Abstract:
An integrated process for hydrogen gas production includes:
       a. operating a water electrolysis cell with an external source of electricity to produce oxygen and hydrogen;   b. optionally operating an air separation unit to produce additional oxygen for the process;   c. introducing a hydrocarbon feedstock into a membrane wall gasification reactor with an ash-forming material and steam, and oxygen from the electrolysis cell and, optionally, oxygen from the air separation unit to produce hot raw synthesis gas;   d. passing the hot raw synthesis gas from the gasification reactor to a steam-generating heat exchanger to produce steam and a cooled raw synthesis gas;   e. introducing the steam generated in the heat exchanger into a turbine to produce electricity to operate the electrolysis cell; and   f. recovering the hydrogen gas from the water electrolysis cell and, optionally, subjecting the synthesis gas to a water-gas shift reaction to increase the hydrogen content and recovering the hydrogen.

Description:
RELATED APPLICATIONS 
       [0001]    This application claims priority to provisional patent application U.S. Ser. No. 61/659,206 filed Jun. 13, 2012, the contents of which are incorporated herein by reference. 
     
    
     BACKGROUND OF THE INVENTION 
       [0002]    1. Field of the Invention 
         [0003]    The present invention relates to processes for the production of hydrogen from an integrated water electrolysis cell and hydrocarbon gasification reactor. 
         [0004]    2. Description of Related Art 
         [0005]    Gasification is well known in the art and it is practiced worldwide with application to solid and heavy liquid fossil fuels, including refinery bottoms. The gasification process uses partial oxidation to convert carbonaceous materials, such as coal, petroleum, biofuel, biomass and other hydrocarbon-containing materials with oxygen at high temperature, i.e., greater than 800° C., into a synthesis gas (“syngas”), steam and electricity. The syngas consists of carbon monoxide and hydrogen and can be burned directly in internal combustion engines, or used in the manufacture of various chemicals, such as methanol via known synthesis processes, and to make synthetic fuels via the Fischer-Tropsch process. 
         [0006]    For refining applications, the main process block is known as the Integrated Gasification Combined Cycle (IGCC), which converts the feedstock into hydrogen, power and steam.  FIG. 1  shows the process flow diagram of a conventional IGCC system  100  of the prior art, which includes a feed preparation section  102 , a gasification reactor  104 , an air separation unit  180 , a syngas quench and cooling unit  110 , a water-gas shift reactor  120 , an acid gas removal (AGR) and sulfur recovery unit (SRU)  130 , a gas turbine  140 , a heat recovery steam generator (HRSG)  150 , and a steam turbine  160 . 
         [0007]    In a conventional IGCC, a feedstock is introduced via a feed line  101  to the feed preparation section  102 . The prepared feedstock is then passed to the gasification reactor  104  with a predetermined amount of oxygen  103  produced from the air separation unit  180 . The feedstock is partially oxidized in the gasification reactor  104  to produce a hot syngas  106  which is conveyed to the syngas quench and cooling unit  110 . Hot syngas  106  is cooled with boiler feed water  156  to produce cooled syngas  114  and steam. A portion of the steam (steam  112 ) is used in the water-gas shift reactor  120  to produce shifted gas  122 , and another portion of the steam (steam  116 ) is consumed in the heat recovery steam generator  150 . Shifted gas  122  is treated in the AGR/SRU  130  to separate carbon dioxide  136 , sulfur  138 , and hydrogen syngas recovery  132 . A portion of the hydrogen syngas recovery  132  (gas turbine feed  134 ) is passed to the gas turbine  140  with air feed  142  to produce electricity  144 . High pressure discharge  146  from the gas turbine  140  is conveyed to the HRSG  150  to generate steam which is used in the steam turbine  160  to produce additional electricity  162 . 
         [0008]    The air separation unit  180  and most of the downstream processes utilize mature technologies with high on-stream reliability factors. However, the gasification reactor  104  has a relatively limited lifetime that can be as short as from 3 to 18 months, depending upon the characteristics of the feed and the design of the unit. 
         [0009]    Three principal types of gasification reactor technologies are moving bed, fluidized bed and entrained-flow systems. Each of the three types can be used with solid fuels, but only the entrained-flow reactor has been demonstrated to efficiently process liquid fuels. In an entrained-flow reactor, the fuel, oxygen and steam are injected at the top of the gasifier through a co-annular burner. The gasification reaction usually takes place in a refractory-lined vessel which operates at a pressure of about 40 bars to 60 bars and a temperature in the range of from 1300° C. to 1700° C. 
         [0010]    There are two types of gasifier wall construction: refractory and membrane. The gasifier conventionally uses refractory liners to protect the reactor vessel from corrosive slag, thermal cycling, and elevated temperatures that range from 1400° C. to 1700° C. The refractory wall is subjected to the penetration of corrosive components from the generation of the syngas and slag, and thus subsequent reactions in which the reactants undergo significant volume changes that result in strength degradation of the refractory materials. The replacement of refractory linings can cost several millions of dollars a year and several weeks of downtime for a given reactor. Up until now, the solution has been the installation of a second or parallel gasifier to provide the necessary continuous operating capability, but the undesirable consequence of this duplication is a significant increase in the capital costs associated with the unit operation. 
         [0011]    On the other hand, membrane wall gasifier technology uses a cooling screen protected by a layer of refractory material to provide a surface on which the molten slag solidifies and flows downwardly to the quench zone at the bottom of the reactor. The advantages of the membrane wall reactor include reduced reactor dimensions as compared to other systems; an improved average on-stream time of 90%, as compared to an on-stream time of 50% for a refractory wall reactor; elimination of the need to have a parallel reactor to maintain continuous operation as in the case of refractory wall reactors; and the build-up of a layer of solid and liquid slag that provides self-protection to the water-cooled wall sections. 
         [0012]    In a membrane wall gasifier, the build-up of a layer of solidified mineral ash slag on the wall acts as an additional protective surface and insulator to minimize or reduce refractory degradation and heat losses through the wall. Thus the water-cooled reactor design avoids what is termed “hot wall” gasifier operation, which requires the construction of thick multiple-layers of expensive refractories which will remain subject to degradation. In the membrane wall reactor, the slag layer is renewed continuously with the deposit of solids on the relatively cool surface. The solids that form the slag must be introduced in the hydrocarbon feed in whole or in part. Where the hydrocarbon feed contains insufficient or no ash forming material, it must be supplemented or provided entirely by a source of ash in a separate feed. Further advantages include short start-up/shut down times; lower maintenance costs than the refractory type reactor; and the capability of gasifying feedstocks with high ash content, thereby providing greater flexibility in treating a wider range of coals, petcoke, coal/petcoke blends, biomass co-feed, and liquid feedstocks. 
         [0013]    There are two principal types of membrane wall reactor designs that are adapted to process solid feedstocks. One such reactor uses vertical tubes in an up-flow process equipped with several burners for solid fuels, e.g., petcoke. A second solid feedstock reactor uses spiral tubes and down-flow processing for all fuels. For solid fuels, a single burner having a thermal output of about 500 MWt has been developed for commercial use. In both of these reactors, the flow of pressurized cooling water in the tubes is controlled to cool the refractory and ensure the downward flow of the molten slag. Both systems have demonstrated high utility with solid fuels, but not with liquid fuels. 
         [0014]    For the production of liquid fuels and petrochemicals, a key parameter is the mole ratio of hydrogen-to-carbon monoxide in the dry syngas. This ratio is usually between 0.85:1 and 1.2:1, depending upon the feedstock characteristics. Thus, additional treatment of the syngas is needed to increase this ratio up to 2:1 for Fischer-Tropsch applications through the water-gas shift reaction represented by CO+H 2 O→CO 2 +H 2 . In some cases, part of the syngas is burned together with some off gases in a combined cycle to produce electricity and steam. The overall efficiency of this process is between 44% and 48%. 
         [0015]    Electrolysis of water is the decomposition of water into oxygen and hydrogen gas by passing an electric current through the water.  FIG. 2  shows a schematic diagram of an electrochemical cell which has two electrodes: a cathode and an anode. The electrodes are placed in the water and externally connected with a power supply. At a certain critical voltage, hydrogen is produced at the cathode and oxygen is produced at the anode. The reactions proceed as follows: 
         [0000]      2H + (aq)+2e − →H 2 (g) (cathode)   (1)
 
         [0000]      4OH − (aq)→2H 2 O+O 2 (g)+4e − (anode)   (2)
 
         [0016]    The minimum necessary cell voltage for the start-up of electrolysis, E 0   cell , is given under standard conditions, as represented by the following: 
         [0000]    
       
         
           
             
               
                 
                   
                     E 
                     Cell 
                     0 
                   
                   = 
                   
                     
                       
                         - 
                         Δ 
                       
                        
                       
                           
                       
                        
                       
                         G 
                         0 
                       
                     
                     nF 
                   
                 
               
               
                 
                   ( 
                   3 
                   ) 
                 
               
             
           
         
       
     
         [0017]    where ΔG 0  is the change in the Gibbs free energy under standard conditions;
       n is the number of electrons transferred; and   F is Faraday&#39;s constant which is 96,485 C.       
 
         [0020]    There are three types of water electrolyzers categorized by the types of electrolyte used: alkaline, proton exchange membrane and solid oxide. The most common type is the alkaline electrolyzer which can be either unipolar or bipolar.  FIG. 3  is a schematic diagram of a unipolar electrolyzer of the prior art. The unipolar electrolyzer resembles a tank and has electrodes connected in parallel. A membrane or a diaphragm is placed between the cathode and anode, which separates the hydrogen and oxygen as the gases are produced, but allows the transfer of ions. The bipolar electrolyzer resembles a filter press. Bipolar electrolyzers consist of many cells, as many as 100-160, which are connected in series to the circuit. Each electrode, with the exception of the two terminal electrodes, functions as a cathode at one end and an anode at the other. Electrolysis cells are connected in series, and hydrogen is produced on one side of the cell and oxygen on the other side of the cell. 
         [0021]    In general, the operating conditions for electrolysis plants with normal or slightly elevated pressure includes an electrolyte temperature in the range of from 70 to 90° C., a cell voltage in the range of from 1.85 to 2.05 V, a power consumption in the range of from 4 to 5 KWh/m 3 , and a hydrogen production at a purity of 99.8% or higher. Pressure electrolysis units operate at a pressure in the range of from 6 to 200 bars, and the operating pressure has no significant influence on the power consumption. Because of its high energy consumption and substantial capital investment, water electrolysis is currently used for only 4% of world hydrogen production. 
         [0022]    It is also known that operation of the electrolysis cell at high temperatures improves the efficiency. This optional heating step can be used to advantage when a high temperature heat source is available to increase the cell operating temperature. 
         [0023]    While both the gasification and water electrolysis processes are well developed and suitable for their intended purposes, their combination and applications in conjunction with upgrading crude oil and its fractions do not appear to have been developed. 
         [0024]    The problem addressed by the present invention is therefore to provide a method for the economical production of hydrogen from an integrated water electrolysis cell and hydrocarbon gasification reactor. 
       SUMMARY OF THE INVENTION 
       [0025]    The present invention broadly comprehends the production of hydrogen from an integrated water electrolysis cell and hydrocarbon gasification reactor. 
         [0026]    In accordance with one embodiment, the integrated process for the production of hydrogen gas includes the steps of: 
         [0027]    a. introducing water into an electrolysis cell and operating the electrolysis cell with an external source of electricity to produce oxygen and hydrogen; 
         [0028]    b. introducing a hydrocarbon feedstock into a membrane wall gasification reactor with an external source of steam and optionally a source of ash, and the oxygen produced from the electrolysis cell; 
         [0029]    c. subjecting the hydrocarbon feedstock to partial oxidation to produce a hot raw synthesis gas; 
         [0030]    d. passing the hot raw synthesis gas to a steam generating heat exchanger to produce steam and a cooled raw synthesis gas; 
         [0031]    e. introducing the steam into a turbine to produce electricity; 
         [0032]    f. operating the electrolysis cell with the electricity produced from step (e); and 
         [0033]    g. recovering the hydrogen gas from the electrolysis cell. 
         [0034]    In accordance with another embodiment, the process for the production of hydrogen gas includes the steps of: 
         [0035]    a. introducing water into an electrolysis cell and operating the electrolysis cell with an external source of electricity to produce oxygen and hydrogen; 
         [0036]    b. introducing air into an air separation unit to produce oxygen; 
         [0037]    c. introducing a hydrocarbon feedstock into a membrane wall gasification reactor with an external source of steam and ash, and a combined oxygen stream composed of oxygen produced from the electrolysis cell and oxygen recovered from the air separation unit; 
         [0038]    d. subjecting the hydrocarbon feedstock to partial oxidation to produce a hot raw synthesis gas; 
         [0039]    e. passing the hot raw synthesis gas to a steam generating heat exchanger to produce steam and a cooled raw synthesis gas; 
         [0040]    f. introducing the steam from the heat exchanger into a turbine to produce electricity; 
         [0041]    g. operating the electrolysis cell with the electricity produced from step (f); and 
         [0042]    h. recovering the hydrogen gas from the electrolysis cell. 
         [0043]    In accordance with additional embodiments, a process and apparatus for the production of hydrogen gas further includes a water-gas shift reaction vessel for subjecting the synthesis gas to the water-gas shift reaction represented by CO+H 2 O→CO 2 +H 2 , to thereby increase the volume of hydrogen in the shifted syngas. 
         [0044]    Other aspects, embodiments, and advantages of the process of the present invention are discussed in detail below. Moreover, it is to be understood that both the foregoing information and the following detailed description are merely illustrative examples of various aspects and embodiments, and are intended to provide an overview or framework for understanding the nature and character of the claimed features and embodiments. The accompanying drawings are included to provide illustration and a further understanding of the various aspects and embodiments. The drawings, together with the remainder of the specification, serve to explain principles and operations of the described and claimed aspects and embodiments. 
         [0045]    The economic advantages of the integrated process of the invention will vary with the local costs and availability of electricity, raw materials and process gases, e.g., oxygen and hydrogen. As will be apparent to one of ordinary skill in the art, the costs for engineering, design, construction, operation and maintenance of the water electrolysis unit are favorable when compared to those of an air separation plant. 
     
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
         [0046]    The foregoing summary, as well as the following detailed description will be best understood when read in conjunction with the attached drawings in which: 
           [0047]      FIG. 1  is a schematic diagram of an integrated gasification-combined cycle process of the prior art; 
           [0048]      FIG. 2  is a schematic diagram of an electrochemical cell of the prior art; 
           [0049]      FIG. 3  is a schematic diagram of a unipolar electrolyzer or electrolysis cell of the prior art; 
           [0050]      FIG. 4  is a schematic diagram of one embodiment of the process of the present invention for the production of hydrogen gas from an integrated water electrolysis cell and hydrocarbon gasification reactor; 
           [0051]      FIG. 5  is a schematic diagram of another embodiment of the process for the production of hydrogen gas from an integrated water electrolysis cell and hydrocarbon gasification reactor; 
           [0052]      FIG. 6  is a schematic diagram of an integrated crude oil upgrading process for the production of combined distillates products, and the production of hydrogen gas from a vacuum residue feedstock; 
           [0053]      FIG. 7  is a schematic diagram of an integrated crude oil upgrading process for the production of upgraded hydrocarbon products, and the production of hydrogen gas from a vacuum residue feedstock; 
           [0054]      FIG. 8  is a schematic diagram of an integrated crude oil upgrading process for the production of upgraded hydrocarbon products, and the production of hydrogen gas from a petcoke feedstock; and 
           [0055]      FIG. 9  is a schematic diagram of an integrated crude oil upgrading process for the production of upgraded hydrocarbon products, and the production of hydrogen gas from asphalt feedstock. 
       
    
    
     DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS 
       [0056]    Two embodiments for the production of hydrogen gas from an integrated water electrolysis cell and hydrocarbon gasification reactor will be described with reference to the schematic diagram of  FIGS. 4 and 5 . 
         [0057]    Referring to  FIG. 4 , an integrated water electrolysis cell and hydrocarbon gasification reactor apparatus  200  includes an electrolysis cell  210 , a turbine  220 , a membrane wall gasification reactor  230 , a heat exchanger  236 , and a water-gas shift reaction vessel  240 . Note that while the embodiment of apparatus  200  described herein includes a water-gas shift reaction vessel to enhance the output of hydrogen by conversion of some or all of the carbon monoxide in the syngas, alternative embodiments similar to apparatus  200  can be practiced without the water-gas shift reaction vessel. 
         [0058]    Electrolysis cell  210  includes an inlet for receiving water, an outlet for discharging produced oxygen and an outlet for discharging produced hydrogen. Electrolysis cell  210  is initially operated using an external source of electricity  208 . The energy requirement is then switched to the electricity  207  produced by turbine  220  using steam  206  generated from membrane wall gasification reactor  230 . The energy requirement for electrolysis cell  210  may be supplemented by external source of electricity  208  in case the supply of electricity  207  is insufficient. 
         [0059]    Membrane wall gasification reactor  230  includes an inlet for introducing a mixture of a hydrocarbon feedstock, a controlled amount of steam and optionally an ash-containing material, and oxygen produced by the electrolysis cell  210 . Membrane wall gasification reactor  230  also includes an outlet for discharging hot raw syngas. Heat exchanger  236  includes an inlet for receiving hot raw syngas discharged from membrane wall gasification reactor  230 , an outlet for discharging a cooled raw syngas and an outlet for discharging steam. 
         [0060]    The optional water-gas shift reaction vessel  240  includes an inlet for receiving cooled raw syngas  209  discharged from heat exchanger  236 , and a conduit for introducing a controlled amount of steam. Water-gas shift reaction vessel  240  also includes an outlet for discharging the hydrogen rich shifted syngas product. 
         [0061]    In the practice of the method of this embodiment, water  201  is introduced into electrolysis cell  210  which is initially operated using an external source of electricity  208  to produce oxygen  202  and hydrogen  203 . A hydrocarbon feedstock  204  is introduced as a pressurized feedstream into the membrane wall gasification reactor  230  along with a predetermined amount of steam  205  and ash  213 , and oxygen  202  produced from electrolysis cell  210 . The hydrocarbon feedstock  204  is partially oxidized in the membrane wall gasification reactor  230  to produce hydrogen and carbon monoxide in the form of a hot raw syngas. 
         [0062]    Hot raw syngas is passed to the heat exchanger  236  to produce a cooled raw syngas  209 . Steam  206  discharged from the heat exchanger  236  is passed to turbine  220  to produce electricity  207  for the sustained operation of electrolysis cell  210  without or with a limited requirement for external electricity  208 . 
         [0063]    In certain embodiments, at least a portion of the cooled raw syngas  209  is conveyed to the water-gas shift reaction vessel  240  with a predetermined amount of steam  211 . Hydrogen production is increased through the water-gas shift reaction in the presence of steam represented by CO+H 2 O→CO 2 +H 2 . The content of carbon monoxide is reduced to less than 1 mole % after the water-gas shift reaction. A mixture of hydrogen, carbon dioxide, unreacted carbon monoxide and other impurities is discharged via an outlet as shifted syngas  212 . High purity hydrogen gas is optionally recovered by a process such as pressure swing adsorption (PSA), or by use of membranes, absorption, adsorption, or a combination thereof. 
         [0064]    Referring now to  FIG. 5 , another embodiment of an integrated water electrolysis cell and hydrocarbon gasification reactor apparatus  300  is schematically illustrated. Apparatus  300  includes an electrolysis cell  310 , a turbine  320 , a membrane wall gasification reactor  330 , a heat exchanger  336 , a water-gas shift reaction vessel  340 , and an air separation unit  350 . Note that while the embodiment of apparatus  300  described herein includes a water-gas shift reaction vessel to enhance the output of hydrogen by conversion of some or all of the carbon monoxide in the syngas, alternative embodiments similar to apparatus  300  can be practiced without the water-gas shift reaction vessel. 
         [0065]    Electrolysis cell  310  includes an inlet for receiving water, an outlet for discharging produced oxygen  302   a  and an outlet for discharging produced hydrogen  303 . Electrolysis cell  310  is initial operated using an external source of electricity  308 . The energy source is then at least partially switched to the electricity  307  produced by turbine  320  using steam  306  generated by hot syngas from membrane wall gasification reactor  330 , while continuing supply the electrolysis cell  310  with the external source of electricity  308 . This increases the oxygen output from the electrolysis cell  310 , which improves the efficiency of hydrocarbon gasification in the membrane wall reactor  330 . Air separation unit  350  includes an inlet for receiving air and an outlet for discharging separated oxygen  302   b.    
         [0066]    Membrane wall gasification reactor  330  includes an inlet for introducing a mixture of a hydrocarbon feedstock  304 , a controlled amount of steam  305  and optionally an ash-containing material  313 , and a combined oxygen stream  302  which composed of oxygen  302   a  produced from the electrolysis cell  310  and oxygen  302   b  recovered from air separation unit  350 . Membrane wall gasification reactor  330  also includes an outlet for discharging hot raw syngas. Heat exchanger  336  includes an inlet for receiving hot raw syngas discharged from membrane wall gasification reactor  330 , an outlet for discharging a cooled raw syngas and an outlet for discharging steam. 
         [0067]    The optional water-gas shift reaction vessel  340  includes an inlet for receiving cooled raw syngas  309  discharged from heat exchanger  336 , and a conduit for introducing a controlled amount of steam. Water-gas shift reaction vessel  340  also includes an outlet for discharging the hydrogen-rich shifted syngas product. 
         [0068]    In the practice of the method of this embodiment, water  301  is introduced into electrolysis cell  310  which is initially operated using an external source of electricity  308  to produce oxygen  302   a  and hydrogen  303 . A hydrocarbon feedstock  304  is introduced as a pressurized feedstream into the membrane wall gasification reactor  330  along with a predetermined amount of steam  305  and ash  313 , and a combined stream of oxygen  302  which composed of oxygen  302   a  produced from electrolysis cell  310  and oxygen  302   b  recovered from air separation unit  350 . The additional oxygen  302   b  increases the oxygen input to gasification reactor  330 , which improves the efficiency of hydrocarbon oxidation. 
         [0069]    The hydrocarbon feedstock  304  is partially oxidized in the membrane wall gasification reactor  330  to produce hydrogen and carbon monoxide in the form of a hot raw syngas. Hot raw syngas is passed to the heat exchanger  336  to produce a cooled raw syngas  309 . Steam  306  discharged from heat exchanger  336  is passed to turbine  320  to produce electricity  307  for the sustained operation of electrolysis cell  310  without or with a reduced requirement for the externally supplied electricity  308 . 
         [0070]    In certain embodiments, at least a portion of the cooled raw syngas  309  is conveyed to the water-gas shift reaction vessel  340  with a predetermined amount of steam  311 . Hydrogen production is increased through the water-gas shift reaction in the presence of steam represented by CO+H 2 O→CO 2 +H 2 . The content of carbon monoxide is reduced to less than 1 mole % after the water-gas shift reaction. A mixture of hydrogen, carbon dioxide, unreacted carbon monoxide and other impurities is discharged via an outlet as shifted syngas  312 . High purity hydrogen gas is optionally recovered by a process such as pressure swing adsorption (PSA), or by use of membranes, absorption, adsorption, or a combination thereof. 
         [0071]      FIGS. 6-9  illustrate applications of the integrated electrolysis and gasification unit in various crude oil upgrading processes.  FIG. 6  is a schematic diagram of an integrated crude oil upgrading process and apparatus  400  for the production of combined distillates products, and the production of hydrogen gas from vacuum residue feedstock. Apparatus  400  includes an atmospheric distillation unit (ADU), a vacuum distillation unit (VDU) and an integrated water electrolysis cell and hydrocarbon gasification reactor as shown in  FIG. 4  or  5 . For simplicity of illustration in the drawings, the integrated water electrolysis cell and hydrocarbon gasification reactor apparatus is hereinafter referred to as “Electrolysis Gasification Island.” 
         [0072]    Referring to  FIG. 6 , crude oil  1  is introduced into the ADU to produce distillates  2  and an atmospheric residue  3 . The atmospheric residue  3  is the passed to the VDU to produce vacuum distillates  4  and a vacuum residue  6 . A combined distillates  5  is recovered containing distillates  2  and vacuum distillates  4 . The vacuum residue  6  is introduced into the membrane wall gasification reactor as the feedstock to produce hydrogen gas as described above in connection with  FIGS. 4 and 5 . 
         [0073]      FIG. 7  is a schematic diagram of an integrated crude oil upgrading process and apparatus  500  for the production of upgraded hydrocarbon products, and the production of hydrogen gas from vacuum residue feedstock. Apparatus  500  includes an ADU, a VDU, a hydrotreating unit, a hydrocracking unit and an Electrolysis Gasification Island. Crude oil  1  is introduced into the ADU to produce distillates  2   a  and an atmospheric residue  3 . Distillates  2   a  are hydrotreated with an external source of hydrogen to produce hydrotreated distillates  2   b.  Atmospheric residue  3  is passed to the VDU to produce vacuum distillates  4   a  and vacuum residue  6 . Vacuum distillates stream  4   a  is hydrocracked with an external source of hydrogen to produce hydrocracked vacuum distillates  4   b.  A combined upgraded hydrocarbon stream  5  is recovered from hydrotreated distillates  2   b  and hydrocracked vacuum distillates  4   b.    
         [0074]    Vacuum residue  6  is introduced into the membrane wall gasification reactor as the feedstock to produce hydrogen gas as described above in connection with  FIGS. 4 and 5 . Hydrogen produced from the Electrolysis Gasification Island is recovered as the hydrogen source for the hydrotreating unit and hydrocracking unit, thereby minimizing the external hydrogen requirement. 
         [0075]      FIG. 8  is a schematic diagram of an integrated crude oil upgrading process and apparatus  600  for the production of upgraded hydrocarbon products, and the production of hydrogen gas from a petroleum coke, or petcoke, feedstock. Apparatus  600  includes an ADU, a VDU, a hydrotreating unit, a hydrocracking unit, a coking unit and an Electrolysis Gasification Island. Crude oil  1  is introduced into the ADU to produce distillates  2   a  and an atmospheric residue  3 . Distillates  2   a  are hydrotreated with an external source of hydrogen to produce hydrotreated distillates  2   b.  Atmospheric residue  3  is passed to the VDU to produce vacuum distillates  4   a  and a vacuum residue  6 . Vacuum distillates  4   a  are hydrocracked with an external source of hydrogen to produce hydrocracked vacuum distillates  4   b.  A combined upgraded hydrocarbon stream  5  is recovered from hydrotreated distillates  2   b  and hydrocracked vacuum distillates  4   b.    
         [0076]    Vacuum residue  6  is introduced into the coking unit to produce coker distillates  6   b  and petcoke  6   a.  The coker distillates  6   b  are recycled to the steps of hydrotreating and hydrocracking. The petcoke  6   a  is conveyed to the membrane wall gasification reactor as the feedstock to produce hydrogen gas as described above in connection with  FIGS. 4 and 5 . Hydrogen produced from the Electrolysis Gasification Island is recovered as the hydrogen source for the hydrotreating unit and hydrocracking unit, thereby minimizing the hydrogen requirements from an external source. 
         [0077]      FIG. 9  is a schematic diagram of an integrated crude oil upgrading process and apparatus  700  for the production of an upgraded hydrocarbon stream, and the production of hydrogen gas from asphalt feedstock. Apparatus  700  includes an ADU, a VDU, a hydrotreating unit, a hydrocracking unit, a solvent deasphalting unit and an Electrolysis Gasification Island. Crude oil  1  is introduced into the ADU to produce distillates  2   a  and an atmospheric residue  3 . Distillates  2   a  are hydrotreated with an external source of hydrogen to produce hydrotreated distillates  2   b.  Atmospheric residue  3  is passed to the VDU to produce vacuum distillates  4   a  and a vacuum residue  6 . Vacuum distillates  4   a  are hydrocracked with an external source of hydrogen to produce hydrocracked vacuum distillates  4   b.  A combined upgraded hydrocarbon stream  5  is recovered from hydrotreated distillates  2   b  and hydrocracked vacuum distillates  4   b.    
         [0078]    Vacuum residue  6  is introduced into the solvent deasphalting unit to produce deasphalted oil  6   b  and asphalt  6   a.  Deasphalted oil  6   b  is recycled to the hydrocracking unit. Asphalt  6   a  is conveyed to the membrane wall gasification reactor as the feedstock to produce hydrogen gas as described above in connection with  FIGS. 4 and 5 . Hydrogen produced from the Electrolysis Gasification Island is recovered as a hydrogen source for the hydrotreating unit and hydrocracking unit to minimize the hydrogen requirement from the external source. 
         [0079]    In general, the operating conditions for the membrane wall gasification reactor include a temperature in the range of from 900° C. to 1800° C.; a pressure in the range of from 20 bars to 100 bars; a mole ratio of oxygen-to-carbon content of the feedstock in the range of from 0.5:1 to 10:1, in certain embodiments from 1:1 to 5:1, and in further embodiments from 1:1 to 2:1; a mole ratio of steam-to-carbon content of the feedstock in the range of from 0.1:1 to 10:1, in certain embodiments from 0.1:1 to 2:1, and in further embodiments from 0.4:1 to 0.6:1. 
         [0080]    In general, the operating conditions for the water electrolysis cell include a temperature in the range of from 10° C. to 70° C.; a pressure in the range of from 1 to 30 bars; and a voltage in the range of from 1 to 5 V. 
         [0081]    The properties of the syngas subjected to the water-gas shift reaction are at a temperature in the range of from 150° C. to 400° C.; a pressure in the range of from 1 bar to 60 bars; and a mole ratio of water-to-carbon monoxide in the range of from 5:1 to 3:1. 
         [0082]    The operating conditions for the coking, solvent deasphalting, hydrotreating and hydrocracking units are as follows: 
         [0000]    
       
         
               
             
               
               
               
             
               
               
               
               
             
           
               
                 TABLE 1 
               
             
             
               
                   
               
               
                 Operating Conditions 
               
             
          
           
               
                 Process Units 
                 Operable Range 
                 Preferred Range 
               
               
                   
               
             
          
           
               
                 Delayed Coking 
                   
                   
                   
               
               
                 Temperature 
                 ° C. 
                 425-650  
                 450-510 
               
               
                 Pressure 
                 Bar 
                 1-20 
                 1-7 
               
               
                 Hydrotreating 
               
               
                 Temperature 
                 ° C. 
                 300-400  
                 320-380 
               
               
                 Pressure 
                 Bar 
                 20-100 
                 30-60 
               
               
                 LHSV 
                 h −1   
                 0.5-10   
                 1-2 
               
               
                 H2/Oil 
                 SLt/Lt 
                 100-500  
                 100-300 
               
               
                 Catalyst Support 
                   
                 Alumina or Silica- 
                 Alumina or Silica- 
               
               
                   
                   
                 Alumina 
                 Alumina 
               
               
                 Catalyst Active Metals 
                   
                 Group VI, VII or 
                 Co/Mo or Ni/Mo or 
               
               
                   
                   
                 VIIIB 
                 Co/Ni/Mo 
               
               
                 Hydrocracking 
               
               
                 Temperature 
                 ° C. 
                 350-500  
                 350-450 
               
               
                 Pressure 
                 Bar 
                 50-200 
                  80-150 
               
               
                 LHSV 
                 h −1   
                 0.5-5   
                 0.5-2   
               
               
                 H2/Oil 
                 SLt/Lt 
                 500-2500 
                  500-1000 
               
               
                 Catalyst Support 
                   
                 Alumina or Silica- 
                 Alumina or Silica- 
               
               
                   
                   
                 Alumina or Zeolites 
                 Alumina 
               
               
                 Catalyst Active Metals 
                   
                 Group VI, VII 
                 Co/Mo or Ni/Mo 
               
               
                   
                   
                 or VIIIB 
                 or Co/Ni/Mo 
               
               
                 Solvent Deasphalting 
               
               
                 Temperature 
                 ° C. 
                 below the solvent&#39;s 
                 below the solvent&#39;s 
               
               
                   
                   
                 critical temperature 
                 critical temperature 
               
               
                 Pressure 
                 Bar 
                 below the solvent&#39;s 
                 below the solvent&#39;s 
               
               
                   
                   
                 critical pressure 
                 critical pressure 
               
               
                 Solvents to oil Ratio 
                 h −1   
                 1:20 to 20:1 
                 1:5 to 5:1 
               
               
                 Adsorbent 
                   
                 attapulgus clay, alumina, silica, 
                 attapulgus clay, alumina, silica, 
               
               
                   
                   
                 activated carbon, spent zeolites, 
                 activated carbon, spent zeolites, 
               
               
                   
                   
                 spent catalysts composed of 
                 spent catalysts composed of 
               
               
                   
                   
                 alumina and silica alumina, 
                 alumina and silica alumina, 
               
               
                   
                   
                 and mixtures thereof. 
                 and mixtures thereof. 
               
               
                 Adsorbent to Oil Ratio 
                   
                 20:0.1 W/W, and 
                 5:0.1 W/W, and 
               
               
                   
                   
                 preferably 10:1 W/W 
                 preferably 5:1 W/W 
               
               
                 Adsorbent Surface area 
                 m 2 /g 
                 10-500 
                  10-500 
               
               
                 Adsorbent Pore Size 
                 °A 
                  10-5000 
                  10-750 
               
               
                 Adsorbent pore volume 
                 cc/g 
                 0.1-0.5  
                 0.1-0.4 
               
               
                   
               
             
          
         
       
     
         [0083]    Distinct advantages are offered by the apparatus and processes described. Valuable hydrogen and oxygen gases and electricity can be efficiently produced for on-site refinery use. In particular, the oxygen produced by the water electrolysis cell is supplied to the gasification reactor, while electricity indirectly produced from the operation of the gasification reactor is provided to power the water electrolysis cell. The need for a costly air separation unit is fully or partially eliminated. The process of the present invention can be practiced to particular advantage when hydrogen is needed for hydroprocessing and natural gas is not available. This is usually the case in refineries when full conversion is required to meet the demand for cleaner and lighter products, such as gasoline, jet fuel, and diesel transportation fuels. 
       EXAMPLE 
       [0084]    The apparatus described in  FIG. 7  is used to illustrate the present invention. A one hundred thousand barrels per day (KBPD) of Arab light crude oil, the properties of which are shown in Table 2 below, was introduced as a feedstock into an ADU and the atmospheric residue passed to a VDU. 
         [0000]    
       
         
               
             
               
               
               
             
               
               
               
             
           
               
                 TABLE 2 
               
             
             
               
                   
               
               
                 Properties of Arab Light Crude Oil 
               
             
          
           
               
                   
                 Name 
                 Crude Oil 
               
               
                   
                   
               
             
          
           
               
                   
                 SG 
                 0.869 
               
               
                   
                 API Gravity 
                 31.4 
               
               
                   
                 Sulfur, W % 
                 1.94 
               
               
                   
                 Nitrogen, ppmw 
                 842 
               
               
                   
                 MCR, W % 
                 5.36 
               
               
                   
                 C5-Asphalthenes, W % 
                 2.45 
               
               
                   
                 Ni, ppmw 
                 5 
               
               
                   
                 V, ppmw 
                 17 
               
               
                   
                   
               
             
          
         
       
     
         [0085]    The distillates and vacuum gas oil fractions were obtained from the crude oil and passed to the respective hydrotreating and hydrocracking units to remove the impurities. The vacuum residue fraction was sent to the Electrolysis Gasification Island to produce hydrogen needed for the hydrotreating and hydrocracking steps. Material balances are given in Table 3. The stream numbers referred to in Table 3 correspond to the streams in  FIG. 7 . 
         [0000]    
       
         
               
             
               
               
               
               
             
               
               
               
               
             
           
               
                 TABLE 3 
               
             
             
               
                   
               
               
                 Material Balance 
               
             
          
           
               
                   
                 Stream 
                 Stream # 
                 Flow, Kg/h 
               
               
                   
                   
               
             
          
           
               
                   
                 Crude Oil 
                 1  
                 331,442 
               
               
                   
                 Distillates 
                 2a 
                 184,945 
               
               
                   
                 Hydrotreated Distillates 
                 2b 
                 186,374 
               
               
                   
                 Atmospheric Residue 
                 3  
                 146,497 
               
               
                   
                 Vacuum Distillates 
                 4a 
                 76,342 
               
               
                   
                 Hydrotreated Vacuum Distillates 
                 4b 
                 77,747 
               
               
                   
                 Vacuum Residue 
                 6  
                 70,155 
               
               
                   
                 Hydrogen 
                 7  
                 9,075 
               
               
                   
                 Hydrogen to Hydrocracking 
                 7a 
                 −1,469 
               
               
                   
                 Hydrogen To Hydrotreating 
                 7b 
                 −1,405 
               
               
                   
                 Power (MW) 
                 8  
                 1,439 
               
               
                   
                   
               
             
          
         
       
     
         [0086]    Table 4 summarizes the material balance within the Electrolysis Gasification Island. The stream numbers referred to in Table 4 correspond to the streams in  FIG. 4 . 
         [0000]    
       
         
               
             
               
               
               
               
             
               
               
               
               
             
           
               
                 TABLE 4 
               
             
             
               
                   
               
               
                 Gasification Island Material Balance 
               
             
          
           
               
                   
                 Stream # 
                 Stream # 
                 Flow, Kg/h 
               
               
                   
                   
               
             
          
           
               
                   
                 Water 
                 201 
                 81,107 
               
               
                   
                 Oxygen 
                 202 
                 72,095 
               
               
                   
                 Hydrogen 
                 203 
                 9,075 
               
               
                   
                 Vacuum Residue 
                 204 
                 70,155 
               
               
                   
                 Power (MW) 
                 207 
                 1,944,640 
               
               
                   
                   
               
             
          
         
       
     
         [0087]    The gasification reactor was operated at 1045° C. and 28 bars. The ratio of steam-to-carbon was 1:1 by weight. The ratio of oxygen-to-carbon was 1:1 by weight. The water electrolysis cell was operated at 25° C. and atmospheric pressure. 
         [0088]    The method and system of the present invention have been described above and in the attached drawings; however, modifications derived from this description will be apparent to those of ordinary skill in the art and the scope of protection for the invention is to be determined by the claims that follow.