Process for increasing the H2 content of synthesis gas

Abstract

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

Description

[Technical Field]

[0001] The present invention relates to a process for increasing the H content of synthesis gas, preferably using hot outlet gas of an autothermal reforming process and / or a partial oxidation process of hydrocarbons. According to the present invention, an NH3 stream is fed to the hot outlet gas for initiating thermally induced NH3 reforming. [Background technology]

[0002] Autothermal reforming (ATR) and partial oxidation of hydrocarbons (POx) processes are commonly used to produce synthesis gas. These processes are crucial for producing synthesis gas with a specific H:CO:CO molar ratio. The following equations (1)-(3) explain, in a simplified manner, the key processes within the reformer for such processes. In these equations, CH4 is shown to represent other possible hydrocarbons. Equation (4) shows the partial oxidation (POx) of CH4 (which also represents any other hydrocarbon). POx can be applied with or without a catalytic material. However, common to these reforming processes is the fact 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 contains very little hydrogen. (1) CH4 + 1.5O2 ⇔ CO + 2H2O (2) CH4 + H2O ⇔ CO + 3H2 (3) CO + H2O ⇔ CO2 + H2 (4) CH4 + 0.5O2 ⇔ CO + 2H2

[0003] The reforming process is applied to produce a synthesis gas having a specific stoichiometric number R (also referred to herein as the R value), where R is determined by the following formula: R=[c(H2)-c(CO2)] / [c(CO2)+c(CO)] where c(H), c(CO), and c(CO) represent the molar concentrations of H, CO, and CO, respectively, in the syngas stream. Typically, the stoichiometric number R produced by the ATR / POx process is less than 2. Therefore, for example, for a methanol production process where the R value must be greater than 2, additional hydrogen must be added. For example, hydrogen can be added directly, e.g., from the electrolysis of water.

[0004] WO 2019 / 038251 A1 discloses an autothermal ammonia decomposition process in which oxygen and ammonia are simultaneously fed to an ATR reactor to produce a product gas containing nitrogen and hydrogen. U.S. Pat. Nos. 8,691,182 B2 and 8,961,923 B2 disclose a process for the decomposition of ammonia in which gaseous ammonia and oxygen are mixed and combusted, preferably at temperatures above 1100° C. However, the process is not related to the production of synthesis gas.

[0005] As mentioned above, autothermal reforming processes such as POx and ATR of natural gas or hydrocarbons essentially produce a hydrogen-poor synthesis gas. This means that additional hydrogen must be added to obtain a synthesis gas suitable for methanol production. The hot outlet gas of the POx / ATR process is typically used for steam generation. Summary of the Invention [Problem to be solved by the invention]

[0006] It was therefore an object of the present invention to provide a process for increasing the H2 content of synthesis gas in a particularly resource-efficient manner. [Means for solving the problem]

[0007] Surprisingly, it has been found that the high temperature of the outlet gas, for example, from an ATR and / or POx process, can serve as an energy source for endothermic NH 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 dispersion, or high-temperature stable catalytic materials. Thus, it has been surprisingly found that the endothermic NH reforming process, in combination with the hot outlet gas, for example, from an ATR and / or POx process, can increase the H content of the synthesis gas and, in particular, adjust the stoichiometry R of the resulting synthesis gas. The resulting synthesis gas, with its increased H content, can then be used for specific downstream applications. For NH reforming, a key step in producing hydrogen, the underlying reaction equation can be formulated as follows: (5) 2NH3⇔N2+3H2

[0008] Therefore, the present invention facilitates sustainable ATR / POx-based reforming processes, for example, in conjunction with methanol production sites, when NH3 is produced from renewable resources and the ATR / POx feedstock is biobased (renewable). Considering resource costs, it may be preferable to use NH3 instead of hydrogen, for example, from water electrolysis. Furthermore, NH3 is known to store chemically significant amounts of H2. Therefore, in-situ generation of H2 by NH3 reforming is more cost-effective and can be applied statically, especially when wind or solar power for generating H2 via other processes is down. A further advantage of the present invention is the opportunity to apply it to any feedstock for autothermal reforming, such as natural gas, biogas, or other hydrocarbons. [Brief explanation of the drawings]

[0009] [Figure 1]Figure 1 shows the activity measured according to Reference Example 1, in particular the reactor activity for NH conversion when SiC is used as the inert material (measurement points are indicated by diamonds). The horizontal axis shows the temperature in °C and the vertical axis shows the NH conversion in %. The dotted line relates to the exponential fit for the reactor containing SiC. DETAILED DESCRIPTION OF THE INVENTION

[0010] The unit bar (abs) is 1 bar = 10 5 means absolute pressure, which is equal to Pa.

[0011] The present invention is further illustrated by the following series of embodiments and combinations of embodiments, which can be obtained from the indicated dependencies and backward references. In particular, it should be noted that in each instance where a range of embodiments is mentioned in connection with terms such as "the process according to any one of embodiments 1 to 4," it is meant that all embodiments within this range are expressly disclosed to those skilled in the art, i.e., the use of this term should be understood by those skilled in the art to be synonymous with "the process according to any one of embodiments 1, 2, 3, and 4." Furthermore, it is expressly pointed out that the following series of embodiments represents an appropriately structured portion of the present description directed to general and preferred aspects of the present invention, rather than a series of claims determining the scope of protection.

[0012] Accordingly, the present invention provides a process for increasing the H2 content of a gas stream comprising H2 and CO (synthesis gas), comprising: (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 to 1600°C; (ii) providing a second feed gas stream comprising NH3; (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 to N2 and H2. The present invention relates to a process including:

[0013] The temperature of the first gas stream provided in (i) is preferably 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.

[0014] If the temperature of the first gas stream provided in (i) is in the range of 800-1600°C, according to a first alternative, the temperature of the first gas stream provided in (i) is preferably in the range of 900-1200°C, more preferably in the range of 950-1000°C.

[0015] If the temperature of the first gas stream provided in (i) is in the range of 800-1600°C, according to a second alternative, the temperature of the first gas stream provided in (i) is preferably in the range of 1100-1500°C, more preferably in the range of 1325-1375°C.

[0016] Preferably, the first gas stream provided in (i) has a molar ratio of H2 to CO greater 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.

[0017] Preferably, the first gas stream provided in (i) comprises HO, and the first gas stream provided in (i) has a molar ratio of H to HO greater 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.

[0018] Preferably, the first gas stream provided in (i) comprises HO, and the first gas stream provided in (i) has a molar ratio of CO to HO greater 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.

[0019] The first gas stream supplied in (i) preferably contains 35 to 75% by volume, more preferably 45 to 65% by volume, of H2.

[0020] The first gas stream supplied in (i) preferably contains 5 to 45% by volume of CO, more preferably 12 to 36% by volume.

[0021] The first gas stream provided in (i) contains H2O, and the first gas stream provided in (i) preferably contains 0.1 to 30% by volume, more preferably 0.3 to 25% by volume, of H2O.

[0022] The first gas stream provided in (i) contains CO2, and preferably the first gas stream provided in (i) contains 0.1 to 30% by volume of CO2, more preferably 0.3 to 25% by volume.

[0023] Preferably, the first gas stream provided in (i) comprises 0-5% by volume, more preferably 0-4.0% by volume, more preferably 0-3.3% by volume of CH4.

[0024] The first gas stream provided in (i) preferably comprises 0-5% by volume, more preferably 0-2.5% by volume, more preferably 0-1.0% by volume of N2.

[0025] The first gas stream provided in (i) preferably contains 0-1 vol. %, more preferably 0-0.5 vol. %, more preferably 0-0.1 vol. % Ar.

[0026] The first gas stream provided in (i) preferably comprises 0-1 vol. %, more preferably 0-0.5 vol. %, more preferably 0-0.1 vol. % O2, and the first precursor gas stream provided in (i) preferably does not comprise O2.

[0027] Preferably, the first gas stream provided in (i) comprises 0-1% by volume of NH3, more preferably 0-0.1% by volume, more preferably 0-0.01% by volume of NH3.

[0028] Preferably, the first gas stream provided in (i) comprises CO2.

[0029] The first gas stream provided in (i) preferably has a stoichiometric number R1 of less than 2.00, where R1 is represented by the formula (I): R1=[c1(H2)-c1(CO2)] / [c1(CO2)+c1(CO)](I) where c1(H2), c1(CO2), and c1(CO) represent the molar concentrations of H2, CO2, and CO, respectively, in the first gas stream. is defined according to

[0030] Preferably, the first gas stream provided in (i) comprises a gas stream obtainable or obtained by one or more of a waste gasification reaction, a biomass gasification reaction, an autothermal reforming reaction, and a partial oxidation reaction of one or more hydrocarbons, wherein the hydrocarbons are selected from the group consisting of (C1-C 10 )alkanes, more preferably (C1-C8)alkanes, more preferably (C1-C7)alkanes.

[0031] Providing a first gas stream according to (i) comprises: (i.1) providing a first precursor gas flow comprising CH4; (i.2) providing a second precursor gas flow comprising O2; (i.3) contacting a second precursor gas stream with the first precursor gas stream to react CH4 and O2 to CO, H2, and optionally H2O.

[0032] When providing a first gas stream according to (i) comprises (i.1), (i.2) and (i.3), it is preferred that the first precursor gas stream provided in (i.1) further comprises H2, and more preferably the first precursor gas stream provided in (i.1) has a CH4 to H2 molar ratio greater 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, more preferably in the range of 30:1 to 33:1.

[0033] Furthermore, when providing a first gas stream according to (i) comprises (i.1), (i.2) and (i.3), it is preferred that the first precursor gas stream provided in (i.1) further comprises CO2, and more preferably the first precursor gas stream provided in (i.1) has a molar ratio of CH4 to CO2 in the range of 1:1 to 300:1, more preferably 2:1 to 275:1, more preferably 10:1 to 225:1.

[0034] If the first precursor gas stream provided in (i.1) further comprises CO2, according to a first alternative, it is preferred that the first precursor gas stream provided in (i.1) has a CH4 to CO2 molar ratio in the range of 200:1 to 275:1, more preferably in the range of 230:1 to 250:1.

[0035] If the first precursor gas stream provided in (i.1) further comprises CO2, according to a second alternative, it is preferred that 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, more preferably in the range of 2.2:1 to 5.0:1.

[0036] Furthermore, when providing a first gas stream according to (i) comprises (i.1), (i.2) and (i.3), it is preferred that the first precursor gas stream provided in (i.1) has a molar ratio of H to CO of less than 20:1, more preferably in the range of 0 to 15:1, more preferably in the range of 0 to 10:1.

[0037] Furthermore, when providing a first gas stream according to (i) includes (i.1), (i.2) and (i.3), it is preferred that the first precursor gas stream provided in (i.1) contains 40-96 vol. %, more preferably 65-95 vol. % CH4.

[0038] If the first precursor gas stream provided in (i.1) comprises 40-96% by volume, then according to a first alternative, the first precursor gas stream provided in (i.1) preferably comprises 90-95% by volume, more preferably 91-94% by volume, of CH4.

[0039] If the first precursor gas stream provided in (i.1) comprises 40-96% by volume, then according to a first alternative, the first precursor gas stream provided in (i.1) preferably comprises 65-75% by volume, more preferably 68-71% by volume, of CH4.

[0040] Furthermore, when providing a first gas stream according to (i) includes (i.1), (i.2) and (i.3), it is preferred that the first precursor gas stream provided in (i.1) contains 0-10 vol. %, more preferably 0-3.5 vol. %, more preferably 0-3.1 vol. % H2.

[0041] Furthermore, when providing a first gas stream according to (i) includes (i.1), (i.2) and (i.3), it is preferred that the first precursor gas stream provided in (i.1) contains 0-35 vol. % CO2, more preferably 0.1-32 vol. % CO2.

[0042] If the first precursor gas stream provided in (i.1) comprises 0-35% by volume, then according to a first alternative, the first precursor gas stream provided in (i.1) preferably comprises 0.1-2.0% by volume, more preferably 0.2-0.8% by volume, of CO2.

[0043] If the first precursor gas stream provided in (i.1) comprises 0-35% by volume, then according to a second alternative, the first precursor gas stream provided in (i.1) preferably comprises 20-32% by volume, more preferably 25-31% by volume, of CO2.

[0044] Furthermore, when providing a first gas stream according to (i) comprises (i.1), (i.2) and (i.3), it is preferred that the first precursor gas stream provided in (i.1) comprises 0-5 vol. %, more preferably 0-2.5 vol. %, more preferably 0-2.4 vol. % of a (C2-C7) alkane.

[0045] Furthermore, when providing a first gas stream according to (i) includes (i.1), (i.2) and (i.3), it is preferred that the first precursor gas stream provided in (i.1) contains 0-5 vol. %, more preferably 0.1-2.5 vol. %, more preferably 0.3-2.2 vol. % N2.

[0046] Furthermore, when providing a first gas stream according to (i) comprises (i.1), (i.2) and (i.3), it is preferred that the first precursor gas stream provided in (i.1) comprises 0-1 vol. %, more preferably 0-0.5 vol. %, more preferably 0-0.1 vol. % HO, wherein the first precursor gas stream provided in (i.1) is more preferably free of HO.

[0047] Furthermore, when providing a first gas stream according to (i) includes (i.1), (i.2) and (i.3), it is preferred that 95-100% by volume, more preferably 99-100% by volume, more preferably 99.9-100% by volume of the second precursor gas stream provided in (i.2) consists of O2.

[0048] Furthermore, when providing a first gas flow according to (i) includes (i.1), (i.2) and (i.3), the second precursor gas flow provided in (i.2) has a volumetric flow rate of 1,000 to 10,000 m 3 / h range, more preferably 3,800 to 6,900 m 3 / h range, more preferably 4,100 to 6,600 m 3 / h is preferable.

[0049] Furthermore, when providing a first gas stream according to (i) comprises (i.1), (i.2) and (i.3), it is preferred that the second precursor gas stream 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, more preferably in the range of 5,900 to 9,400 kg / h.

[0050] Furthermore, when providing a first gas stream according to (i) comprises (i.1), (i.2) and (i.3), it is preferred that the contacting according to (i.3) is carried out at a pressure in the range of 1 to 70 bar (abs), more preferably in the range of 10 to 60 bar (abs), more preferably in the range of 20 to 50 bar (abs).

[0051] The second gas stream provided in (ii) preferably has a different chemical composition than the first gas stream provided in (i).

[0052] The second gas stream provided in (ii) has a volumetric flow rate of 100 to 10,000 m 3 / h range, more preferably 1,100 to 8,700 m 3 / h range, more preferably 1,400 to 8,400 m 3 / h is preferable.

[0053] 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.

[0054] The temperature of the second gas stream provided in (ii) is preferably in the range of 100 to 500°C, more preferably in the range of 250 to 350°C, more preferably in the range of 275 to 325°C.

[0055] The contacting in (iii) is preferably carried out in a reactor.

[0056] Preferably, the contacting of 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 (abs), more preferably in the range of 10 to 80 bar (abs), more preferably in the range of 20 to 70 bar (abs), more preferably in the range of 25 to 60 bar (abs).

[0057] The contacting in (iii) is preferably carried out at a temperature in the range of 850 to 1400°C, more preferably in the range of 950 to 1350°C.

[0058] When the contacting in (iii) is carried out at a temperature in the range of 850-1400°C, according to a first alternative, it is preferred that the contacting in (iii) is carried out in a reactor, the reactor comprising an inert material, more preferably the contacting in (iii) is carried out at a temperature in the range of 850-1200°C, more preferably in the range of 875-1100°C, and the inert material more preferably comprises one or more of quartz, SiC, alpha alumina, steatite, BN, Si3N4, and ceramic.

[0059] When the contacting in (iii) is carried out at a temperature in the range of 850 to 1400°C, according to a second alternative, it is preferred that the contacting in (iii) is carried out in a reactor, the reactor comprising a catalytic material, and the contacting in (iii) is more preferably carried out at a temperature in the range of 700 to 925°C, more preferably in the range of 750 to 900°C.

[0060] If the reactor comprises a catalytic material, it is preferred that the catalytic material comprises a metal M1, where M1 is Ni, Co, or Ni and Co.

[0061] When the catalytic material comprises a metal M1, where M1 is Ni, Co, or Ni and Co, it is preferred that the catalytic material 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 the group consisting of Li, K, Na, Cs, Mg, Ca, Sr, Ba, Mo, Fe, Ru (including mixtures of two or more thereof), more preferably the group consisting of K, Na, Cs, Ba, Mo, Fe, Ru (including mixtures of two or more thereof), more preferably the group consisting of K, Ba, Mo, Fe, Ru (including mixtures of two or more thereof), and more preferably M2 comprises Fe, Ru, or Fe and Ru, more preferably M2 comprises Ru, more preferably M2 is Ru.

[0062] Furthermore, when the catalytic material comprises a metal M1, and M1 is Ni, Co, or Ni and Co, it is preferred that the catalytic material further comprises one or more support materials on which the metal M1 or the metals M1 and M2 are supported, and wherein the one or more support materials are more preferably selected from the group consisting of Al2O3, SiO2, ZrO2, CeO2, MgO, CaO, and mixtures of two or more thereof, more preferably the group consisting of Al2O3, SiO2, ZrO2, CeO2, and mixtures of two or more thereof, more preferably the group consisting of Al2O3, SiO2, and mixtures thereof, and more preferably the support material comprises Al2O3.

[0063] Furthermore, when the catalytic material comprises a metal M1, where M1 is Ni, Co or Ni and Co, it is preferred that the catalytic material further comprises a metal M2 as defined herein, and that the catalytic material exhibits an M2:M1 atomic ratio 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, more preferably 40:60 to 50:50.

[0064] Where the catalytic material comprises a metal M2 as defined herein and exhibits an M2:M1 atomic ratio in the range of 0.1:99.9 to 80:20, it is preferred that M2 comprises Fe, more preferably is Fe, and 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, more preferably 40:60 to 50:50.

[0065] Furthermore, when the catalytic material comprises a metal M2 as defined herein and exhibits an M2:M1 atomic ratio in the range of 0.1:99.9 to 80:20, it is preferred that M2 comprises, more preferably is, Ru, and 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, more preferably 5:95 to 6:94.

[0066] Furthermore, when the catalytic material contains a metal M1, and M1 is Ni, Co, or Ni and Co, the catalytic material preferably further contains Al and O.

[0067] When the catalytic material further contains Al and O, the catalytic material preferably contains Ni as the metal M1, and more preferably the metal M1 is Ni.

[0068] When the catalyst material contains Ni as the metal M1, it is preferable that the catalyst material further contains Mg, and the molar ratio of Ni:Mg:Al 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), more preferably 1:(2.0-2.4):(4.0-4.4).

[0069] Furthermore, when the catalytic material comprises Ni as metal M1, according to a first alternative, it is preferred that 95 to 100% by weight, more preferably 97 to 100% by weight, more preferably 98 to 100% by weight, more preferably 99 to 100% by weight, more preferably 99.5 to 100% by weight, more preferably 99.9 to 100% by weight of the catalytic material consists of Ni, Mg, Al, and O.

[0070] Furthermore, when the catalytic material comprises Ni as metal M1, according to a second alternative, it is preferred that 95 to 100% by weight of the catalytic material consists of M2, Ni, Mg, Al, and O, more preferably 97 to 100% by weight, more preferably 98 to 100% by weight, more preferably 99 to 100% by weight, more preferably 99.5 to 100% by weight, more preferably 99.9 to 100% by weight.

[0071] Furthermore, when the catalytic material further contains Al and O, the catalytic material preferably contains Co as the metal M1, and more preferably the metal M1 is Co.

[0072] When the catalyst material contains Co as the metal M1, it is preferable that the catalyst material further contains La, and the molar ratio of Co:La:Al 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), more preferably 1:(1.3-1.7):(10-12).

[0073] Furthermore, when the catalytic material comprises Co as metal M1, according to a first alternative, it is preferred that 95 to 100% by weight of the catalytic material consists of Co, La, Al, and O, more preferably 97 to 100% by weight, more preferably 98 to 100% by weight, more preferably 99 to 100% by weight, more preferably 99.5 to 100% by weight, more preferably 99.9 to 100% by weight.

[0074] Furthermore, when the catalytic material comprises Co as metal M1, according to a second alternative, it is preferred that 95 to 100% by weight of the catalytic material consists of M2, Co, La, Al, and O, more preferably 97 to 100% by weight, more preferably 98 to 100% by weight, more preferably 99 to 100% by weight, more preferably 99.5 to 100% by weight, more preferably 99.9 to 100% by weight.

[0075] In (iii), it is preferable that 90 to 100% by volume, more preferably 94 to 100% by volume, and even more preferably 96 to 100% by volume of NH3 is converted.

[0076] The gas stream obtained in (iii) preferably comprises H2, CO and CO2, wherein the gas stream obtained in (iii) more preferably comprises H2, CO and CO2, and ... syngas is 2.00 or more, more preferably in the range of 2.02 to 2.15, and more preferably in the range of 2.04 to 2.06, and R syngas is represented by formula (II): R syngas =[c syngas (H2)-c syngas (CO2)] / [c syngas (CO2)+c syngas (CO)](II) (In the formula, c syngas (H2), c syngas (CO2), and c syngas (CO) represent the molar concentrations of H, CO, and CO in the gas stream obtained in (iii), respectively. is defined according to

[0077] The gas stream obtained in (iii) preferably 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.

[0078] The gas stream obtained in (iii) preferably 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.

[0079] The gas stream obtained in (iii) preferably 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.

[0080] The gas stream obtained in (iii) preferably contains 50-85% by volume of H2, more preferably 58-80% by volume, more preferably 61-75% by volume.

[0081] The gas stream obtained in (iii) preferably contains 0 to 10% by volume of CH4, more preferably 0 to 5% by volume, more preferably 0 to 4.0% by volume.

[0082] The gas stream obtained in (iii) preferably contains 0.1 to 20.0% by volume of CO2, more preferably 1.5 to 12.0% by volume, more preferably 1.8 to 11.3% by volume.

[0083] The gas stream obtained in (iii) preferably contains 0.1 to 20.0% by volume of N2, more preferably 1.8 to 13.0% by volume, more preferably 2.3 to 12.1% by volume.

[0084] The gas stream obtained in (iii) preferably comprises 0-1 vol. %, more preferably 0-0.5 vol. %, more preferably 0-0.1 vol. % HO, and the first precursor gas stream provided in (i.1) preferably does not comprise HO.

[0085] The process is (iv) separating the residual NH3 from the gas stream obtained in (iii) to obtain a purified gas stream. It is preferred that the composition further comprises:

[0086] Furthermore, the present invention relates to a process for the preparation of an alcohol, preferably methanol, using a gas stream comprising H and CO, and optionally further comprising CO, wherein the gas stream is obtained according to any one of the embodiments disclosed herein, and the process comprises: (v) using the gas stream obtained in (iii) or the purified gas stream obtained in (iv) as a feed stream. Includes.

[0087] Furthermore, the present invention provides a method for the production of hydrocarbons, preferably (C 10 -C 20 ) a process for the preparation of an alkane, or an ether, preferably dimethyl ether, wherein the gas stream is obtained according to any one of the embodiments disclosed herein, and the process comprises: (v) using the gas stream obtained in (iii) or the purified gas stream obtained in (iv) as a feed stream. Includes.

[0088] The unit bar (abs) is 1 bar = 10 5 means absolute pressure, which is equal to Pa.

[0089] The present invention is further illustrated by the following series of embodiments and combinations of embodiments, which can be obtained from the indicated dependencies and backward references. In particular, it should be noted that in each instance where a range of embodiments is mentioned in connection with terms such as "the process according to any one of embodiments 1 to 4," it is meant that all embodiments within this range are expressly disclosed to those skilled in the art, i.e., the use of this term should be understood by those skilled in the art to be synonymous with "the process according to any one of embodiments 1, 2, 3, and 4." Furthermore, it is expressly pointed out that the following series of embodiments represents an appropriately structured portion of the present description directed to general and preferred aspects of the present invention, rather than a series of claims determining the scope of protection.

[0090] 1. A process for increasing the H2 content of a gas stream containing H2 and CO (syngas), comprising: (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 to 1600°C; (ii) providing a second feed gas stream comprising NH3; (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 to N2 and H2. The process includes:

[0091] 2. The process of embodiment 1, wherein the temperature of the first gas stream provided in (i) is in the range of 800 to 1600°C, preferably in the range of 875 to 1450°C, more preferably in the range of 900 to 1425°C.

[0092] 3. The process of embodiment 2, wherein the temperature of the first gas stream provided in (i) is in the range of 900 to 1200°C, preferably in the range of 950 to 1000°C.

[0093] 4. The process of embodiment 2, wherein the temperature of the first gas stream provided in (i) is in the range of 1100 to 1500°C, preferably in the range of 1325 to 1375°C.

[0094] 5. The process of any one of embodiments 1 to 4, wherein the molar ratio of H2 to CO in the first gas stream provided in (i) is 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, more preferably in the range of 1.6:1 to 3.4:1.

[0095] 6. The process of any one of embodiments 1 to 5, wherein the first gas stream provided in (i) comprises HO, and wherein the molar ratio of H to HO in the first gas stream provided in (i) is 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, more preferably in the range of 1.8:1 to 190:1.

[0096] 7. The process of any one of embodiments 1-6, wherein the first gas stream provided in (i) comprises HO, and wherein the molar ratio of CO to HO in the first gas stream provided in (i) is greater 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, more preferably in the range of 0.5:1 to 105:1.

[0097] 8. The process of any one of the preceding embodiments, wherein the first gas stream provided in (i) comprises 35-75% by volume, preferably 45-65% by volume, of H2.

[0098] 9. The process of any one of embodiments 1 to 8, wherein the first gas stream provided in (i) comprises 5 to 45% by volume, preferably 12 to 36% by volume, of CO.

[0099] 10. The process of any one of embodiments 1-9, wherein the first gas stream provided in (i) comprises HO, and wherein the first gas stream provided in (i) comprises 0.1-30% by volume, preferably 0.3-25% by volume, of HO.

[0100] 11. The process of any one of embodiments 1 to 10, wherein the first gas stream provided in (i) comprises CO2, and the first gas stream provided in (i) comprises 0.1 to 30% by volume of CO2, preferably 0.3 to 25% by volume.

[0101] 12. The process of any one of embodiments 1 to 11, wherein the first gas stream provided in (i) comprises 0-5 vol.%, preferably 0-4.0 vol.%, more preferably 0-3.3 vol.% CH4.

[0102] 13. The process of any one of embodiments 1 to 12, wherein the first gas stream provided in (i) comprises 0-5 vol. %, preferably 0-2.5 vol. %, more preferably 0-1.0 vol. % N2.

[0103] 14. The process of any one of embodiments 1 to 13, wherein the first gas stream provided in (i) comprises 0-1 vol. %, preferably 0-0.5 vol. %, more preferably 0-0.1 vol. % Ar.

[0104] 15. The process of any one of embodiments 1 to 14, wherein the first gas stream provided in (i) comprises 0-1 vol.%, preferably 0-0.5 vol.%, more preferably 0-0.1 vol.% O2, and the first precursor gas stream provided in (i) more preferably does not comprise O2.

[0105] 16. The process of any one of embodiments 1 to 15, wherein the first gas stream provided in (i) comprises 0-1 vol.% NH3, preferably 0-0.1 vol.%, more preferably 0-0.01 vol.% NH3.

[0106] 17. The process of any one of embodiments 1-16, wherein the first gas stream provided in (i) comprises CO2.

[0107] 18. The stoichiometric number R1 of the first gas stream provided in (i) is less than 2.00, and R1 is represented by the formula (I): R1=[c1(H2)-c1(CO2)] / [c1(CO2)+c1(CO)](I) where c1(H2), c1(CO2), and c1(CO) represent the molar concentrations of H2, CO2, and CO, respectively, in the first gas stream. 18. The process according to any one of embodiments 1 to 17, wherein the process is defined according to

[0108] 19. The first gas stream provided in (i) comprises a gas stream obtainable or obtained by one or more of a waste gasification reaction, a biomass gasification reaction, an autothermal reforming reaction, and a partial oxidation reaction of one or more hydrocarbons, wherein the hydrocarbons are selected from the group consisting of (C1-C 10 19. The process of any one of embodiments 1 to 18, wherein the alkyl group is selected from the group consisting of (C1-C8)alkanes, preferably (C1-C7)alkanes, more preferably (C1-C8)alkanes.

[0109] 20. Providing a first gas flow according to (i) (i.1) providing a first precursor gas flow comprising CH4; (i.2) providing a second precursor gas flow comprising O2; (i.3) contacting a second precursor gas stream with the first precursor gas stream to react CH and O to CO, H, and optionally HO. 20. The process of any one of embodiments 1 to 19, comprising:

[0110] 21. The process of claim 20, wherein the first precursor gas stream provided in (i.1) further comprises H2, and preferably the molar ratio of CH4 to H2 in the first precursor gas stream provided in (i.1) is greater than 20:1, preferably in the range of 20:1 to 43:1, more preferably in the range of 27:1 to 36:1, more preferably in the range of 30:1 to 33:1.

[0111] 22. The process of embodiment 20 or 21, wherein the first precursor gas stream provided in (i.1) further comprises CO2, and preferably the molar ratio of CH4 to CO2 in the first precursor gas stream provided in (i.1) is in the range of 1:1 to 300:1, preferably 2:1 to 275:1, more preferably 10:1 to 225:1.

[0112] 23. The process of embodiment 22, wherein the molar ratio of CH4 to CO2 in the first precursor gas stream provided in (i.1) is in the range of 200:1 to 275:1, preferably in the range of 230:1 to 250:1.

[0113] 24. The process of embodiment 22, wherein the molar ratio of CH4 to CO2 in the first precursor gas stream provided in (i.1) is in the range of 2:1 to 10:1, preferably in the range of 2.2:1 to 5.0:1.

[0114] 25. The process of any one of embodiments 20 to 24, wherein the molar ratio of H2 to CO2 in the first precursor gas stream provided in (i.1) is less than 20:1, preferably in the range of 0 to 15:1, more preferably in the range of 0 to 10:1.

[0115] 26. The process of any one of embodiments 20 to 25, wherein the first precursor gas stream provided in (i.1) comprises 40 to 96 vol. %, preferably 65 to 95 vol. % CH4.

[0116] 27. The process of embodiment 26, wherein the first precursor gas stream provided in (i.1) comprises 90-95 vol. %, preferably 91-94 vol. % CH4.

[0117] 28. The process of embodiment 26, wherein the first precursor gas stream provided in (i.1) comprises 65-75 vol. %, preferably 68-71 vol. % CH4.

[0118] 29. The process of any one of embodiments 20-28, wherein the first precursor gas stream provided in (i.1) comprises 0-10 vol.%, preferably 0-3.5 vol.%, more preferably 0-3.1 vol.% H2.

[0119] 30. The process of any one of embodiments 20 to 29, wherein the first precursor gas stream provided in (i.1) comprises 0 to 35 vol. % CO2, preferably 0.1 to 32 vol. % CO2.

[0120] 31. The process of embodiment 30, wherein the first precursor gas stream provided in (i.1) comprises 0.1-2.0 vol. %, preferably 0.2-0.8 vol. % CO2.

[0121] 32. The process of embodiment 30, wherein the first precursor gas stream provided in (i.1) comprises 20-32 vol. %, preferably 25-31 vol. % CO2.

[0122] 33. The process of any one of embodiments 20-32, wherein the first precursor gas stream provided in (i.1) comprises 0-5 vol.%, preferably 0-2.5 vol.%, more preferably 0-2.4 vol.% (C2-C7)alkane.

[0123] 34. The process of any one of embodiments 20 to 33, wherein the first precursor gas stream provided in (i.1) comprises 0 to 5 vol. %, preferably 0.1 to 2.5 vol. %, more preferably 0.3 to 2.2 vol. % N2.

[0124] 35. The process of any one of embodiments 20-34, wherein the first precursor gas stream provided in (i.1) comprises 0-1 vol.%, preferably 0-0.5 vol.%, more preferably 0-0.1 vol.% HO; and wherein the first precursor gas stream provided in (i.1) more preferably does not comprise HO.

[0125] 36. The process of any one of embodiments 20 to 35, wherein 95 to 100 vol.%, preferably 99 to 100 vol.%, more preferably 99.9 to 100 vol.% of the second precursor gas stream provided in (i.2) consists of O2.

[0126] 37. The volumetric flow rate of the second precursor gas stream provided in (i.2) is between 1,000 and 10,000 m 3 / h range, preferably 3,800 to 6,900 m 3 / h range, more preferably 4,100 to 6,600 m 3 37. The process of any one of embodiments 20 to 36, wherein the heating time is in the range of / h.

[0127] 38. The process of any one of embodiments 20 to 37, wherein the mass flow rate of the second precursor gas stream provided in (i.2) is 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.

[0128] 39. The process according to 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 (abs), preferably in the range of 10 to 60 bar (abs), more preferably in the range of 20 to 50 bar (abs).

[0129] 40. The process of any one of embodiments 1-39, wherein the second gas stream provided in (ii) has a different chemical composition than the first gas stream provided in (i).

[0130] 41.(ii) The volumetric flow rate of the second gas stream provided in 3 / h, preferably 1,100 to 8,700 m 3 / h range, more preferably 1,400 to 8,400 m 3 41. The process of any one of embodiments 1 to 40, wherein the heating time is in the range of 1 / h.

[0131] 42. The process of any one of embodiments 1 to 41, wherein the mass flow rate of the second gas stream provided in (ii) is 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.

[0132] 43. The process of any one of embodiments 1 to 42, wherein the temperature of the second gas stream provided in (ii) is in the range of 100 to 500°C, preferably in the range of 250 to 350°C, more preferably in the range of 275 to 325°C.

[0133] 44. The process of any one of embodiments 1 to 43, wherein the contacting in (iii) is carried out in a reactor.

[0134] 45. The process of any one of embodiments 1 to 44, wherein the contacting of 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 (abs), preferably in the range of 10 to 80 bar (abs), more preferably in the range of 20 to 70 bar (abs), more preferably in the range of 25 to 60 bar (abs).

[0135] 46. ​​The process of any one of embodiments 1 to 45, wherein the contacting in (iii) is carried out at a temperature in the range of 850 to 1400°C, preferably in the range of 950 to 1350°C.

[0136] 47. The process of embodiment 46, wherein the contacting in (iii) occurs in a reactor, the reactor comprising an inert material, and preferably, the contacting in (iii) occurs at a temperature in the range of 850 to 1200°C, preferably in the range of 875 to 1100°C, and the inert material preferably comprises one or more of quartz, SiC, alpha alumina, steatite, BN, Si3N4, and ceramic.

[0137] 48. The process of embodiment 46, wherein the contacting in (iii) is carried out in a reactor, the reactor comprising a catalytic material, and preferably, the contacting in (iii) is carried out at a temperature in the range of 700 to 925°C, preferably in the range of 750 to 900°C.

[0138] 49. The process of embodiment 48, wherein the catalytic material comprises a metal M1, wherein M1 is Ni, Co, or Ni and Co.

[0139] 50. The process of embodiment 49, wherein the catalytic material 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 Li, K, Na, Cs, Mg, Ca, Sr, Ba, Mo, Fe, Ru (including mixtures of two or more thereof), more preferably K, Na, Cs, Ba, Mo, Fe, Ru (including mixtures of two or more thereof), more preferably K, Ba, Mo, Fe, Ru (including mixtures of two or more thereof), wherein M2 more preferably comprises Fe, Ru, or Fe and Ru, more preferably M2 comprises Ru, more preferably M2 is Ru.

[0140] 51. The process of embodiment 49 or 50, wherein the catalytic material further comprises one or more support materials on which the metal M1 or the metals M1 and M2 are supported, the one or more support materials being preferably selected from the group consisting of Al2O3, SiO2, ZrO2, CeO2, MgO, CaO, and mixtures of two or more thereof, more preferably Al2O3, SiO2, ZrO2, CeO2, and mixtures of two or more thereof, more preferably Al2O3, SiO2, and mixtures thereof, more preferably the support material comprising Al2O3.

[0141] 52. The process 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, more preferably 40:60 to 50:50.

[0142] 53. The process of embodiment 52, wherein M2 comprises Fe, preferably is Fe, and the catalyst 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, more preferably 40:60 to 50:50.

[0143] 54. The process of embodiment 52 or 53, wherein M2 comprises Ru, preferably is Ru, and the catalyst 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, more preferably 5:95 to 6:94.

[0144] 55. The process of any one of embodiments 49-54, wherein the catalytic material further comprises Al and O.

[0145] 56. The process of embodiment 55, wherein the catalytic material comprises Ni as the metal M1, preferably, the metal M1 is Ni.

[0146] 57. The process of embodiment 56, wherein the catalyst further comprises Mg, and the molar ratio of Ni:Mg:Al 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), more preferably 1:(2.0-2.4):(4.0-4.4).

[0147] 58. The process of embodiment 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.%, more preferably 99.9 to 100 wt.% of the catalyst material consists of Ni, Mg, Al, and O.

[0148] 59. The process of embodiment 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.%, more preferably 99.9 to 100 wt.% of the catalyst material consists of M2, Ni, Mg, Al, and O.

[0149] 60. The process of embodiment 55, wherein the catalytic material comprises Co as the metal M1, preferably, the metal M1 is Co.

[0150] 61. The process of embodiment 60, wherein the catalyst further comprises La, and the molar ratio of Co:La:Al 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), more preferably 1:(1.3-1.7):(10-12).

[0151] 62. The process of embodiment 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.%, more preferably 99.9 to 100 wt.% of the catalyst material consists of Co, La, Al, and O.

[0152] 63. The process of embodiment 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.%, more preferably 99.9 to 100 wt.% of the catalyst material consists of M2, Co, La, Al, and O.

[0153] 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.

[0154] 65. The gas stream obtained in (iii) comprises H2, CO and CO2, and preferably the stoichiometry R of the gas stream obtained in (iii) syngas is 2.00 or more, more preferably in the range of 2.02 to 2.15, more preferably in the range of 2.04 to 2.06, and R syngas is represented by formula (II): R syngas =[c syngas (H2)-c syngas (CO2)] / [c syngas (CO2)+c syngas (CO)](II) (In the formula, c syngas (H2), c syngas (CO2), and c syngas (CO) represent the molar concentrations of H, CO, and CO in the gas stream obtained in (iii), respectively. 65. The process according to any one of embodiments 1 to 64, wherein the process is defined according to

[0155] 66. The process of any one of embodiments 1 to 65, wherein the molar ratio of H2 to CO in the gas stream obtained in (iii) is 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.

[0156] 67. The process of any one of the preceding embodiments, wherein the molar ratio of H2 to CO2 in the gas stream obtained in (iii) is 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.

[0157] 68. The process of any one of embodiments 1 to 67, wherein the molar ratio of CO to CO2 in the gas stream obtained in (iii) is 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.

[0158] 69. The process of any one of the preceding embodiments, wherein the gas stream obtained in (iii) comprises 50-85% by volume, preferably 58-80% by volume, more preferably 61-75% by volume, of H2.

[0159] 70. The process of any one of embodiments 1-69, wherein the gas stream obtained in (iii) comprises 0-10 vol.%, preferably 0-5 vol.%, more preferably 0-4.0 vol.% CH4.

[0160] 71. The process of any one of embodiments 1 to 70, wherein the gas stream obtained in (iii) comprises 0.1 to 20.0 vol. % CO2, preferably 1.5 to 12.0 vol. %, more preferably 1.8 to 11.3 vol. % CO2.

[0161] 72. The process of any one of the preceding embodiments, 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.

[0162] 73. The process of any one of embodiments 1-72, wherein the gas stream obtained in (iii) comprises 0-1 vol.%, preferably 0-0.5 vol.%, more preferably 0-0.1 vol.% HO, and wherein the first precursor gas stream provided in (i.1) more preferably does not comprise HO.

[0163] 74. The process is (iv) separating the residual NH3 from the gas stream obtained in (iii) to obtain a purified gas stream. 74. The process of any one of embodiments 1 to 73, further comprising:

[0164] 75. A process for the preparation of alcohol, preferably methanol, using a gas stream comprising H2 and CO, optionally further comprising CO2, wherein the gas stream is obtained according to any one of embodiments 1 to 74, and the process comprises: (v) using the gas stream obtained in (iii) or the purified gas stream obtained in (iv) as a feed stream. The process includes:

[0165] 76. A hydrocarbon, preferably (C 10 -C 20 7.) A process for the preparation of an alkane or an ether, preferably dimethyl ether, wherein the gas stream is obtained according to any one of embodiments 1 to 74 disclosed herein, and the process comprises: (v) using the gas stream obtained in (iii) or the purified gas stream obtained in (iv) as a feed stream. The process includes: The present invention is further illustrated by the following examples and comparative examples. [Example]

[0166] The following Reference Examples, Examples and Comparative Examples were simulated using Aspen Plus software Version 11.

[0167] Reference Example 1: Measurement of the blind activity of a reactor in NH3 reforming The reactor blind activity was measured for a reference case where SiC was used as the inert material. The NH3 pressure was set at 30 bar (abs), the HO content was set at 0.5 vol.%, and the gas space velocity was set at 4000 h -1 The NH3 conversion was measured at different temperatures as shown in Figure 1. As can be seen from the results shown in Figure 1, the NH3 conversion at a temperature of 650 °C was about 4% when SiC was used as the inert material. At a temperature of 780 °C, the NH3 conversion can be assumed to be about 100%.

[0168] Example 2 and Comparative Example 3: Natural Gas-Based Partial Oxidation (POx) Combined with NH3 Reforming 10,000Nm 3Partial oxidation (POx) of natural gas feedstock with a feed of 10000 kJ / h was considered as a reference. Table 1 shows the composition of the inlet stream and the amount of oxygen required for the POx process. The synthesis gas produced was relatively low in hydrogen (R value = 1.67). Additional hydrogen was required to reach an R value of 2.05. In Example 2, a specific amount of NH3 was added to provide an appropriate amount of hydrogen, while in Comparative Example 3, hydrogen was added directly. As can be seen from the data given in Table 1, the added NH3 decomposed during an endothermic reaction, which significantly reduced the outlet temperature from 1350 °C to 1111 °C. In this case, no catalytic material was required because thermally induced decomposition of NH3 occurred. Table 2 shows the final synthesis gas composition after the addition of NH3 or hydrogen.

[0169] [Table 1]

[0170] [Table 2]

[0171] [Table 3]

[0172] Example 4 and Comparative Example 5: Biogas-based partial oxidation (POx) combined with NH3 reforming 10,000Nm 3A partial oxidation (POx) process of biogas feedstock with a feed of 0.1 s / h was considered as a reference. The biogas contained a higher CO2 content than the natural gas used in Example 2 and Comparative Example 3. Therefore, a larger amount of NH3 had to be fed to the hot outlet of the partial oxidation to reach 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 biogas conversion and NH3 addition. In comparison, hydrogen was added directly in Comparative Example 5. Compared to Example 2, a larger amount of NH3 was added and converted, resulting in a larger decrease in outlet temperature (from 1,350 °C to 671 °C). In this case, a catalytic material was required because thermally induced decomposition was not fast enough at temperatures below 700 °C. Since the hot outlet was combined with a catalytic material for NH3 reforming, essentially an adiabatic process step was involved. Table 4 shows the final syngas composition of the biogas-based POx process combined with NH3 reforming.

[0173] [Table 4]

[0174] [Table 5]

[0175] [Table 6]

[0176] Example 6 and Comparative Example 7: Natural Gas-Based ATR Combined with NH3 Reforming 10,000 Nm for natural gas-based autothermal reforming (ATR) process 3The feedstock of 1000kJ / h was defined as the reference. The ATR process generally has a lower outlet temperature compared to the POx process, and the synthesis gas is generally a little richer in hydrogen (R-value of 1.80). In Example 6, NH3 was fed to the outlet stream, while in Comparative Example 7, hydrogen was added directly. Since the outlet temperature of the ATR was lower (975°C), at least an inert material was applied as the contact material for NH3 reforming. The temperature was reduced from 975 to 884°C by the endothermic NH3 reforming process. Table 5 shows the composition of the inlet stream and the oxygen requirement for the ATR process. Table 6 shows the composition of the produced synthesis gas with an R-value of 2.05.

[0177] [Table 7]

[0178] [Table 8]

[0179] [Table 9]

[0180] Example 8 and Comparative Example 9: Biogas-based ATR combined with NH3 reforming 10,000Nm 3The ATR process using biogas feedstock with a feed of 10 ...

[0181] [Table 10]

[0182] [Table 11]

[0183] [Table 12]

[0184] References - International Publication No. 2019 / 038251A1 Brochure - U.S. Patent No. 8,691,182 B2 - U.S. Patent No. 8,961,923 B2

Claims

1. H ２ and CO (synthesis gas) ２ 1. A method for increasing the content, said method comprising: (iv) CO and H ２ and optionally CO ２ providing a first gas stream further comprising: (v) NH ３ providing a second feed gas stream comprising: (vi) Said NH ３ At least a part of N ２ and H ２ contacting said second gas stream provided in (ii) with said first gas stream provided in (i) to convert A method comprising:

2. (i) of the first gas stream ２ 2. The process of claim 1 , wherein the molar ratio of CO to CO is greater than 0.1:

1.

3. The first gas stream provided in (i) is 35 to 75% by volume of H ２ 3. The method of claim 1 or 2, comprising:

4. 4. The method of any one of claims 1 to 3, wherein the first gas stream provided in (i) comprises 5 to 45% by volume of CO.

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

6. (i) the stoichiometric number R1 of the first gas stream provided in (i) is less than 2.00, and R １ is represented by formula (I): R １ =[c １ (H ２ )-c １ (CO ２ )] / [c １ (CO ２ )+c １ (CO)](I) (In the formula, c １ (H ２ ), c １ (CO ２ ), and c １ (CO) and H in the first gas flow, respectively. ２ , CO ２ , and the molar concentration of CO The method according to any one of claims 1 to 5, wherein the method is defined according to

7. The first gas stream provided in (i) comprises a gas stream obtainable or obtained by one or more of a waste gasification reaction, a biomass gasification reaction, an autothermal reforming reaction, and a partial oxidation reaction of one or more hydrocarbons, wherein the hydrocarbons are selected from the group consisting of (C １ -C １０ 7. The method of claim 1, wherein the alkane is selected from the group consisting of:

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

10. 10. The method of claim 9, wherein the contacting in (iii) occurs in a reactor, the reactor comprising an inert material.

11. 10. The method of claim 9, wherein the contacting in (iii) occurs in a reactor, the reactor containing the 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 comprises: (iv) removing residual NH from the gas stream obtained in (iii) to obtain a purified gas stream. ３ Separating 13. The method of any one of embodiments 1 to 12, further comprising:

14. H ２ and CO, optionally CO ２ 14. A process for the preparation of alcohols using a gas stream which further comprises: (v) using the gas stream obtained in (iii) or the purified gas stream obtained in (iv) as a feed stream. A method comprising:

15. H ２ and CO, optionally CO ２ 14. A process for the preparation of hydrocarbons or ethers using a gas stream which is obtained according to any one of claims 1 to 13, said process comprising: (v) using the gas stream obtained in (iii) or the purified gas stream obtained in (iv) as a feed stream. A method comprising:

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