Hydrogo.. s)o"Dthcsis gases and their derivativcs
Chap.... )
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 = 64.6·C, dio = 0.792(11) praduced 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 methanol 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 20
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 practi~ 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 o~idation
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 ammonia. 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 • 106 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 interesting 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:
an
(a) Feedstock pretreatment designed to remo\'e 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.
~
1
Fuel oil/coal
:J:
';1
a
(~
co,
I
N.
I
II
\';U2 AD50rplion
~+H,S
'a
t
1!l a-
s-
II
"-
3.
iia.
a
(b)
(8)
..111. 1.23.
Uus~
schemes r
00 V.I
84
Chapter 1
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 "
I
T ("C) "I. H,O/CH.= 1 H,fCO ........... - .................. '2- H:O/CH. = 1.5 H,/CO ............................... 3. HzO;CH. =:! Hz/CO ............................. 4- HzO:CH. = 3.5 Hz/CO ..............................
...........
650
700
800
850
990
4.66
4.00
3.07
3.00
3.00
4.63
3.96
3.70
3.70
5.00
4.70
4.54
4.48
5.75 6.90
.
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 ~ith 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
Hydrogen.. syur.hcsis gases and their derivatives
Chap'" 1
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 loop~. 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 CO 2 + 3Hi
;:t ;:t
~98
CH]OH CH]OH + H 20
=-90.8 kllmol
(1.1)
. ~98 = -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 Mf~98
= 41.3 kllmol
(U)
so that reaction (1.1) is the basic step, for which: t.H~(Jl
=-
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)
= 8,~0 -
7.697 in T
= 4,764 -
1.945 In T + 5.102 + 5.630. 10,,3 T - 2.170 . 10- 6 T2Il1l.
+ 22.697 + 3.922.10-] T + 0.514.
10- 6
T1(U)
and In Kp (Eq. 1.3)
T
.
• The actual deflDition of this constant: K (Eq 1 1) _ ( N ei,OH P " Nco.
'
N} )(
Nit •• p2
(10) From P. Boucot (IFF). (11) From P. Boucot (lFP).
i'ei,OH )
7co • i'H;
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 coeIflci~t of product i. so~------------~----------~
Pressure (1 O°Pa 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; carb on eUIClency = (per cent) t<. •
number of moles of ethanol produced 100 x number of moles of (CO + 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
87
Hydrogen. synthesis gases and their derivatives
80~
__
230
~
____
240
~
__
250
~
__
~~
260
270
__
~
__
280
~
__
~~
290
Equilibrium f'seudo-temperature ("C)(I)
Fig. 1.26. Jnfluenceof~peratureand pressure on carbon yield (case of a reformed gas produced by steam treatment). (I) Pseudo-temperature = Reaction temperature - Approach to equilibrium.
100
~
95
V
:!!
~
c: a
-,'"..
80
V Haphlha v:: ..... ~
90
i!
85
CH.
Id
~
V 5
8
6
9
lQ
Pressure (105 Pa abSolute)
Fig. 1.27. Influence of type of feedstock. treated by steam reforming. on carbon yield.
The gains in selectivity are directly related important side reactions are:
to the actual thermal level The most
(a) Reaction of residual carbon dioxide with hydrogen: ._ COl
(b) Methanation:
+..3Hz .... CH 3 0H + H 20
88
Chap.er I
Hydro!!"D. synthesis gases and their dcri,-..tivC5
leI Formation of methyl ether: 2CH 30H - 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=
(A
+ B.
Pco+ C. PH, +D ,PQI,OH)
3
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 . 106 Pa absolute, the approach to equilibrium capable of being reached is about 12"C for CO conversion and 7°C for/COl conversion. These calculations show that the production of methanol is favored by: (a) (h) (c) (d)
Elevation of pressure. Reduction of temperature. Increase of the CO/COl ratio in the synthesis gas. Increase of the hydrogen content of the reformed feed, at least for pressures above 6 _ 106 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 _ 106 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 synthesis 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 Temperature 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 temperatures 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. .\[ontecatini, Badger, BASF, Haldor- Topsoe, Hoechst-Uhde. Humphrey and Glasgow, Hydrocarbon 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 . 2 8 ) . ' I(b) Lurgi : tbe isothermal reactor features ca~alysts 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.
a..ptorl
Hydrogen.. synthesis gases and their deri".th"es
90
.
Inlet
Catalyst·
~I~
Charging Manhole - -
'-'==""""'f
Steam
•
1'"----~--1C:t:'::==~=::::::::~
--1------
n
Steam
Cstalvsf
Disdrarge Manhole
(a) compressor (b) FIg. 1.28.
Methanol manufacture. Typical reactors.
a. ICI
Lurgi reactor.
As a rule, this process offers the following conversion }ields:
Conversion lper cent)
co .................... . CO, ... ~ ............... .
Once-through
I
Total
45 to 60' 20 to 40
I
90 to 97 80 to 92
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 compressor 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
lPSeparator
f
Purification
Light ~ompounds
Purge
, :r:
.~
.~
f. 1 i
er l!.
...
~.
D.
B
Condun••
Recycle Make-up S:ntheslS gas Compressor compressor
Fill' 1.19.
t., Refined methanol
Towa/er
treatment
Crud.. alcohol.
Methanol manufacture. lei process. ~
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, SNAM 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 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Typical technology. . . . . . . . . . . . . . . . . . . . . . . . . . ...... _-..- ._.-...
Make-up CO, . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . I'mdl/clio" capacity (t/day) .................. . lIaltery limits investmellts (10' lJS$) ........... .
--" --- .._-----_._---
Natural gas lei
Luh"r (Operulnrs per shirt) .... , .............•
Lurgi
.... _ - ' - ' - ' - -r"-'-- - - -
No
No
Ves
1,000
1,800
1,800
75
130 111
-_ .. - . .:.- 1--'_--
or
COllsumptinn per ton meth"nol RII \y I1Hllcl'ial.!l Nutunll gas (10' kJ) .............•••... Naphtha (t) ...................••.... , Residues (t) , .. ,.,., ...•• ,',", .••• ," Co,lI ( t L " " " " , . , , . , " , . , . , " , . , ' " Oxygen (t) " " , . , ' , ..........• ,', ...• Carbon dioxide (t) ................... . lIy-rroducts Sulfur (kg) .......................... . Utilities Sleam (t) ............................ . Fuel (106 kJ) ........................ . Electricity (kWh) ........... '......•..... Cooling water (m') ...............•.... Process water (m'> ................... . Cutalysts lInd eh.mienls (US$) . , .... , •.• , , ,
Naphtha
-,----
32(3) 10 33.5(4)
Vacuum residues
COlli
Texaco
Kurpcrs/Tutzck
No
No
No
No
1,800
500
1,800
I,HOO
..----.
120 45 135 _----------_
.
220
.
2KO'" I
33.5
32.0
O.~S
0.90
2.05 (l.8S O.S 30 0.12
,._..•
(-) 0.5
65 90 2 2.1
55
60
190 I 2.1
ISS 3 2.1
7
7
_-_
...•
7
0.8 IS
35 245
)()
4.5
55
17 270 340
I
2 I
2.6
1.4
2.6
7
15
2U
6
(%)
(II
~.I\~:~~\.~~~t~~lh~~.:::::::::::::::::::::::::::::::::::::::::
43
(2) Coul olorog. and prururullon ... , ......................... .
\2
GusiflCQ\ion ............................................ . Conversion with Ileum ... ................................ . Aeid BU" removal ....................................... .. Methanolaynlhcllil uncJ purirlClltion •• .. ~ ................... . Air dislillallon ......................................... .. Antipollution tNalmont ........................ .
P\1clhllnul 5yn,hctiia ...... . '11' ............ ................ . I'urificlition ... ....... , ............. , .................... .
36 9
1'0101 .............................................. .
100
(3) Imprn ... ..:d process.
11
,4, Induding abuut 3(15 . 10· kJ as reedslock.
Tofl'\
3 JS
S t3 t3
29 2 IINI
94
Cllapterl
Hydrogen. synlhesis gases and their deri'.atives
TABLE 1.25 A \"'EAAOE COM~ERC1AL SPEOFlCATlO!'oo'S OF METH."-~OL FOR CP.E.\UCALS
A
Grade
AA
99.85
MethaJlol (% Wt) min. .•. : ••••....... d~~(lJ .............. _ ............................ -: ...... ..
7928
Acetone and aldehydes (ppm) max. ••••• Acetone (ppm) max. •••.••••...••••••• Elbanol (ppm) max. .•.•••••••••.•. : •• Acids (as acetic acid) (ppm) max. •.••.•• H,O (ppm) max. •.....•.•..•.... ; •... Distillation range at 1.013 • 10· Pa absolnte .•....•..•.• Color (Pt/Co scale) max. .•............ Non-volatile residue (g1i00 ml) ....... . Permanganate test at 17 to 18"C min. .. .
30
99.85 792.8
30 20 10 30 1,000
30 . 1.500
t"C must include 6-U"C t"C must include 64.6"C 5 5 0.001 0.001 30 30
(1) SpeQlic gravilY, 68.0/68.0.
TABLE 1.26 MEmANoL PROOIJCnON o\ND CONStlMPTlOS IS
Geographic areas
Iwestern Europe
Uses ("Ie product) Acetic acid ..••.•.••••.••.....•....•. Cblorometbanes ..•••...•..•......... Dimethylterephlbalate .•...•••...•.... Formaldehyde .•.•..•.•......•••.•.•. Methyl metbacrylate Melbyl tertio butyl ether ••....•...•••. ' Gasoline blending Solvent ..•••.........•••.••.....•...
................. ....................
MisccIlaneous III Total
•••••••••••• '.' •••••••
.........................
Sources (% product) Natural gas ................•........ Offgas, refInery gases _ .••.••••••••••• Residues, fueL ....•••.............•. Coal ............................... Naphtha and other ...................
4 4 4 48 2 5' 9 14 10
100 .' 75
1984
Uoited' States
I
Japan IWor14
6
12 8 1 34 3 7 8 7 20
9 4 1 45 7
13 21
25
100
100
100
56
100
79 7 10 1 3
4 5 37
2 4 5 12
20 13 4 7
22
.........................
100
100
100
100
Production (10" t!year) .................. Capacity (10· t!year),2] .................. Consumption (10· tjyear) ......•.........
2.0 2.8 3.5
3.4 4.6 3.8
0.26 0.40 1.23
13.1 16.9 12.8
Total
(I) Methylbalides. methyl."e chloride. methybJmiDes. agricultural productS.. ~'llthetic resins. polyvinylalcoho1s.. 1986 the worldwide production capacity of methanol reached 10.S. 10· ,·year ..ilb tho foUowing
(2) In
distribution: United States. . . . . . .. .. . Canada... ............. LatiD America. . .. .. . . ..
4.0
Western Europe ........
\.8
East= Europe. . . . . . . . . Africa.................
0.8
:...5 5.6 O.S
Middle East .. • . . . . . • • .. Japan................. Asia and Far Easl.. .. .. .
\,7
0.3 3.3
