The History of Ammonia to 2012 Harry Vroomen Vice President, Economic Services The Fertilizer Institute November 19, 2013 www.tfi.org Presentation Outline • Nitrogen Before Haber-Bosch Ammonia • Fritz Haber, Carl Bosch, BASF and Anhydrous Ammonia • Haber-Bosch Ammonia Production Starts • Ammonia Production Expands • Nitrogen Demand – Global and U.S. Profile • Importance of Haber-Bosch N (nutrients) to mankind 1770’s - Birth of Modern Chemistry Joseph Priestly Jan Ingenhousz English Minister Dutch Physician (1733 – 1804) (1730 – 1799) Discovered the Fundamentals of Photosynthesis Source: Enriching the Earth, Vaclav Smil, 2001. 1770’s - Birth of Modern Chemistry Carl Wilhelm Scheele Daniel Rutherford Antoine Laurent Lavoisier Swedish Chemist English Botanist French Chemist (1742 – 1786) (1749 – 1819) (1743 – 1794) “discovered” N named “azote” First Realization that Nitrogen Makes up Most of the Atmosphere Source: Smil, 2001. 1800’s - Value of N in Crop Production Demonstrated Jean-Baptists Boussingault Justin von Liebeg French Chemist German Chemist (1802 – 1887) (1803 – 1873) Scientific Experiments Left No Doubt About Nitrogen’s Crucial Role in Crop Production! John Bennet Lawes Joseph Henry Gilbert English Scientist English Chemist (1814 – 1900) (1817 – 1901) Source: Smil, 2001. Birth of Anhydrous Ammonia – NH3 Claude-Louis Berthollet 1784 – Berthollet becomes aware that the element French Chemist (1748 – 1822) “azote” joins with hydrogen to form ammonia Georg Friedrich Hildebrand German Professor 1795 –The first failed attempt to combine N and H (1764 - 1816) More than a dozen chemists 1800’s – Conducted experiments to synthesize ammonia 1900 –Ostwald though he had succeeded in synthesizing ammonia –Tests by Carl Bosch for BASF proved him wrong; NH3 production was result of contaminants in machine Wilhelm Ostwald German Chemist (1853 – 1932) Source: Smil, 2001, The Alchemy of Air, Thomas Hager, 2008. Nitrogen Sources: Pre Haber-Bosch Manures (barnyard and other) Guano (solidified bird excrement accumulated on subtrop/tropical islands) Chilean Nitrate (sodium nitrate) Coke‐Oven Gas (by‐product) Ammonium Sulfate ‐ Coke oven gases produced primarily in the steel industry ‐ Produced by reacting recovered coke oven ammonia with sulfuric acid Nitrogen Fixation Processes: • Electric Arc Process (1901 –Niagara Falls) Uses electrical current to combine N and oxygen in the air to form nitric oxide (NO) (NO) Nitric Acid Calcium Nitrate/Sodium Nitrate • Cyanamide Process (1907 –Italy) Limestone burned to form calcium oxide; fused with coke in electric furnace calcium carbide Calcium carbide (CaC2) reacted with N at high temperature to form calcium cyanamide (CaCN2) Calcium cyanamide (CaCN2) ammonia; ammonium phosphates; nitric acid; ammonium nitrate Source: Smil, 2001. N Production as Guano Extraction, Pre Haber-Bosch 425 400 375 350 1840’s ‐ Guano shipments to England and NY City 325 ‐ mostly from Peru 300 1856 Guano Islands Act 275 Congressional protection was afforded to discoverers of guano deposits off islands & reefs in the Caribbean and Pacific. 250 225 200 Conversion rates: 175 thousand metric tons N 150 1860 & 1870 12% N 125 1880 7% N 100 1890 4% N 75 1900 3% N 1910 & 1913 2% N 50 25 0 1860 1870 1880 1890 1900 1905 1910 1913 Source: Hager, 2008; Smil, 2001. Chilean Nitrate Production, Pre Haber-Bosch 425 400 375 350 Chilean nitrates first reached 325 the European and American 300 markets in the 1840’s 275 250 225 200 175 thousand metric tons N 150 125 100 75 50 25 0 1860 1870 1880 1890 1900 1905 1910 1913 Source: Smil, 2001. Coke-oven Gas (by-product) AS Production, Pre Haber-Bosch 425 400 375 350 325 300 275 250 225 200 175 thousand metric tons N 150 125 100 75 50 25 0 1860 1870 1880 1890 1900 1905 1910 1913 Source: Smil, 2001. Pre Haber-Bosch N Production, Excluding Ammonia - 1913 425 400 375 350 325 300 275 250 225 200 175 150 thousand metric tons N 125 100 75 Nitrogen Fixation Processes 50 25 0 Guano Chilean Nitrate Coke‐oven gas AS Cyanamide Electrical Arc Source: Smil, 2001. Evaluating Haber’s Machine Heinrich von Brunck August Bernthsen Carl Bosch CEO of BASF BASF Director of Research BASF Chemist Fritz Haber Global N Production Thousand short tons N 0 50 100 150 200 250 300 350 400 450 500 Chilean nitrate (sodium nitrate) Chile Germany Great Britain United 1913 - 0.844 mil. tons N States Norway France Canada 1913 Haber-Bosch Belgium Cyanamide 2% 5% Italy Japan By-product 36% Chile 58% Russia Other Source: Morrison, 1937. Global N Production Thousand short tons N 0 50 100 150 200 250 300 350 400 450 500 Chile Germany Great Britain United 1913 - 0.844 mil. tons N States Norway 1934 - 1.972 mil. tons N France Canada 1934 Belgium Chile 7% Cyanamide Italy 11% Japan By-product 18% Haber-Bosch Russia 64% Other Source: Morrison, 1937. German Haber-Bosch Ammonia Production 2.0 WW II 1939-45 Economic Recovery 1924-29 1.5 Economic Turmoil Hitler Gains Power 1929-38 1.0 Million metric tons ammonia Postwar 0.5 WW I Chaos 1914-18 0.0 1913 1915 1917 1919 1921 1923 1925 1927 1929 1931 1933 1935 1937 1939 1941 1943 1945 Source: Ammonia production data taken from Smil, 2001. U.S. Ammonia Production 2.0 WW II 1921: Atmospheric N Corp. ‐ Syracuse, NY 1939-45 ‐ Modified Haber‐Bosch ‐ 15/40 tons per day 1.5 ‐ Sold for refrigeration Great Depression 1929-41 1928: Allied Chemical ‐ Hopewell, VA ‐ 270 tons per day by 1930 ‐ First to focus on fertilizer 1.0 Million metric tons NH3 WW I Dust Bowl 0.5 1914-18 1931-39 0.0 1910 1915 1920 1925 1930 1935 1940 1945 Source: Nelson, 1990; Data: 1910-1940 - Smil, 2001; 1943-1945 - U.S. Geological Survey. U.S. Ammonia Production 4.5 U.S. emerges from WWII with strongest economy 4.0 Becomes largest global ammonia producer CAGR Accounts for 1/3 of global production growth in 1950's 13.4% 3.5 Set trends for modern day production: ‐ natural gas as hydrogen source ‐ plant location near feedstock and transportation 3.0 ‐ integration of NH3 synthesis with downstream materials 2.5 2.0 Million metric tons NH3 1.5 1.0 0.5 0.0 1945 1946 1947 1948 1949 1950 1951 1952 1953 1954 1955 1956 1957 1958 1959 Sources: Nelson, 1990; Data, U.S. Geological Survey. U.S. Ammonia Production, 1945-1998 25 Postwar Prosperity, 1945-1973 20 15 Growth in nutrient application rates, espec. corn & wheat 10 Million metric tons NH3 5 Adoption of hybrid corn varieties 0 1945 1947 1949 1951 1953 1955 1957 1959 1961 1963 1965 1967 1969 1971 1973 1975 1977 1979 1981 1983 1985 1987 1989 1991 1993 1995 1997 Source: U.S. Geological Survey, IFA, TFI. U.S. Ammonia Production, 1945-1998 25 20 FSU Ammonia Production Surpasses U.S. in 1981 15 10 Million metric tons NH3 5 0 1945 1947 1949 1951 1953 1955 1957 1959 1961 1963 1965 1967 1969 1971 1973 1975 1977 1979 1981 1983 1985 1987 1989 1991 1993 1995 1997 Source: U.S. Geological Survey, IFA, TFI. U.S. Ammonia Production 18 1999-2008 16 High U.S. Natural Gas Prices > 40% drop in Prod Capacity 14 12 10 8 Million metric tons NH3 6 4 2 0 1990 1991 1992 1993 1994 1995 1996 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006 2007 2008 2009 2010 2011 2012 Source: TFI, IFA. CHINA 隨著食品在手，你安心 “With food in hand, you have peace of mind” China – The Great Famine 1,400 1,300 Causes: 1,200 Mao's Great Leap Forward => Including Ag. reforms 1,100 Drought Floods 1,000 Other “Worst mass starvation 900 in recorded history” 800 700 600 500 Midyear Population -Midyear Population Million Estimated Deaths in Millions: - 17 (Zhenghua - endorsed 45 Million people is: 400 The Great Famine by Chinese Gov’t) = 43 Largest U.S. Cities Today! 1958 - 1961 - 30 (Bannister, 1987) In 1958, only 12 countries with 300 - 36 (Yang, 2008) populations > 45 Mil., excl. China - 45 (Dikötter, 2010) 200 - 55 (Xiguang, 2005) 100 0 1950 1952 1954 1956 1958 1960 1962 1964 1966 1968 1970 1972 1974 1976 1978 1980 1982 1984 1986 1988 1990 1992 1994 1996 1998 2000 2002 2004 2006 2008 2010 2012 Source: Tombstone, Yang Jinsheng, 2008; Mao’s Great Famine, Frank Dikötter, 2010; U.S. Census Bureau. China Ammonia Production, 1941-1960 400 361 300 1958 Population: 646.7 Million! Great Famine 200 thousand metric tons N 125 100 39 9 0 1941 1942 1943 1944 1945 1946 1947 1948 1949 1950 1951 1952 1953 1954 1955 1956 1957 1958 1959 1960 Data Source: 1941 and 1957, Dong Gaojie, 1989; 1950 and 1960, Long Xingmao, 1987. China Ammonia Production, 1960-1980 15 12.28 12 1973 - In response to rising demand, China imports 13 large ammonia-urea plants from: USA 1960's - Minister of Chemical Industry: Netherlands Japan 9 10 ammonia plants, mostly medium sized France 2 ammonia plants imported from: Great Britain Italy 6 1 urea plant imported from: Million metric tons N 4.98 Netherlands 3 0.36 0 1960 1961 1962 1963 1964 1965 1966 1967 1968 1969 1970 1971 1972 1973 1974 1975 1976 1977 1978 1979 1980 Source: Data: Huang Gaoqiang, Beijing University; Information - The Chemical Fertilizer Industry in China: A Review and its Outlook, Wang, Wang, Mai, et al, IFA, 2009. China Ammonia Production, 1980-1991 25 20 0.5 MMT N/year 15 10 Million metric tons N 5 0 1980 1981 1982 1983 1984 1985 1986 1987 1988 1989 1990 1991 Data Source: IFA. China Ammonia Production, 1980-1991 25 1991: China Surpasses FSU as the Largest Ammonia Producer 20 FSU Production 15 10 Million metric tons N 5 0 1980 1981 1982 1983 1984 1985 1986 1987 1988 1989 1990 1991 Data Source: IFA.