report

Transcript

1 Water Requirements the Petroleum of Refining Industry LOUIS E. OTTS, JR. By WATER REQUIREMENTS OF SELECTED INDUSTRIES GEOLOGICAL WATER-SUPPLY PAPER 1330-G SURVEY UNITED 1963 GOVERNMENT PRINTING OFFICE, WASHINGTON : STATES

2 UNITED STATES OF THE INTERIOR DEPARTMENT STEWART UDALL, Secretary L. GEOLOGICAL SURVEY Thomas B. Nolan, Director U.S. For by the Superintendent of Documents, sale Government Printing Office Washington, D.C. 20402

3 CONTENTS Page 287 Abstract____________________________________________________ 287 Introduction. _____________________________________________________ scope_______________________-________________.____ Purpose 287 and used-------_-------------------__-------_----_-_- 290 How is water requirements.-____--___-____-_______________-_-_-_-____ 294 Quantitative 294 Published information________________________________________ the Findings 294 of survey..._______________________________________ water___-__-------__-----______-------_-_------- of Sources 294 Total requirements.________________________________________ 298 requirements._____--_-______-__-___-_____--__ Cooling-water 300 Requirements selected operations.________________________ 300 for requirements_________--___---___-_____-_______-___-__ Water-quality 309 Cooling water.________________________________________________ 311 Published information______________________________________ 311 of this survey___________-_____-____-_____________- 312 Findings water Boiler-feed 316 makeup__--___--_--_----_---__----_---___-_-_- information____________________________-_________ 318 Published of this survey________________--_____-__-_____-___- 318 Findings Process and sanitary water_-________________-___--___-_-__--_-__ 321 Factors affecting use_______________________________________ 325 water of water___-_-_--_-_-_-__----_----_----_-_-__------- Availability 326 326 ofrefinery_---___---__----_----_----_---------_----_----__ Size of processes,.___________________________________________ 326 Types procedures.._____-___________-____________---_----__- 327 Operating Quality and characteristics of water______________________ 327 physical Refinery water_____________________________________________ 328 waste Future water requirements.----------------------------------------- 329 Location of refineries.--____--_________-_-_---__----_----__-___- 329 Growth of 331 industry_______-_________--___-___--___---__------ States.._._-__-________- in refining in Trends United petroleum 335 the Summary. ________________________________________________________ 336 Quantitative water requirements.----.---------------------..------ 336 Qualitative requirements--____-_--___-______-__--__-_----- 337 water Trends in water requirements_...________________________________ 337 Selected references____________-___-______-_____-_----_--------_-- 338

4 IV CONTENTS ILLUSTKATIONS 3. a hypothetical refinery.__________-..__ In pocket Flowsheet PLATE of Page Map location of refineries surveyed.-_________ 42. 289 FIGURE showing intake. showing use of water and _______ 301 Diagram 43. source showing frequency distribution of selected 44 48. Graphs chemi- constituents untreated: cal in for 44. 314 once-through Water cooling__________________ for cooling...________________ 315 Water 45. recirculated water for 46. feed-__________-_______ 319 Makeup boiler Process 322 47. water______--___-----____-_-_---______ Sanitary service water_----__--__---___-____ 323 48. and Graphs showing: 49-51. Demand 49. refinery products in the United for major the world, 1950-60.___________ 333 and free States runs by petroleum refineries 50. the United Crude in and the free world, 1950-60-___________ 334 States Crude oil runs by refineries and demand for pe- 51. ;products in United States, 1920- troleum the curves to 1966____________ 336 60,with extended TABLES Page Published 1. unit water requirements of selected total TABLE _. ______________________________________ . refineries. 295 unit water requirements of selected processes.. 296 2. Published amount and intake of the refineries Source 3. of water 298 1955, of cooling system____ 299 water Total 4. by intake, type of and type 5. Water requirements and use disposition by refinery, ______________--______--_-_-----_- 302 type of of cooling type by water, cooling circulating Gross 6. 1955, ___________ and by type of system 304 _________ refinery- cooling 7. Cooling-water makeup, 1955, by type of system 305 and refinery..---.---------------------- of type by Consumptive water, 1955, 8. by cooling of cooling type 306 by type of refinery. _________-___------_ system and 307 of units- distillation crude ________ requirements Water 9. 308 Water operations.- ----------- 10. selected requirements of correction 11. common for of methods and effects Undesirable 309 _ in _______-___________----_-_- constituents water__ 311 untreated water for all uses.__ 12. Quality characteristics of water 13. Quality Ameri- by suggested tolerances cooling of 311 Works can Water Association___________-__--_---_-

5 CONTENTS V Page TABLE characteristics of untreated cooling water._____ 313 14. Quality of makeup water for cooling_______________ 317 15. Treatment Quality characteristics of 16. boiler-free water untreated makeup-.-___-____________-_-_____-_-__--___-_.__ 320 Suggested 320 tolerances for boiler-feed water_ 17. water-quality 18. of makeup for boiler-feed water____________ 321 Treatment 19. Quality characteristics of untreated process and sanitary water.-_._______-______-_____--________--___-_-__ 324 Treatment makeup for process water.______________ 325 20. of 21. of makeup for sanitary water_______________ 325 Treatment 22. Waste-water treatment..._.____________--_-_-_---__ 329 23. of the median of selected quality characteris- Summary tics of untreated water used for various refinery purposes_ ______________________________________ 337

6

7 WATER REQUIREMENTS SELECTED INDUSTRIES OF REQUIREMENTS OF PETROLEUM REFINING WATER THE INDUSTRY Louis JR. 1 E. By OTTS, ABSTRACT in of water 3,500 withdrawn daily gallons 1955 for use by About million was in the United States. This was about 3 percent of petroleum esti- refineries the daily of industrial water in the United States in 1955. mated withdrawal refine of gallons of water was required to average a barrel of crude oil, An 468 the median was 95 gallons of water and barrel of crude charge; withdrawals per ranged 6.5 to 3,240 gallons per barrel. from percent of water requirements of the petroleum refineries sur- Ninety-one the reused for One-third of the refineries was their cooling water from veyed cooling. to more than 50 times. Only 17 10 used once-through cooling systems. refineries Refineries recirculating cooling systems circulated about twice as much cool- with makeup water needed about 25 times less ing ; however, they consumed about but 24 times more water per barrel of charge than refineries using once-through cool- ing systems. average noncracking used about 375 gallons of water per barrel The refinery which average less than the 471-gallon crude, of refineries with cracking of is units, are of various processing composed and the water facilities. Refineries of such requirements varied ; median makeup needs ranged from about 125 units gallons barrel for polymerization and alkylation units to 15.5 gallons per per for distillation units. barrel percent sources water Refinery-owned 95 of of the makeup-water re- supplied quirements. Surface-water sources provided 86 percent of the makeup-water de- mand. Less 1 percent of the makeup water was obtained from reprocessed than sewage. municipal INTRODUCTION AND SCOPE PURPOSE of report the results This a survey presents water used in the man- of ufacture of petroleum products from crude oil and is one of a series describing water requirements of selected industries that are of the i Professor of Civil Engineering, University of Maryland, College Park, Md. 287

8 288 WATER OF SELECTED INDUSTRIES REQUIREMENTS importance. The is designed to serve the dual purpose national report basic of national defense planning and of information providing for business will industry. This information to providing assistance and and planning location of new refineries in the expansion helpful be the ones. A knowledge of the water requirements of industry is of existing planning needed most effective use of the water resources of for the areas. specific A of 1955 refinery operations was made in the summer survey field collected of data for 1955 were 1956; so that information for and fall entire year would be available. Sixty-one, or 21 an of the re- percent, fineries in 1955 were visited. They processed 30 percent of operating crude oil in the country during 1955. Refineries were se- the refined give size, wide range in to geographic location, and processes lected a fig 42.) The refineries surveyed included no natural-gaso- used. (See plants, and no attempt was made to obtain information line the on water of the other divisions of the oil industry namely, requirements for production of crude oil, transportation of crude exploration and or refinery products, and marketing oil petroleum products. of Information obtained on the source was water, the adequacy of of the supply, the quality and treatment of the water, and the disposal of waste. on the amounts of gross and makeup water required, Data amount reused, amount used consumptively, and the amount of the the obtained and the complete refineries were for their compo- effluent for of units. obtained on use was water for cooling, nent Information feed, processing and sanitary. Information on the crude charge boiler production of the refineries was also obtained in order to compute and water unit use. in 1951, J. K. Searcy (written communication) of the U.S. Early Survey on information Geological the water intake of 63 obtained petroleum and 29 natural gasoline plants in the United refineries States, but he did not obtain details on the use of water within the re- fineries. Information 48 of the petroleum refineries were incor- for in report where applicable. porated this literature was carefully reviewed to obtain information on the The of requirements the industry and to obtain an understanding water of the water-supply problems of the industry. Special acknowledgment is given to the officials and management of the petroleum refineries who refineries permitted to visit their author and who supplied infor- the mation on water use at their refineries. The author is indebted to his of colleague, D. Mussey, who made the survey O. the petroleum refin- eries in western Pennsylvania.

9 Refineries cracking facilities with A Refineries without cracking facilities FIGURE 42. Location of refineries surveyed, 1956. to 00

10 290 WATER OF SELECTED INDUSTRIES REQUIREMENTS WATER IS HOW USED use The in a petroleum refinery is for cooling. Rela- of major water of processing, are used for boiler feed, quantities tively small water protection, purposes. miscellaneous fire Simon- sanitary services, and noted a typical 50,000-barrels-per-day refinery gener- (1952) sen that than 1,000 million Btu. per hr and that about 50 ates more percent this is removed by water. Allowing for other water uses and of heat water, 30 rise in the cooling temperature he estimated a °F assuming would require about 40,000 gpm the per minute) to refinery (gallons this of heat. This quantity amount water would have sup- remove of the domestic requirements plied the city of Toledo, Ohio, in 1952. of In refining, vapors are reduced to liquids in condensers, petroleum coolers are to lower the temperature of liquid products to and used handling. cooling is the normal safe medium used in permit Water and units; save both heat refineries water by cooling these however, products with raw charging stocks and other cooler high-temperature streams. liquid requirements of early refineries were small, and the uses of Water Water were as the refining process. simple was needed only water as cooling and for generating sufficient for for the pumps. In steam contrast, the modern refining process both the use of water are and varied and complicated. The quantity and the quality of water re- quired by entire refinery and in individual operations are affected the the type refinery process. The principal processes used are by of polymerization, and treating and cracking, alkylation, distillation, descriptions of petroleum refining finishing. refining Detailed and can be found in the literature. equipment skimming or topping refinery separates crude oil by distillation A gasoline, oil, fuel into gas oil, and reduced crude. Atmos- kerosene, refining distillation the first step in generally crude oil. The pheric is oil is generally warmed by heat exchange crude a fluid to be with cooled. use of the crude oil The a cooling medium reduces the as amount of cooling water required. The hot oil partially vaporizes as it enters fractionating tower. The lightest vapors are drawn off the condensed the the tower and are of as gasoline; other fractions at top drawn from the tower as side streams. Water-cooled are ex- heat changers overhead streams and cool tower side streams. condense reduced crude from atmospheric distillation may be further The processed by vacuum distillation, by steam distillation, or by a com- bination of to provide lubricating oil fractions or asphalt base both crude stocks. fractions of the heavier oil may be fractionated The without danger of decomposition or cracking in these units, as the lower oil distilled at temperatures is than those in atmospheric units.

11 PETROLEUM REFINING 291 INDUSTRY vacuum distillation consists of a pipe still and a distillation A unit at a pressure that is maintained by the use tower operated reduced condenser or steam jets barometric vacuum pumps. This of a and water and steam. Because the separations ob- requires equipment both distillation towers are not perfect, the undesirable fractions tained in streams are vaporized and are removed by steam stripping in in side towers as stripping columns. Steam is also auxiliary short, known pumping and heating. used for manufacture lubricants, the the lubricating-oil base stock is In of vacuum distillation or by propane deasphalting. The prepared by stock is then dewaxed base chilling and cold filtering or pressing, by or solvent dewaxing. Water is used for making brine solutions by refrigeration units lubricating-oil plants. Steam is used for in of clays, and heating. filter pumping, cleaning the breaking down of large molecules into smaller Cracking is mole- Cracking an important process, because is not only gives cules. it increase in the gasoline yield an 70 to 85 percent of the charge but to also the quality of the yield. About 50 percent of the gaso- improves produced country this line is obtained by cracking. Cracking in and processes thermal or catalytic, be thermal cracking may be may either liquid phase or vapor phase. Thermal cracking units operate at temperatures from 800° to 1200°F and at pressures ranging ranging 600 to pounds per square inch. Catalytic cracking units from 1,000 catalyst the hasten the change in molecular structure of a utilize to cracked operate being at temperatures and pressures material and than those of thermal cracking units. generally lower could be considered to be the reverse of cracking, Polymerization it as a process that combines two or more molecules to form a larger is The pe- is used largely to change the byproduct molecule. process gases cracking are produced in troleum into high-grade motor that a and fuel. Polymerization can be fuel thermal or a catalytic aviation process, but thermal polymerization is not used extensively today. In the process, complex saturated molecules are formed alkylation an the a saturated and of unsaturated molecule. Alky- by combination can be a thermal, a thermal-catalytic, or a catalytic process, lation but most applications are catalytic. Alkylate is the product commercial principal of and is the process component of many high-octane the motor fuels and aviation gasolines. Cracking, polymerization, alkylation units use water for cool- and They and other heat transfer operations. ing use steam for regen- for erating catalysts, pumping, and heating. to Products be treated to improve color, odor, or stability or must remove sulfur, gums, or other corrosive substances before the product

12 292 WATER OF SELECTED INDUSTRIES REQUIREMENTS marketable. Caustic acid treating, clay treating, oxidation is treating, sweetening, and extraction are some of the sweetening, copper solvent remove light alter the impurities in to distillates. methods used or for used and acid solutions and caustic product washing. is Water for are treated with acids, by contact with or percolation Lubricating oils or by solvent extraction methods. Both steam and water through clay, clays to and to clean filter solvents in lubricant treat- used are recover ing operations. with oils crude associated should be removed before the Brines many distilled to prevent serious corrosion of refining equipment. oils are are generally removed from crude oils by scrubbing with water. Brines A refinery composed of a combination of several unit processes, is no two will use exactly the same process. A diagram- but refineries of It refinery is shown plate 3. flowsheet is not a flowsheet matic a recommended specific nor is it a refinery, refinery design. It of any illustrates how several of the more important processes may be merely by a refinery to provide the products desired. The designa- utilized by of of a refinery will be determined type the combinations tion the processes used. of manner in which cooling The is used varies with local con- water ditions. water will be used once Generally areas where it is plenti- in ful and cheap. On the other hand, where water is in short supply and its cost high, makeup water requirements are kept to a minimum by is the cooling many times. One type of reuse system uses reusing water a for operations with low-temperature demands and as coolant water the warmed water to satisfy then requirements of higher reuses cooling operations. In the recirculating type of cooling system, temperature absorbs heat as it flows through water and coolers. The condensers heat by the water is removed by evaporative cooling in cool- acquired towers, or cooling ponds, or evaporative condensers, and ing spray cooled water is reused. Most refineries the once-through cooling use for operations and several types some water reuse for other of operations. The conventional recirculating cooling system in a modern petro- leum refinery cooling towers to transfer the heat absorbed by the uses to the atmosphere. The rate at which water is pumped into water the tower the known as cooling gross circulating rate. Evaporation and is through windage as water passes occur the cooling tower, and losses some water is drained from the system to prevent excessive mineral concentrations. water remaining is returned to the cooling sys- The tem to be reused and is known as recirculated water. A quantity of the water to the evaporation and windage losses and to equivalent withdrawal for mineral concentration control is added to the recircu-

13 PETROLEUM REFINING 293 INDUSTRY water to the gross circulating rate. This replacement lated maintain as is makeup known water. makeup use in a refinery is water for boiler largest of The second uses of steam are feed. stripping, steam distillation, and The chief for The comes in contact steam the products distillation. vacuum with operations, and generally the steam condensate is so in these highly that cannot be reused for boiler feed or for other pur- contaminated it is in used for process heating, for pumping, and, Steam poses. also for The electric power. refineries, condensate from some generating usually and of these systems is condensers reused as boiler- the traps water or as feed for other water needs. makeup Smaller of water are generally needed for process opera- amounts sanitary and services, fire protection, and other uses. The tions, plant during but fire will be large, requirements the average require- water a be for during -a year will protection negligible. Some re- ments fire use separate fire-protection systems, whereas others use water fineries the other or from water systems of the refinery to fight fires. cooling increased latter less desirable, as the is water needs during The method fire must be entirely or partially a by a decrease in water uses offset in refining process. Some refineries the require water for com- also pany housing, and refineries with dock facilities may supply the water needs of tankers. oil is used consumptively and nonconsumptively by the Water both industry. use is water that is dis- refining Consumptive petroleum the atmosphere or that is incorporated charged the products of to in process Water Works Assoc. (Am. Group, 1953). Evapora- the Task and windage losses in a cooling tower and the discharge tion process of steam the atmosphere are examples o.f consumptive use. The dis- into of cooling water, cooling-tower blowdown, and charge once-through to waste of the condensate from a steam trap or examples discharge of effluents not of consumptive uses. The sum of and uses consumptive and effluents equals the makeup water. Makeup water may be new or reused. Water that is used for the first time new makeup water, whereas water that was used in one is another or is being reused in and as makeup is process operation as reused makeup water. The sum known new makeup water for of all operations for a day is refining to the daily water in- equivalent take of the refinery. actual The water is the circulating quantity of water circulat- gross ing in a system. It is the same quantity as the makeup water if water recirculated, is only once and discharged to waste. If water is used it is the sum of the makeup and the recirculated water.

14 294 WATER OF SELECTED INDUSTRIES REQUIREMENTS REQUIREMENTS QUANTITATIVE PUBLISHED INFORMATION of petroleum and processing given in Most descriptions refining not Those data on water requirements. do that the literature include information usually show the total water requirements give do such not subdivide the water needs by process or by type of use. and do requirements water selected refineries are given in Published of The variation between maximum and minimum water 1. wide table shown by the four Standard Oil Co. requirements Ohio refineries is of in table. One of these the that had a once-through reported refineries system used 1,870 gallons of water to refine a barrel of water crude oil, another that recirculated all cooling water required only whereas gallons per The possible reduction in water requirements 73 barrel. refineries of suggested by this example many water conservation. by is reduction example conservation is the water in water re- Another of of the Baton Rouge refinery of the Esso Standard Oil Co. quirements to Miller and others (1953), in its early days the Baton According for refinery 100 gallons of water about each gallon of Rouge used processed. Now, even though more crude and treatment for heat each of crude are required gallon to cracking and other inten- owing sive refining processes, the use of water has been reduced to 23 gallons per gallon crude. of literature shows refinery processes have wide ranges of The that barrel The water used per of of feed requirements. gallons water selected refinery processes are given stock table 2. Processes for in large requirements are deasphalting, coking, water with reforming, catalytic cracking. and OF THIS SUB-VET FINDINGS typical A petroleum refinery of today has a daily capacity (median) Approximately about of crude oil. barrels 22.5 million gal- of 16,000 of water circulate daily in the ons water systems within the several refinery. maintain this circulation rate To refinery needs a source the of water capable of providing 2 mgd (million gallons per day). SOURCES OF WATER water of refineries surveyed obtained 61 from both sur- Most the sources and wells, although some face water from only one obtained source. refinery used sewage effluent, One nine used saline ground and water or saline surface water to supply part of their requirements. intake About of the total daily percent was from surface sources; 86 nearly 14 percent was from wells; and 0.1 percent was sewage effluent. (See 3.) Company-owned facilities supplied about 95 percent table of percent. daily water intake, and public facilities supplied about 5 the

15 PETROLEUM REFINING INDUSTRY 295 1. water requirements of selected refineries total Published TABLE unit per expressed barrels of crude charge per day. Unit water is is expressed in gallons in [Size of refinery use charge where otherwise noted] barrel except of crude product Refinery or information Source of Unit use Size Refinery (') _ Lubricating __ _ _ _ Bell (1959). 440 (') Do. 540 (') Do. Do____-_____-____________ 630 Do. Do____. _.____.____._.____ 1,020 0) Do. Do. __._________..__..__._ 1,850 0) Do. and cracking ________ Skimming 910 0) (') Do. 250 skimming, half lubricating __ Half _ Do. only 25 percent. Topping _ 210 0) 3770 (') Oil refining ___ __________ . Jordan (1946). (') _ _ _ _ refinery Complete Bell (1959). 800 Virginia Yorktown, _ ___ Amoco, 000 35, Petroleum Proc- 43 (1957b). essing Do. cooling) ___ water Sea (for _ 3,060 Torrance General Refinery, Partin (1953). 120, 34 000 Richfield Watson Oil Refinery, Corp. __ ___ ____ Do. __ 44 000 114, Oil Refinery, Wilmington Union ___ Co_ __ _ _ ___ _ 110, 000 Do. ___ _.__ _ _ Fresh water. 55 Do. 420 refinery, McPherson National Cooperative Refinery Associa- __ tion __ ___ __ and Aeschliman 25, 47-52 000-28, 000 (1957;. others of Standard Oil Co. Ohio: Simonsen (1952). 21, 000 __ Ohio, 1,870 Toledo, refinery __ Do. 311 44, 000 Ohio, Cleveland, refinery____ Do. 144 39, 000 Do. refinery __ Latonia, Kentucky, 73 000 15, Standard Esso Co.: Oil Baton Rouge, Louisiana, re- 232, 000 Co. Oil Standard 966 (1950). Do. 924 __ Cooling water. 134, 900 982 Do. 953 Do. Product ) 2 ( Besselievre (1952). 357 4 7-10 ( 2 ) Do German (1943). *25 (') gasoline Aviation Youngquist _ _ _ (1942). 3 1 given in source. Data not Gallons per barrel of product. plants. 8 Average of a number of 4 Gallons per gallon ot product.

16 OF INDUSTRIES REQUIREMENTS WATER SELECTED 296 unit of selected processes requirements 2. TABLE water Published is expressed in barrels of crude charge per day. Unit water use expressed in gallons [Size of refinery unit of charge where otherwise noted] per barrel except crude information of Source Size Unit use Process AMMONIA ANHYDROUS (') _ _ _____ Service water. _ Processing Petroleum 2 12, 800 (1956a). (') 165 2 Do. ALKYLATION acid : Sulfuric (Kellogg) Refinery 1: 374 Petroleum Processing 0) (1957a). 3, 3 841 Do. water. __ Cooling (0 2: Refinery 83 (') 3 Do. 410 3 4, Do. 0) 3: Refinery 3 111 Do. 0) (') Do. Cooling 3 4, 637 _ _ __ water. Process HF: (Phillips): 3 1 __ Oil Journal ... _____ Steam. Gas and 0) (1955a). 68 3 Do. (0 CRACKING CATALYTIC Thermofor percolation: continuous (') Petroleum 22 Processing (1956c). (') Do. _ ... water Cooling _ 1,333 Houdry: Scott and ____ Kimball __ _____ Steam 3 000 10, (1948). Do. 1,840 000 10, _____________________ Water_ Fluid: Read (1946). 6 2,000 Do. _ 360 Cooling --_-___-___ water 2,000 Fluid: ___ __________ ___ Steam and 12 Kimball Scott 10, 000 (1948). Water. ___ ____ Do. ___ __ 1,350 10, 000 Thermofor: __ _ _________ _ Steam. 9 Do. 000 10, Do. 1,082 Water. _____________________ 10, 000 Thermofor: Boiler water to (1948). Pfarr kiln _ _ _ _ 12 4,500 Do. 536 4,500 7 Do. steam Net consumed. 4,500 CATALYTIC HYDROGENATION Autofining: Journal Gas and Oil __ 4 ___ _______ _ Steam. 3,500 (1955b). Do. 27 Cooling water __ ___ _ _____ 3,500 footnotes at end of table. See

17 PETROLEUM REFINING INDUSTRY 297 Published requirements of selected processes Continued TABLE water unit 2 of Source information Unit use Size Process Con. HYDBOGENATION CATALYTIC Hydrodesulfurization : Indiana: of Co. Oil Standard Petroleum Processing 1 8,500 (1956f). Do. 315 8,500 Cooling water. process: HDS Gulf West oil, fixed bed : crude Texas __ Cooling __ water McAfee and others 1,460 000 20, (1955). Do. 10 20, 000 : Modified 4 fixed-bed Do. 3,750 water- 20, 000 Cooling Do. 20 000 20, Hydrogen treating: Processing Petroleum Cooling _ _____ water 432 10, 000 (1956e). Do. 7 10, 000 ISOMERIZATION : Co.) (Phillips Catalytic Petroleum (') Refiner Petroleum 82 and Oil (1956b) and Gas Journal (1956b). ( ) l Do. 45 Do. circulating 1,500 Water, gross 0) : Refining) (Atlantic Pentafining Total: Petroleum Processing __ __ __ _ Steam 2 2,000 (1956d). Do. 114 2,000 Pentafiner: Do. 2 1,783 Do. 22 1,783 splitter: Pentane Do. Steam __ _ ______ 0 3,758 Do. 92 758 3, plant: Once-through and Nordburg Arnold ___ _ _ Steam ___ 10 4,000 (1956). Do. 396 4,000 recycling Plant hydrocarbon: Do. __ ___ Steam ___ 80 4,000 Do. water Cooling 2,520 4,000 REFORMER CATALYTIC Hydroforming: (1951). Murphree water Cooling _ 821 10, 000 Do. 10 10, 000 Hyperforming: Petroleum Processing _ _ _ _ _ _ Cooling water 344 1, 100 (1955). octanes: Powerforming for Petroleum Processing Steam _____ _____ 1 000 10, (1957c). Do. _____ Cooling water __ 533 000 10, end of table. See footnotes at 690-234 O 63 3

18 298 OF INDUSTRIES REQUIREMENTS WATER SELECTED unit requirements of selected processes Continued TABLE 2. water Published information Source of Process Unit use Size PROCESS S0 EXTRACTION 2 Straight SO refineries: 2 Refinery 1: Wilkinson and others 0) ______________ 8 Steam..-. (1953). Do. Cooling water________ 750 Refinery 2: Do. 9 Steam_.______________ Do. water__________ 0) Cooling 830 Refinery 3: Do. Steam________________ 10 Do. 930 0) Cooling water.___________ Modified refinery: Do. 13 Steam..._________________ 0) Do. 1,600 Cooling water______________ 0) CRACKING THERMAL Thermal refinery: cracking Scott and Kimball 10, Steam____-_________... 5 000 (1948). Do. 392 Water...__________________ 10, 000 coking: Fluid Processing Petroleum Steam______________________ 10, 000 6 (1956b). Do. 864 10, water______________ Cooling 000 Visbreaking: Boone and Ferguson 16, Steam______________________ 7 240 (1954). Do. 266 water______________ 16, Cooling 240 Size not per 1 product. of barrel ' Gallons of water given. bottoms light vacuum Kuwait 4 furnace catalytic produced. ammonia ton per water of Gallons 2 of distillate blend. oil the Source amount of water TABLE of and refineries visited, in million 3. intake per day gallons All Percent Number Surface water Ground water of total Source of water intake and refineries Saline Fresh Total Total Saline Fresh ' 10. Public... -_ 1.3 3.0 2.4 6.1 6.1 0.6 243 Self-supplied. .7 157 86 157 85 self Public and supplied-.-._-- 666 321 37 629 37 308 100 919 All 126 1.3 sources. 122 792 484 3.1 308 Percent of total .1 intake..._ 100 .4 53 33 TOTAL REQUIREMENTS The average unit water intake of the refineries surveyed by the author and Searcy was 468 gallons per barrel. The U.S. Bureau by showed Mines and others, 1959) (White that 2.54 billion barrels of of crude oil was refined in 1954. The U.S. Bureau of the Census of (1957) a total water intake reported 1,220 billion gallons for pe-

19 PETROLEUM REFINING INDUSTRY 299 troleum the same year. These values indicate an average refineries in of 480 per barrel of crude refined in 1954. The water intake gallons refineries between averages indicates that the two close agreement the representative. were surveyed average water intake was 468 gallons per barrel of Although the most oil, used less than average amounts.' The median crude refineries was crude gallons per barrel of intake charge. (See table water 95 from The for 109 refineries ranged intake 6.5 to 3,240 4.) water per barrel of crude charge and depended on the type of re- gallons finery, variations the refining process, and whether or not water in recirculated. The water intake for refineries that recir- was median was of 57 gallons per barrel water charge as compared culated only the gallons those that used for once-through system. Refineries to 700 cracking units used less makeup water than those with crack- without units; ing median water intake for the former was 75 gallons per the of the as compared to 100 gallons for barrel latter. charge system, 4. water TABLE 1955, by type of cooling Total in gallons per barrel intake, of crude charge [Data from 61 refineries surveyed in 1966 and 48 in 1951] system cooling of Type Type refinery of Once- All systems Combined through Reuse r REFINERIES ALL refineries. Number of _ ___ ____. 109 30 17 62 _ Minimum ______ _ _ 6.5 46 133 6.5 quartile_ ___ _ ________ Lower 108 49 300 35 Median __ ____ ____ ___ 240 95 57 700 Upper 285 quartile__ ___ __ ___ _ 800 1,200 86 _____ _ __ ___ Maximum 3,240 1,950 3,240 403 571 468 81 1,360 CRACKING REFINERIES WITH _ _____ __ 91 __ refineries. Number of 27 12 52 _______ _____ _ Minimum 17 46 133 17 quartile ____ ___ Lower _ ____ 105 54 300 42 __ 100 ____ Median___ __ 280 700 63 ____ _______ Upper 280 quartile __ _ L 850 92 1,300 2,210 _______ ______ ______ __ Maximum 1,950 2,210 403 Average. _ _ ___________ 471 574 1,450 80 REFINERIES WITHOUT CRACKING 18 _ _ refineries. Number of _ _ 3 10 5 _ _ _ _ Minimum. 6.5 186 6.5 quartile.. _ _ _ _ _______ 26 Lower 15 Median ___ __ _ _____ 75 550 27 Upper ___ _ ____ 260 quartile___ 50 3,240 _ _ Maximum.- ______ 249 3,240 374 Average. .- _ _ _____ 128 720 112

20 300 WATER OF SELECTED INDUSTRIES REQUIREMENTS total gross was considerably greater than intake or The circulation because new was used more than once by most some makeup, water gross per was 1,400 gallons median barrel refineries. The circulation makeup compared 95 gallons of new as per barrel and charge of to 14 gallons to 7,290 gallons (table 5). Kefineries with- ranged from units out less gross circulation; their median re- cracking required compared 500 barrel of charge as per to 1,600 was gallons quirement barrel for cracking refineries. gallons values also indi- per Median that with cracking units consume refineries water than those cate more cracking units: 38 gallons without barrel of charge as compared per to gallons per barrel. This is because refineries with cracking 24 generally circulate wi.ter per barrel than those without units more units. cracking COOLING-WATER REQUIREMENTS percent of the water About of the refineries surveyed in 91 intake was used for cooling. The balance was used as shown in figure 1956 The water of 43. used for purposes other than for cooling amount for amount water makeup is shown as one value, as the and boiler-feed each individual the several for uses was negligible. of gross 6, and 8 show the Tables circulation, the makeup, and 7, the consumption of cooling water by type of cooling system and by type of The median and average makeup-water uses for refinery. and for types of water use, except cooling, of refineries with total all with exceeded given for those values no cracking units the cracking corresponding cooling-water values were units. for re- The larger without units; this difference was cracking to the greater fineries due by refineries without cracking use of once-through cooling, which units has larger makeup-water needs. correspondingly with cooling systems circulated approxi- Refineries recirculating twice as much cooling water, used about 25 times less makeup, mately of consumed 24 times as much water per barrel about crude charge and as those with once-through systems. REQUIREMENTS FOR SELECTED OPERATIONS Petroleum is by subjecting crude oil or other petroleum refined the to of processes. Information on series water uses of materials a processing units may therefore be useful in individual the analyzing water of petroleum refineries. requirements water available, for Where total makeup data used by the proc- the essing units and the amounts used by each for cooling, boiler feed, and other uses were obtained during the survey. Sim- miscellaneous ilar for gross circulation, consumptive uses, and quantities of data effluents were obtained where available. Because data on the quanti- the ties types of charges to and various process units were not avail-

21 Sanitary and other \ water ^ 14 percent Ground FIOUEE 43. Source and use of water Intake. CO O

22 CO o to barrel type of use and type of refinery, in gallons per and of crude charge TABLE disposition by Water requirements 5. jj units cracking without Refineries refineries Refineries with cracking units All "" 5 Boiler- Boiler- Boiler- and disposition Water Sanitary requirements Sanitary Sanitary 3 Total and and Cooling Cooling water Total feed Cooling feed Total and feed *° water other other water water water water water water other water water water water » Hrl : circulation Gross H § 14 14 61 61 w 14 14 61 61 47 _ _ refineries Number of 47 47 47 H 14 Minimum. 14 _________ . 0 7.5 5 39 12 5.5 5. 7.5 0 88 0 14 ______ Lower quartile _ 190 2.2 . 8 1,100 § 145 20 750 1,200 22 850 3.5 23 1,400 | 500 25 400 1 3. 1,550 8.5 27 1,350 11 1,600 10 22 _ quartile 42 ______ Upper 2,050 900 960 3 34 2, 2,000 100 1,900 35 25 483 3, 240 39 7,220 7,220 3, 120 7,290 483 166 141 7,290 166 11 19 29 44 1,620 699 o 644 1,670 1,710 1,660 28 19 *] makeup: New 14 61 14 Number 61 109 of refineries 47 __ 61 14 47 47 OB 91 18 6.5 2.6 2.6 H Minimum. 5.4 _ ____________ 6.5 17 0 0 0 0 0 0 25 --__-_ quartile 12 2.0 13 8 . Lower _ 49 6.8 54 14 30 3.0 26 B 3.0 o 75 19 19 95 56 70 100 19 8.0 60 8.3 11 20 260 Upper ------ quartile _ 31 U 175 26 285 400 250 25 280 17 Maximum. 125 39 _ _________ 79 3,120 240 o 3,240 3, 3,120 125. 1,880 79 2,210 60 374 11 Average. __ __________ 17 468 374 471 418 20 20 376 16 17 : Consumption 14 14 Number __ of refineries 61 61 61 61 2 14 14 47 47 47 47 3 o 0 0 0 0 0 0 0 0 0 0 0 S 6.0 Lower 3.4 12 quartile 1.2 _ 0 _ 27 24 2.5 .6 18 0 0 g 24 Median ___________ -_ 2.8 0 25 9.0 26 10 38 36 0 8.7 0 H 57 24 quartile _ ------ Upper 36 27 20 .3 .3 20 55 .8 53 36 125 ____ Maximum __ _.__ 52 94 304 1.4 34 13 125 125 304 94 13 16 Averaee - - _________ __ 28 1.2 6.4 10 3 . 29 10 1.2 40 9.8 39

23 Effluent: refineries __ 61 61 of 61 Number 47 47 61 47 14 47 14 14 14 4. 6 0 0 0 0 1.5 0 0 0 0 0 0 9 _ Lower ______ 1 1. . quartile 1.0 5.5 2.8 20 5.4 1.8 24 .7 4.9 9.0 9 _ _ _ Median. 6. 8 __ 8. 21 23 5.0 7.2 51 1.8 45 38 60 3.0 6 Q 110 200 16 17 18 150 80 19 400 12 330 121 Maximum 121 ____________ 120 3, 3,120 1,860 79 120 3, 3,120 1,940 79 39 48 __ Average --_______- 17 374 12 17 345 12 343 371 407 11 429 10 NOTE. The summation of the median, quartile, minimum, maximum and average water-use values for various types of water may not always equal the corresponding total type water The median water-use value for cooling may be that of one refinery, whereas the median for some other value. of water use or for the total may be that of the same or another refinery. O CO O CO

24 WATER SELECTED INDUSTRIES REQUIREMENTS OF 304 water able, divided by the capacities of the requirements total were in (1956c) Oil and Gas Journal given to obtain process units the barrel water-use gallons of water per in of capacity. unit the values either vacuum or crude, Distillation less makeup and units, require circulation barrel of crude charge than cracking units owing gross per much distillation temperature in the the processes as com- to lower 9 to processes. (See tables cracking and 10.) Consump- pared the of cooling water in distillation units is also less than in cracking tion Similarly, new for and consumption of boiler-feed units. makeup distillation is less than for cracking units. by units water Gross circulating cooling water, 1955, by TABLE of cooling system and 6. type of in gallons per refinery, of crude charge type barrel cooling system Type of of refinery Type All Reuse Combined Once through systems ALL REFINERIES Number ___ of refineries _ ______ _ 7 61 24 30 Minimum _________ 189 7.5 5 161 7. 750 520 1,300 410 1.590 1,350 700 200 1, ___ _ _ Upper quartile ______ 1,900 1,900 1,290 1.750 120 3, Maximum _ ________ 3,250 7,220 7,220 Average __________ ______ 1,620 804 1,630 1,700 REFINERIES WITH CRACKING refineries . _ ______ of Number ___ 2 47 24 21 _ Minimum 39 _____ 819 39 _ ___ Lower quartile- _ ___ __ 100 1, 1,400 880 _ _ _ _ Median _ __ _____ 1,550 1,680 1,500 Upper _ _ _ _ _ quartile 2,050 1,980 2,030 _ __ Maximum _ ______ _ _ __ _ 7,220 3,250 7,220 1,640 1,650 Average 1,740 REFINERIES WITHOUT CRACKING Number 3 14 of refineries. _ . _ 5 6 7.5 161 5 7. 145 _____ quartile. Lower 400 520 140 900 Upper quartile ______ ______ 120 __ 3, Maximum 120 3, 1,030 ___ ______ _ __ Average________ 64 693 606

25 PETROLEUM REFINING INDUSTRY 305 by Cooling-water makeup, 1955, by type of cooling system TABLE 7. type of and refinery, in gallons per barrel of crude charge system cooling of Type Type of refinery All Combined Reuse Once systems through REFINERIES ALL Number 61 refineries. of 24 7 30 ___ _ ___ __ Minimum 6 2. 161 25 6 2. 25 15 370 61 740 140 60 30 _ quartile _ Upper _ 250 48 1,500 500 _ Maximum _ ___ __ ___ 3, 120 120 3, 1,880 178 376 784 45 511 CRACKING WITH REFINERIES 47 21 2 24 25 2. 6 6 2. ___ Lower quartile __ _ _ _ 30 20 68 Median __ _________ 56 150 34 175 620 52 ___ _____ Maximum _ _ _ 1,880 1,880 178 Average __ _______ ___ __ 374 515 46 CRACKING REFINERIES WITHOUT 14 3 5 6 ___ ___ Minimum. 5. 4 161 5. 4 12 70 520 11 __ ______ quartile Upper 400 ___ _____ ___ Maximum 120 3, 3, 120 31 Average __ _______ _ 418 693 23 690-234 O 63

26 REQUIREMENTS SELECTED OF WATER INDUSTRIES 306 1955, type type of cooling system and by TABLE 8. Consumptive by cooling water, barrel of crude charge per gallons refinery, of in Type system cooling of of Type refinery Combined All Reuse Once systems through REFINERIES ALL of Number refineries _______ _ _ _ 61 7 24 30 Minimum.. _________ ____ 0 0 0 .8 22 12 12 _ Median __ __ _ ___ _ __ ___ 33 25 24 0 48 29 36 ____ ___ _ _ _ __ Maximum _ _ 74 48 94 94 _____ ____ ___ ___ ______ Average. _ 29 3 1. 28 31 REFINERIES WITH CRACKING refineries Number of _ ____ __ ___ 21 2 47 24 Minimum _ _ __________ _ 0 0 .8 18 23 16 28 26 25 quartile ___ _____ __ Upper 36 39 34 74 94 94 29 29 31 REFINERIES WITHOUT CRACKING refineries 3 ____ Number of _ ____ _ 14 5 6 ______ Minimum ___ __ 0 0 1. 4 quartile.- _ ___ ___ ______ Lower .6 3. 3 9.0 0 9. 6 27 Upper quartile. ____ _____ ___ 23 52 Maximum ______________ _ 48 30 __ ___ Average... __ ___ _____ ___ 9.8 2. 5 16

27 per TABLE distillation units, in gallons of water crude barrel of crude charge of 9. Water requirements obtained from 9 refineries without cracking and 25 refineries with cracking] [Computed from data Cooling water Boiler-feed water water Total disposition and requirements Water Total Cracking Cracking Noncracking Total Total Noncracking Cracking Noncracking Gross circulation o i 34 8.6 0.7 8.6 0.7 13 4.8 44 IQft 160 fiQ 3.7 175 63 175 3.0 6.8 5. 8 5 4. 300 340 290 310 12 440 300 7QO 470 690 quartile. ___--_-_----_---_--_-------- 11 430 Upper 7.8 29 510 445 __ ________--___---- Maximum.----.--- __ 905 435 905 435 70 725 916 916 748 5. 1 356 512 347 7.5 46 352 365 560 New make-up Q I 4 6 2.7 0 0 0 0 0 4.6 1 7 8. 8. 4.8 8 1. -__ ___-___---- __ 5 - Lower _ quartile_-_ 4.0 12. 1.4 3.9 21 3. 5 10 43 7.9 16 2.9 7.9 51 11 K 00 6. 9 Upper 62 26 210 ________--_--______--------- quartile. 4.9 18 74 35 - 725 ----- __ __ - ___ -___ - - _ Maximum... 725 12 652 44 725 44 725 660 451 63 3.4 85 3.8 90 9.3 461 67 o Consumption 0 0 0 0 0 0 0 0 0 1. . £ 2 2.5 2.8 .9 .3 .3 4.2 3.8 7 Q ________ ______ - _____ ___ __ Median. 12 1.3 5.4 6.0 .9 3.0 6.7 20 '4.3 7 3. 7.1 21 12 15 8.0 10 34 31 12 31 31 26 31 52 42 52 1 1. 2. 5 1 6. 4.3 6.2 1.2 7.4 7.5 6.7 Effluent __.__ __ __ ________ ________ __ Minimum 0 0 0 0 0 0 0 0 0 Q 3 . 9 __ 1.0 1.7 Lower ________-----_----__ quartile. ____ .2 .05 2.4 2.7 .05 2.4 17 .9 1.6 3.0 .6 5.2 4.5 27 9 49 2. 170 Upper ___ quartile__ 2.2 13 ____________ __ -_--__ 17 6.9 125 59 725 44 652 725 745 19 44 745 660 444 2. 2. 2 5 7.7 55 78 __ _--___---------- Average.-.------------ 81 453 58

28 TABLE 10. selected operations, in gallons of water per barrel of crude charge Water requirements of in Journal (1956c)] as reported [Charge Gas Oil and 00 Thermal Crude cracking Vacuum distilla- Catalytic distillation reforming cracking Catalytic Polymerization Alkylation units units tion units units units units units requirements Water and disposition Cool- Cool- Cool- Cool- Cool- Cool- Cool- Total Boiler Boiler Boiler Boiler Total Boiler Total Total Total Boiler Total Boiler Total ing ing feed feed feed ing feed ing feed ing ing feed feed ing ^ circulation Gross » 16 14 13 19 14 19 17 34 34 23 34 14 17 22 20 16 9 23 10 24 10 » 19 23 .8 13 36 8.6 806 9.7 294 1.4 21 299 21 .4 .7 4.2 0 88 840 0 64 H 3.7 140 118 160 175 260 520 270 4.4 2.2 2.8 700 520 1,440 1,400 670 4.0 47 8.0 1,400 1,250 £> 300 5.5 310 215 230 950 500 5.8 2,350 51 500 1,000 8.3 5.0 35 11 2,600 840 3,300 1,000 2,000 470 345 11 11 15 16 4SO 510 12 1,150 4,400 1,230 950 3,500 1,400 1,400 950 92 4,200 4,790 68 435 17 905 655 916 39 11,840 2,480 158 12, 010 2,470 i 133 954 177 278 2,060 1,900 7,080 2,100 2,040 7,010 356 8.1 7.5 365 223 882 348 10 5.4 334 32 2,470 961 26 884 7.4 2,940 3,290 78 2,350 874 H makeup New 34 15 34 15 15 14 10 10 17 17 19 9 20 23 21 22 16 16 34 24 23 2.5 24 .8 .07 4.6 1.5 13 3.9 1.0 8.4 39 6.7 .3 6.2 0 .7 0 1.8 0 0 0 1.4 12 16 1.8 4.9 4.3 4.8 26 1.9 3.3 57 13 19 82 23 12 8.7 64 27 15 5.2 10 3.5 123 108 6.1 28 125 16 12 69 22 31 4.0 19 26 38 8.0 5.0 37 21 25 165 74 62 31 140 6.9 235 54 390 50 8.8 11 43 34 12 38 43 53 49 7.3 50 13 429 725 562 150 127 23 1,330 93 36 1,200 44 1,180 725 1,340 623 781 294 96 80 707 4.2 254 396 195 18 3.8 61 322 85 27 37 3.6 29 116 90 81 6.3 109 45 7.2 73 Consumption 9 10 34 10 14 13 14 34 16 14 34 16 19 17 17 23 19 22 24 20 23 1.3 1.2 0 0 0 0 0 0 0 0 0 4.1 0 0 4.1 0 0 0 0 0 0 Lower quartile.. ... 35 19 3.5 3.8 .3 2.5 .1 25 20 3.0 .3 16 4.3 3.8 15 10 5.0 .08 0 7.6 .8 20 1.3 79 6.0 44 2.2 7.9 60 5.7 37 12 3.3 1.3 15 17 22 1.9 1.4 12 19 8.2 quartile 116 _______ 92 35 Upper 8.0 12 4.3 64 42 9.0 5.6 17 7.2 67 24 31 25 15 26 19 8.8 6.0 31 221 53 31 168 52 133 282 238 9.5 96 40 23 103 46 18 21 80 98 88 50 15 77 6.2 1.2 37 60 6.1 7.4 48 14 12 2.1 18 6.4 10 3.3 1.4 23 5.3 2.7 20 3 B H Effluent QQ 10 34 10 34 9 16 13 14 34 14 16 19 14 23 17 22 17 23 19 24 20 ... 0 0 Minimum 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 4.4 2.2 1.6 ... quartile Lower 16 .05 1.0 2.7 .7 1.8 .01 1.5 2.0 1.2 2.2 1.0 5.0 .01 0 0 .2 .9 41 11 6.2 4.1 3.0 33 .9 2.2 5.2 28 1.6 4.6 5.5 .5 11 .7 3.0 7.6 .9 6.0 5.3 91 24 .._____ 59 quartile Upper 49 100 60 2.9 7.2 115 34 12 14 1.7 2.2 25 14 5.2 24 17 2.4 20 477 127 349 1,200 44 1,180 745 725 744 108 20 22 102 5.6 294 671 20 1,240 9.5 16 1,240 173 46 133 232 1.6 299 78 3.5 2.5 81 1.8 19 11 20 76 85 27 2.5 9 66 2.6

29 PETROLEUM REFINING INDUSTRY 309 WATER-QUALITY REQUIREMENTS uses various within a refinery have different water- of The water example, a gulf coast refinery described For in quality requirements. salty water is used by once-through cooling, and Resen (1957) for water is used for high-pressure boilers. demineralized high-quality quality Although less important than quantity for petro- water is refineries, water of good quality is desirable. Most sources of leum a both and quantities provide suitable qualities for all water sufficient needs. refineries use sources that will yield sufficient water Most and will satisfy the water requirements by treatment. In quality some special equipment is installed to permit low-quality refineries to be without treatment for some processes. As cost is water used treatment factor choosing between the in of water of the deciding quality and the installation of special equipment for its use, poor is of problem quality economics. Brooke (1954) showed that com- a treating softening of all cooling water became profitable plete and less than 4 years in provided many intangible benefits. and Technical literature contains many references to methods of treat- ing the intake water of petroleum refineries (Forbes, 1954a and b; Kelly, 1946). effects, and methods of Usual tolerances, undesirable the constituents in water as suggested by of removal undesirable and b) and Betz (1950) are given in table 11. Forbes (1954a common Undesirable methods of correction for and constituents 11. effects TABLE water in from Forbes (1954a) and Betz (1950)] [Data modified Undesirable after Residual limit of Method or Usual Impurity effects treatment, tolerance correction (ppm) sulfide. Hydrogen <1 Odor, corrosion, and <0.5 ppm. Aeration, Chlorina- demand. chlorine tion, Filtration. and 5-10 dioxide. Carbon Corrosion if alkalinity Aeration, neutraliza- Alkalinity is low. tion with alkalies, treatment and acid Carbon dioxide of boiler-feed wastes. Oxygen. <0.007 pitting. and Corrosion in deaeration. Hot ppm <0.007 boilers and 0.1-0.3 vacuum Cold deaera- economizers. tion. Suspended solids. flow, Impede water <5 <5 and Sedimentation ppm. transfer, heat retard filters. aid corrosion. <1 chemi- Plus coagulant cals where necessary. Oil. Causes sludges to 5 Coalecing followed (7 1 ppm ppm form of bake on in skimming. by max). scale. Causes boiler foaming. <1 Absorption with pre- followed formed floe filtration. by

30 WATER INDUSTRIES REQUIREMENTS OF SELECTED 310 constituents effects methods of Undesirable for common and TABLE 11. correction Continued water in from Forbes (1954a) and Betz (1950)] [Data modified Undesirable Usual of Method Residual after limit or effects Impurity tolerance correction treatment, (PPm) Promotes Any exchange Cation boiler foam- Alkalinity. desired For 300 boilers, residual. ppm. (hydrogen cycle) . ing; in COz forms steam causing con- addi- acid Sulfuric Concentration corrosion; densate ratio: ^60 tion; with or lime boiler causes em- ice, 30-50 For inter- brittlement; ppm. gypsum. without with For drinking, feres pH control. <300 ppm. Anion exchange. <3 Chlorides. Generally 100-300 Boiler foaming and ppm corrosion. max where possible. 17-25 treatment. Barium Sulfate. formation. 100-300 ppm Scale max possible. where 0-3 exchange. Anion Adsorption 10-0. Fe- on Silica. 30 0. 3-20 Scale. depend- ppm, ; 2 (OH)aorMg(OH) ing on boiler exchanged anion pressure. with without or fluoride addition. 0.1-0.3 Aeration followed by Iron and 0.3 ppm. scale. and Corrosion filtration (pH con- manganese. be may trol ; required) deionization. 25-35 lime Calcium. Cold soda. Generally 60-80 Scale formation. process for ppm 12-15 soda. Hot lime use boilers; and max. ppm 0-10 0-5 exchange Cation or (sodium hydro- gen cycle) . 0-5 Ca. as Same Magnesium. formation. 60-80 Generally Scale max. ppm 0-5 Sodium. Cation exchange foaming Boiler Low possible. as (hydrogen cycle). corrosion. analyses obtained of untreated water from 82 sources Chemical were by 56 of the refineries visited in used Of these analyses, 47 1956. were by the refineries and furnished were obtained from U.S. Ge- 35 ological Survey publications. Analyses of water supplied by private water companies municipalities were of the water delivered t^ the or The d and physical characteristics of un refineries. chemical for given uses are water in table 12. all the minimum water-quality requirements for cooling, boil- Because erfeed, process, and sanitary water are different, requirements for use each discussed separately. For each are of water, a brief use discussion is given of the desired characteristics and suggested toler- the ances, source and quality of untreated water, and the water- treatment methods for each type of water used.

31 PETROLEUM REFINING INDUSTRY 311 TABLE of untreated water for all uses Quality 12. characteristics parts based million unless otherwise indicated. These data are in on individual [Data expressed per and are balanced analyses] observations available not Concentration Number Constituent samples of Minimum Maximum Median Lower Upper quart ile ile quart 60 (SiOs) Silica 18 12 2.4 6.6 52 14 .10 .57 38 .00 .04 220 42 _ Calcium (Ca)-. . 18 2.8 69 64 83 25 12 63 4.4 .7 266 ... 19 (Na+K) 54 potassium and Sodium 34 1.0 7.8 484 270 167 17 76 69 565 (SOO - Sulfate _ ~ 152 17 .8 59 64 1600 66 (C.)_ 15 1.0 28 Chloride 75 1.2 .1 .4 Fluoride __ - ... (F)-_- . .0 .0 28 8.1 1.5 - _ 3 )-. Nitrate 4.5 (NO ___ .4 .0 28 520 3500 265 146 46 50 Hardness as COs: 850 275 Total 144 10 67 76 550 56 20 63 0 0 22 10 5 1 3 19 9.1 pH__ ... _ _ _. . 7.8 7.6 6.0 74 7.2 COOLING WATER Water for the largest use in refineries, ranges in quality cooling, sea water once-through systems to high-quality water for from for In be cooling water should systems. of sufficient- circulating general, good to keep corrosion, scale formation, organic slimes, ly quality deposits of sediment to a minimum. Temperature and a major is consideration the selection of a source, especially where once- in cooling water used. Quality tolerances of through for cooling as is are suggested American Water Works Association the given in by table 13. TABLE 13. Quality tolerances of cooling water suggested by American Water Works Association [Data from Am. Water Works Assoc. (I960)] modified Limiting values or property (ppm) Constituent Hardness as CaCO3________________________________________________ 50 (Fe)___._________________________________________________ . 5 Iron (Mn)__________________________________________________ 5 Manganese . plus . 5 Iron manganese__-----_-__--________-_-___-__-_-_---------_-_- 50 Turbidity______________________________________ Corrosiveness.____________________________________________________ None Slime formation ___________________________________________________ None PUBIJSHED INFORMATION In an extensive survey of refinery cooling-water systems, Helwig and McConomy (1957) that fouling and corrosion occurred in reported all systems when no treatment was provided. They cooling-water noted that where dissolved solids, specific conductance, temperatures, and velocities were high, corrosion was accelerated. Their survey in-

32 312 WATER OF SELECTED INDUSTRIES REQUIREMENTS that, in corrosion increased in circulating-water sys- dicated general, the pH below 7.5, whereas corrosion was mild if tems if dropped above actively Refineries were was and effectively com- the pH 8.0. corrosion by chemical treatment, cathodic pro- fouling bating and the use of special construction materials. The most tection, and method^ treatment were (a) pH adjustment with prevalent reported and or (b) control of slime ash, algae growth with acid soda sulfuric other algicides, and chlorine control of corrosion and fouling and (c) polyphosphates, chromates, and silicates. Helwig and McCon- with also reported on the effectiveness and cost of the various types omy of chemical treatment. (1951) also the objectives and techniques of Miller discussed He that when open-circulating treatment. cooling-water noted were used, treatment problems increased owing cooling-water systems concentration effects. to water, areas water, such In sea low-quality is used by coastal as for cooling. An average use of 128.5 mgd of sea water refineries for most in the Bay way refinery of the Standard Oil Co. (1950) cooling described "The Lamp." is in successful utilization of sewage effluent for cooling and for The water Big the boiler-feed Spring refinery of the Cosden Petroleum by is reported by McCormick and Wetzel (1954). Sewage efflu- Corp. ent created such problems as foaming in boilers and excessive slime growth in systems, but these problems were corrected by cooling of standard procedures. The authors noted modifications treatment due the the additional expense of to increased with exception that, the cost of treating sewage chlorine is only slightly demand, effluent than cost of treating the comparable natural water. higher chemically OF THIS SURVEY FINDINGS In the survey data were obtained on the chemical and physical 1956 of untreated cooling water used by 68 petroleum characteristics the The chemical analysis of one treated refineries. effluent as sewage delivered the refinery was obtained, to no analyses of sea water but were included. Several refineries use the same source of water for once-through and cooling systems. The sum of the num- circulating therefore, of cooling water will not of always be equal ber analyses the total number of to of water from all sources. analyses Table shows the chemical 14 physical characteristics of un- and treated water that was supplied to the circulating cooling systems of 48 refineries to the once-through systems of 26 others. Mini- and lower quartile, median, upper quartile, and maximum values mum, are given for each constituent and characteristic of once-through and are circulating for which there water a sufficient number of samples.

33 TABLE Quality of untreated cooling water 14. characteristics not in per million unless otherwise indicated. These are based on individual expressed available and are parts balanced analyses] [Results observations Circulated Once-through Constituent Concentration Concentration or Number property of Number Min- Min- Max- Max- samples Lower of Lower Upper Upper quar- quar- quar- quar- imum Median imum imum samples imum Median tile tile tile tile Silica (SiOs) 14 24 46 2.4 7.2 5.8 12 22 2.4 34 9.8 60 -------- ------ (Fe). Iron 12 1.0 14 19 .04 . 71 . .00 .02 .00 23 . 15 8.7 72 204 16 4.0 204 51 45 83 28 41 2.8 18 Magnesium (Mg) __________ 13 13 28 4.2 24 1 . 7 83 27 83 40 4. .7 and Sodium potassium (Na+K)_____. _. -____ 102 13 1.0 52 19 146 52 6.2 6.2 266 1.0 17 (HC0 Bicarbonate ___--_. ) 3 17 142 248 484 484 30 198 68 22 45 332 113 (SO.) Sulfate 14 156 536 145 30 . 8 558 40 38 .8 68 18 (01) ___________ Chloride 1.0 26 32 64 12 900 30 900 58 52 1.0 19 _ Fluoride __ _ (F)______ 15 .2 1.2 1 . .5 .2 14 1.2 .0 1 .0 .0 . (N0 Nitrate )----_-------- 3 2.0 14 .0 2.6 12 7. 5.6 6 1.5 .9 .7 .0 .3 46 442 46 629 228 296 21 624 97 193 1,170 32 as : Hardness 3 CaC0 Total ____ __ __-_-_ 12 52 850 33 160 326 160 850 319 68 51 10 27 5 550 10 550 56 22 0 58 40 0 0 __ _ Color_____ 3 1 10 13 14 14 7 1 5 22 3 8 T->HT ____________________ pH 6.0 9.1 7.4 31 7.0 7.2 49 7.6 6.4 7.8 7.9 8. 9 00 I 1 00

34 WATER OF SELECTED INDUSTRIES REQUIREMENTS 314 information solids, total hardness, bicarbon- dissolved Additional on sulfates is shown in figures 44 and 45. ates, and 30 san tples Ui C O I L INDICATED m E2 V\ 100 200 300 400 500 6C J (SO ), IN PARTS PER MILLION SULFATE 4 samples 30 600 200 100 500 400 300 IN (HCO,), PER MILLION BICARBONATE PARTS 33 samples E3 800 200 300 500 600 700 400 100 HARDNESS AS , IN PARTS PER MILLION 3 TOTAL CaCO 200 400 600 800 0 SOLIDS, IN PARTS PER MILLION DISSOLVED FIGURE 44. Frequency of selected chemical constituents in untreated water distribution once-through cooling. for used for once-through Waters for circulating cooling were and similar in quality; however, water used for once-through cooling was higher of quality. The use of higher quality water for once- slightly through cooling is not due to higher requirements but is probably areas due the availability of better quality water in to of plentiful supply where recirculation is not necessary.

35 PETROLEUM REFINING INDUSTRY 315 40 samples 600 100 200 300 400 500 SULFATE ), IN PARTS PER MILLION 4 (SO I 5 1 samples 45 600 300 400 500 100 200 3 ), IN PARTS PER MILLION (HCO BICARBONATE I 51 samples

36 316 WATER OF SELECTED INDUSTRIES REQUIREMENTS refinery intake is treated to provide the desired quality Most water the water. from only 10 of water 39 sources of cooling Although of water was given once-through which varied from cooling treatment, to and filtration, water from sedimentation of the 69 screening 52 of circulating water was given some type sources treatment. Table of 15 the methods used for treating once-through and circulating shows water the refineries visited. cooling at BOILER-FEED WATER MAKEUP amounts of high-quality water are used by petroleum re- Large fineries to low- and high-pressure steam. Untreated water is produce not satisfactory for this use; therefore, careful considera- generally tion is given to the selection and treatment of makeup water for boiler-feed to excessive corrosion, scale formation and em- prevent brittlement. plant gulf coast industrial a indicates the importance Experience at high-quality boiler feed. During World War I the plant had three of one boilerhouses: steam, one on standby, and one being cleaned. on and The was not treated, water the average on-stream time boiler-feed for a boiler was 2 to 3 weeks. Later the feed water was given internal for treatment, boilers could be operated the as long as 2 months and between cleanings. Modern boilers, which operate on softened and will internally waters, may never need cleaning and treated be opened only for annual inspection (Brooks, 1954).

37 TABLE of makeup water for cooling Treatment 15. refer to frequency of use of various types of water treatment. Prior treatment of purchased water is not considered] [Figures Once-through cooling water Circulating cooling water Self-supplied Public Self-supplied Public supplied supplied treatment Type of Ground Total Total Surface water Surface water Surface water Ground water Ground Surface water water Sewage water effluent Fresh Fresh Fresh Fresh Fresh Saline Saline Saline Saline Saline Fresh Fresh 1 10 1 12 8 4 4 1 4 5 30 _. Screening... ______ 1 1 1 6 4 1 _____ _ Sedimentation 1 1 5 4 1 Filtration.--. ________ 1 5 1 3 3 3 Softening: 1 10 1 5 3 - 3 1 1 1 1 1 algae Disinfection and control: 12 1 1 20 2 Chlorination. _____ 7 3 Organic com- pounds--------- 1 1 2 9 5 13 2 1 1 1 Other_-__------- 8 Corrosion scale and control: 10 Chromates. _______ 2 2 6 21 3 2 4 2 12 1 3 1 2 3 Dianodic_____--_- 15 1 27 4 1 3 3 pH adjustments- _. 1 1 __ __ _ Other.. 8 6

38 318 WATER OF SELECTED INDUSTRIES REQUIREMENTS INFORMATION PUBLISHED many textbooks and manuals on industrial water condi- There are example: Nordell, Powell, 1954; Betz, 1950; and tioning (for 1951; 1947) problems discuss the general Co., caused by the Permutit that water and the treatments used to remove in impurities boiler-feed The boiler-feed water problems of petroleum undesirable impurities. are problems individual however, and require refineries, usually for specialized satisfactory treatments solutions. the solution described a makeup-water problem (1957) Eesen of boilers, at the Port for Tex., refinery of the high-pressure Arthur, Oil by the use of Corp., treatment. The surface water Gulf special for boiler-feed makeup in used generation of low pressure steam the had treated by coagulation, gravity filtration, and zeolite soften- been Steam turbines to drive centrifugal compressors and ing. obtained required steam use of high-pressure steam. This equipment other the of free be to prevent the deposition of silica on the tur- must silica which causes reduced efficiencies and early maintenance shut- bines, The downs. high-quality water for the high-pressure boilers desired obtained passing the gravity-filtered makeup water through an was by demineralization unit, which lowers the mineral ion-exchange con- tent less than 6 ppm of to solids and the silica content to dissolved less than .01 ppm. McCormick and (1954) described the use of sewage effluent Wetzell of hard water for boiler-feed water makeup. In instead ground the ranging was using water with hardness 1944 from early refinery problem 1,300 Scaling was a serious to in boilers and in 700 ppm. heat exchange equipment, and water treatment experts could other provide a practical solvent for the scale. In July 1944, Cosden not for Big of the sewage effluent from the city of contracted Spring, use At effluent the Tex. used for boiler-feed water makeup was first by the hot-lime process, anthracite filtration, and internal treated phosphate treatment in the boiler drums. This treatment was not entirely satisfactory foaming and priming resulted. McCormick as Wetzel however, that satisfactory operation was at- and reported, by changing to a hot-phosphate treatment in an external tained treater followed the injection of a foam suppressing agent by the boiler into drum. FINDINGS OF THIS SURVEY Chemical analyses of the untreated makeup waters for boiler feed used by refineries surveyed were obtained where possible. Anal- the sources: were of water from 55 yses 40 were company wells obtained or surface water, 14 were public supplies, and 1 was sewage effluent. could Two from company wells samples be classified as slightly to

39 PETROLEUM REFINING INDUSTRY 319 the others, 1957), as and dissolved solids saline (Krieger moderately both were over 1,000 ppm. None of the content surveyed of refineries sea for boiler-feed makeup. used water characteristics quality untreated makeup water for boiler The of used at 54 refineries are given in table 16. Figure 46 shows the feed 5 36 samples 70 30 50 10 40 60 20 SILICA PARTS PER MILLION (SiO 2 ), IN 100 200 300 400 500 0 600 3 IN PARTS PER MILLION (HCO ), BICARBONATE 45 samples 800 300 400 500 600 700 200 100 HARDNESS AS CaCO 3 , IN PARTS PER MILLION TOTAL 32 samples ^^1 1200 0 600 800 1000 200 400 IN PARTS PER MILLION DISSOLVED SOLIDS, 46. Frequency distribution of selected chemical constituents in untreated makeup FiotJEB water for feed. boiler distribution some important chemical constituents in frequency for makeup boiler-feed water. Water-quality tolerances for boiler-feed water makeup suggested by Moore (1940) are shown in table 17. A comparison of the quality characteristics of untreated water with the suggested tolerances in- the a need for treatment by most refineries. dicates Many of the refineries employed industrial water consultants to make water analyses, to interpret these analyses, and to recommend

40 SELECTED REQUIREMENTS WATER OF INDUSTRIES 320 untreated makeup water TABLE boiler-feed 16. Quality characteristics of million unless otherwise indicated. These are based on individual observa- [Results expressed in parts per not balanced available and are analyses] tions Concentration Number of property or Constituent Upper Lower samples Maximum Minimum Median quartile quartile Silica 60 ... 19 (SiOj). ... 12 6.9 2.4 36 7.2 Iron .58 - __ __.__..__ (Fe).. .10 .03 .00 24 173 68 39 2.8 43 18 56 25 14 4.1 43 .7 266 69 24 (Na+K)-___ and Sodium potassium 1.0 6.0 21 484 270 186 86 22 49 148 Sulfate (S)*... - _-.- 558 62 .8 18 45 ... 465 Chloride ...___.____ (Cl). 74 33 18 1.0 54 1.2 .5 .1 .2 .0 15 7.6 ). ... 3 4.0 (NO Nitrate .7 1.5 .0 15 286 622 1170 151 46 33 Hardness CaCOs: as 272 644 142 Total... ... 66 10 55 416 52 14 44 0 0 22 14 5 1 3 10 7.8 9.1 7.2 DH.._ _. 7.6 _ 6.4 51 TABLE tolerance for boiler-feed water water-quality 17. Moore [Data from (1940)] water-quality tolerance (ppm.) Suggested pressure (psi) at indicated Constituent >400 250-400 150-250 0-150 4 _ __ 10 consumed _ Oxygen 3 15 .0 .0 14 4 . 1. Dissolved oxygen 1 2 3 5 2 0 0 sulfide (H 2 S) Hydrogen 10 2 40 _____ 80 hardness as CaCO Total 3 .01 .05 oxide (AljOs)- -- Aluminum 5 . 5 5 1 20 40 Silica ______ (SiOi)__________. 0 5 30 ) ______ Bicarbonate 3 (HCO 1 _ 50 20 40 100 )__ (CO 200 Carbonate _ _ ____ 3 15 30 40 Hydroxide (OH)______ 50 ___ __ 50 100-1, 500 ___ 3 Total solids __ ___ _ _ 500 500-2, 500-3, 000 2 5 40 Color... _____ _____ _______ 80 9. 6 9.0 8.4 8. ___ (minimum) value pH 0 1 5 ______ _ Turbidity... _ _ 10 20 Sulfate-carbonate 4 ratio 3:1 8:1 2:1 1:1 - )__ 3 :Na,CO 4 (Na,SO Limits applicable only to feed water entering boiler, not to original water supply. 1 2 Except odor in live steam would be objectionable. when Depends on design of boiler. 3 4 Society of Mechanical Engineer standards. American treatment of the boiler-feed water. In other refineries consideration of problems water quality and treatment ranged from giving no of to staff problems to assigning several full-time thought members to the work. the the 137 sources of makeup Of for boiler feed, 3 received no water treatment by the refinery; 2 were municipal supplies and 1 was a company External treatment of makeup water for boiler feed, well. either by the lime-soda or by the zeolite process, was the most common and method 18). Internal treatment with chemicals for scale (table corrosion control was second in frequency of use.

41 PETROLEUM REFINING INDUSTRY 321 TABLE for boiler-feed water Treatment of 18. makeup treatment of various types of water treatment. Prior of of purchased water frequency [Figures refer to use not considered] is supplied Public Self-supplied treatment Type Surface of Ground water Ground Surface Sewage Total water water water effuent Fresh Fresh Fresh Saline Fresh treatment. _ _ _ _ _ _ No 1 2 3 Coagulation. _ _ _____ ____ 1 2 3 Sedimentation. _______ 6 4 2 _____ Filtration.. _ ___ _ 8 2 4 2 Softening: ___ _ Lime-soda. _ _ 1 28 2 4 16 4 1 Zeolite. ________ 27 10 10 7 Distillation _ ___ _____ 1 1 Other ___ _ ___ ___ _ 6 2 1 3 Disinfection con- and algae trol: 4 Organic compounds, _____ 4 Other _ ____ ____ _ __ 2 2 control: Corrosion and scale Phosphates __ ___ _ _ 1 18 2 1 11 2 1 ____ _ ___ Dianodic___ 1 1 Deaeration _ _ __ 2 2 protec- Embrittlement tors _ __ 1 1 5 pH _ ___ _ adjustment. 2 1 2 Antifoam. ____ _ __ 5 2 1 2 _ Other. __ ____ __ 15 _ 2 10 1 2 PROCESS AND SANITARY WATER The quantity water used for process and sanitary services is of compared to for other refinery uses, but some of this negligible that of quality the highest is used by the refinery. water necessity for process water vary widely with the purpose Quality tolerances which it is used. In general, for waters should be clear, color- process less, free from iron, manganese, hydrogen sulfide, and organic and (Nordell, washing Water for product growths may need to 1951). a equivalent drinking water or of be higher quality, whereas water to for general refinery cleanup may be much lower in quality. Sanitary and service may also vary in quality. Water used in wash- water may drinking. of lower quality than that for houses Water for be usually sanitary drinking quality standards suggested by satisfies local State health departments. These standards are generally or equivalent to those of the U.S. Public Health Service (1956). Usual- same ly quality of water and very often the same water is used in the washhouses and sanitary fixtures. Fifty quality analyses of water used for sanitary purposes and 49 obtained analyses process water were of in the survey. Water from

42 WATER INDUSTRIES REQUIREMENTS OF SELECTED 322 Part rivers one (two was saline. and of the proc- sources three well) of one refinery was supplied by sea water, but no chemical ess needs are this was obtained. Figures 47 and 48 water frequency analysis of 10 41 samples 155 V////A 100 500 400 300 200 600 PER (SO 4 ), IN PARTS SULFATE MILLION 100 200 300 400 500 600 PER PARTS MILLION BICARBONATE (HCO 3 ), IN samples 45 J 5553 0 01 UJ 900 700 100 200 300 400 500 600 800 CD 5 IN AS CaCO 3 , HARDNESS PARTS PER MILLION TOTAL D Z samples 32 3200 3600 200 400 600 800 1000 1200 IN PARTS PER MILLION DISSOLVED SOLIDS, FIGURE 47. Frequency of selected chemical constituents in untreated process distribution water. distribution showing the occurrence of dissolved solids, total charts bicarbonates, and sulf ates in untreated process and sanitary hardness, Table water. shows median, maximum, minimum, and quartile 19 values the chemical and physical constituents of these waters. of Extensive, partial, or no treatment of refinery intake water may be necessary to the desired water quality for process and sanitary provide methods Tables and 21 list the needs. used to treat process and 20 sanitary water at the refineries surveyed. Water for these needs other received treatment at the refinery than water used for less pur- poses because public supplies that had received previous treatment

43 PETROLEUM REFINING INDUSTRY 323 15 10 39 samples O 0 100 200 300 400 500 600 4 ), IN SULFATE PER MILLION (SO PARTS samples 42 0 100 200 300 400 500 600 IN BICARBONATE (HCO 3 ), MILLION PER PARTS h-" O samples 46 200 300 400 500 600 100 700 AS CaCO 3 , IN PARTS PER TOTAL HARDNESS MILLION 33 samples 400 800 1000 200 600 1200 DISSOLVED PARTS PER MILLION SOLIDS, IN FIGURE 48. Frequency distribution of selected chemical constituents in un- treated sanitary service water. and the refineries of process water for a quarter of the were and the source the of water for half of sanitary refineries. Process water from source only 18 of the 58 sources and sanitary water from only 13 of the 65 sources treatment at the refinery. Several refineries had received multiple sources of water; the low-quality needs were supplied from were sources no treatment, and the high-quality needs receiving ob- tained from sources receiving previous treatment.

44 SELECTED INDUSTRIES REQUIREMENTS OF WATER 324 i-H OS i-H lO a 'OOO CO CO COCOCOIO * ^ CO O ^H 1> 1C CO CO CO i-H CO CO I> TJ( ^ CO ^ lO ^H i-H C3 ^ w 03 ^H~ (M OS ^* CO 00 s| && ' ,-H Tt< COI> ' lO-^OlM 1C O C? lO CO ^ t> C3 CO ! ' CO ^ ^ 1>- CO OS CO o- , COI> ,-i ' OOOOS 'cOO 1-1 GO COI> 0) ^H (M CO Tt«M (M (M i-l ,-H CO (S ^H (M ,-H ^ IS (M « EH GO <* O O ^HiO ^ COI> ' CO (MO CO GO -^ I> GO ' * i-H ' si II ,-H 00 CD !> CD GO CD GO CIS ^^ CD a a ^HCO i-il> °i-< ' 'cO OO (M '(M ' ss S| C3 OB M <3 ^3 CO 1C (M i-l lO OS (M CO lOGOOOOS COO CO SS CO (N Tt< CO * (M CO CO (M (M CO * * |«1 C3 g g OS (MCO a 5 &< COO CO .a -^ | C^l C^^iOCO GOiO lO C9 -S a o -O C^l !> C^l !> *-O CO CO !> ?? S lO i-l CO CO (M CO (MlO i-l _C9 3 iCt^ co OOlOOSIM * O(M '(M-* 'i-ii-l CO i-l i-l OS CO ' i lO i-l GO O (M § (M (M (M 2 PH (M &=§ (M i-l -* OS Tt<0 ^^M cot^ Os ' ' CO O I> ^5 ,-H " i-( OO OC) C3 GO 1C i-l (M i-H CO 1-3 o 1 S 1-1 1-1 o- a o O O O ^ GO (M 3 "d os a COCO ^5 CD C^l C^ i*^ t^* i*^ CO 1-1 s g « § « 3 lO OS § ' r^ x f-a ^* CO CO C^l CO CO C^l ^f ^* ^^ i 1 i~H CO H is § ° S g « a 'S CO g Ho c5 a a O 1 C3 M W ^2" 03 " ^3^ 2 ^ S_^3 v G- __^ S 3 g ^ §_ ° *c--26ogg a o ^ O d O Q x_xfij ^. QJ ^ ^ Q O "T" O 3 J ^ 'X s^x S S S o3 *^ -*^ "C *C ~£* ^ E^ fcn o o3 Cj ^ k^lTd r^ j^, 'i^ Q O fcn tW O oM a 0 ^AoS^^slolisw

45 PETROLEUM REFINING INDUSTRY 325 Treatment makeup for process water TABLE of 20. frequency of use of [Figures types of water treatment. Prior treatment of purchased water refer to various considered] is not supplied Public Self-supplied Total Surface Ground water treatment Type Ground of Surface water water water Fresh Fresh Saline Fresh Fresh Saline 2 17 10 37 3 4 1 1 1 2 __. Coagulation _ _--_____ 1 1 1 1 6 1 1 1 3 Softening: 2 1 1 2 1 1 Other. _ _____ _ _-_.. 2 1 1 Disinfection con- algae and 1 1 Corrosion control: scale and 3 1 2 1 1 1 1 _____ __ adjustment pH I 3 Other_-----_-__----_-_ 1 1 21. Treatment of makeup for sanitary water TABLE refer to frequency of use of various types of water treatment. Prior treatment of purchased water [Figures not considered] is supplied Public Self-supplied Total Surface water Ground treatment Type of Ground water Surface w ater water Fresh Saline Fresh Fresh Saline Saline Fresh No _______ treatment 1 53 32 17 1 1 1 _ _ 2 __ Coagulation _ 1 1 _ _ _ _ Sedimentation. 2 2 ___ ______ Filtration. 4 1 1 2 Softening: Lime-ash. _ _____ 3 3 . _ Zeolite _ 3 2 1 Other... 1 1 Disinfection and algae control: 9 1 2 1 5 scale Corrosion and control : 1 Deaeration__ ___ 1 _ __ __ _ Other 1 1 AFFECTING USE FACTORS WATER results of the current The were studied to find an explanation survey for the wide variation in water use. The effect of availability of type water, refinery, operating procedures, of of process, and tem- size investigated. and quality of the water upon the water use was perature

46 326 WATER OF SELECTED INDUSTRIES REQUIREMENTS OF WATER AVAILABILITY to seems use, but its effect is actually due to affect Location water availability unit water. The of makeup-water re- the variation of of refineries varied with the runoff the the area of quirements surveyed the refinery was located. The water in of refineries in arid which uses in the runoff was 1 inch or less were compared with the areas which areas the which in runoff was more than 10 inches. in uses requirements of 20 refineries in high-runoff areas makeup-water The 100 gallons per barrel of charge, whereas only 4 refineries exceeded in arid had makeup requirements this high. The median make- locations use in locations was about 75 gallons per barrel of up-water arid gallons the whereas high-runoff areas was about 250 median charge, for barrel. per SIZE OF REFINERY of the data indicate that the unit makeup-water require- Analyses of were refineries surveyed ments not directly affected by size. the though large refineries had greater makeup-water require- Even the than smaller refineries, the greater requirements were due ments fac- to tors than size. other than refineries capacities Five more with 100,000 barrels per day of were visited during the 1956 survey, and each was located in an area with an supply of water. Four of the five refineries required abundant than average of makeup water, owing to the large pro- more amounts once-through Therefore, water used. of the greater portion cooling the makeup used were due to of favorable water situa- amounts water at the refinery locations rather than to their sizes. tions There was negligible difference in the average makeup-water needs a 100,000 refineries between 10,000 and capacities barrels per day of with those with capacities less than 10,000 and The average make- barrels. up of both size groups requirements less than those of refineries were with capacities in excess of 100,000. The negligible of size on water requirements is further illus- effect average by variation in the small unit gross circulating- trated the needs among the three size water groups. TYPES PROCESSES OF units type refinery The processing of and the operating proce- and dures affect the water requirements. The water requirements of refin- eries cracking units were considerably larger than the require- with ments of those without cracking units. Table 5 shows that the median gross requirements and the makeup-water require- circulating-water ments for gallons with cracking facilities were 1,600 and 100 refineries

47 PETROLEUM REFINING 327 INDUSTRY barrel of respectively. The corresponding values for refin- per charge, cracking eries and 75 gallons per barrel. were without 500 several units, and the combination have processing refineries Most affects the of use of the refinery. Unit water require- the units water processing units are ments in tables 9 and 10. Median of shown needs the processes ranged from about 125 gallons makeup-water for per for and barrel units to 15.5 gallons polymerization per alkylation for distillation units. barrel OPERATING PROCEDURES requirements of refineries can be substantially re- Makeup-water duced by as much cooling and other water as possible. recirculating is essential use such systems in arid and other water-short areas. It to should where be used measures low-quality water Conservation also city treated use or where high-priced be water must be must before used. 10,000 cracking refinery with A facilities and a once- barrel-per-day cooling would require a source of makeup-water of through system million gallons per day, based upon 7 median water-use value the shown table 4. If a in cooling-water system were used for circulating the same refinery, probably no more than 630,000 gallons of makeup water would required daily. be 16 of 21 refineries in arid locations reused their water Although the 10 areas only 6 refineries in high-runoff than reused their more times, many times. water this for average and data unit-makeup-water use by lefin- The median with once-through, eries and combined cooling systems circulating, (table show the decrease in makeup-water requirements when water 4) reused. is operating temperatures and pressures of boilers affect the qual- The for ity that must be supplied water boiler-feed makeup. The qual- of ity requirements of feed water become more exacting as operating pressures and increase. Suggested water-quality toler- temperatures in of some chemical constituents in boiler-feed ance concentrations at certain operating pressures are given in table water 17. QUALITY PHYSICAL CHARACTERISTICS OF WATER AND temperature Water the use of water by refineries. Several affects refineries that used water from rivers for cooling had auxiliary ground- the water use in summer when for river temperatures were too supplies high for effective cooling. Other refineries continued using the river cooling supply increased the withdrawal for but as the river tempera- ture increased.

48 328 WATER OF SELECTED INDUSTRIES REQUIREMENTS water may substantial treatment before it can Low-quality require Treated be usually used in a recirculating cooling sys- water used. is discharged once-through waste from a than system. In tem rather to the cooling solids content of the water increases recirculating a system, evaporation. The solids content owing the recirculating water is to of by a part of the circulating water (tower blow- reduced discarding by new addition of and makeup water which contains less the down) Therefore, the quantity of makeup water required solids. dissolved a recirculating system increases with a decrease in water quality, for low-quality because will become concentrated and require dilu- water sooner than water. tion high-quality WATER REFINERY WASTE refineries consist of products chemicals (especially from Waste oils, sulfides, and phenols), and acids, solids. The alkalies, suspended sources these wastes are equipment of and spills, re- major leakages during shutdown or startup of equipment, leases from condensate steam-stripping waste water from crude oil desalters and operations, storage equipment cleaning, regeneration of ion-exchange from tanks, backwashing of filters, boiler and cooling tower blowdowns, units, water, storm and washhouses. lavatories, clays from Spent treating units and bottom sediments from clay separators and traps are examples of waste solids in refineries. Spent clays are disposed of by dumping, whereas the other waste usually are withdrawn slurry and pumped to settling ponds. solids as is refineries for each refinery. Some treatment treat Waste different collect stream its source, and others waste all wastes for treat- each at in a single plant. Most modern ment segregate their wastes refineries so similar wastes are collected for treatment in one plant, and the that streams treatment require special waste are treated at the source. that commonly The of refinery wastes treatment is to remove oils initial by an API gravity-type separator. The remaining oil is treated to break the emulsion. chemical wastes petroleum refineries must receive indi- Some from treatment. and alkaline waste waters are neutralized by vidual Acid with mixing other. Sulfides in waste water are neutralized and each stripped an absorption tower. Phenols in waste water have been in treated by aerobic biological processes and in trickling niters, oxida- tion ponds, cooling towers. and is waste at Sanitary refineries water collected in a separate most sewer system and treated in septic tanks, primary settling tanks, and oxidation or discharged into city sewers. ponds, Waste-water are methods used by the refineries surveyed treatment

49 PETROLEUM REFINING INDUSTRY 329 shown The most common method of waste treatment was table in 22. which used for treating 41 waste-water separator, the was API streams received no treatment at the re- streams. Eleven waste-water of but were discharged into city sewers. finery, these five treatment Waste-water TABLE 22. occurrence of Frequency Refineries Treatment Refineries cracking with without Total facilities cracking facilities separator _ _ _ _ API _ 34 41 7 ___ __ . __ Ponding __ 14 16 2 Sedimentation ___ _ _ _ _ __ 6 6 2 ___ Coagulation __ __ __ 2 2 _____ I Filtration 1 Skimming _ _ 5 2 3 _ - _ 1 pH adjustment. 1 __ I Chlorination__ ____ 1 3 2 tank _ sewage) Septic or (sanitary cesspool 1 11 _ No treatment..- _ __ _ _ 4 7 FUTURE WATER REQUIREMENTS noted and (p. 325), many factors affect the total As the previously water requirements of petroleum refineries. The effect of some unit factors on water needs are rather uncertain, whereas the effect of others can more accurately determined. Analysis of some of these be is necessary make a reasonably accurate estimate of the fu- factors to industry requirements the petroleum refining of and of the ture water of the United States in which new refineries will probably be areas located. LOCATION REFINERIES OF factors must be considered in selecting sites for Important that refineries are sources of crude petroleum proximity to a market oil, for the refinery output, and the transportation facilities available. The necessary utilities and labor supply available and their cost are other factors less importance. of has but a minor factor in site selection, Water in water-short been refinery operations have been adapted to conserve water. Fac- areas tors other than water will probably -continue to control selection of refineries future water conservation within but will become more sites, important. An analysis of current refinery locations should be useful since areas are in refineries are currently located which areas of possible future expansion.

50 330 WATER OF SELECTED INDUSTRIES REQUIREMENTS were 294 refineries in the United States with an There operating operating average 8,380,801 barrels per day in 1955 capacity total of refineries scattered through 37 States from These were (Kirby, 1956). Approximately three-fourths of the coast refiner- to coast. operating of national capacity were located the the 12 percent ies 90 within Texas, California, Louisiana, Pennsylvania, Illinois, Indi- States of Jersey, ana, Oklahoma, Kansas, Michigan, and Wyoming. New Ohio, in the capacity was located operating Texas, and of total One-fourth capacity of Texas combined with that the California and refining of accounted more than one-half of the for capacity Louisiana operating the Nation. of tidewater location, the nearness The a crude-oil supply, and the to cheap abundant supply of natural gas available for fuel are fac- and that make gulf coast areas of Texas and Louisiana an excellent tors the petroleum large and account for the for number of location refineries oil in area. Most of the crude located used by the re- refineries this in this area is transported by fineries from inland Texas and pipelines Louisiana fields, and the major part of the refinery output is trans- oil by markets. to east coast ported Reuse of water is the general tanker are in area. Some industrial plants this using sea water suc- practice cessfully for cooling, and air-cooled heat exchangers are also used to supplement water cooling. coast refineries usually market oriented and are located East are population such as Philadelphia, New York City, large centers, near The larger refineries are at and because most of Boston. tidewater, crude-oil is delivered by supply from South America, the tankers Middle East, or the gulf coast. Reuse of cooling water the not as is general this area. Many east coast refineries have long used sea in for several new tidewater refineries are using sea water cooling; for cooling. water California largest the second Although crude-producing State in is crude Nation, the not produce sufficient it oil to meet all west does coast demands, and crude from Canada, South America, Sumatra, and the East is imported to supply the deficit. Most west Middle centers refineries near such population located as Los An- coast are San Francisco, and the Puget geles, area, because these centers Sound provide large market for the a output. The Los Angeles refinery area is one of the few places in the country that has all the important conditions for favorable refinery location namely, a large source a refined crude, large market for of products, and excellent transpor- a tation facilities. An additional condition favoring the area for re- is finery is the natural gas that location available for use as fuel. The

51 PETROLEUM REFINING 331 INDUSTRY deterrent to expansion in this area is the water short- single refinery in age. Sound area are connected to Canadian the Refineries Puget pipeline, to expansion in this area by supply the west oil and fields probable. In addition to these tidewater refineries, is coast demands are located in or near oil fields supply-oriented the Cen- refineries in Valley California. tral of water essential in the water-short Los Angeles of is Conservation therefore most refineries recirculate cooling water. area, and Recir- of water is also a common cooling in refineries in the culation practice Valley area. Sea water has been used for Central by refineries cooling in Los Angeles and San Francisco areas. the midwestern refineries located near markets and are sup- Most are from refineries oil fields. Some primarily located plied midcontinent area rivers in the Great Lakes navigable use water transpor- on and but pipelines are used extensively by most refineries in the Mid- tation, to crude west oil to the refinery and finished products to transport are Large in this area centers Chicago, Kansas City, market. refining St. Louis. and refineries are this area Many located adjacent to large rivers or in and have sufficient water to use once-through cooling systems. lakes Other parts of this area have water-shortage problems, and refineries reduce their requirements by recirculating cooling water. water refinery locations been increased manyfold with the Possible have the pipeline. The source of crude supply of transcontinental advent extended from can oil field to any point along or to the terminus be the a pipeline, and refinery markets can be expanded to include any of connected the territory refinery by a pipeline. to will affect the selection of future refinery loca- Pipelines possibly by allowing more consideration to be given to water availability. tions Eefineries could located in areas with favorable water supplies, and be could carry crude supplies to refineries and deliver finished pipelines petroleum products to market areas. GROWTH OF INDUSTRY petroleum refining began in 1854 when Samuel W. The industry constructed small refinery in Pittsburgh, Pa. The refinery Kier a 5 barrels of distilled oil per day and produced a cheap illuminat- crude ing similar to coal oil. The oil of the industry was limited expansion by the small supply of crude oil that could be reclaimed from creeks, springs, and wells in the Oil Creek area of Pennsylvania. salt United The well in the oil States was successfully completed first by Colonel Edwin L. Drake in Titusville, Pa., on August 27, 1859. drilled Thereafter, additional wells were many in the area, and many

52 332 WATER OF SELECTED INDUSTRIES REQUIREMENTS were constructed keep pace with the rapidly increasing refineries to oil production. were very simple, because the refineries refining Early operations to (kerosene) illuminating oil mainly by simple were operated obtain these refineries the lighter and more volatile In distillation. early the heavy residue remaining after the kerosene gasoline ob- and was were worthless and were either discarded or burned. tained considered was and being used as fuel, residue poor quality lubricants This soon 1865. manufactured oil as early as crude The quality of were from and other products continued to improve as refining meth- lubricants improved. The advent of the automobile in the early 1900's ods a demand gasoline and lubricating oils which soon exceeded created for that forced be supplied by simple distillation and quantities the could of operations. development secondary the cracking process was The in 1913; it is a thermal Burton introduced process for converting high-boiling cracking of petroleum fractions into of low boiling points for use as gasoline. This was hydrocarbons first successfully cracking process to be operated the in commercial United Many (Kraemer, 1941). the new refining processes such States catalytic cracking, polymerization, alkylation, and reforming have as been developed and are used by refineries to meet the continuing de- mand for and better gasoline for automobiles. more in just over 100 years the petroleum industry has Thus, slightly a of beginning to one from the largest industries in the simple grown ranks with transportation, public utilities, and agricul- which world Refining has grown from Kier's single 5-barrel-per-day refinery ture. an industry consisting of 294 refineries processing an average of to 1955. barrels oil per day in crude Large modern refineries 7,480,000 of increased in complexity and size have include single refineries capa- to ble producing about 3,850 gallons of motor gasoline, 900 gallons of of home heating oil, 300 quarts of motor oil, and hundreds of other products in minute. 1 water have accompanied the growth of the Increased requirements industry. As the number, size, and complexity of refineries refining increased, the water requirements of the industry increased. Al- total though water needs have increased, the unit water requirements total have decreased as the industry grew. This decrease was caused by improved water-conservation that generally accompany ad- practices water ditional resulting from refinery growth. Estimates of needs the future growth of the petroleum refining industry should serve as accurate a for making a reasonably guide appraisal of the future water requirements.

53 PETROLEUM REFINING INDUSTRY 333 Figure the increases in demand for major petroleum prod- 49 traces the free States and in the in world from 1950 through 1960 United ucts the percentage distribution of the total demand between indicates and United States the the free world. and Hill, and Winger (1957) noted that demand for major Hammer, products at the free world increased refinery an average annual in and rate percent during the 1920-56, 6.3 the demand accelerated in of the post-World War II period to an average of 7.9 percent per year. The annual of increase was about 6 percent in both of these periods rate the States. in United the end of World War II the demand for refinery At was products 2.588 barrels per year for million free world, including 1,792 mil- the lion barrels per year in the United States. The demand in the United CO 1960 1958 100 1950 1960 1952 1954 1958 1956 FIGURE 49. Demand for major refinery products in the United States and the free world by (A) quantity and (B) percent, 1950-60.

54 334 WATER OF SELECTED INDUSTRIES REQUIREMENTS increased to million barrels per year in 1955 and to 3,042 States 2,634 increased in The free-world demand 1960. at a faster million barrels to 4,329 million barrels in 1955. rate quantities and percentages of crude runs to refineries in the The States 1950 the free world from United through 1960 are shown and in figurfe Annual percentage increases 50. crude charges to refineries in in the United States approximately paralleled the yearly increases the in refinery products in major period 1950 through for demand Average increases in yearly rates of crude runs to refineries 1960. percentage the world slightly exceeded the average free increase in 1958 1960 1950 1954 1956 1952 100 1960 1950 1952 1956 1958 1954 FIGURE 50. Crude runs to petroleum refineries in the United States and the free world by (A) quantity and (B) percent, 1950-60.

55 PETROLEUM REFINING 335 INDUSTRY demand for products during the same period. Crude runs in refinery in to States amounted to 1,730 million barrels the refineries United 1946 in increased to 2,730 million barrels in 1955 and to per year and world in Crude runs to free 1960. refineries were million 2,953 barrels barrels in 1946, 4,945 million barrels in 1955, and 2,475 million 6,528 barrels 1960. million in PETROLEUM TRENDS THE UNITED STATES REFINING IN IN Materials Commission (1952) estimated that President's The Policy consumption of petroleum the in the United States 1975 products amount about 5 billion barrels per to or 13.7 million barrels would year, day. This would be an average increase in per demand of domestic about percent per year between 1950 and 1975. On this basis, the 3 demand for would amount to 10.4 million barrels per domestic 1966 day. Hammer, Winger (1957) noted a Hill, in the rate slackening and the growth for petroleum products in demand United States and of in a lesser degree in the free world; however, these authors predict to that the demand for petroleum products in the United States domestic percent increase annual rate of 5 an between 1956 and 1966 will at provide a domestic demand of and million barrels per day by 1966. 14.3 An in the demand for increase products in the United petroleum States at an average rate of 2.0 to 2.5 percent per year from 1960 to 1965 is by Jameson (1960). He assumed that the total de- estimated for crude would increase by only 1.0 to 1.5 percent per year mand oil same demand The lower rate of the for crude will be due for period. being of demand for petroleum products the satisfied by in- to part production of natural-gas liquids and increased yield creased addi- of tional products from a barrel of crude oil. lighter 51 the total domestic demand for petroleum prod- Figure shows and the crude oil runs to refineries ucts the United States from 1920 in through Since 1946 the domestic 1960. has grown at an demand average rate of 5 percent per year, and refinery runs have increased at 4 per year. Assuming the same annual rates of growth, percent probable have curves to show the the demand and crude I extended in 1966. This extension indicates runs probable domestic demand a of million barrels per year, or 4,746 million barrels per day in 13.0 1966. This value is somewhat higher than the demand of 10.4 million barrels per calculated for 1966 from data published by the Presi- day Materials Policy Commission (1952) but lower than the 14.3 dent's million barrels per day estimated for 1966 by Hill, Hammer, and Winger (1957). The extension of the of curve indicates probable runs crude-run

56 WATER OF SELECTED INDUSTRIES REQUIREMENTS 336 i r i i i i T r i i i i i i j3.0 a-2.0 demand Domestic u.1.0 O "Crude runs oil .8 i ' ' i ' i ' ' ' I I I I I i ' i i 1928 1924 1936 1940 1944 1948 1952 1956 1960 1964 1920 1932 for 51. Crude by refineries and demand runs petroleum products in the FIGURE oil States, 1920-60 with curves extended to United 1966. 3,736 barrels per year, or 10.2 million barrels per day in million On the of this value and the average unit water-require- 1966. basis water value 1956 survey, a probable the intake of 4,770 ment of gallons per day will be needed by petroleum refineries million the in United in 1966. States SUMMARY QUANTITATIVE REQUIREMENTS WATER survey was not conducted to determine the minimum amounts This was water by refineries, but it used primarily concerned with the of current water requirements of the petroleum refining industry. The average intake of the refineries surveyed in 1951 and water was 468 per barrel of crude charge. The median intake 1956 gallons 1,400 circulation 95 gallons and was gallons per barrel, and gross In 1955 the estimated average total water requirements respectively. the petroleum refining industry was 3,500 mgd, or about 3 per- for of of estimated daily withdrawal cent industrial water in the the United States. water-use values for Median with cracking facilities were refineries greater than those for refineries without cracking facilities. The median intake refineries with cracking facilities was 100 gallons for per barrel crude, and the per circulation was 1,600 gallons of gross barrel. The corresponding values for refineries without cracking units were 75 gallons and 500 gallons per barrel. Consumptive of water in the petroleum refining industry is use high; the median for the refineries surveyed was 36 gallons per barrel, The or percent of the intake. 40 high consumptive use is mainly due

57 PETROLEUM REFINING INDUSTRY 337 to evaporation and to windage losses in cooling the accumulative towers. WATER REQUIREMENTS QUALITATIVE refining quality for the petroleum desirable in- Water is good of quantity available is of more importance than however, dustry; the The quality needed will differ with the use within the the quality. but most provide the necessary quality by refinery, refineries treatment. values selected chemical constituents and physical char- Median of untreated once-through and recirculated acteristics used for of water boiler feed makeup, process operations, and sanitary purposes cooling, summarized are table 23. in Water for once-through cooling by the refineries surveyed used of slightly quality than that used for circulating cool- was higher use for higher quality water The once-through cooling was ing. of due to higher quality requirements but resulted from probably not favorable water situation at the refinery location. Petroleum re- the fineries large amounts of high-quality water to produce steam. used water for generally not satisfactory Untreated this use, and care- was selection and treatment of makeup for boiler-feed water was ful necessary to prevent scale formation, excessive corrosion, and embrittlement. 23. of the median of selected quality characteristics of untreated TABLE Summary for refinery purposes used various water in parts per million unless otherwise indicated. These data [Results based on individual expressed are available are not balanced and observations analyses] or property Constituent Sanitary water Cooling Process Circulated Boiler-feed operations purposes oiice-through makeup _...__ (SiO 2 Silica ). 12 11 12 14 9.8 10 . . . 12 12 (Fe)__ ___ ____ Iron .10 .15 (Ca) Calcium 52 36 45 39 51 Magnesium 14 (Mg) __ 10 14 13 13 -- Sulfate (SOO 40 89 62 38 68 as hardness Total CaCO --------- 126 3 200 142 160 160 Color__-___________ 3 5 5 8 5 6 7. 7.6 ___________ pH__ 7.6 7.4 7.6 IN WATER REQUIREMENTS TRENDS petroleum-refining The is a relatively new industry that industry is accustomed to change. The industry is quick to adopt new refining methods equipment that increase the operating efficiency of the and refinery. There is a tendency for petroleum refineries to reuse an increasing amount of water, especially cooling water, with a resulting

58 338 WATER OF SELECTED INDUSTRIES REQUIREMENTS in refinery This decrease, however, is accompanied decrease intake. increase in use and a decrease in waste-water dis- by an consumptive are air cooling to further conserve refineries charge. Some using limited temperature reductions are required. water where only REFERENCES SELECTED 1957, R. P., and Ward, John, D., Study of a Kansas oil P. Selm, Aeschliman, problem, in Transactions of the seventh annual conference refinery waste sanitary engineering: Univ. Eng. and Architecture Bull. 40, on Kansas Lawrence, p. Kans. 5-13, ed.), 1953 ed.), American (6th (5th Waste water Institute, Petroleum 1958 v. 1 of Manual on disposal of refinery containing New York, oil, wastes: Petroleum Div. Refining. Am. Inst., v. (2d 1953 (4th 1951 Chemical wastes, ed.), 3 of Manual on ed.), of refinery wastes: disposal York, Am. Petroleum Inst., Div. Refining. New American Works Association, Inc., 1950, Water quality and treatment, Water ed.: New Am. Water Works Assoc., 451 p. 2d York, Works Task Group, 1953, Water conservation in Water Association American Water Works Assoc. Jour., v. 45, no. industry: p. 1249-1260. Am. 12, Ralph, Kemnitzer, Wm. J., 1931, and in the United States Arnold, Petroleum possessions: New York, Harper Bros., p. 79. and H. 1959, Bell, American petroleum refinery: Princeton, N.J., D. Van Nostand S., 538 p. Co., ed.: B., Industrial waste Besselievre, 2d 1952, New York, McGraw- E. treatment, Book Co., 391 p. Hill W. and Betz, L. D., 1950, Betz handbook of industrial water conditioning: H. Betz, W. and L. D. H. 200 p., 141 figs. Philadelphia, Boone, M. G., and Ferguson, D. F., 1954, Visbreaking still the basic process for fuel reduction: and Gas Jour., v. 52, no. 46, p. 166-168. Oil Maxey, 1954, of softening cooling water: Petroleum Refiner, Brooke, Economics no. p. 145-146. 33, v. 10, B., 1954, Sea water as an industrial coolant: Petroleum Refiner, Brooks, W. no. 33, v. 10. Investment G., Pogue, J. F. 1956, and patterns in the world Coqueron, E., industry: New York, The Chase Manhattan Bank, 55 p. petroleum Forbes, M. 1954a, Water supply and quality, pt. 1 of Water problems and C., solutions: Refiner, v. 33, no. 4, p. 122-126. their Petroleum 1954b, Water analysis interpretation, pt. 2 of Water problems <>ir Petroleum solutions: v. 33, no. 6, p. 169-171. Refiner, of Arthur 1943, Administrative policies Gorman, the Water Division office E., of War Utilities: Am. Water Works Assoc. Jour., v. 35, no. 7, p. 846-852. Helwig, J. and McConomy, H. F., 1957, How 31 refineries condition cooling- D., systems: no. Oil and Gas Jour., v. 55, water 48, p. 101-106. The R. J., 1959, Petroleum processing principles and applications: Hengstebeck, York, McGraw-Hill Book Co., 348 p. New Hill, K. E., Hammar, H. D., and Winder, J. G.. 1957, Future growth o f the world petroleum : New York, Chase Manhattan Bank, 44 p. industry forecast M. Janieson, 1960, A review and S., of U.S. demand for crude oil: Jr., Washington, D.C., Indep. Petroleum Assoc. of Am., 4 p. Water Jordan. E., 1946, Industrial requirements for water: Am. H. Works Assoc. Jour., v. 38, no. 1, p. 65-68.

59 PETROLEUM REFINING 339 INDUSTRY R. W., Water treatment in refineries: Petroleum Refiner, v. 25, Kelly, 1946, p. no. 143-144. 8, for and A., 1948, Refinery tools J. producing high-octane Kimball, T. Scott, B., Midyear Mtg. of Am. Petroleum Institute's gasoline: Proceedings, 13th 28M, Refining, 121-132. Div. v. p. in 1956, refineries, G., cracking plants Petroleum, the United J. Kirby, including 1, 1956: U.S. Bur. Mines Inf. Circ. 7761, States, p., 10 tables. January 12 A. 1941, Developments in petroleum refining technology in the Kraemer, J., U.S. Mines Inf. Circ. 7172. States: Bur. United A., Hatchett, J. L., and Poole, J. L., 1957, Preliminary Krieger, of the R. survey resources the United States: U.S. Geol. of Water-Supply saline-water Survey 1374,172 p. Paper E. W., and Love, S. K., 1954a, States east of the Mississippi River, pt. 1 Lohr, of The utility of public water supplies in the United States, 1952: industrial Geol. Survey Paper 1299,639 p. U.S. Water-Supply of States the Mississippi River, pt. 2 of The industrial utility 1954b, west water supplies in the United States, 1952: U.S. of Survey public Geol. Paper 461 p. Water-Supply 1300, in A., Estimated K. of water 1957, the United States, 1955: MacKichan, use Geol. Survey Circ. 398,18 p. U.S. Jerry, C. McAfee, W., Summers, C. R., Jr., Hirsch, J. H., and Home, Montgomery, upgrading A., Gulf HDS process for The crudes and residues: New W. 1955, Am. Petroleum Inst. Proc., Sec. 3 of Refining, v. 35, p. York, 312-323. McCormick, G., and Wetzel, O. K., Jr., 1954, Water supply E. sewage from effluent: Petroleum Refiner, v. 33, no. 11, p. 165-167. Mekler, Valentine, Schutte, A., and Whipple, T. T., 1953, Continuous-coking process shows to handle heavy feed stocks: Oil and Gas Jour., v. 52, ability 28, p. no. 201-203. 1951, Miller, techniques of cooling-water treatment: Objectives Durando, and Gas v. 50, no. 6, p. 139,141,144-150. and Oil Jour., E., Entriken, Miller, P., and Geiser, F. J., 1953, Conservation of water in J. P. and petrochemical industries, in Proceedings of the Second petroleum Symposium on Water Conservation and Industrial Development, Annual 19-20, Louisiana November State Univ. and Agr. and Mech. Coll., 1952: Expt. Bull. 38, p. 46-53. Eng. Sta. E. W., 1940, Progress report of the committee on quality tolerances of Moore, for England uses: New water Water Works Assoc. Jour., v. 54, industrial 2, 261-274. no. p. The E. 1951, Fluid Murphree, orming: V., Hague, Third World Petroleum hydrof Congress Proc., Section IV, Oil processes involving chemical conversions, p. 215-224. McGraw- W. Petroleum refinery engineering 3d ed.: New York, 1949, Nelson, L., Book Co., Inc., 715 p. Hill W. S., and Arnold, R. C., 1956, Higher octanes by Norburg, isomate process the in annual refinery review: World Petroleum, v. 27, no. 8, 68-73. 1956 and Eskel, Water treatment for industrial 1951, other uses: New York, Nordell, Reinhold Publishing Corp., 523 p. 166-167. Oil Journal, 1955a, HF alkylation Phillips: v. 53, no. 46, p. Gas and 1955b, Autofining: v. 53, no. 46, p. 170-171. 1956a, Catalytic reforming and feed desulfurization: v. 54, no. 46, p. 159. 54, butane catalytic isomerization: v. Normal no 46, p. 182. 1956b, 1956c, Report on United States operating refineries: v. 54, no. 46, p. 215-237.

60 340 WATER OF SELECTED INDUSTRIES REQUIREMENTS J. L., Water conservation a byproduct of industrial waste con- Partin, 1953, Sewage trol Wastes, v. 25, no. 9, p. 1050-1059. and : Industrial 1949, Company, handbook: New York, The Permutit conditioning Water The, p. 462 Permutit Co., Hyperforming; v. 10, Petroleum 8, p. 1194-1195. Processing, 1955, no. Anhydrous v. 11, no. ammonia: p. 87-89. 1956a, 1, Coke and lighter products: v. 11, 3, p. 135-137. 1956b, no. 1956c, oil improvement by Thermofor continuous percolation: v. 11, Lube p. 7, no. 137-139. Isomerization of normal paraffins: v. 11, no. 10, p. 101-103. 1956d, Hydrogen treating: v. 11, no. 11, p. 130. 1956e, Hydrodesulfurization: v. 11, no. 11, p. 131. 1956f, 1957a, Sulfuric acid alkylation: v. 12, no. 4, p. 107-109. 1957b, latest built for high yields: v. 12, no. 5, p. 216-219. Amoco's 1957c, Powerforming octanes : v. 12, no. 6, p. 117-119. for 1956a, 253. catalytic reforming: v. 35, no. 9, p. 214 and Refiner, Petroleum SBK Catalytic v. : 1956b, 35, no. 9, p. 253. isomerization S., 1948, Refinery tools for producing high-octane gasoline discussion: Pfarr, J. 13th Midyear Mtg. of Am. Petroleum Institute's Div. Refining, Proceedings v. 28M, 133-136. p. M. H., Johnson, C. A., Sze, M., C., and Campagnolo, J.F., Pichler, Chervenak, The "H-oil" process: Oil and Gas Jour. v. 55, no. 39, p. 109-111, 1957, 113. Powell, T., 1954, Water conditioning for industry: New York, McGraw-Hill S. Co., 548 p. Book Materials Policy Commission, President's Projection of 1975 materials de- 1952, mand, in Resources for freedom, v. 2, The outlook for key commodities: Washington, U.S. Printing Office, p. 129. Govt. Davis, 1946, fluid-catalytic cracking unit for the smaller refiner: Read, A v. no. 5, p. 119-122. Refiner, Petroleum 25, 1957, How Gulf purifies its boiler water: Oil and Gas Jour., v. Resen, Larry, no. 6, 106-110. 55, p. G., Talco 1946, Boiler-water conditioning at C. Refinery: Petroleum Jr., Rook, 25, no. 12, p. 129. v. Refiner, R. N., 1956, The Shreve, process industries: New York, McGraw-Hill chemical Book 1004 p. Co., and R. How four oil refineries use water: Sewage 1952, Indus. Simonsen, N., v. 24, no. 11. Wastes, Oil Co. (New Jersey), 3950, Water for Standard New York, The Lamp, v. 32, oil: no. p. 24-26. 1, water Bureau the Census, U.S. Industrial of use: U.S. Bur. Census Bull. 1957, MC-209 Supp. (1954 Census of Manufactures separate), 51 p. U.S. Public Service, 1956, Public Health Service drinking water stand- Health p. : Repts., v. 61, no. 11, Health 371-384, 1946; reissued March ards Public as Repr. 2697, 14 p. 1956 of G. and Wolf, C. J., 1957, Refining process glossary (descriptions Unzelman, H., processes) Petroleum Processing, v. ; no. 5, p. 97-148. 12, White, A. G., Coumbe, A. T., Colby, D. S., and Seeley, E. M., 1959, Crude petroleum and petroleum in Minerals Yearbook, 1958, v. 2, Fuels: U.S. Bur. products Mines, 313-430. of p. W. F., Ghublikian, J. R., Wilkinson, Obergfell, P., 1953, The SO 2 extraction and process for aroinatics recovery: Chem. Eng. Prog., v. 49, no. 5, p. 257-262. Expt. Youngquist, V., 1942, Water and war production: Ohio Eng. C. Sta. News, v. 14, no. 4, p. 21-24. o

Related documents

RIE Tenant List By Docket Number

RIE Tenant List By Docket Number

SCRIE TENANTS LIST ~ By Docket Number ~ Borough of Bronx SCRIE in the last year; it includes tenants that have a lease expiration date equal or who have received • This report displays information on ...

More info »
The Health Consequences of Smoking   50 Years of Progress: A Report of the Surgeon General

The Health Consequences of Smoking 50 Years of Progress: A Report of the Surgeon General

The Health Consequences of Smoking—50 Years of Progress A Report of the Surgeon General U.S. Department of Health and Human Services

More info »
Final rule: Home Mortgage Disclosure (Regulation C)

Final rule: Home Mortgage Disclosure (Regulation C)

BILLING CODE: 4810- -P AM BUREAU OF CONSUMER FINANCIAL PROTECTION 1003 12 CFR Part Docket No. CFPB -0019 -2014 RIN 3170- AA10 Home Mortgage Disclosure (Regulation C) AGENCY: Consumer Financial Protect...

More info »
2018 Physical Activity Guidelines Advisory Committee Scientific Report

2018 Physical Activity Guidelines Advisory Committee Scientific Report

2018 Physical Activity Guidelines Advisory Committee Scientific Report To the Secretary of Health and Human Services

More info »
435 441 458 467r e

435 441 458 467r e

WT/DS435/R, WT/DS441/R WT/DS458/R, WT/DS467/R 28 June 2018 Page: (18 - 1/884 4061 ) Original: English AUSTRALIA CERTAIN MEASURES CON CERNING TRADEMARKS, – PACKAGING IONS AND OTHER PLAIN GEOGRAPHICAL I...

More info »
Financial Abuse of Elderly People vs. Other Forms of Elder Abuse: Assessing Their Dynamics, Risk Factors, and Society’s Response

Financial Abuse of Elderly People vs. Other Forms of Elder Abuse: Assessing Their Dynamics, Risk Factors, and Society’s Response

The author(s) shown below used Fede ral funds provided by the U.S. Department of Justice and prepared the following final report: Document Title: Financial Abu se of Elderly People vs. Other Forms of ...

More info »
Fourth National Report on Human Exposure to Environmental Chemicals Update

Fourth National Report on Human Exposure to Environmental Chemicals Update

201 8 Fourth National Report on Human Exposure to Environmental Chemicals U pdated Tables, March 2018 , Volume One

More info »
A Comprehensive Report on School Safety Technology

A Comprehensive Report on School Safety Technology

The author(s) shown below used Federal funds provided by the U.S. Department of Justice and prepared the following final report: A Comprehensive Report on School Safety Document Title: Technology Auth...

More info »
a i5199e

a i5199e

Status of the Main Report World’s Soil Resources © FAO | Giuseppe Bizzarri INTERGOVERNMENTAL INTERGOVERNMENTAL TECHNICAL PANEL ON SOILS TECHNICAL PANEL ON SOILS

More info »
SR288.PS

SR288.PS

113th Congress S. Report ! " SENATE 2d Session 113–288 REPORT of the SENATE SELECT COMMITTEE ON INTELLIGENCE COMMITTEE STUDY of the CENTRAL INTELLIGENCE AGENCY’S DETENTION AND INTERROGATION PROGRAM to...

More info »
vol9 organic ligands

vol9 organic ligands

C HERMODYNAMICS HEMICAL T OMPOUNDS AND C OMPLEXES OF OF C U, Np, Pu, Am, Tc, Se, Ni and Zr O ELECTED WITH RGANIC L IGANDS S Wolfgang Hummel (Chairman) Laboratory for Waste Management Paul Scherrer Ins...

More info »
Implementation Handbook For The Convention On The Rights Of The Child

Implementation Handbook For The Convention On The Rights Of The Child

IMPLEMENTATION HANDBOOK FOR THE CONVENTION ON THE RIGHTS OF THE CHILD FULLY REVISED THIRD EDITION IMPLEMENTATION HANDBOOK IMPLEMENTATION HANDBOOK FOR THE CONVENTION ON THE FOR THE CONVENTION ON THE RI...

More info »
G:\COMP\PHSA\PHSA.bel

G:\COMP\PHSA\PHSA.bel

G:\COMP\PHSA\PHSA-MERGED.XML PUBLIC HEALTH SERVICE ACT [As Amended Through P.L. 115–408, Enacted December 31, 2018] References in brackets ¿ ø¿ ø are to title 42, United States Code TITLE I—SHORT TITL...

More info »
UNSCEAR 2008 Report Vol.I

UNSCEAR 2008 Report Vol.I

This publication contains: VOLUME I: SOURCES SOURCES AND EFFECTS Report of the United Nations Scientific Committee on the Effects of Atomic Radiation to the General Assembly OF IONIZING RADIATION Scie...

More info »
a i4787e

a i4787e

2015 ISSN 2412-5474 nimal genetic resource diversity underpins the supply livestock products and A services across a wide range of production environments. It promotes resilience and serves as a basis...

More info »
Software Design Specification

Software Design Specification

Software Design Specification Z-Wave Application Command Class Specification SDS13781 Document No.: Version: 11 The document describes the Z-Wave Command Classes and associated Commands Description: u...

More info »
June2018CUR

June2018CUR

CHANCELLOR'S UNIVERSITY REPORT JUNE 25 2018

More info »
The 9/11 Commission Report

The 9/11 Commission Report

Final FM.1pp 7/17/04 5:25 PM Page i THE 9/11 COMMISSION REPORT

More info »
mar19 medpac entirereport sec

mar19 medpac entirereport sec

MARCH 2019 Report to the Congress: Medicare Payment Policy REPOR G RESS T TO THE CON Medicare Payment Policy | March 2019 Washington, DC 20001 425 I Street, NW • Suite 701 • (202) 220-3700 • Fax: (202...

More info »