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Development of Modern Low Energy Ammonia Technology

IP.com Disclosure Number: IPCOM000219869D
Publication Date: 2012-Jul-17

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J. R. LeBlanc and J. R. Cassata

INTRODUCTION

     Ammonia is the lar~gest volume industrial, chemical made. It is the single most important component of world food production. For this reason the commer~ial development ~ ammonia produ~:tien is considered one of the more significant technological advancements to benefit ~ankind. Because of its importance to world ~ivilization~ e~forts are continuously under'way to improve the process. Since produ(zing ammenia is veiny ener'Qy intensives, improvements in efficiency have been given

dra;natisally in the 197()~s.
of production .'_-o~-~t has become an ever the total co~t of making ammonia.

HISTORICAL BACKGROUND

     In the early part aT this c:entury a rapidly e::par~ding worldwide demand for nitrogen ;ertilizer began to develop. S~;udies were under'way at several locations on the ~:hemistry ~,f ammonia formation in anticipation of developing a

develop an
cyanamide with water yielding

/

high priority° This emphasis when energy prices escalated

Since then the energy component increasing fraction ¢:,f

Some researchers were attempting to
the reaction eT calcium ammonia and calcium carbonate.


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The calcium c~anamide was produced via the reaction of calcium carbide with nitrogen. Others attempted to derive ammonia from nitric.oxide obtained by passing air through an electric arc a~ 5~400°F. German physical chemist Fritz

Haber~ based en his backgreund in electrochemistry and thermodynamics of gas phase reactions~ was convinced ammonia c~uld be made by the direct Eixation.~f hydrogen and nitrogen.

     In his early studies Haber showed that a stoic.hiometric hydrogen and nitrogen mixture yielded only about 1 percent amr~~onia at atmospheri¢~ pressure and 1,800~F. In later tests at higher pr'essure, Haber showed that although the reaction did not approach complete conversion, a signi;icant amount o'~ am~'r~onia co~id be ~ormed over- osmium. This led to the concept o; recycling the unreacted gases back to the ammonia reactor with {eed/e;{luent heat exchange.

     Carl Bosch took Haber~s laboratory procedure and developed a i~iommercial ammonia proi_~ess. In 1909, Bosch demonstrated the commercial plant c(incept in a laboratery bench scale apparatus. However, before a commercial process could become a reality, an inexper;sive and reliable hydr-ogen source was required as well as an eEfective yet inexpensive catalyst.

     In ea-ly pilot plaot tests, hydrogen was supplied by electr(]lysis. Later, water' gas was chosen as the preferred hydrogen source, and nitrogen was purified cryogenically from air. C02 was removed from the crude synthesis gas by


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scrubbing with potash and CO was removed by scrubbing with caustic soda.

     A very ext, ensive testing pregram invelving thousands o~ experiments was undertaken tôind a suitable less expensive catalyst as an alternative to the scarce and difficult to handle esmium. By 1911~ A. Mittasch optimized a synthesis catalyst o~ alkali promoted magnetite contain...