48 Tall Oil and Naval Stores 1
YUN JEN and Ε. E. McSWEENEY
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J. J. Chemicals, Inc., Savannah, GA 31406 Marcam, Inc., Savannah, GA 31411
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History of Naval Stores Production Statistics of Naval Stores Processes of Naval Stores Gum Naval Stores Wood Naval Stores Tall Oil Naval Stores Chemistry of Naval Stores Rosin Turpentine Fatty Acid Major Uses of Naval Stores and Their Trends Rosins Turpentine Fatty Acid Tree Stimulation
History of Naval Stores The history of Naval Stores in the United States dates back more than 400 years when the early explorers needed pitch tar and rosin for ship caulking (1, 2). As the population gradually moved southward, the center of the naval stores activities also shifted (3). In the mid-1600s, the Connecticut River was the region where most naval store production was concentrated. Around the early 1700s, the a c t i v i t i e s moved gradually southward through Virginia into North Carolina. In the late 1800s, the states of Georgia, Alabama, and F l o r i d a became the center of naval store operations. These southeastern states remain the major producing areas of naval stores today. The varieties of naval store operations grew as the years went by. Prior to 1910, all of the naval stores were derived from l i v i n g coniferous trees. Flows of oleoresin were collected from a r t i f i c i a l wounds in these trees, and this type of naval stores is known as gum naval stores. In the early days, a box was a c t u a l l y cut into the 0097-6156/85/0285-1159S06.25/0 © 1985 American Chemical Society
Tess and Poehlein; Applied Polymer Science ACS Symposium Series; American Chemical Society: Washington, DC, 1985.
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tree to c o l l e c t the r e s i n and the c o l l e c t e d o l e o r e s i n was separated i n t o turpentine and r o s i n i n a s t i l l , which i n c i d e n t a l l y was a l s o used f o r the purpose of making whiskey. As science and technology developed, numerous improvements were made to f a c i l i t a t e c o l l e c t i o n and increase y i e l d s . A s i g n i f i c a n t impact to the gum naval stores was made when the wooden box was r e p l a c e d by earthenware or metal cup and a s h a l l o w c u t r a t h e r than a deep gash was found t o be s u f f i c i e n t for gum c o l l e c t i o n , thus preserving the bulk of the wood f o r lumber stock. I n the l a t e 1940s, an important technique o f a p p l y i n g a s u l f u r i c a c i d paste on the wound f o r t h e purpose of i n c r e a s i n g o l e o r e s i n f l o w was d i s c o v e r e d . I n s p i t e of these improvements, the operations of gum naval stores are i n t r i n s i c a l l y labor i n t e n s i v e and not e a s i l y adaptable to mechanization. In the past 50 years, t h e r e has been a steady downward t r e n d of gum n a v a l store production. H i s t o r i c a l l y , 1908 was the biggest crop year ever i n the h i s t o r y o f n a v a l s t o r e s (4J; gum r o s i n p r o d u c t i o n was w e l l over 1 b i l l i o n pounds. During the 1915-25 period, a new type of naval store operation emerged i n the South. P l a n t s were b u i l t t o e x t r a c t n a v a l s t o r e s from the stumps o f v i r g i n p i n e s t h a t had been l e f t i n the ground a f t e r lumbering. The extract i s further separated i n t o turpentine, pine o i l , and r o s i n . T h i s , known as t h e wood n a v a l s t o r e s , i s sometimes c a l l e d s t e a m - d i s t i l l e d naval stores, although steam i s no longer used. The f i r s t p l a n t was b u i l t a t Gulfport, Miss., i n 1909. In 1913 and 1916, Newport I n d u s t r i e s b u i l t p l a n t s a t Bay M i n e t t e , Ala., and Pensacola, F l a . In 1910, Hercules Powder Co., p a r t l y due to i t s i n t e r e s t i n e x p l o s i v e s required to excavate stumps and p a r t l y due t o i t s i n t e r e s t i n the p a p e r - s i z e b u s i n e s s , decided t o e n t e r t h i s market by e s t a b l i s h i n g e x t r a c t i o n p l a n t s at Brunswick, Ga., and Hattiesburg, Miss. Several other p l a n t s were established s h o r t l y thereafter i n Louisiana, M i s s i s s i p p i , and F l o r i d a . The emergence of l a r g e - v o l u m e p r o d u c t i o n o f wood n a v a l s t o r e s i n c o n t r a s t t o gum n a v a l stores allowed the former to become the predominant f a c t o r i n the i n d u s t r y from the e a r l y 1910s t o the l a t e 1960s. T o t a l r o s i n production exceeded the b i l l i o n - p o u n d l e v e l i n a number of years, the l a t e s t having been 1966. Improvements were made i n wood naval stores i n which the extracted dark r o s i n was refined t o pale grades, equivalent to c o l o r s of the gum rosin. As the wood n a v a l store industry a c t i v i t i e s expanded, the stumps near the e x t r a c t i o n p l a n t s r a p i d l y became depleted. For continuing o p e r a t i o n , the i n d u s t r y had t o search and h a r v e s t stumps from d i s t a n t l o c a t i o n s or seek the s c a t t e r e d f i r s t - g r o w t h stumps t h a t became a v a i l a b l e as f o r e s t s were c l e a r cut f o r pulpwood, r e s u l t i n g i n h i g h e r raw m a t e r i a l c o s t . Stumps o f m a r g i n a l q u a l i t y and excessive d i r t found t h e i r way to the e x t r a c t i o n p l a n t , contributing to poor y i e l d and i n e f f i c i e n t operation. These problems, combined with the high labor costs, caused many p l a n t s to c l o s e i n the 1960s. This trend continued through the 1970s and 1980s, r e s u l t i n g i n there being only one producer operating two p l a n t s by 1985. The r a p i d growth of s u l f a t e p u l p i n g i n the South i n the 1940s and 1950s l e d to the b i r t h of the t h i r d type of naval stores i n t h i s country, the t a l l o i l n a v a l s t o r e s . I n the t a l l o i l n a v a l s t o r e operation, the oleoresinous materials i n the trees are recovered i n the p u l p i n g process i n the forms of s u l f a t e t u r p e n t i n e and crude t a l l o i l . The crude t a l l o i l , comprising r o s i n and f a t t y acid, can
Tess and Poehlein; Applied Polymer Science ACS Symposium Series; American Chemical Society: Washington, DC, 1985.
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48.
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be f r a c t i o n a t e d i n t o purer forms of these components. U n l i k e the other two types of n a v a l s t o r e s , the t a l l o i l process i s h i g h l y automated and r e q u i r e s very l i t t l e manual l a b o r . In the e a r l y 1940s, West V i r g i n i a P u l p and Paper Co. operated a rudimentary d i s t i l l a t i o n p l a n t to r e f i n e t a l l o i l to a crude form of r o s i n and f a t t y a c i d w h i l e Union Bag and Paper Co. s t a r t e d the p r o d u c t i o n of a c i d - r e f i n e d t a l l o i l . The l a t t e r p r o c e s s c a u s e d some polymerization as w e l l as c o l o r improvement, r e s u l t i n g i n a l i g h t c o l o r e d , n o n c r y s t a l l i z i n g t a l l o i l . In 1949, A r i z o n a Chemical i n s t a l l e d a vacuum d i s t i l l a t i o n u n i t on a commercial s c a l e to separate t a l l o i l i n t o h i g h - q u a l i t y f a t t y acids and rosin. S i m i l a r u n i t s were subsequently placed i n operation by Hercules, Union Camp, Newport (now R e i c h h o l d ) , Crosby (now Westvaco), Westvaco, and Glidden (now Sylvachem). By 1970, the t a l l o i l naval stores became t h e major f a c t o r i n t h e t o t a l U.S. p r o d u c t i o n of r o s i n and turpentine. The d i s t i l l a t i o n c a p a c i t y has o u t s t r i p p e d the s u p p l y f o r a number of years and w i l l p r o b a b l y continue to do so. T h i s imbalance was further extended by Georgia P a c i f i c ' s completion of a new p l a n t i n 1980. This p l a n t uses t h i n f i l m evaporators and packed columns f o r dry d i s t i l l a t i o n t h a t has been p o p u l a r i n Europe f o r s e v e r a l years. R e l a t i v e merits of steam and dry d i s t i l l a t i o n were reviewed i n a recent Pulp Chemicals Association Meeting (5, 6). Production S t a t i s t i c s of Naval Stores (7, 8) As shown i n F i g u r e 1, r o s i n p r o d u c t i o n peaked at over 500,000 tons i n the e a r l y 1960s and since has decreased sharply to a low of about 275,000 tons i n the r e c e s s i o n of 1975. Gum r o s i n i n the U n i t e d States has been i n a steady d e c l i n e since the e a r l y 1930s and now i s an i n s i g n i f i c a n t p a r t of the t o t a l , a l t h o u g h i t c o n t i n u e s to be a major f a c t o r i n world production, p a r t i c u l a r l y i n China and Portugal (9.)· Wood r o s i n p r o d u c t i o n peaked i n the e a r l y 1950s and has d e c l i n e d s t e a d i l y s i n c e , but i t may be l e v e l i n g out f o r the near f u t u r e , e s p e c i a l l y i f the Pinex process i s s u c c e s s f u l . T a l l o i l r o s i n c l i m b e d from i t s i n t r o d u c t i o n i n the e a r l y 1950s u n t i l i t peaked i n 1972 and 1973. Currently i t accounts f o r about two-thirds of the U.S. p r o d u c t i o n and s h o u l d keep the t o t a l about at the c u r r e n t l e v e l of 340,000 tons f o r the f o r e s e e a b l e f u t u r e w i t h the p o s s i b i l i t y of some very s l i g h t growth (10). Unfortunately, i t i s quite c e r t a i n that crude t a l l o i l and the r o s i n derived therefrom w i l l not grow at the same rate as pine pulp production, 2% per year, for a v a r i e t y of reasons such as r e c y c l i n g of waste paper, c u t t i n g of younger trees, increasing use of pine chips as w e l l as hardwood, and the export of crude t a l l o i l f o r use per se or f o r f r a c t i o n a t i o n i n Japan and Europe. Better recovery of the p o t e n t i a l t a l l o i l i n the pinewood consumed i s an achievement to be hoped f o r but r e a l i s t i c a l l y cannot be expected to improve much. New p u l p i n g processes may a l s o a f f e c t both quantity and q u a l i t y of t a l l o i l , but i t i s too e a r l y to make any predictions. Turpentine p r o d u c t i o n from the t h r e e types of n a v a l s t o r e s f o l l o w s the same pattern as r o s i n (Figure 2). However, due probably to the simple method of recovery, s u l f a t e turpentine dominated the other two sources as e a r l y as 1955. The near-term outlook i s f o r a steady r a t e of t u r p e n t i n e p r o d u c t i o n . A comprehensive r e v i e w of turpentine production and use was given r e c e n t l y (11).
Tess and Poehlein; Applied Polymer Science ACS Symposium Series; American Chemical Society: Washington, DC, 1985.
Downloaded by EAST CAROLINA UNIV on January 4, 2018 | http://pubs.acs.org Publication Date: September 25, 1985 | doi: 10.1021/bk-1985-0285.ch048
1162 APPLIED POLYMER SCIENCE
Tess and Poehlein; Applied Polymer Science ACS Symposium Series; American Chemical Society: Washington, DC, 1985.
48.
JEN AND
McSWEENEY
Tall Oil and Naval Stores
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I t i s of i n t e r e s t to note t h a t r o s i n and t u r p e n t i n e , the two major naval store products, are subject to v i o l e n t p r i c e movement s i m i l a r to other types of commodities. For example, r o s i n s o l d f o r 24
