Process for increasing H2 content in syngas

Abstract

The present invention relates to a process for increasing the H2 content in synthesis gas, preferably using the hot outlet gas of an autothermal reforming process and / or a process for the partial oxidation of hydrocarbons. In particular, it has been surprisingly found that an endothermic NH3 reforming process can be combined with a hot outlet gas, e.g., from an ATR and / or POx process, to increase the H2 content in the syngas.

Description

Technical Field

[0001] The present invention relates to a method for increasing the H2 content in synthesis gas, which method preferably uses hot outlet gas of an autothermal reforming process and / or a process for partial oxidation of hydrocarbons. According to the invention, an NH3 stream is fed into the hot outlet gas to initiate thermally induced NH3 reforming. Background Art

[0002] Autothermal reforming (ATR) and partial oxidation of hydrocarbons (POx) processes are commonly used to generate synthesis gas. The methods are very important for generating synthesis gas with a certain H2:CO:CO2 molar ratio. The following equations (1)-(3) describe in a simplified manner the processes within the reformer that are important for such methods. In the equations, the CH4 shown also represents other possible hydrocarbons. Equation (4) shows the partial oxidation (POx) of CH4 (again also represents any other hydrocarbon). POx can be applied with and without catalytic materials. However, what these reforming methods have in common is that the outlet gas is very hot (up to 1350°C due to the exothermic nature of combustion with oxygen) and the synthesis gas produced is quite hydrogen-poor.

[0003] (1)

[0004] (2)

[0005] (3)

[0006] (4)

[0007] The reforming process is applied to generate a synthesis gas having a certain stoichiometric number R (also designated herein as R value), where R is defined according to the following formula:

[0008] R=[c(H2)–c(CO2)] / [c(CO2)+c(CO)],

[0009] Where c(H2), c(CO2) and c(CO) represent the molar concentrations of H2, CO2 and CO in the synthesis gas stream, respectively. Typically, the stoichiometric number R generated by the ATR / POx process is less than 2. Therefore, for example, for methanol production processes where the R value must be greater than 2, additional hydrogen must be added. For example, hydrogen can be added directly, for example from the electrolysis of water.

[0010] WO 2019 / 038251 A1 relates to an autothermal ammonia cracking process and discloses co-feeding oxygen and ammonia into an ATR reactor for preparing a product gas containing nitrogen and hydrogen. US 8,691,182 B2 and US 8,961,923 B2 relate to the cracking of ammonia and disclose a process in which gaseous ammonia and oxygen are mixed and burned, preferably at a temperature above 1100° C. However, the process does not involve the preparation of synthesis gas.

[0011] As mentioned above, autothermal reforming processes of natural gas or hydrocarbons like POx and ATR essentially produce a synthesis gas that is depleted in hydrogen. This means that additional hydrogen must be added to make the synthesis gas particularly suitable for methanol production. The hot outlet gas of the POx / ATR process is usually used for steam generation. DETAILED DESCRIPTION

[0012] It is therefore an object of the present invention to provide a method for increasing the H 2 content in synthesis gas in a particularly resource-efficient manner.

[0013] Surprisingly, it has been found that the high temperature of the outlet gas, for example, of an ATR and / or POx process, can be used as an energy source for endothermic NH3 reforming. Furthermore, it has been surprisingly found that, depending on the temperature of the hot outlet gas, it is not necessary to use catalytic materials, inert materials for heat distribution, or high temperature stable catalytic materials. Thus, it has been surprisingly found that an endothermic NH3 reforming process can be combined with hot outlet gas, for example, from an ATR and / or POx process, to increase the H2 content in the synthesis gas, in particular to adjust the stoichiometric number R of the resulting synthesis gas. Thus, the resulting synthesis gas with an increased H2 content can be used for specific downstream applications. For NH3 reforming, which is a key step for generating hydrogen, the basic reaction equation can be represented as equation (5).

[0014] (5)

[0015] Therefore, when NH3 is produced by renewable resources and the ATR / POx raw material is bio-based (renewable raw material), the present invention promotes a sustainable ATR / POx-based reforming method, for example, in combination with a methanol production site. Taking into account resource costs, it is preferred to use NH3 rather than hydrogen, for example, from water electrolysis. In addition, it is known that NH3 chemically stores a large amount of H2. Therefore, it is more cost-effective to produce H2 in situ by NH3 reforming, and it can be applied in a static manner, especially even when wind or solar energy for generating H2 by other methods is unavailable. Another advantage of the present invention is the opportunity to apply it to any raw material (like natural gas or biogas or other hydrocarbons) for autothermal reforming.

[0016] The unit bar (absolute) refers to absolute pressure, where 1 bar is equal to 10 5Pa.

[0017] The present invention is further illustrated by the following group of embodiments and the combination of embodiments obtained by the dependencies and back-references as shown. In particular, it should be noted that in each case where a series of embodiments is mentioned, for example, in the context of a term such as "a method as described in any one of embodiments 1 to 4", each embodiment in this series is intended to be clearly disclosed to the technician, that is, the wording of this term should be understood by the technician as synonymous with "a method as described in any one of embodiments 1, 2, 3 and 4". In addition, it is explicitly pointed out that the following group of embodiments is not a group of claims that determine the scope of protection, but represents an appropriate structural part of this specification related to the general and preferred aspects of the present invention.

[0018] The present invention therefore relates to a method for increasing the H2 content of a gas stream comprising H2 and CO (synthesis gas), the method comprising

[0019] (i) providing a first gas stream comprising CO and H2 and optionally further comprising CO2, wherein the first gas stream has a temperature in the range of 750°C to 1600°C;

[0020] (ii) providing a second gas stream comprising NH3;

[0021] (iii) contacting the second gas stream provided in (ii) with the first gas stream provided in (i) to convert at least a portion of the NH3 into N2 and H2.

[0022] Preferably, the first gas stream provided in (i) has a temperature in the range of 800 to 1600°C, more preferably in the range of 875 to 1450°C, more preferably in the range of 900 to 1425°C.

[0023] In case the first gas stream provided in (i) has a temperature in the range of 800°C to 1600°C, it is preferred according to the first alternative that the first gas stream provided in (i) has a temperature in the range of 900°C to 1200°C, more preferably in the range of 950°C to 1000°C.

[0024] In case the first gas stream provided in (i) has a temperature in the range of 800°C to 1600°C, it is preferred according to the second alternative that the first gas stream provided in (i) has a temperature in the range of 1100°C to 1500°C, more preferably in the range of 1325°C to 1375°C.

[0025] Preferably, the first gas stream provided in (i) has a molar ratio of H2 to CO higher than 0.1:1, more preferably in the range of 0.1:1 to 10:1, more preferably in the range of 1.0:1 to 5.0:1, more preferably in the range of 1.6:1 to 3.4:1.

[0026] Preferably, the first gas stream provided in (i) comprises H2O, and wherein the first gas stream provided in (i) has a molar ratio of H2 to H2O higher than 0.1:1, more preferably in the range of 0.1:1 to 250:1, more preferably in the range of 1.0:1 to 200:1, more preferably in the range of 1.8:1 to 190:1.

[0027] Preferably, the first gas stream provided in (i) comprises H2O, and wherein the first gas stream provided in (i) has a molar ratio of CO to H2O higher than 0.1:1, more preferably in the range of 0.1:1 to 150:1, more preferably in the range of 0.4:1 to 120:1, more preferably in the range of 0.5:1 to 105:1.

[0028] Preferably, the first gas stream provided in (i) comprises 35 to 75 vol-%, more preferably 45 to 65 vol-% H2.

[0029] Preferably, the first gas stream provided in (i) comprises 5 to 45 vol-% CO, more preferably 12 to 36 vol-%.

[0030] Preferably, the first gas stream provided in (i) comprises H2O, and wherein the first gas stream provided in (i) comprises 0.1 to 30 vol-%, more preferably 0.3 to 25 vol-% H2O.

[0031] Preferably, the first gas stream provided in (i) comprises CO2, and wherein the first gas stream provided in (i) comprises 0.1 to 30 vol-%, more preferably 0.3 to 25 vol-% CO2.

[0032] Preferably, the first gas stream provided in (i) comprises 0 to 5 vol-%, more preferably 0 to 4.0 vol-%, more preferably 0 to 3.3 vol-% CH4.

[0033] Preferably, the first gas stream provided in (i) comprises 0 to 5 vol-%, more preferably 0 to 2.5 vol-%, more preferably 0 to 1.0 vol-% N2.

[0034] Preferably, the first gas stream provided in (i) comprises 0 to 1 vol-%, more preferably 0 to 0.5 vol-%, more preferably 0 to 0.1 vol-% Ar.

[0035] Preferably, the first gas flow provided in (i) comprises 0 to 1 vol-%, more preferably 0 to 0.5 vol-%, more preferably 0 to 0.1 vol-% O2, wherein the first precursor gas flow provided in (i) is more preferably free of O2.

[0036] Preferably, the first gas stream provided in (i) comprises 0 to 1 vol-% NH3, more preferably 0 to 0.1 vol-%, more preferably 0 to 0.01 vol-% NH3.

[0037] Preferably, the first gas stream provided in (i) comprises CO2.

[0038] Preferably, the first gas stream provided in (i) has a stoichiometric number R1 below 2.00, wherein R1 is defined according to formula (I):

[0039] R1=[c1(H2)–c1(CO2)] / [c1(CO2)+c1(CO)](I),

[0040] Wherein c1(H2), c1(CO2) and c1(CO) represent the molar concentrations of H2, CO2 and CO in the first gas flow, respectively.

[0041] Preferably, the first gas stream provided in (i) comprises a gas stream obtainable or obtained by one or more of the following: a gasification reaction of waste, a gasification reaction of biomass, an autothermal reforming reaction, and a partial oxidation reaction of one or more hydrocarbons, wherein the hydrocarbons are selected from (C1-C 10 )alkanes, more preferably (C1-C8)alkanes, more preferably (C1-C7)alkanes.

[0042] Preferably, providing the first gas stream according to (i) comprises

[0043] (i.1) providing a first precursor gas flow comprising CH4;

[0044] (i.2) providing a second precursor gas flow comprising O2;

[0045] (i.3) contacting the second precursor gas stream with the first precursor gas stream to react CH4 with O2 to produce CO, H2 and optionally H2O.

[0046] In the case where the first gas flow provided according to (i) includes (i.1), (i.2) and (i.3), it is preferred that the first precursor gas flow provided in (i.1) further contains H2, wherein the first precursor gas flow more preferably has a molar ratio of CH4 to H2 higher than 20:1, more preferably in the range of 20:1 to 43:1, more preferably in the range of 27:1 to 36:1, and even more in the range of 30:1 to 33:1.

[0047] In addition, in the case where the first gas flow provided according to (i) includes (i.1), (i.2) and (i.3), it is preferred that the first precursor gas flow provided in (i.1) further contains CO2, wherein the first precursor gas flow provided in (i.1) more preferably has a molar ratio of CH4 to CO2 in the range of 1:1 to 300:1, more preferably in the range of 2:1 to 275:1, and more preferably in the range of 10:1 to 225:1.

[0048] In case the first precursor gas flow provided in (i.1) further comprises CO2, according to the first alternative it is preferred that the first precursor gas flow provided in (i.1) has a molar ratio of CH4 to CO2 in the range of 200:1 to 275:1, more preferably in the range of 230:1 to 250:1.

[0049] In case the first precursor gas flow provided in (i.1) further comprises CO2, according to the second alternative it is preferred that the first precursor gas flow provided in (i.1) has a molar ratio of CH4 to CO2 in the range of 2:1 to 10:1, more preferably in the range of 2.2:1 to 5.0:1.

[0050] In addition, in the case where the first gas flow provided according to (i) includes (i.1), (i.2) and (i.3), it is preferred that the first precursor gas flow provided in (i.1) has a molar ratio of H2 to CO2 less than 20:1, more preferably in the range of 0 to 15:1, and more preferably in the range of 0 to 10:1.

[0051] Furthermore, in the case where the first gas flow provided according to (i) comprises (i.1), (i.2) and (i.3), preferably, the first precursor gas flow provided in (i.1) contains 40 to 96 vol. %, more preferably 65 to 95 vol. % CH4.

[0052] In case the first precursor gas flow provided in (i.1) comprises 40 to 96 vol-%, it is preferred according to the first alternative that the first precursor gas flow provided in (i.1) comprises 90 to 95 vol-%, more preferably 91 to 94 vol-% CH4.

[0053] In case the first precursor gas flow provided in (i.1) comprises 40 to 96 vol-%, it is preferred according to the first alternative that the first precursor gas flow provided in (i.1) comprises 65 to 75 vol-%, more preferably 68 to 71 vol-% CH4.

[0054] In addition, in the case where the first gas flow provided according to (i) includes (i.1), (i.2) and (i.3), it is preferred that the first precursor gas flow provided in (i.1) contains 0 to 10 volume-%, more preferably 0 to 3.5 volume-%, more preferably 0 to 3.1 volume-% H2.

[0055] Furthermore, in the case where the first gas flow provided according to (i) comprises (i.1), (i.2) and (i.3), preferably, the first precursor gas flow provided in (i.1) contains 0 to 35 vol.-%, more preferably 0.1 to 32 vol.-% CO2.

[0056] In case the first precursor gas flow provided in (i.1) comprises 0 to 35 vol-%, it is preferred according to the first alternative that the first precursor gas flow provided in (i.1) comprises 0.1 to 2.0 vol-%, more preferably 0.2 to 0.8 vol-% CO2.

[0057] In case the first precursor gas flow provided in (i.1) comprises 0 to 35 vol-%, it is preferred according to the second alternative that the first precursor gas flow provided in (i.1) comprises 20 to 32 vol-%, more preferably 25 to 31 vol-% CO2.

[0058] In addition, in the case where the first gas flow provided according to (i) includes (i.1), (i.2) and (i.3), it is preferred that the first precursor gas flow provided in (i.1) contains 0 to 5 volume-%, more preferably 0 to 2.5 volume-%, more preferably 0 to 2.4 volume-% of (C2-C7) alkanes.

[0059] In addition, in the case where the first gas flow provided according to (i) includes (i.1), (i.2) and (i.3), it is preferred that the first precursor gas flow provided in (i.1) contains 0 to 5 volume-%, more preferably 0.1 to 2.5 volume-%, more preferably 0.3 to 2.2 volume-% N2.

[0060] In addition, in the case where the first gas flow provided according to (i) includes (i.1), (i.2) and (i.3), it is preferred that the first precursor gas flow provided in (i.1) contains 0 to 1 volume-%, more preferably 0 to 0.5 volume-%, more preferably 0 to 0.1 volume-% H2O, wherein the first precursor gas flow provided in (i.1) more preferably does not contain H2O.

[0061] In addition, in the case where the first gas flow provided according to (i) includes (i.1), (i.2) and (i.3), it is preferred that 95 to 100 volume-%, more preferably 99 to 100 volume-%, more preferably 99.9 to 100 volume-% of the second precursor gas flow provided in (i.2) consists of O2.

[0062] In addition, in the case where the first gas flow provided according to (i) includes (i.1), (i.2) and (i.3), it is preferred that the second precursor gas flow provided in (i.2) has a flow rate of 1,000 to 10,000 m / s. 3 In the range of 3,800 to 6,900 m / h, more preferably in the range of 3,800 to 6,900 m / h 3 In the range of 4,100 to 6,600 m / h, more preferably in the range of 4,100 to 6,600 m / h 3 Volume flow rate in the range of / h.

[0063] In addition, in the case where the first gas flow provided according to (i) includes (i.1), (i.2) and (i.3), it is preferred that the second precursor gas flow provided in (i.2) has a mass flow rate in the range of 3,000 to 12,000 kg / h, more preferably in the range of 5,500 to 9,800 kg / h, and more preferably in the range of 5,900 to 9,400 kg / h.

[0064] In addition, in the case where the first gas flow provided according to (i) includes (i.1), (i.2) and (i.3), it is preferred that the contact according to (i.3) is carried out at a pressure in the range of 1 to 70 bar (absolute value), more preferably in the range of 10 to 60 bar (absolute value), and more preferably in the range of 20 to 50 bar (absolute value).

[0065] Preferably, the second gas stream provided in (ii) has a different chemical composition than the first gas stream provided in (i).

[0066] Preferably, the second gas stream provided in (ii) has a flow rate of 100 to 10,000 m / s. 3 In the range of 1,100 to 8,700 m / h, more preferably 1,100 to 8,700 m / h 3 In the range of 1,400 to 8,400 m / h, more preferably 1,400 to 8,400 m / h 3 Volume flow rate in the range of / h.

[0067] Preferably, the second gas stream provided in (ii) has a mass flow rate in the range of 100 to 7,000 kg / h, more preferably in the range of 900 to 6,600 kg / h, more preferably in the range of 1,100 to 6,400 kg / h.

[0068] Preferably, the second gas stream provided in (ii) has a temperature in the range 100 to 500°C, more preferably in the range 250 to 350°C, more preferably in the range 275 to 325°C.

[0069] Preferably, the contacting in (iii) is carried out in a reactor.

[0070] Preferably, contacting the second gas stream with the first gas stream according to (iii) is carried out at a pressure in the range of 1 to 90 bar (absolute), more preferably in the range of 10 to 80 bar (absolute), more preferably in the range of 20 to 70 bar (absolute), more preferably in the range of 25 to 60 bar (absolute).

[0071] Preferably, the contacting in (iii) is carried out at a temperature in the range of 850°C to 1400°C, more preferably in the range of 950°C to 1350°C.

[0072] In case the contacting in (iii) is carried out at a temperature in the range of 850°C to 1400°C, it is preferred according to the first alternative that the contacting in (iii) is carried out in a reactor and wherein the reactor comprises an inert material, and wherein the contacting in (iii) is more preferably carried out at a temperature in the range of 850°C to 1200°C, more preferably in the range of 875°C to 1100°C, wherein the inert material more preferably comprises one or more of quartz, SiC, alpha alumina, talc, BN, Si3N4 and ceramics.

[0073] In case the contacting in (iii) is carried out at a temperature in the range of 850°C to 1400°C, it is preferred according to the second alternative that the contacting in (iii) is carried out in a reactor, and wherein the reactor contains a catalytic material, and wherein the contacting in (iii) is more preferably carried out at a temperature in the range of 700°C to 925°C, more preferably in the range of 750°C to 900°C.

[0074] In case the reactor comprises a catalytic material, it is preferred that the catalytic material comprises a metal M1, wherein M1 is Ni, Co or Ni and Co.

[0075] In the case where the catalytic material comprises a metal M1 (wherein M1 is Ni, Co or Ni and Co), preferably, the catalytic material further comprises a metal M2 selected from the group consisting of alkali metals, alkaline earth metals, Mo, Fe, Ru (including mixtures of two or more thereof), more preferably selected from the group consisting of Li, K, Na, Cs, Mg, Ca, Sr, Ba, Mo, Fe, Ru (including mixtures of two or more thereof), more preferably selected from the group consisting of K, Na, Cs, Ba, Mo, Fe, Ru (including mixtures of two or more thereof), more preferably selected from the group consisting of K, Ba, Mo, Fe, Ru and mixtures of two or more thereof, wherein M2 more preferably comprises Fe, Ru or Fe and Ru, wherein more preferably M2 comprises Ru, wherein more preferably M2 is Ru.

[0076] In addition, in the case where the catalytic material comprises a metal M1 (wherein M1 is Ni, Co or Ni and Co), it is preferred that the catalytic material further comprises a carrier material on which one or more metals M1 or metals M1 and M2 are loaded, wherein the one or more carrier materials are more preferably selected from the group consisting of Al2O3, SiO2, ZrO2, CeO2, MgO, CaO and a mixture of two or more thereof, more preferably selected from the group consisting of Al2O3, SiO2, ZrO2, CeO2 and a mixture of two or more thereof, more preferably selected from the group consisting of Al2O3, SiO2 and a mixture thereof, wherein more preferably the carrier material comprises Al2O3.

[0077] Furthermore, where the catalytic material comprises a metal M1, wherein M1 is Ni, Co or Ni and Co, it is preferred that the catalytic material further comprises a metal M2 as defined herein, and it is preferred that the catalytic material exhibits an atomic ratio of M2:M1 in the range of 0.1:99.9 to 80:20, more preferably 0.5:99.5 to 75:25, more preferably 1:99 to 70:30, more preferably 5:95 to 65:35, more preferably 15:85 to 60:40, more preferably 30:70 to 55:45, and more preferably 40:60 to 50:50.

[0078] In case the catalytic material comprises a metal M2 as defined herein and exhibits an atomic ratio of M2:M1 in the range of 0.1:99.9 to 80:20, it is preferred that M2 comprises, more preferably is Fe, and wherein the catalytic material exhibits an atomic ratio of M2:M1 in the range of 1:99 to 80:20, preferably 5:95 to 75:25, more preferably 10:90 to 70:30, more preferably 20:80 to 65:35, more preferably 30:70 to 60:40, more preferably 35:65 to 55:45, and more preferably 40:60 to 50:50.

[0079] Furthermore, in case the catalytic material comprises a metal M2 as defined herein and exhibits an atomic ratio of M2:M1 in the range of 0.1:99.9 to 80:20, it is preferred that M2 comprises, more preferably is Ru, and wherein the catalytic material exhibits an atomic ratio of M2:M1 in the range of 0.1:99.9 to 30:70, preferably 0.5:99.5 to 30:70, more preferably 1:99 to 20:80, more preferably 3:97 to 10:90, and more preferably 5:95 to 6:94.

[0080] Furthermore, in the case where the catalytic material contains metal M1 (wherein M1 is Ni, Co, or Ni and Co), it is preferred that the catalytic material further contains Al and O.

[0081] In the case where the catalytic material further comprises Al and O, it is preferred that the catalytic material comprises Ni as the metal M1, wherein more preferably the metal M1 is Ni.

[0082] In the case where the catalytic material comprises Ni as the metal M1, it is preferred that the catalytic material further comprises Mg, wherein the Ni:Mg:Al molar ratio is more preferably in the range of 1:(0.1-12):(0.5-20), more preferably 1:(0.5-8):(1-12), more preferably 1:(1-5):(3-8), more preferably 1:(1.5-3):(3.5-5), and more preferably 1:(2.0-2.4):(4.0-4.4).

[0083] Furthermore, in case the catalytic material comprises Ni as metal M1, it is preferred according to the first alternative that 95 to 100 wt.-%, more preferably 97 to 100 wt.-%, more preferably 98 to 100 wt.-%, more preferably 99 to 100 wt.-%, more preferably 99.5 to 100 wt.-%, and more preferably 99.9 to 100 wt.-% of the catalytic material consists of Ni, Mg, Al and O.

[0084] Furthermore, in case the catalytic material comprises Ni as metal M1, according to the second alternative it is preferred that 95 to 100 wt.-%, more preferably 97 to 100 wt.-%, more preferably 98 to 100 wt.-%, more preferably 99 to 100 wt.-%, more preferably 99.5 to 100 wt.-%, and more preferably 99.9 to 100 wt.-% of the catalytic material consists of M2, Ni, Mg, Al and O.

[0085] Furthermore, in the case where the catalytic material further contains Al and O, it is preferred that the catalytic material contains Co as the metal M1, wherein the metal M1 is more preferably Co.

[0086] In the case where the catalytic material comprises Ni as the metal M1, it is preferred that the catalytic material further comprises La, wherein the Co:La:Al molar ratio is more preferably in the range of 1:(0.1-8):(1-50), more preferably 1:(0.5-5):(3-30), more preferably 1:(0.8-3):(5-20), more preferably 1:(1-2):(8-15), and more preferably 1:(1.3-1.7):(10-12).

[0087] Furthermore, in case the catalytic material comprises Co as metal M1, it is preferred according to the first alternative that 95 to 100 wt.-%, more preferably 97 to 100 wt.-%, more preferably 98 to 100 wt.-%, more preferably 99 to 100 wt.-%, more preferably 99.5 to 100 wt.-%, and more preferably 99.9 to 100 wt.-% of the catalytic material consists of Co, La, Al and O.

[0088] Furthermore, in case the catalytic material comprises Co as metal M1, according to the second alternative it is preferred that 95 to 100 wt.-%, more preferably 97 to 100 wt.-%, more preferably 98 to 100 wt.-%, more preferably 99 to 100 wt.-%, more preferably 99.5 to 100 wt.-%, and more preferably 99.9 to 100 wt.-% of the catalytic material consists of M2, Co, La, Al and O.

[0089] Preferably, in (iii), 90 to 100 vol-%, more preferably 94 to 100 vol-%, more preferably 96 to 100 vol-% of the NH3 is converted.

[0090] Preferably, the gas stream obtained in (iii) comprises H2, CO and CO2, wherein the gas stream obtained in (iii) more preferably has a stoichiometric number R equal to or greater than 2.00, more preferably in the range of 2.02 to 2.15, more preferably in the range of 2.04 to 2.06. 合成气 , where R 合成气 According to formula (II):

[0091] R 合成气 =[c 合成气 (H2)–c 合成气 (CO2)] / [c 合成气 (CO2)+c 合成气 (CO)](II),

[0092] where c 合成气 (H2), c 合成气 (CO2) and c合成气 (CO) represent the molar concentrations of H2, CO2 and CO in the gas stream obtained in (iii), respectively.

[0093] Preferably, the gas stream obtained in (iii) has a molar ratio of H2 to CO in the range of 0.5:1 to 10.0:1, more preferably in the range of 1.0:1 to 7.5:1, more preferably in the range of 1.9:1 to 4.8:1, more preferably in the range of 2.1:1 to 4.6:1.

[0094] Preferably, the gas stream obtained in (iii) has a molar ratio of H2 to CO2 in the range of 0.5:1 to 40.0:1, more preferably in the range of 4.9:1 to 36.0:1, more preferably in the range of 5.4:1 to 35.0:1.

[0095] Preferably, the gas stream obtained in (iii) has a molar ratio of CO to CO2 in the range of 0.1:1 to 21.0:1, more preferably in the range of 0.8:1 to 17.0:1, more preferably in the range of 1.0:1 to 15.0:1.

[0096] Preferably, the gas stream obtained in (iii) comprises 50 to 85 vol-%, more preferably 58 to 80 vol-%, more preferably 61 to 75 vol-% H2.

[0097] Preferably, the gas stream obtained in (iii) comprises 0 to 10 vol-%, more preferably 0 to 5 vol-%, more preferably 0 to 4.0 vol-% CH4.

[0098] Preferably, the gas stream obtained in (iii) comprises 0.1 to 20.0 vol-%, more preferably 1.5 to 12.0 vol-%, more preferably 1.8 to 11.3 vol-% CO2.

[0099] Preferably, the gas stream obtained in (iii) comprises 0.1 to 20.0 vol-%, more preferably 1.8 to 13.0 vol-%, more preferably 2.3 to 12.1 vol-% N2.

[0100] Preferably, the gas stream obtained in (iii) comprises 0 to 1 vol-%, more preferably 0 to 0.5 vol-%, more preferably 0 to 0.1 vol-% H2O, wherein the first precursor gas stream provided in (i.1) is more preferably free of H2O.

[0101] Preferably, the method further comprises

[0102] (iv) separating residual NH3 from the gas stream obtained in (iii) to obtain a purified gas stream.

[0103] Furthermore, the present invention relates to a process for the preparation of alcohol, preferably methanol, using a gas stream comprising H2 and CO and optionally further comprising CO2, wherein the gas stream is obtained according to any of the embodiments disclosed herein, wherein the process comprises

[0104] (v) using the gas stream obtained in (iii) or the purified gas stream obtained in (iv) as feed stream.

[0105] Still further, the present invention relates to a method for preparing hydrocarbons, preferably (C 10 -C 20 ) an alkane or an ether, preferably dimethyl ether, the method employing a gas stream comprising H2 and CO and optionally further comprising CO2, wherein the gas stream is obtained according to any one of the embodiments disclosed herein, wherein the method comprises

[0106] (v) using the gas stream obtained in (iii) or the purified gas stream obtained in (iv) as feed stream.

[0107] The unit bar (absolute) refers to absolute pressure, where 1 bar is equal to 10 5 Pa.

[0108] The present invention is further illustrated by the following group of embodiments and the combination of embodiments obtained by the dependencies and back-references as shown. In particular, it should be noted that in each case where a series of embodiments is mentioned, for example, in the context of a term such as "a method as described in any one of embodiments 1 to 4", each embodiment in this series is intended to be clearly disclosed to the technician, that is, the wording of this term should be understood by the technician as synonymous with "a method as described in any one of embodiments 1, 2, 3 and 4". In addition, it is explicitly pointed out that the following group of embodiments is not a group of claims that determine the scope of protection, but represents an appropriate structural part of this specification related to the general and preferred aspects of the present invention.

[0109] 1. A method for increasing the H2 content in a gas stream containing H2 and CO (syngas), the method comprising

[0110] (i) providing a first gas stream comprising CO and H2 and optionally further comprising CO2, wherein the first gas stream has a temperature in the range of 750°C to 1600°C;

[0111] (ii) providing a second gas stream comprising NH3;

[0112] (iii) contacting the second gas stream provided in (ii) with the first gas stream provided in (i) to convert at least a portion of the NH3 into N2 and H2.

[0113] 2. The method of embodiment 1, wherein the first gas stream provided in (i) has a temperature in the range of 800°C to 1600°C, preferably in the range of 875°C to 1450°C, more preferably in the range of 900°C to 1425°C.

[0114] 3. The method of embodiment 2, wherein the first gas stream provided in (i) has a temperature in the range of 900°C to 1200°C, preferably in the range of 950°C to 1000°C.

[0115] 4. The method of embodiment 2, wherein the first gas stream provided in (i) has a temperature in the range from 1100°C to 1500°C, preferably in the range from 1325°C to 1375°C.

[0116] 5. The method of any one of embodiments 1 to 4, wherein the first gas stream provided in (i) has a molar ratio of H2 to CO greater than 0.1:1, preferably in the range of 0.1:1 to 10:1, more preferably in the range of 1.0:1 to 5.0:1, and even more in the range of 1.6:1 to 3.4:1.

[0117] 6. The method of any one of embodiments 1 to 5, wherein the first gas stream provided in (i) comprises H2O, and wherein the first gas stream provided in (i) has a molar ratio of H2 to H2O greater than 0.1:1, preferably in the range of 0.1:1 to 250:1, more preferably in the range of 1.0:1 to 200:1, and even more in the range of 1.8:1 to 190:1.

[0118] 7. The method of any one of embodiments 1 to 6, wherein the first gas stream provided in (i) comprises H2O, and wherein the first gas stream provided in (i) has a molar ratio of CO to H2O higher than 0.1:1, preferably in the range of 0.1:1 to 150:1, more preferably in the range of 0.4:1 to 120:1, and even more in the range of 0.5:1 to 105:1.

[0119] 8. The method of any one of embodiments 1 to 7, wherein the first gas stream provided in (i) comprises 35 to 75 vol-%, preferably 45 to 65 vol-% H2.

[0120] 9. The method of any one of embodiments 1 to 8, wherein the first gas stream provided in (i) comprises 5 to 45 vol-%, preferably 12 to 36 vol-% CO.

[0121] 10. The method of any one of embodiments 1 to 9, wherein the first gas stream provided in (i) comprises H2O, and wherein the first gas stream provided in (i) comprises 0.1 to 30 vol-%, preferably 0.3 to 25 vol-% H2O.

[0122] 11. The method of any one of embodiments 1 to 10, wherein the first gas stream provided in (i) comprises CO2, and wherein the first gas stream provided in (i) comprises 0.1 to 30 volume-%, preferably 0.3 to 25 volume-% CO2.

[0123] 12. The method of any one of embodiments 1 to 11, wherein the first gas stream provided in (i) comprises 0 to 5 vol-%, preferably 0 to 4.0 vol-%, more preferably 0 to 3.3 vol-% CH4.

[0124] 13. The method of any one of embodiments 1 to 12, wherein the first gas stream provided in (i) comprises 0 to 5 vol-%, preferably 0 to 2.5 vol-%, more preferably 0 to 1.0 vol-% N2.

[0125] 14. The method of any one of embodiments 1 to 13, wherein the first gas stream provided in (i) comprises 0 to 1 vol-%, preferably 0 to 0.5 vol-%, more preferably 0 to 0.1 vol-% Ar.

[0126] 15. A method as described in any one of embodiments 1 to 14, wherein the first gas flow provided in (i) contains 0 to 1 volume-%, preferably 0 to 0.5 volume-%, more preferably 0 to 0.1 volume-% O2, wherein the first precursor gas flow provided in (i) is more preferably free of O2.

[0127] 16. The method of any one of embodiments 1 to 15, wherein the first gas stream provided in (i) comprises 0 to 1 vol-% NH3, preferably 0 to 0.1 vol-%, more preferably 0 to 0.01 vol-% NH3.

[0128] 17. The method of any one of embodiments 1 to 16, wherein the first gas stream provided in (i) comprises CO2.

[0129] 18. The method of any one of embodiments 1 to 17, wherein the first gas stream provided in (i) has a stoichiometric number R1 of less than 2.00, wherein R1 is defined according to formula (I):

[0130] R1=[c1(H2)–c1(CO2)] / [c1(CO2)+c1(CO)](I),

[0131] Wherein c1(H2), c1(CO2) and c1(CO) represent the molar concentrations of H2, CO2 and CO in the first gas flow, respectively.

[0132] 19. The method of any one of embodiments 1 to 18, wherein the first gas stream provided in (i) comprises a gas stream obtainable or obtained by one or more of: a gasification reaction of waste, a gasification reaction of biomass, an autothermal reforming reaction, and a partial oxidation reaction of one or more hydrocarbons, wherein the hydrocarbons are selected from (C1-C 10 )alkanes, preferably (C1-C8)alkanes, more preferably (C1-C7)alkanes.

[0133] 20. The method of any one of embodiments 1 to 19, wherein providing the first gas stream according to (i) comprises

[0134] (i.1) providing a first precursor gas flow comprising CH4;

[0135] (i.2) providing a second precursor gas flow comprising O2;

[0136] (i.3) contacting the second precursor gas stream with the first precursor gas stream to react CH4 with O2 to produce CO, H2 and optionally H2O.

[0137] 21. A method as described in Example 20, wherein the first precursor gas flow provided in (i.1) further comprises H2, wherein the first precursor gas flow preferably has a molar ratio of CH4 to H2 higher than 20:1, preferably in the range of 20:1 to 43:1, more preferably in the range of 27:1 to 36:1, and even more in the range of 30:1 to 33:1.

[0138] 22. A method as described in Example 20 or 21, wherein the first precursor gas flow provided in (i.1) further contains CO2, wherein the first precursor gas flow provided in (i.1) preferably has a molar ratio of CH4 to CO2 in the range of 1:1 to 300:1, preferably in the range of 2:1 to 275:1, and more preferably in the range of 10:1 to 225:1.

[0139] 23. The method of embodiment 22, wherein the first precursor gas flow provided in (i.1) has a molar ratio of CH4 to CO2 in the range of 200:1 to 275:1, preferably in the range of 230:1 to 250:1.

[0140] 24. The method of embodiment 22, wherein the first precursor gas stream provided in (i.1) has a molar ratio of CH4 to CO2 in the range of 2:1 to 10:1, preferably in the range of 2.2:1 to 5.0:1.

[0141] 25. A method as described in any of Embodiments 20 to 24, wherein the first precursor gas flow provided in (i.1) has a molar ratio of H2 to CO2 less than 20:1, preferably in the range of 0 to 15:1, and more preferably in the range of 0 to 10:1.

[0142] 26. The method of any one of embodiments 20 to 25, wherein the first precursor gas flow provided in (i.1) comprises 40 to 96 vol-%, preferably 65 to 95 vol-% CH4.

[0143] 27. The method of embodiment 26, wherein the first precursor gas flow provided in (i.1) comprises 90 to 95 vol-%, preferably 91 to 94 vol-% CH4.

[0144] 28. The method of embodiment 26, wherein the first precursor gas flow provided in (i.1) comprises 65 to 75 vol-%, preferably 68 to 71 vol-% CH4.

[0145] 29. The method of any one of embodiments 20 to 28, wherein the first precursor gas flow provided in (i.1) comprises 0 to 10 vol-%, preferably 0 to 3.5 vol-%, more preferably 0 to 3.1 vol-% H2.

[0146] 30. The method of any one of embodiments 20 to 29, wherein the first precursor gas flow provided in (i.1) comprises 0 to 35 vol-%, preferably 0.1 to 32 vol-% CO2.

[0147] 31. The method of embodiment 30, wherein the first precursor gas flow provided in (i.1) comprises 0.1 to 2.0 vol-%, preferably 0.2 to 0.8 vol-% CO2.

[0148] 32. The method of embodiment 30, wherein the first precursor gas flow provided in (i.1) comprises 20 to 32 vol-%, preferably 25 to 31 vol-% CO2.

[0149] 33. A method as described in any of embodiments 20 to 32, wherein the first precursor gas flow provided in (i.1) contains 0 to 5 volume-%, preferably 0 to 2.5 volume-%, more preferably 0 to 2.4 volume-% of (C2-C7) alkanes.

[0150] 34. A method as described in any of Embodiments 20 to 33, wherein the first precursor gas flow provided in (i.1) contains 0 to 5 volume-%, preferably 0.1 to 2.5 volume-%, more preferably 0.3 to 2.2 volume-% N2.

[0151] 35. A method as described in any one of Examples 20 to 34, wherein the first precursor gas flow provided in (i.1) contains 0 to 1 volume-%, preferably 0 to 0.5 volume-%, more preferably 0 to 0.1 volume-% H2O, wherein the first precursor gas flow provided in (i.1) is more preferably free of H2O.

[0152] 36. A method as described in any of embodiments 20 to 35, wherein 95 to 100 volume-%, preferably 99 to 100 volume-%, more preferably 99.9 to 100 volume-% of the second precursor gas flow provided in (i.2) consists of O2.

[0153] 37. The method of any one of embodiments 20 to 36, wherein the second precursor gas flow provided in (i.2) has a flow rate of 1,000 to 10,000 m / s. 3 / h range, preferably between 3,800 and 6,900 m / h 3 In the range of 4,100 to 6,600 m / h, more preferably in the range of 4,100 to 6,600 m / h 3 Volume flow rate in the range of / h.

[0154] 38. A method as described in any of Embodiments 20 to 37, wherein the second precursor gas flow provided in (i.2) has a mass flow rate in the range of 3,000 to 12,000 kg / h, preferably in the range of 5,500 to 9,800 kg / h, more preferably in the range of 5,900 to 9,400 kg / h.

[0155] 39. The method of any one of embodiments 20 to 38, wherein the contacting according to (i.3) is carried out at a pressure in the range of 1 to 70 bar (absolute value), preferably in the range of 10 to 60 bar (absolute value), more preferably in the range of 20 to 50 bar (absolute value).

[0156] 40. The method of any one of embodiments 1 to 39, wherein the second gas stream provided in (ii) has a different chemical composition than the first gas stream provided in (i).

[0157] 41. The method of any one of embodiments 1 to 40, wherein the second gas stream provided in (ii) has a flow rate of 100 to 10,000 m / s. 3 / h range, preferably 1,100 to 8,700 m / h3 In the range of 1,400 to 8,400 m / h, more preferably in the range of 1,400 to 8,400 m / h 3 Volume flow rate in the range of / h.

[0158] 42. The method of any one of embodiments 1 to 41, wherein the second gas stream provided in (ii) has a mass flow rate in the range of 100 to 7,000 kg / h, preferably in the range of 900 to 6,600 kg / h, more preferably in the range of 1,100 to 6,400 kg / h.

[0159] 43. The method of any one of embodiments 1 to 42, wherein the second gas stream provided in (ii) has a temperature in the range of 100°C to 500°C, preferably in the range of 250°C to 350°C, more preferably in the range of 275°C to 325°C.

[0160] 44. The method of any one of embodiments 1 to 43, wherein the contacting in (iii) is performed in a reactor.

[0161] 45. A method as described in any of Examples 1 to 44, wherein contacting the second gas stream with the first gas stream according to (iii) is carried out at a pressure in the range of 1 to 90 bar (absolute value), preferably in the range of 10 to 80 bar (absolute value), more preferably in the range of 20 to 70 bar (absolute value), more preferably in the range of 25 to 60 bar (absolute value).

[0162] 46. ​​The method of any one of embodiments 1 to 45, wherein the contacting in (iii) is performed at a temperature in the range of 850°C to 1400°C, preferably in the range of 950°C to 1350°C.

[0163] 47. A method as described in Example 46, wherein the contacting in (iii) is carried out in a reactor, and wherein the reactor contains an inert material, and wherein the contacting in (iii) is preferably carried out at a temperature in the range of 850°C to 1200°C, preferably in the range of 875°C to 1100°C, wherein the inert material preferably includes one or more of quartz, SiC, α-alumina, talc, BN, Si3N4 and ceramics.

[0164] 48. A method as described in Example 46, wherein the contacting in (iii) is carried out in a reactor, and wherein the reactor contains a catalytic material, and wherein the contacting in (iii) is preferably carried out at a temperature in the range of 700°C to 925°C, preferably in the range of 750°C to 900°C.

[0165] 49. The method of embodiment 48, wherein the catalytic material comprises a metal M1, wherein M1 is Ni, Co, or Ni and Co.

[0166] 50. A method as described in Example 49, wherein the catalytic material further comprises a metal M2 selected from the group consisting of alkali metals, alkaline earth metals, Mo, Fe, Ru, including mixtures of two or more thereof, preferably selected from the group consisting of Li, K, Na, Cs, Mg, Ca, Sr, Ba, Mo, Fe, Ru, including mixtures of two or more thereof, more preferably selected from the group consisting of K, Na, Cs, Ba, Mo, Fe, Ru, including mixtures of two or more thereof, more preferably selected from the group consisting of K, Ba, Mo, Fe, Ru and mixtures of two or more thereof, wherein M2 more preferably comprises Fe, Ru or Fe and Ru, wherein more preferably M2 comprises Ru, wherein more preferably M2 is Ru.

[0167] 51. A method as described in Example 49 or 50, wherein the catalytic material further comprises one or more carrier materials on which the metal M1 or the metal M1 and M2 are loaded, wherein the one or more carrier materials are preferably selected from the group consisting of Al2O3, SiO2, ZrO2, CeO2, MgO, CaO and a mixture of two or more thereof, more preferably selected from the group consisting of Al2O3, SiO2, ZrO2, CeO2 and a mixture of two or more thereof, more preferably selected from the group consisting of Al2O3, SiO2 and a mixture thereof, wherein more preferably the carrier material comprises Al2O3.

[0168] 52. The method of any one of embodiments 49 to 51, wherein the catalytic material further comprises a metal M2 as defined in embodiment 50, and wherein the catalytic material exhibits an M2:M1 atomic ratio in the range of 0.1:99.9 to 80:20, preferably 0.5:99.5 to 75:25, more preferably 1:99 to 70:30, more preferably 5:95 to 65:35, more preferably 15:85 to 60:40, more preferably 30:70 to 55:45, and more preferably 40:60 to 50:50.

[0169] 53. A method as described in Example 52, wherein M2 includes, preferably is Fe, and wherein the catalytic material exhibits an M2:M1 atomic ratio in the range of 1:99 to 80:20, preferably 5:95 to 75:25, more preferably 10:90 to 70:30, more preferably 20:80 to 65:35, more preferably 30:70 to 60:40, more preferably 35:65 to 55:45, and more preferably 40:60 to 50:50.

[0170] 54. A method as described in Example 52 or 53, wherein M2 includes, preferably is Ru, and wherein the catalytic material exhibits an M2:M1 atomic ratio in the range of 0.1:99.9 to 30:70, preferably 0.5:99.5 to 30:70, more preferably 1:99 to 20:80, more preferably 3:97 to 10:90, and more preferably 5:95 to 6:94.

[0171] 55. The method of any one of embodiments 49 to 54, wherein the catalytic material further comprises Al and O.

[0172] 56. The method of embodiment 55, wherein the catalytic material comprises Ni as the metal M1, wherein preferably the metal M1 is Ni.

[0173] 57. A method as described in Example 56, wherein the catalytic material further comprises Mg, wherein the Ni:Mg:Al molar ratio is preferably in the range of 1:(0.1-12):(0.5-20), more preferably 1:(0.5-8):(1-12), more preferably 1:(1-5):(3-8), more preferably 1:(1.5-3):(3.5-5), and more preferably 1:(2.0-2.4):(4.0-4.4).

[0174] 58. A method as described in Example 56 or 57, wherein 95 to 100 wt.-%, preferably 97 to 100 wt.-%, more preferably 98 to 100 wt.-%, more preferably 99 to 100 wt.-%, more preferably 99.5 to 100 wt.-%, and more preferably 99.9 to 100 wt.-% of the catalytic material consists of Ni, Mg, Al and O.

[0175] 59. A method as described in Example 56 or 57, wherein 95 to 100 wt.-%, preferably 97 to 100 wt.-%, more preferably 98 to 100 wt.-%, more preferably 99 to 100 wt.-%, more preferably 99.5 to 100 wt.-%, and more preferably 99.9 to 100 wt.-% of the catalytic material consists of M2, Ni, Mg, Al and O.

[0176] 60. The method of embodiment 55, wherein the catalytic material comprises Co as metal M1, wherein preferably the metal M1 is Co.

[0177] 61. A method as described in Example 60, wherein the catalytic material further comprises La, wherein the Co:La:Al molar ratio is preferably in the range of 1:(0.1-8):(1-50), more preferably 1:(0.5-5):(3-30), more preferably 1:(0.8-3):(5-20), more preferably 1:(1-2):(8-15), and more preferably 1:(1.3-1.7):(10-12).

[0178] 62. A method as described in Example 60 or 61, wherein 95 to 100 wt.-%, preferably 97 to 100 wt.-%, more preferably 98 to 100 wt.-%, more preferably 99 to 100 wt.-%, more preferably 99.5 to 100 wt.-%, and more preferably 99.9 to 100 wt.-% of the catalytic material consists of Co, La, Al and O.

[0179] 63. A method as described in Example 60 or 61, wherein 95 to 100 wt.-%, preferably 97 to 100 wt.-%, more preferably 98 to 100 wt.-%, more preferably 99 to 100 wt.-%, more preferably 99.5 to 100 wt.-%, and more preferably 99.9 to 100 wt.-% of the catalytic material consists of M2, Co, La, Al and O.

[0180] 64. The process of any one of embodiments 1 to 63, wherein in (iii), 90 to 100 vol-%, preferably 94 to 100 vol-%, more preferably 96 to 100 vol-% of the NH3 is converted.

[0181] 65. The method of any one of embodiments 1 to 64, wherein the gas stream obtained in (iii) comprises H 2 , CO and CO 2 , wherein the gas stream obtained in (iii) preferably has a stoichiometric number R 2 equal to or greater than 2.00, more preferably in the range of 2.02 to 2.15, more preferably in the range of 2.04 to 2.06. 合成气 , where R 合成气 According to formula (II):

[0182] R 合成气 =[c 合成气 (H2)–c 合成气 (CO2)] / [c 合成气 (CO2)+c 合成气 (CO)](II),

[0183] where c 合成气 (H2), c 合成气 (CO2) and c 合成气(CO) represent the molar concentrations of H2, CO2 and CO in the gas stream obtained in (iii), respectively.

[0184] 66. The method of any one of embodiments 1 to 65, wherein the gas stream obtained in (iii) has a molar ratio of H2 to CO in the range of 0.5:1 to 10.0:1, preferably in the range of 1.0:1 to 7.5:1, more preferably in the range of 1.9:1 to 4.8:1, more preferably in the range of 2.1:1 to 4.6:1.

[0185] 67. The method of any one of embodiments 1 to 66, wherein the gas stream obtained in (iii) has a molar ratio of H2 to CO2 in the range of 0.5:1 to 40.0:1, preferably in the range of 4.9:1 to 36.0:1, more preferably in the range of 5.4:1 to 35.0:1.

[0186] 68. The method of any one of embodiments 1 to 67, wherein the gas stream obtained in (iii) has a molar ratio of CO to CO2 in the range of 0.1:1 to 21.0:1, preferably in the range of 0.8:1 to 17.0:1, more preferably in the range of 1.0:1 to 15.0:1.

[0187] 69. The method of any one of embodiments 1 to 68, wherein the gas stream obtained in (iii) comprises 50 to 85 vol-%, preferably 58 to 80 vol-%, more preferably 61 to 75 vol-% H2.

[0188] 70. The process of any one of embodiments 1 to 69, wherein the gas stream obtained in (iii) comprises 0 to 10 vol-%, preferably 0 to 5 vol-%, more preferably 0 to 4.0 vol-% CH4.

[0189] 71. The method of any one of embodiments 1 to 70, wherein the gas stream obtained in (iii) comprises 0.1 to 20.0 volume-%, preferably 1.5 to 12.0 volume-%, more preferably 1.8 to 11.3 volume-% CO2.

[0190] 72. The method of any one of embodiments 1 to 71, wherein the gas stream obtained in (iii) comprises 0.1 to 20.0 vol-%, preferably 1.8 to 13.0 vol-%, more preferably 2.3 to 12.1 vol-% N2.

[0191] 73. A method as described in any one of embodiments 1 to 72, wherein the gas stream obtained in (iii) contains 0 to 1 volume-%, preferably 0 to 0.5 volume-%, more preferably 0 to 0.1 volume-% H2O, wherein the first precursor gas stream provided in (i.1) is more preferably free of H2O.

[0192] 74. The method of any one of embodiments 1 to 73, wherein the method further comprises

[0193] (iv) separating residual NH3 from the gas stream obtained in (iii) to obtain a purified gas stream.

[0194] 75. A process for the preparation of an alcohol, preferably methanol, using a gas stream comprising H2 and CO and optionally further comprising CO2, wherein the gas stream is obtained according to any one of embodiments 1 to 74, wherein the process comprises

[0195] (v) using the gas stream obtained in (iii) or the purified gas stream obtained in (iv) as feed stream.

[0196] 76. A method for preparing hydrocarbons, preferably (C 10 -C 20 ) an alkane or an ether, preferably dimethyl ether, the method employing a gas stream comprising H2 and CO and optionally further comprising CO2, wherein the gas stream is obtained according to any one of embodiments 1 to 74, wherein the method comprises

[0197] (v) using the gas stream obtained in (iii) or the purified gas stream obtained in (iv) as feed stream.

[0198] The present invention is further illustrated by the following examples and comparative examples.

[0199] Experimental Section

[0200] The following reference examples, examples and comparative examples were simulated using Aspen Plus software version 11.

[0201] Reference Example 1: Determination of the blind activity of the reactor in NH3 reforming

[0202] The blank activity of the reactor was determined as a reference case, in which SiC was used as inert material. The NH3 pressure was set to 30 bar (absolute), the H2O content was set to 0.5 vol-%, and the gas hourly space velocity was set to 4000 h -1 The NH3 conversion was determined at different temperatures, such as Figure 1 As shown. Figure 1From the results shown in , it can be seen that for the case of using SiC as the inert material, the NH3 conversion rate at a temperature of 650° C. is about 4%. It can be assumed that at a temperature of 780° C., the NH3 conversion rate is about 100%.

[0203] Example 2 and Comparative Example 3: Combination of natural gas partial oxidation (POx) and NH3 reforming

[0204] Will be 10,000Nm 3 / h feed partial oxidation of natural gas feedstock (POx) is taken as a reference. Table 1 shows the composition of the inlet flow and the amount of oxygen required for the POx process. The synthesis gas produced is relatively poor in hydrogen (R value = 1.67). In order to achieve an R value of 2.05, additional hydrogen is required. In Example 2, a specific amount of NH3 required to transport the appropriate amount of hydrogen is added, and in Comparative Example 3 hydrogen is added directly. As can be inferred from the data given in Table 1, the added NH3 decomposes in an endothermic reaction, which leads to a significant reduction in the outlet temperature from 1350°C to 1111°C. In this case, no catalytic material is required because thermally induced decomposition of NH3 occurs. Table 2 shows the composition of the final synthesis gas after adding NH3 or hydrogen.

[0205] Table 1

[0206] Natural gas based POx with and without NH3.

[0207]

[0208]

[0209] Table 2

[0210] Final syngas composition after POx and NH3 removal based on natural gas.

[0211]

[0212]

[0213] Example 4 and Comparative Example 5: Biogas-based partial oxidation (POx) combined with NH3 reforming

[0214] Will have 10,000Nm 3 / h feed of biogas feedstock (POx) is taken as a reference. Biogas contains a higher CO2 content than the natural gas used in Example 2 and Comparative Example 3. Therefore, a higher amount of NH3 must be fed to the hot outlet of the partial oxidation to achieve an R value of 2.05. Table 3 shows the composition of the inlet stream and the oxygen required for the POx process. Example 4 shows the biogas conversion and the addition of NH3. In contrast, hydrogen is added directly in Comparative Example 5. Since a higher amount of NH3 is added and converted compared to Example 2, the reduction in outlet temperature is stronger (from 1,350°C to 671°C). In this case, a catalytic material is required because the thermally induced decomposition is not fast enough at temperatures below 700°C. Since the hot outlet is combined with a catalytic material for NH3 reforming, it basically includes an adiabatic process step. Table 4 shows the final syngas composition of the biogas-based POx process combined with NH3 reforming.

[0215] Table 3

[0216] Biogas-based POx with and without NH3 addition

[0217]

[0218]

[0219] Table 4

[0220] The corresponding syngas composition after POx and NH3 removal from biogas

[0221]

[0222] Example 6 and Comparative Example 7: Combination of ATR and NH3 Reforming Based on Natural Gas

[0223] For the natural gas based autothermal reforming (ATR) process, 10,000 Nm 3 / h of raw material is defined as reference. Compared with the POx process, the ATR process generally has a lower outlet temperature, and the hydrogen of the synthesis gas is generally slightly richer (R value is 1.80). In Example 6, NH3 is fed into the outlet stream, and hydrogen is directly added in Comparative Example 7. Since the temperature at the outlet of the ATR is relatively low (975°C), at least an inert material is applied as a contact material for NH3 reforming. The temperature is reduced from 975°C to 884°C by an endothermic NH3 reforming process. Table 5 shows the composition of the inlet stream and the oxygen required for the ATR process. Table 6 shows the composition of the synthesis gas produced, where the R value is 2.05.

[0224] Table 5

[0225] ATR process based on natural gas with and without NH3 addition.

[0226]

[0227]

[0228] Table 6

[0229] Composition of syngas after natural gas-based ATR after NH3 removal

[0230]

[0231] Example 8 and Comparative Example 9: Biogas-based ATR combined with NH3 reforming

[0232] Will have 10,000Nm 3 / h feed of biogas feedstock is defined as a reference. Compared with natural gas, biogas is rich in CO2. Therefore, relatively more NH3 must be fed into the hot outlet of the ATR to achieve an R value of 2.05. Table 7 shows the composition of the inlet stream and the oxygen required for the ATR process. Table 7 shows the biogas conversion rate. NH3 was added in Example 8, and hydrogen was directly added in Comparative Example 9. Since a relatively large amount of NH3 was added and converted, the reduction in outlet temperature was even stronger (from 975°C to 578°C). In this case, a catalytic material is required because the thermally induced decomposition is not fast enough at temperatures below 700°C. Since the hot outlet is combined with a catalytic material for NH3 reforming, an adiabatic process step is basically included. Table 8 shows the final syngas composition of the biogas-based ATR process combined with NH3 reforming.

[0233] Table 7

[0234] Biogas-based ATR method with and without NH3 addition

[0235]

[0236]

[0237] Table 8

[0238] Syngas composition after biogas-based ATR after NH3 removal

[0239] BRIEF DESCRIPTION OF THE DRAWINGS

[0240] Figure 1: shows the activity determined for the case according to reference example 1, in particular for the case using SiC as inert material, in terms of NH3 conversion (the measurement points are depicted as diamonds). The temperature is plotted in ° C. on the abscissa and the NH3 conversion is plotted in % on the ordinate. The dashed line relates to the approximation of the exponential function for the reactor containing SiC.

[0241] References

[0242] -WO 2019 / 038251 A1

[0243] -US 8,691,182 B2

[0244] -US 8,961,923 B2

Claims

1. A method for increasing the H2 content in a gas stream containing H2 and CO (syngas), the method comprising (iv) providing a first gas stream comprising CO and H2 and optionally further comprising CO2, wherein the first gas stream has a temperature in the range of 750°C to 1600°C; (v) providing a second gas stream comprising NH3; (vi) contacting the second gas stream provided in (ii) with the first gas stream provided in (i) to convert at least a portion of the NH3 into N2 and H2.

2. The method of claim 1, wherein: The first gas stream provided in (i) has a molar ratio of H2 to CO greater than 0.1:

1.

3. The method according to claim 1 or 2, wherein: The first gas stream provided in (i) comprises 35 to 75 vol-% H2.

4. The method according to any one of claims 1 to 3, wherein: The first gas stream provided in (i) comprises 5 to 45 vol-% CO.

5. The method according to any one of claims 1 to 4, wherein: The first gas stream provided in (i) comprises CO 2 , and wherein the first gas stream provided in (i) comprises 0.1 to 30 vol-% CO 2 .

6. The method according to any one of claims 1 to 5, wherein: The first gas stream provided in (i) has a stoichiometric number R1 below 2.00, wherein R1 is defined according to formula (I): R1=[c1(H2)–c1(CO2)] / [c1(CO2)+c1(CO)](I), Wherein c1(H2), c1(CO2) and c1(CO) represent the molar concentrations of H2, CO2 and CO in the first gas flow, respectively.

7. The method according to any one of claims 1 to 6, wherein: The first gas stream provided in (i) comprises a gas stream obtainable or obtained by one or more of the following: a gasification reaction of waste, a gasification reaction of biomass, an autothermal reforming reaction, and a partial oxidation reaction of one or more hydrocarbons, wherein these hydrocarbons are selected from (C1-C 10 ) group composed of alkanes.

8. The method according to any one of claims 1 to 7, wherein: The second gas stream provided in (ii) has a different chemical composition than the first gas stream provided in (i).

9. The method according to any one of claims 1 to 8, wherein: The contacting in (iii) is carried out in a reactor.

10. The method of claim 9, wherein: The contacting in (iii) is performed in a reactor, and wherein the reactor comprises an inert material.

11. The method of claim 9, wherein: The contacting in (iii) is performed in a reactor, and wherein the reactor comprises a catalytic material.

12. The method of claim 11, wherein: The catalytic material comprises a metal M1, wherein M1 is Ni, Co or Ni and Co.

13. The method according to any one of claims 1 to 12, wherein: The method further comprises (iv) separating residual NH3 from the gas stream obtained in (iii) to obtain a purified gas stream.

14. A process for the preparation of alcohols, the process employing a gas stream comprising H2 and CO and optionally further comprising CO2, wherein the gas stream is obtained as claimed in any one of claims 1 to 13, wherein the process comprises (v) using the gas stream obtained in (iii) or the purified gas stream obtained in (iv) as feed stream.

15. A process for the preparation of hydrocarbons or ethers using a gas stream comprising H2 and CO and optionally further comprising CO2, wherein the gas stream is obtained as claimed in any one of claims 1 to 13, wherein the process comprises (v) using the gas stream obtained in (iii) or the purified gas stream obtained in (iv) as feed stream.

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