Presentazione di PowerPoint

1

SO2 removal from metallurgical process off gasby Michele Genova

Environmental protection and industrial activity in the North Norilsk. 11-14 September, 2012NMilano, 18 Aprile 2012Environmental protection and industrial activity in the North - Norilsk. 11-14 September, 20121 OutlineIntroductionGas cleaning unitSulphur Dioxide Concentration UnitSulphur Recovery UnitSulphur Storage and Handling FacilitiesConclusion

NMilano, 18 Aprile 2012Environmental protection and industrial activity in the North - Norilsk. 11-14 September, 2012Our groupSix leading companies operating worldwidePermanent Employees: 57,000NMilano, 18 Aprile 2012Environmental protection and industrial activity in the North - Norilsk. 11-14 September, 2012

41%38%8%5%5%3%Sales by CompanyTechint Group Revenues: Over USD 24 billion as of Dec 31, 2011Our group

NMilano, 18 Aprile 2012Environmental protection and industrial activity in the North - Norilsk. 11-14 September, 20124Available services: Feasibility Studies Basic and FEED Detail Engineering Project Management Procurement Services Construction Construction Management Project Financing Commissioning Operation and Maintenance

What we do

NMilano, 18 Aprile 2012Environmental protection and industrial activity in the North - Norilsk. 11-14 September, 20125INTRODUCTIONTechint is involved to design & implement the technical solutions for elementary sulphur recovery from flue gases coming from metallurgical plant.

The adopted technical solutions consent to reduce the sulfur emissions of 95% wt producing Elementary Sulfur. NMilano, 18 Aprile 2012Environmental protection and industrial activity in the North - Norilsk. 11-14 September, 2012Purification and cooling of the flue gas streamPhysical absorption of sulfur dioxideStripping of sulfur dioxideCooling and compression of the sulfur dioxide productReduction of sulfur dioxide to hydrogen sulfideSulfur recovery unitLiquid and solid sulfur storage facilitiesThe selected processes includes the following units:INTRODUCTIONNMilano, 18 Aprile 2012Environmental protection and industrial activity in the North - Norilsk. 11-14 September, 2012The aim of the cleaning unit is to purify the flue metallurgical gases before sending them to the SO2 concentration units.

In the flue gas cleaning unit all the impurities such as heavy metals, sulfuric acid mist and halogens are removed to avoid the following implications on the downstream equipment:Corrosion of the EquipmentHigh consumption of solventContamination of the product.

FLUE GAS CLEANINGNMilano, 18 Aprile 2012Environmental protection and industrial activity in the North - Norilsk. 11-14 September, 2012

FLUE GAS CLEANINGNMilano, 18 Aprile 2012Environmental protection and industrial activity in the North - Norilsk. 11-14 September, 2012Reverse Jet ScrubberHot gas quenchingParticulate removalAcid gas absorptionUses large orifice liquid injectorsNon-atomizingNon-plugging

FLUE GAS CLEANINGSource: MECSNMilano, 18 Aprile 2012Environmental protection and industrial activity in the North - Norilsk. 11-14 September, 2012

Uses pressure drop effectively Doubles removal efficienciesReduces costs by using multiple Reverse Jets in single inlet barrelFLUE GAS CLEANING

Multiple Jet ScrubberSome advantages of the technology are:Source: MECSNMilano, 18 Aprile 2012Environmental protection and industrial activity in the North - Norilsk. 11-14 September, 2012110FLUE GAS CLEANINGWet Electrostatic Precipitators

Source: GEA BischoffNMilano, 18 Aprile 2012Environmental protection and industrial activity in the North - Norilsk. 11-14 September, 2012FLUE GAS CLEANING

Source: GEA BischoffNMilano, 18 Aprile 2012Environmental protection and industrial activity in the North - Norilsk. 11-14 September, 2012SO2 CONCENTRATION

Source: MECSPhysical Absorption SystemSelectively absorbs SO2 from the gas streamSO2 emissions - 300 ppmv or lessSome contaminants like CO2 are also absorbed to a lesser extentSO2 is stripped from the solvent with heatNMilano, 18 Aprile 2012Environmental protection and industrial activity in the North - Norilsk. 11-14 September, 2012Physical vs Chemical AbsorptionPhysical AbsorptionAprotic SolventNo Chemical ReactionsLower Solvent LossSimple ChemistryOrganic systemLower Steam UsageHigher L/G Follows Henrys LawChemical AbsorptionProtic SolventMany Chemical ReactionsHigher Solvent LossComplex ChemistryAqueous systemHigher Steam UsageLower L/GNo Henrys LawSO2 CONCENTRATIONNMilano, 18 Aprile 2012Environmental protection and industrial activity in the North - Norilsk. 11-14 September, 2012Process Differences Chemical versus Physical SolventMuch more energy required for regenerating chemical solvent.Capital cost for regenerating chemical solvent is higher than for physical solvent.More process steps for regenerating chemical solvent.Absorption step is similar.SO2 CONCENTRATIONNMilano, 18 Aprile 2012Environmental protection and industrial activity in the North - Norilsk. 11-14 September, 2012SO2 CONCENTRATION

NMilano, 18 Aprile 2012Environmental protection and industrial activity in the North - Norilsk. 11-14 September, 2012SO2 ConcentrationInlet Gas Conditions of SO2 concentration units Gas Stream contaminants (Particulate, Acid Mist) have a significant impact on solvent loss:10 mg/Nm3 Particulate Desired20 mg/Nm3 Acid Mist DesiredProduct SO2 StreamConcentrated SO2 up to 98% wt, with some impurities, particularly CO2, depending on inlet gas conditions and water saturatedNMilano, 18 Aprile 2012Environmental protection and industrial activity in the North - Norilsk. 11-14 September, 2012SO2 ConcentrationReference Project

Design basis300,000 Nm3/h0.2% SO2Performance100 ppm SO298% SO2 after CO2 strippingSource: MECSNMilano, 18 Aprile 2012Environmental protection and industrial activity in the North - Norilsk. 11-14 September, 201220

Sulphur Recovery UnitNMilano, 18 Aprile 2012Environmental protection and industrial activity in the North - Norilsk. 11-14 September, 2012201120121Sulphur Recovery Unit (SRU)The sulphur recovery unit could include the following section:SO2 Feeding to SRUThermal stage (Burner, furnace & Waste heat Boiler)Catalytic stage (Claus Reactors and Condensers)Tail gas incinerator and heat recoverySulphur degassing storage and exportSulphur solidification (if any) and solid sulphur handling systemsNMilano, 18 Aprile 2012Environmental protection and industrial activity in the North - Norilsk. 11-14 September, 20122111211Sulphur recovery facilities are provided to produce sulphur from concentrated streams of sulphur dioxide.

The overall sulphur recovery is at least 95% based on the SO2 feed to the concentrator units. Losses from the concentrator units mean that the sulphur recovery facilities need to recover more than 95% of the sulphur fed to them.

Sulphur Recovery Unit (SRU)NMilano, 18 Aprile 2012Environmental protection and industrial activity in the North - Norilsk. 11-14 September, 201223The heart of this special SRU is the thermal reactor where the SO2 is reduced to H2S and sulphur by a combination of reducing gases generated from the combustion of the natural gas.

The furnace gases are cooled in the WHB, which is used to generate steam for process heating in the Claus unit. The excess high pressure steam is exported. The gases react during cooling in the WHB tubes and the sulphur species in the outlet tail gas are mainly H2S, SO2, COS, CS2 and sulphur vapour.

Sulphur Recovery Unit (SRU)NMilano, 18 Aprile 2012Environmental protection and industrial activity in the North - Norilsk. 11-14 September, 2012231123124The overall reactions taking place in thermal reactor during the direct reduction of SO2 can be summarized in:Sulphur Recovery Unit (SRU)@ ~ 1200 C2SO2 + + 4H2S CH4 S2 + 2H2O + CO26SO2 + 4CH4 S2 + 4H2O + 4CO2 @ ~ 1200 C(4n+m) 2CnHm +mH2O + 2nCO2The heat will be provided by the combustion of fuel gas:2O2NMilano, 18 Aprile 2012Environmental protection and industrial activity in the North - Norilsk. 11-14 September, 2012241124125The gases heated at the correct temperature using a steam heater enter in the Claus reactors where H2S and SO2 react to form more sulphur, the process gases flow to the condensers; the condensed sulphur drained to the degassing system via a seal leg.

The tail gases from the final Claus condenser containing Sulphur compounds and about 4% H2 and 6% CO, are incinerated at 800C to convert all the sulphur compounds to SO2. Sulphur Recovery Unit (SRU)NMilano, 18 Aprile 2012Environmental protection and industrial activity in the North - Norilsk. 11-14 September, 2012251125126The effluent from the incinerator is cooled in the incinerator WHB before be discharged to the existing chimney. The steam is generated at adequate pressure in the WHB so that this can be used as heating steam for the Claus. The steam pressure in the WHB will be selected in order that the tube wall temperature is higher than the sulphuric acid dew point to avoid corrosion in the chimney.

Sulphur Recovery Unit (SRU)NMilano, 18 Aprile 2012Environmental protection and industrial activity in the North - Norilsk. 11-14 September, 2012261126127Sulphur is rundown from the condensers to a sulphur collection pit with sufficient capacity for 24 hour hold-up of the produced sulphur. The sulphur is degassed sufficiently to reduce odour during the solidification of the sulphur.

Sulphur is circulated around the pit via sulphur pumps in order to stir the liquid and reduced Hydrogen Sulfide content.. Sulphur Recovery Unit (SRU)NMilano, 18 Aprile 2012Environmental protection and industrial activity in the North - Norilsk. 11-14 September, 20122711271Sulphur Recovery UnitReference ProjectClient :WEPECType :SRU + TGTProcess :LGIApplication :RefineryCapacity :315 t/dayHydraulically equivalent to 1 train to be design for MZ Copper plantSite :ChinaSource: LGI

NMilano, 18 Aprile 2012Environmental protection and industrial activity in the North - Norilsk. 11-14 September, 2012The liquid Sulphur could be solidify or sale as well as it is. The granulation unit consists of packaged granulating systems, complete with one liquid sulphur conditioning system. The conditioning system consists of a liquid-sulphur filter, liquid-sulphur cooler, liquid-sulphur day vessel and sulphur day vessel pumps for liquid sulphur feed to the granulators. The granulator system could be sized to granulate the total capacity of sulphur. Each unit could produce up to 400 metric tonnes of high quality granules per day. Storage and PackingNMilano, 18 Aprile 2012Environmental protection and industrial activity in the North - Norilsk. 11-14 September, 2012SummaryTo optimize the size of SRU, you install the SO2 concentration unit, using a physical solvent to reduce also the OPEX.To minimize the solvent degradation, you clean the metallurgical process off gas to remove all the impurities such as heavy metals, sulfuric acid mist and halogens.SO2 from metallurgical process off gas could be efficiently removed using a modified Claus process with a special thermal reactor. The aim of this reactor is to optimize the ratio of SO2 and H2S before to feed the process gas to Claus converters.With the presented process you recover not less than 95% of Sulphur, contributing significantly to reduce the pollution of the environmental. NMilano, 18 Aprile 2012Environmental protection and industrial activity in the North - Norilsk. 11-14 September, 201230The author thanksLE GAZ INTEGRALMECSGEA BISCHOFF for the permission to use their information.AcknowledgementsNMilano, 18 Aprile 2012Environmental protection and industrial activity in the North - Norilsk. 11-14 September, 201231

32Michele Genova - email: michele.genova54@gmail.commobile +39 335 7750 947THANK YOU FORYOUR ATTENTION

SO2 removal from metallurgical process off gasNMilano, 18 Aprile 2012Environmental protection and industrial activity in the North - Norilsk. 11-14 September, 201232Chart10.410.380.080.050.050.03

Sheet1Torta per Presentation StdSales by CompanySales by Region41%10%38%8%8%4%5%37%5%41%3%Sales by CompanySales by Region

Sheet1000000

Sheet200000

Sheet3

Chart1000.35005204980.1013250.58905674880.18131842110.61328289470.20839010670.88118383130.32530657891.02924868420.40413604681.1882058050.49062631581.491739640.78393552631.54120657890.82417529841.82320013431.23189868422.03716578951.76645893032.11990653262.11182631582.42578483794.34630921052.55445657896.81034232672.5704286487.09808289473.08774605260.25091314613.59437105260.28335501744.10099605260.31551649164.36764078950.33003424114.67161578950.3451463825.30623026320.37456561096.03683684210.40313927836.74611184210.42873851627.69536710530.45475648478.59129342110.4761459121

PhysicalChemicalSulfur Dioxide in Liquid Phase (mole %)SO2 Partial Pressure (kPa)Sulfur Dioxide Solubilityin Physical and Chemical Absorbents

Sheet1Dimethyl Aniline and XylidineChart Values in cmXDMAXyl-H2Ogm/LDMAXyl-H2O0.000.000.000.000.000.001.121.150.1929.190.610.101.901.930.3449.521.020.182.852.890.6174.281.520.323.803.820.9299.042.010.484.824.791.47125.632.520.775.815.792.31151.433.051.226.736.743.96175.413.552.087.697.698.15200.434.054.298.148.1913.31212.164.317.018.628.76224.674.619.599.95249.965.2410.5811.32275.765.9611.5112.65300.006.6612.5014.43325.807.5913.3516.11347.968.48Physical PropertiesSO2MW=64.06Density=1.4340gm/ccV=44.6722DMAMW=121.210Density=0.9564gm/ccV=126.7322XylidineMW=121.210Density=0.9850gm/ccV=123.0558H2OMW=18.015Density=0.9982gm/ccV=18.0473Xyl-H2OMW=69.613Density=0.9867gm/ccV=70.5516For DMAXso2wSO2VmixMWmixdmixgm SO2/lgm SO2/lErrorYso2Henry0.05570.0302122.1639118.02850.966129.192029.19200.00000.6182.63000.09210.0509119.1722115.94490.972949.522249.52220.00001.0283.79720.13420.0757115.7207113.54110.981274.283374.28320.00001.5286.14750.17390.1001112.4635111.27270.989499.044399.0443-0.00002.0187.87580.21410.1258109.1644108.97500.9983125.6299125.62990.00002.5289.49700.25090.1504106.1423106.87031.0069151.4335151.4335-0.00003.0592.30290.28340.1728103.4801105.01631.0148175.4127175.41270.00003.5595.14570.31550.1959100.8409103.17821.0232200.4344200.4344-0.00004.0597.49090.33000.206699.6496102.34851.0271212.1634212.16330.00004.3199.26240.34510.217998.4095101.48491.0313224.6742224.67420.00004.61101.52210.37460.240495.995499.80361.0397249.9566249.95660.00005.24106.25640.40310.263193.650698.17061.0483275.7601275.7602-0.00015.96112.31850.42870.284091.549996.70761.0563300.0001300.00000.00016.66118.02070.45480.305989.414995.22071.0649325.8036325.8036-0.00007.59126.92510.47610.324587.659793.99831.0723347.9582347.9583-0.00018.48135.3367For Xylidine-Water MixtureXso2wSO2VmixMWmixdmixgm SO2/lgm SO2/lErrorYso2Henry0.03180.029369.729269.43610.995829.192029.1920-0.00000.1023.91780.05350.049469.167869.31561.002149.522249.5222-0.00000.1825.43450.07940.073668.496069.17151.009974.283274.2832-0.00000.3230.72000.10490.097367.837269.03011.017699.044499.04430.00000.4835.08620.13170.122567.143868.88141.0259125.6299125.62990.00000.7744.65450.15720.146566.484368.73981.0339151.4335151.4335-0.00011.2258.79200.18040.168465.882868.61081.0414175.4127175.41270.00002.0887.80290.20420.191065.266768.47861.0492200.4345200.43440.00014.29159.63940.21520.201564.981968.41751.0529212.1634212.16330.00017.01247.37861 atm=101.3250XSO2PhysicalChemical0000.03180.35005204980.1013250.05350.58905674880.18131842110.05570.61328289470.20839010670.07940.88118383130.32530657890.09211.02924868420.40413604680.10491.1882058050.49062631580.13171.491739640.78393552630.13421.54120657890.82417529840.15721.82320013431.23189868420.17392.03716578951.76645893030.18042.11990653262.11182631580.20422.42578483794.34630921050.21412.55445657896.81034232670.21522.5704286487.09808289470.25093.08774605260.28343.59437105260.31554.10099605260.33004.36764078950.34514.67161578950.37465.30623026320.40316.03683684210.42876.74611184210.45487.69536710530.47618.5912934211Henry's Law Constant83.7972at T =20Hsln=10.82114.4240996875at T =25

&APage &P

Sheet1

PhysicalChemicalSulfur Dioxide in Liquid Phase (mole %)SO2 Partial Pressure (kPa)Sulfur Dioxide Solubilityin Physical and Chemical Absorbents

Sheet2

&APage &P

Sheet3

&APage &P

Sheet4

&APage &P

Sheet5

&APage &P

Sheet6

&APage &P

Sheet7

&APage &P

Sheet8

&APage &P

Sheet9

&APage &P

Sheet10

&APage &P

Sheet11

&APage &P

Sheet12

&APage &P

Sheet13

&APage &P

Sheet14

&APage &P

Sheet15

&APage &P

Sheet16

&APage &P

Chart34.94.94.923.54.9114.2

PhysicalChemicalGas Strength (% SO2)Solvent Loss (lb/MMSCF)Solvent LossPhysical vs Chemical Absorpiton

Sheet1Comparison of Solvent LossSO2 ConcPhysicalChemical0%4.94.94%4.923.58%4.9114.2Solvent LossLinde AG DataSachtleben Chemie-Dynamit Nobel PlantFlow =29000NM3/hrfrom Linde AG Reference ListLoss =10Ton/yrfrom Pilot Plant ReportLoss =2.46lb/MMSCFInventory =20TonTurnover =50.0%per yearLegnica in PolandFlow =225000NM3/hrfrom Pilot Plant ReportLoss =133.3333333333Ton/yrfrom Pilot Plant ReportLoss =4.22lb/MMSCFInventory =220TonTurnover =60.6%per year

&APage &P

Sheet1

PhysicalChemicalGas Strength (% SO2)Solvent Loss (lb/MMSCF)Solvent LossPhysical vs Chemical Absorpiton