A new approach to the production of custom-made synthesis gas using Texaco's partial oxidation technology
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The Texaco Synthesis Gas Generation Process (TSGGP) has been used commercially since 1950 to produce a mixture of hydrogen and carbon monoxide - synthesis gas - by partial oxidation of hydrocarbons. Recent process developments and favorable economics have resulted in renewed interest in the partial oxidation of natural gas. This paper describes the main features of Texaco's partial oxidation technology and its ability to produce a wide range of pre-determined gas compositions to suit downstream requirements. The addition of controlled amounts of carbon dioxide or steam into the reaction system offers a simple method of adjusting the hydrogen-to-carbon oxide ratio of the product gas. The use of advanced computer control makes it possible to design the plant for on-line control and optimization, with flexibility for future operation at other regimes, depending on revised economic conditions. The paper describes some commercial applications to illustrate the process design flexibility.Keywords:
Partial oxidation
Partial pressure
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Natural gas, due to its abundance and low cost, is a major future source as a feedstock for the petroleum and chemical industry. For strategic or economic reasons, it may be undesirable to transport natural gas to potential markets or to use it for transportation fuels. This provides an incentive to investigate various routes to convert natural gas to higher hydrocarbons. Methane, which accounts for over 60% of natural gas, is used today as a source of hydrogen, for ammonia production and to manufacture methanol through steam reforming to the synthesis gas mixtures. However, direct methane conversion to higher hydrocarbon has a high economic incentive as a result of bypassing the synthesis gas step. Recent process development studies have investigated various options for the conversion of natural gas to valuable hydrocarbons. This paper discusses the prospects for direct natural gas conversion by three routes: oxidative coupling to ethylene and higher hydrocarbons, oxidation to methanol or formaldehyde. and oxidation to aromatics by nitrous oxide. Current research activities in the area of natural gas oxidation are reviewed in terms of process conditions, reactor design, catalyst performance in terms of methane conversion and selectivities to various products. Future challenges in reactor and process design for methane oxidation are highlighted.
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The first section of the presentation will provide general information about hydrogen including physical data, natural abundance, production and consumption figures. This will be followed by detailed information about current industrial production routes for hydrogen. Main on-purpose production for hydrogen is by classical steam reforming (SR) of natural gas. A brief overview of most important steps in stream reforming is given including reforming section, CO conversion and gas purification. Also the use of heavier than methane feedstocks and refinery off-gases is discussed. Alternative routes for hydrogen production or production of synthesis gas are autothermal reforming (ATR) or partial oxidation (POX). Pros and Cons for each specific technology are given and discussed. Gasification, especially gasification of renewable feedstocks, is a further possibility to produce hydrogen or synthesis gas. New developments and current commercial processes are presented. Hydrogen from electrolysis plants has only a small share on the hydrogen production slate, but in some cases this hydrogen is a suitable feedstock for niche applications with future potential. Finally, production of hydrogen by solar power as a new route is discussed. The final section focuses on the use of hydrogen. Classical applications are hydrogenation reactions in refineries, like HDS, HDN, hydrocracking and hydrofinishing. But, with an increased demand for liquid fuels for transportation or power supply, hydrogen becomes a key player in future as an energy source. Use of hydrogen in synthesis gas for the production of liquid fuels via Fischer-Tropsch synthesis or coal liquefaction is discussed as well as use of pure hydrogen in fuel cells. Additional, new application for biomass-derived feedstocks are discussed. (orig.)
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A new process, called OXAR (OXidation And Reforming) has been invented to manufacture synthesis or reducing gases which are rich in hydrogen and carbon monoxide. One of the main features of this process is its apparent ability to accept a wide variety of raw materials. Solid, liquid and gaseous fuels have been combusted in a 1 tonne/hour development unit to produce a high temperature carbon dioxide and steam mixture, which has been used in the same chamber to reform a hydrocarbon-containing gas. In general synthesis gas of 80-95% purity (on a dry basis) has been produced. Many gaseous feedstocks might be suitable for reforming in OXAR. The process could be relevant to many industries including the chemical, refining, metallurgical, power and fuel industries. Application in the emerging coal conversion industry is of special interest. It is concluded that the process offers opportunity for optimising the use of a number of important resources, however, considerable development work is still required to verify this potential.
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Air Products, in collaboration with the U.S. DOE and other partners, is developing ceramic membrane technology for the generation of hydrogen and synthesis gas. These membranes are non-porous, multi-component metallic oxides that operate at high temperatures and have exceptionally high oxygen flux and selectivities. Such membranes are known as Ion Transport Membranes, or ITMs. Synthesis gas is an important intermediate product required for the production of liquid transportation fuels from natural gas. Preliminary cost estimates indicate that ceramic membrane reactors could decrease the capital cost for syngas by more than one third. This reduction would have a very significant impact on the costs of liquid transportation fuels derived from natural gas. Work still in progress also shows significant potential savings for hydrogen production, especially for production capacities appropriate for hydrogen based fuel cell applications. This paper defines ITMs and explains how they work. The paper also identifies the major program goals and summarizes our progress. The overall program objectives and schedule are also presented.
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This chapter is concerned with the historical uses and methods of producing hydrogen from fossil fuels. It discusses partial oxidation of residual fractions and older methods which utilize coal or coke since they appear to have potential as gaseous and liquid hydrocarbons become scarce and more expensive. Hydrogen is one of the most important yet least visible of all large-volume chemicals. The choice of processing conditions is determined by the hydrogen content of the fuel and the method of supplying the heat necessary to sustain the reactions. The development of liquefaction and gasification industries will bring about the demand for enormous quantities of hydrogen. A commercially available alternative for producing a synthesis gas from coal is to use an atmospheric gasifier followed by a compression step. The chapter discusses the operation and economics of four commercial processes for manufacturing hydrogen: catalytic decomposition of methane, catalytic steam reforming, catalytic partial oxidation, and noncatalytic partial oxidation.
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