Material balances

Before carrying out these material balances, the following assumptions and conclusions were made: A basis of 100 kmol/hr of fresh methanol was fed to the reactor. Conversion of methanol in the reactor is 97% Ratio of methanol to oxygen fed to the reactor is 2.5:1 Since the percentage of the desired reaction is 60 while the undesired is 40, the selectivity of the process is 1.5 Conversion of methanol was 97% In the absorption column all the entering H2, N2 and O2 goes off as off gas. The exiting liquid stream had specifications of, 1.5 wt% methanol, 43.5 wt% formaldehyde and 55 wt% water. The flow rate of water fed to the absorption column is 65% of the entering gas flow rate. 99% of the entering formaldehyde was absorbed in the liquid stream. In the distillation column there were 99% of methanol and water from the feed in the tops and bottoms product respectively. Scaling up was done after conducting these balances to achieve a formaldehyde yield of 72000 tonnes/yr. No methanol in off-gas

Nomenclature: M- Methanol, O- Oxygen, F- Formaldehyde, W- Water, H- Hydrogen, N- Nitrogen Xin- liquid mole fraction of component i in stream n. Yin- vapour mole fraction of component i in stream n. Fi- Molar flow rate of specie I (kmol/hr)

Ni- Number of moles of specie i Molecular weights: Water = 18 Methanol = 32 Formaldehyde = 30 Hydrogen = 2 Oxygen = 32 Nitrogen = 28

REACTOR

F = 293.54 YM = 0.351 YO = 0.136 YF = 0 YW = 0.007 YH = 0 YN = 0.509

Reactor

F = 365.60 YM = 0.0085 YO = 0.027 YF = 0.273 YW = 0.170 YH = 0.109 YN = 0.412

( ) 60% .1 ( ) 40% .2

Component M O F W H N

Input (kmol/hr) 103.061 40 0 2.086 0 150.476

Consumed (kmol/hr) 1 + 2 0.51 -1 - 2 -1 -2 ____________

Output (kmol/hr) 103.061 -1 - 2 -0.51 + 40 1 + 2 2.086 +1 2 150.476

1 + 2 = 0.97 * 103.061
= 99.97

1/ 2 = 0.6/0.4 = 1.5

Therefore 1 = 1.52 So 2.52 = 103.061

1 = 59.981 2 = 39.988

Flow rates of components in reactors outlet:

FM = 103.061 (59.981 + 39.988) = 3.092 kmol/hr

FO = 40 + (0.5 * 59.981) = 10.009 kmol/hr

FF = (59.981 + 39.988) = 99.969 kmol/hr

FW = 2.086 + 59.981 = 62.067 kmol/hr

FH = 39.988 kmol/hr

FN = 150.467 kmol/hr

Total molar flow rate of outlet stream = (3.092 + 10.009 + 99.969 + 62.067 + 39.988 + 150.467) = 365.60 kmol/hr Outlet Compositions: YM = 3.092/365.60 = 0.0085, YW = 62.067/365.60 = 0.170, YO = 10.009/365.60 = 0.027, YH = 39.988/365.60 = 0.109, YF = 99.969/365.60 = 0.273 YN =150.467/365.60 = 0.412

ABSORBER

L0 = 237.64 XW = 1

G1 = 292.553 YO = 0.034 YF = 0.003 YW = 0.311 YH = 0.137 YN = 0.514

Absorber

GN+1 = 365.60 YW = 0.170 LN = 310.69 XM = 0.01 XF = 0.319 XW = 0.671 YM = 0.008 Y O = 0.027 Y F = 0.273 YH = 0.109 YN = 0.411

Overall Balance: Entering liquid flow rate LO = 0.65 * 365.60 = 237.64 kmol/hr Specifications for liquid outlet stream based on literature: 1.5 wt% methanol, 43.5 wt% formaldehyde and 55 wt% water.

Taking a basis of 100 kg these can be converted to mol fractions. NM = mass fraction/molecular weight = 1.45/32 = 0.0453 NF = 43.514/30 = 1.450

NW = 55.036/18 = 3.0576

NT = NI = 0.0453 + 1.450 + 3.0576 = 4.5503

XM = NM/ NT = 0.0453/4.5503 = 0.01

XF = 1.450/4.5503 = 0.3186

XW = 3.0576/4.5503 = 0.6714

M balance: Input = Output : =

365.60 * 0.00845 = LN * 0.01 LN = 310.69 kmol/hr

From overall balance = 365.60 + 237.64 310.69 = 292.80 kmol/hr

Using the assumption of 99% absorption of formaldehyde in the absorption column its flow rate in the exiting vapor can be determined:

= 0.01 * (365.60 * 0.2734) = 1.00 kmol/hr

Water balance: (365.60 * 0.170) + (237.64 * 1) = (292.80 * = 0.3113 ) + (310.69 * 0.6714)

All the H, N and O goes off as off gas therefore their flows in the outlet gas is the same as those in the entering gas. So flows in the exit gas: FH = 39.988 kmol/hr, FF= 1.00 kmol/hr, FN = 150.467 kmol/hr, FW = 91.08 kmol/hr FO = 10.009 kmol/hr

Outlet Compositions: YO = 10.009/292.80 = 0.034, YH = 39.988/292.80 = 0.137, YF = 1.00/292.80= 0.003, YN =150.467/292.80 = 0.514 YW = 91.08/292.80= 0.311,

DISTILLATION COLUMN

D = 5.147 XM = 0.5947 XW = 0.4053 F = 310.69 XM = 0.01 XF = 0.319 XW = 0.671

Distillation Column

W = 305.54 XM = 0.0001 XF = 0.3239 XW = 0.676 Assumptions: Constant molal overflow. Light Key Component: methanol. Heavy Key Component: water. 99% of methanol from the feed in the tops product. 99% of water from the feed in the bottoms product. Formaldehyde is the heavier than heavy key component Sharp separation (i.e. no heavier than heavy key component in the tops product)

FM in tops = = 0.99 * (310.69 *0.01) = 3.061 kmols/hr

FM in bottoms = (310.69 *0.01) 3.061 = 0.031 kmols/hr

FW in bottoms = = 0.99 *(310.69 *0.671) = 206.54 kmols/hr

FW in tops

= (310.69 *0.671) 206.54 = 2.086 kmols/hr

FF in bottoms = = (310.69 *0.319) = 98.97 kmols/hr

Distillate product (D) = FM in tops + FW in tops = 3.061 + 2.086 = 5.147 kmols/hr

Bottoms product (W) = FM in bottoms + FW in bottoms + FF in bottoms = 0.031 + 206.54 + 98.97 = 305.54 kmols/hr Tops Compositions: XM = 3.061/5.147 = 0.5947, XW = 2.086/5.147 = 0.4053

Bottoms Compositions: XM = 0.031/305.54 = 0.0001, XW = 206.54 /305.54 = 0.676, XF = 98.97/305.54 = 0.3239

Energy Balances

Before conducting energy balances at various points in the plant, the following data was obtained from various literature sources. This data was essential because without it preliminary energy balances would not have been able to be conducted. Temperature and pressure of fresh methanol 30oC, 101.35 kpa. Temperature and pressure of fresh air 25oC, 101.35 kpa Temperature and pressure of recycle stream 68.3oC, 110.32 kpa Pressure of methanol stream leaving the pump 241.32 kpa Temperature and pressure of mixed methanol stream out of the heat exchanger 150oC, 199.95 kpa Pressure of air stream leaving the compressor- 241.32 kpa Temperature of air stream leaving the heater- 150oC Pressure of mixed methanol and air stream- 199.95 kpa Temperature and pressure of effluent leaving the reactor- 345oC, 172.37 kpa Temperature of reactor outlet stream leaving the first cooler- 250oC Temperature of reactor outlet stream leaving the second cooler- 140oC Pressure drop across the valve- 34.47 kpa Temperature and pressure of water stream entering the absorption column- 30oC, 137.9 kpa Zero pressure drop across the absorption column Temperature of stream leaving the cooler- 102oC Outlet pressure of bottoms product from the distillation column after being pumped265.45 kpa Temperature and pressure of water stream added after the pump- 30oC, 265.45 kpa Temperature of contents in storage tank

The following table comprises of heat capacity data used in conducting the energy balances: Component Methanol State liquid gas Water liquid gas Oxygen Nitrogen Hydrogen gas gas gas a x 103 75.86 42.93 75.4 33.46 29.10 29.00 28.84 34.28 b x 105 16.83 8.301 c x 108 d x 1012

___________ ___________ -1.87 -8.03 _________ -3.593 1.311 -2.871 -0.8698 -8.694

___________ __________ 0.6880 1.158 0.2199 0.00765 4.268 0.7604 -0.6076 0.5723 0.3288 __________

Formaldehyde gas

Cp = a + bT + cT2 + dT3 (T in oC) Source: Felder and Rouseu

Mixing Point between streams 1, 2 & 3 P = 110.32 kpa T = 68.3 oC NM = 8.47, NW = 5.775 P = 101.35 kpa T = 30 oC NM = 276.83
Mixing Point

P = 101.35 kpa T = 31.59 oC NM = 285.30