Patent Publication Number: US-2022234019-A1

Title: Process of steam reforming with low carbon dioxide emissions

Description:
CROSS-REFERENCE TO RELATED APPLICATIONS 
     This patent application claims priority from Italian patent application no. 102019000008280 filed on Jun. 6, 2019, the entire disclosure of which is incorporated herein by reference 
     TECHNICAL FIELD 
     The present invention relates to a steam reforming process, in particular for producing synthesis gas, ensuring a high reduction of carbon dioxide emissions, higher than 90%. 
     BACKGROUND ART 
     As known, synthesis gas (syngas) is a gas mixture essentially formed by hydrogen (H2) and carbon monoxide (CO) and containing, in smaller amounts, methane (CH4), carbon dioxide (CO2), nitrogen and other inert gases. 
     The synthesis gas is commonly produced by means of a hydrocarbon (such as methane) steam reforming reaction, performed in a reforming reactor (reformer). 
     Generally the steam reforming process is performed in a tubular reactor composed of one or more rows of tubes arranged inside a combustion chamber, which provides heat for developing the reaction (which is highly endothermic) by means of heat exchange mainly by radiation. The tubular reactor can be possibly preceded by an adiabatic pre-reforming step and it is normally preceded by a charge purification step. Downstream of the reforming reactor it is known arranging a section for converting the carbon monoxide by a shift reaction, followed by a section for cooling the synthesis gas and purifying the obtained hydrogen, normally comprising a so-called Pressure Swing Adsorption (PSA) unit. 
     The known steam reforming processes are not completely satisfactory and have some drawbacks. 
     Firstly, the CO2 emissions related to the process are very significant: for each ton of hydrogen produced by this method, 9 tons of CO2 are produced as well. 
     Furthermore, the energy efficiency of the process, if integrated with a CO2-capturing step, is not satisfactory as regards emission reduction, if it is performed on the gas conversion section. Actually due to the combustion section importing combustible gas the maximum capture percentage is limited to about 65% of the total CO2 produced. For the alternative fume-capturing system this limit is overcome and it is possible to obtain a capture up to 90-95%, with resulting dramatic overall efficiency losses in generating the energy necessary for purification, together with an increase of installation costs, which can actually lead to doubling the overall cost of the plant. 
     DISCLOSURE OF INVENTION 
     It is an object of the present invention to provide a steam reforming process, in particular for producing synthesis gas, which overcomes the herein noted drawbacks of the prior art. 
     It is a further object of the invention to provide a process that is particularly advantageous as regards CO2-capturing efficacy and efficiency, using in particular a reforming reactor, used as a supplement to the traditional steam reformer, which is not affected by even relevant thermal expansions and which is not only fully efficient and reliable but also of simple and cost-effective construction and installation. Such reactor employs as heating means the gas effluent coming from the ultra-high temperature steam reformer (beyond 920° C.), allowing to keep a syngas at the outlet of the integrated section with a methane content that is lower than 2%, this result non being obtainable, cost-effectively, with the present integrated installations of the state of the art. 
     In particular, it is an object of the invention to provide a process that is advantageous in terms of operation costs and installation requirements, and that further allows for a high CO2 emission reduction (higher than 90%, approximately between 92 and 98%). 
     Such result can be obtained by coupling a specific equipment (gas heated reformer), described in the following paragraphs, into an innovative process chain which by providing a double shift section at medium and low temperature with intermediate cooling and a CO2-capturing unit allows to obtain a highly decarburized syngas (hydrogen content even beyond 97% prior to the PSA purification section). The possibility to use this syngas as a combustible for the reforming section (instead of methane or fuel gas) allows to obtain an overall very high CO2 capture, higher that at least 90% and even up to 98%, a result which cannot be reached by the current state of the art. 
     The present invention thus relates to a steam reforming process, in particular for producing synthesis gases, as defined in the enclosed claim  1 , and also, as regards the preferred additional characters, in the dependent claims. 
     The invention thus provides a steam reforming process which allows to avoid supplying combustible gas and generating exceeding high pressure steam, reducing the gas to be treated and improving the quality of the leaving synthesis gas and thus being particularly advantageous in terms of functioning costs and installation requirements, in addition to emission reduction. 
     Furthermore, the process of the invention is particularly advantageous in that it employs a reactor which, simply, cost-effectively and fully efficiently, avoids the problems typically related to high thermal expansions. 
     A steam reforming reactor substantially comprises a vessel which houses a bundle of tubes supported by a pair of tubesheets. A process fluid that is subject to one or more reactions passes through the tubes; a heating means provides heat to the tubes, for example through the circulation of a heating fluid which lightly touches the outside of the tubes in the region between the tubesheets. 
     In the steam reforming reactors a significant differential thermal expansion takes place between tubes and tubesheets supporting them and delimit the passage area of the heating fluid which provides heat to tubes and, therefore to the process fluid. 
     A situation such as the one just described occurs, for example, in steam reforming reactors where hydrocarbon reforming takes place for producing synthesis gas. Similar problems can be in any case found in other applications where significant differential thermal expansions occur. 
     In fact, the process fluid passing through the tubes is a reactant mixture containing hydrocarbons and steam and it is sent through the tubes, which are filled with a catalyst and are heated outside by a heating means, generally a hot gas which lightly touches the outside of the tubes. 
     The tubes of a reforming reactor have a considerable length, typically several metres, and are subject to significant temperature variations. Consequently, tubes are subject, in use, to significant thermal expansions in a longitudinal direction, typically in the order of several centimetres. As tubes are constrained to tubesheets, the thermal expansion may cause damages. 
     In order to overcome the problem, it is known providing the tube ends with devices that allow for a differential expansion. 
     The known systems may not however be completely satisfactory, in particular they may be complicated, not completely efficient or poorly reliable, relatively expensive during the production and installation step. 
     According to the invention, in the reforming process a reactor having characteristics such to avoid the problems related to tube thermal expansion is employed. 
    
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
       Further features and advantages of the present invention will become clear from the following description of an embodiment thereof, with reference to the figures in the appended drawings, wherein: 
         FIG. 1  is a longitudinal section schematic view of a reactor, in particular a steam reforming reactor, to be used in the reforming process according to the invention; 
         FIG. 2  is an enlarged scale view of the detail II in  FIG. 1 ; 
         FIG. 3  is a block diagram which illustrates the steam reforming process, in particular for producing synthesis gas, according to the invention and using of the reactor of  FIG. 1 . 
     
    
    
     BEST MODE FOR CARRYING OUT THE INVENTION 
     In  FIG. 1  a reactor, in particular a reforming reactor (or reformer), is generally indicated by 1. In the herein described non-limiting example, the reactor  1  is used in particular for steam reforming hydrocarbons for producing synthesis gases. 
     The reactor  1  comprises an outer vessel  2  extending along and about a longitudinal axis A. 
     In particular the vessel  2  has a substantially cylindrical central portion  3  and two axially opposite end caps  4 , provided with respective connectors  5  defining an inlet  7  and an outlet  8  for a process fluid passing through the reactor  1 . 
     The reactor  1  then comprises a tube bundle  10  formed by a plurality of reaction and thermal exchange tubes  11 , that extend parallel between each other and with the axis A inside the vessel  2  and precisely of the central portion  3 . 
     The tubes  11  are supported by an upper tubesheet  12  and a lower tubesheet  13 , placed at respective opposite longitudinal ends of the portion  3  and fixed to a side wall  14  of the vessel  2 . 
     Tubes  11  extend along respective longitudinal axes X, parallel to axis A of the reactor  1 , between respective longitudinal opposite ends  15 ,  16  respectively joined to the upper tubesheet  12  and to the lower tubesheet  13 . 
     Tubesheets  12 ,  13  are transversal and substantially perpendicular to the axis A and delimit inside the reactor  1 : a process fluid supply zone  21 ; a process and heat exchange zone  22 ; and a process fluid extracting zone  23 . 
     The process fluid supply zone  21  is placed above the upper tubesheet  12  and it is provided with the inlet  7  for supplying the process fluid. 
     The process and heat exchange zone  22  is placed between the two tubesheets  12 ,  13  and has an inlet duct  24  and an outlet duct  25  for a heating fluid, communicating with the inside of the reactor  1  through the vessel  2  side wall  14 . 
     The inlet duct  24  is placed near and above the lower tubesheet  13 , while the outlet duct  25  is placed near and below the upper tubesheet  12 . 
     The process fluid extracting zone  23  is placed below the lower tubesheet  13  and it is provided with the outlet  8  from which the process fluid leaves the reactor  1 . 
     The tubes  11  extend through the zone  22  and project axially from the tubesheets  12 ,  13  in the zones  21 ,  23  at the respective ends  15 ,  16  that are open to allow the passage of the process fluid. 
     If, as in the herein described example, the reactor  1  is intended for hydrocarbon steam reforming, tubes  11  are filled with a suitable catalyst, for example a nickel-based standard catalyst; tubes  11  are advantageously provided with supporting elements  25 , placed inside tubes  11  near the respective ends  16  and shaped so as to support the catalyst. 
     The zone  22  can optionally house deflectors or other conveying elements to guide at least partially the heating fluid along preferential paths and improve the heat exchange between the heating fluid and the tubes  11 . 
     For example, the tubes  11  are provided with respective sheath tubes  27  placed about respective tubes  11  and defining about the tubes  11  annular ducts wherein the heating fluid passes through. 
     The sheath tubes  27  extend from the upper tubesheet  12  until a pre-established height above the inlet duct  24 ; the sheath tubes  27  are closed on top, near the upper ends of tubes  11  and tubesheet  12 , and are open at the bottom to let the heating fluid enter. 
     The tubes  11  are fixed and optionally welded to the upper tubesheet  12 , for example by means of respective flanges  28  radially projecting from the ends  15  of the tubes  11  and rest on an upper face of the tubesheet  12  in the zone  21 . 
     The tubes  11  are connected to at least one of the tubesheets  12 ,  13 , for example to the lower tubesheet  13 , by means of respective expansion devices  30 , which allow the ends  16  of tubes  11  to slide axially with respect to the tubesheet  13  to compensate longitudinal thermal expansions of the tubes  11 . 
     In particular, as shown in greater detail in  FIG. 2 , each device  30  comprises a tubular sealed metal compensator  31  placed about the end  16  of the tube  11  and along the tube  11 . Each tube  11  is provided with an individual sealed metal compensator  31  acting on that tube  31  regardless of devices  30  and other tubes  11 . 
     In the shown non-limiting embodiment, though not necessarily, the sealed metal compensator  31  is substantially conformed as a bellows and extends along and about the axis X of the respective tube  11  and has an axial series of undulations, i.e. a series of annular ridge portions and annular throats alternate with one another. 
     The sealed metal compensator  31  is made of metal material, preferably multi-ply metal material (i.e. consisting of a plurality of plies of metal material layered and welded to one another). 
     The sealed metal compensator  31  is provided with a pair of opposite end portions  32 ,  33 , placed at respective axially opposite ends of the sealed metal compensator  31  and fluid-sealingly joined respectively to the tubesheet  13  and to an end  16  of a tube  11 . In particular, the opposite end portions  32 ,  33  of each sealed metal compensator  31  are respectively sealed to the tubesheet  13  and to an end  16  of a tube  11 . 
     In the illustrated embodiment, though not necessarily, the end portion  32  is welded to a connection element  34  projecting from a lower face of the tubesheet  13 . 
     Preferably, the end portions  32 ,  33  are defined by respective cylindrical collars about the axis X, and fitted about and welded to respective cylindrical contact surfaces of the connection element  34 , which is in turn defined by a cylindrical sleeve, and of the end  16  of the tube  11 . 
     According to an aspect of the invention, the reactor  1  is used in a hydrocarbon steam reforming process to produce synthesis gas. 
     The reactor  1  is therefore supplied with a process fluid containing a hydrocarbon feedstock, such as natural gas or methane, and steam. 
     The process fluid is supplied to the reactor  1  at high temperature and pressure through the inlet  7 ; in zone  21 , the process fluid penetrates the tubes  11 , crossing them top-down passing through the zone  22  where it receives heat from the heating fluid; passing through the tubes  11  the process fluid comes into contact with the catalyst and is subject to reforming reactions forming hydrogen. A reforming effluent leaves the tubes  11 , substantially containing hydrogen, steam, methane and carbon oxides, and passes through the zone  23  and then leaves the reactor  1  through the outlet  8 . 
     The heating fluid enters the zone  22  from the inlet duct  24 , crosses the zone  22  bottom-up exchanging heat with the tubes  11 , and is thus removed through the outlet duct  25 . 
     Thanks to the particular constructive feature of the reactor  1 , it can be advantageously integrated in a process layout where a steam reformer, in which the heat for the reforming reactions is provided by an external heating fluid, is associated with a gas heated reformer (GHR), in which the reformed effluent leaving the reformer is instead used as a heating fluid to provide heat to the process fluid to be reformed. 
     In particular, the reactor  1  is advantageously used as a gas-heated reformer in a steam reforming process for producing synthesis gases ensuring a high reduction of carbon dioxide emissions, higher than 90%, as hereinafter described in detail with reference to the diagram in  FIG. 3 . 
     In the process scheme illustrated in  FIG. 3 , a hydrocarbon feedstock gas stream, such as natural gas o methane, after being optionally pre-treated in a pre-treating or pre-reforming section  50 , is supplied to a first reforming section  51 , comprising a gas-heated reformer, where a steam reforming process takes place forming a partially reformed effluent, mainly containing hydrogen (H2), carbon monoxide (CO), water (H2O) and residual methane (CH4). 
     In the gas heated reformer, the heat necessary for the reforming reactions is supplied by a fraction of the partially reformed effluent leaving the same reformer. 
     The partially reformed effluent leaving the section  51  is sent to a second steam reforming section  52  where, in a radiant chamber placed outside the catalytic tubes, a combustion with air, optionally pre-treated in an air pre-treating section  53  (in particular, an air pre-treating section, where air is preheated), is performed, to have a higher carbon monoxide and hydrogen concentration and a lower concentration of residual methane. 
     From section  52  a synthesis gas is obtained which is then treated: in a synthesis gas shift and cooling section  54 , where carbon monoxide and water present in the synthesis gas react to give hydrogen and carbon dioxide; in a CO2-capturing section  55 , where carbon dioxide is removed from the synthesis gas; and finally in a separating section  56 , for example comprising a PSA (pressure swing adsorption) unit, to obtain a high concentration hydrogen gas stream. 
     Advantageously, the synthesis gas shift and cooling section  54  comprises a medium temperature shift unit and a low temperature shift unit connected in series; or a shift unit operating in a low temperature isotherm mode. 
     Tail gases extracted from the separating section  56  are recirculated to the reformer of section  52  together with a portion (adapted to fulfil the thermal demand of the steam reformer) of the decarburized syngas leaving the CO2-capturing section  55 . 
     In case an intermediate purity hydrogen is required (97%-98% of hydrogen content) instead of a high purity hydrogen, it would be possible to remove the PSA section  56 . 
     The described invention allows to avoid supplying combustible gas and generating exceeding high pressure steam, reducing the gas to be treated and improving the quality of the leaving synthesis gas and thus being particularly advantageous in terms of functioning costs and installation requirements, in addition to emission reduction. 
     It is understood that changes and variants can be brought to the herein described and illustrated process without departing from the scope of the enclosed claims.