costs of reducing S02 emissions and improving effluent water quality from refineries prepared by the CONCAWE ‘Ad hoc Group on Investment for Environmental Protection in the Petroleum Refining Industry L. Bardone P. Baudoin F. Bordet JV. Delfosse L. Ferrari F. Goethe! E.K. Johnson E.J. Molt M. Nesse B.EH. Pettyfer P. Vuillermet (Od. Walther This report does not necessarily represent the views of any company participating in CONCAWE Reproduction permitted with due acknowledgement © CONCAWE Den Haag March 1977, report nr. 5/77CONTENTS SUMMARY 1. INTRODUCTION 2. GENERAL. 2.1 REFINERY CONFIGURATIONS S02 EMISSIONS BASIC ASSUMPTIONS Refinery Capacity Crude Slate Product Quality Refinery Consumption (Refinery Fuel and Loss)% wt on Crude Distribution of Finished Prouducts (% Weight) Further Assunptions SO EMISSION CONTROL Facilities for S02 Emission Control Calculation of SO, Emission Control COST OF CONTROL FACILITIES OPERATING Costs ENERGY REQUIREMENT CONCLUSIONS ON COST OF REDUCING SO, EMISSIONS EFFLUENT WATER TREATMENT CONTINUOUSLY CONTAMINATED STREAMS Process Unit Drainage Crude Tanks Drainage Polluted Condensate Discharges From Laboratory Discontinuous Effluents Rain Water Sanitary Waters Boiler Blow-Down and Domineralization Unit Backwash ACCIDENTALLY CONTAMINATED STREAMS Discontinuous Effluents Blow-Down From Cooling Tower Rain Water ‘TREATMENT UNITS 1 For Continuously Contaminated Waters 2 For Accidentally Contaminated Waters 3 For Boiler Blow-Down and Demineralization Unit Backwash Streans For Sanitary Water For Sludges Resulting From Water Treatment page ©ee eeIIIw3 a un 14 14 7 7 47 47 47 18 as 18 19 19 19 19 19 19 20 20 21 21 21 21EFFLUENT WATER QUALITY COST ESTIMATES Investment Cost Operating Costs ENERGY REQUIREMENTS ‘COMPARISON TERTIARY TREATMENT CONCLUSIONS ON COST OF IMPROVING EFFLUENT WATER QUALITY COST ESCALATION APPENDIX I - Refinery Configurations - Detailed Description APPENDIX II - Description of the Water Treating Processes APPENDIX III - Calculation Procedure for Comparison of Investment and Operating Cost FLY SHEET - Refinery Configuration NOTE ‘The disconinuity of the page numbering is due to some blank pages that had been normally numbered in the original hard copy but left out of the scanned file in order to reduce the digital file size. 22 23 23 25 25 26 30 30 a1 33 43 51 53SUNMARY There is a relation between the costs associated with control facilities and the degree of control for both SO, emissions and water effluent quality from refineries This study has been limited to the extra investment, operating cost, and energy requirement associated with reducing $0, emissions and improving water effluent beyond the levels normally expected to be achieved in newly built oi] refineries The basic levels taken for this study are those resulting from an integrated modern refinery having a sulphur recovery unit which removes 95% of the sulphur in its feed, minimum water effluent quantities, and effluent facilities comprising interceptors for primary separation of oil by gravity For reducing S0, emissions by means of a sulphur recovery plant giving 95% recovery of sulphur in its feed, the investment is in the range of $ 0.5-0.8 million* per ton/hour $0, reduction. By comparison, when tail gas clean-up facilities are added to achieve 99% recovery of sulphur, the extra investment is in the range of $ 9.5-12.7 million* per ton/hour SO, reduction, The extra operating cost is in the range of $ 530-590* per ton SO, removed, compared with an operating cost in the range of $ 13-29% per ton SO, removed for 95% recovery For improving effluent water quality and assuming minimum water quantities, an investment in the range of $ 1.8-2.5 million® is required, depending on the refinery complexity, to achieve an expected oil content of less than 50 ppm. To achieve 50%, improvement in effluent quality raises the investment by 14-20% and to achieve 90% improvement the investment increases by 120-128%. In other words the original investment doubles. The extra operating cost to achieve 90% improvement is 227-250% higher. The increase in energy requirement was also calculated for improving effluent water quality in terms of equivalent fuel oil requirements. This energy consumption increases 2.5-3.3 times for 50% improvement and 19.6-22.8 times for 90% improvement The last stages of improvement are always expensive and the cost is out of proportion to the expected improvement. The question should always be raised whether such expenditures are not better made in other areas of environmental control where more significant improvement could be obtained. %) § are US dollars valued at 1 January 1975.Cones INTRODUCTION ‘The growing public concern for environmental protection has led national governments and intergovernmental bodies to devote increasing attention to the possibility of reducing the emission of pollutants from industry sources ‘The Commission of the European Economic Community has initiated a study on the "Problem of Pollution and Nuisances originating from Energy Production". The OECD (Organization for Economic Cooperation and Development) has completed a study on air pollution from fuel combustion in stationary sources. Nationa’ governments continue to have an interest in restricting industry emissions and exhibit a growing interest in the expenditure and incremental energy requirements associated with environmental control facilities. In the case of the oil industry these expenditures fall into two categories. One includes the cost incurred to meet new constraints on the environmental quality characteristics of petroleum products and the other the cost of minimizing undesirable emissions from operating installations Two studies of the first category have already been published by CONCAWE. They deal respectively with the cost of reducing gasoline lead content and fuel oil sulphur content. These studies were initiated following inquiries for information from the Commission of the European Economic Community which is concerned with preparation of draft directives on these issues This study is concerned with the costs and energy implications associated with reducing SO) emissions and improving water effluent quality in various types of newly built refineries (grass root), which are representative of some presently operating, and of possible future construction. The investment implications for existing refineries would be expected to be considerably higher. The control of other emissions will incur additional cost and energy use, but these have not been included in this study. Many assumptions were necessary during the study to make a quantitative assessment of the cost and energy implications. These assumptions are representative for each of the cases considered and correspond to a hypothetical situation of a refinery built in Europe for operation in the 1980's. Because of the large number of factors involved, five hypothetical refinery configurations of different complexity have been selected and various degrees of pollution control have been assumed by applying control techniques of increasing severity to these theoretical refinery cases. The control techniques have been applied in a logical optimized sequence. In a practical situation the treatment steps may overlap and the particular sequence selected for a refinery will depend on a variety of factors, which are different for any refinery location.Acknowledgement is due to Messrs. L. Bardone and L. Ferrari who carried out the calculation work on the basis of the selected refinery cases.GENERAL The cost of reducing refinery emissions depends to a large extent on the refinery complexity and on the level of emission control to be achieved In order to carry out the present study it was necessary therefore to consider a number of refinery configurations of an increasingly complex nature For each refinery case, different steps were examined corresponding ‘to increasing severity of emission control. By comparing the data obtained it is possible to assess the increased cost and energy requirements as a function of the severity of the emission control All investment and operating costs are referred to US dollars at 1 January 1975 REFINERY CONFIGURATIONS Five refinery configurations were selected. These represent modern refineries operating at present, or which could be expected to operate in the foreseeable future, if the requirement for low sulphur levels in fuel oi] continues to increase. Block diagrams of these refineries and detailed descriptions are given in full as Appendix I. The complexity increases in the following order: Case R, S, T, U and V. (For easy reference a fly sheet table has been included inside the back cover and readers are asked to refer to this fly sheet.) Briefly they are composed of the following process units and are based on a crude running capacity of 10 million tons per year. Case R is a conventional hydroskimming refinery with crude desalting and atmospheric distillation with hydro- desulphurization units for naphtha, kerosene, light and heavy gasoil, catalytic reforming, light ends recovery, 95% sulphur recovery and sour water stripping units Case S is the same as R with the addition of vacuum distillation, vacuum gasoil hydrodesulphurization and naphtha steam reforming for hydrogen production Case T is the same as R with the addition of reduced crude hydro- desulphurization and naphtha steam reforming for hydrogen production. Case U is the same as R to which has been added a vacuum distillation unit, fluid catalytic cracking and gas recovery, deasphalting, hydrodesulphurization of vacuum Gasoil, deasphalted oi1 and cycle oil, gasoline sweetening and asphalt partial oxidation for hydrogen production.Case V is the same as T with the addition of a naphtha steam cracking unit of 400,000 ton/year ethylene production capacity. It will be noted that cases 8, T, U and V, which include desulphurization of heavy fractions, such as vacuum gasoil or reduced crude, are not typical of existing refineries in Europe ‘These cases have been included as examples of refineries which may possibly be constructed in the future ‘The refinery cases taken include those environmental control items which are now considered essential in a modern refinery and would be integrated with the overall design. These items are: - amine washing = 80) monitoring system - tall stack - sour water stripper ~ segregated sewers - impermeable tank basins ~ sulphur recovery plant - air cooling to minimize cooling water requirements.fin 1. a S07 EMISSIONS BASIC ASSUMPTIONS The quantity of SO) produced in a refinery depends on a large number of parameters. For a quantitative assessment the following assumptions were made for hypothetical situation in the 1980's Refinery Capacity 10 million tons crude per year (crude distillation operating days 330). In refinery case V naphtha (1,117,750 tons/year) is imported for the steam cracking unit. Crude Slate: The crude slate assumed for this study has been that taken by the Commission of the European Communities as representative for 1980 in the EEC countries* i.e. Middle East 80% wt, African 15% wt, North Sea 5% wt. The calculated average sulphur content for this overall crude mix is approximately 1% wt. Product Quality Motor gasoline: Premium 98 RON (87 MON) at 0.40 g Pb/1t Regular 90 RON at 0.15 g Pb/1t maximum. Ratio Premium/Regular: 80/20% wt. LPG: LPG is assumed to be 50% wt C)-50% wt C, Middle and heavy distillates: Kerosene is hydrotreated in every case Gasoil Pool: 0.3% wt Sulphur. Residual fuel oils: Case R Ss T UY Sulphur content, % wt 3.00 2.00 1.00 1.00 1.00 Refinery Consumption (Refinery Case R 8 T u v Refinery Consumption 4.5 5.49 6.27 7.72 8.78 *) Document XVII/125/73. Table 5, Revision F prepared by EEC Directorate General for Energy "Economic aspects of a possible reduction of atmospheric emissions of sulphur arising from the burning of oil products".‘This study assumes refinery fuel consisting of a mixture of fuel oil and fuel gas meeting the specific maximum fuel sulphur content. ‘The costs associated with burning low sulphur fuel oil as refinery fuel are not included in this study. CONCAWE report 13/72 (and its supplement) discusses the extra costs introduced by separate desulphurization of residual fuel oils, if required. Distribution of Finished Products (% Weight) Refinery case R s T u v Ethylene : = = = 39 Propylene : = : 06 | 20 8 fractions = = 14 20 LPs 4 | 14 15 | 20 13 Naphtha + gasotine 193 | 194 | 199 | 302 | 180 Kerosene and middle distilates gee | 372 | 375 | 311 | 303 Heavy residuals a2 | 413 | 40 | 337 | 375 Sulphur | 03 | o7 1 13 10 100.0 100.0 100.0 100.0 tooo | L —_________L J Further Assumptions In order to decrease the capacity of the reduced crude HDS plant in refinery case T and V, it was assumed that during the shut down of one of the parallel reactor trains in the HDS, the high sulphur content residue that cannot be hydrotreated would be stored in tankage and subsequently blended with desulphurized residuum to meet the sulphur content specification of fuel oil. In refinery case U fuel oil is made up of desulphurized Vacuum Gasoil and Deasphalted Oil, asphalt and desulphurized Heavy Gasoil 802 EMISSION CONTROL Facilities for $0, Emission Control The first stage of SO) emission control is both amine washing of fuel gases and sulphur recovery in a Claus plant giving 95% recovery of the sulphur fed to the plant. The second stage of S02 emission control is a desulphurization plant for tail gases from the Claus plants which will produce sulphur as end-product. The tail gas cleaning unit is assumed to increase the recovery of sulphur to 992 Sulphur recovery units without tail gas clean-up facilities can also be built to recover 97% of sulphur at a relatively small incremental investment of between 15-20% of the sulphur plant. It should be noted, however, that a sustained sulphur removal in excess of 97% has not been proved generally applicable If the catalyst is regenerated in the hydrodesulphurization units there is an increase in $0, emission. This increase can be counterbalanced by burning a fuel mix of lower sulphur content in the refinery during the regeneration period. Alternatively, the gases from the regeneration are routed to the tail gas clean-up where 99% sulphur recovery can be obtained. This third stage of SO, control requires investment for suitable modification of the tail gas treatment and some modification of the desulphurizer regeneration facilities. The sulphur is assumed to be produced in the ratio of 80% solid to 20% liquid as final product. A separate stack for the tail gas plant is also assumed. The technology assumed for the reduction of S07 emission in this study is believed to be the best and most efficient available and includes back-up for equipment taken out of service All investments and operating costs are referred to US$ at 1 January 1975. Cal lation of SO) Emission Control Taking into account the assumptions described in the preceding paragraphs the SO) emission has been calculated for the various control steps applied to each of the five refineries. Table 1 indicates the contribution of fuel combustion to the $0) emission. Table 2 indicates the total $0, emission from fuel combustion and from recovery of sulphur resulting from hydrodesulphuri zation units at 0%, 95% and 99% sulphur recovery levels, using the facilities mentioned in Section 3.2.1. Table 2 also indicates the total emissions with and without the modifications to the tail gas treatment plant permitting to control the SO) produced during the catalyst regeneration.Table 1 — SO, Emission from Fuel Combustion (annual average) Refinery (1) Refinery fuel comprises oil and gas and assumed at these levels for the purpose of this study. (2) Coke burn off from FCC included in refinery fuel Refinery fuel crude owe 4.30 4.69 827 672 778 Table 2 — Total SO; Emission Fuel sulphur (1) owt max. Sulphur from | iettonyer_| SO; ton/hour emission (1) Including emission from fuel combustion See also section 3.2 for sulphur recovery level. (2) The increase of SO; emission during regeneration periods of the hydrodesulphurizer ‘can be counterbalanced as indicated previously at the end of paragraph 3.1.6. (page 8) COST OF CONTROL FACILITIES The cost of the different control steps discussed earlier have been estimated for the five refinery cases R through V. The facilities included in each case are shown on the following table As can be seen the increasing index number corresponds to increasing control severity. 10 Refinery Recovery % | ToraS0, | TotaS0, | Hydrodesulphurizer case in sulphur | emission (1) | emission (2) | regeneration plant ‘ton/hour | during HDS days/year regeneration ton/hour ~ ai a ° 82 i R, 95 24 | ees 99 18 19 6 | s, ° 184 s: 95 20 | Ss. 99 13 16 ° th | 0 281 | th | 95 27 } oa 99 16 19 36 us ° 30.2 | us 95 31 Us 99 20 | 10 vs ° 280 Ve 95 33 vs 99 22 2 | 36Table 3 — Control Facilities Included Refinery case R Ro ] Ry Ry {index ves comparison See to indicat eel of emision cn witht any sulphur recovery) uw | bd | ou wef | wy fiw _ | a Facilities Claus sulphur plant « 7 x Tags eerup = fe] Y x HDS Regeneration gas treating = * x OPERATING CosTS Operating costs included, are: capital depreciation and interest on invested capital, labour, maintenance, overhead expenses, and variable costs comprising utilities and chemicals consumption Capital depreciation and interest on capital invested were taken as an annual capital charge of 25% of the investment, Labour was based on an overall cost of $ 12,000 per man year Maintenance and overheads were taken as 2% and 0.8% respectively of capital. The net utilities cost in the variable element includes the credit for steam produced by the sulphur recovery unit. The corresponding investment, operating costs and incremental energy requirements are shown on Table 4 and on the graph series, Figure 1, for a refinery with capacity of 10 million tons/year. unconcawe Table 4 — Cost of $0; Control Level | Total SO, emission Basic ‘SO, control facilities of ton/hour refinery control investment v— | Operating cost| Invest: a 10°S (2) | required | US é/t. crude |ment FOE*)/ye Jcost (3) 0° $ Ry 82 322 eS = Ry 24 Bare 139 52 Ry 18 6292 278 90 (1.9 for 6 days/yr Re 1.8 7535 322 10.4 3) 184 405 = = = Ss; 20 Base 20.8 99 Ss 13 11180 513 169 (1.6 for 9 days/ye) Ss 13 20120 60.8 199 iets [284 aT = = S th 27 Base 2A 140 % 16 25679 725 24.4 (1.9 for 36 days/y Ts 16 31080 85.9 28.4 Uy 30.2 531 = = = Us 31 Base 28.1 147 Us 20 27273 76.1 257 (2.1 for 10 days/yr) Us 2.0 29058 Vi 28.0 758 = = Va 33 Base 29.4 147 Vs 22 24881 759 257 (2.5 for 36 days/ye) Ve 22 28248 849 28.4 (1) Explained in Section 3.3. (2) Total refinery investment includes amine scrubbing facilities but excludes the cost increment for SO control facilities which are shown in the last column (US $ at 1.1.75). (3) Tail gas unit investment costs based on limited experience available *) Fuel Oil Equivalent. 12om caw From these data the following comparisons have been calculated by the procedure given in Appendix ITI. Table 4.1— Investment Comparison — 10°$/ton SO; removed per hour Refinery R s T u v Range ‘sulphur recovery 95 08 06 06 0s 06 05-08 99 14 10 09 09 1.0 09-14 95.99, 127 10.0 95 | 100 100 95-127 Table 4.2 — Operating Cost Comparison ~ $/ton SO; removed Refinery R s i u v Range %% sulphur | recovery | 95. | 29 15, 13 13, 15, 13— 29 99 55 38 35 34 7 34-55 | 9599 | 590 860 | 520 550 540 530 — 590, The Figures No.1 and 2 on pages 13 and 14 have been derived from the Tables 2 and 4 to show investments and operating costs against the reduction in SO emission which can be obtained. In Figure 2 the incremental investment (million $) and operating cost (million § /year) have been plotted against the reduction in S02 emission (ton/hour) obtained by the sulphur recovery unit for each of the refinery types. Using the same scales we have plotted incremental investment and operating cost for the tail gas unit. It can be seen from Figure 2 how much greater is the investment and operating cost of the tail gas unit for a given reduction in S07 emissions. The incremental cost of removing sulphur from HDS regeneration gas evel of control 3 to 4) is seen to be even higher than improving from 95% to 99% recovery. 13.ENERGY REQUIREMENT The extra energy requirement for 99% sulphur recovery compared with 95% sulphur recovery calculated from electric power and fuel requirements and converted to Fuel Oil Equivalent (FOE) as given in Table 4 is in the range 0.1 - 0.3% of the annual refinery CONCLUSIONS ON COST OF REDUCING S02 EMISSIONS From the investment and operating cost comparison the following conclusions are made: 1) the investment to reduce SO) emissions by using a sulphur plant with 95% recovery is in the range of 0.5 - 0.8 million $ per ton/hour $0; reduction; 2) when tail gas clean-up facilities are added to the sulphur plant to give 99% recovery the extra investment is in the range 9.5 - 12.7 million $ per ton/nour SO reduction; 3) the operating cost for 95% recovery is in the range $ 13 to $ 29 per ton SO, removed; 4) the extra operating cost for 99% recovery is in the range $ 530 to $ 590 per ton SO, removed ‘The last few percent of sulphur recovered in such facilities is always very expensive and the cost is out of proportion to the improvement achieved. The question should always be raised whether such expenditures are not better made in other areas of environmental control where the improvement achieved would be more significant. 14Figure 1 — Reduction of SO; Emission ret, EGY equament Operating cox Investment cos Bet Gor wonvear FOE USeton ere tors Bet 102030 20.40 6080 102030 T T T ] wel TBO IB . | a] | Eo yy 5 Ry | 1} | J ime TI 5, [bose] | | | al] 1 | | 5, | } 1 | s. I 1, bom ] 1} | |e b ] ] 1 oon 1 te ] ] yo fs cr T T vs oow | Dp fu T | | us ] ] 1) Ju | us 1 ] u. LT | vel ease } } Ms I L_ | Va ] J Vs ve ve J 5 J ] 102030 30a 60 1020concawe Figure 2 Irwestment cost (10°S) 7 my _ = ‘ : nae oot ' 10 $8 ~—|10 ; ; : ; 5 AR e = 5 ; eas) 3 b, i ie g — fo | en: Omi et 0 ye 0G erry oping Cn 0 8h re ey e : ; ; | 6 T | 5 fe __| sg s s | EB Trav asenn | eat Boy Bed, | z j es! | | Bol i 4 a Reduction in SO, emission ton/hour 16con wa EFFLUENT WATER TREATNENT The effluent treating processes considered in this study are briefly described in Appendix II. A block diagram, with a material balance of the treatment units for each of the five refinery cases R through V, is given in Figure 9 of Appendix II. The estimated quantities of water discharged are given in a Table for each refinery case R, S, T, U and V in Appendix II and these quantities have been arrived at by assuming reasonable control of water usage and reasonable peak flow rates arising from natural conditions of climate and location. Peak flows from all possible combinations of climate and location, such as exceptional storm conditions, have not been included in order not to overestimate the cost and energy implications. Liquid effluents are considered in two groups. The first group includes the water streams which are continuously contaminated and the second group includes those streams, which may be accidentally contaminated. The two groups of streams flow to the treating unit through separate sewer systems. A short description of the effluent streams in each group follows. CONTINUOUSLY CONTAMINATED STREAMS These include the following streams: Process water and polluted condensate originating from process units and process steam discharged as polluted condensate. de Tanks Drainage The average water content of crude oil is assumed to be 1% by volume. Crude tank drainage is assumed to be collected in a tank and then pumped at a constant flow rate to the treating units. If crude tanks are equipped with mixers the water in crude can be handled at a steady rate in a desalter or by the process units. Polluted Condensate The quantities of steam consumed for other than process purposes a74. G.e. steam pumps, piping flushing, etc.) are established on the basis of actual values observed in existing refineries. Discharges From Laboratory A constant maximum quantity of 5 m! /hour was assumed for the 5 refinery types Discontinuous Effluents These streams includ - wash water from plant areas - discharges after hydraulic tests of equipment - discontinuous discharges from various services inside polluted areas - wash water used following spillages in loading areas and pumping stations and in the crude pipeline (or marine) terminal. ‘The flow rates shown in the block diagram for refinery cases R, S, T, U and V were obtained as a result of surveys conducted in existing refineries and correspond to minimum values assuming severe control on water usage. Water from fire fighting has not been included as it arises only in emergency Rain Water These streams comprise rain water falling on areas where hydro- carbon spillages may occur (e.g. process area, areas under the manifolds of the storage tanks and transfer lines; rail and road loading points; (marine) terminal arrival point of the crude pipeline; pipeway area). In order to avoid oversizing of the treating units, this oily water from the tankage area may be stored in basins and subsequently passed to the waste water treatment plant. The peak flow rate is estimated on the following basi: Refinery [8 s T u v | ‘Area (mm?) 110,000 | 120,000 | 120,000 | 125,000 | 130,000 Max. rain (rom in 15 min.) | 12 2 2 12 12 (rom in 24 hrs.) [120-110 | 100-110 | 100-110 | 100110 | 100-110 1s4.2.2 Rain water pumping station and storage basin (or tank) sizes can vary according to climatic conditions at the refinery location. Sanitary Waters Reported values are peak values for simultaneous discharges from canteen, showers and sanitary services Boiler Blow~Down and Demineralization Unit Backwash This stream is normally acid or basic and requires neutralization before discharge. ACCIDENTALLY CONTAMINATED STREAMS These include the following streams Discontinuous Effluents These are discontinuous discharges from various services in clean areas. The flow rates shown on the block diagrams for refinery cases R, S, T, U and V were based on surveys conducted in existing refineries and correspond to minimum values resulting from severe control on water usage. Blow-Down From Cooling To1 Air cooling for process units has been maximized in order to reduce water consumption. The water used for after-cooling circulates through cooling towers. The required water for make up amounts to about 5% of the cooling water circulation. The corresponding blow-down rate is calculated on the basis of cooling water circulation required by process units (Tables R to V of Appendix II) plus the estimated power plant cooling water requirements Rain Water These streams comprise: - rain water from the areas where hydrocarbon spillage is unlikely to occur (roads, railway outside the loading area). 19Conc: ‘The peak flow rate is estimated on the following basis Refinery R s T u v ‘Area (mm?) 64,000 | 77,000 | 77,000 | 83,000 | 87,000 Max. rain 12 2 12 12 12 {mm in 15 min.) | {mm in 24 hrs.) 300-110 | 100-110 | 100-110 | 100-110 | 100.110 Rain water pumping station and storage basin (or tank) sizes may vary according to climatic conditions at the refinery location TREATMENT UNITS The sequence of treating units for the liquid effluents is shown in the block diagram, Figure 9 of Appendix II. The same treatment sequence is assumed in the five refinery cases (R through V). The size of the units is adapted to the flow rates and pollutant content in the respective effluents. The treated effluents are assumed to flow together to the receiving water. ‘The sequence shown here is only one of many possible choices which have to be considered in the context of location, effluent quality requirement, refinery layout, etc. It should not be taken as a recommendation or as being in any way typical of refineries which already treat effluent water to standards more stringent than assumed in sensitivity case 1. The refiner should always be free to make the most economic choice of treatment combinations to suit the site, the effluent quality levels imposed and the quality of the receiving waters. It should be kept in mind that a design to accommodate all extreme conditions and resulting flow rates would require extra capability to cover all possible climatic and geographical situations. These extreme requirements have not been included in this study in order to give. a reasonable cost assessment. Ballast water facilities have also not been included since these vary according to the refinery and its location. The treatment that can be applied to the various streams is as follow: For Continuously Contaminated Water: ~ sand trap (where necessary to protect pumping station) ~ rain water storage (including preliminary gravity separation) = oil-water separation (including pack-type plate interceptors) ~ dissolved air flotation 20- biological treatment - final clarification (where necessary to meet effluent criteria) - final aeration (where necessary to meet effluent criteria). 4.3.2 For Accidentally Contaminated Waters: - sand trap (where necessary to protect downstream pumping station) - rain water storage (including preliminary gravity separation) - oil-water separation - dissolved air flotation (where necessary to meet effluent criteria) - filtration (with sand filters) (where necessary to meet effluent criteria). 4.3.3 For Boiler Blow-Down and Demineralization Unit Backwash Streams Which are Small in Quantity Compared With Other Streans The provided treatments are equalization and neutralization. Then the neutralized stream can be mixed with other treated streams and due also to the small amount of this stream in comparison with other treated streams, the characteristics of the total discharged stream are acceptable for temperature and dissolved oxygen. 4.3.4 For Sanitary Water: - screening - biological treatment (with waters in 4.3.1) 4.3.5 For Sludges Resulting From Water Treatm ~ thickening - dewatering (with centrifuge or belt filter/pressure filter) - incineration (with fluid bed incinerator) - ash thickening - ash dewatering (with vacuum filter) The method of sludge disposal depends on the amount and type of sludge produced. Methods of disposal inside and outside the refinery are referred to in CONCAWE report No. 2/75 "Incineration of Refinery Wastes". For the purpose of this study sludge treatment has been included for sensitivity cases 2.2 and 3 only as an example of one disposal method which could be applied in a refinery 21EFFLUENT WATER QUALITY The objective of the study was to evaluate the additional cost resulting from the increasing complexity of waste water treatment. The increasing complexity of treatment is represented by the following sensitivity cases: Case 1: gravity separation Case 2.1: gravity separation + flotation Case 2.2: gravity separation + flotation + sludge treatment Case 3: gravity separation + flotation + secondary treatment + sludge treatment Each sensitivity case has been considered for each of the five refinery cases (R through V) described in chapter 2 of this report and Appendix I. In each sensitivity case the water treatment facilities are designed to give the same effluent water quality, regardless of the refinery case and the pollutant load. The level of effluent water quality expected on the average for each of the sensitivity eases is given in Table 5 following. For sensitivity case 2, two cases 2.1 and 2.2, with and without sludge treatment are given depending on whether chemicals are used in the flotation treatment. Table 5 — Water Quality for the Sensitivity Cases Parts per million Sensitivity cases (ppm), except pH and Oy 1 24 22 3 oil (4) 50 25 n15(2 | ns Suspended sotids | It 50 ft50 30 cop (1) ai e100 80 B00, (1) ai ai 125 Phenols, ai 15.0 not HS ai ai 10.112) | tt 0.08 pH ai 651085 651085 Dissolved oxygen ai ai 60" (0;) saturation Where: It less than ai—asinflux (1) Assuming primary water has negligible BOD and COD values. (2) Lower values expected if chemicals are used in flotation. (3) All analysis according to APHA standard methods or equivalent. (4) By infra-red spectrophotometric analysis after carbon tetra chloride (CCl, extraction. 22-5.1 COST ESTIMATES Investment Cost The investment cost of the effluent treatment units for the five refinery cases (R-V) have been estimated as follows ~ for each refinery the total investment cost for the complete series of effluent treatment units has been estimated; - for each refinery the proportion of the investment costs for each of the following sections has been estimated: Section 1: Basic effluent treatment including sand traps, pumping stations, rain water storage tanks and gravity separators for continuously and accidentally contaminated streams Section Flotation treatment including dissolved air flotators for continuously and accidentally contaminated streams. Section including aeration basin, secondary clarifier, final aeration basin for continuously contaminated streams sand filters for accidentally contaminated streams Section 4: Sludj including sludge thickening, dewatering and incineration, ash thickening and dewatering, for sludges arising from complete treatment of continuously and accidentally contaminated streams Section including chemicals storage and dosing equipment, control room, motor control centre, ete. This section is common to all sensitivity cases considered. For establishing cost estimates of sludge treatment and ancillary equipment it was assumed that these would be of adequate size to service the complete range of the water treatment units including gravity separators, flotators and secondary treatment, ‘The total investment costs of the complete effluent treatment units for each refinery case are indicated below in millions of US dollars (10° $), based on the exchange rates of 1 January 1975.[[etnery case 8 Total effluent investment 10°S The investment for each section as a percentage of the total effluent treatment investment cost has been calculated and found to be almost the same for the 5 refinery cases. These percentages are indicated below. Section 1 36 Section 2 8 Section 3 23 Section 4 25 Section 5 8 Total 100 Using these percentages and the total effluent investment cost the investment costs for the sensitivity cases as listed in item 3.4 have been obtained as shown in Table 6. As indicated earlier, Section 5 covers all the ancillary equipment required for operating the Sections 1 to 4. Some parts of Section 5 are not required when treatment consists of Sections 1 or 1+2 only. However, since a detailed breakdown of such facilities would be rather cumbersome, the sensitivity cases 1 and 2 have been considered to include the Section 5, and the actual investment would be within 10% of the figures indicated. This gives an over- estimate of the cost of the base case, and correspondingly the differences for the further cases 2 and 3, will be somewhat underestimated. For sensitivity case 2, investment figures are shown, with and without Section 4, which may be required and can be built later depending on whether chemicals are used in Section 2. Table 6 ~ Estimated Investment (10° $} Sensitivity, Level of ] Refinery case | case control (sections R s T u voi 24Operating Costs Operating costs included are: a) capital charges (25% of investment per year), b) labour, maintenance, overhead expenses, and ©) variable costs of utilities and chemicals. ‘The estimated total operating costs of effluent treatment including Sections 1 to 5 for the various refinery cases are given below. Table 7 — Total Operating Costs of Effluent Treatment (1000 S/yr) Refinery case R Ss T | u v Total operatingcost | 1438 | 1611 | 1584 | 1764 | 2000 The total operating costs for the effluent treatment in the various sensitivity cases have been estimated as follows: Table 8 ~ Effluent Treatment Operating Costs (1000 $/yr) Senatvty Love of Refinery ease oe contol aos feections nafs [qt v included) | 1 145 «20 | 490 | 400 | 519 | soe 21 1295 507 | 653 | 652 | 700 | 23 22 rosa naa | 1271 | 1260 | 1988 | 1637 3 H2egeaes vaoe | tert | 1564 | 1764 | 2000 Note: The operating com in US é/ton oferude i obtained by dividing the above figures by 100 for use in Table 10 and Fig. 3 ENERGY REQUIREMENTS The energy requirement for the various sensitivity cases was calculated from the electric power and fuel oil requirements and converted to Fuel Oil Equivalent (F.0.E.). The figures obtained for each refinery case and the different sensitivity cases are shown in Table 9.Cor iCal Table 9 — Energy Requirements Tons/Year Fuel Oil Equivalent (FOE) Sensitivity Level of Refinery case case control (sections rk | s T vu fv included) 145 as| 109] 109] 132) 181 24 14245 201| 316| 299| 369| 459 22 1424415 sags | 2001] 1732) 2372 | 3233 3 14283445, 1e3a| 2490) 2146| 2040 | 4021 COMPARISON Many parameters are required to characterise effluent water quality and no single figure can summarise oil, COD, BODs, pH, oxygen, etc. However, for the purpose of a cost and energy comparison it is necessary to have a single parameter. For this study the expected oi1 content has been taken as the most significant parameter. The reference case for the comparison is sensitivity case 1 with an expected of1 content less than 50 ppm. Graphical comparison of investment and operating cost and energy requirement for the sensitivity cases and refinery cases has been made (Figure 3) against the expected oil content of the effluent (Table 5) Table 10 is a synopsis of Tables 6, 8 and 9 which has been utilised to draw the series of graphs in Figure 3 (page 29) 26‘Table 10 — Cost of Water Effluent Quality Improvement Refinery Water Treatment Facilities Case Expected | Total Increased | Operating | Investment a ot refinery | eneray cost cost content (1) | investment | required | US ¢/t. erude| 10° $ ppm 10°s. (FOE) (2) ton/year R | a2 RI 150 88 44 18 R24 I 25 291 60 24 R22(3) 115 1,488, 114 32 R3 5 11838 144 a4 s 405 st ft50 109 48 20 $24 125 316 65 23 $2.2 (3) 115 2,001 127 35 83 nS 2,490 16.1 45 T 491 1 ir60 109 48 20 T24 25 299 65 23 12.2 (3) fe 15 1,732 125 35 13 tS 2.148 158 45 uv 631 ut 50 132 52 22 | u2t 125 369 74 25 U22(3) 115 2,372 13.9 38 u3 6 2,940 176 49 v 754 vi 80 181 60 25 v2a 1 25 459 82 30 v2.2(3) a5 3,233 16.4 44 va te | 4,021 21.0 87 a Expected water quality from Table 5. (2) Includes amine scrubbing facilities but not SO; control facilities (US § at 1.1.75). (3) Includes sludge treatment and control systems, as defined in paragraph 4.4 (a 27 Letter refers to refinery type (paragraph 2.2) Index refers to sensitivity cases (paragraph 4.4 and Tables 6 and 8).From Table 10 using the expected oi1 content of the effluent as the single parameter to measure the improvement, the increases in investment, operating cost and energy requirement for each refinery case have been calculated for - 50% improvement i.e. expected oil content less than 25 ppm - 90% improvement i.e. expected oil content less than 5 ppm - improvement from 50% to 90% i.e. expected oil content from less than 25 ppm to less than 5 ppm. These increases are given in Table 11 as percentages of the cost for the reference case for investment and operating cost and as a factor times the reference case for the energy required. ‘Table 11 — Comparison of Investment, Operating Cost and Energy Increases L Refinery case eS TT UV tnyestment Ranges incrense | S47: imarovernent w2 | 7] 5] | se | 20 80% improvement 122.128 | 127 | 128 | 125 | 122 | 128 Improvement 50/'t090% | 90.96 | 96 | 9 | 95 | 96 | 90 Operating cost mereae 50% improverment aa7 | 36 | a5 | a5] a | a 907 improvement 227250 | 227 | 235 | 229 | 236 | 250 Improvement s07sroeo% | 140186 | 140 | a7 | 143 | 148 | 158 Energy required Factor Factor 50% imaroverent 25-33 | 33] 29| 27 25 90% improvement 196228 | 209 | 228 | 196 | 223 | 22 [ Improvement so7roso% | 6388 | ss] 79| 72| 79} 88 ‘The range of the percentage increases for investment for the 5 refinery casas show agreement between’ 14 20% for S0%% improvement 122 — 128% for 90% improvement 90 ~ 96% for 50 10.90% improvement ‘The range of the percentage inoreases for operating cast for the § refinery eases show agreement between: 35~ 37% for 60% improvement 227 — 280% for 90% improvement 140 — 156% for 50 to 90% improvement ‘The range of factor increases for eneray required for the 6 refinery cases show agreement: 2.8- 33 for 50% improvement 196-228 for 90% improvement 6.3— 88 for 50 to 90% improvement 28Figure 3 — Cost and Energy Requirement for Water Effluent Improvement Expected Energy requirement Operating cost Investment cost ollontent 10° ton/year FOE US ¢/ton crude 10" case rem 12 3 4 510 15 20 1203 4 5 6 to, T 50 it 25 25 15 Tae Refinery cases FV as indicated 29TERTIARY TREATMENT Further purification of the effluent water can be achieved by using additional treatment steps. As an example filtration, such as active carbon filtration, could improve the effluent quality to the levels indicated below: oil ppm 1t 3.5 Suspended solids "lt 20 cop "lt 40 BoD "It 20 Phenols "Ut 0.01 HS "Lt 0.01 1t = less than ‘These technologies, however, are not yet fully developed for application in the oi1 industry and the figures above are only given as an indication of the quality levels which might be expected. ‘The limited data and experience available on the investment and operating costs for tertiary treatment such as active carbon filtration can only lead to a rough indication of the order of magnitude costs. For tertiary treatment in a refinery of 10 million tons/year the order of investment would be upwards of 1 million $. This indicates that the additional costs for tertiary treatment are high, particularly when compared with the extra improvement attained. To provide a higher degree of security to ensure that water effluent quality never exceeds a particular value would involve further extra investment. CONCLUSIONS ON COST OF IMPROVING EFFLUENT WATER QUALITY Using expected oil content as a measure of effluent quality, and assuming minimum water quantities, an investment of $ 1.8 - 2.5 million is required, depending on the refinery complexity, to achieve an expected oil content of less than 50 ppm. To achieve 50% improvement in effluent quality (i.e. oil content less than 25 ppm) extra investment between 14 - 20% would be required. To achieve 90% improvement in effluent quality (i.e. oi1 content less than 5 ppm) extra investment between 122 - 128% would be required. ‘The extra operating cost to achieve 50% improvement is between 35 - 37% higher and for 90% improvement is 227 - 250% higher Bearing in mind that base costs have been overestimated and extra costs correspondingly underestimated (see paragraph 4.5.1), the forementioned incremental costs should be taken as minimum values The energy consumption increases by factors of between 2.5 and 3.3 for 50% improvement between 19.6 and 22.8 for 90% improvement. In other words, the extra energy required to achieve 90% improvement is 6 - 8 times the energy required for 50% improvement 30COST ESCALATION Investment and operating costs given in the report are those applicable on 1 January, 1975. Escalation of operating costs as a function of inflation and variations of crude price can be assessed by considering separately the operating cost components related firstly to material and manpower (M), and secondly to energy cost (B) (fuel and electric power). The relative contribution of these two components to the total cost depends on the type of process which is being considered. ‘These components are represented by the two parameters, M and E in the formula shown below. By using this formula it is possible to calculate the operating cost variations as a result of material manpower and energy cost fluctuations. E = onergy ae f of operating cont the 1-78 teved ¥ = cost of crude cil in UB 8/ton in the year considered Yo = cost of crude oil in US $/ton on 1.1.75 (equal to 70 US $/ton). Approximate values of M and E have been established as follows for the various cases: 80, control Rofinery cases | om E 85 is | 7 25 Rotinery cases im E a1 [10 | 0 R24 | 95 5 R223 85 1 |APPENDIX 1 REFINERY CONFIGURATIONS ~ DETAILED DESCRIPTION REFINERY CASE R Simple Hydroskimming Refinery The incoming crude oil passes via a single stage desalter to the atmospheric crude oil distillation unit (CDU). Here it is fractionated into a primary distillate (CDU overheads), kerosene light gas oi1 and heavy gas oil cuts, taken as separate sidestreams, and an atmospheric residue (reduced crude). The primary distillate (CDU overheads) passes to the distillate hydrotreater (DHT) and associated stabiliser. Here the sulphur compounds present are reacted with hydrogen over a catalyst to give a substantially sulphur-free product and HS. The stabiliser overheads are taken via an amine absorber (MEA), for HyS removal to the gas plant where propane and butane are recovered for sales liquid petroleum gas (LPG), together with some butane required for motor gasoline blending (to control volatility), and the balance predominantly C), C2 and unrecovered C3/Ci, hydrocarbons, is routed to refinery fuel. The stabiliser bottoms (C5~175°C approximately) are fractionated into an isopentane stream, which is routed to motor gasoline blending, an n-pentane stream, which is routed to the naphtha pool (LDF) for disposal as chemical feedstock, and a Cg~175°C stream which provides the feedstock for the catalytic reformer (CR), the balance being routed to the naphtha (LDF) pool and to motor gasoline (regular grade) blending. The catalytic reforming unit (CRU) upgrades the low octane number C,-175°C naphtha, in the presence of a catalyst into a high octane motor gasoline blending component (catalytic reformate) and produces additionally propane and butane which are routed to the LPG recovery plant, and a hydrogen-rich off-gas. The catalytic reformate yield is dependent on severity of operation; 80% wt yield on reformer feed has been assumed in the present cases. The kerosene, light gas oil and heavy gas oil sidestreams from the CDU are each catalytically hydrodesulphurized (HDS) before passing to the appropriate product pools. The HDS process is similar to the DHT in which sulphur compounds are reacted with hydrogen over a catalyst, the sulphur being removed as H>S. More severe reaction conditions are employed than in the DHT and the sulphur present in the middle distillate stream can be reduced by up to 90% wt. The off-gas from the catalytic reformer provides adequate hydrogen to meet the needs of the DHT and HDS units. In the present case 80% wt desulphurization has been assumed. The sour off-gas from the HDS units is amine treated (MBA) for HS removal. All spent amine is routed to the amine recovery plant, from whence regenerated amine is returned for reuse for further H)S absorption, whilst the liberated H,S passes to the sulphur plant for recovery of elemental sulphur by the Claus process using parallel units to provide security in the event of any one of the units being taken out of service. 33APPENDIX I-2 The atmospheric residue from the CDU, less the amount required to supplement fuel gas for the refinery's own consumption, passes to the fuel oil pool REFINERY CASE S Basic Refinery Cas: th Indirect Fuel 011 Desulphurizatio ‘This refining scheme has been included to illustrate a possible route to producing fuel oils with sulphur contents intermediate between that possible from the simple hydroskimming refinery (refinery R), and direct residue desulphurization (refinery T) These intermediate sulphur levels are more easily and less expensively achieved by "indirect desulphurization” in which the atmospheric residue from the CDU is split by vacuum distillation (DU) into distillate and residue, the distillate then being hydrodesulphurized and recombined with some or all of the untreated vacuum residue in the fuel oil pool ‘The crude oil distillation and subsequent treatment of the overheads and sidestreams from the CDU are again comparable with the simple hydroskimming refinery (refinery R). The atmospheric residue from the CDU passes to the Vacuum Distillation Unit (VDU where it is split, (nominal cutpoint 550) into a vacuum distillate and a vacuum residue. The total vacuum distillate is sent to the HDS unit where it is desulphurized giving a low sulphur component for fuel oil blending, a small yield of gasoline which is routed to the DHT, and sour off-gas which is amine treated for H2S removal and then routed to refinery fuel. The off-gas from the catalytic reformer is no longer sufficient to meet the hydrogen needs of the vacuum distillate HDS in addition to the Kero/gas oil HDS and DHT units, It is thus necessary to provide hydrogen production facilities, and this is accomplished by steam reforming of naphtha. In this process, steam is reacted with naphtha (preferentially the n-pentane stream) over a catalyst at moderate temperatures to produce principally hydrogen (ca 98 mol % purity), carbon dioxide, which is removed by absorption using a regenerable solvent, and light hydrocarbon condensate The vacuum residue is sent to the fuel oil pool with a small proportion going to refinery fuel, along with some of the desulphurized vacuum distillate, the proportions of these two streams being such that when combined with the refinery fuel gas the sulphur content of the total fuel consumed within the refinery is 1% wt. The proportions of high sulphur vacuum residue, and desulphurized vacuum distillate in the fuel oil product pool are such that the resulting pool sulphur content is 2.0% wt Amine regeneration and sulphur recovery facilities are again provided. 34APPENDIX I-3 REPINERY CASE T Refinery Case R with Residue Desulphurization (RDS) The CDU and the configuration of units processing the overheads and sidestreams from crude distillation are substantially unchanged from refinery case R. Two stage desalting of the crude oil input to the CDU has been introduced to reduce the possibility of catalyst contamination in the residue desulphurization plant In addition to the CDU overheads, the DHT now treats the small gasoline product stream from the RDS product fractionator. This stream arises from the break-down during residue hydro- desulphurization to material boiling below ca. 175°C and amounts to 4% wt on feed to the RDS. The residue from the CDU is routed partly to the residue desulphurization unit (RDS) and the balance to the fuel 011 pool (via intermediate tankage as mentioned later). The RDS unit comprises three reactors in parallel feeding into a common product fractionation system. This arrangement permits individual reactors to be taken off stream for catalyst replacenent/regeneration whilst maintaining throughput on the other two reactors Intermediate tankage is provided for high sulphur residue during such shut-downs. This residue is blended with low sulphur residue produced when all three reactors are in operation to maintain the overall sulphur level in the fuel oil product pool at 1% wt. The reactions occurring in the RDS unit are similar to those in the DHT and middle distillate HDS plant. Conditions are, however, more severe and the consumption of hydrogen is necessarily much greater ‘The additional hydrogen required for residue hydrodesulphuriza~ tion is produced by steam reforming of naphtha as in refineries S and V, as a supplement to the hydrogen-rich catalytic reformer off-gas. The products from the RDS unit are low sulphur fuel oil component (90% wt yield on feed, 84% sulphur removal assumed), a gasoline stream already mentioned, and sour off-gas. The latter is amine treated for 2S removal and routed to refinery fuel. Spent amine regeneration and sulphur recovery plant are provided as in refinery case R, albeit of larger capacity. ‘The proportion of desulphurized residue routed to refinery fuel is such that the total refinery fuel (gas + liquid) has a sulphur content of 1% wt. REFINERY CASE U Refinery with Vac (recy m Distillation and Fluid Catalytic Cracking In this réfining scheme the crude distillation and subsequent treatment of the overheads and sidestreams from the CDU areAPPENDIX I-4 comparable with the simple hydroskimming refinery (refinery case R). Since catalytic cracked gasoline from the FCC is available for motor gasoline blending, a smaller capacity catalytic reformer is employed and thus more of the straight-run naphtha (depentaniser bottoms) is shared between the motor gasoline pool and sales naphtha (LDF). ‘The atmospheric residue from the CDU passes to the Vacuum Distillation Unit (VDU) where it is split as in refinery case S into a vacuum distillate and vacuum residue. The major part of the vacuum distillate is fed to the Fluid Catalytic Cracker (FCC). In this process the relatively large molecules of the high boiling range feedstock are cracked to give lighter products in the gas gasoline and gas oil boiling ranges. The reactor products pass to the iractionator and gas recovery plant, from which propane, propylene, butane and butylene can be recovered for sales, fuel gas is routed to refinery fuel, gasoline is routed via a sweetening stage to the motor gasoline pool, and the gas oil product is hydrodesulphurized (HDS) and routed to the gasoil and/or fuel oil pool. The small proportion of gasoline produced in the HDS is sent to the DHT, whilst the sour off-gas is amine treated to remove HS and passed to refinery fuel. ‘The vacuum residue is passed to the solvent deasphalting plant, where solvent extraction is carried out using a recoverable light paraffinic hydrocarbon solvent. This process concentrates in the separated raffinate the heavy cyclic compounds and metallic constituents of the residue which can poison the hydro~ desulphurization catalyst. The extract from this process having low metals content - deasphalted oil - goes, together with the vacuum distillate surplus from FCC feed, to a hydrodesulphuri za~ tion (HDS) unit. This HDS unit produces low sulphur blending component for fuel oil, a small proportion of light gasoline which is sent to the DHT (with the CDU overheads), and a sour off-gas which is amine treated for Hy$ removal and routed to refinery fuel. A proportion of the precipitated asphalt is used as feedstock for hydrogen production by the partial oxidation process. This is a convenient way of utilising high sulphur residual material which would otherwise be used in fuel oil blending, with a consequent increase in sulphur content of that product. In this process the preheated asphalt and oxygen, together with a small quantity of steam, are reacted in a non-catalytic unit. The hydrogen produced is required to augment catalytic reformer off-gas for hydro- desulphurization duty. The sulphur present in the feed to the partial oxidation process is converted to H,$ which is removed by amine absorption ‘The balance of the precipitated asphalt is routed to fuel oil blending Amine regeneration and sulphur recovery facilities are provided as in the previous schemes. 36