Material Balance Hydrotreater Reactor

In CPC specification does not provide data for total sulfur (Mercaptans, Disulfides, Sulfides + thiophenes, sulfur, Polysulfide) available in naphtha feed. It just represents sulfur content and hydrogen sulfide content in the naphtha feedstock. It is assumed that amount of total sulfur is equal to the sulfur content in the naphtha feedstock.

(http://www.ceypetco.gov.lk/Ceypetco_Products.htm#CP19)

Hydrotreater
Inlet flow rates to the Hydrotreater
Naphtha Naphtha feed rate =245.45MT/day

Hydrogen For hydrotreating of naphtha should be 100 is desired.

(A design report on catalytic hydrotreating OF 4500 bbl / day,(30 m3/hr) of raw naphtha, Engr. Waqar Ali Khan,page-16)

Density of naphtha

= (650+720)/2 = 685 kgm-3

Therefore, volumetric flow rate of naphtha

= = 358.33m3/Day

Therefore, Required Hydrogen flow rate

= 358.33 x 100 = 35833 m3/Day

Hydrogen Mass flow rate for hydrotreating naphtha =35833 x 0.081/1000 = 2.9MT/Day

Sulfur Amount of sulfur in naphtha Amount of sulfur in feed Sulfur feed rate = 50ppm or 50mg/kg = = 12.273kg/Day

Calculation for Outlet Flow Rates

The objective of Naphtha hydrotreating in naphtha steam reforming process is to reduce sulfur up to or less than 0.5ppm

Let, Sulfur content in product is 0.2ppm Percentage of sulphur in the product =

= = 0.4% Percentage of sulphur converted to H2 S = 100 - 0.4 =99.6%

Reacted sulphur in the reactor

= 12.273 x 0.996 = 12.224 kg /day

Unreacted sulfur in the product

= 12.273 x 0.004 kg/day = 0.0491 kg/day

H2

H2 S = 12.224 kg/day = = 0.764 kg/Day

Reacted Sulfur Required Hydrogen

Unreacted Hydrogen in the product

= 2.9 x 1000- 0.764 = 2899.236 kg/Day

H2S in the product Stream

= = 12.988 kg/Day

Outlet flow rates from the Hydrotreater

Hydrotreated naphtha (Naphtha + Unreacted Sulfur) Hydrogen Hydrogen sulfide 245.437 MT/Day 2.899 MT/Day 12.988 kg/Day

Amount of sulfur in the outlet stream is negligible. Therefore we assume naphtha feed rate to be the same as the inlet.

Components Hydrotreated Naphtha Hydrogen Hydrogen sulfide Total

Flow Rate (MT/Day) 245.437 2.899 0.012988 248.348988

% 98.8271 1.16731 0.00590 100

Hydrotreater

Components Hydrogen

Flow Rate Weight (MT/Day) % 2.9 100

Components Naphtha

Flow Rate (MT/Day) 245.45

% 100

Here, Total Material In = 248.35 MT/day Total Material Out = 248.349 MT/Day 248.35 MT/day Therefore Material in = Material out

Material in to the Hydrotreater Component Flow Rate (MT/Day) Naphtha+Sulfur Hydrogen 245.45 2.9 98.88323 1.11677 %

Material out from the Hydrotreater Component Flow Rate

(MT/Day) (Naphtha + Unreacted 245.437 Sulfur)

98.8271 1.16731 0.00590 100

Hydrogen Hydrogen sulfide

2.899 0.012988 248.35

Total

248.35

100

Total

Desulfurization
The natural gas or naphtha feed were heated to 285-400 C and then passed through one or two bed of ZnO in the form of tablets, spheres, or extrudates where the function of the catalyst depends on the chemical reaction:

ZnO + H2S

ZnS + H2O

Usually zinc oxide catalyst is used as a mixture of ZnO and alumina as a binder in addition to some filler. In general 90 % wt of ZnO is quiet acceptable. On using naphtha as feed the hydrogen sulfide being reduced to 0.02 ppm.

Inlet flow rates of the desulfurization reactor

Hydrogen Naphtha Hydrogen Sulfide Required ZnO

2.899 MT/Day
245.437MT/Day

12.988 kg/Day (52.3ppm) 31.07 kg/day

Calculation for Outlet Flow Rates

The gas leaves the purification section with a sulfur content of <1ppm at essentially the same temperature. (Ullaman Vol.A13,page 326) Here the feed purification system sulfur content in output stream is maintained at 0.02ppm Percentage of hydrogen sulfide in the product = = = 0.038% Percentage of H2S desulfurized Desulfurized H2S in the reactor H2S in the outlet stream = (100 - 0.038) %= 99.962% = 12.988 x 0.99962 = 12.983 kg/Day = (12.988 -12.983) kg/Day = 0.005 kg/day Hydrogen and naphtha flows quantity remain constant throughout the desulfurization reactor. But large amount of H2S desulfurized in the reactor bed.

Output flow of the desulfurization reactor

Hydrogen Naphtha Hydrogen sulfide ZnS

2.899 MT/Day
245.437 MT/Day

0.005 kg/day 0.0372073MT/Day

Components H2O Hydrogen Naphtha Hydrogen sulfide Total

Flow Rate (MT/Day) 0.00690444 2.899

245.437

% 0.0027 1.16733 98.8299 0.00007 100

0.000005 245.3429094

Components ZnO

Flow rate (MT/Day) 0.03107

% 100 Desulfurizer

Components ZnS

Flow rate (MT/Day) 0.0372073

% 100

Components

Flow rate (MT/Day) 98.8271 1.16731 0.00590 100 2.899 0.012988 248.348988

(Naphtha+UnreactedSulfur) 245.437 Hydrogen Hydrogen sulfide Total

Material in to the desulfurization reactor Material Flow Rate (MT/Day)

(Naphtha + 245.437

Material in to the desulfurization reactor Material Flow Rate (MT/Day) %

98.8127 1.1671 0.00522 0.01498

Hydrogen Naphtha Hydrogen sulfide ZnS H2O

2.899
245.437

1.1671 98.8127 0.000002013 0.01498 0.002766 100

Unreacted Sulfur)

Hydrogen

2.899

Hydrogen sulfide 0.012988 ZnO 0.03707

0.000005 0.0372073 0.00687 248.386058

Total

248.38608

100

Total

General formula of naphtha (Ullaman Vol.A13, page 326) Mass of naphtha in feed Mole of carbon in naphtha feed

= CnH2.2n = 245.437 MT/Day =

= 17.2 x 103 kmol/day

Calculation for inlet Flow Rates

Steam Steam is added to the inlet feed to give ratio of 3mole of steam per mole of carbon. (Ullaman Vol.A13, page 326) Therefore,

=3
Steam mole flow rate = 17.2 x 103 x 3 kmol/day = 51600 kmol/day Steam flow rate = 928.8MT/day

Input Flow rates to the reformer

H2O Hydrogen Naphtha Steam

0.00687 MT/Day 2.899 MT/Day 245.437 MT/Day 928.8MT/Day

Calculation for Outlet Flow Rates

Assume that naphtha entering to the reformer completely react with steam. CnH2.2n (Naphtha) + n H2O = = 311.117 MT/Day Similarly, CO mass flow rate in the product H2 mass flow rate in product = 483.96 MT/Day = 72.59 MT/Day n CO + 2.1n H2

Required steam flow rate

Assume that 0.1 fraction of CO in above reaction is converted into the CO2 and H2 presence of H2O. CO + H2O CO2 + H2

CO contributes for the shift reaction

= 483.96 x 0.1 MT/Day = 48.396 MT/day

Required steam flow rate for shift reaction CO2 mass flow rate in product stream Formed H2 in shift reaction

= 31.112 MT/Day = 76.051 MT/day = 3.457 MT/Day

Naphtha

= 0

Steam

= 928.8 MT/Day - (311.117 MT/Day+31.112 MT/day) +0.0073 MT/Day = 586.578 MT/Day

H2

=2.899 MT/Day + 72.59MT/Day + 3.457 MT/Day = 78.946 MT/Day

CO

= 483.96 MT/Day *0.9 = 435.564 MT/Day

CO2

= 76.051 MT/Day

Output Flow rates from the reformer

Naphtha Steam H2 CO CO2 0 586.578 MT/Day 78.946 MT/Day 435.564 MT/Day 76.051 MT/Day

Input mass flow rate Output mass flow rate

= 1177.133 MT/Day = 1177.139 MT/day 1177.13 MT/Day

Reformer

Components H2O Hydrogen Naphtha Steam Total Component Naphtha Steam H2 CO CO2 Total

Flow Rate (MT/Day) 0.00687 2.899 245.437 928.8 1177.13287 Flow Rate(MT/Day) 0 586.578 78.946 435.564 76.051 1177.13287

% 0.00058362 0.24627 20.85023 78.90292 100 % 0 49.83082 6.76599 37.00192 6.40127 100

Material in to the Reformer Material Flow Rate (MT/Day) Steam Naphtha Hydrogen H2O Total in 928.8
245.437

Material out from the Reformer % Material Flow Rate (MT/Day) 78.90292 20.85023 0.24627 0.00058362 100 CO Steam Hydrogen Carbon Dioxide Total out 435.564 586.578 78.946 76.051 1177.13287 37.00192 49.83082 6.76599 6.40127 100 %

2.889 0.00687 1177.13287

High Temperature Shift Reactor (HTS Reactor)

Inlet flow rate to the HTS reactor

Steam H2 CO CO2

586.578 MT/Day 78.946 MT/Day 435.564 MT/Day 76.051 MT/day

From literature amount of CO remaining after conversion =7.9% (mole percentage) Suppose x mol of CO is reacted CO + H2O CO2 + H2

After the reaction quantities of the each components

nCO nsteam nH2 nCO2

= = = =

from the literature amount of CO remaining after the conversion is 7.9% 7.9 = =

X Therefore reacted CO mol

= 8497605.648mol = 8497605.648mol

Therefore output moles of each component at the outlet nCO = = 7058251.495mol nsteam = = 24090061.02mol nH2 = = 47970605.65mol nCO2 = = 10226037.47mol

Outlet flow rates from the HTS reactor

CO Steam H2 CO2 197.6310419MT/Day 433.6210984MT/Day 95.9412113MT/Day 449.94565MT/Day

Component

Flow Rate (MT/Day)

Steam H2 CO CO2 Total

433.6210419 95.9412113 197.6310419 449.94565 1177.139

36.83686 8.15037 16.7891 38.22367 100

High Temperature Shift Reactor

Component

Mass Flow Rate (MT/Day)

Steam H2 CO CO2 Total

586.578 78.946 435.564 76.051 1177.139

49.83082 6.76599 37.00192 6.40127 100

Material in to the HTS Material CO Steam Hydrogen Carbon Dioxide Total in Flow Rate 435.564 586.578 78.946 76.051 1177.139 % 37.00192 49.83082 6.76599 6.40127 100

Material out from the HTS Material CO Steam Hydrogen Carbon Dioxide Total out Flow Rate 197.6310419 433.6210984 95.9412113 449.94565 1177.139 % 16.7891 36.83686 8.15037 38.22367 100

Low Temperature Shift Reactor (LTS Reactor)

Inlet flow rate to the LTS reactor
CO 197.6310419MT/Day Steam 433.6210984MT/Day H2 CO2 95.9412113MT/Day 449.94565MT/Day

It is assumed that CO remaining after conversion =0.4% (mole percentage)

Suppose x mol of CO reactes CO + H2O CO2 + H2

After the reaction quantities of the each components n CO nsteam nH2 nCO2 0.4= = = = =

= 6770151.291mol

Therefore reacted CO mol

= 6770151.291mol

Therefore output moles of each component at the outlet

nCO

= = 288100.184mol

nsteam

= = 17319909.73mol

nH2

= = 54740756.94mol

nCO2

= = 16996188.79mol

Outlet flow rates from the LTS reactor

CO Steam H2 CO2 8.066805152MT/Day 311.7583751MT/Day 109.4815139MT/Day 747.8323068MT/Day

Component

Mass Flow Rate (MT/Day)

CO Steam Hydrogen Carbon Dioxide Total out

8.066805152 311.7583751 109.4815139 747.8323068 1177.13900

0.685289 26.48441476 9.30064452 63.52965171 100

Component

Mass Flow Rate (MT/Day)

CO Steam Hydrogen Carbon Dioxide Total in

197.6310419 433.6210984 95.9412113 449.94565 1177.139

16.7891 36.83686 8.15037 38.22367 100

Material in to the LTS Material CO Steam Hydrogen Carbon Dioxide Total in Flow Rate 197.6310419 433.6210984 95.9412113 449.94565 1177.139 % 16.7891 36.83686 8.15037 38.22367 100 Material CO Steam Hydrogen

Material out from the LTS Flow Rate 8.066805152 311.7583751 109.4815139 747.8323068 1177.13900 % 0.685289 26.48441476 9.30064452 63.52965171 100

Carbon Dioxide Total out

Condensate Drum
Output stream conditions of low temperature shift reactor. Pressure 18bar Temperature 212.77oC Saturate steam temperature at 18bar = 205.9oC

Therefore effluent steam from LTS is at superheated region. Take condensate collector operating temperature as 105oC and its pressure 17 bar (Hydrogen from Steam-Methane Reforming with CO2 Capture, John C. Molburg and Richard D. Doctor, Page 12) Saturated water temperature at 17bar Tsaturate be condensed. > 204.272oC

condensate drum operating temperature

Therefore in condensate collecting vessel we can assume that all the steam which in product stream will

Inlet flow rate to the Condensate Drum

CO 10.01063504MT/Day Steam 313.00798014MT/Day H2 CO2 109.3426689MT/Day 744.7777172MT/Day

Outlet flow rate from the Condensate Drum

CO 10.01063504MT/Day

H2 CO2

109.3426689MT/Day 744.7777172MT/Day

Material accumulated in Condensate Drum

Condensate 313.00798014MT/Day

CO H2 CO2

8.066805152MT/Day 109.4815139/Day 747.7777172MT/Day

Condensate 311.7583751MT/Day

Condensate Drum

CO 8.066805152MT/Day Steam 311.7583751MT/Day H2 109.4815139MT/Day CO2 747.8323068MT/Day

Material in to the Condensate Drum Material Flow Rate

Material out from the Condensate Drum Material Flow Rate

CO Steam Hydrogen Carbon Dioxide Total in

8.066805152MT/Day 311.7583751MT/Day 109.4815139MT/Day 747.8323068MT/Day 1177.139001MT/Day

CO Hydrogen Carbon Dioxide Total out

8.066805152MT/Day 109.4815139MT/Day 747.7777172MT/Day 865.3260363MT/Day

Material accumulated in Condensate Drum Material Condensate Flow Rate 311.7583751MT/Day

Pressure Swing Adsorption

Inlet flow rate to the PSA
CO Hydrogen Carbon Dioxide 8.066805152MT/Day 109.4815139MT/Day 747.7777172MT/Day

Calculation for outlet flow stream from the PSA

It is assumed that 99.6% of purity for final product. Ullaman Vol.A13, page 327 Total amount of CO and CO2 available in the product stream after PSA unit 99.6= X Removal efficiency of PSA = 0.43968MT/Day = = 99.9418%

Outlet flow rate from the PSA

Hydrogen CO + Carbon Dioxide 109.4815139MT/Day 0.43968MT/Day

Hydrogen CO + Carbon Dioxide

109.4815139MT/Day 0.43968MT/Day

CO and CO2 accumulated 755.4048424MT/Day

PSA Unit

CO Hydrogen

8.066805152MT/Day 109.4815139MT/Day

Carbon Dioxide 747.7777172MT/Day

Material in to the PSA unit Material CO Carbon Dioxide Hydrogen Total in Flow Rate 8.066805152MT/Day 747.8323068MT/Day 109.4815139MT/Day 865.3806259MT/Day Material CO + CO2 Hydrogen Total out

Material out from the PSA unit Flow Rate 0.43968MT/Day 109.4815139MT/Day 109.9211939MT/Day

Material accumulated in PSA unit Material CO and CO2 Flow Rate 755.4048424MT/Day