CAEN ψ FEATURE
Oil Production: Soles for Chemicals ο
ii- WELLS are
deeper; oil and
gas
production is up; secondary recovery is in wider use; corrosion control is in creasing. These are some of the factors behind an increasing use of chemicals for petroleum production. In 1957, t h e market value of chemi cals used in -this field reached an esti mated $260 million. And market ob servers estimate the volume will reach $270 million by I960, over $ 3 5 0 million by 1965. Past experience shows that as com plexity of oil production increases, so does the use of chemicals. T h e field is a complex one now because of the many different and widespread regions which produce petroleum, the diverse methods used, and t h e many auxiliary operations needed. And this complexity can b e expected to increase as production tech niques get more sophisticated. Thus, oil production holds much promise as a fast growing market for chemicals over both the near and long term.
W h y the Demand Specific reasons for this expected growth can be cited in each major use category. Well drilling goes deeper each year; it reached an average depth of 4 1 1 3 feet for U. S. wells in 1957. And the number of deep wells (over 13,000 feet) increases rapidly as drill ing techniques improve. Hence, there follows a large increase in drilling fluid needs. For example, on the Texas Culf Coast, a well drilled to 8500 feet takes an estimated $7500 worth of drilling fluids. A well t o 15,000 feet will re quire upwards of $100,000 in drilling fluids. Next in size of present and potential market for chemicals is that of well completion and stimulation. Demand for these chemicals was small when ce menting and then acidizing were first introduced. During the past 20 years.
however, consumption lias increased to where acid, acidizing additives, and ce ment chemical additives have an im portant volume. A more recent innova tion—hydraulic fracturing of rock for mations—greatly increased chemicals* use. As use of water for fracturing in creases, so wOl the demand for demulsifiers and water loss additives. In the field of production (primary recovery), chemicals find use in many ways. Various observers of crude oil production estimate that from 3 5 to 6 0 rr of crude produced in the U. S. requires some kind of chemical treat ment. This may include demulsifiers, corrosion inhibitors, scale inhibitors, foam depressants, paraffin solvents and inhibitors, and gas dehydrators and sweetening agents. Of the chemicals used in these applications, demulsifiers and corrosion inhibit*»™ i w e i v e most attention and account for the largest part of chemicals used in production. Perhaps the greatest progress in oil production methods during the past 2 0 years is in secondary recovery. Today's principal secondary recovery methods are water flooding and gas injection. In 1957, some 190 million barrels or 6.5r/* of the U. S. total were produced by pattern water flooding alone. Pro ducers treated about half of the 4 to 5 billion barrels of fresh and salt water injected into reservoirs last year as pat tern, pressure maintenance water flood ing, or for disposal. Chemicals are used in secondary recovery as conditioners, bactericides, corrosion inhibitors, and scale preventers. Small quantities of surfactants find use to increase injectivity or prevent swelling of clays in the reservoir. As to future secondary recovery, con servative estimates indicate that 12 bil lion barrels of reserves are available by water flooding. If 10 to 15 times this volume of water will be needed, as shown by present experience, then 120 to 180 billion barrels of water will be
injected. All of «which means a sub stantial market for chcir*icals.
Selling Is Unusucil Applying chemicals t o oil production poses some unique problems quite dif ferent it&m those commonly found in the chemical industry. For example» time» temperature,» and pressure condi tions can usually be controlled and varied in chemical plante to meet prop erties of the materials in process. These conditions cannot: be changed when treating oil wells-. In the permafrost zones of Alaska, t h e earth is frozen for roughly the first 1Ο0Φ feet, while in Southwest Texas and »ther parts of the world, temperatures in deep wells have exceeded 400° F . kmd in wells over 20,000 feet deep* pressures as high as 20,000 pounds per squtare inch are en countered in efforts to maintain the hy drostatic head of the drilling fluid to overbalance forimation pressures. Tim ing, too, is an important factor, for a chemical reaction must be delayed until the mixture can b e puunped into place in a formation two to Rve miles deep. This might take 3 0 minutes to 3 hours, including a safety factor. Supplying chemicals needed for these widely varying conditions found in drilling and oil production requires much technical service on the part of the seller. In addition, specialized equipment and rapid delivery are es sential t o successful selling of oil field chemicals. For instance, if a driller needs a chemical immediately to pre vent shutting down a jrig that costs $ 5 0 an hour to operate, he will pay for fast delivery service. Oil field cheonicals are usually pur chased on a local field or district level, and often by field personnel such as the drilling foreman, drilling engineer, a district production superintendent, and the pumper (o»r "switcher/* as he is called for flowing wells.) Thus, the OCT.
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These chemicals and specialties ploy a part in c r u d e o i l production Crude Oil Demulsifiers. High molecular wt· surface active agents, sulfonates, etc· Corrosion Inhibitors· Film forming amines, neutralize», aldehydes, etc. Scale Inhibitors. Dispersing agents, polyphosphates, organic séquestrants Foam Depressants. Silicone antifoams» amine defoamers, alcohols Surface Active A g e n t s . Non ionics, anionics, and cationlcs Paraffin Solvents. Aromatic solvents, chlorinated hydrocarbons, carbon disulfide Paraffin Inhibitors· Special surface agents in solvents Bactericides. Chlorine, chlorinated phenols, quaternaries, antibiotics, and aldehydes W a t e r Conditioners (inorganic). Alkalies and coagulants, caustic, soda ash, ferric sulfate, alum, etc. Séquestrants. Polyphosphates, ethyfenedlaminetetraacetic acid, citric acid Acids, Inhibited. Generally inhibited 1 5 % H O with or without surface active agents Gas Dehydrators. Glycols, alcohols, silica gel Gas Sweetening. Amine-glycol mix
Resolve crude oil emulsions Protect against HLS» C 0 2 , and other acids Prevent scale in producing equipment and infection syr terns Break foam in equipment and tanks Well stimulation for in· creased production or Increase injectivity. Remove paraffin deposits in wells, lines, and tanks Prevent agglomeration of paraffin crystals Control aerobic and anaerobic bacteria and algae in injection waters Clarify and soften water for injection Prevent precipitation of divalent metal salts which plug formation Open up carbonate formations and increase flow Remove moisture from produced gas Remove H 2 S, C 0 2 , and moisture from produced gas
M o r e a n d d e e p e r w e l l s h a v e doubled f o o t a g e d r i l l e d in last 2 0 y e a r s . . .
1937
'39
'41
M3
*45
*47
*49%
'51
\53 ¥~-*f/M
70
CftEN
OCT.
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• Cement slurries must have the correct conditioning chemicals. •Formation cores must b e analyzed to find out what effect fracturing fluids will have. • A, proper corrosion inhibitor a n d denmlsifier must be found for acidizing. • Qil»water emulsions produced from a well must b e typed to select the best deimilsifier.
Developing New Uses Oil company research on n e w products is largely long range. T h e objective; to find products that have a relatively large future sales volume. Efforts of service companies, on the other
a n d m a y add the same a m o u n t of f o o t a g e over the n e x t 10 y e a r s
I
New Wells Drilled (in thousands)
sales approach must IK* geared to a close personal basis. Here arises the problem faced b y new producers who expect to enter the oil production chemicals field: They must build a group to provide the needed sales and service that the industry expects. And technical service is expected t o increase, with field service labs becoming important in sales. Each particular well needs Individual attention b y technical service or sales personnel- Some things to consider;
Average Well Depth in Feet (in hundreds)
*55
*57
'58
*59
*OQ
*6\
'62
*08
Increasing use of corrosion control is one of the factors causing the expanding market for chemicals used in oil production. For a pumping well, inhibitors are in-
hand, are often in a specialized field, with improving their own particular product or service the goal. These may have small potential volume. Still, the volume must justify the re search costs. L o w potential sales volume is a major reason for many unsolved problems. For example, a good organic base metal corrosion in hibitor for acid—one that is effective above 130° F.—has been needed fοί α long time. But since 80 r r of wells treated have temperatures below 130° F., the potential sales volume of such a compound, if developed, would be below $100.000. However, deeper drilling and a desire to replace inorganic type inhibitors are incentives to develop such a compound. Another unique trait of chemicals used in oil production is their rapid obsolescence. Average use time of a chemical in the oil well sendee industry is seldom more than two years. Those chemicals which find extremely little use—considered failures by the industry —bring this time down. Thus, fast changing chemical needs of oil or serv
jected d o w n the annulus between the well's tubing and casing. Some wells use gas lift. Here, inhibitors for this type are injected into the pipelines to the wells
ice companies pose problems in getting sufficient returns to justify research and development costs. As a general rule, mark-ups on chemicals are o n a break even basis, with profits for the com pany coming from services rendered. These services, in addition to warehous ing in scattered and remote areas and quick delivery, include use of very ex pensive equipment, trained operating personnel, and technical advice.
Future Trends Does the oil production industry ex pect rapid growth for its chemical de mands? In some parts, yes. In others, demand may be less rapid than pre dicted, and may possibly decline due to changes in production methods and chemical needs. Growth will depend on both economic and technological factors. The most important factor will be demand for petroleum. Because of production limits (in the U . S. today, roughly 3 million barrels per day are held back), water flooding may not
grow as fast as forecast, assuming no change in world peace or political con ditions. Likewise, demand for petro leum will influence drilling and rework ing old wells. Slowed U. S. drilling has been offset to some extent by in creased foreign drilling. Technological factors are many. Most relate directly to economics. For example, while surfactants now avail able—particularly the nonionics—do a good job to improve injectivity of water, still no field test to date shows that the surfactant could be justified on the basis of increased oil recovery. As wells are drilled deeper, more high strength alloy steels are used to withstand the greater pressures and temperatures. More efficient corrosion inhibitors will have to be found or present ones more cheaply produced. Similarly, as the pattern of oil pro duction changes with the diminishing reserves of high quality crude petro leum, more paraffin solvents and demulsifiers to treat crudes are used. A very large part of oil production's cost is drilling. It is here that producOCT.
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C&EN
? 1
EXTREME PURITY
DELHI-TAYLOR TRIPLE-TESTED AROMATICS Deljy nitration! grade Benzene and T o î u c ï ï c 3mut uçixmi / x y i v î i o *xc*v6 SSSt ο îïCVr
standard in pmrity a n d uniformity. T h e y are sulfur and thiophene-free with r e markably low iparaffin content. Delhi-Taylor kiceps a careful watch over product purity^ through its unique "Triple-Testing" procedure. T h e first test i s made on-stream where rigid process, control s t a n d a r d s a r e maintained; tlxe second test is made in storage to rnak*e certain that the product maintains its faigh quality during storage; the final tiest sample is taken from the barge or Hank car before it is released to the customer. This strict qutality control formula is your assuranae that Delhi-Taylor a r o matics will readily meet t h e most stringent specifications.
tioii personnel help to make important savings to offset rising equipment and wage costs. Basically, cost saving will come from drilling more feet per day. Chemical products are sought that will make hard rock easier to g e t through, clear cuttings faster from the formation face, minimize dispersion of drilled particles, and get maximum separation of the particles from the fluid at the surface. Air may become an important drilling fluid if rapid and positive methods are perfected to shut off water-bearing formations. Liquid plastics injected into wells show promise for this use. Other additives to seal water seeps are sought for t h e air stream. Greater control of gelation and density of drilling muds, through new chemical additives, may reduce loss of mud into formations and hence cost. More efficient, b u t more costly, m u d materials may thus b e economically re-used. These additives could be a step toward maximum use of power expended in drilling by adjusting flow properties to take greater advantage of mud hydraulic action. In the end, an entirely synthetic drilling fluid, with heavy liquids supplying the continuous
phase, may be possible if solids a r c removed a n d the fluid remixed o n each circulation. As wells get deeper, additives t o control gelation a n d density m u s t also give satisfactory viscosity and filtration for the mud above 450° F . ~ n o w encountered occasionally. An alternate possibility will b e new liquid compositions, with a minimum amount of dense suspended solids» that give thermal stability a n d adequate density t o cont r o l high pressure fluids. Researchers are working now to d e velop chemicals that may solve other problems. Some of the more unusual; control of water loss in wells, paraffin deposition, higher température drilling fluids, m u d loss control, and better fracturing fluids. Whether these chemical needs and others as yet unknown will b e met depends in a few instances on technical needs, b u t in most, on economics. T h e changing patterns of the industry will change some of the present needs. But in any case, oil production as a n outlet for chemicals will provide a rapidly growing specialty market for some materials as well as a substantial market for many others. •
This article has been prepared by the staff of C&EN in collaboration ivith a group of members of the Chemical Marketing and Economics Division of the ACS. It was originally suggested by the success of a symposium on ine suojeci in tnu ouït rutnvtsw -n^S meeting, in which those men were the authors; Robert T. Means, Continental Oil, and John J. Glover, Jefferson Chemical, were chairmen. The final result, fust completed and checked for accuracy of figures and soundness of perspective by the collaborators, is a product of the work of the following: F. W . J ESSEN. The University of Texas Introduction t o Chemicals for C r u d e O i l Production G E O R G E R. G R A Y , Drilling Fluids Corp. Chemicals m O i l - W e l l Drilling Fluids ROBERT B. ROSENE, Dowelt, Inc. Chemicals for C o m p l e t i o n and Stimulation of O i l and Gas W e l l s C L A R E N C E N O R M A N and J . L. H A R L A N , Humble Oil and Refining Co. Chemicals for O i l and Gas Production—Primary and Secondary ROBERT S. FIRST, Industrial Consultant Channels of Distribution and Companies in the Industry F R A N C I S M . A N D E R S O N , Halliburton OH Well Cementing Co. Technical Services Required for the Proper A p p l i c a t i o n of Chemicals on O i l Production
DËËHI
ra^DR
M . A . W H I T F I E L D , The Western Co. Industries W o r k i n g Together for the Common
CHOMICAL. DIVISION
DELHI TAYLOROIL CORP. 4 1 5 Madison A v e . 72
C & EM
·
Hew Yor* 17f N.Y.
O C T . ! 3.
19 58
Good
Credit for general assistance, coordination, and checking is due J o h n J. Glover, Jefferson; and Robert T. Means, Continental.
