Catalyst for coupling reservoir rock debris as well as preparation method and application of catalyst

Abstract

The invention belongs to the technical field of new materials, and provides a catalyst for coupling reservoir debris and a preparation method and application thereof, and the preparation method comprises the following steps: (1) carrying out microwave treatment on the reservoir debris to obtain modified debris; and (2) dipping the modified rock debris in a metal dipping solution, and then carrying out microwave treatment to obtain the catalyst for coupling reservoir rock debris. According to the method, the catalytic action of the reservoir rock debris is utilized, the reservoir rock debris is modified through microwaves, and the rock debris and NiCrO metal oxide are compounded for heat treatment, so that the efficiency of catalyzing crude oil to produce hydrogen can be effectively improved, and the rock debris has a certain catalytic action by activating the rock debris. The method provided by the invention is simple, has low process requirements, can efficiently prepare the catalyst coupled with reservoir debris, and is convenient for large-scale application in hydrogen production from crude oil.

Description

Technical Field

[0001] This invention relates to the field of new materials technology, and in particular to a catalyst for coupling reservoir rock fragments, its preparation method, and its application. Background Technology

[0002] Crude oil-to-hydrogen production is an important research direction in the petrochemical field. Its core is to convert crude oil and its derivatives into hydrogen through various processes to meet the clean energy needs of industries such as refining and chemicals. Compared to natural gas, hydrogen is an energy source with lower carbon intensity. The potential for large-scale application of hydrogen energy in future energy systems has prompted researchers to focus on hydrogen production from heavy and extra-heavy oil reservoirs.

[0003] In-situ catalytic hydrogen production from heavy oil reservoirs involves multiple series and parallel chemical reactions. The catalyst mainly acts on the following key mechanisms: (1) Catalytic hydrothermal cracking: In a high-temperature steam environment, the catalyst (especially the transition metal catalyst) can effectively break the heteroatom bonds such as CS, CN and CO in the heavy oil molecule and promote the breaking of CC bonds. This not only reduces the viscosity of the oil, but also releases gases such as H2, CH4 and CO2. The catalyst accelerates the removal of heteroatoms and the hydrocracking reaction of hydrocarbons, providing more precursors for subsequent hydrogen production reactions; (2) Catalytic steam methane reforming and water-gas shift reaction: The methane (CH4) generated by hydrothermal cracking and the preceding reaction undergoes a reforming reaction with steam under the action of the catalyst (SMR: CH4 + H2O → CO + 3H2), and the generated CO is then converted into more H2 through the water-gas shift reaction (WGSR: CO + H2O → CO2 + H2). (3) Catalytic coke gasification: Coke (C) produced by thermal cracking reacts with steam to form a gasification reaction (C+H2O→CO+H2), which is one of the main sources of hydrogen in in-situ hydrogen production. Alkali metals, alkaline earth metals, and transition metals (such as Ni, Fe) can effectively catalyze the coke gasification reaction, reduce the reaction temperature, prevent excessive coke deposition that could cause formation blockage, and maximize hydrogen production. (4) Water-gas shift reaction (WGSR, CO+H2O→CO2+H2), which converts CO produced by SMR and coke gasification into more hydrogen. Current research mainly focuses on catalytic hydrogen production on the ground, with little attention paid to the catalytic effect of the oil reservoir itself. Summary of the Invention

[0004] The purpose of this invention is to study the catalysis of oil reservoirs and to provide a catalyst coupled with reservoir cuttings, its preparation method, and its application.

[0005] To achieve the above-mentioned objectives, the present invention provides the following technical solution: This invention provides a method for preparing a catalyst coupled with reservoir cuttings, comprising the following steps: (1) The reservoir rock cuttings were microwave-treated to obtain modified rock cuttings; (2) The modified rock fragments are immersed in a metal impregnation solution and then microwaved to obtain the catalyst of the coupled reservoir rock fragments.

[0006] Preferably, the power of the microwave processing in step (1) is 600~1200W and the time is 1~10min.

[0007] Preferably, the metal impregnation solution in step (2) comprises nickel nitrate hexahydrate, chromium nitrate nonahydrate, and water; The mass ratio of nickel nitrate hexahydrate to chromium nitrate nonahydrate is 1.5~1.6:2.1~2.2; The mass-to-volume ratio of nickel nitrate hexahydrate to the metal impregnation solution is 1.5~1.6g:8~12mL.

[0008] Preferably, the mass-to-volume ratio of the modified rock chips and the metal impregnation solution in step (2) is 1~3g:8~12mL.

[0009] Preferably, the soaking time in step (2) is 3 to 5 hours.

[0010] Preferably, the power of the microwave processing in step (2) is 600~1200W.

[0011] Preferably, the microwave treatment time in step (2) is 1 to 10 minutes.

[0012] The present invention also provides a method for preparing the catalyst for coupled reservoir cuttings and the resulting catalyst.

[0013] The present invention also provides the application of the catalyst of the coupled reservoir cuttings in crude oil to hydrogen production.

[0014] This invention provides a method for preparing a catalyst coupled with reservoir rock cuttings, comprising the following steps: (1) microwave treatment of reservoir rock cuttings to remove impurities such as moisture and construct a porous structure to obtain modified rock cuttings; (2) immersion of the modified rock cuttings in a metal impregnation solution followed by microwave treatment to decompose the metal source and deposit it on the rock cuttings, thereby obtaining the composite catalyst of reservoir rock cuttings and metal. This invention utilizes the catalytic effect of reservoir rock cuttings, modifies them through microwave treatment, and heat-treats the composite of rock cuttings and NiCrO metal oxide to effectively improve the efficiency of catalytic hydrogen production from crude oil. By activating the rock cuttings, they acquire a certain catalytic effect. The method provided by this invention is simple, has low process requirements, and can efficiently prepare a catalyst coupled with reservoir rock cuttings, facilitating its large-scale application in crude oil hydrogen production. Attached Figure Description

[0015] Figure 1This is a composition diagram of the reservoir rock fragments in Example 1. Detailed Implementation

[0016] This invention provides a method for preparing a catalyst coupled with reservoir cuttings, comprising the following steps: (1) The reservoir rock cuttings were microwave-treated to obtain modified rock cuttings; (2) The modified rock fragments are immersed in a metal impregnation solution and then microwaved to obtain the catalyst of the coupled reservoir rock fragments.

[0017] In this invention, the power of the microwave processing in step (1) is preferably 600~1200W, more preferably 700~1100W, and even more preferably 800~1000W; the time is preferably 1~10min, more preferably 2~8min, and even more preferably 4~6min.

[0018] In this invention, the metal impregnation solution in step (2) comprises nickel nitrate hexahydrate, chromium nitrate nonahydrate and water.

[0019] In this invention, the mass ratio of nickel nitrate hexahydrate to chromium nitrate nonahydrate is preferably 1.5~1.6:2.1~2.2, more preferably 1.52~1.58:2.12~2.18, and even more preferably 1.54~1.56:2.14~2.16.

[0020] In this invention, the mass-to-volume ratio of nickel nitrate hexahydrate to the metal impregnation solution is preferably 1.5~1.6g:8~12mL, more preferably 1.52~1.58g:9~11mL, and even more preferably 1.54~1.56g:9.5~10.5mL.

[0021] In this invention, the mass-to-volume ratio of the modified rock chips and the metal impregnation solution in step (2) is preferably 1~3g:8~12mL, more preferably 1.5~2.5g:9~11mL, and even more preferably 1.8~2.2g:9.5~10.5mL.

[0022] In this invention, the soaking time in step (2) is preferably 3 to 5 hours, more preferably 3.5 to 4.5 hours, and even more preferably 3.8 to 4.2 hours.

[0023] In this invention, after the impregnation in step (2) is completed, the solvent is evaporated and dried; the evaporation temperature is preferably 60~80℃, more preferably 65~75℃, and even more preferably 68~72℃, and the solvent is dried after evaporation until there is no obvious liquid; the drying temperature is preferably 60~80℃, more preferably 65~75℃, and even more preferably 68~72℃; the drying time is preferably 2~6h, more preferably 3~5h, and even more preferably 3.5~4.5h.

[0024] In this invention, the power of the microwave processing in step (2) is preferably 600~1200W, more preferably 700~1100W, and even more preferably 800~1000W.

[0025] In this invention, the microwave treatment time in step (2) is preferably 1 to 10 minutes, more preferably 2 to 8 minutes, and even more preferably 4 to 6 minutes.

[0026] The present invention also provides a method for preparing the catalyst for coupled reservoir cuttings and the resulting catalyst.

[0027] The present invention also provides the application of the catalyst of the coupled reservoir cuttings in crude oil to hydrogen production.

[0028] The technical solutions provided by the present invention will be described in detail below with reference to the embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0029] Example 1

[0030] Take dried reservoir rock cuttings, denoted as YX, and the composition of the reservoir rock cuttings is as follows: Figure 1 As shown.

[0031] Reservoir rock cuttings were placed in a crucible, and the microwave treatment power was controlled at 900W for 5 minutes, denoted as YX-M900; the microwave treatment power was controlled at 600W for 5 minutes, denoted as YX-M600; and the microwave treatment power was controlled at 1200W for 5 minutes, denoted as YX-M1200.

[0032] Prepare a 10 mL metal impregnation solution by mixing 1.56 g of nickel nitrate hexahydrate and 2.11 g of chromium nitrate nonahydrate. Place 2.0 g of modified rock cuttings into the above metal impregnation solution and stir for 4 h. Then evaporate the solvent in a 70 °C water bath. After there is no obvious liquid, dry in a 70 °C oven for 4 h. Treat with microwaves at 600 W for 5 min, denoted as YX / NiCrO-M600; treat with microwaves at 900 W for 5 min, denoted as YX / NiCrO-M900; treat with microwaves at 1200 W for 5 min, denoted as YX / NiCrO-M1200.

[0033] Comparative Example 1

[0034] Reservoir rock cuttings were placed in a crucible and heated to 600℃ at a rate of 10℃ / min, and calcined for 4 hours to obtain heat-treated modified rock cuttings, denoted as YX-C600.

[0035] Comparative Example 2

[0036] Unactivated reservoir rock cuttings were impregnated, solvent evaporated and dried in the same manner as in Example 1, and then heated to 600°C at a rate of 10°C / min and calcined for 4 hours to obtain a sample, denoted as YX / NiCrO-N600.

[0037] Comparative Example 3

[0038] After the reservoir rock cuttings were subjected to microwave pretreatment, impregnation, solvent evaporation and drying as described in Example 1, they were heated to 600°C at a rate of 10°C / min and calcined for 4 hours to obtain the sample, which was denoted as YX / NiCrO-C600.

[0039] Performance testing

[0040] The elemental composition of crude oil is shown in Table 1.

[0041] The properties of crude oil are shown in Table 2.

[0042] Table 1. Elemental Composition of Crude Oil

[0043] Table 2 Properties of Crude Oil

[0044] The catalyst and crude oil were mixed at a mass ratio of 1:5 and reacted at 500℃ and 2MPa. The test results are shown in Table 3.

[0045] Table 3 Test Results

[0046] As shown in Table 3, (1) the reservoir cuttings exhibited low catalytic activity, with a gas-phase conversion rate of only 9% and a low hydrogen content of 5% in the product. After heat treatment and microwave heat treatment, the catalytic activity was improved, with microwave activation showing a greater improvement. (2) The optimal power for microwave treatment of reservoir cuttings was 900 W. (3) The composite catalyst formed by the activated cuttings and NiCrO showed higher activity after microwave treatment compared to conventional heat treatment, with a conversion rate reaching 100% and a maximum hydrogen content of 29% in the product.

[0047] This invention activates and modifies rock cuttings, then combines the activated reservoir rock cuttings with metal oxides, and uses microwave treatment to form a composite catalyst for catalytic hydrogen production from crude oil, thus improving the catalytic performance of the rock cuttings. Furthermore, the catalyst prepared under microwave irradiation exhibits better conversion activity and hydrogen selectivity. The development of rock cuttings catalytic function is beneficial for the future development of in-situ catalytic hydrogen production from underground reservoirs.

[0048] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A method of preparing a catalyst for coupling reservoir fines, characterized by, The method comprises the following steps: (1) microwave treatment of reservoir debris to obtain modified debris; (2) the modified debris is immersed in a metal impregnating solution and then subjected to microwave treatment to obtain the catalyst coupled with reservoir debris.

2. The method of claim 1, wherein the catalyst is prepared by the steps of: The power of the microwave treatment in step (1) is 600-1200 W, and the time is 1-10 min.

3. The method for preparing the catalyst coupled with reservoir cuttings as described in claim 2, characterized in that, The metal impregnating solution in step (2) comprises nickel nitrate hexahydrate, chromium nitrate nonahydrate and water; The mass ratio of the nickel nitrate hexahydrate and the chromium nitrate nonahydrate is 1.5-1.6:2.1-2.2; The mass-volume ratio of the nickel nitrate hexahydrate and the metal impregnating solution is 1.5-1.6 g:8-12 mL.

4. The method for preparing the catalyst coupled with reservoir cuttings as described in claim 3, characterized in that, The mass-volume ratio of the modified debris and the metal impregnating solution in step (2) is 1-3 g:8-12 mL.

5. The method for preparing the catalyst coupled with reservoir cuttings as described in claim 4, characterized in that, The time of the immersion in step (2) is 3-5 h.

6. The method of claim 5, wherein the catalyst is prepared by the steps of: The power of the microwave treatment in step (2) is 600-1200 W.

7. The method of claim 6, wherein the catalyst is prepared by the steps of: The time of the microwave treatment in step (2) is 1-10 min.

8. The catalyst coupled with reservoir debris prepared by the method of any one of claims 1-7.

9. The use of the catalyst coupled with reservoir debris of claim 8 in the production of hydrogen from crude oil.

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