PLANT FOR PRODUCTION OF HYDROGEN AND METHOD FOR OPERATING THIS PLANT

Abstract

The invention relates to a plant for production of hydrogen, and to a method for operating this plant, comprising a steam reforming reactor having a furnace, in which reactor water and at least one carbonaceous energy carrier are reacted to form a hydrogen-containing crude synthesis gas, and at least one cleaning device for purifying the crude synthesis gas, to which the crude synthesis gas is fed from the steam reforming via at least one feed line. According to the invention, upstream of one of the at least one cleaning devices at least one return line branches off from the feed line, through which the crude synthesis gas is at least in part recirculated into the furnace of the steam reforming reactor.

Claims

1-16. (canceled)

17. A plant for production of hydrogen comprising a steam reforming reactor having a furnace, in which reactor water and at least one carbonaceous energy carrier are reacted to form a hydrogen-containing crude synthesis gas, and at least one cleaning device for purifying the crude synthesis gas, to which cleaning device the crude synthesis gas is fed from the steam reforming via at least one feed line, characterized in that, upstream of one of the at least one cleaning devices, at least one return line branches off from the at least one feed line, through which return line the crude synthesis gas is at least in part recirculated into the furnace of the steam reforming reactor.

18. The plant according to claim 17, wherein at least one cleaning device is a pressure-swing adsorption.

19. The plant according to claim 17, wherein the synthesis gas contains carbon monoxide and hydrogen.

20. The plant according to claim 17, wherein at least one further cleaning device is a scrubber for CO.sub.2 removal, a dryer for removal of water or a low-temperature synthesis gas separation plant for separating off CO.

21. The plant according to claim 17, wherein at least one return line for residual gas that has been separated off leads from at least one cleaning device into the furnace of the steam reforming reactor.

22. The plant according to claim 17, wherein a metering device is provided in at least one return line for metering the recirculated gas.

23. The plant according to claim 17, wherein a first measuring device for determining the volume flow rate (V.sub.m) of the recirculated crude synthesis gas from at least one of the cleaning devices, and a second measuring device for determining the volume flow rate (V.sub.G) of the carbonaceous energy carrier fed into the furnace of the steam reforming reactor are provided.

24. The plant according to claim 23, wherein a metering device is provided in at least one return line for metering the recirculated gas, wherein the metering device is constructed in such a manner that it sets the volume of the recirculated synthesis gas either on the basis of a theoretical value V.sub.S1, where $V_{S.Math..Math.1}=V_m+\frac{F.Math.V_G.Math.H_{i\left(G\right)}.Math.{\eta }_G}{H_{i\left(S\right)}.Math.{\eta }_S}$ where TABLE-US-00008 V.sub.S Theoretical value of the volume flow rate of m.sup.3 s.sup.−1 the recirculated crude synthesis gas V.sub.m Actual volume flow rate of the recirculated m.sup.3 s.sup.−1 residual gas from at least one cleaning device V.sub.G Volume flow rate of the carbonaceous energy carrier fed m.sup.3 s.sup.−1 into the furnace averaged over the last three minutes F Furnace factor — H.sub.i(G) Heating value of the carbonaceous energy carrier J/kg H.sub.i(S) Heating value of the crude synthesis gas J/kg η.sub.G Efficiency value of the carbonaceous energy carrier — η.sub.S Efficiency value of the crude synthesis gas — and F has a value between 0.7 and 1.2, or sets it on the basis of a theoretical value V.sub.S2, where $V_{S.Math..Math.2}=\frac{V_L}{a}$ where TABLE-US-00009 V.sub.S2 Theoretical value of the volume flow rate m.sup.3 s.sup.−1 of the recirculated crude synthesis gas V.sub.L Volume flow rate of the air m.sup.3 s.sup.−1 a Correction factor — and a has a value between 1.05 and 1.15.

25. The plant according to claim 17, wherein a feed line for air into the furnace of the steam reforming reactor and a measuring device for determining the volume flow rate of the air are provided.

26. The plant according to claim 25, wherein a metering device is provided in at least one return line for metering the recirculated gas, wherein the metering device is constructed in such a manner that it sets the volume of the recirculated synthesis gas either on the basis of a theoretical value V.sub.S1, where $V_{S.Math..Math.1}=V_m+\frac{F.Math.V_G.Math.H_{i\left(G\right)}.Math.{\eta }_G}{H_{i\left(S\right)}.Math.{\eta }_S}$ where TABLE-US-00010 V.sub.S Theoretical value of the volume flow rate m.sup.3 s.sup.−1 of the recirculated crude synthesis gas V.sub.m Actual volume flow rate of the recirculated m.sup.3 s.sup.−1 residual gas from at least one cleaning device V.sub.G Volume flow rate of the carbonaceous energy carrier fed m.sup.3 s.sup.−1 into the furnace averaged over the last three minutes F Furnace factor — H.sub.i(G) Heating value of the carbonaceous energy carrier J/kg H.sub.i(S) Heating value of the crude synthesis gas J/kg η.sub.G Efficiency value of the carbonaceous energy carrier — η.sub.S Efficiency value of the crude synthesis gas — and F has a value between 0.7 and 1.2, or sets it on the basis of a theoretical value V.sub.S2, where $V_{S.Math..Math.2}=\frac{V_L}{a}$ where TABLE-US-00011 V.sub.S2 Theoretical value of the volume flow rate m.sup.3 s.sup.−1 of the recirculated crude synthesis gas V.sub.L Volume flow rate of the air m.sup.3 s.sup.−1 a Correction factor — and a has a value between 1.05 and 1.15.

27. A method for operating a plant for production of synthesis gas, the method comprising the steps of: reacting water and at least one carbonaceous energy carrier in a steam reforming reactor having a furnace to form a crude synthesis gas; and purifying the crude synthesis gas in at least one cleaning stage, wherein the crude synthesis gas is at least in part recirculated into the furnace before passing through the at least one cleaning stage.

28. The method according to claim 27, wherein the crude synthesis gas is recirculated in the amount of a theoretical value V.sub.S1, and in that the theoretical value of the volume of the recirculated synthesis gas V.sub.S1 is determined as $V_{S.Math..Math.1}=V_m+\frac{F.Math.V_G.Math.H_{i\left(G\right)}.Math.{\eta }_G}{H_{i\left(S\right)}.Math.{\eta }_S}$ where TABLE-US-00012 V.sub.S Theoretical value of the volume flow rate of m.sup.3 s.sup.−1 the recirculated crude synthesis gas V.sub.m Actual volume flow rate of the recirculated m.sup.3 s.sup.−1 residual gas from at least one cleaning stage V.sub.G Volume flow rate of the carbonaceous energy carrier fed m.sup.3 s.sup.−1 into the furnace averaged over the last three minutes F Furnace factor — H.sub.i(G) Heating value of the carbonaceous energy carrier J/kg H.sub.i(S) Heating value of the crude synthesis gas J/kg η.sub.G Efficiency value of the carbonaceous energy carrier — η.sub.S Efficiency value of the crude synthesis gas — where F has a value between 0.7 and 1.2.

29. The method according to claim 27, wherein the crude synthesis gas is recirculated in the amount of a theoretical value V.sub.S2, in that air is fed to the steam reforming reaction, and in that the theoretical value of the recirculated synthesis gas V.sub.S2 is determined as $V_{S.Math..Math.2}=\frac{V_L}{a}$ where TABLE-US-00013 V.sub.S2 Theoretical value of the volume flow rate m.sup.3 s.sup.−1 of the recirculated crude synthesis gas V.sub.L Volume flow rate of the air m.sup.3 s.sup.−1 a Correction factor — where a has a value between 1.05 and 1.15.

30. The method according to claim 29, wherein the theoretical values V.sub.S1 and V.sub.S2 are determined and in that the crude synthesis gas is recirculated in the amount of a theoretical value V.sub.S, wherein the theoretical value V.sub.S of the recirculated synthesis gas corresponds to the smaller of the two theoretical values V.sub.S1 and V.sub.S2.

31. The method according to claim 27, wherein, in the event of changes in the amount of the recirculated synthesis gas, the theoretical value V.sub.S, V.sub.S1 or V.sub.S2 is selected in a ramp.

32. The method according to claim 27, wherein the method is carried out during the startup of the plant or during the malfunction of at least one of the cleaning stages.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0068] Further features, advantages and possible applications of the invention result from the subsequent description of the drawings and the exemplary embodiments. In this case, all described and/or pictorially presented features, alone or in any combination, are the subject matter of the invention, independently of the summary thereof in the claims and the dependency reference thereof.

[0069] FIG. 1 shows a plant according to the invention for production of hydrogen and

[0070] FIG. 2 shows a plant according to the invention for production of hydrogen and carbon monoxide.

DETAILED DESCRIPTION OF THE INVENTION

[0071] FIG. 1 shows a steam reforming reactor 20, into which, firstly, via line 10, a carbonaceous energy carrier, preferably a gas consisting of at least 80% by weight of methane, is fed. Via line 26, as also via line 24, parts of this energy carrier are branched off and introduced as fuel gas into the furnace of the steam reforming reactor 20.

[0072] Via line 21 and a compressor or a blower 22, flue gas is withdrawn from the furnace chamber of the steam reforming reactor 20 and in this case, simultaneously, the pressure in the furnace chamber is controlled.

[0073] Via line 11 and a compressor or a blower 12, in addition, air is introduced into the system. Expediently, as shown, the air is first passed through a heat exchanger 25 in the flue gas waste-heat system of the steam reforming reactor and in this manner takes up heat from the exhaust gas escaping from the steam reforming reactor 20 before it passes preheated into line 23. From line 23, then, the air is fed into the actual steam reforming reactor 20.

[0074] Via line 27, the resultant crude synthesis gas is withdrawn from the steam reforming reactor 20 and passed into a pressure-swing adsorption 40. There, hydrogen is obtained having a degree of purity of 99 mol %, preferably 99.9 mol %, particularly preferably 99.99 mol %, and withdrawn via line 41. The residual gas from the pressure-swing adsorption is recirculated via line 42 to the furnace of the steam reforming reactor 20.

[0075] Via line 46, crude synthesis gas can be branched off before passing through the pressure-swing adsorption 40 and conducted into the furnace of the steam reforming reactor 20. In this case, the line 46 can open out into the return line 42, or else directly into the furnace of the steam reforming reactor 20.

[0076] FIG. 2 represents the plant according to the invention for generating carbon monoxide and hydrogen. The carbonaceous energy carrier is fed in via line 10, from which, via line 26, parts of the fuel gas are introduced into the furnace of the steam reforming reactor 20. The gas used as carbonaceous energy carrier contains at least 80% by weight of methane.

[0077] Air for the combustion is fed into the furnace of the steam reforming reactor 20 via line 11 and the one compressor or a blower 12. Preferably, in this case, the air in the stack of the steam reforming reactor 20 is passed via a heat exchanger 25 and then, via line 23, is fed into the furnace of the steam reforming reactor 20.

[0078] The crude synthesis gas generated in the steam reforming 20 is fed via line 27 to a CO.sub.2 scrubber 30. The CO.sub.2 that is separated off here is recirculated via line 31 to the steam reforming 20 in order here to be further converted at least in part to carbon monoxide in a CO-shift reaction.

[0079] The purified crude synthesis gas is fed via line 32 to a dryer 33 in which water still originating from the steam reforming is removed.

[0080] The crude synthesis gas then passes via line 34 into a low-temperature synthesis gas separation plant 35 in which it is separated into a hydrogen-rich gas 37, the carbon monoxide 36 and various residual gas streams 45. The hydrogen-rich gas is fed via line 37 to the pressure-swing adsorption 40 in which the hydrogen product is removed via line 41. The various cleaning processes are designed in a form such that the required degrees of product purity are reliably achieved.

[0081] Residual gas then passes back via return line 42 into the furnace of the steam reforming oven.

[0082] In addition, return lines 43, 44, 45 and 45′ branch off from the respective cleaning stages 30, 33 and 35, in such a manner that, via the return lines 45 and 45′ from the low-temperature synthesis gas separation plant 35, via the return line 44 from the dryer and the return line 43 from the CO.sub.2 scrubber 30, also in each case crude synthesis gas can be branched off and transferred to the return line 42 through which it then passes into the furnace of the steam reformer.

[0083] The recirculation of the various fuel gases 24, 26, 42, 44, 45, 45′, 46, 47 to the burner of the steam reforming reactor 20 need not necessarily take place in a shared collecting line, but can also be implemented separately. This could proceed, for example, by means of two different collections at a different pressure level.

[0084] Via return line 47, the crude synthesis gas can also be recirculated to the furnace of the steam reformer even before passing through any of the cleaning devices 30, 33, 35, 40. Therefore, in the event of malfunction of any cleaning stage, the crude synthesis gas can be tapped and recirculated to the furnace, in such a manner that the amount of energy fed to the furnace and also the gas stream fed remain constant and no fluctuations in the steam reformer itself occur.

[0085] As a result, long idle times in the event of malfunction of one of the downstream cleaning stages can be reliably prevented. Furthermore, during startup, the cleaning stages can be switched on stepwise and a recycling of gas into the furnace of the steam reformer can already be switched on before the complete plant is running. As a result, considerable amounts of the carbonaceous energy carrier can be saved, which must otherwise be used for the furnace.

[0086] Furthermore, measuring devices are situated in the lines 11, 26 and 42 in order to determine the respective volume streams of the gases flowing through these lines 11, 36 and 42. In detail, in this case, the volume stream of the air fed in through the line 11 is measured using measuring device 63, the volume stream of the residual gas stream recirculated through the line 42 into the furnace of the steam reforming reactor 20 is measured using measuring device 61 and the volume stream of the energy carrier conducted through the line 26 into the furnace of the steam reforming reactor 20 is measured using measuring device 62. Suitable measuring devices are, in particular, turbine meters, rotating-vane meters, direct displacement meters, Pitot tubes, coriolis meters and ultrasonic flow metering methods.

[0087] On the basis of these values, in the manner shown the theoretical value for the volume of the crude synthesis gas stream recirculated via line 46 and/or 47 can be calculated. This theoretical value is under closed-loop or open-loop control via the metering device 51, preferably a valve, in return line 46 and the metering device 52, preferably a valve, in return line 47. Here, metering devices having integrated mass flow or volume stream measurement can also be used.

Exemplary Embodiments

[0088] Table 1 shows the composition of the volume stream in the respective lines for a plant constructed according to the invention according to FIG. 1 for production of hydrogen in mol %.

[0089] Table 2 shows the composition of the volume stream in the respective lines for a plant constructed according to the invention according to FIG. 2 for production of hydrogen and carbon monoxide in mol %.

TABLE-US-00006 TABLE 1 Stream compositions in the lines of a structure according to the invention for production of hydrogen. Line 10 11 21 23 26 27 (1) 41 42 46 H.sub.2 (mol %) 0 0 0 0 0 75.08 100 26.58 98.43 CO (mol %) 0 0 0 0 0 4.45 0 13.13 0.46 CO.sub.2 (mol %) 1.1 0.03 19.73 0.03 1.1 16.1 0 47.42 0.01 H.sub.2O (mol %) 0 0.959 17.56 0.959 0 0.306 0 0.904 0.09 N.sub.2 (mol %) 2 77.36 60.79 77.36 2 0.442 0.005 1.296 0.06 O.sub.2 (mol %) 0 20.73 1.2 20.73 0 0 0 0 0.00 CH.sub.4 (mol %) 89 0 0 0 89 3.618 0 10.67 1.17 Remainder (mol %) 7.7 0.925 0.722 0.925 7.7 0 0 0 0 (1) Dry, after condensate deposition

TABLE-US-00007 TABLE 2 Stream compositions in the lines of a structure according to the invention for production of hydrogen and carbon monoxide. Line 10 11 21 23 26 27 (1) 32 36 H.sub.2 (mol %) 0 0 0 0 0 65.8 70.8 0 CO (mol %) 0 0 0 0 0 21.4 23 99 CO.sub.2 (mol %) 0.1 7.25 7.25 7.25 0.1 6.97 0 0 H.sub.2O (mol %) 0 22 22 22 0 0.35 0.2 0 N.sub.2 (mol %) 0.9 68.6 68.6 68.6 0.9 0.22 0.25 0.6 O.sub.2 (mol %) 0 1.33 1.33 1.33 0 0 0 0 CH.sub.4 (mol %) 98 0 0 0 98 5.29 5.7 0 Remainder (mol %) 1.3 0.8 0.8 0.8 1.3 0 0 0 Line 37 41 42 43 44 45 45′ 47 H.sub.2 (mol %) 97.9 99.997 86.3 11.3 1.67 0 84.3 51 CO (mol %) 0.59 0.0001 3.91 3.3 69.8 0 10.1 3.75 CO.sub.2 (mol %) 0.01 0 0.04 66.9 0 0 0 0.04 H.sub.2O (mol %) 0.15 0 1 17.4 0 0 0 0.7 N.sub.2 (mol %) 0.05 0.003 0.33 0.02 28.5 0 0.22 1.8 O.sub.2 (mol %) 0 0 0 0 0 0 0 0 CH.sub.4 (mol %) 1.27 0.0001 8.43 1.14 0 100 5.36 42.5 Remainder (mol %) 0 0 0 0 0 0 0.01 0.2 (1) Dry, after condensate deposition

[0090] 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.

[0091] The singular forms “a”, “an” and “the” include plural referents, unless the context clearly dictates otherwise.

[0092] “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.

[0093] “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.

[0094] 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.

[0095] 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.

[0096] 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.

LIST OF REFERENCE SIGNS

[0097] 10, 11 Line

[0098] 12 Pump

[0099] 20 Steam reforming reactor with furnace

[0100] 21 Line

[0101] 22 Compressor

[0102] 23, 24 Line

[0103] 25 Heat exchanger

[0104] 26, 27 Line

[0105] 30 Scrubber

[0106] 31, 32 Line

[0107] 33 Dryer

[0108] 34 Line

[0109] 35 Low-temperature synthesis gas separation plant

[0110] 36, 37 Line

[0111] 40 Pressure-swing adsorption

[0112] 41 Line

[0113] 42-47 Return line

[0114] 51, 52 Metering device

[0115] 61-63 Measuring device