Chap .... ) Hydrogo..

s)o"Dthcsis gases and their derivativcs

81
1.3.6 Uses and producers
Table 1.21 provides an idea of the average commercial specifications of anhydrous
ammonia depending on uses for the production of fertilizers, refrigeration and metallurgy.
Table 1.22 shows the uses of ammonia in 1984 in Western Europe, the United
States, Japan and the world. as well as production, capacities and consumption for these
geographic areas. Capacities are also given for 1986.
1.4 METIIANOL SYNTHESIS
Methanol or methyl alcohol (mp = -97.8"C, bpl.013 = 64.6C, dio = 0.792(11) pra-
duced by the distillation of wood. accounts for only a few per cent of total production.
This also applies to its production by the direct oxidation of hydrocarbons. Most metha-
nol is syntliesized from mixtures of H
2
, CO and CO
2
,
1.4.1 Preparation of synthesis gas
MethaJiol production is chiefly based on the implementation of the following reaction:
CO + 2H2 <::t CH]OH
To a lesser deiree, it also relies on the conversion of carbon dioxide:
CO
2
+ 3H
2
<::t CH
3
0H + H
2
0
Hence, according to the proportion of CO and CO
2
, the gaseous mixture required
for conversion must have a hydrogen to carbon molar ratio between 2 and 3(81. Such a
gas can be obtained., as mentioned above, by partial oxidation, gasifIcation, or steam
reforming.
1.4.1.1 Schemes iuvohing partial oxidation with oxygen
To convert methane (9' (see Fig. 1.5), it is theoretically possible to adjust the oxygen
content to obtain an emuent in which the H
2
/CO ratio is dose to 2 In it is
necessary to consider the losses resulting from \he formation of methane during the
synthesis of methanol. and aim for an H
2
/CO ratio of aroUDd 2.25, which is ideal for
this conversion.
t7) Specifu:.gravity. 68.0'39.2.. . ... . ..
(S) The overall stoichiometry i. such lhal H,/(CO + 1.5CO,) = 2.
19) Contrary to the D.na1 objecU\e in the production of hydrogen or ammonia. the intermeriialc formation
of CO! does not need to be 3,oidcd in the manufacture of methanOL Hence.. in this case.. the paniaJ
of methane can otTer an economically inreTeSting solutio!l..
82
Hydrogen, synthesis gases and their derivauvcs Chap.er 1
This value can be obtained by diverting part of the gas stream to a steam converter
that removes excess CO and supplies an equivalent amount of hydrogen (shift conversion),
Using a standard absorption process, it is then necessary to mI\ove the CO
2
up to the
maximum concentration acceptable 'by the catalyst employed to conduct the methanol
synthesis.
The basic scheme is hence very similar to those used to produce hydrogen and am-
monia. The same applies to the converDon of heavy products, for which partial oxidation
and gasification are generally more suitable. The presence of sulfur compounds in the
raVo' materials used requires the consideration of two main variants, depending on the
poss:ibilities of the catalyst for CO shift conversion (diagrams a and b in Fig. 1.23),
(a) Scheme a: this catalyst cannot tolerate sulfur derivatives. The feedstock must
therefore first be desulfurized to a residual sulfur content of 0.05 to 0.1 ppm. The
gas then partly passes through the CO conversion unit, and is then remixed with
the untreated fraction and partly decaroonated.
(b) Scheme b: the catalyst is resistant to sulfur compounds. Partial CO conversion
. is follo-wed by simultaneous desulfurization and decacbonation.
In both schemes, the installation of a sulfur barrier (such as zinC 'oxide) is recommended
to protect the synthesis catalyst, which does not tolerate sulfur compounds.
With the processes currently uS to obtain methanol., which operate at low pressure
(6 to 9 10
6
Pa absolute). it is possible to eliminate the auxiliary .compressor, which was
formerly indispensable to introduce the synthesis gas in the requisiie operating conditions.
Among the other teChnological variants are two efiluent cooling possibilities at the
exit of partial oxidation or gasifIcation, namely the generation of high-pressure steam
or direct water quench. The latter is uninteresting for the production of methanol, since
intensive conversion is not the ultimate objective.
Since desulfurization must be total whereas decarbonation is only partial, it is inte-
resting to employ a solvent capable of removing not only HlS but also COS, perfonoing
, this selectively in relation to CO
2
, The idea,l processes in these conditions are those
employing physical solvents (Selexol, Rectisol. etc.), '"
1.4.1.2 Schemes based on hydrocarbon steam reforming
.'
These are considerably simplifIed in comparison \\ith those for the production of
high-purity hydrogen or synthesis gas for ammonia. This is because CO conversion,
Cal removal and methanation are eliminated. Howe\'er, an auxiliary compressor is
necessary in this case,
A5 shown in Fig. 1.24, the unit is reduced to t,,;o major sections:
(a) Feedstock pretreatment designed to remo\'e an traces of sulfur compounds or
other impurities detrimental to the synthesis catalyst. such as chlorine.
(b) The steam reforming furnace with its auxiliary flue-gas heat recovery facilities.
This simplifIcation is associated with the actual reforming operation which, as shown
by Table 1.23, leads. for methane, to a hydrogen:carbon ratio normally lying between
3 and 4, depending on the CO and Cal content of the effluent, whereas the desired
value should lie between 2 and 3.
Fuel oil/coal
co,
I N. I II
\';U2 AD50rplion
(8) (b)
.. 111. 1.23. schemes r<lr medUlllol nUlllufuc!lIrc using parlinl oxidation .


1
:J:
';1
a

'a
t
1
!l
a-
s-
II
"-
3.
ii
a.
a
00
V.I
84
"I.
'2-
Hydrogen_ synthesis gases and tbeir deri""atives
Fig. 1.24. Base scheme for methanol manufacture using steam
reforming.
TAJILE 1.23
H,O/CH. ltATIO VARIATIONS IN STEAM 1lEF0l\MlNO "
T ("C)
I
650 700 800 850
H,O/CH.= 1
H,fCO ........... - .................. ........... 4.66 4.00 3.07 3.00
H:O/CH. = 1.5
H,/CO ............................... 5.75 4.63 3.96 3.70
Chapter 1
990
3.00
3.70
3. HzO;CH. =:!
.
Hz/CO ............................. 6.90 5.00 4.70 4.54 4.48
4- HzO:CH. = 3.5
Hz/CO .............................. 10.25
The gas obtained from methane is hence either too rich in hydrogen, or too poor in
carbon. This can be remedied as follows:
(a) By purging. which results in a loss of energy connected in particular with the
separation and compression of excess hydrogen.
(b) Or by the addition of CO
2
, taken for example from the CO, removal unit
associated ~ i t ammonia production, or recovered from the lIue gases of the
reforming furnace. This addition can be made upstream or downstream of the
steam reforming unit. The former alternative is more interesting in principle,
because part of the CO, is then converted to CO, and, in the case of a temporary
Chap'" 1
Hydrogen.. syur.hcsis gases and their derivatives
85
shortage of make-up carbon dioxide, the composition of the reformed gas varies
only slightly.
Unconverted methane present in the reforming emuent behaves in the successive
operations like an inert diluent. To prevent its build-up in the recycle. which constitutes
the methanol "synthesis a purge is necessary.
The carbon deficit observed in methane steam refonning does not occur if naphtha
feedstock is converted. In autothermal processes using fuel oil as a feedstock. suffIcient
quantities of excess carbon dioxide are available within the installation itself. This gas
is recycled from a scrubbing uniL
1.4.2 Thermodynamic aspects of methanol synthesis
The two main reactions used for'inethanol synthesis:
CO + 2H2 ;:t CH]OH =-90.8 kllmol (1.1)
CO
2
+ 3Hi ;:t CH]OH + H
2
0 . = -49.5 klimol (12)
are exothermic and endentropic.
The second may be considenid as the resultant of conversion (1.1) and of the reverse
reaction of CO steam conversion
= 41.3 kllmol
(U)
so that reaction (1.1) is the basic step, for which:
= - 74,653 - 63.98 T + 32.61 T2 + 8.53 10-
6
T3 - 7.77 10-
0
T
4
(lO)
As shown in Fig. 1.25, to calculate the production of methanol at thermodynamic
equilibrium, in accordance with temperature and pressure conditions. use can be made
of the expressions of tbe equilibrium constant Kp as a function of these parameters, i.e. :
Equations such as:
In Kp (Eq. 1.1) = - 7.697 in T + 22.697 + 3.922.10-] T + 0.514. 10-
6
T1(U)
and
In Kp (Eq. 1.3) = 4,764 - 1.945 In T + 5.102 + 5.630. 10,,3 T - 2.170 . 10-
6
T2Il1l.
T .
The actual deflDition of this constant:
K (Eq 1 1) _ ( N
ei,OH
' N} )( i'ei,OH )
P " - Nco. Nit p2 7co i'H;
(10) From P. Boucot (IFF).
(11) From P. Boucot (lFP).
86
Hydrogen. synlhcsi$ gases and their derivatives Chlp'er 1
and
where
XI = moles kg of product i in the mixture,
/I'T = total uumber of moles kg,
i. = activity or fugacity of product i.

Pressure
(1 OPa absolute)
300
Temperaturet"cl
Fig. l.25. Equihorium of metJulnol synthesis from a reformed gas
produced by the steam reforming of methane.
1.4.3 Kinetic aspects of methanol syntbesis
!
Practically speaking. in order to achieve the simultaneous conversiou of CO and CO,
to methanol, one can also introduce the concept of carbon efficiency, defIned as follows;
b
t<. number of moles of ethanol produced 100
car on eUIClency = x
(per cent) number of moles of (CO +
in the synthesis gas
Experimental correlations are then made, such as those in Figs. 126 and 1.27, which
furnish the following for effiuents produced by steam reforming;
I al For a methane feedstock, the pseudo-equilibrium temperature at which a given
carbon efftciency can be obtained at a given pressure.
(bl The influence of feedstock (methane or naphtha) on the pressure to be applied
to obtain the same efftciency.
Chapt ... l Hydrogen. synthesis gases and their derivatives
__ ____ __ __ __ __ __
230 240 250 260 270 280 290
Equilibrium f'seudo-temperature ("C)(I)
Fig. 1.26. pressure on carbon yield (case
of a reformed gas produced by steam treatment).
(I) Pseudo-temperature = Reaction temperature - Approach to
equilibrium.
100
95

:!!

c:
90
a
i!
..
-,'"
85
CH.
V
V
v::
Haphlha


.....
Id
V
80
5 6
8 9
lQ
Pressure (10
5
Pa abSolute)
Fig. 1.27. Influence of type of feedstock. treated by steam reforming.
on carbon yield.
87
The gains in selectivity are directly related to the actual thermal level The most
important side reactions are:
(a) Reaction of residual carbon dioxide with hydrogen:
._ COl + . .3Hz .... CH
3
0H + H
2
0
(b) Methanation:
88 Hydro!!"D. synthesis gases and their dcri,-..tivC5 Chap.er I
leI Formation of methyl ether:
2CH
3
0H - CH3-0-CH3 -+- H
2
0
The fIrSt two conversions are limited by reducing the CO, content in the synthesis
gas employed, and also, and above all, by limiting the reaction temperature to 400"c.
Below this temperature, the methanation rate remains low, or eYen negligible, on the
catalysts employed.
The kinetic equation which expresses the results of CO conversion to methanol is
due to Natta, and is written :
P . pl _ PCH,OH
CO, H, Kp
r= 3
(A + B. Pco+ C. PH, +D ,PQI,OH)
where A, B, C and D are constants which depend on the catalyst used. The calculation
of the pressures appearing in this expression must take account of the activities.
An analysis of this equation shows that, as in the case of ammonia synthesis, the
maxinlum conversion rate at any point of the reactor can only be achieved by establishing
a temperature gradienL This must be supplemented by the analysis of the kinetics relative
to the reverse reaction of CO shift conversion. The models that caD be constructed on
the basis of published experimental results (ll) show that, with catalysts based.on copper
oxide, at 5 . 10
6
Pa absolute, the approach to equilibrium capable of being reached is
about 12"C for CO conversion and 7C for/COl conversion.
These calculations show that the production of methanol is favored by:
(a) Elevation of pressure.
(h) Reduction of temperature.
(c) Increase of the CO/COl ratio in the synthesis gas.
(d) Increase of the hydrogen content of the reformed feed, at least for pressures above
6 _ 10
6
Pa absolute.
Lowering the temperature results in slower reaction rates, and consequently a poor
approach to thermodynamic equilibrium. Activators must be used to overcome these
drawbacks.
.'
Two main types of catalyst are available industrially:
(a) Zincrcbromium systems which. until the late 19605, accounted for virtually all
methanol production. Consisting of homogeneous mixtures of chromium and
zinc oxides, they were subsequently superseded b) copper-based catalysts. This
was due to their low relative activity, which required operation between 300 aod
400"C. At this temperature, a pressure of about 3() to 35 _ 10
6
Pa absolute is
necessary to attain satisfactory conversion rates. and this incurs a high cost in
terms of energy and economics.
(b) Copper-based systems, familiar for many years for their performance but originally
highly sensitive to certain poisons, especially sulfur and halogenated compounds.
(12) From P. Bouco! (lFPI.
Chapter 1 89
The improvement in catalyst resistance and tbe production of impurity-free syn-
thesis gases led to tbeir industrialization. Hence it is now possible to achieve
comparable or bener performance than tbat allowed by zinc/chromium systems.
to tbe extent tbat tbe great selectivity of copper-based catalysts reduces the
quantity of by-productS.. by operating between 240 and 270"C. at only 5 to 10 10" Pa
absolute. with VHSV ranging from 10,000 to 15,000 h -I STP (Standard Tempera-
ture PJeSsure) and catalyst lives of over three years. This decisive improvement was
achieved on the initiative of ICI.
1.4.4 Processes
The existence of two generations of catalysts on the industrial scale accordingly
contributed to the development or two main types of process:
The earliest operate at high pressure, betwee-; 30 and 35 10" Pa absolute, at tempe-
ratures from 350 to 400"c, in reactors which are:
(a) Isothermal (ie. with catalyst tubes, externally cooled by gas circulation or, more
generally, coolant fluid). .
(b) Or adiabatic (i.e. with multistage catalyst beds. "ith intermediate cooling by
injection of a quenching fluid).
These tecbnologies bave been industrialized by Chemico (Chemical Consrruction),
Commercial Solvents, Foster Wheeler-Casale. Girdler, leI. I m'enta- Vulcan, Lummus. .\[on-
tecatini, Badger, BASF, Haldor- Topsoe, Hoechst-Uhde. Humphrey and Glasgow, Hydrocar-
bon Research, Kellogg, Kuhlmann, Pritchard, Power Gas. SIR (Societa ItaIiDna Resine),
Stone and Webster, Sumiromo etc.
The latest operate at low pressure, preferably between 5 and 10. 10" Pa absolute,
at temperatures from 240 to 270"c, in vertical reactors of design varying with the _
company. The main current industrial technologies are those of the following licensors:
(a) ICI: commercialized since 1970. tbis process is the most widespread and accounts
for more than balf of all methanol production capacity existing in 1986 worldwide.
and for 70 per cent of projects under way. Using a single catalyst bed, cooled by
injection of a quenching gas by means oflozenge axial flow distributors, tbistype
of adiabatic reactor can be scaled up directly to unit production capacities of
3000 t/day (diagram a in Fig. 1.28).' I-
(b) Lurgi : tbe isothermal reactor features c ~ l y s t s tube side and boiling water shell
side. so that high pressure steam is obtained (diagram b in Fig. 1.28).
(c) Ammonia-Casale: the reactor features multiple catalyst beds, with intermediate
cooling by gas gas beat exchange and axial as well as radial flow, with low pressure
drops. It can be scaled up directly to unit production capacities of 5000 tlday.
(d) Topsoe.' the reactor features radial flow across three concentric catalyst beds in
separate vessels. Heat exchange is e."'tternal.
Ie) Jlitsubishi etc.
90
Hydrogen.. synthesis gases and their deri".th"es a..ptorl
.
Catalyst
Charging Manhole - -
'-'==""""'f --1------
Inlet
Steam
n
Steam
Cstalvsf
Disdrarge Manhole
(a)
(b)
FIg. 1.28. Methanol manufacture. Typical reactors.
a. ICI <eaaor.
b. Lurgi reactor.
As a rule, this process offers the following conversion }ields:
co .................... .
CO, ... ............... .
Conversion lper cent)
Once-through I
45 to 60'
20 to 40
I
Total
90 to 97
80 to 92
compressor
Figure 1.29 shows the basic flow sheet of the methanol synthesis and purification
section obtained according to leI technology. Whether produced by steam refonmng
or partial oxidation. the product gas ftrst passes through a double-body make-up com-
pressor and is then mixed with the recycle gas. The mixture is then picked up by a
circulator consisting of a single-body centrifugal compressor. dri,'en by a back-pressure
steam turbine. At the exit. the pressurized gas is preheated by beat exchange with the
reactor effiuent, and then divided into two streams:
(a) The first (about 40 per cent) is sent to the reactor after undergoing supplementary
preheating. also by countercurrent flow with the products formed.
(h) The second (60 per cent) is used as a quenching fluid. injected at different levels
of the reactor. to achieve effective temperature control
Reactor
HP Separator
Purge
Recycle Make-up
Compressor compressor
lPSeparator
Light
Condun t.,
S:ntheslS
gas
Refined
methanol
Fill' 1.19. Methanol manufacture. lei process.
Purification
Towa/er
treatment
Crud ..
alcohol.
f
:r:

,

f.
1
i
er
l! .
...

D.
B

92 Hydrogen. s}uthesis pscs and their derhlltives
OuIp r 1
At the exit of the reaction zone, the gas stream obtained is first cooled by heating the
feed and water required by the high-pressure steam generators. and then by passage
through an air-cooled exchanger in which the methanol and water are condensed.
Gas:liquid separation is then carried Out in a vertical drum, operating under pressure.
The gas fraction is essentially recycled: a purge helps to keep the inert gas content in
the reaction loop at a suitable leveL The crude methanol is degassed by flash and
then distilled. It contains 17 to 23 per cent weight of water, 0.4 per cent of impurities
(dimethyl ether. methyl formate, ethanol, propanol, butanols etc.), and must therefore
be purified in a series of two columns, to meet commercial specifications of methanol
for chemical uses (10 ppm ethanol for Grade AA). The first is a light-ends column that
eliminates the light components (gas, ethers, ketones etc.). while the second performs the
following separations:
fa) At the top. purified methanol, drawn of! below the pasteurization section.
(b) The hea\icr alcohols as a sidestream.
(c) Water at the bottom.
Remarks. Due to problems of phase separation in the presence of water and the formation
of vapor locks that are detrimental to motor operation, the use of. methanol as a fuel
requires the addition of higher molecular weight oxygen compounds (higher alcohols
than ethanol in particular). For such an application, it is important to lnaintain certain
impurities in the methanol product, or even to favor their fonilation. Thus, the purification
flow sheet can be simplified by combining light ends separation and rectification in a
single operation, or by increasing the content of the higher bomologucs of methanol by
conducting the conversion in the same reactor (Lurgi, Vulcan etc.) or in different units,
for better control of the changes in the reaction medium (IF P, SN AM Progetti etc.).
Recent developments are aimed to manufacture methanol in a liquid or mixed phase.
This applies to the technologies designed jly Aker, Chemical Sysrems, IFP etc.
1.4.5 Economic data
Table 1.24 summarizes the economic data available on methanol production from
various feedstocks and by various processes.
1.4.6 Uses and producers
Table 1.25 gives the average commercial specifications of chemical grade methanol.
Table 1.26 lists the applications of methanol in Western Europe, the United States,
Japan and the world in 1984. as well as the production. capacities and consumption for
these geographic areas. Capacities are also give.n for 1986 .
T""ul.:!4
ft.-thltIANII'. rK4nJtI4"IIl'N l:t "()Nen"ll: n ....TA
(Fruncc condilions. mid .. 1986)
Raw lUu(criul . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Natural gas
-,----
Naphtha Vacuum residues COlli
Typical technology. . . . . . . . . . . . . . . . . . . . . . . . . . lei Lurgi Texaco Kurpcrs/Tutzck
...... _-.. - ._.-... .. .. _-'-'-'- -r"-'-- ---
Make-up CO, . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . No No Ves No No No No
I'mdl/clio" capacity (t/day) .................. . 1,000 1,800
-_ .. - . .:.-
1--'_--
lIaltery limits investmellts (10' lJS$) ........... . 75 130
111
--" --- .._-----_._---
COllsumptinn per ton or meth"nol
R II \y I1Hllcl'ial.!l
Nutunll gas (10' kJ) ................
32(3) 10 33.5(4)
Naphtha (t) ....................... ,
Residues (t) , .. ,.,., ... ,',", . ,"
Co,lI (tL"""",.,,.,",.,.,",.,'"
Oxygen (t) "",.,', .......... ,', ...
Carbon dioxide (t) ................... .
lIy-rroducts
Sulfur (kg) .......................... .
Utilities
Sleam (t) ............................ .
Fuel (10
6
kJ) ........................ .
Electricity (kWh) ........... ' ...........
Cooling water (m') ...................
Process water (m'> ................... .
Cutalysts lInd eh.mienls (US$) . , .... , . , , ,
Luh"r (Operulnrs per shirt) .... , .............
65
90
2
2.1
,._ .. _-_ ...
7
(II
P\1clhllnul 5yn,hctiia ...... . '11' ............ ................ .
I'urificlition ... ....... , ............. , .................... .
1'0101 .............................................. .
(3) Imprn ... ..:d process. 11
,4, Induding abuut 3(15 . 10 kJ as reedslock.
(%)
43
\2
36
9
100
1,800 1,800 500 1,800 I,HOO
.. ----.
120 135 45 220 2KO'"
. _-------_ . -----
I
32.0 33.5

0.90
2.05
(l.8S
O.S
30 )()
0.12 (-) 0.5 0.8 4.5
IS 17
55 60 35 55 270
190 ISS 245 2 340
I 3 I I 6
2.1 2.1 2.6 1.4 2.6
7 7 7 15 2U
(2) Coul olorog. and prururullon ... , ......................... .
GusiflCQ\ion ............................................ .
Conversion with Ileum ... ................................ .
Aeid BU" removal ....................................... ..
Methanolaynlhcllil uncJ purirlClltion .. ................... .
Air dislillallon ......................................... ..
Antipollution tNalmont ........................ .
Tofl'\
3
JS
S
t3
t3
29
2
IINI
94
Hydrogen. synlhesis gases and their deri'.atives Cllapterl
TABLE 1.25
A \"'EAAOE SPEOFlCATlO!'oo'S OF FOR CP.E.\UCALS
Grade
MethaJlol (% Wt) min. .. : .......
.............. _ ............................ -: ...... ..
Acetone and aldehydes (ppm) max.
Acetone (ppm) max. ....
Elbanol (ppm) max. .... :
Acids (as acetic acid) (ppm) max. ..
H,O (ppm) max. ............ ; ...
Distillation range
A
99.85
7928
30
30
. 1.500
AA
99.85
792.8
30
20
10
30
1,000
at 1.013 10 Pa absolnte ........
Color (Pt/Co scale) max. .............
t"C must include 6-U"C
5
t"C must include 64.6"C
5
Non-volatile residue (g1i00 ml) ....... . 0.001 0.001
Permanganate test at 17 to 18"C min. .. . 30 30
(1) SpeQlic gravilY, 68.0/68.0.
TABLE 1.26
MEmANoL PROOIJCnON o\ND CONStlMPTlOS IS 1984
Geographic areas Iwestern Europe
Uoited' States
I Japan IWor14
Uses ("Ie product)
Acetic acid ............... 4 12 9 6
Cblorometbanes ................ 4 8 4 4
Dimethylterephlbalate ........... 4 1 1 5
Formaldehyde .............. 48 34 45 37
Methyl metbacrylate ................. 2 3 7 2
Melbyl tertio butyl ether ........ ' 5' 7 4
Gasoline blending .................... 9 8 5
Solvent .................... 14 7 13 12
MisccIlaneous III '.' 10 20 21 25
Total ......................... 100 100 100 100
Sources (% product)
.'
Natural gas ........................ 75 56 100 79
Offgas, refInery gases _ .. 20 7
Residues, fueL .................. 22 13 10
Coal ............................... 4 1
Naphtha and other ................... 7 3
Total ......................... 100 100 100 100
Production (10" t!year) .................. 2.0 3.4 0.26 13.1
Capacity (10 t!year),2] .................. 2.8 4.6 0.40 16.9
Consumption (10 tjyear) ............... 3.5 3.8 1.23 12.8
(I) Methylbalides. methyl."e chloride. methybJmiDes. agricultural productS.. resins. polyvinylalcoho1s..
(2) In 1986 the worldwide production capacity of methanol reached 10.S. 10 ,year .. ilb tho foUowing
distribution:
United States. . . . . . .. .. . 4.0
Canada... ............. \.8
LatiD America. . .. .. . . .. 0.8
Western Europe ........ :...5
East= Europe. . . . . . . . . 5.6
Africa................. O.S
Middle East .. . . . . . .. \,7
Japan................. 0.3
Asia and Far Easl.. .. .. . 3.3