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Published on January 24, 2008

Author: Marco1

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Fra gnist til global aktør:  Fra gnist til global aktør Presentasjon for Norges Tekniske Vitenskapsakademi, 16.03.2005 From reducing to oxidising atmosphere Photo with permission from NASA:  From reducing to oxidising atmosphere Photo with permission from NASA Reducing atmosphere: N2 CH4 NH3 CO2 H2O H2 Oxidising atmosphere: N2 O2 CO2 H2O Lack of nutrient-N Photosynthesis 6CO2+ 6H2O=>6O2 +C6H12O6 Biological N-fixation N2+6H++6e-=>2NH3 Early protein & life from organic salt soup?? SO4 + CH4+CO2+ NH3 +Ur=> -CH20NH2-S- => Photosynthesis 6CO2+ 6H2O=>6O2 +C6H12O6 Liebig discovered that plants take up minerals - the base for increased food production:  Liebig discovered that plants take up minerals - the base for increased food production Organic matter recycling of residues Theory until mid 19th century: Crops grow by feeding on soil organic matter (Aristoteles, 350 B.C.) Discovery: organic matter is broken down to minerals by soil bacteriae. Minerals = plant nutrients and are taken up by crops (Liebig,1840) recycling of residues recycling of residues Food Food Food Proof: application of minerals as plant nutrients increased yield and enabled much higher food production Organic matter Organic matter Plant nutrients in mineral fertilizer A positive energy balance with fertilizers:  A positive energy balance with fertilizers GJ/ha Solar energy captured in extra biomass when using fertilizer Solar energy in biomass produced without fertilizer On field activities etc. Fertilizer (170 kg N/ha) Nutrient sources of productivity boost in agriculture:  Nutrient sources of productivity boost in agriculture Source: IFA,Worldmarkets.com 2.4% average annual fertilizer volume growth 1970-2000 Tonnes of wheat per hectare Mineral fertilizer Manure Soil fertility Nutrient source Nitrogen and carbon cycle, relation to photosynthesis:  Nitrogen and carbon cycle, relation to photosynthesis N2 S CO2 CH4 -CH2- Fossile fuel N2 NH3 CO2 CO2 N2 -CH2-CONH2 NH3 NO3 NO2 NH3 P2O5 K2O SO4 Mg Ca ++ Soil organics and minerals CO2 N2 NH3 Industrial N-fixation 1% of fuel Biological N-fixation Photosynthesis N2 SO2 CO2 Sedimentation respiration decomposition de-nitrification Unique and Complementary Greatness from cooperation :  Unique and Complementary Greatness from cooperation Kristian Birkeland and Sam Eyde Air dissociation, the key reactions:  Air dissociation, the key reactions O2  O + O dissociation of oxygen, kO2 N2  N + N dissociation of nitrogen, kN2 NO  N + O dissociation of NO, kNO N N Birkeland electric arc principle:  Birkeland electric arc principle N S electrode ~ ~electrode B F + v Birkeland & Eyde, Electric Arc reactor:  Birkeland & Eyde, Electric Arc reactor A magnetic field was used to expand the alternating arc into a large disc-shaped “flame” The air was entering perpendicular to the electric arc disc, through a perforated ceramic distributor, and following a radial flow through the arc before leaving the reactor through a circumferential channel. The reactor design gave a relatively uniform averaged temperature profile. The reactor was lacking a counter-current heat-recovery principle. Electric arc pilot plant and final internal design:  Electric arc pilot plant and final internal design Photo from electric arc in operation:  Photo from electric arc in operation Electrodes Magnetic pole The electric arc is forming an alternating flat hemisphere on both sides of the two electrodes Once the arc was established, the air was ionised, and the arc was burning like a stable white flame Electric Arc Reactor, equilibrium calculation:  Electric Arc Reactor, equilibrium calculation O O N N O O N O N O N N O O N N O O O O N N 4000K NO is also decomposing 3500K Max NO is formed 2200K reaction become slow O N N O N N O N N N Production of ”Norgessalpeter” Calcium Nitrate:  Production of ”Norgessalpeter” Calcium Nitrate Air Electric Arc Steam H2O NO NO CaCO3 HNO3 Cooling Steam prod El.Pow. Absorption Acid prod Digestion of lime Evaporation Cooling crushing Ca(NO3)2 CO2 H2O H2O NOx Ca(NO3)2 The nitrogen process chain, 1905:  The nitrogen process chain, 1905 N -oxidation Air N2+O2 El. Power NO Abs. HNO3 H2O O2 N2 + O2 = 2NO 4NO+ 2H2O + 3O2 = 4HNO3 The nitrogen process chain, R&D 1906-1930:  The nitrogen process chain, R&D 1906-1930 NH3-oxidation NH3 synthesis Air O2 NO Abs. HNO3 H2O NH3 + 2O2 = H2O + HNO3 O2 N2 + H2 = 2NH3 ?? ??? ? N2+H2 ?? ?? Haaber-Bosch ammonia synthesis:  Haaber-Bosch ammonia synthesis H H N N H H N N H N N N H H H H H N N 300 atm, 550 C H H N H (lq) (g) H H N N Haber-Bosch, ammonia synthesis:  Haber-Bosch, ammonia synthesis 3H2 + N2 2NH3(l) Ammonia converter with catalyst beds Cooling & Steam production Compression mixed gas Loop circulation Ammonia separation Ammonia condensation H2O(liq) H2O(g) The nitrogen process chain, Hydro 1928-1990:  The nitrogen process chain, Hydro 1928-1990 NH3-oxidation NH3 synthesis Air Electrolysis H2O El. Power N2 NO Abs. HNO3 H2O O2 Air sep. NH3 + 2O2 = H2O + HNO3 2N2 + 6H20 = 3O2 + 4NH3 O2 O2 N2+H2 H2 The nitrogen process chain, Hydro 1967-2005:  The nitrogen process chain, Hydro 1967-2005 NH3-oxidation NH3 synthesis Air O2 Reforming, CO shift, CO2 removal Methanation and purification CH4 O2 N2 Air CO2 N2+H2 Abs. HNO3 H2O H2O 7CH4 + 10 H2O + 8N2 + 2O2 = 16NH3 + 7CO2 NH3 + 2O2 = H2O + HNO3 NO O2 Technical improvement, Nitrogen fixation:  Technical improvement, Nitrogen fixation The technology development in the 20th century have reduced the energy consumption down towards the practical and theoretical minimum. Steam reforming of methane has a stoichiometric minimum of 25,5 GJ/tN including a steam export of 2 GJ/tN, (LHV) LHV of ammonia is 18,6 GJ/tN Nitrophosphate process:  Nitrophosphate process Digestion Crystallisation Filtration Neutralisation Calcium Nitrate Plant Evaporation HNO3 Ca3(PO4)2 Ca(NO3)2 NH3(g) NH3(l) NH3(g) H2O(g) H2O(l) NPK Particulation CN conversion CaCO3 (s) AN CO2(g) Porsgrunn fertiliser complex 2005:  Ammonia Plant 500 kt/year 3 Nitric Acid plants 1250 kt/year 1900 kt/y NPK 620 kt/y CN Porsgrunn fertiliser complex 2005 CH4 Phosphate Rock Yara’s history and growth:  1996: Acquisition of Nutrite in Canada and Italian fertilizer operations 1999-2001 Agri Turnaround Acquisition of Kynoch in S. Africa and Trevo in Brazil March 2004: De-merger of Hydro Agri and listing in the Oslo Stock Exchange under the name Yara International ASA 1973: Joint venture in Qatar – QAFCO 1979-86: Acquisitions in Netherlands, Sweden, Denmark, U.K., Germany and France. Terminal in China 1991: Acquisition of ammonia plants in Trinidad and nitrate plant in Rostock, Germany 1905: World's first production of nitrogen fertilizer at Notodden, Norway 1928: Porsgrunn Plant, Norway 1946: Market operations in North America 1972: Market operations in Thailand Yara’s history and growth Unique global distribution network:  Unique global distribution network “On the ground” in ~50 countries, sales to more than 120 countries, more than 160 plants/terminals/warehouses Sales office Major plant No. of plants/ terminals/ warehouses 27 Biotechnololgy, challenge or opportunity:  Biotechnololgy, challenge or opportunity Biotechnology and genetic engineering may succeed in giving rice and wheat the ability to utilise the symbiosis with nitrogen fixing bacteria. Biological nitrogen fixation may develop in support to industrial photosynthesis as new basis for bio-protein production. Biotechnology will put focus food quality and subsequently crop demand for nutrients farming practices. This is actively supported by Yara. Recycling, requires make-up of nutrients :  Recycling, requires make-up of nutrients Farm recycling Regional recycling Global household recycling NH3 N2 N2O CH4 N2 N2 NO3 NH3 P2O5 K2O SO4 Ca Mg ++ CH4 Technology change drivers:  Technology change drivers N-oxidation NH3 synthesis Air O2 Reforming, CO shift, CO2 removal Methanation and purification CH4 O2 N2 Air CO2 N2+H2 Abs. HNO3 H2O H2O NO O2 The hydrogen society: Sustainable energy bio, wind, solar, wave,.. Fuel-cell, membrane, micro plants CO2 handling Ammonia synthesis: High activity Rt catalysts H2-membranes NO production: New B-E O2-membranes Fuel cell technology Nano-technology High intensity process NH3 based power generation Energy components; GJ/tN for different technologies and energy basis:  Energy components; GJ/tN for different technologies and energy basis Assumptions made for Electric Arc: 10% NO from 10 bar reactor 80% energy efficiency Slide32:  Global responsibility Healthy food for plants…:  ... yields healthy food for people Healthy food for plants… Join the celebration !:  Join the celebration ! Yara is 100 years old, however we are anything but old and gray. We are mature and experienced while energetic and young… 100 Years Young, in fact! Support slides:  Support slides Electric Arc equilibrium conversion of N2:  Electric Arc equilibrium conversion of N2 Electric Arc dissociation product of N2 in air:  Electric Arc dissociation product of N2 in air Advantages with the Birkeland – Eyde process:  Advantages with the Birkeland – Eyde process Scientific simplicity solving the key question, O2+N2->2NO The plasma reaction was a step change from other processes Using magnetic field to control arc intensity and size for large capacity units The downstream process to finished product was short and simple Theoretical energy consumption; only 6,4 GJ/tN Marginal or sunk cost of electricity was low all hydro-electrical power projects Nitric Acid had a high value and potential as an intermediate product. The product development tree starting from Nitric Acid is still valid in Yara today Easy to sell to investors Simple process, clear performance criteria, nice market. Agronomic value of Nitrates was known, and differentiation and segmentation was possible against ammonium sulphate which was the competitor product. Electric Arc vs. Haaber-Bosh:  Electric Arc vs. Haaber-Bosh Electric Arc N-fix at extremely high temperatures 2000-4000 oC Elevated pressure or quenching required for higher yield, but practically difficult Direct fixation in plasma conditions Thermodynamic equilibrium; 2 % conversion of Nitrogen Extraction of converted N from reaction loop not possible Heat recovery difficult due to materials and direct connection to absorption Only electricity possible as heat energy input Nitric Acid is a commercially good basis for nitrate fertilisers like calcium nitrate and nitrate and nitrite chemicals Haaber Bosh N-fix at lower temperature, 500 oC High pressure required and possible higher yield. Use of catalyst for N-dissociation 10-20% conversion of N Extraction of converted N from reaction loop Heat recovery possible Energy input was Hydrogen Coke and hydrocarbon processes Electrolysis of water High purity hydrogen and nitrogen required for catalyst. Ammonia energy carrier and basis for other fertiliser products like, ammonium sulphate, urea, nitric acid, ammonium nitrate,.. Industrial Nitrogen-fixation 1900 J.W.Mellor, Inorganic and theoretical chemistry; “The fixation of atmospheric nitrogen” p 366:  Industrial Nitrogen-fixation 1900 J.W.Mellor, Inorganic and theoretical chemistry; “The fixation of atmospheric nitrogen” p 366 Nitrogen-Oxygen, Electric Arc Birkeland & Eyde, Shönherr, Kowlasky & Moscicky, Pauling, Scott, Island. Hydrogen-Nitrogen, Iron Catalyst Haber-Bosch Nitrogen-Vann, metallic absorption of N Serpeck, minor industrial capacity Cyanamid, Nitrogen reaction with Calcium Carbide Frank & Caro, process used by Odda, Niagara falls and other industrial actors Cyanide, Atmospheric Nitrogen to Cyanide Bucher Combustion processes, NOx problem as of today Häusser & Bender Slide41:  Ammonia Synthesis CH4 Energy components; GJ/tN for different technologies and energy basis:  Energy components; GJ/tN for different technologies and energy basis Assumptions made for Electric Arc: 5% NO from 10 bar reactor 60% energy efficiency Schönherr, Electric arc:  Schönherr, Electric arc The Schönherr reactor, was in many ways better than the Birkeland-Eyde reactor. Counter current heat recovery, quenching and pressure control. BASF, Haber & König, achieved very promising results in their research laboratories. 10% NO from air! Air in Air out Water Centerline Electric Arc Electric Arc pilot in glass tube

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