Butane hydrogenolysis process with safe thermal operation

Abstract

The present invention relates to a butane hydrogenolysis process for producing one or more than one desired hydrogenolysis product. The process involves introducing an initial feed stream comprising a butane feed and a hydrogen feed into a reactor system comprising a plurality of reactors arranged in series, e.g., no more than 10 reactors. Each of these reactors contains a butane hydrogenolysis catalyst loaded in a specific catalyst loading such that each reactor other than the first reactor in series has a higher catalyst loading than the previous reactor. In addition, each reactor is configured to operate at a higher reactor temperature rise than the previous reactor. The process can include using a diluent, preferably methane, on the feed stream in one or more reactors. The invention also relates to a reactor system for carrying out a butane hydrogenolysis process.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to European application No. 22171195.5 filed on May 2, 2022 and European application No. 22206481.8 filed on November 9, 2022. Technical Field

[0003] The present invention relates to the field of butane hydrogenolysis, and in particular to a butane hydrogenolysis method and a reactor system suitable for carrying out butane hydrogenolysis. Background Art

[0004] Butane is widely used in the chemical industry as part of a method for producing natural gas, distillates and other refinery products. For example, light olefins and light alkanes can be obtained from a butane (C4) stream by thermal steam cracking, hydrocracking reactions and / or by hydrogenolysis reactions. However, it has been found that the yield of olefins including ethylene and propylene generated by thermal steam cracking of butane feedstock is relatively low. Therefore, catalytic butane hydrogenolysis has been proposed as an alternative to thermal steam cracking to improve the yield and selectivity of high-value hydrocarbon products such as ethane.

[0005] To ensure high efficiency of the butane hydrogenolysis process, butane conversion should be high (e.g., 90% and above) while maintaining excellent ethane selectivity (e.g., 70% and above). High butane conversion levels and high ethane selectivity can be achieved by increasing the temperature rise in the reactor (reactor temperature rise) or increasing the number of reactors arranged in series. Since butane hydrogenolysis involves a strongly exothermic reaction, the option of maximizing the reactor temperature rise may not be appropriate because such reactor temperature rise beyond a certain point may lead to thermal runaway.

[0006] One of the methods to adjust the reactor temperature rise is to control the temperature at the reactor inlet when the feed is introduced. However, due to the strongly exothermic chemical reaction, the performance of butane hydrogenolysis is very sensitive to even small fluctuations in temperature, especially at the reactor inlet, which can lead to thermal runaway in some cases. The consequence of thermal runaway is not only an adverse effect on the selectivity of ethane and other desired products, but also such thermal runaway may cause serious safety issues in daily plant production.

[0007] Therefore, to ensure safer thermal operation while ensuring high butane conversion and high product selectivity, operating limits are set to limit the temperature rise of each reactor. As an alternative, butane conversion and ethane selectivity can be improved by maximizing the number of reactors in series. However, the limit on the number of reactors is determined by capital cost considerations and operating cost considerations. Therefore, it is desirable to strike a balance between maximizing the reactor temperature rise and the number of reactors deployed for hydrogenolysis while achieving sufficiently high butane conversion and product selectivity without the risk of thermal runaway.

[0008] In the past, the public has been able to obtain several publications related to butane hydrogenolysis. US202203335 relates to a butane hydrogenolysis method. The patent publication discloses a method comprising controlling the introduction of a butane feed stream and hydrogen into a first hydrogenolysis reactor so that the molar ratio of hydrogen to butane in the reactor is controlled to be between 0.3:1 and 0.8:1.

[0009] WO2020061012 relates to a method for treating butane, more specifically to a method for the reactive separation of n-butane and isobutane.

[0010] Therefore, one of the objects of the present invention is to provide a butane hydrogenolysis process that can achieve an appropriate level of butane conversion and high ethane selectivity while reducing the risk of thermal runaway. Another object of the present invention is to provide a butane hydrogenolysis process that is configured to mitigate thermal runaway even when there are slight temperature fluctuations at the reactor inlet. Another object of the present invention is to provide a reactor system suitable for performing butane hydrogenolysis, which system involves a minimum number of fixed bed reactors arranged in series, which are configured to achieve sufficiently high butane conversion and ethane selectivity while mitigating thermal runaway. Another object of the present invention is to provide a diluent added to the butane hydrogenolysis process to mitigate thermal runaway while achieving a sufficiently high butane conversion. Another object of the present invention is to provide a diluent added to a reactor system suitable for performing butane hydrogenolysis to mitigate thermal runaway while achieving a sufficiently high butane conversion. Summary of the invention

[0011] Therefore, one or more objects of the present invention are achieved by a butane hydrogenolysis process for producing one or more desired hydrogenolysis products, wherein the process comprises the steps of:

[0012] a) providing a reactor system comprising a plurality of "N" reactors arranged in series, wherein "N" is an integer ≤ 10, preferably ≤ 5; wherein the first reactor in the series is denoted as R 1 The last reactor in the series is denoted as R N The penultimate reactor in the series is denoted as R N-1 , the remaining reactors are represented as 2 to (N-2) in sequence;

[0013] b) In the expression R X A feed stream comprising butane feed and hydrogen feed is introduced into the "X" reactor of the reactor, and an Xth hydrogenolysis product stream is generated under butane hydrogenolysis conditions; wherein the Xth hydrogenolysis product stream comprises unreacted butane feed, hydrogenolysis product and unreacted hydrogen;

[0014] i. Among them, R X is from the reactor R 1To reactor R N-1 Any one of the reactors arranged in series;

[0015] ii. Wherein, "X" is an integer ≥1 and ≤N-1, wherein when "X" = 1, introduced into the first reactor R 1 The feed stream in is the initial feed stream introduced into the reactor system;

[0016] c) introducing at least a portion of the Xth hydrogenolysis product stream into a subsequent reactor, which is denoted by R X+1 The (X+1) reactor is provided with a hydrogenolysis reactor, and generates a (X+1) hydrogenolysis product stream under butane hydrogenolysis conditions; wherein the (X+1) hydrogenolysis product stream comprises unreacted butane feed, hydrogenolysis products and unreacted hydrogen;

[0017] i. Among them, reactor R X+1 It is closely connected to the reactor R X The latter reactor;

[0018] d) If "N" > 2, repeat steps b) and c) for (N-2) times until R N The Nth hydrogenolysis product stream is generated in the reactor; wherein, if the Nth hydrogenolysis product stream is introduced into the reactor R X+1 The feed stream contains at least a portion of the feed stream in the immediately preceding reactor R X The Xth hydrogenolysis product stream generated in the step of: the Nth hydrogenolysis product stream comprises unreacted butane, hydrogenolysis products and unreacted hydrogen,

[0019] i. If "N" is 2, the second reactor R 2 The generated second hydrogenolysis product stream is the Nth hydrogenolysis product stream;

[0020] e) recovering at least a portion of the hydrogenolysis product from the Nth hydrogenolysis product stream to obtain one or more than one desired hydrogenolysis product;

[0021] From R 1 To R N Each reactor in series includes:

[0022] i. a reactor vessel; and

[0023] ii. a catalyst bed disposed in a reactor vessel, the catalyst bed comprising: a butane hydrogenolysis catalyst, wherein the butane hydrogenolysis catalyst is loaded with a catalyst loading (CL); wherein from R 2 To R N The catalyst loading (CL) of each reactor is 5% to 150%, preferably 15% to 120%, preferably 25% to 110%, preferably 30% to 80% higher than the catalyst loading of the immediately preceding reactor;

[0024] iii. wherein the method is carried out in the following manner, from R 2 To R N The reactor temperature rise of each reactor is 1°C to 50°C, preferably 2°C to 40°C, preferably 5°C to 35°C higher than the reactor temperature rise of the immediately preceding reactor; wherein one or more than one desired hydrogenolysis products are selected from ethane, propane, methane and mixtures thereof.

[0025] In some embodiments of the present invention, from R 2 To R N Each of the reactors is operated at a mass space velocity (WHSV) of the butane feed stream that is 5% to 70%, preferably 10% to 60%, preferably 20% to 60% lower than the mass space velocity (WHSV) of the butane feed stream operated in the immediately preceding reactor; and / or the process further comprises introducing a diluent into one or more of the R 1 To R N in a reactor, wherein the preferred diluent is methane.

[0026] Preferably, the method further comprises introducing a diluent into one or more R 1 To R N Preferably, the diluent has a butane concentration higher than 80%, preferably higher than 90%, preferably higher than 100%, preferably higher than 120%, preferably higher than 140% relative to the butane concentration present in the reactor into which the diluent is introduced.

[0027] In some embodiments of the present invention, when X=1, the second reactor R 2 The catalyst loading of the first reactor R 1 The catalyst loading is 25% to 110% higher, preferably 35% to 80%, preferably 40% to 70%, preferably 50% to 70%.

[0028] In some embodiments of the present invention, the step of recovering at least a portion of the hydrogenolysis product from the Nth hydrogenolysis product stream comprises:

[0029] a) feeding at least a portion of the Nth hydrogenolysis product stream to a separation unit to form a hydrogenolysis product stream, an unreacted hydrogen stream, and a separated butane stream comprising n-butane and isobutane;

[0030] b) recovering at least a portion of the hydrogenolysis product from the hydrogenolysis product stream to obtain one or more than one desired hydrogenolysis product;

[0031] c) feeding the separated butane stream to an isomerization unit to obtain an n-butane-rich stream; and

[0032] d) recycling at least a portion of the n-butane-rich stream and the unreacted hydrogen stream back to the1 To R N in one or more reactors.

[0033] In some embodiments of the present invention, the first reactor R 1 When the temperature rise of the reactor is ≤110°C, preferably ≤100°C, preferably ≤90°C, preferably ≤70°C, preferably ≤60°C, preferably ≤50°C, preferably ≤40°C, the first reactor R 1 The initial reactor inlet temperature (T inlet1 ) is increased by ≥0.5°C and <3.0°C, preferably ≥1.0°C and <3.0°C, preferably ≥2.0°C and ≤2.5°C, wherein the reactor temperature rise is determined as (T outlet1 -T inlet1 ), where T outlet1 The first reactor R 1 The outlet reactor temperature is T inlet1 The first reactor R 1 The initial inlet temperature.

[0034] In some embodiments of the present invention, one or more desired hydrogenolysis products are selected from ethane, propane, methane and mixtures thereof, preferably one or more desired hydrogenolysis products are ethane, which is produced with a selectivity of ≥60.0%, preferably ≥65.0%, preferably ≥70.0%, preferably ≥75.0% relative to the total molar concentration of all hydrogenolysis products.

[0035] In some embodiments of the present invention, additional butane feed and / or hydrogen feed is introduced into the (X+1) reactor (R) along with the Xth hydrogenolysis product stream. X+1 In some embodiments of the present invention, the butane feed and / or the unreacted butane feed comprises a mixture of normal butane and / or isobutane.

[0036] In some embodiments of the present invention, the feed stream comprising butane feed and hydrogen feed may also comprise a small amount of hydrocarbon compounds comprising hydrocarbons having three, or five, or six, or eight carbon atoms.

[0037] In some embodiments of the present invention, the ratio of the molar concentration of n-butane present in the Nth hydrogenolysis product stream to the molar concentration of n-butane present in the initial feed stream is ≤ 0.4, preferably ≤ 0.3, preferably ≤ 0.2, preferably ≤ 0.1, preferably ≤ 0.05. 1 The ratio of the molar concentration of n-butane in the resulting first hydrogenolysis product stream (first hydrogenolysis product stream) to the molar concentration of n-butane present in the initial feed stream is ≤ 0.95, preferably ≤ 0.85, preferably ≤ 0.70, preferably ≤ 0.5.

[0038] In some embodiments of the present invention, the step of recovering at least a portion of the hydrogenolysis product from the Nth hydrogenolysis product stream comprises the step of feeding at least a portion of the Nth hydrogenolysis product stream to a hydrocracking reactor to obtain a hydrocracking product stream comprising one or more than one desired hydrogenolysis product.

[0039] In some embodiments of the present invention, the butane hydrogenolysis catalyst is selected from:

[0040] (i) a bimetallic supported catalyst comprising a support, a first catalytic metal, a second catalytic metal and an optional binder, wherein the first catalytic metal and the second catalytic metal are different,

[0041] (ii) a monometallic supported catalyst comprising a third catalytic metal, a support and optionally a binder, or

[0042] (iii) a mixture of (i) and (ii),

[0043] Among them, the first catalytic metal, the second catalytic metal and the third catalytic metal are independently selected from iridium (Ir), platinum (Pt), rhodium (Rh), ruthenium (Ru), rhenium (Re), palladium (Pd), molybdenum (Mo), tungsten (W), nickel (Ni) or cobalt (Co) or any combination thereof.

[0044] In some embodiments of the present invention, the butane hydrogenolysis catalyst comprises a bimetallic supported catalyst comprising Ir and Pt, and wherein the support comprises alumina, a zeolite, or both, wherein the zeolite comprises ZSM-5 zeolite, ZSM-11 zeolite, Y zeolite, high silica Y zeolite, USY zeolite, EU-1 zeolite, EU-2 zeolite, beta zeolite, L zeolite, ferrierite, CHA zeolite, SSZ-16 zeolite, Nu-3 zeolite, sigma-1 zeolite, or silicalite-1, or any combination thereof, and optionally wherein a binder, if present, is selected from alumina, titania, silica, or a combination thereof.

[0045] In some embodiments of the present invention, the reactor system comprises a plurality of four reactors (N=4) arranged in series, wherein the first reactor in the series is denoted as R 1 The fourth reactor in the series is denoted by R 4 , and the remaining reactors in the series are denoted as R 2 and R 3 , wherein the second reactor R 2 The catalyst loading of the first reactor R 1 The catalyst loading is 25% to 110%, preferably 35% to 80%, preferably 40% to 70%, preferably 50% to 70%, wherein the initial feed stream is introduced into the first reactor (R 1) and from the fourth reactor R 4 A fourth hydrogenolysis product stream generated in the process is obtained to obtain one or more than one desired hydrogenolysis products.

[0046] In some preferred embodiments of the present invention, the present invention relates to a reactor system for carrying out the butane hydrogenolysis process according to one or more embodiments of the present invention, wherein the reactor system comprises a plurality of "N" reactors arranged in series, wherein "N" is an integer ≤10, preferably an integer ≤5; wherein the first reactor in the series is denoted as R 1 The last reactor in the series is denoted as R N The penultimate reactor in the series is denoted as R N-1 , the remaining reactors are represented as 2 to (N-2) in sequence;

[0047] a) Where R 1 To R N Each reactor includes:

[0048] i. a reactor vessel; and

[0049] ii. a catalyst bed disposed in the reactor vessel and extending in the direction of reactant flow, wherein the catalyst bed comprises a butane hydrogenolysis catalyst loaded with a catalyst loading (CL); wherein from R 2 To R N The catalyst loading (CL) of each reactor is 5% to 150%, preferably 15%, higher than the catalyst loading of the immediately preceding reactor.

[0050] to 120%, preferably 25% to 110%, preferably 30% to 80%;

[0051] b) First reactor R 1 is configured to operate under the condition that the reactor temperature rise is ≤110°C, preferably ≤100°C, preferably ≤90°C, when the first reactor R 1 The initial reactor inlet temperature (T inlet1 ) is increased by ≥0.5°C and <3.0°C, preferably ≥1.0°C and <3.0°C, preferably ≥2.0°C and ≤2.5°C, wherein the reactor temperature rise is determined as (T outlet1 -T inlet1 ), where T outlet1 The first reactor R 1 The outlet reactor temperature is T inlet1 The first reactor R 1 The initial inlet temperature of the first reactor R 1 configured to receive an initial feed stream; and

[0052] c) wherein the reactor system is configured to achieve a total n-butane conversion of ≥ 60.0%, preferably ≥ 70.0%, preferably ≥ 80.0%, preferably ≥ 95.0%; and

[0053] d) Among them, from R 2 To R N Each reactor is configured to have a reactor temperature rise of 1°C to 50°C, preferably 2°C to 40°C, preferably 5°C to 35°C, compared to the reactor temperature rise of the immediately preceding reactor; optionally, wherein R 1 To R N At least one of the reactors has an inlet for receiving a diluent gas.

[0054] Preferably, R 1 To R N At least one of the reactors has an inlet for receiving a diluent gas.

[0055] In an embodiment of the invention, the present invention relates to a reactor system including a feed stream or other well-known devices, which is used to introduce a diluent into the hydrogenolysis reactor, the diluent preferably being methane. It can be a separate feed stream fed directly to the hydrogenolysis reactor, or it can be a feed stream premixed with a butane feed and a hydrogen feed. In this way, there is either a separate inlet for the diluent feed in the hydrogenolysis reactor, or an inlet in a butane feed, a hydrogen feed, or a combined butane / hydrogen feed, depending on the configuration. The added diluent acts as a heat carrier to reduce low temperature rise at the same butane conversion rate.

[0056] Methane is a preferred diluent. The addition of a methane diluent provides an additional benefit, namely, under the same temperature rise limit, dilution can safely increase the butane conversion rate of each reactor. This can also reduce the number of reactors required to achieve the same total butane conversion rate. In other embodiments of the present invention, the present invention relates to a method comprising introducing a diluent into the hydrogenolysis process, wherein the diluent is preferably methane. The added methane acts as a heat carrier, which can reduce the temperature rise at the same butane conversion rate. The addition of a methane diluent provides an additional benefit, namely, under the same temperature rise limit, dilution can safely increase the butane conversion rate of each reactor. This can also reduce the number of reactors required to achieve the same total butane conversion rate.

[0057] Other objects, features and advantages of the present invention will become clearer from the following drawings, specific embodiments and examples. However, it should be understood that although these drawings, specific embodiments and examples show specific embodiments of the present invention, they are only used as illustrations and are not intended to be limiting. In addition, it is expected that this specific embodiment will make changes and modifications within the nature and scope of the present invention apparent to those skilled in the art. In other embodiments, features from specific embodiments can be combined with features from other embodiments. For example, features from some specific embodiments can be combined with features from any other embodiment. In other embodiments, additional features can be added to the specific embodiments described herein. BRIEF DESCRIPTION OF THE DRAWINGS

[0058] For a better understanding of the present invention, reference is now made to the following description in conjunction with the accompanying drawings, in which:

[0059] 1 is a schematic diagram of a butane hydrogenolysis process according to an embodiment of the present invention, which includes four fixed bed adiabatic reactors in series connected to a separation unit and an isomerization unit for recovering one or more desired hydrogenolysis products.

[0060] 2 is a schematic diagram of a butane hydrogenolysis process according to an embodiment of the present invention comprising four fixed bed adiabatic reactors in series connected to a hydrocracking unit for recovering one or more than one desired hydrogenolysis products. DETAILED DESCRIPTION

[0061] The following include definitions of various terms, expressions, and phrases used throughout this specification.

[0062] The word "a" or "an" when used with the terms "comprising," "including," "containing," or "having" in the claims and / or specification may mean "one / a kind of," but is also consistent with the meaning of "one or more than one / a kind of or more than one," "at least one," and "one or more than one / a kind of or more than one." The words "comprising," "having," "including," or "containing" are inclusive or open-ended and do not exclude additional, unmentioned elements or method steps. The methods of the present invention may "comprise," "consist essentially of," or "consist of" specific ingredients, components, compositions, etc. disclosed throughout this specification.

[0063] In the context of the present invention, the hydrogenolysis of butane involves the reaction schemes shown in (1) to (3):

[0064] nC 4 H 10 + H 2 → 2 C 2 H 6 (1)

[0065] nC 4 H 10 + H 2 → C 3 H 8 + CH 4 (2)

[0066] iC 4 H 10 + H 2 → C 3 H 8 + CH 4 (3).

[0067] Reaction Scheme 1 is the desired hydrogenolysis reaction, while Reaction Scheme 2 and Reaction Scheme 3 show side reactions. Therefore, the term "one or more than one desired hydrogenolysis product" used throughout this disclosure refers to ethane and optionally small amounts of propane and methane produced by the butane hydrogenolysis process. More specifically, the expression "one or more than one desired hydrogenolysis product" used throughout this disclosure refers to a hydrocarbon product selected from ethane, propane, methane, and mixtures thereof.

[0068] The expressions "catalyst loading" or "catalyst loading" used interchangeably throughout this disclosure refer to the total weight of butane hydrogenolysis catalyst normalized to the reactor volume, including the weight of the catalyst support and the weight of the optional binder, i.e., the weight present in the reactor bed of a particular reactor and relative to the reactor volume. For identical reactors in series, the catalyst loading is simply the mass of the catalyst.

[0069] The term "reactor temperature rise" as used throughout this disclosure for a given reactor refers to the increase in temperature within the reactor due to the exothermic hydrogenolysis reaction in the reactor. The reactor temperature rise measures the increase in temperature within the reactor from the time the butane feed stream and the hydrogen feed stream are introduced into the reactor until the resulting hydrogenolysis product is removed from the reactor. The reactor temperature rise is determined as (T outlet -T inlet ), where T outlet is the final outlet reactor temperature when the hydrogenolysis products are removed from a particular reactor, and T inlet is the initial inlet temperature measured upon introduction of the feed stream.

[0070] The term "latter reactor" refers to a reactor located adjacent to a previous reactor, which receives the hydrogenolysis product stream generated by the previous reactor.

[0071] The term "previous reactor" refers to a reactor located adjacent to the previous reactor, the hydrogenolysis product stream generated by which is introduced into the subsequent reactor.

[0072] The term "thermal runaway" refers to a reactor temperature rise exceeding 110°C during the hydrogenolysis reaction, or a reactor temperature rise within the reactor when the reactor inlet temperature fluctuates.

[0073] As used throughout this disclosure with respect to any feed stream or hydrogenolysis product stream, the term "at least a portion" means > 80.0%, preferably > 95.0%, preferably > 99.0%, preferably 100.0% of the stream.

[0074] The term "a plurality of "N" reactors arranged in series" refers to an arrangement of "N" reactors arranged in series such that an initial feed stream is introduced into the first reactor in the series, and each reactor in the series produces a hydrogenolysis product stream which is introduced as part of the feed into the next reactor until a final hydrogenolysis product stream is recovered from the last reactor or the Nth reactor in the series. The variable "N" is introduced for the purpose of defining the total number of reactors involved in the butane hydrogenolysis process. For the purposes of the present invention, the first reactor R 1 is the first reactor in the series into which the initial feed stream is introduced to start the butane hydrogenolysis process. For purposes of this invention, the last reactor in the series is R N , wherein an Nth hydrogenolysis product stream is generated and one or more than one hydrogenolysis products are subsequently recovered therefrom.

[0075] The term "denoted by R X The "X" reactor" is used to define the specific reactor in the series, where R X is from the reactor R 1 To reactor R N-1 Any one of the reactors arranged in series. Define reactor R X The purpose of the invention is to illustrate the steps of the butane hydrogenolysis process involving a reactor in which R X Each reactor is defined to generate a hydrogenolysis product stream upon receiving a feed stream.

[0076] The term "R X+1 The (X+1) reactor” refers to the reactor R X Reactor R X+1 is configured to receive a hydrogenolysis product stream. Defined as R X+1 The reactor is relative to the reactor R X defined.

[0077] The term "Nth hydrogenolysis product stream" refers to the last hydrogenolysis product stream produced by the last reactor in a series arrangement comprising "N" reactors.

[0078] The present invention is based in part on the discovery of a process for conducting butane hydrogenolysis to produce one or more desired hydrogenolysis products. The process of the present invention involves the use of a plurality of fixed bed reactors arranged in series so that each subsequent reactor, except the first reactor, has a progressively greater reactor temperature rise and progressively greater catalyst loading than the previous reactor in the series.

[0079] For example, according to the present invention, except for the first reactor, each reactor in the series can have a catalyst loading of 5% to 150%, preferably 15% to 120%, preferably 25% to 110%, preferably 30% to 80% higher than the catalyst loading of the immediately preceding reactor vessel in the series, and a reactor temperature rise of 1°C to 50°C, preferably 2°C to 40°C, preferably 5°C to 35°C higher than the reactor temperature rise of the immediately preceding reactor. The catalyst loading and reactor temperature rise of the entire series reactor are gradually increased according to the amount specified by the present invention, which significantly reduces the risk of thermal runaway, while ensuring high butane conversion and high ethane selectivity.

[0080] Thus, in some aspects of the invention, the invention relates to a butane hydrogenolysis process for producing one or more than one desired hydrogenolysis product, wherein the process comprises the steps of:

[0081] a) providing a reactor system comprising a plurality of "N" reactors arranged in series, wherein "N" is an integer ≤ 10, preferably ≤ 5; wherein the first reactor in the series is denoted as R 1 The last reactor in the series is denoted as R N The penultimate reactor in the series is denoted as R N-1 , the remaining reactors are represented as 2 to (N-2) in sequence;

[0082] b) In the expression R X A feed stream comprising butane feed and hydrogen feed is introduced into the "X" reactor of the reactor, and an Xth hydrogenolysis product stream is generated under butane hydrogenolysis conditions; wherein the Xth hydrogenolysis product stream comprises unreacted butane feed, hydrogenolysis product and unreacted hydrogen;

[0083] i. Among them, R X is from the reactor R 1 To reactor R N-1 Any one of the reactors arranged in series;

[0084] ii. Wherein, "X" is an integer from 1 to (N-1),

[0085] iii. Wherein, when "X" = 1, introduced into the first reactor R 1 The feed stream in is the initial feed stream introduced into the reactor system;

[0086] c) introducing at least a portion of the Xth hydrogenolysis product stream into a subsequent reactor, which is denoted by R X+1 The (X+1) reactor is provided with a hydrogenolysis reactor, and generates a (X+1) hydrogenolysis product stream under butane hydrogenolysis conditions; wherein the (X+1) hydrogenolysis product stream comprises unreacted butane feed, hydrogenolysis products and unreacted hydrogen;

[0087] i. Among them, reactor R X+1 It is closely connected to the reactor R X The latter reactor;

[0088] d) If "N" > 2, repeat steps b) and c) for (N-2) times until R N The Nth hydrogenolysis product stream is generated in the reactor; wherein, if the Nth hydrogenolysis product stream is introduced into the reactor R X+1 The feed stream contains at least a portion of the feed stream in the immediately preceding reactor R X The Xth hydrogenolysis product stream generated in the step, then the Nth hydrogenolysis product stream comprises unreacted butane, hydrogenolysis products and unreacted hydrogen;

[0089] i. If "N" is 2, the second reactor R 2 The generated second hydrogenolysis product stream is the Nth hydrogenolysis product stream;

[0090] e) recovering at least a portion of the hydrogenolysis product from the Nth hydrogenolysis product stream, thereby obtaining one or more than one desired hydrogenolysis product. 1 To R N Each reactor in series includes:

[0091] i. Reactor vessel;

[0092] ii. a catalyst bed disposed in a reactor vessel, wherein the catalyst bed comprises: a butane hydrogenolysis catalyst, wherein the butane hydrogenolysis catalyst is loaded with a catalyst loading (CL); wherein from R 2 To R N The catalyst loading (CL) of each reactor is 5% to 150%, preferably 15% to 120%, preferably 25% to 110%, preferably 30% to 80% higher than the catalyst loading of the immediately preceding reactor;

[0093] iii. wherein the method is carried out in the following manner, from R 2 To R N The reactor temperature rise of each reactor is 1°C to 50°C higher than the reactor temperature rise of the immediately preceding reactor, preferably 2°C to 40°C, preferably 5°C to 35°C;

[0094] Wherein, one or more than one desired hydrogenolysis products are selected from ethane, propane, methane and mixtures thereof.

[0095] In order to carry out the butane hydrogenolysis process, a suitable reactor system may be used. For example, the reactor system may include a plurality of "N" reactors arranged in series, wherein "N" is an integer ≤ 10, preferably an integer ≤ 5; wherein the first reactor in the series is denoted as R 1 The last reactor in the series is denoted by R N The penultimate reactor in the series is denoted as R N-1 , the remaining reactors are represented by 2 to (N-2) in sequence. Preferably, "N" is an integer >1 and ≤10, preferably "N" is an integer >1 and ≤5, preferably "N" is an integer >1 and ≤4.

[0096] Preferably, in some embodiments of the present invention, each of the "N" reactors (1 to N) arranged in series is operated adiabatically. Preferably, in some embodiments of the present invention, each of the reactors in series is a fixed bed adiabatic reactor. In some embodiments of the present invention, R 1 To R N Each of the reactors has the same dimensions including the same reactor volume. In some embodiments of the invention, at least one or more than one reactor has dimensions including the reactor volume that are different from the remaining set of reactors. In this case, the catalyst loading is the mass (kg) of the catalyst normalized relative to the appropriate reactor size such as reactor volume.

[0097] For example, in some embodiments of the present invention, if the number of reactors arranged in series is 10, then "N" is 10. Therefore, the first reactor is represented by R 1 The second to last reactor is denoted as R 9 The last reactor in the series is denoted as R 10 The remaining reactors can be represented by R 2 To R 8 Similarly, if the number of reactors arranged in series is 4, then "N" is 4. Therefore, the first reactor is denoted as R 1 The second to last reactor is denoted as R 3 The last reactor in the series is denoted as R 4 The remaining reactor can be represented by R 2 .

[0098] The initial feed stream comprises a butane feed stream and a hydrogen feed, which are present as reactants in appropriate proportions. The butane feed comprises, for example, n-butane and isobutane. In some embodiments of the present invention, the flow rates (e.g., flowmeters, valves, etc.) of the butane feed (e.g., butane WHSV) and the hydrogen feed to the hydrogenolysis reactor system can be controlled to maintain the first reactor R1 The molar ratio of hydrogen to butane (n-butane to isobutane) in the butane feed stream is less than 1, preferably 0.3:1 to 0.8:1, or 0.3:1, 0.35:1, 0.4:1, 0.45:1, 0.5:1, 0.55:1, 0.60:1, 0.65:1, 0.70:1, 0.75:1, 0.80:1 or any range or value therebetween. The butane feed stream may comprise a mixture of butane (e.g., n-butane and isobutane) and a small amount of other hydrocarbon compounds.

[0099] In some embodiments of the present invention, the butane feed and / or unreacted butane feed comprises a mixture of normal butane and / or isobutane. 1 The initial feed stream introduced in the reactor has a suitable molar concentration of normal butane and isobutane. For example, the butane feed stream may include a mixture of butane (e.g., normal butane and isobutane) and a small amount of other hydrocarbon compounds.

[0100] In some embodiments of the present invention, the butane feed stream may contain small amounts of other hydrocarbon compounds and n-butane. For example, such hydrocarbon compounds may have three carbon atoms (C 3 hydrocarbons), or five carbon atoms (C 5 Hydrocarbon compounds) six carbon atoms (C 6 Hydrocarbon compounds). N-butane may be present in the butane feed stream in an amount of ≥50.0 mol%. For example, the amount of n-butane may be ≥50.0 mol%, ≥55.0 mol%, ≥60.0 mol%, ≥65.0 mol%, ≥70.0 mol%, ≥75.0 mol%, ≥80.0 mol%, ≥85.0 mol%, ≥90.0 mol%, ≥95.0 mol%, ≥99.9 mol%, or any range or value therebetween. In some embodiments of the invention, the amount of n-butane may be ≥50 mol% and ≤99.0 mol%, ≥55.0 mol% and ≤90.0 mol%, ≥60.0 mol% and ≤85.0 mol%, ≥65.0 mol% and ≤80.0 mol%, or ≥70.0 mol% and ≤75.0 mol%, or any range therebetween.

[0101] For example, a feed stream comprising butane feed and hydrogen feed is introduced into a feed stream denoted as R X and evaluating an Xth hydrogenolysis product stream; wherein the Xth hydrogenolysis product stream comprises unreacted butane feed, hydrogenolysis products, and unreacted hydrogen; wherein R X is from the reactor R 1 To reactor R N-1 Any one of the reactors arranged in series; wherein X is an integer ≥1 and ≤N-1, wherein when X=1, the first reactor R is introduced 1The feed stream is the initial feed stream introduced into the reactor system.

[0102] For example, when the number of reactors arranged in series is 4, then N = 4. X It can be reactor R 1 , R 2 and R 3 For example, an initial feed stream comprising butane feed and hydrogen may be introduced into the first reactor R 1 For example, R 1 , R 2 and R 3 Each reactor of the first reactor R can generate a corresponding hydrogenolysis product stream, which includes unreacted butane feed, hydrogenolysis products and unreacted hydrogen. 1 A first hydrogenolysis product stream can be generated, reactor R 2 The second hydrogenolysis product stream is generated, and the reactor R 3 A third hydrogenolysis product stream is generated.

[0103] For each Xth hydrogenolysis product stream generated, at least a portion of the Xth hydrogenolysis product stream can be introduced into the immediately following reactor, which is represented by R X+1 The (X+1) reactor is connected to the butane hydrogenolysis condition to generate the (X+1)th hydrogenolysis product stream. For example, when the number of reactors arranged in series is 4 (N=4), for the first round when X=1, under the butane hydrogenolysis condition, the first reactor R 1 (R X The first hydrogenolysis product stream (Xth hydrogenolysis product stream) generated is introduced into the second reactor R 2 (R X+1 ), followed by butane hydrogenolysis conditions to produce a second hydrogenolysis product stream (the (X+1)th hydrogenolysis product stream).

[0104] According to the present invention, if the number of reactors arranged is greater than 2 (i.e., N>2), the method steps for producing the Xth hydrogenolysis product stream and producing the (X+1)th hydrogenolysis product stream are repeated (N-2) times until the last or final reactor (R N In other words, the process is repeated until the (X+1)th hydrogenolysis product stream is the Nth hydrogenolysis product stream. N-1 The resulting (N-1) hydrogenolysis product stream is introduced into R N The last or final reactor in the series, thereby generating an Nth hydrogenolysis product stream.

[0105] Therefore, if N=4, there will be two more runs. For example, for the second run or X=2, the second hydrogenolysis product stream (Xth hydrogenolysis product stream) is introduced into the third reactor R3 (X+1 reactor), and then generating a third hydrogenolysis product stream (the (X+1)th hydrogenolysis product stream) under butane hydrogenolysis conditions.

[0106] For the third round when X=3, under butane hydrogenolysis conditions, from the third reactor R 3 (R X The third hydrogenolysis product stream (Xth hydrogenolysis product stream) generated is introduced into the fourth reactor R 4 (R X+1 ), followed by butane hydrogenolysis conditions to produce a fourth hydrogenolysis product stream (Nth hydrogenolysis product stream).

[0107] The Nth hydrogenolysis product stream is the final hydrogenolysis product stream, from which the hydrogenolysis product is recovered to obtain one or more desired hydrogenolysis products. For example, in some embodiments of the present invention, when the number of reactors in series is 4 (N=2), in the third reactor R 3 The second hydrogenolysis product stream is introduced into the reactor to generate a third hydrogenolysis product stream.

[0108] By the third reactor R 3 The third hydrogenolysis product stream (Xth hydrogenolysis product stream) is introduced into the fourth reactor R 4 Thus, the fourth hydrogenolysis product stream is the Nth hydrogenolysis product stream, and these steps are repeated twice starting with the second hydrolysis product stream until the fourth hydrolysis product stream is generated.

[0109] Therefore, when N=2, the Nth hydrogenolysis product stream is the second hydrogenolysis product stream.

[0110] The final hydrogenolysis product stream or the Nth hydrogenolysis product stream once in the last reactor R N At least a portion of the hydrogenolysis product from the Nth hydrogenolysis product stream may be recovered to obtain one or more than one desired hydrogenolysis product.

[0111] In some embodiments of the present invention, the step of recovering at least a portion of the hydrogenolysis product from the Nth hydrogenolysis product stream comprises:

[0112] a) feeding at least a portion of the Nth hydrogenolysis product stream to a separation unit to form a hydrogenolysis product stream, an unreacted hydrogen stream, and a separated butane stream comprising n-butane and isobutane;

[0113] b) recovering at least a portion of the hydrogenolysis product from the hydrogenolysis product stream to obtain one or more than one desired hydrogenolysis product;

[0114] c) feeding the separated butane stream to an isomerization unit to obtain an n-butane-rich stream; and

[0115] d) recycling at least a portion of the n-butane-rich stream and the unreacted hydrogen stream back to the reactor from R 1 To R N in one or more reactors.

[0116] Preferably, the separated butane stream comprising isobutane and n-butane, when introduced into an isomerization unit, converts the isobutane into n-butane using known isomerization processes, thereby forming an n-butane-rich stream.

[0117] In some embodiments of the present invention, additional butane feed and / or hydrogen feed is introduced into the (X+1) reactor (R) along with the Xth hydrogenolysis product stream. X+1 For example, when N=4, additional butane feed and / or hydrogen feed may be introduced into any R 2 , R 3 or R 4 Preferably, in some embodiments of the present invention, in the step of recovering at least a portion of the hydrogenolysis product from the Nth hydrogenolysis product stream, the n-butane-rich stream and the unreacted hydrogen generated therefrom can be recycled back to the R 1 To R N in one or more reactors.

[0118] Alternatively, in some embodiments of the present invention, the step of recovering at least a portion of the hydrogenolysis product from the Nth hydrogenolysis product stream comprises the step of feeding at least a portion of the Nth hydrogenolysis product stream to a hydrocracking reactor to obtain a hydrocracking product stream comprising one or more than one desired hydrogenolysis product.

[0119] In some embodiments of the present invention, one or more than one desired hydrogenolysis product is selected from ethane, propane, methane and mixtures thereof. Preferably, in some embodiments of the present invention, wherein one or more than one desired hydrogenolysis product is ethane, its selectivity relative to the total molar concentration of all hydrogenolysis products is ≥60.0%, preferably ≥65.0%, preferably ≥70.0%, preferably ≥75.0%.

[0120] The total conversion of n-butane achieved by the process is sufficiently high, for example, at least 60% of the n-butane present in the initial feed stream can be converted under the hydrogenolysis conditions. Therefore, in some embodiments of the present invention, the ratio of the molar concentration of n-butane present in the Nth hydrogenolysis product stream to the molar concentration of n-butane present in the initial feed stream is ≤0.4, preferably ≤0.3, preferably ≤0.2, preferably ≤0.1, preferably ≤0.05.

[0121] The inventors have surprisingly discovered that when each of the "N" reactors in series (except the first reactor) is purposefully configured to have a progressively increased catalyst loading compared to the previous reactor in the series, the butane hydrogenolysis process of the present invention results in high n-butane conversion while reducing the risk of thermal runaway. X+1 The catalyst loading of the reactor R is greater than that of the immediately preceding reactor R that generates the hydrogenolysis product stream. X The catalyst loading of R is 5% to 150%, preferably 15% to 120%, preferably 25% to 110%, preferably 30% to 80%. In other words, in some embodiments of the present invention, R 2 To R N The catalyst loading (CL) of each reactor is 5% to 150%, preferably 15% to 120%, preferably 25% to 110%, preferably 30% to 80% higher than the catalyst loading of the immediately preceding reactor.

[0122] For example, the increase in catalyst loading can be calculated by using the following formula: ((CLsr–CLpr) / CLpr)×100, where CLsr is the catalyst loading of the latter reactor and CLpr is the catalyst loading of the former reactor, where CLsr>CLpr.

[0123] In some embodiments of the present invention, the first reactor R 1 When the temperature rise of the reactor is ≤110°C, preferably ≤100°C, preferably ≤90°C, preferably ≤70°C, preferably ≤60°C, preferably ≤50°C, preferably ≤40°C, the first reactor R 1 The initial reactor inlet temperature (T inlet1 ) is increased by ≥0.5°C and <3.0°C, preferably ≥1.0°C and <3.0°C, preferably ≥2.0°C and ≤2.5°C, wherein the reactor temperature rise is determined as (T outlet1 -T inlet1 ), where T outlet1 The first reactor R 1 The outlet reactor temperature is T inlet1 The first reactor R 1 The initial inlet temperature.

[0124] Preferably, in some embodiments of the present invention, the first reactor R 1 When the reactor temperature rise is ≥20°C and ≤110°C, preferably ≥20°C and ≤100°C, preferably ≥20°C and ≤90°C, preferably ≥20°C and ≤70°C, preferably ≥20°C and ≤60°C, preferably ≥20°C and ≤50°C, preferably ≥20°C and ≤40°C, the first reactor R 1The initial reactor inlet temperature (T inlet1 ) is increased by ≥0.5°C and <3.0°C, preferably ≥1.0°C and <3.0°C, preferably ≥2.0°C and ≤2.5°C, wherein the reactor temperature rise is determined as (T outlet1 -T inlet1 ), where T outlet1 The first reactor R 1 The outlet reactor temperature is T inlet1 The first reactor R 1 The initial inlet temperature.

[0125] When the catalyst loading and reactor temperature rise of the second reactor are appropriately increased relative to the catalyst loading and reactor temperature rise of the first reactor, the effect of gradually increasing the catalyst loading and reactor temperature rise of the entire reactor reduces the R 1 Risk of thermal runaway. Reduce the first reactor R 1 The risk of thermal runaway in the series may be particularly useful because the first reactor has the highest risk of thermal runaway compared to any other reactor in the series due to the higher concentrations of reactants (butane feed and hydrogen feed) introduced in the first reactor compared to the remaining reactors in the series.

[0126] The first reactor R can be fully controlled 1 The n-butane conversion in the first reactor R is reduced to reduce the risk of thermal runaway, thereby resulting in an n-butane conversion of at least 5.0%. 1 The ratio of the molar concentration of n-butane in the resulting first hydrogenolysis product stream (first hydrogenolysis product stream) to the molar concentration of n-butane present in the initial feed stream is ≤ 0.95, preferably ≤ 0.85, preferably ≤ 0.70, preferably ≤ 0.5.

[0127] As another option to mitigate thermal runaway, the operating conditions of the butane feed in terms of mass space velocity (WHSV) can be adjusted to maximize n-butane conversion while reducing any risk of thermal runaway. The mass space velocity (WHSV) can be determined by dividing the butane mass flow rate expressed in (kg / hour) by the catalyst loading expressed in (kg).

[0128] In some embodiments of the present invention, it is configured to receive the X The hydrogenolysis product stream of the reactor R X+1 , operated at a mass space velocity (WHSV) based on the butane feed stream, which is higher than that of reactor R X The mass space velocity (WHSV) of the operation is 5% to 70% lower, preferably 10% to 60% lower, preferably 20% to 60% lower. In other words, from R 2 To R NEach reactor is operated at a mass space velocity (WHSV) based on the butane feed stream that is 5% to 70%, preferably 10% to 60%, preferably 20% to 60% lower than the mass space velocity (WHSV) based on the butane feed stream operated in the immediately preceding reactor.

[0129] The reduction in mass space velocity can be calculated by using, for example, the following formula: ((WHSVsr-WHSVpr) / WHSVpr)×100, where WHSVsr is the mass space velocity of the latter reactor, and WHSVpr is the mass space velocity of the former reactor, where WHSVsr<WHSVpr.

[0130] The reactor conditions of the present invention may include temperature, pressure, WHSV based on butane feed, or a combination thereof. In some embodiments of the present invention, when "N" reactors in series are used, the reactor inlet temperature of each reactor may be 240°C to about 300°C, 245°C to 290°C, 250°C to 285°C, 260°C to 280°C, or any value or range therebetween. In some preferred embodiments of the present invention, the reactor inlet temperature of each of the "N" reactors in series is 245°C to 290°C.

[0131] In some embodiments of the invention, the pressure may be about 101 kPa (1.01 bar) to 1000 kPa (10 bar), 200 kPa to 100 kPa, 500 kPa to 1000 kPa, or any range or value therebetween.

[0132] In some embodiments of the present invention, the WHSV of each of the "N" reactors in series based on butane feed may be about 1 h -1 About 50h -1 , 1h -1 , 2h -1 , 3h -1 , 4h -1 , 5h -1 , 6h -1 , 7h -1 , 8h -1 , 9h -1 , 10h -1 , 20h -1 , 21h -1 , 22h -1 , 23h -1 , 24h -1 , 25h -1 , 26h -1 , 27h -1 、28h -1 , 29h -1、30h -1 , 35h -1 , 40h -1 , 45h -1 , 50h -1 , or any range or any value in between.

[0133] Therefore, from the second reactor R 2 The WHSV based on butane feed for the remaining reactors in the initial "N" series of reactors can be determined using the following constraints: X The hydrogenolysis product stream of the reactor R X+1 , operated at a mass space velocity (WHSV) based on the butane feed stream, which is higher than that of reactor R X The mass space velocity (WHSV) for medium operation is 5% to 70% lower, preferably 10% to 60% lower, preferably 20% to 60% lower.

[0134] Each of the "N" reactors in series may include one or more heating devices and / or cooling devices (e.g., insulation, electric heaters, jacketed heat exchangers on the wall) or controllers (e.g., computers, flow valves, automated valves, etc.) that can be used to control the reaction temperature, reactor inlet temperature, and pressure of the reaction mixture.

[0135] Thus, in some embodiments of the present invention, the reactor configured to receive the hydrogenolysis product stream is R X+1 The reactor has a reactor temperature rise of 1°C to 50°C, preferably 2°C to 40°C, preferably 5°C to 35°C, higher than the reactor temperature of the immediately preceding reactor configured to generate the hydrogenolysis product stream. In other words, in some embodiments of the present invention, the process is carried out in the following manner: 2 To R N The reactor temperature rise of each reactor is 1°C to 50°C higher than the reactor temperature rise of the immediately preceding reactor, preferably 2°C to 40°C, preferably 5°C to 35°C.

[0136] The calibrated increase in reactor temperature rise may be achieved by controlling the temperature at the reactor inlet by any suitable means, such as using a heat exchanger, adjusting the catalyst loading in the reactor and the mass space velocity (WHSV) of the butane feed stream.

[0137] Without wishing to be bound by any particular theory, the reactor R 1 To R N The catalyst loading in each reactor and the calibration of the reactor temperature rise are increased, thereby reducing the risk of thermal runaway while ensuring high butane conversion and high selectivity to hydrogenolysis products, especially ethane.

[0138] In some preferred embodiments of the present invention, the reactor system for carrying out the hydrogenolysis process comprises a plurality of four reactors (N=4) arranged in series, wherein the first reactor in the series is denoted as R 1 The fourth reactor in the series is denoted by R 4 , and the remaining reactors in the series are denoted as R 2 and R 3 , wherein the second reactor R 2 The catalyst loading of the first reactor R 1 The catalyst loading is 25% to 110%, preferably 35% to 80%, preferably 40% to 70%, preferably 50% to 70%, wherein the initial feed stream is introduced into the first reactor (R 1 ) and from the fourth reactor R 4 A fourth hydrogenolysis product stream generated in the process is obtained to obtain one or more than one desired hydrogenolysis products.

[0139] Referring to Figure 1, in some preferred embodiments of the present invention, the present invention relates to a butane hydrogenolysis process using four fixed bed reactors arranged in series to produce one or more than one desired hydrogenolysis product. For example, these process steps may include the following steps:

[0140] a) providing a reactor system (100) comprising a plurality of four reactors (104), (106), (108) and (110) arranged in series, wherein "N" is 4; wherein the first reactor (104) in the series is denoted as R 1 The last reactor in the series is the fourth reactor (110), denoted by R 4 The second to last reactor in the series is the third reactor (108), denoted by R 3 The remaining reactor is the second reactor (106), denoted by R 2 ;

[0141] b) introducing an initial feed stream (101) comprising a butane feed (103) and a hydrogen feed (105) into a first reactor (104) and generating a first hydrogenolysis product stream (107) under conditions for hydrogenolysis of butane;

[0142] c) the first hydrogenolysis product stream (107) can be introduced into a second reactor (106) to generate a second hydrogenolysis product stream (109) under butane hydrogenolysis conditions;

[0143] d) the second hydrogenolysis product stream (109) may be introduced into a third reactor (108) to produce a third hydrogenolysis product stream (111) under butane hydrogenolysis conditions; and

[0144] e) the third hydrogenolysis product stream (111) may be introduced into a fourth reactor (110) to produce a fourth hydrogenolysis product stream (113) under butane hydrogenolysis conditions; and

[0145] f) recovering at least a portion of the hydrogenolysis product from the fourth hydrogenolysis product stream (113) and obtaining one or more desired hydrogenolysis products, the one or more desired hydrogenolysis products preferably being ethane.

[0146] In some embodiments of the present invention, the butane hydrogenolysis conditions of the first reactor (104) include an inlet temperature of ≥240°C and ≤300°C, preferably ≥265°C and ≤275°C, ≥15h -1 and ≤40h -1 , preferably ≥15h -1 and ≤35h -1 Based on the mass space velocity (WHSV) of the butane feed stream and a pressure of 101 kPa (1.01 bar) to 1000 kPa (10 bar).

[0147] In some embodiments of the present invention, the butane hydrogenolysis conditions of the second reactor (106) include an inlet temperature of ≥240°C and ≤300°C, preferably ≥260°C and ≤265°C, ≥10h -1 and ≤20h -1 Based on the mass space velocity (WHSV) of the butane feed stream and a pressure of 101 kPa (1.01 bar) to 1000 kPa (10 bar).

[0148] In some embodiments of the present invention, the butane hydrogenolysis conditions of the third reactor (108) include an inlet temperature of ≥240°C and ≤300°C, preferably ≥260°C and ≤265°C, ≥5h -1 and ≤10h -1 Based on the mass space velocity (WHSV) of the butane feed stream and a pressure of 101 kPa (1.01 bar) to 1000 kPa (10 bar).

[0149] In some embodiments of the present invention, the butane hydrogenolysis conditions of the fourth reactor (110) include an inlet temperature of ≥240°C and ≤300°C, preferably ≥260°C and ≤265°C, ≥1h -1 and ≤5h -1 Based on the mass space velocity (WHSV) of the butane feed stream and a pressure of 101 kPa (1.01 bar) to 1000 kPa (10 bar).

[0150] In some embodiments of the present invention, the step of recovering the hydrogenolysis product from the fourth hydrogenolysis product stream (113) comprises the following steps:

[0151] a) feeding the fourth hydrogenolysis product stream (113) to a separation unit (112) to form a hydrogenolysis product stream (115), an unreacted hydrogen stream (119) and a separated butane stream (117) comprising isobutane and normal butane;

[0152] b) recovering at least a portion of the hydrogenolysis product from the hydrogenolysis product stream (115) and obtaining one or more desired hydrogenolysis products, wherein the one or more desired hydrogenolysis products are preferably ethane;

[0153] c) feeding the separated butane stream (117) to an isomerization unit (114) to obtain an n-butane-rich stream (121); and

[0154] d) recycling the n-butane-rich stream (121) back to the second reactor (106) and recycling the unreacted hydrogen stream (119) back to the third reactor (108).

[0155] In some embodiments of the present invention, the n-butane-rich stream (121) can be recycled back to the first reactor (104) (not shown in Figure 1). In some embodiments of the present invention, the n-butane-rich stream (121) can be recycled back to the second reactor (106) (not shown in Figure 1). In some embodiments of the present invention, the n-butane-rich stream (121) can be recycled back to the third reactor (108) (not shown in Figure 1).

[0156] In some embodiments of the present invention, the unreacted hydrogen gas stream (119) can be recycled back to the first reactor (104) (not shown in Figure 1). In some embodiments of the present invention, the unreacted hydrogen gas stream (119) can be recycled back to the second reactor (106) (not shown in Figure 1).

[0157] In some embodiments of the present invention, the second reactor R 2 The catalyst loading of (106) is greater than that of the first reactor R 1 The catalyst loading of (104) is 5% to 150% higher, preferably 15% to 120% higher, preferably 25% to 110% higher, preferably 30% to 80% higher. 3 The catalyst loading of (108) is greater than that of the second reactor R 2 The catalyst loading of (106) is 5% to 150% higher, preferably 15% to 120% higher, preferably 25% to 110% higher, preferably 30% to 80% higher. 4 The catalyst loading of (110) is greater than that of the third reactor R 3The catalyst loading of (108) is 5% to 150% higher, preferably 15% to 120% higher, preferably 25% to 110% higher, and preferably 30% to 80% higher.

[0158] Preferably, in some embodiments of the present invention, the second reactor R 2 The catalyst loading of (106) is greater than that of the first reactor R 1 The catalyst loading of (104) is 25% to 110% higher, preferably 35% to 80%, preferably 40% to 70%, preferably 50% to 70%. Preferably, in some embodiments of the present invention, the second reactor R 2 The catalyst loading of (106) is greater than that of the first reactor R 1 The catalyst loading of (104) is 40% to 70% higher, preferably 50% to 70%.

[0159] In some embodiments of the present invention, the second reactor R 2 The temperature rise of the reactor (106) is greater than that of the first reactor R 1 The temperature of the reactor (104) is increased by 1°C to 50°C, preferably 2°C to 40°C, preferably 5°C to 35°C. In some embodiments of the present invention, the third reactor R 3 The temperature rise of the reactor (108) is greater than that of the second reactor R 2 The reactor temperature of (106) is increased by 1°C to 50°C, preferably by 2°C to 40°C, preferably by 5°C to 35°C.

[0160] In some embodiments of the present invention, the second reactor R 4 The temperature rise of the reactor (110) is higher than that of the third reactor R 3 The reactor temperature of (108) is increased by 1°C to 50°C, preferably by 2°C to 40°C, preferably by 5°C to 35°C.

[0161] Referring to Figure 2, in some embodiments of the present invention, the step of recovering the hydrogenolysis product from the fourth hydrogenolysis product stream (113) includes feeding at least a portion of the fourth hydrogenolysis product stream (113) into a hydrocracking reactor (122) to obtain a hydrocracking product stream (123) containing one or more desired hydrogenolysis products, preferably, the one or more desired hydrogenolysis products are ethane.

[0162] In some embodiments of the present invention, the first hydrogenolysis product stream (107) passes through a heat exchanger (116) before the first hydrogenolysis product stream (107) is introduced into the second reactor (106). In some embodiments of the present invention, the second hydrogenolysis product stream (109) passes through a heat exchanger (118) before the second hydrogenolysis product stream (109) is introduced into the third reactor (108). In some embodiments of the present invention, the third hydrogenolysis product stream (111) passes through a heat exchanger (120) before the third hydrogenolysis product stream (111) is introduced into the fourth reactor (110). Although Figures 1 and 2 show the presence of a heat exchanger, in some embodiments of the present invention, in some other embodiments of the present invention, a heat exchanger may not be required to achieve the purposes of the present invention.

[0163] In some preferred embodiments of the present invention, the present invention relates to a butane hydrogenolysis process using five fixed bed reactors arranged in series to produce one or more than one desired hydrogenolysis product. For example, these processing steps may include the following steps:

[0164] a) providing a reactor system comprising a plurality of five reactors arranged in series, wherein "N" is 5; wherein the first reactor in the series is denoted as R 1 The last reactor in the series is the fifth reactor, denoted by R 5 The second to last reactor in the series is the fourth reactor, denoted by R 4 , the remaining reactor is the second reactor R 2 With the third reactor R 3 ;

[0165] b) introducing an initial feed stream comprising a butane feed and a hydrogen feed into a first reactor and generating a first hydrogenolysis product stream under conditions for hydrogenolysis of butane;

[0166] c) the first hydrogenolysis product stream may be introduced into a second reactor to generate a second hydrogenolysis product stream under conditions for hydrogenolysis of butane;

[0167] d) the second hydrogenolysis product stream may be introduced into a third reactor to generate a third hydrogenolysis product stream under butane hydrogenolysis conditions;

[0168] e) the third hydrogenolysis product stream may be introduced into a fourth reactor to generate a fourth hydrogenolysis product stream under butane hydrogenolysis conditions;

[0169] f) the fourth hydrogenolysis product stream may be introduced into a fifth reactor to generate a fifth hydrogenolysis product stream under butane hydrogenolysis conditions;

[0170] g) recovering at least a portion of the hydrogenolysis product from the fifth hydrogenolysis product stream and obtaining one or more desired hydrogenolysis products, wherein the one or more desired hydrogenolysis products are preferably ethane. The one or more desired hydrogenolysis products are selected from ethane, propane, methane and mixtures thereof.

[0171] Preferably, in some embodiments of the present invention, for a reactor system having five reactors, the second reactor R 2 The catalyst loading of the first reactor R 1 The catalyst loading of the second reactor R is 25% to 110% higher, preferably 35% to 80%, preferably 40% to 70%, preferably 50% to 70%. Preferably, in some embodiments of the present invention, the second reactor R 2 The catalyst loading of the first reactor R 1 The catalyst loading is 40% to 70% higher, preferably 50% to 70% higher. In some embodiments of the present invention, for a reactor system having five reactors, the reactor temperature rise of the reactor configured to receive the hydrogenolysis product stream is 1°C to 50°C higher than the reactor temperature rise of the previous reactor configured to generate the hydrogenolysis product stream, preferably 2°C to 40°C, preferably 5°C to 35°C.

[0172] In some preferred embodiments of the present invention, the present invention relates to a butane hydrogenolysis process using two fixed bed reactors arranged in series to produce one or more than one desired hydrogenolysis product. For example, these processing steps may include the following steps:

[0173] a) providing a reactor system comprising a plurality of 2 reactors arranged in series, wherein "N" is 2; wherein the first reactor in the series is denoted as R 1 , the last reactor in the series is denoted as R 2 A second reactor;

[0174] b) introducing an initial feed stream comprising a butane feed and a hydrogen feed into a first reactor and generating a first hydrogenolysis product stream under conditions for hydrogenolysis of butane;

[0175] c) the first hydrogenolysis product stream may be introduced into a second reactor to generate a second hydrogenolysis product stream under conditions for hydrogenolysis of butane;

[0176] d) recovering at least a portion of the hydrogenolysis product from the second hydrogenolysis product stream and obtaining one or more desired hydrogenolysis products, wherein the one or more desired hydrogenolysis products are preferably ethane.

[0177] Preferably, in some embodiments of the present invention, for a reactor system having two reactors, the second reactor R 2 The catalyst loading of the first reactor R 1The catalyst loading of the second reactor R is 25% to 110% higher, preferably 35% to 80%, preferably 40% to 70%, preferably 50% to 70%. Preferably, in some embodiments of the present invention, the second reactor R 2 The catalyst loading of the first reactor R 1 The catalyst loading is 40% to 70% higher, preferably 50% to 70%.

[0178] In some embodiments of the present invention, a second reactor R is configured to receive a hydrogenolysis product stream. 2 The reactor temperature rise is 1°C to 50°C, preferably 2°C to 40°C, preferably 5°C to 35°C higher than the reactor temperature rise of the previous reactor configured to generate the hydrogenolysis product stream.

[0179] In some embodiments of the present invention, a methane diluent is added to at least one of the reactors 104, 106, 108, 110. The amount of methane required to reduce the temperature rise during the butane conversion process is appropriately adjusted. In some embodiments of the present invention, the methane diluent is c) at least a portion of a) the initial feed stream 101 and b) at least one hydrogenolysis product stream 107, 109, 111 introduced into at least one reactor 104, 106, 108, 110. The amount of methane required to reduce the temperature rise during the butane conversion process is appropriately adjusted. Although other diluents including mixed gas diluents can be used, methane is preferred. Methane is preferred because methane has been generated in the reaction, separation of methane is not difficult and should have been completed in the process, and methane has a relatively high heat capacity. Other possible diluents include nitrogen and other hydrocarbon compounds.

[0180] The following includes specific examples illustrating some embodiments of the present invention. The examples are for illustrative purposes only and are not intended to limit the present invention. It should be understood that the embodiments and aspects disclosed herein are not mutually exclusive, and these aspects and embodiments can be combined in any manner. Those of ordinary skill in the art will readily identify parameters that change or adjust to produce substantially the same results.

[0181] Example 1

[0182] Purpose: A butane hydrogenolysis process according to features of the present invention is demonstrated.

[0183] For the purpose of the examples, four cases were simulated using Python-based Pyomo software, where "IE" represents a method simulated according to the method of the present invention, where the catalyst loading and reactor temperature rise were configured to gradually increase according to the present invention. CE1 to CE3 represent comparative examples. For the purpose of the examples, the catalyst loading is simply the mass of catalyst in a given reactor, since the simulation assumes identical reactors in series.

[0184] Each of the four cases (IE, CE1, CE2 and CE3) involves a butane hydrogenolysis process with four fixed bed reactors arranged in series. For the purpose of the present invention, for each process IE, CE1, CE2 and CE3, four fixed bed reactors of the same size with the same volume were used.

[0185] The catalyst used in each process was a 0.3 wt% Pt-0.3 wt% Ir / γ-Al 2 O 3 -HZSM-5 catalyst composition. The catalyst carrier is composed of 80 wt% H-ZSM-5 and 20 wt% γ-Al 2 O 3 Composition. H-ZSM-5 has 280% SiO 2 / Al 2 O 3 .

[0186] Method steps: Referring to FIG. 1 or FIG. 2 , the butane hydrogenolysis method steps of each reference case (IE, CE1 to CE3) include the following steps:

[0187] a) providing a reactor system (100) comprising four reactors (104), (106), (108) and (110) arranged in series; wherein the first reactor (104) in the series is denoted by R 1 The last reactor (110) in the series is the fourth reactor, denoted by R 4 The second to last reactor in the series is the third reactor (108), denoted by R 3 The remaining reactor (106) is the second reactor, denoted by R 2 ;

[0188] b) introducing an initial feed stream (101) comprising a butane feed (103) and a hydrogen feed (105) into a first reactor (104) and generating a first hydrogenolysis product stream (107) under conditions for hydrogenolysis of butane;

[0189] c) introducing the first hydrogenolysis product stream (107) into a second reactor (106) to generate a second hydrogenolysis product stream (109) under butane hydrogenolysis conditions;

[0190] d) the second hydrogenolysis product stream (109) may be introduced into a third reactor (108) to produce a third hydrogenolysis product stream (111) under butane hydrogenolysis conditions; and

[0191] e) the third hydrogenolysis product stream (111) may be introduced into a fourth reactor (110) to produce a fourth hydrogenolysis product stream (113) under butane hydrogenolysis conditions; and

[0192] f) recovering the hydrogenolysis product from the fourth hydrogenolysis product stream (113) and obtaining one or more than one desired hydrogenolysis product, preferably ethane.

[0193] Operating parameters: For each case, the pressure in all reactors was kept constant at 7.9 bar. The ratio of n-butane to isobutane in the initial feed stream was 6:4. The total WHSV for all four reactors was kept constant at 3.0 h -1 The following table provides the operating parameters for the remaining cases.

[0194] Table 1

[0195]

[0196]

[0197] The following table provides the percentage increase or decrease in the previous reactor parameters. 1 , the parameter values ​​are shown in the table above.

[0198] Table 2

[0199]

[0200] result: The results for thermal runaway, n-butane conversion and ethane selectivity are shown below:

[0201] Table 3

[0202]

[0203]

[0204] The inventive process IE differs from the other comparative processes in that the catalyst loading in the reactor gradually increases along the flow of reactant and product streams, and the reactor temperature rise also gradually increases. As can be clearly seen from the above table, for the inventive process (IE), the process parameters are configured in such a way that even with a 2.5°C temperature variation at the inlet of the first reactor, thermal runaway does not occur, thereby ensuring the desired stability of the process and a low sensitivity to fluctuations in the reactor inlet temperature.

[0205] In addition, for the inventive process IE, the ethane selectivity in the first reactor is very high, close to 72%. The ethane selectivity in the first reactor is particularly important because the butane concentration is highest in the first reactor R1, and the appropriate ethane selectivity in the first reactor R1 will help to give the desired selectivity to the overall ethane selectivity in a particular hydrogenolysis process. The inventive process IE has a similar selectivity in the first reactor as the process CE2. However, it can be seen that the process CE2 is more sensitive to fluctuations in the inlet reactor temperature, and even a 2.5°C increase in the reactor temperature can lead to thermal runaway. Therefore, from these examples, it can be clearly demonstrated that a gradual increase in catalyst loading and reactor temperature rise within the limits specified in the present invention will lead to the achievement of one or more of the objects of the present invention.

[0206] Example 2

[0207] In order to demonstrate the advantages of introducing methane diluent into the hydrogenolysis reactor, the following examples are provided. It should be understood that the data are all from simulations. Methane acts as a heat carrier and can reduce the low temperature rise at the same butane conversion. Therefore, under the same temperature rise limit, dilution can safely increase the butane conversion of each reactor. This can also reduce the number of reactors required to achieve the same total butane conversion.

[0208] The following two tables (Case 1 in Table 4 and Case 2 in Table 5) show the simulation results. All simulations used the same mass space velocity (WHSV = 3) and number of reactors (R 1 , R 2 , R 3 and R 4 ). In the table, C1, ΔT, Ti, X(nC4) and S(C2) represent the CH4 / C4 molar ratio of the first reactor (C4 = isobutane + n-butane), the temperature rise of each reactor, the inlet temperature, the n-butane conversion and the ethane selectivity, respectively. In these simulations, methane was added only in the first reactor. This is the preferred embodiment because the first stage has the highest reactant concentration and is most susceptible to runaway. Although the benefits are not as great, diluent can be added to any one or more reactors. The total temperature rise for all four reactors for Case 1 and Case 2 is 220°C and 240°C. In the table, C1 (0%) is a reference without any methane diluent. It should be noted that we introduced a gradual temperature rise (e.g., 35, 50, 65, 70) in each reactor because it has the potential to reduce the risk of thermal runaway. In addition, interstage hydrogen injection was introduced because it can mitigate the previously disclosed catalyst deactivation.

[0209] In summary, the butane conversion of each reactor increases with increasing methane dilution. At methane dilutions exceeding 80% butane concentration, we are able to achieve similar (or target) butane conversion levels (>90%) across the three reactors compared to the reference case in Tables 4 and 5.

[0210] Table 4 Case 1 - Total temperature rise = 220°C

[0211]

[0212] Table 5 Case 2 - Total temperature rise = 240°C

[0213]

[0214] Although the embodiments and advantages of the present application have been described in detail, it should be understood that various changes, substitutions and modifications can be made herein without departing from the essence and scope of the embodiments defined in the appended claims. In addition, the scope of the present application is not intended to be limited to the specific embodiments of the processes, machines, manufactures, compositions, devices, methods and steps described in the specification. As a person of ordinary skill in the art, it will be easily understood from the above disclosure that the processes, machines, manufactures, compositions, devices, methods or steps currently existing or to be developed later can be used to perform the substantially same functions or achieve substantially the same results as the corresponding embodiments described herein. Therefore, the appended claims are intended to include such processes, machines, manufactures, compositions, devices, methods or steps within their scope.

Claims

1. A butane hydrogenolysis process for producing one or more than one desired hydrogenolysis product, comprising: a) providing a reactor system comprising a plurality of "N" reactors arranged in series, wherein "N" is an integer ≤ 10, preferably an integer ≤ 5; wherein the first reactor in the series is denoted as R1, and the last reactor in the series is denoted as R N The penultimate reactor in the series is denoted as R N-1 , the remaining reactors are represented as 2 to (N-2) in sequence; b) In the expression R X A feed stream comprising butane feed and hydrogen feed is introduced into an "X" reactor of the reactor, and an Xth hydrogenolysis product stream is generated under butane hydrogenolysis conditions; wherein the Xth hydrogenolysis product stream comprises unreacted butane feed, hydrogenolysis product and unreacted hydrogen; i. Among them, R X From reactor R1 to reactor R N-1 Any one of the reactors arranged in series; ii. wherein "X" is an integer ≥1 and ≤N-1, wherein when "X" = 1, the feed stream introduced into the first reactor R1 is the initial feed stream introduced into the reactor system; c) introducing at least a portion of the Xth hydrogenolysis product stream into a subsequent reactor, which is denoted by R X+1 The (X+1) reactor is provided with a hydrogenolysis reactor, and generates a (X+1) hydrogenolysis product stream under butane hydrogenolysis conditions; wherein the (X+1) hydrogenolysis product stream comprises unreacted butane feed, hydrogenolysis products and unreacted hydrogen; i. Among them, reactor R X+1 It is closely connected to the reactor R X The latter reactor; d) If N>2, repeat steps b) and c) for (N-2) times until R N The Nth hydrogenolysis product stream is generated in the reactor; wherein, if the Nth hydrogenolysis product stream is introduced into the reactor R X+1 The feed stream contains at least a portion of the feed stream in the immediately preceding reactor R X The Xth hydrogenolysis product stream generated in the step of: the Nth hydrogenolysis product stream comprises unreacted butane, hydrogenolysis products and unreacted hydrogen, i. If "N" is 2, the second hydrogenolysis product stream generated by the second reactor R2 is the Nth hydrogenolysis product stream; e) recovering at least a portion of the hydrogenolysis product from the Nth hydrogenolysis product stream to obtain one or more than one desired hydrogenolysis product; From R1 to R N Each reactor in series includes: i. a reactor vessel; and ii. a catalyst bed disposed in a reactor vessel, wherein the catalyst bed comprises: a butane hydrogenolysis catalyst, wherein the butane hydrogenolysis catalyst is loaded with a catalyst loading (CL); wherein from R2 to R N The catalyst loading (CL) of each reactor is 5% to 150%, preferably 15% to 120%, preferably 25% to 110%, preferably 30% to 80% higher than the catalyst loading of the immediately preceding reactor; iii. wherein the method is carried out in the following manner, from R2 to R N The reactor temperature rise of each reactor is 1°C to 50°C, preferably 2°C to 40°C, preferably 5°C to 35°C higher than the reactor temperature rise of the immediately preceding reactor; wherein one or more than one desired hydrogenolysis products are selected from ethane, propane, methane and mixtures thereof.

2. The method according to claim 1, wherein from R2 to R N Each of the reactors R1 to R2 is operated at a mass space velocity (WHSV) of the butane feed stream that is 5% to 70%, preferably 10% to 60%, preferably 20% to 60% lower than the mass space velocity (WHSV) of the butane feed stream operated in the immediately preceding reactor; and / or the process further comprises introducing a diluent into one or more of R1 to R2 N in a reactor, wherein the preferred diluent is methane.

3. The process according to claims 1 to 2, wherein when X=1, the catalyst loading of the second reactor R2 is 25% to 110% higher than the catalyst loading of the first reactor R1, preferably 35% to 80%, preferably 40% to 70%, preferably 50% to 70%.

4. The process according to claims 1 to 3, wherein one or more than one desired hydrogenolysis product is ethane with a selectivity of ≥60.0%, preferably ≥65.0%, preferably ≥70.0%, preferably ≥75.0%, relative to the total molar concentration of all hydrogenolysis products.

5. The process according to claims 1 to 4, wherein an additional butane feed and / or hydrogen feed is introduced into the (X+1) reactor (R) together with the Xth hydrogenolysis product stream. X+1 )middle.

6. The process according to claims 1 to 5, wherein the butane feed and / or unreacted butane feed comprises a mixture of n-butane and / or isobutane.

7. The process according to claims 1 to 6, wherein the ratio of the molar concentration of n-butane present in the Nth hydrogenolysis product stream to the molar concentration of n-butane present in the initial feed stream is ≤0.4, preferably ≤0.3, preferably ≤0.2, preferably ≤0.1, preferably ≤0.

05.

8. The process according to claims 1 to 7, wherein the ratio of the molar concentration of n-butane present in the first hydrogenolysis product stream (first hydrogenolysis product stream) produced by the first reactor R1 to the molar concentration of n-butane present in the initial feed stream is ≤0.95, preferably ≤0.85, preferably ≤0.70, preferably ≤0.

5.

9. The method according to claim 1 to 8, wherein the first reactor R1 is operated under the condition of reactor temperature rise ≤ 110°C, preferably ≤ 100°C, preferably ≤ 90°C, preferably ≤ 70°C, preferably ≤ 60°C, preferably ≤ 50°C, preferably ≤ 40°C, when the initial reactor inlet temperature (T inlet1 ) is increased by ≥0.5°C and <3.0°C, preferably ≥1.0°C and <3.0°C, preferably ≥2.0°C and ≤2.5°C, wherein the reactor temperature rise is determined as (T outlet1 -T inlet1 ), where T outlet1 is the outlet reactor temperature of the first reactor R1, and T inlet1 is the initial inlet temperature of the first reactor R1.

10. The process of claims 1 to 9, wherein the step of recovering at least a portion of the hydrogenolysis product from the Nth hydrogenolysis product stream comprises: a) feeding at least a portion of the Nth hydrogenolysis product stream to a separation unit to form a hydrogenolysis product stream, an unreacted hydrogen stream, and a separated butane stream comprising isobutane and normal butane; b) recovering at least a portion of the hydrogenolysis product from the hydrogenolysis product stream to obtain one or more than one desired hydrogenolysis product; c) feeding the separated butane stream to an isomerization unit to obtain a stream rich in n-butane; and d) recycling at least a portion of the n-butane-rich stream and the unreacted hydrogen stream back to the reactor from R1 to R N in one or more reactors.

11. The process according to claims 1 to 9, wherein the step of recovering at least a portion of the hydrogenolysis product from the Nth hydrogenolysis product stream comprises the step of feeding at least a portion of the Nth hydrogenolysis product stream to a hydrocracking reactor to obtain a hydrocracking product stream comprising one or more than one desired hydrogenolysis product.

12. The process according to claims 1 to 11, wherein the butane hydrogenolysis catalyst is selected from: (i) a bimetallic supported catalyst comprising a carrier, a first catalytic metal, a second catalytic metal and an optional binder, wherein: The first catalytic metal and the second catalytic metal are different, (ii) a monometallic supported catalyst comprising a third catalytic metal, a support and optionally a binder, or (iii) a mixture of (i) and (ii), Among them, the first catalytic metal, the second catalytic metal and the third catalytic metal are independently selected from iridium (Ir), platinum (Pt), rhodium (Rh), ruthenium (Ru), rhenium (Re), palladium (Pd), molybdenum (Mo), tungsten (W), nickel (Ni) or cobalt (Co) or any combination thereof.

13. The process of claim 12, wherein the butane hydrogenolysis catalyst comprises a bimetallic supported catalyst comprising Ir and Pt, and wherein, The support comprises alumina, zeolite, or both, wherein the zeolite comprises ZSM-5 zeolite, ZSM-11 zeolite, Y zeolite, high silica Y zeolite, USY zeolite, EU-1 zeolite, EU-2 zeolite, beta zeolite, L zeolite, ferrierite, CHA zeolite, SSZ-16 zeolite, Nu-3 zeolite, sigma-1 zeolite or silicalite-1, or any combination thereof, and optionally, wherein a binder, if present, is selected from alumina, titania, silica, or a combination thereof.

14. The process according to claims 1 to 13, wherein the reactor system comprises a plurality of 4 reactors (N=4) arranged in series, wherein: The first reactor in the series is denoted as R1, the fourth reactor in the series is denoted as R4, and the remaining reactors in the series are denoted as R2 and R3, wherein the catalyst loading of the second reactor R2 is 25% to 110% higher than the catalyst loading of the first reactor R1, preferably 35% to 80%, preferably 40% to 70%, preferably 50% to 70%, wherein the initial feed stream is introduced into the first reactor (R1), and one or more desired hydrogenolysis products are obtained from the fourth hydrogenolysis product stream generated in the fourth reactor R4.

15. A reactor system for carrying out the butane hydrogenolysis method according to any one of claims 1 to 14, wherein the reactor system comprises a plurality of "N" reactors arranged in series, wherein "N" is an integer ≤10, preferably an integer ≤5; wherein, The first reactor in the series is denoted as R1 and the last reactor in the series is denoted as R N The penultimate reactor in the series is denoted as R N-1 , the remaining reactors are represented as 2 to (N-2) in sequence; a) Where R1 to R N Each reactor includes: i. a reactor vessel; and ii. A catalyst bed disposed in the reactor vessel and extending in the direction of reactant flow, wherein the catalyst bed comprises a butane hydrogenolysis catalyst loaded with a catalyst loading (CL); wherein from R2 to R N The catalyst loading (CL) of each reactor is 5% to 150%, preferably 15% to 120%, preferably 25% to 110%, preferably 30% to 80% higher than the catalyst loading of the immediately preceding reactor; b) The first reactor R1 is configured to operate under the condition that the reactor temperature rise is ≤110°C, preferably ≤100°C, preferably ≤90°C. When the initial reactor inlet temperature (T inlet1 ) is increased by ≥0.5°C and <3.0°C, preferably ≥1.0°C and <3.0°C, preferably ≥2.0°C and ≤2.5°C, wherein the reactor temperature rise is determined as (T outlet1 -T inlet1 ), where T outlet1 is the outlet reactor temperature of the first reactor R1, and T inlet1 is the initial inlet temperature of the first reactor R1; wherein the first reactor R1 is configured to receive an initial feed flow; c) wherein the reactor system is configured to achieve a total n-butane conversion of ≥ 60.0%, preferably ≥ 70.0%, preferably ≥ 80.0%, preferably ≥ 95.0%; and d) Among them, from R2 to R N Each reactor is configured to have a reactor temperature rise of 1°C to 50°C, preferably 2°C to 40°C, preferably 5°C to 35°C, compared to the reactor temperature rise of the immediately preceding reactor; optionally, wherein R1 to R N At least one of the reactors has an inlet for receiving a diluent gas.

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