In 1 9 3 1 practically all gum w a s distilled in more than a thousand fire stills of this type located in remote areas. As of Jan. 1, 1957, only three fire stills were known to b e in operation, Now 20 large central processing plants clean and pre pare g u m produced by many small farmers
O n the surface, not too much c h a n g e ; u n d e r n e a t h , a changing r a w materials picture — t h a t best describes the $150 miHion-a-year . . . .
N a v a l Stores Industry Today Vv H I L E T H E CHEMICAL INDUSTRY gen
erally has b e e n growing by leaps and b o u n d s , there's been a quiet revolution in the making* in the naval stores in dustry. Naval stores themselves haven't grown too much in the past three decades—rosin production in creased from about 420,000 tons in the crop year e n d i n g March 3 1 , 1925, to about ο 10,000 tons this past crop year; turpentine increased from 29.3 million gallons to 3 2 . 3 million gallons in the same period. Instead, t h e big change has come in p r o d u c t sources. Gum naval stores (from living pine trees) have been partly displaced by wood naval stores (from pine stumps). Sulfate naval stores (from the kraft sulfate pulping process) h a v e come up rapidly as a raw materials source. For the industry itself, these new sources have meant a shift from scat tered, back-woods gathering a n d proc 16
C&EN
SEPT.
9,
1957
essing of natural products to larger scale, continuous processing. For the industry's consumers, they have meant raw materials with more closely con trolled properties to be processed chem ically into a myriad of products. Right now, naval stores output di vides about 25-60-15 on a weight basis among gum, wood, and sulfate sources. For the immediate future, sulfate looks likely to grow most. Companies active in sulfate naval stores look for better recovery and refining methods to give them continued expansion. Neither of the other two sources should be counted out, however. For wood naval stores, continued improvement in rosin and turpentine refining methods and new products from rosin and turpen tine will help them expand. For gum naval stores, hopes lie in faster growing and higher yielding pine trees, together with better tapping methods and better forest management.
Tall O i l Is Bright Star Once tall oil meant waste that went to help fire boilers in the sulfate pulp ing industry. Today, it's money in the bank, for now and i n the near future, tall oil and its companion product, sul fate turpentine, loom as the fastest growing part of the naval stores indus try. From a production of 13,250 tons in 1940 (crop year ending March 3 1 ) , crude tall oil rocketed to 297,900 tons by last year (calendar 1956). Sulfate turpentine jumped from 2.8 million gallons to 15.3 million gallons between 1940 and this year (crop years ending March 3 1 ) . Tall oil's popularity comes partly from its being able t o fill need left by dropping output of gum naval stores. But more important have been lower costs for products from tall oil. Large scale commercial refining started in 1942 when Armour Chemical
At Picayune, Miss., Crosby Chemicals refines tall oil to rosin and fatty acids by fractionation. In other portions of this plant, Crosby up-grades rosin extracted from pine stumps for use in paper sizes, resins, and chemicals
began to operate a continuous tall oil fractionating still. I t produced a fatty acid fraction containing 1 to 6% rosin and a rosin fraction containing 7 5 % rosin . T h e next tall oil fractionating plant went on stream in 1949. This plant of Arizona Chemical (jointly owned b y American Cyanamid and International Paper) at Panama City, Fla., removes practically all fatty acids from the rosin fraction to make a solid tall oil rosin. Since that time, six new plants have started u p , Arizona's h a s been expanded, and two are being built today. Combined maximum crude tall oil capacity when the last of these begins running next year will be over 340,000 tons a year. Some tall oil fractionating plants are based on techniques patented by Armour Chemical. Other refiners have their own process. Details vary from plant to plant, but all basically use injected steam and reduced pressures to keep rosin and fatty acids from decomposing.
Crude Tall Oil Production Has Rapid Climb (Thousand tons per year)
600
-
400
200
1940 1943 1945 1947 1948 1950 1952 1954 1956 1958 I 9 6 0 1965 1970 1975 Crop y e a r s
Comeback for Gum? Output of the oldest of the threepart industry—gum naval stores—has
Calendar years
Est.
Sources: USDA figures for 1940-47 crop years ending March 31 Bureau of Census, 1948-56 calendar years 1958-75 estimates Tall Oil Division, Puîp Chemicals Ass'n.
SEPT.
9,
1957
C&EN
17
From T u r p e n t i n e , Chemicals A r e U p , Retail Sales A r e Down
Sulfate N o w Leads as Turpentine Source Gum
I
[Wood
Chemicals
I Other Industrial
Retail Sales
Sulfate (Million gallons p e r year)
(Million gallons p e r year)
30
25
24
20
18
12
10
6
5
1925
1935
1945
1950
1953 1955 1957
1936
Crop year (ending March 31)
Source: U S D A
The Naval Stores Industry "Naval stores" originally meant the pitch and rosin recovered from pine wood and used to calk wooden ships and to tar (waterproof) ship rigging. Now, the definition has expanded to cover almost all chemicals, except pulp and lignin, recovered from pine trees and wood (including s t u m p s ) . Today, the industry has three distinct parts: • Gum Naval Stores obtained by t a p p i n g living pines. T h e "gum," or oleoresin, is collected and distilled to produce turpentine and rosin of various grades, pine oils, and residues (usually grouped together as p i t c h ) . • Wood Naval Stores obtained by solvent extraction of pine stumps. Stumps are left in the soil several years to let extractables concentrate in them, collected, and then chipped at the plant before processing. Rosin and turpentine are major products, although dipentenes, other mono- and di-cyclic hydrocarbons, and pine oil can b e separated. • Sulfate Naval Stores obtained from sulfate (kraft) pulping of pine wood. During digestion, "sulfate turpentine" vaporizes and is collected. Rosin and fatty acids form sodium soaps. These are separated and acidi fied to give a mixture of rosin acids, fatty acids, and nonacids, collectively called tall oil. Naval stores are used in m a n y diverse industries. Over half of the gum a n d wood turpentine goes for paint and varnish thinners at the time of application. Other large quantities of wood turpentine and most sulfate turpentine go into pinene, a chemical raw material for insecticides, medi cines, celluloid, smokeless powder, synthetic resins, synthetic pine oil, a n d many other products. Roughly a third of all rosin produced goes into p a p e r sizes. However chemical and pharmaceutical products passed p a p e r sizes as the major consumer of rosin during the crop year ending March 3 1 , 1957. The other important use of rosin is in making vainishes, paints, gums, and svnthetic resins.
18
C&EN
SEPT.
9,
1957
1941
Τ 946
1951
1953
1955
1957
source:
UOUM
dropped to just about half its 1949 volume. Industry opinion cites higher costs as a major cause. But tied closely to direct production costs have been landowner decisions for an immediate cash income, which caused many to sell their pine trees for pulp wood without recovering naval stores. Another factor: Paper companies have set aside or leased pine tracts to grow pulp wood at the fastest possible rate. T h e re sult has been that only about 1 0 % of the potential pine trees in the naval stores belt is being worked for gum, according to estimates m a d e from a survey by the U. S. Forest Service. O n e industry spokesman says h e ex pects the decline in gum production t o continue for t h e next year or two, with production making a comeback after that. Among t h e reasons he and others point to: • U. S. Forest Service, American Tur pentine F a r m e r s Association, and other organizations h a v e begun efforts to im prove the gum supply by boosting tap ping efficiency, growing new strains of slash pine that will yield more gum, and improving forest m a n a g e m e n t b y tying together programs for growing trees for naval stores, pulpwood, pole, and saw timber. • Education for small landowners will
M a i n Rosin Source Shifts f r o m G u m to W o o d
From Rosin, Chemicals a n d Pharmaceuticals E x p a n d Fastest ι Chemicals & I Pharmaceuticals Paint, Varnish & Lacquer
Wood
(Thousand tons per year)
(Thousand tons per year)
500
300
400
240
300
180
200·
100
II ΓΡΙ II II I I
1925 1935 1945 1S>50 Source: USDA and Bureau of Census a
1953
begin to pay off, showing the-m h o w they can make m o n e y from gurn b y m a n a g i n g their pine stands b e t t e r a n d b y using modern g u m - p r o c e s s i n g meth ods. Research Centers o n Rosin In value and volume, rosin is t r i e most important naval stores p r o d u c t , a n d as such gets most of t h e r e s e a r c h effort regardless of source. Among r e cent developments are fortified paper sizes t h a t combine rosin with maleic a n hydride or fumaric acid. Their use h a s expanded in the p a p e r industry signifi cantly, since they cover fibers more uniformly and resist water b e t t e r . Another recent development fro make a more stable rosin is disprop ortionation. Here, a combination of hydro 1 genation and dehydrogenation of a h i etic acid molecules shifts d o u b l e bonds to give a better p r o d u c t . T h e s e modi fied rosins find use in such specialty items as adhesives, polymerization catalysts, and soaps. Now, lower cost tall oil rosin i s being developed for wider use as a possihle substitute for wood and g u r n rosin. Just h o w far tall oil rosin m a y b e a b l e to go as a replacement still remains open to question, as opinion in t h e industry differs as to w h e t h e r rosin from various sources will meet t h e same
120
l-l I I I I
1955 1957 1936 1941 Crop year (ending March 31)
S u l f a t e rosin production for c a l e n d o r 1 9 5 6 , first y e a r data
j 1 Ester G u m & I ^ Synthetic Resins p|g;p:j P a p e r & F S ^ M ρΌρ#ψ Sixe
1946
1951
1953
1955
1957
Source: U S D A
available
U. S. Tall Oil Fractionation Plants Maximum Estimated. Crude Capac ity (million pounds per year) 9.6
I
I 1 1
Company and Location0 Armour Chemical Chicago, 111.
Plant Designer and Constructor Armour and Foster Wheeler
1 1
Arizona Chemical Panama City, Fla.
Stone & Webster
1 1 1
Heyden-Newport Chemical Bay Minette, Ala.
Heyden-Newport and Rust Engi neering
72
West Virginia Pulp & Paper Charleston, S. C.
Schultz and Bell & Gossett
48
1 1
Crosby Chemicals Picayune, Miss.
Crosby and ers-Wells
96
1955
Hercules Powder Savannah, Ga.
Hercules and Ake Linder
72
1956
1
Hercules and Ake Linder
72
1956
Union Bag-Camp Paper Savannah, Ga.
Foster-Wheeler
48
1956
Glidden Port St. Joe, Fla.
Badger Manufactur ing
48
1 1 1
Franklin, Va.
On
168 1955
Struth-
Stream Date 1942
1
1949 Expansion 1954
1955 ( N o w only in partial 1 operation ) 1
Under construction
Under construction, due on stream Spring 1958 I α Only plants built to fractionate tall oil and which operate continuously or semi1 continuously. Monsanto-Emery Nilro, W . Va.
Badger Manufacturing
48
SEPT.
9,
1957
C&EN
19
specifications. Oae straw in the wind: A reactive resin acid—palustric a c i d has been found in g u m rosin. G u m naval stores experts believe it to b e t h e reason that gum rosin acts differently in some uses. T h e more vigorous treatments used in maiding wood and tall oil rosin isomerize reactive acids present in natural oleoresin to make it different, they say. Research aside, the future for t h e naval stores industry hinges strongly on raw material sources. For gum naval stores, scattered small pine tracts cannot b e worked economically. Furthermore, younger workers get more pay for cutting pulpwood than for "turpentining." There's also the appeal of working in a group a n d living in town. Wood naval stores depend almost entirely on pine stumps as r a w material. Usable stump supplies are declining, because most pine is now c u t for pulpwood at a size that leaves a stump too small to be worth collecting. However, in t h e past 10 years wood naval stores production increased 2 0 % , reached an all-time high last year. Says a representative of t h e wood naval stores industry, "Economically usable stumps will last longer than almost anyone will predict." As for sulfate naval stores, they are tied directly to sulfate pulping. Right now use of hard woods (deciduous species) combined with pine in sulfate pulping grows. This possibly holds down sulfate naval stores' rate of expansion. However, one sulfate pulper points out t h a t as h a r d woods are cut in t h e South, the land will b e replanted with faster growing pines, and sulfate naval stores production should continue to expand. Naval stores' position as a supplier of raw materials to chemical a n d other industries seems assured for the future. Naturally, i t holds its position b y being able to supply desired materials at lower cost than other sources do. As long as the industry meets t h e demand, incentive t o find other r a w materials remains poor. But, as o n e individual points out, the industry must continue to improve its own raw materials supply to maintain this cost advantage.
THE COVERt Tractors w i t h special tools a r e used b y Hercules Powder employees to pull pine stumps f r o m soil· These stumps a r e the priirîary source of r a w materials for the w o o d phase of t h e n a v a l stores industry.
20
C&EN
SEPT.
9,
195 7
INDUSTRY Semiconductor Race Gets Hotter M e r c k enters high purity silicon business; w i t h n e w electronic chemicals division T H E
RACE TO PRODUCE high
purity
silicon continues. A n d the competition gets tougher. Last week Merck announced its entrance into this growing field. To highlight its interest in this product, Merck created a new division to make and sell t h e silicon (C&EN, Sept. 2, page 9 ) . At first, the new division will market electronic grade polycrystalline and single crystal silicon. Pilot scale production is slated to start in early 1958 at the company's Rah way, N. J., plant. Now t h e company is in t h e design stage b u t says it will go on stream by the scheduled date. Merck claims its material will have a resistivity rating—a measure of silicon quality—greater than 1000 ohm-cm., a lifetime in t h e range of 1000 microseconds, a n d impurities less than one part in six billion. • Has a License. For several years Merck has researched silicon and other electronic chemicals. From this came silicon know-how. To strengthen this background, Merck completed a license agreement Aug. 1 with the German firms Siemens & Halske and SiemensSchuckertwerke. Under this agreement Merck can use the German process. But Merck has its own ideas too. Also t h e agreement calls for t h e firms involved to exchange process know-how and technological advances in electronic grade silicon manufacture on a continuing basis. Merck says t h e Siemens firms are ideal ones to associate with in a silicon venture. Both are large electrical equipment manufacturers and have pioneered and played leading roles in electronic grade silicon developments. • Division within α Division. High purity silicon is just the start in elec tronic chemicals for Merck. This is the reason that the company decided to create a new arm. In Merck's organiza tional chart, the electronic chemicals division will be in the firm's chemical division. (Merck has done this be fore with its marine magnesium divi sion.)
does so
Just what other products the new division expects to make and market in t h e future is a question. Other wellknown electronic chemicals include germanium and selenium. But Merck says it plans to enter new fields as yet undeveloped rather than to produce competitive chemicals. • Silicon Market Big. It has been estimated that the high purity silicon market will be a $100 million a year business b y 1962. The product is used to make transistors, diodes, and rectifiers for many uses which formerly required electronic tubes or control systems. The polycrystalline silicon now on t h e market ranges in price from about $300 to $900 a p o u n d - d e p e n d ing on quality. The single crystal ma terial is not available in commercial quantities. With Merck in the field, competition is expected to get tougher. In July, W . R. Grace announced plans to form a company with Pechiney, a French firm, to make high purity silicon (C&EN, July 22, p a g e 2 2 ) . They will follow D u Pont, Sylvania Electric, Eagle-Picher, and Texas In struments who now make this product. Westinghouse also makes the silicon, but for captive use.
Aluminum On and Off Alcoa curtails output because of power suspension; Harvey gets ready t o operate V v ATER
SHORTAGES
in
the
Pacific
Northwest are causing a shut down of Alcoa's smelters a t Vancouver and Wenatchee, Wash. Reservoir levels have dropped so l o w that Bonneville Power Administration has suspended interruptible power delivery to the two plants. Actually, Alcoa was given an offer of provisional power for a short period after suspension of interruptible power, b u t declined in hopes that reser voir levels would rise sufficiently soon
