U.S. patent application number 12/265109 was filed with the patent office on 2009-06-04 for device and method for converting carbon containing feedstock into carbon containing materials having a defined nanostructure.
This patent application is currently assigned to TIMCAL SA. Invention is credited to Frederic Fabry, Francis Fischer, Gilles Flamant, Lauent Fulcheri, Eusebiu Grivei, Patrick Leroux, Jean-Yves Peroy, Nicolas Probst, Richard Smet.
Application Number | 20090142250 12/265109 |
Document ID | / |
Family ID | 8169847 |
Filed Date | 2009-06-04 |
United States Patent
Application |
20090142250 |
Kind Code |
A1 |
Fabry; Frederic ; et
al. |
June 4, 2009 |
DEVICE AND METHOD FOR CONVERTING CARBON CONTAINING FEEDSTOCK INTO
CARBON CONTAINING MATERIALS HAVING A DEFINED NANOSTRUCTURE
Abstract
Apparatus and process for producing carbon black or carbon
containing compounds by converting a carbon containing feedstock,
comprising the following steps: generating a plasma gas with
electrical energy, guiding the plasma gas through a venturi, whose
diameter is narrowing in the direction of the plasma gas flow,
guiding the plasma gas into a reaction area, in which under the
prevailing flow conditions generated by aerodynamic and
electromagnetic forces, no significant recirculation of feedstock
into the plasma gas in the reaction area recovering the reaction
products from the reaction area and separating carbon black or
carbon containing compounds from the other reaction products.
Inventors: |
Fabry; Frederic; (Le Cannet,
FR) ; Grivei; Eusebiu; (La Hulpe, BE) ;
Probst; Nicolas; (Brussels, BE) ; Smet; Richard;
(Aartselaar, BE) ; Peroy; Jean-Yves; (Angoustrine,
FR) ; Flamant; Gilles; (Llo, FR) ; Fulcheri;
Lauent; (Mouans-Sartoux, FR) ; Leroux; Patrick;
(LeCannet, FR) ; Fischer; Francis; (Sins,
CH) |
Correspondence
Address: |
FINNEGAN, HENDERSON, FARABOW, GARRETT & DUNNER;LLP
901 NEW YORK AVENUE, NW
WASHINGTON
DC
20001-4413
US
|
Assignee: |
TIMCAL SA
|
Family ID: |
8169847 |
Appl. No.: |
12/265109 |
Filed: |
November 5, 2008 |
Related U.S. Patent Documents
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
|
|
10380647 |
Sep 22, 2003 |
7452514 |
|
|
PCT/EP01/10835 |
Sep 19, 2001 |
|
|
|
12265109 |
|
|
|
|
Current U.S.
Class: |
423/449.1 |
Current CPC
Class: |
C01B 2203/1695 20130101;
C01B 3/26 20130101; C01B 2203/0861 20130101; C09C 1/485 20130101;
B01J 19/088 20130101; B01J 2219/0236 20130101; B01J 2219/0892
20130101; C01P 2006/19 20130101; B01J 2219/0227 20130101; B01J
2219/0886 20130101; B01J 19/02 20130101; C01B 2203/0277 20130101;
B01J 2219/0839 20130101; C01B 3/22 20130101; C01B 2203/1047
20130101; B82Y 30/00 20130101; B01J 2219/0894 20130101; B01J
2219/0884 20130101; B01J 2219/0811 20130101; C01B 2203/1052
20130101; B01J 2219/0883 20130101; B01J 2219/0898 20130101; C01B
2203/1235 20130101; B01J 19/26 20130101; B01J 2219/0869
20130101 |
Class at
Publication: |
423/449.1 |
International
Class: |
C01B 31/00 20060101
C01B031/00 |
Foreign Application Data
Date |
Code |
Application Number |
Sep 19, 2000 |
EP |
00120115.1 |
Claims
1-10. (canceled)
11. A carbon black having a negative difference between nitrogen
surface area and CTAB (cetyltrimethyl ammonium bromide) surface
area, and an intrinsic density of less than about 1.9
g/cm.sup.3.
12. The carbon black of claim 11, wherein the intrinsic density is
from about 1.5 to about 1.8 g/cm.sup.3.
13. The carbon black of claim 11 having a nitrogen surface area is
from about 5 to about 150 m.sup.2/g and a DBP (dibutyl phthalate
oil) absorption from about 30 to about 300 ml/100 g.
14. The carbon black of claim 11 having a porosity defined by the
following range: -20 M.sup.2/G.ltoreq.N.sub.2SA-CTAB SA<0
M.sup.2/G.
Description
[0001] This application is a divisional of U.S. patent application
Ser. No. 10/380,647, now U.S. Pat. No. 7,452,514, which has a
.sctn. 371 compliance date of Sep. 22, 2003, which is the U.S.
national phase of international patent application No.
PCT/EP01/10835 (WO 02/24819 A1), filed Sep. 19, 2001, which claims
priority to European Patent App. No. 00120115.1, filed Sep. 19,
2000, all of which are incorporated herein by reference in their
entireties for all purposes.
TECHNICAL FIELD
[0002] A process and an apparatus are disclosed for converting
carbon containing feedstock into carbon black or other carbon
containing materials, having a defined nanostructure.
[0003] More than 99% of the carbon black is presently produced by
incomplete combustion processes. By far, the dominant process is a
furnace process developed sixty years ago. Other processes include
channel, thermal and lamp processes. All these industrial processes
are characterized by the combustion of about 40% to 60% of the
feedstock or raw material to generate the necessary heat to crack
the rest of the feedstock. Even though more than 100 different
grades of carbon black are currently offered by commercial
manufacturers, each grade has different specifications and
properties designed to suit particular applications. Further, the
production of new materials is limited by the process chemistry,
i.e., chemical composition and available energy.
[0004] About six million MT (metric tons) of carbon black are
produced worldwide annually. The raw materials used as feedstock
include decant oil for the low quality material (tire
manufacturing), pyrolysis fuel oil (PFO) and coal tar distillates.
Self-decomposition of acetylene is performed to produce high carbon
black grade (40,000 MT) mainly used in battery manufacturing.
Pollutant emission resulting from the 12 million MT of oil used to
produce the carbon black is 22 million MT CO.sub.2 and millions of
MT of SO.sub.x and NO.sub.x.
[0005] PCT/NO92/00196 and PCT/NO96/00167 disclose DC carbon
electrode plasma reactors which produce hydrogen as a primary
product and carbon black material as a secondary product. No
evidence has been given that these processes can produce carbon
black on a commercial scale.
[0006] PCT/EP94/00321 discloses a plasma reactor with three
electrodes, creating a compound arc by applying an AC current to
the electrodes. The feedstock is fed into the reactor by passing it
through an arc zone. According to this disclosure, the reaction
zone, wherein the feedstock is converted into carbon compounds.
Namely into carbon black, is directly below and adjacent to the arc
zone. The feedstock at least partly circulates through the arc
zone. The carbon black produced by this process is a mixture of
carbon materials originated by the various heat treatments. This
process allows the production of different carbon black materials
with different nanostructures.
SUMMARY OF THE DISCLOSURE
[0007] A process and apparatus are disclosed for producing carbon
black with well-defined properties, allowing control of operating
conditions and process parameters to obtain high conversion
efficiency of feedstock and reproducible product quality.
[0008] Furthermore, a new carbon black material is also
disclosed.
[0009] The control of the operating conditions for the production
of carbon black with well-defined properties includes the
preventing of circulation of the feedstock and any products through
the arc zone thus producing carbon black materials with well
defined and consistently reproducible properties. In particular a
venturi allows a better control of the reaction temperature and a
more efficient mixture in the "low temperature region" of the
reaction zone, where the carbon black is produced.
[0010] The process and apparatus work with inexpensive and readily
available carbon containing feedstocks. More specifically,
materials with low combustion enthalpy, e.g., below 80 BMCI (Bureau
of Mines Correction Index), including recycling oil from tire
pyrolysis, can be used as feedstocks.
[0011] One disclosed process comprises: creating a plasma by
directing plasma gas through an electric arc; passing or guiding
the plasma gas through a venturi zone, whose diameter narrows into
a throat in the direction of the plasma gas flow; passing or
guiding the plasma gas into a reaction zone, having a diameter
greater than the throat of the venturi zone; injecting the
feedstock into the plasma gas in the reaction zone downstream of
the venturi zone (after it has passed the throat of the venturi
zone); extracting the reaction products from the reaction zone; and
recovering the carbon black. It is also possible to inject the
feedstock into the throat of the venturi and/or slightly above the
venturi.
[0012] The carbon black is separated from the other reaction
products and has a defined nanostructure. This nanostructure
morphology and texture depends on the operating conditions and are
therefore controllable.
[0013] The plasma gas is injected into the reactor space, not
necessarily through the plasma arc. In a preferred embodiment, the
electric arc is a compound arc, created by at least three
electrodes. Preferably, the electrodes are graphite based
electrodes and the arc is created by connecting a sufficient AC
power source to the electrodes. The current frequency can be the
frequency of the grid using a conventional power source (50-60 Hz)
or it can be higher using a high frequency power switching source.
An increase in the frequency can increase the arc stability,
particularly when using hydrogen as the plasma gas. In this case,
the current frequency is preferably between 500 Hz to 10 kHz.
[0014] The venturi preferably is made from a graphite based
material and is formed as a cone. The downstream side of the
venturi is preferably formed as an edge and therefore building an
abruptly expanding zone. An edge between the throat and the
abruptly expanding zone causes an abrupt expansion of the plasma
gas volume. This is the preferred means to prevent back-flow of
carbon containing material into the area upstream of the venturi
zone outlet, particularly into the plasma forming region, e. g.,
into the arc or arcs. The expanding zone also generates a high
turbulence zone in the flow that is used to increase the mixing
efficiency between the plasma flow and the feedstock and to realize
a homogeneous mixture and a better control of the reaction
temperature.
[0015] The feedstock may comprise or consist of methane, acetylene,
ethylene, propylene, C.sub.4-hydrocarbons including butadiene,
light or heavy oil, even waste oil and/or pyrolysis fuel oil (PFO),
as well as any other material comprising carbon and mixtures of the
above. Preferably, essentially no oxygen or oxygen containing
materials are fed into the arc or into the reactor. Feedstocks
containing limited amounts of oxygen in the molecule, e.g. with an
atomic ratio of oxygen:carbon of up to 1:6 could be used.
[0016] Preferably, the plasma gas is injected axially above the
electrodes, in order to pass directly through the arc. The plasma
gas itself may preferably comprise or consist of hydrogen,
nitrogen, carbon monoxide, argon, helium or any other suitable gas
as well as any mixture of the preceding materials, e.g. a mixture
of up to 50 vol % CO and hydrogen. The off-gas contains in addition
to the plasma gas components essentially solely hydrogen, methane,
acetylene and ethylene and thus is relatively independent of the
hydrocarbon feedstock. If oxygen compounds are used, some CO and a
very small amount of CO.sub.2 are contained in the off-gas.
[0017] Preferably, a part of the off-gas is recycled and used as
plasma gas. This is particularly advantageous, if the recycled
off-gas is composed essentially solely of hydrogen and traces of
hydrocarbons.
[0018] The temperature in the reaction zone is controlled
preferably within a range between 900.degree. C. and 3000.degree.
C., by adjusting the plasma gas flow rate, the electrical energy
and the feedstock flow rate.
[0019] The feedstock is injected through at least one injector,
preferably through two to five injectors. These injectors can be
distributed equally around the circumference of the reaction zone.
The injection of the feedstock can be radially inwards towards the
center of the plasma gas flow or with a substantial tangential
and/or axial component into the outer zone of the plasma gas flow
or the reaction zone to generate a vortex-like flow. The injection
rate is adjusted to the desired reaction temperature depending on
the flow of the hot plasma gas and the nature of the feedstock. A
preferred range is from about 1 to about 10 kWh in the plasma gas
per about 1 kg of carbon in the feedstock.
[0020] The reaction products are of a specifically good quality,
when the process is performed without the use of oxygen.
[0021] In one embodiment, carbon black and hydrogen are produced as
useful products. The disclosed process allows the production of a
variety of products.
[0022] A disclosed method is preferably performed in a reactor for
converting feedstock, comprising carbon within a plasma into carbon
compounds having a defined nanostructure. The method is carried out
in a reactor comprising: [0023] (a) a head portion comprising at
least two electrodes and a plasma gas supply, for creating an
electric arc between the electrodes when a sufficient electric
power is supplied, thus creating an arc zone, [0024] (b) a venturi
portion and [0025] (c) a reaction chamber, comprising at least one
feedstock injector, wherein the venturi portion is placed between
the arc zone and the feedstock injector and narrows towards the
reaction chamber.
[0026] The reactor is preferably of cylindrical shape. The chamber
itself, at least at its inner surface, may be preferably made from
graphite containing material.
[0027] When producing nanostructured carbon material with a
disclosed process, one finds that the structure and quality of the
reaction products depends completely on the process parameters,
mainly on the reaction temperature and on the residence time, but
is surprisingly quite independent of the feedstock. This is the
reason, why even methane or waste oil or various feedstock mixtures
can be used to create high quality carbon materials with a defined
nanostructure.
[0028] The carbon black disclosed herein is characterized by having
a negative difference (commonly called "porosity") between nitrogen
surface area (N.sub.2SA) and the specific surface area of the
carbon black excluse of area contained in micropore, to small to
admit (cetyltrimethyl ammonium bromide or CTAB) or the CTAB surface
area (CTABSA), and an intrinsic density below 1.9, preferably below
1.8, particularly between 1.5 and 1.9 g/cm.sup.3. Thus,
N.sub.2SA<CTAB SA
especially:
-20 m.sup.2/g.ltoreq.N.sub.2SA-CTAB SA<0 m.sup.2/g.
[0029] The preferred carbon black has a nitrogen surface area from
5 to 100 m.sup.2/g and a DBP (di-butyl phthalate oil) absorption
from 30 to 300 ml/100 g. The use of CDBP below refers to DBP
absorption with a compressed sample.
[0030] The disclosed carbon black has the advantage of having a low
density. In, e. g., tire applications, this results in a reduction
of the needed weight of carbon black and in an overall weight
reduction of the final rubber product. Another application of the
new carbon blacks lies in dry cell electrodes.
[0031] The various properties of the carbon black herein claimed
and illustrated are measured by the following standard
procedures:
TABLE-US-00001 Nitrogen surface area (N.sub.2SA): ASTM D3037-93
CTAB SA: ASTM D3765-92 DBP absorption: ASTM D2414-93 CDBP
absorption: ASTM D3493 Intrinsic density by Xylene DIN 12797 (2.5 g
carbon black at 15 torr) Iodine number ASTMD 1510 Sulfur content:
ASTM D 1619 Ash content: ASTM D1506 pH: ASTM D1512 Toluene
discoloration ASTM D1618
BRIEF DESCRIPTION OF THE DRAWINGS
[0032] Additional features and embodiments are described in the
following detailed description and with reference to the drawings
herein.
[0033] FIG. 1 illustrates schematically a complete reactor set-up
for performing the disclosed method; and
[0034] FIG. 2 is a detailed view of the upper part of the reactor
of FIG. 1.
DETAILED DESCRIPTION
[0035] FIG. 1 shows the reactor 1 comprising a reactor chamber 2 of
cylindrical shape, the interior walls are made out of graphite. The
head section 3 of the reactor defines the upper end. Three
electrodes 8 are mounted at the head section 3, are connected to a
power supply 4, being able to deliver a three phase AC current. The
current frequency can be the network frequency (50 to 60 Hz) or any
higher frequency. The lower end of the reactor chamber 2 is
connected to extraction means 5, through which the reaction
products are removed from the reactor. These are directed to
standard separation means 6 e.g. cyclones and/or filters, wherein
the carbon black is separated from hydrogen and other reaction
products.
[0036] A more detailed view of the upper part of the reaction
chamber 2 is shown in FIG. 2. Plasma gas, preferably hydrogen,
nitrogen, carbon monoxide, argon or a mixture thereof is fed into
the reaction chamber 2 through the centre of head section 3 via an
inlet 7. The plasma gas flow rate was adjusted depending on the
nature of the plasma gas and the electrical power between about
0.001 Nm.sup.3/h and about 0.3 Nm.sup.3/h per kW of electric power.
Three graphite electrodes 8 (two are shown in FIG. 2), connected to
the power supply 4, are mounted to the head section 3. The tips of
these electrodes are close enough together to ignite an electric
compound arc in the presence of the plasma gas, when a sufficient
power source is connected to the electrodes. As a result, a plasma
is created within the arc zone 9. The temperature of this plasma is
controlled by the plasma gas flow and the electric power, supplied
to the electrodes 8. The arc zone may be optically controlled
through an opening 15. This allows an automatic control of the
temperature and/or the quantity of the plasma gas flowing into the
reaction zone.
[0037] Below the arc zone 9, a venturi element 11, made of
graphite, is located inside the reactor 1. The speed of the plasma
gas flow is increased when passing the narrow passage or throat 20
of the venturi element 11.
[0038] The plasma gas then enters the reaction zone 10 after
passing the venturi element 11 expanding abruptly, as the lower end
of the venturi is formed as a sharp edge and not as a continuous
widening section. Into the reaction zone 10, the feedstock is
injected through an injector 13, located within the wall 12 of the
reactor chamber 2 just below the venturi 11. The injection of the
feedstock after the venturi improves the mixing between the plasma
gas and the feedstock.
[0039] Preferably, the feedstock is injected through 2 to 5
injectors 13 directly or radially towards the center of the
reaction zone 10. Alternatively, the feedstock may also be injected
in a more tangential manner, thus entering the reaction zone 10 off
centre or with a certain angle co or contra-flow.
[0040] The energy, necessary to control depends upon the reaction
process, the flow rate and nature of the feedstock, and is
controlled via the plasma gas temperature and/or the plasma gas
flow and the power, supplied to the electrodes 8 by the power
supply 4.
[0041] The pressure preferably is slightly above atmospheric
pressure to prevent any inleaking of oxygen. The carbon yield may
even reach 100% when the input energy (plasma flow plus electrical
power) is sufficiently high. Carbon black structure can be
decreased by injection of small quantities of alkaline salts.
Typically, also a quench zone can be used, where e. g. methane or
other suitable quench materials can be introduced.
[0042] In addition to converting carbon containing materials into
carbon with a defined nanostructure, hydrogen of good quality is
also a useful reaction product, when carrying out the process
without the injection of oxygen. This hydrogen may therefore also
be separated. Methane or natural gas are particularly attractive
feedstocks when the production of carbon compounds, particularly
carbon black, and the production of hydrogen are envisioned.
Ethane, ethylene, propane, propylene, butanes, butylenes and
mixtures thereof are further examples of useful feedstocks.
[0043] In the following examples, feature combinations and
embodiments of this invention are illustrated.
[0044] The examples were carried out in a reactor set-up
substantially as shown in FIGS. 1 and 2. A plasma power supply
employing a three phase electricity source up to 666 Hz with a
maximum power of 263 kVA and a current range of up to 400 A was
used to supply electricity to three graphite electrodes having
their tips at the apices of an isosceles triangle.
EXAMPLE 1
[0045] In the reactor described, a plasma was generated at a
nitrogen flow of 9 Nm.sup.3/h. The plasma was operated at a current
of 200 A. As a hydrocarbon feedstock a pyrolysis fuel oil was
employed at a flow rate of 2 kg/h. The pyrolysis fuel oil (PFO) was
fed to the reactor together with an argon carrier gas of 0.5 bar
pressure from a tank which was under pressure between 0.75 and 1
bar. The injector was located 2 cm into the graphite reactor
wall.
[0046] The carbon black formed was removed in a primary and a
secondary filter.
EXAMPLE 2
[0047] In this example, 0.56 Nm.sup.3/h of ethylene was used as a
feedstock. The plasma used was again a plasma with nitrogen gas at
9 Nm.sup.3/h at 200 A. The injection of feedstock done in cycles of
5 minutes; 290 g of carbon black was obtained in the filter.
EXAMPLE 3
[0048] In this example, the conditions were similar to the previous
example with a continuous injection of ethylene at a rate of 0.56
Nm.sup.3/h during 30 minutes.
EXAMPLE 4
[0049] in this example, again under process conditions
corresponding to those of the previous example. In this experiment
ethylene at a rate of 0.56 Nm.sup.3/h was injected for sixteen
minutes. The plasma gas flow was nitrogen at a rate of 9
Nm.sup.3/h.
EXAMPLE 5
[0050] In this example, again under process conditions
corresponding to those of the previous examples. In this experiment
methane at a rate of 0.6 Nm.sup.3/h was injected for ninety
minutes. The plasma gas flow was nitrogen at a rate of 12
Nm.sup.3/h and the current 250 A.
[0051] The carbon black obtained from tests according to examples 1
to 5 was tested with respect to the usual properties. The results
are shown in table 1. In all examples, the carbon yields were high;
it was always possible to reach 100%, e.g. by adjusting energy and
feedstock flow.
TABLE-US-00002 TABLE 1 Carbon black properties Example 1 Example 2
Example 3 Example 4 Example 5 BET 69 75.1 74.6 76 69 (m.sup.2/g)
CTAB 95.7 90.9 (m.sup.2/g) I.sub.2 (m.sup.2/g) 95.2 91.9 DBP 218
210 224 206 221 (ml/100 g) CDBP 94 125 124 127 121 (ml/100 g) pH
7.5 8.98 8.96 8.86 7.76 Ash (%) 0.08 0.32 0.28 C-yield 100 80 75 85
60 Toluene 72 80 87 disc. (%) Sulfur 0.04 0.036 0.074
[0052] The disclosed carbon blacks are obtained by performing the
disclosed method using the claimed apparatus and were tested in
standard rubber compositions (ASTM 3191) and in typical battery
electrode applications. Tables 2 to 6 show the data, resulting from
those tests.
[0053] The carbon blacks IRB#7, N-234 and Ensaco 250 are standard
carbon blacks. Their properties are presented also in order to
allow a comparison with the carbon blacks according to the
invention. These are shown as Examples A to D, whereas Example D is
the same carbon black as the one of example 1 of table 1. The
carbon blacks of examples A to C have been obtained with slightly
different process conditions.
TABLE-US-00003 TABLE 2 Example D (equals Carbon IRB#7, Ensaco
Example 1 Black N-234 250 Example A Example B Example C of table 1)
Process Furnace MMM Plasma Plasma Plasma Plasma Feedstock Decant,
PFO CH4 C8H8 C2H4 PFO PFO, Coal tar
TABLE-US-00004 TABLE 3 Carbon Ensaco Black IRB#7 N-234 250 Ex. A
Ex. B Ex. C Ex. D Nitrogen 80 125 65 65 52 80 69 S.A. (m.sup.2/g)
DBP Abs. 102 125 190 157 153 232 218 (ml/100 g)
Viscosity and Rheometer Data
TABLE-US-00005 [0054] TABLE 4 Carbon Ensaco Black IRB#7 N-234 250
Ex. A Ex. B Ex. C Ex. D ML 1 + 4, 83.6 98.3 103.4 85 73.4 107
100.degree. C. Rheometer at 160.degree. C. Min. 2.91 3.71 4.11 3.03
2.36 4.34 2.77 Torque (dNm) Max. 21.27 26.62 23.42 22.61 19.48
26.59 22.37 Torque (dNm) .DELTA. Torque 18.36 22.91 19.31 19.58
17.12 22.25 19.60 (dNm) T90 14.5 14.96 20 9.34 15.56 9.57 14.21
(minutes)
TABLE-US-00006 TABLE 5 Carbon Ensaco Black IRB#7 N-234 250 Ex. A
Ex. B Ex. C Ex. D Stress-strain on S2 at 500 mm/min Tensile 28.5
31.5 25 23.8 20.4 24.7 21.4 strength MPa Modulus 100% 3.6 3.5 3.3
3.3 2.6 3.9 3.2 (MPa) Modulus 200% 10.5 10.3 7.9 8.7 6.4 9.8 7.8
(MPa) Modulus 300% 19.4 19.8 12.8 14.8 10.9 15.9 13.1 (MPa)
Elongation at 426 443 571 490 551 508 499 break (%) Shore A 70 72
70 69 64 73 67 Rebound (%) 46.2 41.4 41 47.4 51.3 42.9 51.8
Electrical 600 10.sup.3 240 10.sup.3 12.5 1.4 10.sup.3 106 165
10.sup.3 resistivity (Ohm cm)
TABLE-US-00007 TABLE 6 Carbon black - Battery carbon black -
Battery evaluation* Example 4 Super P Open circuit voltage (V)
1.652 1.654 Short circuit current (A) 9 10.7 Time to 1.1 V (hours)
7.42 8.53 Time to 0.9 V (hours) 11.63 12.63 *R20 type battery
having the following composition: MnO2 50.73% NH4Cl 1.92% Carbon
black 10.79% ZnO 0.64% ZnCl2 9.27% H2O 26.63% HgCl2 0.03%
* * * * *