Hydrogen production from an integrated electrolysis cell and hydrocarbon gasification reactor
10422046 ยท 2019-09-24
Assignee
Inventors
Cpc classification
Y02E20/18
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
C10K3/04
CHEMISTRY; METALLURGY
Y02E60/36
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
Y02P20/129
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
Y02P20/10
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
C10G49/007
CHEMISTRY; METALLURGY
International classification
C10K3/04
CHEMISTRY; METALLURGY
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.
Claims
1. An integrated refinery crude oil upgrading and gasification process comprising: a. introducing a crude oil feedstock into an atmospheric distillation unit to produce atmospheric distillate and atmospheric residue; b. recovering the atmospheric residue from the atmospheric distillation unit and introducing it as a feedstock into a vacuum distillation unit to produce vacuum distillate and a vacuum residue; c. introducing water into an electrolysis cell and operating the electrolysis cell with an external source of electricity to produce oxygen and hydrogen; d. recovering the vacuum residue from the vacuum distillation unit and introducing the vacuum residue as a feedstock into a membrane wall partial oxidation gasification reactor with an external source of steam, an ash-forming material, and the oxygen produced by the electrolysis cell and optionally supplemental oxygen produced by an air separation unit, so that the total content of the ash-forming material in the feedstock to the membrane wall partial oxidation gasification reactor is in the range of from 2 W % to 10 W % of the total weight of the feedstock; e. subjecting the vacuum residue and the ash-forming material comprising the feedstock to partial oxidation to produce a hot raw synthesis gas and slag to coat walls of the membrane wall partial oxidation gasification reactor; f. passing the hot raw synthesis gas to a steam generating heat exchanger to produce steam and a cooled raw synthesis gas; g. introducing the steam from the heat exchanger into a turbine to produce electricity; h. operating the electrolysis cell with the electricity produced in step (g); i. recovering the hydrogen from the electrolysis cell; j. recovering the atmospheric distillate from the atmospheric distillation unit; and k. recovering the vacuum distillate from the vacuum distillation unit; wherein the vacuum residue recovered from the vacuum distillation unit has an insufficient amount of ash to coat the walls of the membrane wall partial oxidation gasification reactor without the addition of the ash-forming material as part of the feedstock into the membrane wall partial oxidation gasification reactor being subjected to partial oxidation.
2. The process of claim 1, further comprising mixing the recovered atmospheric distillate with the recovered vacuum distillate to produce an upgraded hydrocarbon stream.
3. The process of claim 1 in which the recovered atmospheric distillate is introduced into a hydrotreater and the recovered vacuum distillate is introduced into a hydrocracker and the hydrogen recovered from the electrolysis cell is introduced into either or both of the hydrotreater and the hydrocracker.
4. An integrated refinery crude oil upgrading and gasification process comprising: a. introducing a crude oil feedstock into an atmospheric distillation unit to produce atmospheric distillate and atmospheric residue; b. recovering the atmospheric residue from the atmospheric distillation unit and introducing it as a feedstock into a vacuum distillation unit to produce vacuum distillate and a vacuum residue; c. recovering the atmospheric distillate from the atmospheric distillation unit and introducing it as a feedstock into a hydrotreating unit; d. recovering the vacuum distillate from the vacuum distillation unit and introducing it as a feedstock into a hydrocracking unit; e. introducing water into an electrolysis cell and initially operating the electrolysis cell with an external source of electricity to produce oxygen and hydrogen; f. recovering hydrogen from the electrolysis cell and introducing it into either or both of the hydrotreating unit and the hydrocracking unit; g. recovering the vacuum residue from the vacuum distillation unit and introducing it as a feedstock into a coking unit to produce coke and coker distillate; h. recovering the coke from the coking unit and introducing it as a feedstock into a membrane wall partial oxidation gasification reactor with an external source of steam, an ash-forming material, and the oxygen produced by the electrolysis cell and optionally supplemental oxygen produced by an air separation unit, so that the total content of the ash-forming material in the feedstock to the membrane wall partial oxidation gasification reactor is in the range of from 2 W % to 10 W % of the total weight of the feedstock; i. subjecting the coke and the ash-forming material comprising the feedstock to partial oxidation to produce a hot raw synthesis gas and slag to coat walls of the membrane wall partial oxidation gasification reactor; j. passing the hot raw synthesis gas to a steam generating heat exchanger to produce steam and a cooled raw synthesis gas; k. introducing the steam from the heat exchanger into a turbine to produce electricity; l. operating the electrolysis cell with the electricity produced in step (k); and m. recovering coker distillate from the coking unit; wherein the coke recovered from the coking unit has an insufficient amount of ash to coat the walls of the membrane wall partial oxidation gasification reactor without the addition of the ash-forming material as part of the feedstock into the membrane wall partial oxidation gasification reactor being subjected to partial oxidation.
5. The process of claim 4 in which the coker distillate is introduced into either or both of the hydrotreating unit and the hydrocracking unit.
6. An integrated refinery crude oil upgrading and gasification process comprising: a. introducing a crude oil feedstock into an atmospheric distillation unit to produce atmospheric distillate and atmospheric residue; b. recovering the atmospheric residue from the atmospheric distillation unit and introducing it as a feedstock into a vacuum distillation unit to produce vacuum distillate and a vacuum residue; c. recovering the atmospheric distillate from the atmospheric distillation unit and introducing it as a feedstock into a hydrotreating unit; d. recovering the vacuum residue from the vacuum distillation unit and introducing it as a feedstock into a solvent deasphalting unit to produce asphalt bottoms and deasphalted oil; e. recovering the vacuum distillate from the vacuum distillation unit and introducing it as a feedstock into a hydrocracking unit; f. introducing water into an electrolysis cell and operating the electrolysis cell with an external source of electricity to produce oxygen and hydrogen; g. recovering the asphalt bottoms from the solvent deasphalting unit and introducing the asphalt bottoms as a feedstock into a membrane wall partial oxidation gasification reactor with steam from an external source, an ash-forming material, and the oxygen produced by the electrolysis cell and optionally, supplemental oxygen produced by an air separation unit, so that the total ash content of the ash-forming material in the feedstock to the membrane wall partial oxidation gasification reactor is in the range of from 2 W % to 10 W % of the total weight of the feedstock; h. recovering hydrogen from the electrolysis cell and introducing it into either or both of the hydrotreating unit and the hydrocracking unit; i. subjecting the asphalt bottoms and the ash-forming material comprising the feedstock to partial oxidation to produce a hot raw synthesis gas and slag to coat walls of the membrane wall partial oxidation gasification reactor; j. passing the hot raw synthesis gas to a steam generating heat exchanger to produce steam and a cooled raw synthesis gas; k. introducing the steam from the heat exchanger into a turbine to produce electricity; l. operating the electrolysis cell with the electricity produced in step (k); and m. recovering the deasphalted oil stream from the solvent deasphalting unit; wherein the asphalt bottoms recovered from the solvent deasphalting unit have an insufficient amount of ash to coat the walls of the membrane wall partial oxidation gasification reactor without the addition of the ash-forming material as part of the feedstock into the membrane wall partial oxidation gasification reactor being subjected to partial oxidation.
7. The process of claim 6 in which the recovered deasphalted oil stream is introduced into the hydrocracking unit.
8. The process of claim 1, 4 and 6, in which the ash-forming material is mixed with a liquid hydrocarbon feedstock upstream of the membrane wall gasification reactor.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
(1) The foregoing summary, as well as the following detailed description will be best understood when read in conjunction with the attached drawings in which:
(2)
(3)
(4)
(5)
(6)
(7)
(8)
(9)
(10)
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
(11) 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
(12) Referring to
(13) 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.
(14) 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.
(15) 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.
(16) 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.
(17) 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.
(18) 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.sub.2O.fwdarw.CO.sub.2+H.sub.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.
(19) Referring now to
(20) Electrolysis cell 310 includes an inlet for receiving water, an outlet for discharging produced oxygen 302a 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 302b.
(21) 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 302a produced from the electrolysis cell 310 and oxygen 302b 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.
(22) 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.
(23) 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 302a 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 302a produced from electrolysis cell 310 and oxygen 302b recovered from air separation unit 350. The additional oxygen 302b increases the oxygen input to gasification reactor 330, which improves the efficiency of hydrocarbon oxidation.
(24) 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.
(25) 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.sub.2O.fwdarw.CO.sub.2+H.sub.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.
(26)
(27) Referring to
(28)
(29) Vacuum residue 6 is introduced into the membrane wall gasification reactor as the feedstock to produce hydrogen gas as described above in connection with
(30)
(31) Vacuum residue 6 is introduced into the coking unit to produce coker distillates 6b and petcoke 6a. The coker distillates 6b are recycled to the steps of hydrotreating and hydrocracking. The petcoke 6a is conveyed to the membrane wall gasification reactor as the feedstock to produce hydrogen gas as described above in connection with
(32)
(33) Vacuum residue 6 is introduced into the solvent deasphalting unit to produce deasphalted oil 6b and asphalt 6a. Deasphalted oil 6b is recycled to the hydrocracking unit. Asphalt 6a is conveyed to the membrane wall gasification reactor as the feedstock to produce hydrogen gas as described above in connection with
(34) 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.
(35) 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.
(36) 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.
(37) The operating conditions for the coking, solvent deasphalting, hydrotreating and hydrocracking units are as follows:
(38) TABLE-US-00001 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.sup.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.sup.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's below the solvent's critical temperature critical temperature Pressure Bar below the solvent's below the solvent's critical pressure critical pressure Solvents to oil Ratio h.sup.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.sup.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
(39) 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
(40) The apparatus described in
(41) TABLE-US-00002 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
(42) 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
(43) TABLE-US-00003 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
(44) Table 4 summarizes the material balance within the Electrolysis Gasification Island. The stream numbers referred to in Table 4 correspond to the streams in
(45) TABLE-US-00004 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
(46) 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.
(47) 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.