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

1770s - Birth of Modern Chemistry

Joseph Priestly
English Minister
(1733 1804)

Jan Ingenhousz
Dutch Physician
(1730 1799)

Discovered the Fundamentals of Photosynthesis

Source: Enriching the Earth, Vaclav Smil, 2001.

1770s - Birth of Modern Chemistry

Carl Wilhelm Scheele

Swedish Chemist
(1742 1786)

Daniel Rutherford
English Botanist
(1749 1819)

Antoine Laurent Lavoisier

French Chemist
(1743 1794)

discovered N

named azote

First Realization that Nitrogen Makes up Most of the Atmosphere

Source: Smil, 2001.

1800s - Value of N in Crop

Production Demonstrated

Jean-Baptists Boussingault
French Chemist
(1802 1887)

Justin von Liebeg

German Chemist
(1803 1873)

Scientific Experiments Left No

Doubt About Nitrogens Crucial
Role in Crop Production!

John Bennet Lawes

English Scientist
(1814 1900)

Joseph Henry Gilbert

English Chemist
(1817 1901)

Source: Smil, 2001.

Birth of Anhydrous Ammonia NH3

Claude-Louis Berthollet
French Chemist
(1748 1822)

Georg Friedrich
Hildebrand
German Professor
(1764 - 1816)

More than a
dozen chemists

1784 Bertholletbecomesawarethattheelement
azotejoinswithhydrogentoformammonia

1795 ThefirstfailedattempttocombineNandH

1800s Conductedexperimentstosynthesizeammonia

1900 Ostwaldthoughhehadsucceededinsynthesizingammonia
TestsbyCarlBoschforBASFprovedhimwrong;
NH3 productionwasresultofcontaminantsinmachine
Wilhelm Ostwald
German Chemist
(1853 1932)

Source: Smil, 2001, The Alchemy of Air, Thomas Hager, 2008.

Nitrogen Sources: Pre Haber-Bosch

Manures(barnyardandother)
Guano(solidifiedbirdexcrementaccumulatedonsubtrop/tropicalislands)
ChileanNitrate(sodiumnitrate)
CokeOvenGas(byproduct)AmmoniumSulfate

Cokeovengasesproducedprimarilyinthesteelindustry
Producedbyreactingrecoveredcokeovenammoniawithsulfuricacid

NitrogenFixationProcesses:
ElectricArcProcess(1901 NiagaraFalls)
UseselectricalcurrenttocombineNandoxygenintheairtoformnitricoxide(NO)
(NO) NitricAcid CalciumNitrate/SodiumNitrate

CyanamideProcess(1907 Italy)
Limestoneburnedtoformcalciumoxide;fusedwithcokeinelectricfurnace calciumcarbide
Calciumcarbide(CaC2)reactedwithNathightemperaturetoformcalciumcyanamide(CaCN2)
Calciumcyanamide(CaCN2) ammonia;ammoniumphosphates;nitricacid;ammoniumnitrate

Source: Smil, 2001.

N Production as Guano Extraction, Pre Haber-Bosch

425
400
375

325

1840s GuanoshipmentstoEnglandandNYCity
mostlyfromPeru

300

1856GuanoIslandsAct

275

Congressionalprotectionwasaffordedtodiscoverersofguano
depositsoffislands&reefsintheCaribbeanandPacific.

thousand metric tons N

350

250
225
200

Conversionrates:

175

1860&1870 12%N
1880
7%N
1890
4%N
1900
3%N
1910&19132%N

150
125
100
75
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
325
300

Chileannitratesfirstreached
theEuropeanandAmerican
marketsinthe1840s

thousand metric tons N

275
250
225
200
175
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

thousand metric tons N

300
275
250
225
200
175
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

thousand metric tons N

275
250
225
200
175
150
125
100
75

Nitrogen Fixation Processes

50
25
0

Guano

Chilean Nitrate

Cokeoven gas AS

Cyanamide

Electrical Arc

Source: Smil, 2001.

Evaluating Habers Machine

HeinrichvonBrunck
CEOofBASF

AugustBernthsen
BASFDirectorofResearch

CarlBosch
BASFChemist

FritzHaber

Global N Production
0

50

100

150

200

250

300

Thousand short tons N

350

400

450

Chilean nitrate (sodium nitrate)

Chile
Germany
Great
Britain
United
States

1913 - 0.844 mil. tons N

Norway
France

1913

Canada
Belgium

Cyanamide
5%

Haber-Bosch
2%

Italy
Japan
Russia

By-product
36%

Chile
58%

Other

Source: Morrison, 1937.

500

Global N Production
0

50

100

150

200

250

300

Thousand short tons N

350

400

450

Chile
Germany
Great
Britain

1913 - 0.844 mil. tons N

United
States

1934 - 1.972 mil. tons N

Norway
France

1934

Canada
Belgium
Italy
Japan
Russia

Chile
7%
Cyanamide
11%

By-product
18%

Haber-Bosch
64%

Other

Source: Morrison, 1937.

500

German Haber-Bosch Ammonia Production

2.0

WW II
1939-45
Economic Recovery
1924-29

Million metric tons ammonia

1.5

Economic Turmoil
Hitler Gains Power
1929-38

1.0

0.5

WW I
1914-18

Postwar
Chaos

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
1939-45

1921:AtmosphericNCorp.

1.5

Syracuse,NY
ModifiedHaberBosch
15/40tonsperday
Soldforrefrigeration

Great Depression
1929-41

Million metric tons NH3

1928:AlliedChemical
Hopewell,VA
270tonsperdayby1930
Firsttofocusonfertilizer

1.0

WW I
1914-18

0.5

Dust Bowl
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.emergesfromWWIIwithstrongest economy
4.0

Becomeslargestglobalammoniaproducer

CAGR
13.4%

Accountsfor1/3ofglobalproductiongrowthin1950's
3.5

Million metric tons NH3

3.0

Settrendsformoderndayproduction:
naturalgasashydrogensource
plantlocationnearfeedstockandtransportation
integrationofNH3synthesiswithdownstreammaterials

2.5

2.0

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

Million metric tons NH3

20

15

Growth in nutrient
application rates,
espec. corn & wheat
10

Adoption of
hybrid corn
varieties

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

Million metric tons NH3

FSU Ammonia Production

Surpasses U.S. in 1981
15

10

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
High U.S. Natural Gas Prices
> 40% drop in Prod Capacity

16

14

Million metric tons NH3

12

10

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

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
Other

Worst mass starvation

in recorded history

900
800
700
600
500

Estimated Deaths in Millions:

- 17 (Zhenghua - endorsed
by Chinese Govt)
- 30 (Bannister, 1987)
- 36 (Yang, 2008)
- 45 (Diktter, 2010)
- 55 (Xiguang, 2005)

The Great Famine

1958 - 1961

400
300
200

45 Million people is:

= 43 Largest U.S. Cities Today!
In 1958, only 12 countries with
populations > 45 Mil., excl. China

100

2012

2010

2008

2006

2004

2002

2000

1998

1996

1994

1992

1990

1988

1986

1984

1982

1980

1978

1976

1974

1972

1970

1968

1966

1964

1962

1960

1958

1956

1954

1952

0
1950

Midyear Population - Million

1,000

Source: Tombstone, Yang Jinsheng, 2008; Maos Great Famine, Frank Diktter, 2010; U.S. Census Bureau.

China Ammonia Production, 1941-1960

400
361

thousand metric tons N

300

Great
Famine

1958 Population: 646.7 Million!

200

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

1973 - In response to rising

demand, China imports 13 large
ammonia-urea plants from:
USA
Netherlands
Japan
France

12

Million metric tons N

1960's - Minister of Chemical Industry:

9

10 ammonia plants, mostly medium sized

2 ammonia plants imported from:
Great Britain
Italy

1 urea plant imported from:

Netherlands

4.98

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

Million metric tons N

20

0.5 MMT N/year

15

10

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

Million metric tons N

FSU Production
15

10

0
1980

1981

1982

1983

1984

1985

1986

1987

1988

1989

1990

1991

Data Source: IFA.

Largest Ammonia Producing Countries

45

53.6 MMT Material

40

35

Production
Increases by
~ 30 MMT NH3!

Million metric tons N

30

25

20

China
Middle East

15

10

India

Russia

USA
5

0
1991 1992 1993 1994 1995 1996 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006 2007 2008 2009 2010 2011 2012

Data Source: IFA.

Top 10 Ammonia Producing Countries in 2012

32%

45

394ammoniaplants=>
53.6MMTMaterial

40

35

Million Metric Tons N

30

China NH3 Production

Nearly 4 times > Russian production

> next 6 largest producers combined

25

20

2nd-9th largest = 40% of global production

15

10

0
Egypt

Saudi
Arabia

Canada

Ukraine

Trinidad

Indonesia

USA

India

Russia

China

Source: Data - IFA; No. of ammonia plants - Zhang and Huang, 2013 IFA PIT Conference, Oct. 2013.

China - Urea Production

30

Largest Urea Importers - 1989-1992 Average

25

0%

5%

10%

15%

20%

25%

30%

35%

China

40%

35.2%

20

Million Metric Tons N

USA
Vietnam
15

9.1%

4.5%

Philippines

2.8%

India

2.8%

United Kingdom

2.8%

France

2.6%

China Imports
6.9 MMT material

10

0
1989 1990 1991 1992 1993 1994 1995 1996 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006 2007 2008 2009 2010 2011 2012

Data Source: IFA.

China - Urea Production

30

Largest Urea Exporters - 2012

27

0%

5%

10%

15%

China

20%
16.2%

24
Russia
21

11.2%

Qatar

9.8%

Million Metric Tons N

Ukraine
18

15

8.4%

Oman

7.3%

Saudi Arabia

7.2%

Iran

6.7%

China Exports
6.9 MMT material

62 MMT Urea (material)

36 MMT Ammonia (2/3)

12

3
1989 1990 1991 1992 1993 1994 1995 1996 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006 2007 2008 2009 2010 2011 2012

Data Source: IFA.

China: DAP Production

million metric tons P2O5

* 1997 40% of global DAP IMPORTS 5.6 MMT material

* 2012 27% of global DAP EXPORTS 10.7 MMT material
Net Difference 16.3 MMT material

0
1992

1993

1994

1995

1996

1997

1998

1999

2000

2001

2002

2003

2004

2005

2006

2007

2008

2009

2010

2011

2012

Data Source: IFA.

China: Phosphate Fertilizer Production

14

26.4 MMT Amm Phos Material

4.9 MMT Ammonia (9%)
12

Share of
Global
Production
1992 2012

million metric tons P2O5

10

DAP
6

2%

42%

MAP 0%

49%

1992

1993

1994

1995

1996

1997

1998

1999

2000

2001

2002

2003

2004

2005

2006

2007

2008

2009

2010

2011

2012

Data Source: IFA.

Global Ammonia Production

170
160
150

>99%ofNproductiontodayisHaberBoschSynthesis!

140
130
120

Million metric tons NH3

110
100

Increased
by57times
sinceWWII

90
80
70
60
50
40
30
20
10
0
1945

1950

1955

1960

1965

1970

1975

1980

1985

1990

1995

2000

2005

2010

Source: 1943-1979: U.S. Geological Survey; 1980-2012: IFA; Smil, 2001.

Global Nitrogen Use by Crop, 2010/11

Other
15%

Wheat
18%

Sugar Crops
4%
Fiber Crops
4%
Other Cereals
5%

Corn
17%

Fruits
6%

Oilseeds
7%
Vegetables
9%

Rice
15%

Source: IFA.

Downstream Nitrogen Fertilizers and Materials from Anhydrous Ammonia

Ammonia

Ammonium Nitrate
- Solid
- Liquor

Oxygen

NH3

Nitric
Acid

Sodium Carbonate

Phosphate Rock

Ammonia

Nitric Phosphate

Nitrogen Solutions

Sulfuric Acid

Also used to produce

plastics, synthetic
fibers and resins,
explosives, and
numerous other
chemical compounds.

Sodium Nitrate

Ammonium Sulfate

Phosphoric Acid

Ammonium Phosphates

Carbon Dioxide

Urea
- Solid
- Liquor
- Diesel exhaust fluid

About 87% for fertilizer!

World Nitrogen Fertilizer Use

2011 - 107.9 million metric tons N
Other N
20%

Ammonium Sulfate
3%
Anhydrous Ammonia
4%

Nitrogen Solutions
5%

Urea
56%

Ammonium Nitrate
5%

Ammonium Phosphates
7%

Source: IFA.

World Nitrogen Fertilizer Use

2011 - 107.9 million metric tons N

China
31%

Other
33%

Indonesia
3%
Pakistan
3%
Brazil
3%

India
16%
USA
11%
Source: IFA.

China - Nitrogen Fertilizer Use

2011 - 33.8 million metric tons N
Other N
7%
Ammonium Phosphates
9%

Other straight N
17%

Urea
67%

Source: IFA.

India - Nitrogen Fertilizer Use

2011 - 17.4 million metric tons N
Other N
11%

Ammonium Phosphates
11%

Urea
78%

Source: IFA.

Global Nutrient Use, 1930-2011

110

100

P2O5

K2O

IndiasurpassesUSAto
become#2inNUse 1998

90

Breakup
oftheFSU

70

ChinasurpassesUSAtobecome#1inNUse 1979
60

50

40

30

NusesurpassesP2O5 use 1960

NusesurpassesK2Ouse 1956

20

USA:accountsfor
35%of Global
NUse 1944

10

Source: Data from IFA.

2010

2008

2006

2004

2002

2000

1998

1996

1994

1992

1990

1988

1986

1984

1982

1980

1978

1976

1974

1972

1970

1968

1966

1964

1962

1960

1958

1956

1954

1952

1950

1948

1946

1944

1942

1940

1938

1936

1934

1932

0
1930

Million Metric Tons Nutrient

80

Growth in Global Nitrogen Use

1999-2011: 23 MMT N
Other
24%

China
43%
(9.9 MMT)

Brazil
8%
(1.7 MMT)

> 75%
India
25%
(5.8 MMT)

Source: IFA.

U.S. Nitrogen Use by Crop, 2010/11

Other
24%

Sugar Crops
1%

Fruits
1%
Corn
49%

Vegetables
1%
Oilseeds
1%
Rice
2%
Other Cereals
3%
Fiber Crops
5%
Wheat
13%

Source: Computed from nutrient application rate data reported by USDA and Commercial Fertilizers, 2011.

U.S. Nitrogen Fertilizer Use

FY2010/11 - 12.84 million tons N
Other N
14%
Ammonium Nitrate
2%

Anhydrous Ammonia
27%

Ammonium Sulfate
2%
Ammonium Phosphates
6%

Urea
22%

Nitrogen Solutions
27%

Source: Commercial Fertilizers, 2011, Association of American Plant Food Control Officials and TFI, April 2013.

 ApplyingAnhydrousAmmonia

Sidedressingnitrogensolutions

U.S. Consumption of Selected Nitrogen Materials

12
11

Nitrogen solutions
10

8
7

urea

Anhydrous ammonia

6
5
4
3
2
1

2010

2008

2006

2004

2002

2000

1998

1996

1994

1992

1990

1988

1986

1984

1982

1980

1978

1976

1974

1972

1970

1968

1966

1964

1962

0
1960

million tons material

Source: Commercial Fertilizers, 2011 and earlier issues.

U.S. Nitrogen Consumption:1850 2010/11

14

13.2 Mil Short Tons N FY2006/07

PIK

12

million short tons N

10

FY1953/54:NusesurpassedK2Ouseforgood
FY1958/59:NusesurpassedP2O5 usefor1st time

100yearstogrowfrom3thousandto1MillionTons!
2

Source: Historical Statistics of the United States, U.S. Census Bureau; Commercial Fertilizers, various issues.

Media Focus

Heres My Plan to Improve Our World

And How You Can Help
Bill Gates, Wired.com, Nov. 12, 2013

These days I get to spend a lot of time trying to advance innovation

that improves peoples lives in the same way that fertilizer did.

 the lives of around half of humanity are made possible by Haber-Bosch nitrogen

Source: Nature Geoscience, Feature Article, Vol. 1, October 2008.

The Haber-Bosch process has been of greater

fundamental importance to the modern world
than the airplane, nuclear energy, spaceflight
or television".
Vaclav Smil, Enriching the Earth, 2001.

Thank You!