By activated carbon is meant carbon which
the agent, which is usually a catalytic oxi has been treated to make it more porous and 85
dizing action, without losing any of the highly absorbent than ordinary carbon.
sorbing value of the charcoal. Activated carbon may be produced by
Another object is to produce a hard, stable heating carbon, such as coal, coke, charcoal,
35 product and to increase the effectiveness of etc., in the presence of mild oxidizing agents
the impregnating agent by its proper dis such as steam, CO, etc., at temperatures
tribution among the particles and in the above 700° C. for several hours. If air 90
pores of the carbonaceous material, thereby is used as the oxidizing agent, the activation
producing a cheaper product and one which is carried on at lower temperature and for
40 will also stand up longer than the impreg a shorter time than when the milder oxidiz
nating agent itself. We have found that ing agents are employed. Carbon thus ac
certain metals and metallic oxides, especial tivated has many times the sorbing power 95
ly silver and silver oxide, copper and its of untreated carbon.
oxides and zinc oxide, are especially well There are a wide variety of methods by
45 adapted to the above mentioned purposes.
which these metals or metallic oxides may
The advantages of impregnating charcoal be incorporated in the carbon, and the re 100
with such metals and oxides are as follows: sultant products have very similar desirable
(1) The greatest benefit is due to increas properties providing care is taken to elimi
ing the catalytic action of the charcoal, nate all soluble salts or organic matter, and
30 which in the case of silver or copper or their to deposit the material in such a way that
oxides results in an increase of 1,000 or it will not be removed by abrasion. Among 105
more per cent in the service time against . the methods which may be used are the pre
such oxidizable gases as arsine for which cipitation of the hydroxides on the carbon
 1,519,470
in aqueous solution, followed by subsequent salt and the latter is reduced by the action
of the charcoal itself at the high tempera
Washing and drying; sublimation of the
metals or oxides and condensation on the ture. This process gives very good results in
carbon; impregnation with a decomposable the case of the nitrate, where oxides of ni
salt of the metal (such as the nitrate) and trogen are driven off. The sulphate works 70
heating to the temperature required for well only in the presence of an excess of air
complete decomposition; the reduction of as copper
to otherwise, some ofwhich
sulphide the sulphate is reduced
injures the sorbing
the metal from a solution of a salt by means properties of the charcoal. In the presence 75
of reducing materials present in or added of air, however, this can be carried out but
to the carbon.
The amounts of impregnating materials there is some loss of charcoal due to oxida
which are used depend upon the purpose tion.
for which the final material is to be em Among the uses for which impregnated
ployed. For catalytic oxidation alone, and coated carbon are of value, the following 80
amounts much less than 1% are practically willCarbon serve as illustrations:
as good as larger amounts; but for reacting lic oxides impregnated with metals or metal
has a high sorbing power or sorp
with acid gases such as phosgene, amounts tive activity for certain gases such as
up to 10 or 12% are desirable. If the char
coal is highly activated, even 10 or 12% chlorine, arsine, phosgene, hydrocyanic acid, 85
will not interfere with its sorbent action, carbon monoxide, cloride of sulphur, etc.
but less active charcoals suffer in this respect Carbon impregnated with certainmetals or
oxides also serves as a most excellent cataly
if the metal or oxide content is increased Zer. The impregnated carbon holds the
beyond 6 or 8%. metal or metallic oxide or both in a porous, 90
For many purposes the preferred material finely divided state. This condition pro
for impregnation of the charcoal is metallic motes chemical activity, and the fine pores
copper or oxides or mixtures of same, and of the metal or oxides together with the fine
in the following specific examples the proc pores of the carbon will
ess employing these materials will be given to react with or combinecause with
certain gases
each other 95
as indicative
30 vention.
of the application of this in under certain conditions.
(1) Charcoal is impregnated with a solu A carbon special use which has been found for
tion of a copper salt, preferably the sulphate the impregnated with metals or
or nitrate. The excess solution is drained oxides is in the removal of phosphine or
arsine from gas mixtures such as ammonia, 100
off and then caustic soda is added to precip acetylene,
itate copper hydroxide in the pores of the monia, or acetylene. etc. or mixtures containing am
charcoal. The charcoal is then washed to Under proper condi
free it from sodium sulphate or other soluble tions, the phosphine and arsine may be
impurities and subsequently dried. Certain quantatively oxidized while the other gases
which are present undergo little or no oxida 105
objections incident to this method are losses tion. It is thus seen that by means of these
of copper on account of excessive precipita impregnated
tion on the outside of the charcoal granules and removal ofcharcoals, selective oxidation
undersirable substances such
and the difficulty of washing out the sodium as arsine and phosphine from gases may be
Salt and free alkali.
(2) Charcoal is impregnated with the brought about. Under these conditions the 10
copper salt and then iron filings, zinc dust or impregnated carbon acts as a catalytic oxi
dizing agent and may also serve as a sorbent
other finely divided metal electro positive to for other gases because the insolubility of
copper
stirringis orscattered
raking.thereon with continued
Electrolytic the impregnating material prevents inter
action ference
causes the copper to precipitate on the sur with the sorptive capacity of the car 115
0. face and in the pores of the charcoal bon for neutral gases. rdinary soluble
granules and to adhere very firmly. The E. with the sorptive properties of theinter
catalyzers introduced into charcoals
char
zinc or iron Sulphate or other salts may be CO
then washed out with hot water and the
material dried preferably at a fairly high The present invention is not limited to the 120.
5 temperature, for example 300°C, in the pres specific details set forth in the foregoing
ence of a small amount of air to complete examples lustrative
which should be construed as ill
and not by way of limitation, and
the removal of the sulphate. in view of the numerous modifications which
(3) In this method the copper is reduced may be effected therein without departing 25
by organic or inorganic reducing agents
30 such as sugar, formaldehyde, etc. There are from the spirit and scope of this invention,
a great number of reducing agents suitable it is desired that only such limitations be
for this purpose. In this process it has been imposed as are indicated in the appended
found that an ammoniacal solution of copper. claims.
55
gives very good results. Claims:
1. Hard, stable, sorbing
-"
material, com 130
(4) Charcoal is heated up with the copper
 1,519,470
prising carbon impregnated with material comprising carbon impregnated with ma
containing metal and metal oxide.
2. Hard, stable, sorbing material, com
prising activated carbon impregnated with
material containing metallic material.
3. Hard, stable, sorbing material, com
prising activated carbon impregnated with
material containing metal and metallic
oxide.
0 4. Hard, stable, sorbing material, com
prising carbon impregnated with material
containing copper.
5. Hard, stable, sorbing material, com
prising activated carbon impregnated with
5 material containing copper.
6. Hard, stable, sorbing material, com
prising activated carbon impregnated with
material containing copper oxide.
7. Hard, stable, catalytic, oxidizing agent,
20
terial containing copper and copper oxide.
8. Hard, E. catalytic, oxidizing agent,
comprising activated carbon impregnated
with material containing copper and copper
oxide. 25
9. Hard, sorbing, catalytic material, com
prising carbon impregnated with material
containing copper, copper oxide, silver and
silver oxide.
10. In a process of producing a sorbing, 30
catalytic oxidizing agent, impregnating act
tivated carbon with a salt of a metal and
then converting the metallic salt into a prod
uct comprising the metal by adding another
finely divided metal thereto, the latter be 35
ing electro positive to the first metal.
ROBERT E. WILSON.
JOSHUA. C. WHETZEL,