Preparation method and application of composite catalyst for oil shale in-situ catalytic pyrolysis

Abstract

The application relates to the technical field of oil field development, in particular to a preparation method and application of a composite catalyst for in-situ catalytic pyrolysis of oil shale. The preparation method of the composite catalyst for in-situ catalytic pyrolysis of oil shale comprises the following steps: step one, a certain amount of 3-mercapto propyl trimethoxysilane and ZMS-5 are weighed and placed in toluene, refluxed at 110 DEG C for 12 hours, cooled, filtered, oxidized at normal temperature for 12 hours by using a certain amount of 30% H2O2, reacted at normal temperature for 12 hours by using a certain amount of 0.5 mol / L H2SO4, cleaned by using distilled water, filtered, placed in a drying box, dried at 110 DEG C for 6 hours, and sulfonated modified ZSM-5 is obtained; step two, active ingredients, 0.1wt%-25wt% Mo salt and 0.1wt%-25wt% W salt, are dissolved in deionized water according to a proportion, stirred and dissolved to form a solution; and step three, the composite catalyst is prepared by using an impregnation and calcination method.

Description

Technical Field

[0001] This invention relates to the field of oilfield development technology, specifically to a method for preparing and applying a composite catalyst for in-situ catalytic pyrolysis of oil shale. Background Technology

[0002] Oil shale is an important unconventional resource with huge reserves. It is considered a powerful alternative to crude oil. The development and utilization of oil shale resources has achieved a transformative breakthrough from "surface dry distillation" to "in-situ extraction". This is of great significance for meeting my country's energy demand and alleviating its dependence on oil imports.

[0003] In-situ catalytic pyrolysis of oil shale can improve oil yield and pyrolysis conversion rate. Catalytic hydropyrolysis is not only an important way to increase oil yield, but also has desulfurization and denitrification effects, significantly improving oil quality. The catalyst mainly consists of metals such as Ni, W, Co, and Mo supported on an acidic carrier. Clearly, composite catalysts composed of metals supported on an acidic carrier can effectively promote the lightening of oil shale oil. However, the activation energy of conventional catalysts for catalytic pyrolysis is too high, and the conversion efficiency of oil shale oil is insufficient. Summary of the Invention

[0004] The purpose of this invention is to provide a method for preparing and applying a composite catalyst for in-situ catalytic pyrolysis of oil shale, thereby solving the problem of excessively high activation energy in catalytic pyrolysis reactions using conventional catalysts.

[0005] To solve the above-mentioned technical problems, the present invention adopts the following technical solution:

[0006] A method for preparing a composite catalyst for in-situ catalytic pyrolysis of oil shale includes the following steps:

[0007] Step 1: Weigh a certain amount of 3-mercaptopropyltrimethoxysilane and ZMS-5 and place them in toluene. Reflux at 110℃ for 12 h, cool, and filter. Oxidize with a certain amount of 30% H2O2 at room temperature for 12 h. React with a certain amount of 0.5 mol / L H2SO4 at room temperature for 12 h. Wash with distilled water, filter, and dry in a drying oven at 110℃ for 6 h to obtain sulfonated modified ZSM-5.

[0008] Step 2: Dissolve 0.1wt%~25wt% of the active ingredient Mo salt and 0.1wt%~25wt% of the active ingredient W salt in deionized water according to the ratio, and stir to dissolve and form a solution;

[0009] Step 3: Prepare composite catalysts by impregnation and calcination.

[0010] A further technical solution is that, in step one, the solid-liquid ratio is 10~30 mL / g.

[0011] A further technical solution is that, in step one, the silicon-to-aluminum ratio of ZSM-5 is 20~400.

[0012] A further technical solution is that, in step two, the mass ratio of the Mo salt to the W salt is 0.3 to 3.0.

[0013] A further technical solution is that, in step three, the content of sulfonated modified ZSM-5 in the prepared composite catalyst is 50wt%~80wt%.

[0014] A further technical solution is that, in step three, the preparation of the composite catalyst by impregnation and calcination includes the following steps:

[0015] S1: Immerse the sulfonated modified ZSM-5 obtained in step one in the solution obtained in step two, with an immersion temperature of 50~60℃ and an immersion time of 2 h.

[0016] S2: The above suspension was heated in an oil bath at 80°C to evaporate its water content, and the resulting solid was placed in a drying oven and dried at 110°C for 6 hours.

[0017] S3: The dried solid was calcined in a muffle furnace for 6 h at a temperature of 400~600℃, and after cooling, nano-MoO3-WO3 / ZSM-5 composite catalyst was obtained.

[0018] A further technical solution is that, in step S3, the dried solid is calcined in a muffle furnace under N2 protection.

[0019] A method for applying the composite catalyst obtained by the preparation method according to any one of claims 1 to 7, comprising the following steps:

[0020] Step 1: Crush the oil shale to a certain particle size and collect oil shale with a particle size of no more than 25 mm;

[0021] Step 2: After the catalyst is mixed evenly with the oil shale, it is fed into a parallel autoclave reactor for catalytic pyrolysis. The oil and gas generated during the pyrolysis process are collected, cooled, and separated to obtain oil shale oil and pyrolysis gas.

[0022] A further technical solution is that, in step two, the amount of catalyst used is 0.1wt% to 15wt% of the oil shale mass.

[0023] Compared with the prior art, the beneficial effects of the present invention are:

[0024] 1. The nano-MoO3-WO3 / ZSM-5 composite catalyst for in-situ catalytic pyrolysis of oil shale exhibits significant synergistic effects among its components, effectively reducing the activation energy required for the reaction, improving oil-gas conversion efficiency, reducing energy consumption, and improving oil quality.

[0025] 2. Sulfonic acid site modification and nano-MoO3-WO3 loading enabled the molecular structure design and performance regulation of in-situ oil shale conversion catalysts, laying a solid foundation for the discovery of more efficient composite catalysts.

[0026] 3. Nano MoO3-WO3 / ZSM-5 composite catalyst, which has a simple synthesis method, low cost, high catalytic efficiency and environmental friendliness. Detailed Implementation

[0027] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the invention.

[0028] Example 1:

[0029] The preparation method of the composite catalyst in this embodiment is as follows: 1 g of MPTMS and 1 g of ZMS-5 with a silicon-to-aluminum ratio of 38-40 were weighed and placed in 40 mL of toluene. The mixture was refluxed at 110℃ for 12 h, cooled, and filtered. Oxidation was carried out with 8 mL of 30% H2O2 at room temperature for 12 h. The mixture was then reacted with 40 mL of 0.5 mol / L H2SO4 at room temperature for 12 h. After washing with distilled water, the mixture was filtered and dried in a drying oven at 110℃ for 6 h to obtain sulfonated modified ZSM-5. 1.72 g of the active ingredient (NH4)6Mo7O was added. 24 . 4H2O was dissolved in deionized water to form a solution; sulfonated modified ZSM-5 was impregnated in the active ingredient solution at an impregnation temperature of 50~60℃ for 2 h, and then heated in an oil bath at 80℃ to evaporate the water. The resulting solid was placed in a drying oven and dried at 110℃ for 6 h; the dried solid was calcined in a muffle furnace for 6 h (under N2 protection) at a controlled temperature of 450℃, and after cooling, the MoO3 / sulfonated modified ZSM-5 composite catalyst was obtained.

[0030] The method for catalytic pyrolysis of oil shale using the catalyst in this embodiment is as follows: the oil shale minerals are crushed and sieved, and oil shale with a particle size not greater than 25 mm is collected; 1 g of the prepared composite catalyst is mixed evenly with 10 g of oil shale (mass ratio of 10%), and 20 mL of H2O is added and fed into a parallel autoclave reactor for catalytic pyrolysis. The oil and gas generated during the pyrolysis process are collected, cooled, and separated to obtain oil shale oil and oil shale gas; the distribution of the pyrolysis products is analyzed, and the results are shown in Table 1.

[0031] Example 2:

[0032] The preparation method of the composite catalyst in this embodiment is the same as that in Example 1, except that the active ingredient is 2.75 g (NH4)6H2W. 12 O 40 • H2O. The method of catalytic pyrolysis of oil shale using the catalyst in this embodiment is the same as in Example 1. The distribution of pyrolysis products was analyzed, and the results are shown in Table 1.

[0033] Example 3:

[0034] The preparation method of the composite catalyst in this embodiment is the same as that in Example 1, except that the active ingredient is 1.72 g (NH4)6Mo7O 24 . 4H2O and 2.75 g (NH4)6H2W 12 O 40 • H2O. The method of catalytic pyrolysis of oil shale using the catalyst in this embodiment is the same as in Example 1. The distribution of pyrolysis products was analyzed, and the results are shown in Table 1.

[0035] Example 4:

[0036] The preparation method of the composite catalyst in this embodiment is the same as that in Example 1, except that the silicon-aluminum ratio of ZSM-5 is 40~50; and the active ingredient is 0.855 g (NH4)6Mo7O. 24 . 4H2O and 1.37 g (NH4)6H2W 12 O 40 • H2O. The method of catalytic pyrolysis of oil shale using the catalyst in this embodiment is the same as in Example 1. The distribution of pyrolysis products was analyzed, and the results are shown in Table 1.

[0037] Example 5:

[0038] The preparation method of the composite catalyst in this embodiment is the same as that in Example 1, except that the silicon-aluminum ratio of ZSM-5 is 40~50; and the active ingredient is 1.37 g (NH4)6H2W. 12 O 40 • H2O. The method of catalytic pyrolysis of oil shale using the catalyst in this embodiment is the same as in Example 1. The distribution of pyrolysis products was analyzed, and the results are shown in Table 1.

[0039] Example 6:

[0040] The preparation method of the composite catalyst in this embodiment is the same as that in Example 1, except that the silicon-aluminum ratio of ZSM-5 is 40~50; and the active ingredient is 0.855 g (NH4)6Mo7O. 24. 4H2O and 2.75 g (NH4)6H2W 12 O 40 • H2O. The method of catalytic pyrolysis of oil shale using the catalyst in this embodiment is the same as in Example 1. The distribution of pyrolysis products was analyzed, and the results are shown in Table 1.

[0041] Example 7:

[0042] The preparation method of the composite catalyst in this embodiment is the same as that in Example 1, except that the silicon-aluminum ratio of ZSM-5 is 40~50; and the active ingredient is 1.71 g (NH4)6Mo7O. 24 . 4H2O and 2.75 g (NH4)6H2W 12 O 40 • H2O. The method of catalytic pyrolysis of oil shale using the catalyst in this embodiment is the same as in Example 1. The distribution of pyrolysis products was analyzed, and the results are shown in Table 1.

[0043] Example 8:

[0044] The preparation method of the composite catalyst in this embodiment is the same as that in Example 1, except that the silicon-aluminum ratio of ZSM-5 is 200~400; and the active ingredient is 1.71 g (NH4)6Mo7O. 24 . 4H2O. The method of catalytic pyrolysis of oil shale using the catalyst in this embodiment is the same as in Example 1. The distribution of pyrolysis products was analyzed, and the results are shown in Table 1.

[0045] Example 9:

[0046] The preparation method of the composite catalyst in this embodiment is the same as that in Example 1, except that the silicon-aluminum ratio of ZSM-5 is 40~50; and the active ingredient is 1.71 g (NH4)6Mo7O. 24 . 4H2O and 1.37 g (NH4)6H2W 12 O 40 • H2O. The method of catalytic pyrolysis of oil shale using the catalyst in this embodiment is the same as in Example 1. The distribution of pyrolysis products was analyzed, and the results are shown in Table 1.

[0047] Example 10:

[0048] The preparation method of the composite catalyst in this embodiment is the same as that in Example 1, except that the silicon-aluminum ratio of ZSM-5 is 40~50; and the active ingredient is 2.57 g (NH4)6Mo7O. 24 . 4H2O and 1.37 g (NH4)6H2W 12 O40 • H2O. The method of catalytic pyrolysis of oil shale using the catalyst in this embodiment is the same as in Example 1. The distribution of pyrolysis products was analyzed, and the results are shown in Table 1.

[0049] Example 11:

[0050] The preparation method of the composite catalyst in this embodiment is the same as that in Example 1, except that the silicon-aluminum ratio of ZSM-5 is 40~50; and the active ingredient is 0.855 g (NH4)6Mo7O. 24 . 4H2O and 4.11 g (NH4)6H2W 12 O 40 • H2O. The method of catalytic pyrolysis of oil shale using the catalyst in this embodiment is the same as in Example 1. The distribution of pyrolysis products was analyzed, and the results are shown in Table 1.

[0051] Example 12:

[0052] The preparation method of the composite catalyst in this embodiment is the same as that in Example 1, except that the silicon-aluminum ratio of ZSM-5 is 200~400; and the active ingredient is 1.71 g (NH4)6Mo7O. 24 . 4H2O. The method of catalytic pyrolysis of oil shale using the catalyst in this embodiment is the same as in Example 1. The distribution of pyrolysis products was analyzed, and the results are shown in Table 1.

[0053] Example 13:

[0054] The preparation method of the composite catalyst in this embodiment is the same as that in Example 1, except that the silicon-aluminum ratio of ZSM-5 is 200~400; and the active ingredient is 2.75 g (NH4)6H2W. 12 O 40 • H2O. The method of catalytic pyrolysis of oil shale using the catalyst in this embodiment is the same as in Example 1. The distribution of pyrolysis products was analyzed, and the results are shown in Table 1.

[0055] Example 14:

[0056] The preparation method of the composite catalyst in this embodiment is the same as that in Example 1, except that the silicon-aluminum ratio of ZSM-5 is 200~400; and the active ingredient is 1.71 g (NH4)6Mo7O. 24 . 4H2O and 2.75 g (NH4)6H2W 12 O 40 • H2O. The method of catalytic pyrolysis of oil shale using the catalyst in this embodiment is the same as in Example 1. The distribution of pyrolysis products was analyzed, and the results are shown in Table 1.

[0057] Example 15:

[0058] The preparation method of the composite catalyst in this embodiment is the same as that in Example 1, except that the silicon-aluminum ratio of ZSM-5 is 38~40 and no active component is loaded. The method of catalytic pyrolysis of oil shale using the catalyst in this embodiment is the same as that in Example 1. The distribution of pyrolysis products was analyzed, and the results are shown in Table 1.

[0059] Example 16:

[0060] The preparation method of the composite catalyst in this embodiment is the same as that in Example 1, except that the silicon-aluminum ratio of ZSM-5 is 40~50 and no active component is loaded. The method of catalytic pyrolysis of oil shale using the catalyst in this embodiment is the same as that in Example 1. The distribution of pyrolysis products was analyzed, and the results are shown in Table 1.

[0061] Example 17:

[0062] The preparation method of the composite catalyst in this embodiment is the same as that in Example 1, except that the silicon-aluminum ratio of ZSM-5 is 200~400; and no active component is loaded. The method of catalytic pyrolysis of oil shale using the catalyst in this embodiment is the same as that in Example 1. The distribution of pyrolysis products was analyzed, and the results are shown in Table 1.

[0063] Table 1 Distribution of pyrolysis products in Examples 1-17

[0064]

[0065] It is evident that, as shown in Table 1, the synergistic effect among the components is significant, indicating that the nano-MoO3-WO3 / ZSM-5 composite catalyst can effectively reduce the activation energy of the catalytic pyrolysis reaction of oil shale to a minimum of 42.78 kJ / mol; improve the oil-gas conversion efficiency, with the oil shale oil yield reaching a maximum of 15.69%; improve the oil quality, with the content of low- and medium-carbon hydrocarbon organic matter reaching a maximum of 71.79%; and the preparation method of this composite catalyst is simple, low-cost, and environmentally friendly.

[0066] Although the invention has been described herein with reference to several illustrative embodiments, it should be understood that many other modifications and implementations can be devised by those skilled in the art, which will fall within the scope and spirit of the principles disclosed herein. More specifically, various variations and modifications can be made to the components and / or layout of the subject matter combination within the scope of the claims disclosed herein. Besides variations and modifications to the components and / or layout, other uses will be apparent to those skilled in the art.

Claims

1. A method for preparing a composite catalyst for in-situ catalytic pyrolysis of oil shale, characterized in that: Includes the following steps: Step 1: Weigh a certain amount of 3-mercaptopropyltrimethoxysilane and ZSM-5 and place them in toluene. Reflux at 110℃ for 12 h, cool, and filter. Oxidize with a certain amount of 30% H2O2 at room temperature for 12 h. React with a certain amount of 0.5 mol / L H2SO4 at room temperature for 12 h. Wash with distilled water, filter, and dry in a drying oven at 110℃ for 6 h to obtain sulfonated modified ZSM-5. Step 2: Dissolve 0.1wt%~25wt% of the active ingredient Mo salt and 0.1wt%~25wt% of the active ingredient W salt in deionized water according to the ratio, and stir to dissolve and form a solution; Step 3: Prepare composite catalysts by impregnation and calcination.

2. The method for preparing a composite catalyst for in-situ catalytic pyrolysis of oil shale according to claim 1, characterized in that: In step one, the solid-liquid ratio is 10~30 mL / g.

3. The method for preparing a composite catalyst for in-situ catalytic pyrolysis of oil shale according to claim 1, characterized in that: In step one, the silicon-to-aluminum ratio of ZSM-5 is 20~400.

4. The method for preparing a composite catalyst for in-situ catalytic pyrolysis of oil shale according to claim 1, characterized in that: In step two, the mass ratio of the Mo salt to the W salt is 0.3 to 3.

0.

5. The method for preparing a composite catalyst for in-situ catalytic pyrolysis of oil shale according to claim 1, characterized in that: In step three, the content of sulfonated modified ZSM-5 in the prepared composite catalyst is 50wt%~80wt%.

6. The method for preparing a composite catalyst for in-situ catalytic pyrolysis of oil shale according to claim 1, characterized in that: In step three, the preparation of the composite catalyst by impregnation and calcination includes the following steps: S1: Immerse the sulfonated modified ZSM-5 obtained in step one in the solution obtained in step two, with an immersion temperature of 50~60℃ and an immersion time of 2 h. S2: The above suspension was heated in an oil bath at 80°C to evaporate its water content, and the resulting solid was placed in a drying oven and dried at 110°C for 6 hours. S3: The dried solid was calcined in a muffle furnace for 6 h at a temperature of 400~600℃, and after cooling, nano-MoO3-WO3 / ZSM-5 composite catalyst was obtained.

7. The method for preparing a composite catalyst for in-situ catalytic pyrolysis of oil shale according to claim 6, characterized in that: In step S3, the dried solid is calcined in a muffle furnace under N2 protection.

8. A method for applying the composite catalyst obtained by the preparation method according to any one of claims 1 to 7, characterized in that: Includes the following steps: Step 1: Crush the oil shale to a certain particle size and collect oil shale with a particle size of no more than 25 mm; Step 2: After the catalyst is mixed evenly with the oil shale, it is fed into a parallel autoclave reactor for catalytic pyrolysis. The oil and gas generated during the pyrolysis process are collected, cooled, and separated to obtain oil shale oil and pyrolysis gas.

9. The method for applying a composite catalyst according to claim 8, characterized in that: In step two, the amount of catalyst used is 0.1wt% to 15wt% of the oil shale mass.

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