INTRODUCTION

In every hydrocarbon industries off-gases are commonly emitted to the environment viz CO2, H2S, SO2. Each gas has its own disadvantages. Out of which we have selected the thiopaq process for treating H2S which s patented by Shell Global Solution in collaboration with Paque. Currently H2S removal from natural gas with subsequent sulphur recovery is mainly performed by amine & clausis plant . In small industries generally hydrogen sulphde is treated by liquidredox reaction process & followed by incineration or injection of the acid gas in empty well. All these treatment having some weakness. So shell-paque THIOPAQ process is a biotechnological process for recovery of sulphur from gaseous stream by absorption into a mild alkaline solution Followed by the oxidation of absorbed sulphide to elemental sulphur by naturally occurring Bacteria known as THIOBACILIUS. These process as following advantages : Minimal chemical consumption. High turndown ratio. Gas treatment as well as sulphur recovery. H2S below 4 PPM can be guaranteed. Essentially 99.9 % of conversion. No replacement of catalyst.

This process has been commercialized in many petrochemical industries along with Pulp & Mining industries. In this project my plant capacity for crude natural gas in 2100,000 M3/day. Out of which 13 ton/day of sulphur is recovered .we also covered the Block diagram, process description, process flow diagram, Energy balance & material balance across absorber. Piping & instrumentation diagram of Absorber including line sizing & Equipment list.

pg. 1

BLOCK DIAGRAM

pg. 2

BLOCK DIAGRAM:

Sweet Gases

NaOH + Air + Water

NaOH Solution

H2S

Absorption Tower

Bio Reactor

De-Watering

Screw Convertor

Block Diagram of Thiopaq Process

Elemental sulphur recovered
pg. 3

PROCESS DESCRIPTION

pg. 4

Process Description

A simplified process flow scheme of the Paques unit is included on the next page. Sour natural gas is routed via a feed gas knockout vessel and a glycol heater to the absorber. Even though the Shell-Paques process is an exothermic process, the latent heat content of the feed gas was so low that heating duty needed to be supplied for this project rather than cooling duty. Application of the heater on the feed gas flow has one major advantage; it allowed the feed gas temperature to be controlled in relation to the solvent temperature, i.e. hydrocarbon condensation control was achieved. The sour natural gas is washed in the absorber countercurrently. This absorber has three packed beds with 2-inch Pall rings. A total draw-off tray combined with a liquid redistribution tray in-between the packed beds ensures proper liquid redistribution. Treated natural gas leaves the top of the absorber and is routed to the sales gas grid via a knockout drum. The loaded THIOPAQ solvent is routed from the absorber to the horizontal flash vessel. The flash gas, which contains some H2S, is washed in the small column on top of the flash vessel. The treated flash gas is routed to flare. Flashed, loaded THIOPAQ solvent is then sent to the bioreactor. A blower supplies air to a distributor in the bottom section of this tank. Part of the oxygen is consumed in reactions with sulfide and sulfur. The distribution of air also ensures that the content of the bioreactor is continuously mixed. Regenerated THIOPAQ solvent is recycled to the main absorber, the flash absorber, the solids separator and to the top of the bioreactor. The last feature is mainly as a pro-active measure to prevent foaming. The bacteria catalyze the regeneration reactions 5 and 6, the reaction of sulfide with oxygen to give either elemental sulfur or sulfate. The reaction that gives elemental sulfur is very much preferred because: It produces a hydroxyl molecule, which can capture a molecule of H2S in the absorber. It produces elemental sulfur, which can be separated fairly easily from the solvent.
pg. 5

We have to accept a small percentage of over-oxidation however since we need to convert all sulfides in the bioreactor. The sulfate production necessitates a continuous bleed from the unit. The bleed stream is taken from a separate calm section of the bioreactor, to minimize the sulfur content. The clarified bleed stream is subsequently aerated. Some bacteria will still be present, they will ensure that all sulfur and sulfide is completely oxidized to sulfate for which the biological oxygen demand is zero. Local legislation required sterilization of the bleed stream; therefore a UV source has been installed after the aeration tank. Bleed water is collected and transported by truck to a nearby Water treating facility. The vent air leaving the bioreactor can contain a little H2S (typically less than 4 ppmv) and is therefore routed to a bio-polisher. This bio-polisher is a tank with a layer of compost; the vent air contains sufficient water vapor to keep this compost filter humid. The vent air is discharged directly into atmosphere. The regenerated solvent leaving the bioreactor typically contains 10 kg sulfur per cubic meter, or roughly one weight percent. The solvent is concentrated into sulfur slurry with around 10 % wt. sulfur content in the solids separator, the clarified water phase is returned to the bioreactor. This sulfur slurry is further concentrated into a sulfur paste, with around 65 % wt sulfur content, in a decanter-centrifuge. The sulfur paste produced at the Paques unit is routed to Landfill.

pg. 6

pg. 7

MATERIAL BALANCE ACROSS ABSORBER

pg. 8

By ideal gas behavior we can calculate the kmoles of natural gas PV=NRT N=PV/RT =12*200000/.08206*283 =103345.91 kmoles/day Basis: 103345.91 kmoles/day of natural gas Methane in feed=0.84429*103345.91 =87253.91 kmoles/day Co2 in feed=0.02506*103345.91 =2589.84 kmoles/day H2s in feed=0.00202*103345.91 =208.75 kmoles/day Other gas=5.16+63+4249+4586.49+2109.29+512.59+890.84+341.04+290.40+218.05+120.91 =13386.77 kmoles

Reactions:H2S+NaOHNaHS+H2O----- 1 CO2+NaOHNaHCO3---------2 NaOH+NaHCO3Na2CO3+H2O-----3 H2S+Na2CO3NaHS+NaHCO3-----4

According to stoichiometry of reaction---1 1kmoles of H2S =1kmole of NaOH 208.75 kmoles of H2S=?

pg. 9

NaOH required=2589.84 kmoles/day. Total NaOH required=208.75+2589.84 kmoles/day Assuming 50%excess NaOH is supplied = 2798.59*1.5 = 4197.88 kmoles/day Assuming 50% concentration NaOH is used =4197.88/0.5 =8395.76 kmoles/Day Amount of water =0.5*8395.76 =4197.88 kmoles/Day 70% conversion of H2S with NaOH =.7*208.75 =146.12 kmoles/Day According to Stoichiometry of reaction 1 NaOH reacted=146.12 kmoles/Day NaHS produced=146.12 kmoles/Day H2O produced = 146.12 kmoles/Day 72% conversion of CO2 with NaOH =.72*2589.84 =1864.68 kmoles/Day According to stoichiometry of reaction 2 1kmoles of CO2= 1kmoles of NaHCO3 1864.68 kmoles of co2=? NaHCO3 produced=1864.84 kmoles/Day
pg. 10

NaOH Reacted = 1864.48 kmoles/day NaOH Unreacted=839.76-(146.12+1864.68) = 6384.96 kmoles/Day Comparing the values NaOH Ureacted and NaHCO3 produced it is found that limiting component is NaHCO3 60% conversion of NaOH with NaHCO3 NaHCO3 reacted =10.6*1864.68 =1118.80 kmoles/Day Na2CO3 Produced =1118.80 kmoles/Day According of stoichiometry of reaction 3 1kmoles of NaHCO3= 1 kmoles of NaOH 1118.86 kmoles of naHCO3=? NaOH required =1118.86kmoles/Day H2O produced =1118.86 kmoles/Day Total NaOH Unreacted =5266.1 kmoles/Day 60 % conversion of H2S and Na2CO3 According of stoichiometry of reaction 4 Na2CO3 reacted =.6*62.62 =37.57 kmoles/Day H2S unreacted =25.028 kmoles/Day NaHCO3 produced=37.17 kmoles/Da NaHS produced=37.17kmoles/Day Co2 leaving absorber =0.28*2589.84 =725.15 kmoles/Day

pg. 11

INPUT DATA SR. NO. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 COMPONENT H2 He N2 Co2 H2S C1 C2 C3 i-C4 n-C4 i-C5 n-C5 C6 C7 NaOH H2O Kmoles/day 5.16 63 4249 2589.84 208.75 87253.91 4586.49 2109.29 512.59 890.84 341.04 290.40 218.05 120.91 8395.76 4197.88 116032.91 OUTPUT OF GASES SR. NO. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 COMPONENT H2 He N2 Co2 H2S C1 C2 C3 i-C4 n-C4 i-C5 n-C5 C6 C7 Kmoles/day 5.16 63 4249 725.17 25.048 87253.91 4586.49 2109.29 512.54 890.84 341.04 290.40 218.05 120.91 101390.8 Kg/hr 10.32 126 59486 31905.148 85.6 1396062.56 137594.7 92808.76 29730.22 51668.72 24554.88 20908.8 18752.3 12091 1876551.02 Kg/hr 10.32 126 59486 113952.96 7097.5 1396062.56 137594.7 92808.76 29730.22 51668.72 24554.88 20908.8 18752.3 12091 335830.4 75561.84 2376236.6

pg. 12

OUTPUT OF LIQUIDS SR. NO. 1 2 3 4 5 COMPONENT NaOH NaHS Na2CO3 NaHCO3 H2O Kmoles/day 5266.1 183.69 1081.29 783.31 5462.86 12067.31 Kg/day 21064.4 10286.64 114616.74 65798.04 98331.48 499676.9

pg. 13

ENERGY BALANCE ACROSS ABSORBER

pg. 14

INPUT DATA:SR. NO. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 COMPONENT H2 He N2 Co2 H2S C1 C2 C3 i-C4 n-C4 i-C5 n-C5 C6 C7 NaOH H2O Kmoles/day 5.16 63 4249 2589.84 208.75 87253.91 4586.49 2109.29 512.59 890.84 341.04 290.40 218.05 120.91 8395.76 4197.88 116032.91 Kg/hr 10.32 126 59486 113952.96 7097.5 1396062.56 137594.7 92808.76 29730.22 51668.72 24554.88 20908.8 18752.3 12091 335830.4 75561.84 2376236.6

OUTPUT DATA:SR. NO. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 COMPONENT H2 He N2 Co2 H2S C1 C2 C3 i-C4 n-C4 i-C5 n-C5 C6 C7 Kmoles/day 5.16 63 4249 725.17 25.048 87253.91 4586.49 2109.29 512.54 890.84 341.04 290.40 218.05 120.91 101390.8 Kg/hr 10.32 126 59486 31905.148 85.6 1396062.56 137594.7 92808.76 29730.22 51668.72 24554.88 20908.8 18752.3 12091 1876551.02

pg. 15

TOTAL LEAVING THE ABSORBER:SR. NO. 1 2 3 4 5 COMPONENT NaOH NaHS Na2CO3 NaHCO3 H2O Kmoles/day 5266.1 183.69 1081.29 783.31 5462.86 12067.31 Kg/day 21064.4 10286.64 114616.74 65798.04 98331.48 499676.9

(Heat with gas feed)+(Heat with NaOH feed)+(Heat of reaction) = (Heat in Vent stream) + (Heat in Bottom stream) Heat In gas feed :-

= 103345.91 320.156 = 33086813.16 kcal/hr. Heat in NaOH feed:-

= 12593.64 0.26 40 = 130973.85 kcal/hr. Heat of Reaction:(-13146.12)+ (-301864.68) + (-101118.86) + (-1237.57) = -69479.4 kcal/hr.

Heat in Vent stream:Q=m

= 101390.8 326.376 = 33091523.74 kcal/hr.

pg. 16

Heat in Bottom:Q=mCpT =12067 0.47 (50-40) = 56714.9 Kcal/hr. (33086813.16) + (130973.85) (69479.4) = (33091523.74) + (56714.9) 33148307.61 = 33148238.6

pg. 17

PIPING & INSTRUMENTATON DIAGRAM OF ABSORBER

pg. 18

pg. 19

LINE SIZING

pg. 20

FOR GAS FEED LINE :

Q = AV Putting the values (2.314) = /4*di2 * 18 = 0.404 m = 16 inches Calculate the Reynolds number Nre = DV\ = (0.404 * 18*11.89)\(0.01) = 8646.40 To calculate the friction factor F = (0.25)\(log(/(3.7D) + (5.74\(Nre^0.9)))2 Where = 150 mm for plastic (roughness factor) Putting the values F = 0.0328 Calculate the pressure drop P = FLV2\2D * 10-5 Where L = length of pipe line Putting the values P = 0.15 bar/100 m Pressure drop within th given range hence it is corrected. FOR NaOH FEED: Q = AV (4.19* 10-3) = ((/4)*D2 )* 2 D = 0.05063 m
pg. 21

D = 2 inches FOR VENT GAS LINE SIZE Q = AV (1.989) = ((/4)*D2 )* 16 D = 0.411 m = 16 inches Calculate the Reynolds number Nre = DV\ = (0.411 * 16*11.73)\(0.01) = 7713.64 To calculate the friction factor F = (0.25)\(log(/(3.7D) + (5.74\(Nre^0.9)))2 Where = 150 mm for plastic (roughness factor) Putting the values F = 0.251 Calculate the pressure drop P = FLV2\2D * 10-5 Where L = length of pipe line Putting the values P = 0.4 bar/100 m Pressure drop within the given range hence it is corrected.

pg. 22

FOR BOTTOM LIQUIDS: Q = AV (8.22* 10-3) = ((/4)*D2)* 5 D = 0.0457 m D = 2 inches.

pg. 23

DESIGN OF ABSORBER

pg. 24

The removal of one or more component from gases by using suitable solvent is known as absorption which is on of the most important process in mass transfer. The purpose of absorbing gases are as followed. For the separation of component having economic value. For removal of undesired compounds.

TYPES OF ABSORBER
Packed column. Plate column.

COMPARISON BETWEEN PACKED & PLATE COLUMN

Packed columns small-diameter columns (less than 0.6m) more choices in materials of construction for packings especially in corrosive service (e.g. plastic, ceramic, metal alloys) lower pressure drop (important in vacuum distillation) Less liquid entrainment low liquid hold-up, especially suitable for thermally sensitive material.

Plate columns variable liquid and/or vapour loads low liquid rates large number of stages and/or diameter high liquid residence time dirty service (plate columns are easier to clean) Presence of thermal or mechanical stress due to large temperature changes which might lead to cracked packings.

Packings The packing are divided in those types which are dumped at random in to the tower & these must be stacked by hand. Dumped packed consisting of unit of to 2 inches in major dimension & are used in roost small Columns. The principal requirements of tower packing are as follows : It must be chemically inert to the fluids in the tower. It must be strong without excessive weight. It must contain adequate passages for the contacting streams without excessive pressure drop. It must provide good contact between the contacting phases.
pg. 25

It should be reasonable in cost. Common packing used are: Berl Saddle. Intalox Saddle. Rasching rings. Pall rings. DESIGNING OF ABSORBER Compositions of components in a gas mixture Entrance Components Kmoles/day 5.16 63 4249 2589.84 208.75 87253.91 4586.49 2109.29 512.59 890.84 341.04 290.40 218.05 120.91 1033345.91 Kg/day 10.32 126 59486 113952.96 7097.5 1396062.56 137594.7 92808.76 29730.22 51668.72 24554.88 20908.8 18752.3 12091 1964847.34

H2 He N2 CO2 H2S C1 C2 C3 i-C4 n-C4 i-C5 n-C5 C6 C7 Total

Compositions of components in a liquid mixture Entrance

components Naoh H2O Total

Kmoles/day 8395.76 4197.88 12593.64

Kg/day 335830.4 75561.84 411392.24

pg. 26

Compositions of components gas mixture at Exit Components H2 He N2 CO2 H2S C1 C2 C3 i-C4 n-C4 i-C5 n-C5 C6 C7 Total Kmole/day 5.16 63 4249 725.117 25.048 87253.91 4586.49 2109.29 512.59 890.84 341.04 290.40 218.05 120.91 101390.8 Kg/day 10.32 126 59486 31905.148 851.632 1396062.56 137594.7 92808.76 29730.22 51668.72 24554.88 20908.8 18752.3 12091 1876551.02

Compositions of components Liquid mixture at Exit Components NaOH NaHS Na2CO3 NaHCO3 H2O Total Kmoles/day 5266.1 183.69 1081.29 783.31 5462.86 12777.25 Kg/day 210644 10286.08 114616.74 65798.04 98331.48 614293.08

Flow rate of liquid entering the absorber: 10.54 kg/s Flow rate of gas entering the absorber: 22.74 kg/s Density of gas: 11.89 kg/m3 Density of liquid at 40C: 2840 Kg/m3 FOR FINDING COLUMN DIAMETER By using the formula Flv = (Lw\Vw)*( v/l)0.5

pg. 27

Flv = 0.03 From fig 1 at 42mm H20/ m 0f packing the ordinate found to be K4 = 1.75 At flooding K4 = 4.5 % Flooding = (1.75/4.5)*100 = 63 % Vw * = (K4v (l-v)/13.1Fp (l\l)0.1)0.5 = (1.75 * 11.89 (2840-11.89) \ (13.1 * 82 *(0.0023/2840)0.1)0.5 = 13.31 kg/m2s Column area required = 22.74\13.31 = 1.708 m2 Diameter of column = ((4\)*1.708)0.5 = 1.47 m2 = 1.5 m2 Column area required = ((/4)*(1.5)2 ) = 1.767 m2 Packing to column diameter ratio = (1.5\0.005) = 30 Percentage of flooding at selected diameter = 63 *(1.55/1.767) = 56 % Could consider reduced diameter.

pg. 28

TO FIND THE HEIGHT OF COLUMN

As the concentration of solute is very small therefore the flow rate of gas & liquid will be constant throughout the column & the operating line as well as equilibrium curve for the system is a straight line. According to the solubility data of H2S & CO2 with NaOH is a straight line with slope 0.203 at 12 bar & 313 K. Y*= 0.203X M=0.203 & Gm = 1.17 kmoles/s M = slope Gm = Gas flow rate Partial pressure of H2S & CO2 Mixture at inlet = (0.02708*760) = 20.58 mm Hg Partial pressure of H2S & CO2 Mixture at outlet = ((0.0075*20.59)) = 0.1544 mm Hg Y1\Y2 = P1\P2 = 20.58\0.1544 = 136. From fig 2 the values obtained are: MGm/Lm NOG 0.6 9.6 0.7 12 0.75 13.8 0.8 16.2

Generally the optimum value taken in 0.7. ((0.203*1.17)\Lm)) = 0.7 Lm = 0.34 Taking material balance across absorber G (Y1-Y2) = L(X1-X2) Assume X2 = 0 1.17(Y1-0.0027) = 0.34(X1-0) Y1 = 0.3 X1+ 0.0027 X1 = 3.44(Y1-0.0027)

pg. 29

Assuming the value of Y then plot a graph of X v/s Y & Y* v/s X Y 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09 0.1 X 0.032 0.0761 0.1212 0.165 0.211 0.254 0.298 0.340 0.384 0.428 Y* 0.000646 0.0154 0.024 0.0335 0.043 0.0515 0.060 0.0069 0.078 0.087

Then plotting the graph the value of NoG = 12 For two inches plastic pall ring HG=0.43 & HL = 0.5 HoG = HG + (MGm/Lm) * HL = 0.43 + (0.7)*0.5 = 0.779 Z = HoG * HoG 12 * 0.779 = 9.35 m Allowance for liquid distribution = 1.2 m Allowance for gas distribution = 1.2m Total height of the column = 9.35 + 1.2 + 1.2 = 11.75 m = 12 m

pg. 30

CALCULATION OF PRESSURE DROP This bed should in two section threby requiring one intermediate combing support & Redistrbution plate. It require one bottom support plate. Pressure drop due to one redistributor plate & one Bottom plate = 2 mm of H2O Total pressure drop = 9.35*0.5 + 2 = 6.67 Kpa = 0.0667 bar Calculation of pressure drop at flooding region P = 3mm H2O / m Packing = 3* 9.35 + 2 = 30.05 Kpa = 0.30 bar

CALCULATION FOR LIQUID HOLDUP

Htw = 0.0004(L/Dp)0.6 L = liquid flow rate in lb/hrft2 Dp = size of packing in Ft. Htw = 0.0004(7771.5/0.164)0.6 = 0.255 ft3 of water/ft3 of volume

pg. 31

pg. 32

EQUIPMENT LIST

pg. 33

Equipments KNOCKOUT DRUMS PUMPS COMPRESSORS BIOREACTORS BLEED WATER TANK SEPERATOR SLURRY HEATER DECANTER HEATER FLASH DRUM STORAGE TANKS

Quantity 2 5 2 1 1 1 1 1 1 1 5

pg. 34

CONCLUSION

pg. 35

Removal of hydrogen sulfide from industrial gases is required for reasons of Environment, health, safety and corrosion free operations. For this reason, the economic viability of H2S removal technologies is based on the minimization of capital and operating cost. This process recover 99.9% of sulphur from crude natural gas.as this process is cheap as compared to any other sulphur recovery processes. The bacteria available are also free no need to purchase it. Also there is no need to replace the bacteria. No need for catalyst. Sulfur is a major nutrient which ranks fifth or sixth in quantity of macronutrients taken up by plants; this is comparable to the demand for phosphorus. Plant leaves can take up sulfur from the atmosphere as very reduced (COS, CS2 and H2S) up to highly oxidized compounds from the atmosphere as very reduced (COS, CS2 and H2S) up to highly oxidized compounds (SO2). However, most of the sulfur is taken up by plant roots as water-soluble sulfate. Because of the adoption of pollution control measures in industrial countries the decrease in SO2 emissions between 1980 and 1987 varied from 22% in Poland to 64% in France. Several countries switched from coal-fired to gas-fired industries at the end of the 1960s.The improvement in air quality was beneficial to natural ecosystems, but from the late 1980s onwards, the decreased sulfur supply resulted in a widespread S deficiency in the soils used for cultivation of several highly S-demanding crops, such as oilseed rape and cereals in Denmark, England, F.R.G. and Scotland.

pg. 36

Fig no : 1

pg. 37

pg. 38

Fig No : 2

Table

pg. 39