Process for producing hydrogen by steam reforming and conversion of co

Abstract

The invention relates to a process for producing hydrogen from a light hydrocarbon source, in which a synthesis gas is generated by steam methane reforming after desulfurization and optionally pre-reforming of the feedstock. The synthesis gas is enriched with hydrogen by steam conversion of carbon monoxide, and is subsequently purified in a pressure swing adsorption unit to give a pure H.sub.2 product and a residual gas mixture containing CH.sub.4, CO, H.sub.2 and CO.sub.2; in accordance with the invention, the conversion step is performed in a cooled reactor in which the heat of the conversion reaction is transferred to a fluid which feeds the burners of the reformer, or to the gas for reforming.

Claims

1. A process for producing hydrogen from a light hydrocarbon source, comprising at least: (a) generating a synthesis gas by steam reforming of said light gaseous hydrocarbons, comprising at least a step (a1) of desulfurizing said hydrocarbons for reforming, a step of steam-reforming the desulfurized hydrocarbons in tubular reactors installed in a furnace of a reformer heated by burners which are fed with fuel by at least a secondary fuel gas, (b) producing hydrogen from the synthesis gas generated in step (a), comprising at least a step (b1) of hydrogen-enriching the synthesis gas by conversion of carbon monoxide according to the exothermic conversion reaction CO+H.sub.2O.fwdarw.CO.sub.2+H.sub.2 and a step (b2) of purifying the synthesis gas in a pressure swing adsorption unit to give a pure H.sub.2 product and a residual gas mixture containing CH.sub.4, CO, H.sub.2 and CO.sub.2, wherein the secondary fuel gas is comprised of at least some of the residual gas mixture produced in the hydrogen production step (b) and a primary fuel gas, wherein the conversion reaction of step (b1) is carried out in a cooled conversion reactor in which some of the heat produced in step (b1) is transferred by indirect heat exchange in the cooled conversion reactor with a first gaseous fluid so as to preheat the first gaseous fluid before the first gas fluid is used in the synthesis gas generation step (a), and in that the hydrogen-enriched synthesis gas leaving the cooled conversion reactor is cooled by indirect heat exchange with a second gaseous fluid before the second gaseous fluid is used in step (a), wherein the first gaseous fluid for preheating is selected from the group consisting of the residual gas mixture feeding the burners of the reformer and the light hydrocarbons for reforming, wherein the second gaseous fluid for preheating is selected from the group consisting of the residual gas mixture feeding the burners of the reformer and the light hydrocarbons for reforming, wherein the first gaseous fluid and the second gaseous fluid are different fluids.

2. The process according to claim 1, wherein the synthesis gas enters the conversion reactor at a temperature T.sub.E, the hydrogen-enriched synthesis gas leaves the reactor cooled to a temperature T.sub.S of less than T.sub.E+40° C.

3. The process according to claim 1, wherein the first gaseous fluid for preheating is the residual gas mixture feeding the burners of the reformer, and the second gaseous fluid for preheating is composed of the light hydrocarbons for reforming.

4. The process according to claim 1, wherein the first gaseous fluid for preheating is composed of the light hydrocarbons for reforming and the second gaseous fluid for preheating is the residual gas mixture feeding the burners of the reformer.

5. The process according to claim 1, wherein for a hydrogen production level and operating conditions which are otherwise similar, the total consumption of light hydrocarbons is decreased by at least 1% relative to a process employing an adiabatic conversion reactor.

6. The process according to claim 1, wherein the synthesis gas enters the conversion reactor at a temperature T.sub.E, the hydrogen-enriched synthesis gas leaves the reactor cooled to a temperature T.sub.S of less than T.sub.E+30° C.

7. The process according to claim 1, wherein the synthesis gas enters the conversion reactor at a temperature T.sub.E, the hydrogen-enriched synthesis gas leaves the reactor cooled to a temperature T.sub.S of less than T.sub.E+10° C.

8. The process according to claim 1, wherein for a hydrogen production level and operating conditions which are otherwise similar, the total consumption of light hydrocarbons is decreased by at least 2%.

9. The process according to claim 1, wherein for a hydrogen production level and operating conditions which are otherwise similar, the total consumption of light hydrocarbons is decreased by at least 3%.

10. The process according to claim 1, wherein the cooled conversion reactor is a plate-corrugated sheet reactor.

11. The process according to claim 1, wherein the cooled conversion reactor is a shell-and-tube reactor and is adapted for circulating the synthesis gas in catalyst-filled tubes and for circulating said first fluid for preheating in the shell.

12. The process according to claim 1, wherein the cooled conversion reactor is a shell-and-tube reactor and is adapted for circulating the synthesis gas in the catalyst-filled shell and for circulating said first fluid for preheating in the tubes.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) Further features and advantages of the invention will become apparent from the description hereinafter of embodiments, which are given by way of illustration but without any limitation, the description being given in relation with the following attached figures:

(2) FIG. 1 represents a schematic view presenting a process for reforming natural gas for final production of hydrogen by PSA, comprising, conventionally, an adiabatic reactor for the water-gas shift reaction.

(3) FIG. 2 is a schematic view presenting a first solution according to the invention, integrating a cooled reactor for the water-gas shift reaction with a process for reforming natural gas for final production of hydrogen by PSA, in which said reactor is cooled via a cold source of the process.

(4) FIG. 3 is a schematic view presenting a second solution according to the invention, integrating a cooled reactor for the water-gas shift reaction with a process for reforming natural gas for eventual production of hydrogen by PSA, in which said reactor is cooled via a cold source of the process, different from the first solution.

DETAILED DESCRIPTION OF THE INVENTION

(5) The comparative performance data of prior-art processes and processes according to the invention are presented in the tables referenced below.

(6) [Table 1] presents comparisons of respective performance data of a process including an adiabatic reactor for the water-gas shift reaction and of a process including a cooled reactor for this same reaction according to the prior art, the conditions overall being otherwise comparable.

(7) [Table 2] presents comparisons of respective performance data of a process including an adiabatic reactor for the water-gas shift reaction and of a first process according to the invention including a cooled reactor for this same reaction, the conditions overall being otherwise comparable.

(8) [Table 3] presents comparisons of respective performance data of a process including an adiabatic reactor for the water-gas shift reaction and of a second process according to the invention including a cooled reactor for this same reaction, the conditions overall being otherwise comparable.

(9) The selected hydrocarbon for reforming is natural gas (NG); other light hydrocarbon sources which may be reformed are suitable in the same way, alone or in combination, including for the purpose of providing the primary fuel. For the numbering of the elements and fluids in the figures, three-digit numbers are used: the hundreds digit corresponds to the reference of the figure, while the two other digits identify the element or fluid referenced.

(10) FIG. 1 represents the conventional integration of an adiabatic reactor for the water-gas shift reaction into the steam reforming process. A mixture 104 composed of process natural gas, which has been desulfurized and pre-reformed beforehand, and of water vapour feeds the reforming tubes 102 which are present in the reforming furnace 101, at a temperature of between 620° C. and 650° C.; in contact with a steam reforming catalyst which is present in the tubes, the hydrocarbons are converted and a synthesis gas 108 exits at the bottom end of the tubes, where it is collected. When it leaves the furnace, the synthesis gas is at a temperature of the order of 900° C. The burners 103 of the furnace, which are intended to supply the tubes with the heat required for reforming, are fed with combustion air 105, which is preheated, and with fuel natural gas 106 and the residues from the PSA unit 107, both of which are available at ambient temperature. The very hot synthesis gas 108 exiting reforming is cooled to a temperature of 360° C. by heat exchange in a boiler 109 with preheated water 110, thereby producing steam 111. At the boiler exit, cooled synthesis gas 112 enters the adiabatic conversion reactor 113 at 360° C., where it undergoes the water-gas shift reaction; some of the carbon monoxide present is converted catalytically therein—via the water vapour present—into carbon dioxide and hydrogen. The synthesis gas 114, enriched with H.sub.2 and CO.sub.2, leaves the conversion reactor 113 at a temperature higher than its entry temperature, of between 420° C. and 430° C., and subsequently gives up heat by passing through a shell-and-tube heat exchanger 115, where it preheats process natural gas 116 to a temperature of 360° C. The preheated process natural gas 117 feeds the desulfurization step of the process (that step not being shown).

(11) FIG. 2 represents a first solution for integration—according to the invention—of a cooled reactor for the water-gas shift reaction. According to this solution, a mixture 204 of process natural gas which has beforehand been desulfurized and pre-reformed, and of water vapour, feeds the tubes 202 of the reforming furnace 201 at a temperature of between 620° C. and 650° C.; on contact with a steam reforming catalyst present in the tubes, the hydrocarbons are converted and a synthesis gas 208 exits at the bottom end of the tubes, where it is collected. On leaving the furnace, the synthesis gas 208 is at a temperature of the order of 900° C., and is subsequently cooled to a temperature of 380° C. in a boiler 209 which is fed with preheated water 210, thereby producing steam 211. At the boiler exit, the cooled synthesis gas 212 enters the cooled reactor 213 for the water-gas shift reaction; some of the carbon monoxide present in the gas is converted in the presence of water vapour and in contact with the catalyst which is placed in a fixed bed 214 in the shell of the reactor 213, the conversion producing carbon dioxide and hydrogen. A bundle of tubes 215 placed within the catalyst bed allows the circulation of the residual PSA gases 207a—the hydrogen-purifying PSA unit is not shown—by circulating in the tubes 215, the gases 207a are preheated; the preheated gases 207b attain a temperature of 357° C. The synthesis gas 216, enriched with H.sub.2 and CO.sub.2, is simultaneously cooled and leaves the reactor at a temperature of 380° C., and then is used as a heat source in a shell-and-tube exchanger 217 for preheating the process natural gas 218 to a temperature of 360° C. The process natural gas thus preheated 219 feeds the desulfurization step of the process—the latter step not being shown.

(12) The burners 203 of the reforming furnace 201 are fed with preheated combustion air 205, with natural gas at ambient temperature 206 and with the preheated residual gases from the PSA unit 207b.

(13) FIG. 3 represents a second solution integrating, in accordance with the invention, a cooled reactor for the water-gas shift reaction into a process for production of synthesis gas by steam reforming of natural gas. According to this solution, a mixture 304 composed of process natural gas which has been desulfurized—and if necessary pre-reformed—beforehand, and of water vapour, enters the reforming tubes 302 of the steam reforming furnace 301. The gas mixture, which enters at a temperature of between 500° C. and 650° C., is contacted with a steam reforming catalyst which is present in the tubes, and the hydrocarbons are converted, the synthesis gas 308 being collected at the exit from the tubes; the gas 308 leaving the steam reforming furnace 301 is at a temperature of between 850° C. and 950° C. It is cooled to a temperature of between 250° C. and 400° C. in a boiler 309 which is fed with preheated water 310 and produces steam 311. The cooled synthesis gas 312 then enters the cooled reactor 313 for the water-gas shift reaction. Some of the carbon monoxide present is converted into carbon dioxide and hydrogen in contact with the catalyst placed in a fixed bed 314 in the shell. A bundle of tubes 315 is placed within the catalyst bed, and a cooling fluid circulates therein, this fluid being composed, according to this second solution example of the invention, of the process natural gas 318 which must be preheated before it enters the desulfurizing unit. The preheated natural gas 319 leaves the bundle of tubes 315 at a temperature of 360° C. and is sent to the desulfurizing unit (which is not shown).

(14) After having given up some of its heat to the natural gas 318, the synthesis gas 316 exits the shift reactor 313 at a temperature of 380° C., and passes subsequently into a shell-and-tube heat exchanger 317, where it provides heat to the residual gas 307a from the PSA unit. The PSA residuals 307b thus preheated to a temperature of 360° C. are sent to the burners 303 of the steam reforming furnace 301. The burners 303 are also fed with combustion air 305, which may or may not have been preheated, and with fuel natural gas 306 at ambient temperature.

(15) The conversion reactors according to the invention that are shown in FIG. 2 and FIG. 3 are shell-and-tube reactors, with the synthesis gas circulating in the shell containing the catalyst, and the gaseous fluid for reheating circulating in the tubes; it would have been possible to employ a shell-and-tube reactor with circulation of the synthesis gas in tubes containing catalyst and with circulation of the fluid for reheating in the shell. It would also have been possible to employ any other type of exchanger, especially a plate-corrugated sheet exchanger.

(16) [Table 1] below represents a comparison of the respective performance data of a process including an adiabatic reactor for the water-gas shift reaction and of a process including an isothermal reactor for this same reaction, the following conditions being otherwise comparable: the hydrogen production level is the same for both configurations (5800 kmol/h); the synthesis gas entering the conversion reactor has the same composition in both cases: 49.3% H.sub.2, 10.2% CO, 5.2% CO.sub.2, 32.2% H.sub.2O, 0.3% N.sub.2, 2.8% CH.sub.4; in the first configuration, the synthesis gas enters the adiabatic reactor (A) at a temperature of 360° C.; the exit temperature is then 428° C.; in the second configuration, the isothermal reactor (I) is itself operated at a temperature of 380° C.

(17) TABLE-US-00001 TABLE 1 Adiabatic Isothermal Variation reactor A reactor I (I-A)/A Consumption of 1972 1929  −2.2% process NG (kmol/h) Consumption of fuel 296 327 +10.6% NG (kmol/h) Consumption of total 2268 2257  −0.5% NG (kmol/h)

(18) The performance data reported for the isothermal reactor are the result of a simulation carried out on the basis of a shell-and-tube reactor employing boiling water as cooling fluid. The comparison of the respective performance data of a process including an adiabatic reactor for the water-gas shift reaction and of a process including an isothermal reactor (cooled, with identical entry and exit temperatures of the natural gas) for this same reaction shows that: with regard to the process NG: the isothermal reactor offers better conversion, allowing a reduction of 2.2% in the amount of process NG required to produce the 5800 kmol/h of hydrogen; with regard to the fuel NG: the PSA residuals (step 6) which are used as secondary fuel are nevertheless less CO-rich than in the case of the adiabatic reactor, and there will therefore be a lower calorific supply, which will have to be compensated otherwise, hence the increase in the consumption of fuel NG by 10.6%; with regard to the total NG: the result is an overall saving of 0.5% in the total consumption of natural gas in a process employing an isothermal reactor according to the prior art, relative to the standard process employing an adiabatic reactor.

(19) [Table 2] represents the comparative performance data of the process of the invention shown in FIG. 2, obtained by simulation, and of the same, conventional process employing an adiabatic shift reactor as in [Table 1]. In both cases, the hydrogen production rate is the same, at 5800 kmol/h of hydrogen, and the synthesis gas composition entering the reactor is the same: 49.3% H.sub.2, 10.2% CO, 5.2% CO.sub.2, 32.2% H.sub.2O, 0.3% N.sub.2, and 2.8% CH.sub.4.

(20) TABLE-US-00002 TABLE 2 Adiabatic Isothermal Variation reactor A reactor I (I-A)/A Entry temp. T.sub.E ° C. 360 380 Exit temp. T.sub.S 428 380 ° C. CO content at 3.33 2.29 reactor exit Temp. of PSA 35 357 residuals ° C. Consumption 1972 1932  −2.0% of process NG Consumption 296 261 −11.8% of fuel NG Total 2268 2193  −3.3% consumption of NG Thermal yield 49.8 51.3 of SMR furnace (%) Production of 73 60 −18.0% excess steam (t/h) CO.sub.2 emitted 2479 2394  −3.4% (kmol/h)

(21) The data presented show that: the PSA residuals, initially at the temperature of 35° C., are preheated in the conversion reactor to a temperature of 357° C., and exchange their heat with the synthesis gas, which enters at the temperature of 380° C. and leaves at the same temperature despite the exothermic heat of the conversion reaction; the amount of heat which needs to be supplied to the reforming by the fuel NG is less, and its consumption is therefore reduced; the preheating of the PSA residuals gives rise to an increase in the thermal yield of the reforming furnace (51.3% instead of 49.8%, or an increase of 1.5%), thereby reducing further the amount of heat which has to be supplied and the consumption of fuel NG; the synthesis gas exiting the conversion reactor is at a temperature very much lower than that of the synthesis gas exiting the adiabatic conversion reactor of the conventional process (380° C. rather than 428° C., or approximately 50° C. lower), thereby providing evidence of the stabilization of the temperature in the conversion reactor, which allows an improvement in the yield of the conversion reaction; consequently, the process NG flow rate required for the same level of hydrogen production is reduced.

(22) [Table 3] shows the comparative performance data of the process of the invention according to FIG. 3, as obtained by simulation, and of the same, conventional process using an adiabatic shift reactor as in [Table 1]. In both cases, the hydrogen production rate of 5800 kmol/h of hydrogen is the same, and the synthesis gas composition entering the reactor is the same: 49.3% H.sub.2, 10.2% CO, 5.2% CO.sub.2, 32.2% H.sub.2O, 0.3% N.sub.2, 2.8% CH.sub.4.

(23) TABLE-US-00003 TABLE 3 Adiabatic Isothermal Variation reactor A reactor I (I-A)/A Entry temp. T.sub.E 360 370 (° C.) Exit temp. T.sub.S 428 380 (° C.) CO content at 3.33 2.28 exit from reactor Temp. of PSA 35 360 residuals (° C.) Consumption of 1972 1933  −2.0% process NG Consumption of fuel 296 261 −11.8% NG Total consumption of 2268 2194  −3.3% NG Thermal yield of SMR 49.8 51.3 furnace (%) Production of excess 73 60 −18.0% steam (t/h) CO2 emitted (kmol/h) 2479 2395  −3.4%

(24) The data presented show that: the PSA residuals, initially at a temperature of 35° C., are preheated to a temperature of 360° C. by exchange of heat with the synthesis gas having left the conversion reactor at a temperature of 380° C.; preheating of the PSA residuals produces an increase in the thermal yield of the reforming furnace (51.3% instead of 49.8%, or an increase of 1.5%), thereby further reducing the amount of heat needing to be supplied and the consumption of fuel NG; the synthesis gas exiting the conversion reactor is at a temperature very much lower than that of the synthesis gas exiting the adiabatic conversion reactor of the conventional process (380° C. rather than 428° C., or approximately 50° C. lower), thereby providing evidence of the stabilization of the temperature in the conversion reactor, which allows an improvement in the yield of the conversion reaction; consequently, the flow rate of process NG required for the same level of hydrogen production is reduced.

(25) In light of these tables, it is noted that the two configurations according to the invention both feature comparable advantages: reduction in the consumption both of process NG and of fuel NG; for a given level of production, the consumption of process NG is reduced by virtue of improved conversion in the cooled reactor for the water-gas shift reaction, while the consumption of fuel NG is reduced by virtue of a judicious selection of the cooling fluid used for removing the heat produced by the conversion reaction outside the conversion reactor; because the latter is linked to the preheating of the PSA residuals, it gives rise to an increase in the thermal yield of the reforming furnace, thereby further reducing the amount of heat which has to be supplied and the consumption of fuel NG; this therefore signifies a greater reduction in the overall consumption of natural gas, compared with the known solutions.

(26) The two solutions proposed by the invention are advantageous: firstly in terms of improved operation of the reforming, as shown by Tables 2 and 3, with a decrease in the consumption of hydrocarbons and an improvement in the thermal yield of the reforming furnace; secondly because the shift reactor operates at a lower temperature, therefore the sintering of the catalyst will be reduced, hence increasing its lifetime.

(27) Other criteria will allow one or other of the solutions to be preferred, according to the case in hand.

(28) The solution employing the PSA residuals as the heat transfer fluid in the reactor is more favourable in the context of updating an existing unit, since it involves fewer modifications to the existing system: the piping of the natural gas preheating system is unchanged; the exchanger for preheating natural gas may stay the same or might require the addition of a number of tubes, depending on its dimensions; the mechanical integration of the unit is subject to few modifications apart from for the conduits transporting the PSA residuals.

(29) The solution employing natural gas as the heat transfer fluid in the reactor will be preferred in the context of the construction of a new unit, since the operation of the unit will be made easier, the reasons being as follows: the start-up sequence is simplified: in this solution, the heat transfer fluid is available at start-up, whereas the PSA residuals (heat transfer fluid in the solution of FIG. 2) are not (the entire chain upstream of the PSA must first be started up, including the conversion reactor). This means that this solution allows direct start-up of the conversion reactor in cooled mode; for the same reason, in the event of complete or partial failure of the PSA, there will be no impact on the operation of the conversion reactor, by contrast with the solution employing the PSA residuals for cooling thereof.

(30) The invention therefore presents many advantages relative to the prior art and to the practice of the skilled person, among those already cited: a reactor which maintains a more stable temperature—a cooled and ideally isothermal reactor—allows an increase in conversion and hence a reduction in the consumption of process natural gas for a given level of hydrogen production; the use of the heat produced by the conversion for heating fluids feeding the reforming significantly decreases the total consumption of hydrocarbons; the judicious use/removal of the heat from the reactor via the preheating of the residues from the PSA unit allows first some of the energy required for the reforming to be supplied and second the thermal yield of the steam reforming furnace to be increased.

(31) This invention also leads to improvements in terms of the plant considered within its environment, including the following: since the consumption of natural gas goes down, the CO.sub.2 emissions will be decreased; the thermal yield of the furnace increases, and the heat is used more effectively internally, and so the production of excess steam will be reduced.

(32) While the invention has been described in conjunction with specific embodiments thereof, it is evident that many alternatives, modifications, and variations will be apparent to those skilled in the art in light of the foregoing description. Accordingly, it is intended to embrace all such alternatives, modifications, and variations as fall within the spirit and broad scope of the appended claims. The present invention may suitably comprise, consist or consist essentially of the elements disclosed and may be practiced in the absence of an element not disclosed. Furthermore, if there is language referring to order, such as first and second, it should be understood in an exemplary sense and not in a limiting sense. For example, it can be recognized by those skilled in the art that certain steps can be combined into a single step.

(33) The singular forms “a”, “an” and “the” include plural referents, unless the context clearly dictates otherwise.

(34) “Comprising” in a claim is an open transitional term which means the subsequently identified claim elements are a nonexclusive listing (i.e., anything else may be additionally included and remain within the scope of “comprising”). “Comprising” as used herein may be replaced by the more limited transitional terms “consisting essentially of” and “consisting of” unless otherwise indicated herein.

(35) “Providing” in a claim is defined to mean furnishing, supplying, making available, or preparing something. The step may be performed by any actor in the absence of express language in the claim to the contrary.

(36) Optional or optionally means that the subsequently described event or circumstances may or may not occur. The description includes instances where the event or circumstance occurs and instances where it does not occur.

(37) Ranges may be expressed herein as from about one particular value, and/or to about another particular value. When such a range is expressed, it is to be understood that another embodiment is from the one particular value and/or to the other particular value, along with all combinations within said range.

(38) All references identified herein are each hereby incorporated by reference into this application in their entireties, as well as for the specific information for which each is cited.