Catalyst for heavy oil methane modification and preparation method and application thereof

Abstract

The invention provides a catalyst for heavy oil methane modification and a preparation method and application thereof, and belongs to the technical field of catalyst manufacturing. The preparation method of the catalyst for heavy oil methane modification comprises the following steps: S1, dissolving a zinc salt, a silver salt, a gallium salt, a nickel salt, citric acid and ethylene glycol in water, and mixing to obtain a mixed solution; wherein the molar ratio of the zinc element to the silver element to the gallium element to the nickel element is x: (1-x): y: (1-y), x is more than or equal to 0.01 and less than or equal to 0.99, and y is more than or equal to 0.01 and less than or equal to 0.99; and S2, carrying out dipping treatment on the carrier by adopting the mixed solution, and sequentially carrying out aging treatment, drying treatment and calcining treatment on the carrier subjected to dipping treatment to obtain the catalyst. The catalyst prepared by the method has a relatively good heavy oil methane modification effect, namely relatively good desulfurization and denitrification effects and relatively high liquid phase yield.

Description

Technical Field

[0001] The present application relates to the technical field of catalyst manufacturing, and in particular to a catalyst for heavy oil to methane reforming, and a preparation method and application thereof. Background Art

[0002] Currently, the conversion of heavy oil to lighter grades relies primarily on hydrogenation technology, which requires large amounts of hydrogen. Since industrial hydrogen primarily comes from coal and natural gas conversion, the conversion process is complex and costly. Therefore, reducing hydrogen consumption and improving the selectivity of value-added products during the heavy oil to lighter grade conversion process are crucial for improving economic efficiency. Methane, due to its abundant reserves, low cost, and high hydrogen-to-carbon atomic ratio, is widely recognized as a green and inexpensive feedstock for hydrogen production. Research has shown that methane can be activated at 400-600°C and participate in heavy oil upgrading reactions, providing a hydrogen source, increasing carbon content, and optimizing product distribution. This mechanism has the potential to reduce the production cost of hydro-upgrading during the heavy oil to lighter grade conversion process. Consequently, the application of methane in heavy oil upgrading has attracted widespread attention from both academia and industry.

[0003] While research on heavy oil-to-methane reforming has made some progress, the catalysts currently used are ineffective, limiting the application and promotion of this technology. Therefore, there is an urgent need to develop a new catalyst with improved heavy oil-to-methane reforming performance. Summary of the Invention

[0004] The purpose of this application is to provide a catalyst for heavy oil near methane reforming, and its preparation method and application. The catalyst prepared by this method has good heavy oil near methane reforming effect, which is manifested as good desulfurization and denitrification effects and high liquid phase yield.

[0005] The embodiment of the present application is implemented as follows:

[0006] In a first aspect, the present invention provides a method for preparing a catalyst for heavy oil to methane reforming, comprising the following steps:

[0007] S1: Dissolve zinc salt, silver salt, gallium salt, nickel salt, citric acid and ethylene glycol in water and mix them to obtain a mixed solution; wherein the molar ratio of zinc element, silver element, gallium element and nickel element is x:(1-x):y:(1-y), 0.01≤x≤0.99 and 0.01≤y≤0.99.

[0008] S2: impregnating the carrier with the mixed solution, and sequentially performing aging, drying and calcining on the impregnated carrier to obtain a catalyst.

[0009] In the prior art, the catalysts commonly used in the heavy oil to methane reforming process are oxides of various metal elements. These traditional catalysts have the problem of poor heavy oil reforming effect. In the present application, the four metal elements containing the above-mentioned ratio are used as active catalytic components, wherein the total molar amount of zinc and silver is the same as the total molar amount of gallium and nickel; then, the citric acid complexation method and the impregnation method are used successively, and the aging treatment, drying treatment and calcination treatment are carried out in sequence to form a perovskite catalyst containing four metal elements at the same time (the perovskite catalyst has a body-centered cubic structure of the general formula ABO3, and the perovskite structure can confine various metal ions in the perovskite lattice to achieve uniform mixing of various metal ions at the atomic level; in addition, the redox and surface properties of the perovskite catalyst can also be flexibly adjusted by replacing or partially replacing the A and / or B sites in the perovskite lattice, thereby facilitating the coordinated construction of a catalyst with high catalytic activity and high stability with a multi-metal active catalytic component). Compared with conventional oxide catalysts containing the same metal elements, the perovskite catalyst has better catalytic activity and structural stability, and can exert a better heavy oil methane reforming effect, that is, it has better desulfurization and denitrification effects and a higher liquid phase yield.

[0010] In some optional embodiments, in step S1, the ratio of the total molar amount of metal elements to the molar amount of citric acid is 1:(1-1.5), or / and the ratio of the total molar amount of metal elements to the molar amount of ethylene glycol is 1:(0.05-0.65).

[0011] In the above technical solution, the molar ratio of the total molar amount of the metal elements to citric acid and ethylene glycol is limited to the above ranges, so that the various raw materials have a more appropriate usage ratio, which helps to fully mix the various raw materials and also allows the various metal ions to be evenly dispersed in the mixed solution.

[0012] In some optional embodiments, the step of dissolving zinc salt, silver salt, gallium salt, nickel salt, citric acid and ethylene glycol in water and mixing includes: first dissolving zinc salt, silver salt, gallium salt and nickel salt in water and mixing to obtain a mixed solution intermediate; then adding citric acid and ethylene glycol to the mixed solution intermediate and mixing.

[0013] In the above technical solution, a step-by-step dissolution and mixing method is adopted, which has the advantages of high dissolution efficiency and high mixing uniformity.

[0014] In some optional embodiments, in step S2, the volumes of the mixed solution and the carrier are the same, or / and the carrier is selected from at least one of molecular sieve, Al2O3, TiO2 and SiO2.

[0015] In the above technical solution, the mixed solution and the carrier are mixed in equal volumes, which has the advantages of good impregnation effect and relatively uniform distribution of metal ions; at the same time, there are many applicable types of carriers, which can provide more feasible implementation plans, thereby facilitating the promotion and application of the technical solution provided in the embodiment of this application.

[0016] In some optional embodiments, in the aging treatment step, the treatment temperature is 20-30°C and the treatment time is 4-24 hours; or / and, in the drying treatment step, the drying temperature is 50-180°C and the drying time is 4-24 hours.

[0017] In the above technical solution, the temperature and time of the aging treatment are limited to the above ranges, which helps to obtain a perovskite catalyst with higher structural stability after subsequent calcination; the temperature and time of the drying treatment are limited to the above ranges, which helps to efficiently remove moisture from the material without damaging the material structure.

[0018] In some optional embodiments, in the calcination treatment step, the calcination atmosphere is air, and the calcination treatment includes a first-stage calcination treatment and a second-stage calcination treatment; wherein, during the first-stage calcination treatment, the calcination temperature is 250-450°C, and the calcination time is 3-7 hours, and during the second-stage calcination treatment, the calcination temperature is 480-850°C, and the calcination time is 4-6 hours.

[0019] In the above technical solution, a step-by-step calcination method is adopted and the temperature and time of the two calcination treatments are respectively limited to the above ranges, which helps to obtain a perovskite-type catalyst with higher structural stability.

[0020] In a second aspect, an embodiment of the present application provides a catalyst for heavy oil to methane reforming, which is prepared using the preparation method provided in the embodiment of the first aspect.

[0021] In the above technical solution, the catalyst used for heavy oil-proximal methane reforming is prepared by the preparation method provided in the embodiment of the first aspect, and the corresponding catalyst is a perovskite-type catalyst, which has the advantage of better heavy oil-proximal methane reforming effect.

[0022] In some optional embodiments, in the step of heavy oil methane reforming, the raw gas includes methane and at least one of hydrogen, natural gas, oilfield associated gas and coalbed methane, and the volume space velocity of the raw gas is 1 to 5 h -1 .

[0023] In the above technical solution, a wide variety of gases other than methane can be selected in the raw gas, which can provide a large number of feasible implementation plans, thereby facilitating the promotion and application of the technical solution of this application; in addition, limiting the volume space velocity of the raw gas to the above range helps to provide more suitable catalytic conditions, thereby improving the heavy oil reforming effect.

[0024] In some optional embodiments, the volume ratio of the feed gas to the heavy oil is (300-3000):1, or / and the mass ratio of the heavy oil to the catalyst is 300:(1-20).

[0025] In some optional embodiments, the treatment temperature is 300-500° C., and the treatment pressure is 2-30 MPa.

[0026] In the above technical solution, in the step of heavy oil methane reforming, the volume ratio of feed gas to heavy oil, the mass ratio of heavy oil to catalyst, the treatment temperature and the treatment pressure are limited to the above ranges, which helps to provide more suitable catalytic conditions and thus improve the heavy oil reforming effect. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] In order to more clearly illustrate the technical solutions of the embodiments of the present application, the following is a brief introduction to the drawings required for use in the embodiments. It should be understood that the following drawings only show certain embodiments of the present application and therefore should not be regarded as limiting the scope. For ordinary technicians in this field, other relevant drawings can be obtained based on these drawings without creative work.

[0028] Figure 1 This is a process flow chart of a method for preparing a catalyst for heavy oil to methane reforming provided in an embodiment of the present application. DETAILED DESCRIPTION

[0029] To make the purpose, technical solutions and advantages of the examples of the present application clearer, the technical solutions in the examples of the present application will be described clearly and completely below. Where specific conditions are not specified in the examples, conventional conditions or conditions recommended by the manufacturer are used. Where the manufacturer of the reagents or instruments is not specified, they are all conventional products that can be purchased commercially.

[0030] It should be noted that “and / or” in this application, such as “Feature 1 and / or Feature 2”, refers to three situations: “Feature 1” alone, “Feature 2” alone, or “Feature 1” plus “Feature 2”.

[0031] In addition, in the description of this application, unless otherwise specified, the meaning of "multiple" in "one or more" refers to two or more; the range of "value a to value b" includes the two end values ​​"a" and "b", and the "unit of measurement" in "value a to value b+unit of measurement" represents the "unit of measurement" of both "value a" and "value b".

[0032] The following is a detailed description of a catalyst for heavy oil to methane reforming according to an embodiment of the present application, as well as its preparation method and application.

[0033] In a first aspect, the present invention provides a method for preparing a catalyst for heavy oil to methane reforming, comprising the following steps:

[0034] S1: Dissolve zinc salt, silver salt, gallium salt, nickel salt, citric acid and ethylene glycol in water and mix them to obtain a mixed solution; wherein the molar ratio of zinc element, silver element, gallium element and nickel element is x:(1-x):y:(1-y), 0.01≤x≤0.99 and 0.01≤y≤0.99.

[0035] S2: impregnating the carrier with the mixed solution, and sequentially performing aging, drying and calcining on the impregnated carrier to obtain a catalyst.

[0036] In the prior art, the catalysts commonly used in the heavy oil to methane reforming process are oxides of various metal elements. These traditional catalysts have the problem of poor heavy oil reforming effect. In the present application, the four metal elements containing the above-mentioned ratio are used as active catalytic components, wherein the total molar amount of zinc and silver is the same as the total molar amount of gallium and nickel; then, the citric acid complexation method and the impregnation method are used successively, and the aging treatment, drying treatment and calcination treatment are carried out in sequence to form a perovskite catalyst containing four metal elements at the same time (the perovskite catalyst has a body-centered cubic structure of the general formula ABO3, and the perovskite structure can confine various metal ions in the perovskite lattice to achieve uniform mixing of various metal ions at the atomic level; in addition, the redox and surface properties of the perovskite catalyst can also be flexibly adjusted by replacing or partially replacing the A and / or B sites in the perovskite lattice, thereby facilitating the coordinated construction of a catalyst with high catalytic activity and high stability with a multi-metal active catalytic component). Compared with conventional oxide catalysts containing the same metal elements, the perovskite catalyst has better catalytic activity and structural stability, and can exert a better heavy oil methane reforming effect, that is, it has better desulfurization and denitrification effects and a higher liquid phase yield.

[0037] It should be noted that the type of metal salt is not limited, and it may be, for example, nitrate.

[0038] As an example, in step S1, the ratio of the total molar amount of the metal element to the molar amount of citric acid is 1:(1-1.5), for example, but not limited to, any one of 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4 and 1:1.5, or a range of values ​​between any two of them; or / and, the ratio of the total molar amount of the metal element to the molar amount of ethylene glycol is 1:(0.05-0.65), for example, but not limited to, any one of 1:0.05, 1:0.1, 1:0.2, 1:0.3, 1:0.4, 1:0.5, 1:0.6 and 1:0.65, or a range of values ​​between any two of them.

[0039] In this embodiment, the molar ratio of the total molar amount of the metal elements to citric acid and ethylene glycol is limited to the above ranges, so that the various raw materials have a more appropriate usage ratio, which helps to fully mix the various raw materials and also allows the various metal ions to be evenly dispersed in the mixed solution.

[0040] As an example, the steps of dissolving zinc salt, silver salt, gallium salt, nickel salt, citric acid and ethylene glycol in water and mixing include: first dissolving zinc salt, silver salt, gallium salt and nickel salt in water and mixing to obtain a mixed solution intermediate; then adding citric acid and ethylene glycol to the mixed solution intermediate and mixing.

[0041] In this embodiment, a step-by-step dissolution and mixing method is adopted, which has the advantages of higher dissolution efficiency and higher mixing uniformity.

[0042] In other possible implementations, a one-step mixing method may be used to form a mixed solution.

[0043] As an example, in step S2, the volumes of the mixed solution and the carrier are the same, or / and the carrier is selected from at least one of molecular sieve, Al2O3, TiO2 and SiO2.

[0044] In this embodiment, the mixed solution and the carrier are mixed in equal volumes, which has the advantages of good impregnation effect and relatively uniform distribution of metal ions; at the same time, there are many applicable types of carriers, which can provide more feasible implementation plans, thereby facilitating the promotion and application of the technical solutions provided in the embodiments of this application.

[0045] It should be noted that the type of molecular sieve is not limited and can be set according to conventional selection in the art. For example, the molecular sieve can be at least one of HZSM-5 molecular sieve, HZSM-11 molecular sieve, HZSM-8 molecular sieve, Hβ molecular sieve, HMCM-41 molecular sieve, HSAPO-34 molecular sieve, HY molecular sieve, HSAPO-5 molecular sieve and HSAPO-11 molecular sieve.

[0046] As an example, in the aging treatment step, the treatment temperature is 20-30°C, for example but not limited to the treatment temperature being any one of 20°C, 22°C, 24°C, 26°C, 28°C and 30°C, or a range between any two of them; the treatment time is 4-24h, for example but not limited to the treatment time being any one of 4h, 6h, 10h, 15h, 20h and 24h, or a range between any two of them.

[0047] In this embodiment, the temperature and time of the aging treatment are limited to the above ranges, which helps to obtain a perovskite-type catalyst with higher structural stability after subsequent calcination.

[0048] As an example, in the drying treatment step, the drying temperature is 50-180°C, for example but not limited to the treatment temperature being any one of 50°C, 60°C, 80°C, 100°C, 120°C, 140°C, 160°C and 180°C, or a range between any two of them; the drying time is 4-24h, for example but not limited to the drying time being any one of 4h, 6h, 8h, 10h, 12h, 14h, 16h, 18h, 20h and 24h, or a range between any two of them.

[0049] In this embodiment, the temperature and time of the drying process are limited to the above ranges, which helps to efficiently remove moisture from the material without damaging the material structure.

[0050] As an example, in the calcination treatment step, the calcination atmosphere is air, and the calcination treatment includes a first stage calcination treatment and a second stage calcination treatment; wherein, during the first stage calcination treatment, the calcination temperature is 250-450°C, for example but not limited to any one of 250°C, 300°C, 350°C, 400°C and 450°C or a range between any two thereof; the calcination time is 3-7h, for example but not limited to 3h, 4h, 5h, 6h and 7h. h any point value or the range between any two of them; during the second stage calcination treatment, the calcination temperature is 480-850°C, for example but not limited to the calcination temperature is 480°C, 500°C, 600°C, 700°C, 800°C and 850°C any point value or the range between any two of them; the calcination time is 4-6h, for example but not limited to the calcination time is 4h, 4.5h, 5h, 5.5h and 6h any point value or the range between any two of them.

[0051] In this embodiment, a step-by-step calcination method is adopted and the temperature and time of the two calcination treatments are respectively limited to the above ranges, which helps to obtain a perovskite-type catalyst with higher structural stability.

[0052] As an example, in the calcination step, the heating rate is 2 to 10°C / min, for example, but not limited to, a heating rate of any one of 2°C / min, 4°C / min, 6°C / min, 8°C / min and 10°C / min, or a range between any two of them.

[0053] It should be noted that any process or step not specifically described or limited in the catalyst preparation process may be arranged according to conventional selection in the art.

[0054] As an example, the process flow chart of the catalyst preparation method can be found in Figure 1 .

[0055] In a second aspect, an embodiment of the present application provides a catalyst for heavy oil to methane reforming, which is prepared using the preparation method provided in the embodiment of the first aspect.

[0056] In the present application, the catalyst for heavy oil-proximal methane reforming is prepared by the preparation method provided in the embodiment of the first aspect, and the corresponding catalyst is a perovskite-type catalyst, which has the advantage of better heavy oil-proximal methane reforming effect.

[0057] As an example, in the step of heavy oil methane reforming, the raw gas includes methane and at least one of hydrogen, natural gas, oilfield associated gas and coalbed methane (that is, the raw gas contains at least one other type of gas in addition to methane), and the volume space velocity of the raw gas is 1 to 5 h -1 , such as but not limited to volumetric space velocity of 1h -1 , 2h -1 , 3h -1 , 4h -1 and 5h -1 Any point value in or any range of values ​​between .

[0058] In this embodiment, a variety of gases other than methane can be selected in the raw gas, which can provide more feasible implementation plans, thereby facilitating the promotion and application of the technical solution of the present application; in addition, limiting the volume space velocity of the raw gas to the above range helps to provide more suitable catalytic conditions, thereby improving the heavy oil reforming effect.

[0059] As an example, the volume ratio of the feed gas to the heavy oil is (300-3000):1, for example, but not limited to, a volume ratio of any one of 300:1, 500:1, 1000:1, 1500:1, 2000:1, 2500:1 and 3000:1, or a range between any two of the volume ratios; or / and, the mass ratio of the heavy oil to the catalyst is 300:(1-20), for example, but not limited to, a mass ratio of any one of 300:1, 300:5, 300:10, 300:15 and 300:20, or a range between any two of the volume ratios.

[0060] As an example, the processing temperature is 300-500°C, for example but not limited to the processing temperature being any point value among 300°C, 350°C, 400°C, 450°C and 500°C, or a range value between any two of them; the processing pressure is 2-30Mpa, for example but not limited to the processing pressure being any point value among 25Mpa, 10Mpa, 15Mpa, 20Mpa, 25Mpa and 30Mpa, or a range value between any two of them.

[0061] In this embodiment, in the step of methane reforming of heavy oil, the volume ratio of feed gas to heavy oil, the mass ratio of heavy oil to catalyst, the treatment temperature and the treatment pressure are respectively limited to the above ranges, which helps to provide more suitable catalytic conditions, thereby improving the heavy oil reforming effect.

[0062] It should be noted that the type of heavy oil is not limited, and may be, for example, at least one of straight-run diesel, catalytic diesel, coker diesel, heavy oil, atmospheric residue, vacuum residue and oil sands asphalt.

[0063] The features and performance of the present application are further described in detail below with reference to the embodiments.

[0064] Example 1

[0065] The present invention provides a method for preparing a catalyst for heavy oil to methane reforming, comprising the following steps:

[0066] S1: Dissolve zinc nitrate, silver nitrate, gallium nitrate, and nickel nitrate in water at a molar ratio of 0.01:0.99:0.01:0.99 and mix to obtain a mixed solution intermediate; then add citric acid and ethylene glycol to the mixed solution intermediate and mix, wherein the ratio of the total molar amount of the metal elements to the molar amount of citric acid is 1:1, and the ratio of the total molar amount of the metal elements to the molar amount of ethylene glycol is 1:0.05, to obtain a mixed solution.

[0067] S2 uses a mixed solution to impregnate the molecular sieve (HZSM-5 molecular sieve) with equal volume, and then the impregnated molecular sieve is aged, dried and calcined in sequence, wherein the aging temperature is 25°C and the treatment time is 4h, the drying temperature is 50°C and the treatment time is 4h, and the calcination treatment is 250°C for 3h and 480°C for 3h (calcination in air atmosphere, heating rate is 2°C / min) to obtain a catalyst.

[0068] Example 2

[0069] The present invention provides a method for preparing a catalyst for heavy oil to methane reforming, comprising the following steps:

[0070] S1: Dissolve zinc nitrate, silver nitrate, gallium nitrate, and nickel nitrate in water at a molar ratio of 0.99:0.01:0.99:0.01 and mix to obtain a mixed solution intermediate; then add citric acid and ethylene glycol to the mixed solution intermediate and mix, wherein the ratio of the total molar amount of the metal elements to the molar amount of citric acid is 1:1.5, and the ratio of the total molar amount of the metal elements to the molar amount of ethylene glycol is 1:0.65, to obtain a mixed solution.

[0071] S2 uses a mixed solution to impregnate the molecular sieve (HZSM-5 molecular sieve) with equal volume, and then the impregnated molecular sieve is aged, dried and calcined in sequence, wherein the aging temperature is 25°C and the treatment time is 24h, the drying temperature is 180°C and the treatment time is 24h, the calcination treatment is 450°C for 7h and 850°C for 6h (calcination in air atmosphere, heating rate is 10°C / min), to obtain a catalyst.

[0072] Example 3

[0073] The present invention provides a method for preparing a catalyst for heavy oil to methane reforming, comprising the following steps:

[0074] S1: Dissolve zinc nitrate, silver nitrate, gallium nitrate, and nickel nitrate in water at a molar ratio of 0.5:0.5:0.5:0.5 and mix to obtain a mixed solution intermediate; then add citric acid and ethylene glycol to the mixed solution intermediate and mix, wherein the ratio of the total molar amount of the metal elements to the molar amount of citric acid is 1:1.2, and the ratio of the total molar amount of the metal elements to the molar amount of ethylene glycol is 1:0.24, to obtain a mixed solution.

[0075] S2 uses a mixed solution to impregnate the molecular sieve (HZSM-5 molecular sieve) with equal volume, and then the impregnated molecular sieve is aged, dried and calcined in sequence, wherein the aging temperature is 25°C and the treatment time is 12h, the drying temperature is 120°C and the treatment time is 12h, and the calcination treatment is 350°C for 4h and 700°C for 5h (calcination in air atmosphere, heating rate is 5°C / min) to obtain a catalyst.

[0076] Example 4

[0077] This embodiment of the present application provides a method for preparing a catalyst for heavy oil methane reforming, which differs from Example 3 only in that: in step S1, zinc nitrate, silver nitrate, gallium nitrate, and nickel nitrate are dissolved in water and mixed in a molar ratio of 0.5:0.5:0.99:0.01 to obtain a mixed solution intermediate.

[0078] Example 5

[0079] This embodiment of the present application provides a method for preparing a catalyst for heavy oil methane reforming, which differs from Example 3 only in that: in step S1, zinc nitrate, silver nitrate, gallium nitrate, and nickel nitrate are dissolved in water and mixed in a molar ratio of 0.5:0.5:0.01:0.99 to obtain a mixed solution intermediate.

[0080] Example 6

[0081] This embodiment of the present application provides a method for preparing a catalyst for heavy oil to methane reforming, which differs from Example 3 only in that in step S2, the molecular sieve is replaced with Al2O3.

[0082] Example 7

[0083] This embodiment of the present application provides a method for preparing a catalyst for heavy oil to methane reforming, which differs from Example 3 only in that in step S2, the molecular sieve is replaced with SiO2.

[0084] Comparative Example 1

[0085] The comparative example of the present application provides a method for preparing a catalyst for heavy oil to methane reforming, comprising the following steps:

[0086] S1: zinc nitrate, silver nitrate, gallium nitrate, and nickel nitrate are dissolved in water at a molar ratio of 0.5:0.5:0.5:0.5 and mixed to obtain a mixed solution intermediate.

[0087] S2 uses a mixed solution to impregnate the HZSM-5 molecular sieve in equal volumes, and then the impregnated molecular sieve is aged, dried and calcined in sequence, wherein the aging temperature is 25°C and the treatment time is 12h, the drying temperature is 120°C and the treatment time is 12h, and the calcination treatment is 700°C for 5h (calcined in an air atmosphere with a heating rate of 5°C / min) to obtain a catalyst.

[0088] Test example

[0089] Heavy oil methane reforming effect test

[0090] The test method is as follows: the catalysts prepared in Examples 1 to 7 and Comparative Example 1 are used as samples, and then each sample is added to a reactor for heavy oil methane reforming, wherein the heavy oil is VRDS residue oil from the Huizhou Petrochemical Residue Oil Hydrotreating Unit (the physical and chemical properties of the residue oil are known), the feed gas includes methane and hydrogen, the volume ratio of methane to residue oil is 300:1, the volume ratio of hydrogen to residue oil is 40:1, and the volume space velocity of the feed gas is 3h -1 The mass ratio of residual oil to catalyst is 20:1, the reaction temperature is 400℃, and the reaction pressure is 3.5Mpa. After the reaction is completed, the liquid phase yield, desulfurization rate and denitrification rate are calculated (wherein, the desulfurization rate is determined after the liquid oil after the reaction is first washed with alkali) and the results are summarized in Table 1.

[0091] Table 1

[0092]

[0093]

[0094] Referring to Table 1, the test results of Examples 1 to 7 and Comparative Example 1 show that the perovskite-type catalyst containing zinc, silver, gallium, and nickel elements prepared in the examples of the present application (wherein the total molar amounts of zinc and silver, and the total molar amounts of gallium and nickel are the same) has a better heavy oil to methane reforming effect than the conventional oxide-type catalyst containing the same elements, specifically, it has better desulfurization and denitrification effects and a higher liquid phase yield.

[0095] The embodiments described above are part of the embodiments of the present application, rather than all of the embodiments. The detailed description of the embodiments of the present application is not intended to limit the scope of the present application for protection, but merely represents selected embodiments of the present application. Based on the embodiments in the present application, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of this application.

Claims

1. A method for preparing a catalyst for heavy oil to methane reforming, characterized in that: The following steps are involved: S1: dissolving a zinc salt, a silver salt, a gallium salt, a nickel salt, citric acid, and ethylene glycol in water and mixing the mixture to obtain a mixed solution; wherein the molar ratio of the zinc element, the silver element, the gallium element, and the nickel element is x:(1-x):y:(1-y), 0.01≤x≤0.99 and 0.01≤y≤0.99; S2: impregnating the carrier with the mixed solution, and sequentially performing aging, drying and calcining on the impregnated carrier to obtain a catalyst.

2. The preparation method according to claim 1, characterized in that In step S1, the ratio of the total molar amount of the metal elements to the molar amount of the citric acid is 1:(1-1.5), or / and the ratio of the total molar amount of the metal elements to the molar amount of the ethylene glycol is 1:(0.05-0.65).

3. The preparation method according to claim 1, characterized in that The steps of dissolving zinc salt, silver salt, gallium salt, nickel salt, citric acid and ethylene glycol in water and mixing the mixture comprise: First, zinc salt, silver salt, gallium salt and nickel salt are dissolved in water and mixed to obtain a mixed solution intermediate; then, citric acid and ethylene glycol are added to the mixed solution intermediate and mixed.

4. The preparation method according to any one of claims 1 to 3, characterized in that In step S2, the mixed solution and the carrier have the same volume, or / and the carrier is selected from at least one of molecular sieve, Al2O3, TiO2 and SiO2.

5. The preparation method according to any one of claims 1 to 3, characterized in that In the aging treatment step, the treatment temperature is 20 to 30° C. and the treatment time is 4 to 24 hours; Or / and, in the drying step, the drying temperature is 50 to 180° C., and the drying time is 4 to 24 hours.

6. The preparation method according to claim 1, characterized in that In the calcination step, the calcination atmosphere is air, and the calcination treatment includes a first-stage calcination treatment and a second-stage calcination treatment; wherein, during the first-stage calcination treatment, the calcination temperature is 250-450°C, and the calcination time is 3-7 hours, and during the second-stage calcination treatment, the calcination temperature is 480-850°C, and the calcination time is 4-6 hours.

7. A catalyst for heavy oil methane reforming, characterized in that: The method is as described in any one of claims 1 to 6.

8. Use of the catalyst according to claim 7 in heavy oil methane reforming, characterized in that: In the step of heavy oil methane reforming, the raw gas includes methane and at least one of hydrogen, natural gas, oilfield associated gas and coalbed methane, and the volume space velocity of the raw gas is 1 to 5h -1 .

9. The use according to claim 8, characterized in that The volume ratio of the raw gas to the heavy oil is (300-3000):1, or / and the mass ratio of the heavy oil to the catalyst is 300:(1-20).

10. The use according to claim 8, characterized in that The processing temperature is 300-500°C, and the processing pressure is 2-30 MPa.

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