Operation of a steam methane reformer by direct feeding of steam rich producer gas from steam hydro-gasification

Information

  • Patent Application
  • 20080021119
  • Publication Number
    20080021119
  • Date Filed
    July 18, 2006
    18 years ago
  • Date Published
    January 24, 2008
    17 years ago
Abstract
An improved, economical alternative method to supply steam and methane to a steam methane reformer (SMR) is accomplished by a combination of procedures, wherein product gas from a steam hydro-gasification reactor (SHR) is used as the feedstock for the SMR by removing impurities from the product stream from the SHR with a gas cleanup unit that operates substantially at process temperatures and pressures and is located between the SHR and SMR.
Description

BRIEF DESCRIPTION OF THE DRAWINGS

For a more complete understanding of the present invention, reference is now made to the following descriptions taken in conjunction with the accompanying drawing, in which:



FIG. 1 is a flow diagram of the process of this invention;



FIG. 2 is a flow diagram of the mass balance of the process; and



FIG. 3 graphically depicts the components produced with and without the invention.





DETAILED DESCRIPTION OF THE INVENTION

This invention provides a combination of procedures, where in one embodiment of the invention, the feedstock for an SMR is a mixture of steam and methane rich product gas generated by means of hydro-gasification of a mixture of carbonaceous material and water in an SHR. The steam is present as a result of superheating the water in the feedstock and serves as an ideal feed stream for the SMR.


The other procedure requires a method of removing impurities from the product stream from the SHR, such as fine particles of ash & char, hydrogen sulfide (H2S) and other inorganic components. These impurities must be removed in order to prevent poisoning of the catalyst used in the SMR while maintaining the SMR feed stream at its high process temperatures. Accordingly, in another embodiment of the invention, a gas cleanup unit is provided that operates at process temperatures and pressures and is located in between the SHR and SMR.


Referring to FIG. 1, a flow diagram of the process is shown. An internally generated hydrogen feed 10 is fed into an SHR 12 along with a carbonaceous feedstock 14 and water 16, which are heated to 750° C. at 400 psi in the SHR 12. The resulting producer gas is directed to a gas clean up filter18, e.g. a candle filter assembly, at about 350° C. at about 400 psi. From there, after removal of sulfur and ash, the effluent is directed to an SMR 20 where synthesis gas is generated and fed to a Fischer-Tropsch reactor 22, from which pure water 24, diesel fuel and/or wax 26 is obtained. A portion of hydrogen is diverted from the SMR20, at 28 to be fed back to the HGR 12. Heat 30 from the Fischer-Tropsch reactor 22 is used to supplement the heat at the SMR.


Operating the unit above the bubbling temperature of the water allows the water to be present as steam in the gaseous product stream from the SHR, thereby enabling the process to retain most of the sensible heat in the effluent stream. A mass balance process flow diagram is shown in FIG. 2. The mass percentages of the product stream at each stage of the process are provided in the figure. ASPEN PLUS™ equilibrium process modeling was used to calculate these values. ASPEN PLUS™ is a commercial computer modeling program ASPEN PLUS™ that allows a process model to be created by specifying the chemical components and operating conditions. The program takes all of the specifications and simulates the model, executing all necessary calculations needed to solve the outcome of the system, hence predicting its behavior. When the calculations are complete, ASPEN PLUS™ lists the results, stream by stream and unit by unit. As shown in FIG. 2, an SHR feedstock of hydrogen and 41% coal slurry results in the production of synthesis gas with a 3.4:1 mole ratio of hydrogen to carbon monoxide in the SMR. The required feed hydrogen for the SHR can be supplied through external means or by internal feedback of a portion of the hydrogen produced in the SMR. In a particular example, a slurry of 41% coal, 52% water and 7% hydrogen is used, obtained following the procedures of Norbecketal. U.S. Ser. No. 10/911,348,


Any filter capable of operating at the process temperature can be used. One such commercially available filter is a candle filter, which is well known to the art. See, for example U.S. Pat. No. 5,474,586, the disclosure of which is incorporated herein by reference. An available gas cleanup unit that can be used in this invention is what is known as a candle filter in which a series of candle-shaped filters are carried in a filter vessel. The candle filters are made of stainless steel metal frit to remove fine particulate matter (ash, inorganic salts and un-reacted char) from the gas stream. The slurry is fed into the vessel at a bottom inlet and filtrate taken out at a top outlet. Particulate matter is taken from another outlet as cake. Sulfur impurities existing in the SHR product gas, mostly in the form of hydrogen sulfide, are removed by passing the product gas through a packed bed of metal oxide sorbents in the gas cleanup unit, particulate matter being taken from a cake outlet.


Active sorbents include, but are not limited to, Zn based oxides such as zinc oxide, sold by Süd-Chemie, Louisville, Ky. Porous metal filter elements are available from Bekaert in Marietta, Ga. in the appropriate forms and sizes, such as Bekpor® Porous Media-which is made from stainless steel sintered fiber matriox with a pore size of 1. These sorbents and filter elements allow the effects of pressure drop and gas-solid mass transfer limitations to be minimized. At a pressure of 28 atm., temperatures in the range of 300° C. to 500° C. and space velocities up to 2000/hr have been used in the desulphurization of SHR product gas. The hydrogen sulfide content of the gas is diminished by means of sulfidation of the sorbents to levels low enough to avoid the deactivation of the SMR catalyst. The used sorbents in the gas cleanup unit can either be replaced with fresh sorbents or regenerated in-situ with diluted air in parallel multiple sorbent beds.


Experimental data demonstrating the successful operation of the SMR with direct feeding of the SHR product stream is shown in FIG. 3. The concentrations of the gas measured at the exit of the SMR are plotted along with the SMR temperature profile. When the temperature of the SMR is low, the major product observed at the SMR exit is methane (since the SHR is the only reactor being operated). As the temperature of the SMR increases, the methane concentration decreases and a corresponding increase in the hydrogen and carbon monoxide concentrations is observed. The final composition of synthesis gas produced in the SMR has a H2:CO mole ratio of 3:1. More generally, the process of this invention can produce composition of synthesis gas having a H2:CO mole ratio range of 2:1 to 6.


The resulting effluent is a synthesis of gases rich in hydrogen, carbon monoxide, and steam. Approximately one third of the hydrogen produced in the SMR is recycled back to the HGR. Consequently, no outside source of hydrogen is needed to maintain steady state operation. The HGR and SMR processes, therefore, may be considered to be chemically self-sustaining. The remaining synthesis gas is then available for the production of fuels and process heat.


In an embodiment of the invention, the synthesis gas is fed to a Fischer-Tropsch reactor in a process that can produce a zero-sulfur, ultrahigh cetane value diesel-like fuel and valuable paraffin wax products. The absence of sulfur enables low pollutant and particle emitting diesel fuels to be realized. Useful by-products can be produced, foe example, purified water, which can be re-cycled to create the slurry feed into the process. The Fischer-Tropsch reactions also produce tail gas that contains hydrogen, CO, CO2, and some light hydrocarbon gases. Hydrogen can be stripped out of the tail gas and recycled either to the HGR or the Fischer-Tropsch reactor. Any small amounts of other gases such as CO and CO may be flared off.


Although the present invention and its advantages have been described in detail, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims. Moreover, the scope of the present application is not intended to be limited to the particular embodiments of the process and apparatus described in the specification. As one of ordinary skill in the art will readily appreciate from the disclosure of the present invention, processes and apparatuses, presently existing or later to be developed that perform substantially the same function or achieve substantially the same result as the corresponding embodiments described herein may be utilized according to the present invention. Accordingly, the appended claims are intended to include such processes and use of such apparatuses within their scope.

Claims
  • 1. A process for converting carbonaceous material to synthesis gas, comprising: simultaneously heating carbonaceous material in the presence of both hydrogen and steam, at a temperature and pressure sufficient to generate a stream of methane and carbon monoxide rich gas product;removing impurities from the producer gas stream; andsubjecting the resultant producer gas to steam methane reforming under conditions whereby synthesis gas comprising hydrogen and carbon monoxide is generated.
  • 2. The process of claim 1 wherein the impurities are removed from the producer gas stream substantially at said temperature.
  • 3. The process of claim 2 wherein the temperature is about 790° C. to about 850° C.
  • 4. The process of claim 1 wherein impurities are removed from the producer gas stream at substantially said pressure.
  • 5. The process of claim 4 wherein the pressure is about 132 psi to 560 psi
  • 6. The process of claim 1 wherein steam methane reforming is conducted under conditions whereby the composition of synthesis gas produced has a H2:CO mole ratio range of 2.1 to 6.1.
  • 7. The process of claim 1 wherein the steam methane reforming is conducted under conditions whereby the composition of synthesis gas produced has a H2:CO mole ratio of 3:1.
  • 8. The process of claim 1 wherein the carbonaceous material comprises municipal waste, biomass, wood, coal, or a natural or synthetic polymer.
  • 9. The process of claim 1 in which synthesis gas generated by the steam methane reforming is fed into a Fischer-Tropsch reactor under conditions whereby a liquid fuel is produced.
  • 10. A process for converting municipal waste, biomass, wood, coal, or a natural or synthetic polymer to synthesis gas, comprising: simultaneously heating carbonaceous material in the presence of both hydrogen and steam, at a temperature of about 790° C. to about 850° C. and pressure about 132 psi to 560 psi whereby to generate a stream of methane and carbon monoxide rich gas product;removing impurities from the producer gas stream substantially at said temperature and pressure;subjecting the resultant producer gas to steam methane reforming under conditions whereby to generate synthesis gas comprising hydrogen and carbon monoxide at a H2:CO mole ratio range of 2:1 to 6; andfeeding synthesis gas generated by the steam methane reforming into a Fischer-Tropsch reactor under conditions whereby a liquid fuel is produced.
  • 11. The process of claim 10 comprising transferring exothermic heat from the Fischer-Tropsch reaction to the hydro-gasification reaction and/or steam methane reforming reaction.
  • 12. An apparatus for converting carbonaceous material to synthesis gas, comprising: a hydro-gasification reactor for simultaneously heating carbonaceous material in the presence of both hydrogen and steam, at a temperature and pressure sufficient to generate a stream of methane and carbon monoxide rich gas product.
  • 13. The apparatus of claim 12 including a Fischer-Tropsch reactor for receiving synthesis gas generated by the steam methane reformer for producing a liquid fuel.
  • 14. The apparatus of claim 13, including means for transferring exothermic heat from the Fischer-Tropsch reaction to the hydro-gasification reactor and/or steam methane reformer.