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Methanol PDF
Methanol PDF
TECHNICAL INFORMATION
& SAFE HANDLING GUIDE
FOR METHANOL
Version 3.0
September 2006
The information, procedures and data presented in this guide are informational only and are without warranty in
any manner as to their accuracy or completeness. Methanex Corporation assumes no liability whatsoever with
respect to the accuracy and completeness of the information, procedures and data presented in this guide and
disclaims all liability arising out of the use of such information, procedures and data.
TABLE OF CONTENTS
10.0 REFERENCES 27
11.0 APPENDIX 28
A copy of the MSDS for methanol can be obtained from the Methanex Corporation web site:
http://www.methanex.com/products/technical.html
ICAO Classification
(air transport)
Class 3
Sub Risks 6.1
Packing II
* Additional exposure data and guidelines can be found in the US EPA Proposed Acute Exposure Guideline [6].
TLV - Threshold Limit Value (ACGIH US 2000) OES - Occupational Exposure Standards (United Kingdom 2001)
MAK - Maximale Arbeitsplatzkonzentrationen (Germany 2001) MAC - Maximale aanvaarde concentratie (the Netherlands 2002)
VME - Valeurs limites de Moyenne d’Exposition (France 1999) VLE - Valeurs limites d’Exposition à court terme (France 1999)
GWBB - Grenswaarde beroepsmatige blootstelling (Belgium 1998) GWK - Grenswaarde kortstondige blootstelling (Belgium 1998)
EC - Indicative occupational exposure limit values (EU directive 2000/39/EC)
MeOH Volume%
20 12.32 23.97 60
25 15.78 29.60 50
30 19.42 35.09
40
35 23.24 40.44
40 27.26 45.68 30
45 31.51 50.78 20
50 35.99 55.78 10
55 40.73 60.65 0
60 45.75 65.42 0 10 20 30 40 50 60 70 80 90 100
65 51.08 70.08
MeOH Weight %
70 56.75 74.64
75 62.78 79.10
80 69.22 83.46
85 76.11 87.73
90 83.50 91.90 Mole % vs Weight % for Methanol-Water Solutions at 20°C
95 91.44 95.99
100 100 100
100
90
80
70
MeOH Mole%
60
50
40
30
20
10
0
0 10 20 30 40 50 60 70 80 90 100
MeOH Weight %
100% Pure
Methanol
Temp Density
°C g/ml.
-90 0.895
-80 0.885
-70 0.876
-60 0.866
-50 0.857
-40 0.847
-30 0.838
-20 0.829
-10 0.819
0 0.810
10 0.800
20 0.791
30 0.782
40 0.772
50 0.763
60 0.753
70 0.744
80 0.734
90 0.725
3.6 Final Volume when Methanol and Water are Mixed (25°C)
99 30 70 97.33
35 65 97.03
98 40 60 96.78
98 45 55 96.58
50 50 96.44
97
55 45 96.36
97 60 40 96.36
65 35 96.42
96
70 30 96.58
0 10 20 30 40 50 60 70 80 90 100
75 25 96.82
Original Volume MeOH before Mixing 80 20 97.17
85 15 97.64
100 90 80 70 60 50 40 30 20 10 0 90 10 98.23
95 5 98.97
Original Volume Water before Mixing
100 0 100
Source Data for graph 3.6: calculated from density and specific volume data
120
100
Vapour Pressure, psia
80
60
40
20
0
0 25 50 75 100 125
Temperature, o C
1,200.0
1,100.0
1,000.0
900.0
Vapour Pressure, psia
800.0
700.0
600.0
500.0
400.0
300.0
200.0
100.0
0.0
100 125 150 175 200 225 250
o
Tem perature, C
0.0550
0.0500
Specific Volume, ft 3/lb
0.0450
0.0400
0.0350
0.0300
0.0250
0.0200
0 25 50 75 100 125 150 175 200 225 250
Tem perature, oC
MeOH Enthalpy
(saturated liquid)
450.0
400.0
350.0
300.0
Enthalpy, BTU/lb
250.0
200.0
150.0
100.0
50.0
0.0
0 25 50 75 100 125 150 175 200 225 250
Te m perature , oC
MeOH Entropy
(saturated liquid)
0.6000
0.5000
0.4000
Entropy, BTU/lb/oF
0.3000
0.2000
0.1000
0.0000
0 25 50 75 100 125 150 175 200 225 250 275
Tem perature, oC
500.0
400.0
Heat of Vap, BTU/lb
300.0
200.0
100.0
0.0
0 25 50 75 100 125 150 175 200 225 250
Te m pe rature , oC
250
Specific Volume, ft 3/lb
200
150
100
50
0
0 10 20 30 40 50 60 70 80
Tem perature, oC
10.00
9.00
8.00
Specific Volume, ft 3/lb
7.00
6.00
5.00
4.00
3.00
2.00
1.00
0.00
50 75 100 125 150 175 200 225 250
Tem perature, oC
MeOH Entropy
(saturated vapour)
1.050
1.000
0.950
0.900
Entropy, BTU/lb/oF
0.850
0.800
0.750
0.700
0.650
0.600
0.550
0 25 50 75 100 125 150 175 200 225 250
Tem perature, oC
MeOH Enthalpy
(saturated vapour)
570.0
560.0
550.0
540.0
530.0
Enthalpy, BTU/lb
520.0
510.0
500.0
490.0
480.0
470.0
460.0
450.0
440.0
0 25 50 75 100 125 150 175 200 225 250
o
Tem perature, C
0 100
Boiling Points of Methanol - Water Solutions 5 92.8
10 88.3
100 15 84.8
95 20 82
25 80.1
90
30 78.2
Tem perature, °C
85 35 76.8
40 75.6
80
45 74.5
75 50 73.5
70 55 72.4
60 71.6
65
65 70.7
60 70 69.8
0 10 20 30 40 50 60 70 80 90 100 75 68.9
80 68
Methanol Mole %
85 67.1
90 66.3
Reference: Properties of MeOH Water System (Table 10 p 20) Commercial Solvents Corporation, Methanol CSC
95 65.4
100 64.6
Methanol Temperature
60
Mass % °C
0 0
50
10 54
Tem perature, °C
40 20 43
30 35
30 40 29
50 24
20 60 21
70 16
10
80 12
90 12
0
100 12
0 10 20 30 40 50 60 70 80 90 100
1200.0
1000.0
Heat of Vaporization, kJ/kg
800.0
600.0
400.0
200.0
0.0
0.0 25.0 50.0 75.0 100.0 125.0 150.0 175.0 200.0 225.0 250.0
o
Temperature, C
2.850
2.800
2.750
2.700
2.650
Cp, kJ/kg-K
2.600
2.550
2.500
2.450
2.400
2.350
2.300
-20 -10 0 10 20 30 40 50 60 70
Temperature, °C
• vegetable oils such as soy, mustard, canola, 4.5 Miscellaneous Uses of Methanol
rapeseed and palm oils; Methanol is also used in the following applications:
• animal fats such as poultry offal, tallow, and
fish oils; and • Crystallization, precipitation and washing of alkali
• used cooking oils and trap grease from metal halide salts
restaurants. • Precipitation of polystyrene and chloroprene
resins
• Washing and drying of powdered coal fractions
Biodiesel is made by chemically reacting these
• Paint stripping
fats and oils are with an alcohol, typically
• Metal surface washing
methanol, to produce an ester, or biodiesel. • Cleaning of ion exchange resins
Although most any alcohol can be used, • Moisture and resin removal from lumber
methanol is preferred because it is relatively • Extraction agent in the oil, chemical and food
inexpensive and allows for the most thorough industries
reaction process. This process is known as • Fondue fuel
trans-esterification. • Fuel for picnic stoves and soldering torches
• De-icer and windshield washer fluid for
For each 10 volumes of biodiesel produced, one automobiles
• Antifreeze for pipeline dehydration.
volume of methanol is used in the process.
Many resins, nylons and rubbers, particularly nitrile Storage areas must be secure from unauthorized
(Buna-N), ethylene propylene rubber (EPDM), Teflon access.
and neoprene are used satisfactorily as components
Grounding
of equipment in methanol service.
Carbide tipped clamps (to ensure good contact
Methods of Construction
through paint) and dip tube filling are generally used
Storage containers and transfer systems must be to guard against ignition from static electricity.
designed according to appropriate engineering
standards, and comply with all legislative
requirements.
The tabulated conversions are derived from true mass densities that have been modified to account for the effect of
air buoyancy that occurs in weigh scale measurements.
• Dry chemical extinguishers should be accessible storage tank farms to cool adjacent structures and
for small fires. An adequate supply of hand-held neighboring tanks in the event of fire.
and wheeled types should be available.
• Hydrants should be strategically placed with Use of Alcohol-Resistant Aqueous Film Forming
adequate hoses. Foam (AR-AFFF) is effective for large-scale fires.
• Small spills should be remediated with sand, Protein-based alcohol-resistant foams are also
earth or other non-combustible absorbent suitable.
material, and the area then flushed with water.
Larger spills should be diluted with water and 7.4 Fire Fighting Personal Protective
diked for later disposal. Equipment
• Lighting should be grounded. Tall vessels and Due consideration must be given to hazards from
structures should be fitted with lightning chemical and heat exposure. Protective fire-fighting
conductors that are securely grounded. structural clothing is not effective protection from
methanol.
7.3 Fire Fighting Techniques
Methanol flames are almost invisible in daylight, In addition to methanol vapours, fire-fighters may be
producing no soot or smoke. They may be detected exposed to combustion products, such as
by the heat generated, a heat haze, or burning of formaldehyde and carbon monoxide which may form
materials in the affected area. under conditions of depleted oxygen. Therefore, fire-
fighters should wear full-face, positive pressure, self-
Dry chemical powder, carbon dioxide (CO2) and contained breathing apparatus or an air line.
alcohol-resistant foam extinguish methanol fires by
oxygen deprivation. Water will remove heat and Chemical protection may be provided with impervious
dilute the liquid methanol. Fog or fine sprays will clothing, gloves and footwear. Suitable materials
absorb methanol vapours, quench heat and provide a include polyvinyl plastic, neoprene or rubber.
curtain shield for upwind advancement to a fire
source.
10.0 REFERENCES
1. Eckhard Fiedler, Georg Gossmann, Burkhard 6. “Proposed Acute Exposure Guideline Levels
Kersebohm, Günther Weiss, Claus Witte, (AEGLs)”, Public Draft, US EPA Office of
BASF Aktiengesellschaft, Ludwigshafen, Pollution Prevention and Toxics, February
Federal Republic of Germany: Ullmann’s 2001
Encyclopedia of Industrial Chemistry, 1990
Vol. A16. Methanol pp.465-486. 7. Chris Barsby, “ Methanol Brochure” Alberta
Gas Chemicals Ltd. Technical memo
2. L.E. Wade, R.B. Gengelbach, J.L. Trumbley No.850220, March 7, 1985.
and W.L. Hallbauer, in Kirk-Othmer Concise
Encyclopedia of Chemical Technology 8. Technical Information from Malcolm Pirnie
(Wiley-Interscience, 1985) Inc., “Evaluation of the Fate and Transport of
Methanol in the Environment”, January 1999.
3. Susan Budavari (ed.): The Merck Index,
Merck Research Laboratories publisher,12th 9. Emergency Response Guidebook,
edition, New Jersey 1996 Transport Canada, Safety and Security,
Dangerous Goods
4. Environmental and Technical Information for
Problem Spills: Methanol, Environment 10. Environment Health Criteria 196, Methanol
Canada, January 1985 International Programme on Chemical Safety
(United Nations Environment Programme,
5. CRC Handbook of Chemistry and Physics, International Labour Organization,
81st Edition World Health Organization) 1997
11.0 APPENDIX
Table 1
Saturated Saturated
Liquid Vapour
Heat of
Temp Temp Vap Press Sp Volume Enthalpy Entropy Vap Sp Volume Enthalpy Entropy
o o 3 o 3 o
F C psia ft /lb Btu/lb Btu/lb/ F Btu/lb ft /lb Btu/lb Btu/lb/ F
32 0 0.571 0.0198 0.0 0.0000 516.0 283.7 516.0 1.050
40 4.444 0.755 0.0199 4.5 0.0098 513.8 215.6 518.3 1.038
50 9.999 1.05 0.0200 10.2 0.0210 511.1 159.7 521.3 1.024
60 15.554 1.44 0.0202 16.0 0.0322 508.1 118.6 524.1 1.010
70 21.109 1.95 0.0203 21.8 0.043 504.9 88.5 526.7 0.996
80 26.664 2.61 0.0204 27.8 0.054 501.4 67.2 529.2 0.983
90 32.219 3.47 0.0206 33.9 0.065 497.8 51.1 531.7 0.971
100 37.774 4.55 0.0207 39.9 0.076 494.1 39.6 534.0 0.959
110 43.329 5.90 0.0208 46.2 0.087 490.1 31.1 536.3 0.947
120 48.884 7.53 0.0210 52.6 0.098 485.9 24.6 538.5 0.937
130 54.439 9.60 0.0211 59.1 0.110 481.5 19.63 540.6 0.926
140 59.994 12.1 0.0212 65.7 0.120 477.1 15.72 542.8 0.916
150 65.549 15.2 0.0214 72.4 0.131 472.4 12.75 544.8 0.906
160 71.104 18.7 0.0216 79.2 0.142 467.5 10.40 546.7 0.897
170 76.659 23.0 0.0217 86.2 0.153 462.4 8.54 548.6 0.888
180 82.214 28.1 0.0219 93.2 0.164 457.1 7.06 550.3 0.879
190 87.769 34.1 0.0221 100.5 0.176 451.5 5.89 552.0 0.871
200 93.324 41.1 0.0222 107.9 0.187 445.7 4.92 553.6 0.863
210 98.879 49.1 0.0224 115.3 0.198 439.8 4.14 555.1 0.855
220 104.434 58.4 0.0226 122.9 0.209 433.7 3.49 556.6 0.848
230 109.989 69.0 0.0228 130.5 0.220 427.4 2.97 557.9 0.840
240 115.544 81.0 0.0231 138.5 0.232 420.7 2.53 559.2 0.833
250 121.099 95.0 0.0233 146.6 0.243 413.8 2.18 560.4 0.826
260 126.654 110 0.0236 154.8 0.254 406.7 1.87 561.5 0.820
270 132.209 127 0.0238 162.9 0.265 399.5 1.62 562.4 0.813
280 137.764 147 0.0241 171.1 0.275 392.2 1.406 563.3 0.806
290 143.319 169 0.0244 179.8 0.287 384.3 1.220 564.1 0.800
300 148.874 194 0.0247 188.9 0.299 376.0 1.056 564.9 0.794
310 154.429 221 0.0250 198.6 0.312 366.7 0.918 565.3 0.788
320 159.984 251 0.0253 208.2 0.325 357.1 0.802 565.3 0.783
330 165.539 284 0.0257 217.2 0.336 347.4 0.703 564.6 0.776
340 171.094 321 0.0261 225.5 0.346 336.8 0.620 562.3 0.767
350 176.649 361 0.0265 232.9 0.355 325.7 0.542 558.6 0.757
360 182.204 404 0.0270 239.5 0.363 314.4 0.476 553.9 0.747
370 187.759 451 0.0275 245.7 0.370 303.1 0.419 548.8 0.735
380 193.314 503 0.0281 252.7 0.378 290.3 0.369 543.0 0.724
390 198.869 560 0.0288 260.2 0.387 276.4 0.324 536.6 0.712
400 204.424 622 0.0296 268.6 0.397 261.1 0.284 529.7 0.700
410 209.979 690 0.0306 279.1 0.408 242.6 0.246 521.7 0.687
420 215.534 764 0.0318 291.0 0.421 222.0 0.212 513.0 0.674
430 221.089 844 0.0332 305.6 0.437 197.9 0.181 503.5 0.660
440 226.644 930 0.0349 321.9 0.455 170.9 0.151 492.8 0.645
450 232.199 1023 0.0375 340 0.475 138.0 0.122 478 0.630
460 237.754 1124 0.0437 363 0.499 92.0 0.085 455 0.599
464 239.976 1155 0.0590 440 0.582 0.0 0.059 440 0.582
(Table reference – Commercial Solvents Corporation Guide, Methanol CSC p. 18)
Table 2
1200.
32 0.0 516.0 2 -20 2.324 25 2.535
1195.
40 4.4 513.8 1 -19 2.328 26 2.541
1188.
50 10.0 511.1 8 -18 2.331 27 2.547
1181.
60 15.6 508.1 8 -17 2.334 28 2.553
1174.
70 21.1 504.9 4 -16 2.338 29 2.560
1166.
80 26.7 501.4 3 -15 2.341 30 2.566
1157.
90 32.2 497.8 9 -14 2.345 31 2.573
1149.
100 37.8 494.1 3 -13 2.348 32 2.579
1140.
110 43.3 490.1 0 -12 2.352 33 2.586
1130.
120 48.9 485.9 2 -11 2.356 34 2.593
1120.
130 54.4 481.5 0 -10 2.359 35 2.599
1109.
140 60.0 477.1 7 -9 2.363 36 2.606
1098.
150 65.6 472.4 8 -8 2.367 37 2.613
1087.
160 71.1 467.5 4 -7 2.371 38 2.620
1075.
170 76.7 462.4 5 -6 2.375 39 2.627
1063.
180 82.2 457.1 2 -5 2.379 40 2.634
1050.
190 87.8 451.5 2 -4 2.384 41 2.641
1036.
200 93.3 445.7 7 -3 2.388 42 2.648
1023.
210 98.9 439.8 0 -2 2.392 43 2.656
1008.
220 104.4 433.7 8 -1 2.397 44 2.663
230 110.0 427.4 994.1 0 2.401 45 2.670
240 115.6 420.7 978.5 1 2.406 46 2.678
250 121.1 413.8 962.5 2 2.410 47 2.685
260 126.7 406.7 946.0 3 2.415 48 2.693
270 132.2 399.5 929.2 4 2.420 49 2.700
280 137.8 392.2 912.3 5 2.425 50 2.708
290 143.3 384.3 893.9 6 2.430 51 2.716
300 148.9 376.0 874.6 7 2.434 52 2.724
310 154.4 366.7 852.9 8 2.439 53 2.731
320 160.0 357.1 830.6 9 2.445 54 2.739
330 165.6 347.4 808.1 10 2.450 55 2.747
Technical Information & Safe Handling Guide for Methanol
Methanex Corporation / 30