Emulsion type catalyst for in-situ oil production of oil shale as well as preparation method and application of emulsion type catalyst

Abstract

The invention discloses an emulsion type catalyst for in-situ oil production of oil shale as well as a preparation method and application thereof, and relates to the field of in-situ development of the oil shale. The emulsion type catalyst is prepared from the following raw materials in parts by weight: 1.01%-18.12% of an active metal component, 0.10%-0.18% of a dispersing agent, 0.02%-0.15% of a surfactant, 0.01%-0.06% of an auxiliary agent and the balance of water. The preparation method comprises the following steps: adding the active metal component, the dispersant, the surfactant and the auxiliary agent into water, and stirring and dispersing under a heating condition until an emulsion is formed. The emulsion type catalyst provided by the invention is easy to inject into a stratum, organic groups contained in the emulsion type catalyst can be in good contact with organic matters in oil shale, enough active components can be provided by a small amount of the emulsion type catalyst, and the emulsion type catalyst has a relatively good catalytic effect on oil shale cracking oil production in an underground in-situ condition simulated in a high-pressure reaction kettle.

Description

Technical Field

[0001] The invention relates to the field of in-situ development of oil shale, and in particular to an emulsion catalyst for in-situ oil generation of oil shale, a preparation method and application thereof. Background Art

[0002] Oil shale resources are abundant and can be used as a supplementary energy resource for petroleum. The in-situ mining technology of oil shale effectively avoids the disadvantages of high cost and greater environmental damage of ground retorting, and can also mine oil shale with deeper burial and thinner reservoir. The Chinese invention patent with the authorization announcement number CN101871339B discloses a method for extracting hydrocarbon compounds from oil shale in situ underground, which uses near-critical water to develop oil shale resources in situ, uses near-critical water as a heat conductor to thermally crack the kerogen in the underground oil shale to generate oil shale oil and gas, and then uses near-critical water to bring the oil shale oil to the surface for further use. The catalyst can reduce the activation energy required for the process of thermal cracking of kerogen, effectively reduce energy consumption, and improve development efficiency. Among the oil shale cracking catalysts synthesized by existing research institutes that can be used in underground in-situ conditions, inorganic catalysts have poor contact with organic matter in oil shale and poor catalytic effect, and organic catalysts have fewer active centers, require more, and are difficult to inject into the formation. Therefore, how to reduce the amount of catalyst while providing sufficient active centers and easily injecting it into the formation to have good contact with the organic matter in the oil shale to play a role has become one of the technical problems that need to be urgently solved in the current in-situ development of oil shale resources. Summary of the invention

[0003] The object of the present invention is to provide an emulsion catalyst for in-situ oil generation from oil shale, a preparation method of the emulsion catalyst and specific applications.

[0004] The technical solution adopted by the present invention is:

[0005] The first aspect of the present invention provides an emulsion catalyst for in-situ oil generation from oil shale, wherein the emulsion catalyst is made of the following raw materials in weight proportion: 1.01%-18.12% active metal component, 0.10%-0.18% dispersant, 0.02%-0.15% surfactant, 0.01%-0.06% auxiliary agent, and the balance is water. The total weight percentage of the raw materials of the emulsion catalyst is 100%.

[0006] Preferably, the active metal component or active metal supplier is an organic metal salt; the carbon number of a single organic group in the organic metal salt is selected from 4-6, 8-12, 17-21, and the active metal in the organic metal salt is at least one of transition metal elements such as Cr, Mn, Fe, Co, Ni, Cu, and Zn. For example, the active metal component can specifically be nickel acetylacetonate, nickel naphthenate, nickel stearate, etc.

[0007] Preferably, the active metal component content is calculated by: calibrating by active metal concentration, and calculating the amount of active metal component according to the relative molecular mass of the specific organic metal salt; the active metal concentration is preferably 0.001-0.12 mol / L.

[0008] Preferably, the dispersant is at least one of monoglyceride and fatty acid amide; the monoglyceride is preferably at least one of glyceryl monostearate and lauric monostearate; the fatty acid amide is preferably at least one of oleamide and erucamide.

[0009] Preferably, the surfactant is a nonionic surfactant, and a fatty amine polyoxyethylene ether is used; the fatty amine polyoxyethylene ether is at least one of dodecylamine polyoxyethylene ether and octadecylamine polyoxyethylene ether. More preferably, at least one of dodecylamine polyoxyethylene ether with an EO addition number of 5 and octadecylamine polyoxyethylene ether with an EO addition number of 10. The above EO addition number refers to the number of additions of ethylene oxide, the same below.

[0010] Preferably, the auxiliary agent is an isomeric alcohol ether; the isomeric alcohol ether is at least one of isomeric decanol polyoxyethylene ether and isomeric tridecanol polyoxyethylene ether. More preferably, at least one of isomeric decanol polyoxyethylene ether with an EO addition number of 6-9 and isomeric tridecanol polyoxyethylene ether with an EO addition number of 8, 10 or 12.

[0011] The interfacial tension of the emulsion catalyst is in the range of 0.006 to 0.254 mN / m, preferably 0.008 to 0.133 mN / m.

[0012] The second aspect of the present invention provides a method for preparing an emulsion catalyst for in-situ oil generation from oil shale, comprising the following steps: weighing active metal components, dispersants, surfactants, additives and water according to the above weight ratios; adding active metal components, dispersants, surfactants and additives into water, and stirring and dispersing under heating conditions until an emulsion is formed. The heating temperature is 40-60°C.

[0013] A third aspect of the present invention provides an application of an emulsion catalyst for in-situ oil generation from oil shale. The emulsion catalyst can be injected into the formation together with water injection into the formation, thereby effectively promoting the oil shale cracking and oil generation process.

[0014] Furthermore, the oil shale is mixed with the above-mentioned emulsion catalyst and cracked to produce oil in a high-pressure reactor under simulated underground in-situ conditions; the cracking oil production temperature is 280-360°C, preferably 300-340°C, and the cracking oil production time is 12-96h, preferably 48-60h; the pressure during the cracking process is not controlled and is the autogenous pressure of water at high temperature; the mass ratio of the oil shale to the emulsion catalyst is 50-100:1, and the mass ratio of the oil shale to water is 1:1-3.

[0015] The oil shale has a dry distillation gas content of 2.24wt%, an oil content of 6.06wt%, a water content of 8.19wt%, and a semi-coke content of 83.51wt%; wherein the content of each component of the oil shale is determined by the Fisher analysis method. Before being mixed with the emulsion catalyst for reaction, the oil shale can be dried at a temperature of 95-105°C for 6-8h. The oil shale is crushed into particles with an average particle size of 830-1700μm.

[0016] The beneficial technical effects of the present invention are:

[0017] The emulsion catalyst provided by the present invention is easy to inject into the formation, the organic groups contained in it can have good contact with the organic matter in the oil shale, and a small amount can provide sufficient active components. In the underground in-situ conditions simulated in the high-pressure reactor, it has a good catalytic effect on the cracking and oil production of oil shale.

[0018] In terms of principle, the inventors of the present invention have discovered that the emulsion catalyst prepared by the present invention can be injected into the formation together with the catalyst when injecting water into the formation. The organic groups contained in the emulsion catalyst can ensure good contact between the catalyst and the oil shale, and a small amount can provide sufficient active metals. The active metals provide more acid sites (mainly Lewis acids). The increase in acid sites accelerates the cracking reaction process of organic matter and can effectively promote the oil shale cracking and oil production process. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 The thermogravimetric curves of various specific application examples and comparative application examples of the present invention are shown in FIG. DETAILED DESCRIPTION

[0020] The following examples will be used to describe in detail the emulsion catalyst provided by the present invention, its preparation method and its application in in-situ cracking of oil shale to generate oil.

[0021] Example 1

[0022] An emulsion catalyst for in-situ oil generation from oil shale, the raw materials used by the catalyst being composed of the following components by weight percentage: 5.14% nickel acetylacetonate, 0.08% glyceryl monostearate, 0.04% erucamide, 0.03% dodecylamine polyoxyethylene ether (AC1205), 0.02% isomeric decanol polyoxyethylene ether (E1006), and 94.69% water.

[0023] A method for preparing an emulsion catalyst for in-situ oil generation from oil shale comprises the following steps: adding nickel acetylacetonate, glyceryl monostearate, erucamide, dodecylamine polyoxyethylene ether (AC1205) with an EO addition number of 5, and isomeric decanol polyoxyethylene ether (E1006) with an EO addition number of 6 in respective weight percentages to water, and mixing and dispersing the mixture at 45°C until an emulsion is formed.

[0024] Example 2

[0025] An emulsion catalyst for in-situ oil generation from oil shale, the raw materials used by the catalyst being composed of the following components by weight percentage: 5.14% nickel acetylacetonate, 0.06% monostearate laurate, 0.07% oleic acid amide, 0.02% dodecylamine polyoxyethylene ether (AC1205), 0.02% isomeric decanol polyoxyethylene ether (E1006), and 94.69% water.

[0026] A method for preparing an emulsion catalyst for in-situ oil generation from oil shale comprises the following steps: adding nickel acetylacetonate, lauric monostearate, oleic acid amide, dodecylamine polyoxyethylene ether (AC1205) with an EO addition number of 5, and isomeric decanol polyoxyethylene ether (E1006) with an EO addition number of 6 in respective weight percentages to water, and mixing and dispersing the mixture at 45°C until an emulsion is formed.

[0027] Example 3

[0028] An emulsion catalyst for in-situ oil generation from oil shale, the raw materials used by the catalyst being composed of the following components by weight percentage: 8.02% nickel cyclohexaneate, 0.05% glyceryl monostearate, 0.06% oleic acid amide, 0.08% dodecylamine polyoxyethylene ether (AC1205), 0.03% isomeric tridecanol polyoxyethylene ether (E1308), and 91.76% water.

[0029] A method for preparing an emulsion catalyst for in-situ oil generation from oil shale comprises the following steps: adding nickel cyclohexaneate, glyceryl monostearate, oleamide, dodecylamine polyoxyethylene ether (AC1205) with an EO addition number of 5, and isomeric tridecanol polyoxyethylene ether (E1308) with an EO addition number of 8 in respective weight percentages into water, and mixing and dispersing them at 50°C until an emulsion is formed.

[0030] Example 4

[0031] An emulsion catalyst for in-situ oil generation from oil shale, the raw materials used by the catalyst being composed of the following components by weight percentage: 8.02% nickel cyclohexaneate, 0.08% monostearate laurate, 0.05% erucamide, 0.06% dodecylamine polyoxyethylene ether (AC1205), 0.02% isomeric decanol polyoxyethylene ether (E1006), and 91.77% water.

[0032] A method for preparing an emulsion catalyst for in-situ oil generation from oil shale comprises the following steps: adding nickel cyclohexaneate, lauric monostearate, erucic acid amide, dodecylamine polyoxyethylene ether (AC1205) with an EO addition number of 5, and isomeric decanol polyoxyethylene ether (E1006) with an EO addition number of 6 in respective weight percentages into water, and mixing and dispersing them at 50°C until an emulsion is formed.

[0033] Example 5

[0034] An emulsion catalyst for in-situ oil generation from oil shale, the raw materials used by the catalyst being composed of the following components by weight percentage: 12.5% ​​nickel stearate, 0.08% monostearate laurate, 0.08% oleic acid amide, 0.15% octadecylamine polyoxyethylene ether (AC1810), 0.06% isomeric decanol polyoxyethylene ether (E1006), and 87.13% water.

[0035] A method for preparing an emulsion catalyst for in-situ oil generation from oil shale comprises the following steps: adding nickel stearate, lauric monostearate, oleic acid amide, octadecylamine polyoxyethylene ether (AC1810) with an EO addition number of 10, and isomeric decanol polyoxyethylene ether (E1006) with an EO addition number of 6 in respective weight percentages to water, and mixing and dispersing the mixture at 60°C until an emulsion is formed.

[0036] Example 6

[0037] An emulsion catalyst for in-situ oil generation from oil shale, the raw materials used by the catalyst being composed of the following components by weight percentage: 12.5% ​​nickel stearate, 0.1% monostearate laurate, 0.08% oleic acid amide, 0.12% octadecylamine polyoxyethylene ether (AC1810), 0.04% isomeric tridecyl alcohol polyoxyethylene ether (E1308), and 87.16% water.

[0038] A method for preparing an emulsion catalyst for in-situ oil generation from oil shale comprises the following steps: adding nickel stearate, lauric monostearate, oleic acid amide, octadecylamine polyoxyethylene ether (AC1810) with an EO addition number of 10, and isomeric tridecanol polyoxyethylene ether (E1308) with an EO addition number of 8 in respective weight percentages to water, and mixing and dispersing the mixture at 60°C until an emulsion is formed.

[0039] Example 7

[0040] Same as Example 5, except that the isomeric decanol polyoxyethylene ether with an EO addition number of 6 (E1006) is replaced by the isomeric decanol polyoxyethylene ether with an EO addition number of 8 (E1008).

[0041] Example 8

[0042] Same as Example 5, except that the isomeric decanol polyoxyethylene ether with an EO addition number of 6 (E1006) is replaced by the isomeric decanol polyoxyethylene ether with an EO addition number of 9 (E1009).

[0043] Example 9

[0044] Same as Example 6, except that the isomeric tridecanol polyoxyethylene ether with an EO addition number of 8 (E1308) is replaced by the isomeric tridecanol polyoxyethylene ether with an EO addition number of 10 (E1310).

[0045] Example 10

[0046] The same as Example 6, except that the emulsion catalyst is composed of the following components: 12.5% ​​nickel stearate, 0.06% monostearate laurate, 0.07% oleic acid amide, 0.03% octadecylamine polyoxyethylene ether (AC1810), 0.02% isomeric tridecanol polyoxyethylene ether (E1312), and 87.32% water. The isomeric tridecanol polyoxyethylene ether uses isomeric tridecanol polyoxyethylene ether (E1312) with an EO addition number of 12.

[0047] The water used in the above-mentioned Examples 1 to 10 can be distilled water.

[0048] The interfacial tension, stability and other physical and chemical properties of the emulsion catalysts prepared in Examples 1 to 10 were tested respectively. The results are shown in Table 1.

[0049] Table 1

[0050]

[0051] It can be seen from Table 1 that the interfacial tension of the emulsion catalyst prepared in the present application ranges from 0.011 to 0.066 mN / m. For the interfacial tension evaluation index, the smaller it is within a certain range, the better the contact performance with organic matter in oil shale.

[0052] In addition, part of the emulsion catalyst prepared in Example 1 to Example 10 was respectively put into a sample bottle. After standing for 3 days, it was found that no stratification occurred, indicating that a uniform emulsion catalyst had been formed.

[0053] Application Example 1

[0054] Weigh 50g of dried oil shale particles, add them into a high-temperature and high-pressure reactor, add distilled water at a rock-water mass ratio of 1:2, weigh 1g of the emulsion catalyst prepared in Example 1 (containing 0.002mol of active component Ni), replace the air in the reactor with nitrogen, set the reaction temperature to 340°C, and the reaction time to 48h. After the reaction is completed and cooled to room temperature, the gas, liquid, and solid three-phase products are taken out respectively, and the oil shale residue is extracted, washed, and dried. Take part of the residue sample and grind it into powder for thermogravimetric testing, and compare it with the thermogravimetric data of the original oil shale sample.

[0055] Application Example 2

[0056] Weigh 50g of dried oil shale particles and add them to a high-temperature and high-pressure reactor. Add distilled water at a rock-water mass ratio of 1:2. Weigh 1g of the emulsion catalyst prepared in Example 3 (containing 0.002mol of active component Ni). Replace the air in the reactor with nitrogen. Set the reaction temperature to 340°C and the reaction time to 48h. After the reaction is completed and cooled to room temperature, take out the gas, liquid and solid three-phase products respectively. Extract the oil shale residue, wash and dry it. Grind some of the residue samples into powder for thermogravimetric testing and compare them with the thermogravimetric data of the original oil shale sample.

[0057] Application Example 3

[0058] Weigh 50g of dried oil shale particles, add them into a high-temperature and high-pressure reactor, add distilled water at a rock-water mass ratio of 1:2, weigh 1g of the emulsion catalyst prepared in Example 5 (containing 0.002mol of active component Ni), replace the air in the reactor with nitrogen, set the reaction temperature to 340°C, and the reaction time to 48h. After the reaction is completed and cooled to room temperature, the gas, liquid, and solid three-phase products are taken out respectively, and the oil shale residue is extracted, washed, and dried. Take some residue samples and grind them into powder for thermogravimetric testing, and compare them with the thermogravimetric data of the original oil shale sample.

[0059] Application Example 4

[0060] Weigh 50g of dried oil shale particles, add them into a high-temperature and high-pressure reactor, add distilled water at a rock-water mass ratio of 1:2, weigh 1g of the emulsion catalyst prepared in Example 10 (containing 0.002mol of active component Ni), replace the air in the reactor with nitrogen, set the reaction temperature to 340°C, and the reaction time to 48h. After the reaction is completed and cooled to room temperature, the gas, liquid, and solid three-phase products are taken out respectively, and the oil shale residue is extracted, washed, and dried. Take some residue samples and grind them into powder for thermogravimetric testing, and compare them with the thermogravimetric data of the original oil shale sample.

[0061] Comparative application example 1

[0062] Weigh 50g of dried oil shale particles and add them to a high-temperature and high-pressure reactor. Add distilled water at a rock-water mass ratio of 1:2. Weigh 2.90g Ni(NO3)2·6H2O (containing 0.01mol of active component Ni) and dissolve it in distilled water and add it to the reactor. Replace the air in the reactor with nitrogen. Set the reaction temperature to 340℃ and the reaction time to 48h. After the reaction is completed and cooled to room temperature, take out the gas, liquid and solid products respectively. Extract the oil shale residue, wash and dry it. Grind some of the residue samples into powder for thermogravimetric testing and compare them with the thermogravimetric data of the original oil shale sample.

[0063] It is generally recognized that the kerogen cracking process in oil shale occurs in the temperature range of 200℃-600℃. By comparing the difference in weight loss between the original sample and the residue in this temperature range, the oil generation rate of the oil shale can be further calculated, thereby indicating the quality of the catalytic performance. The calculation method of weight loss rate and oil generation rate is as follows:

[0064] Weight loss rate:

[0065] Oil yield:

[0066] The weight loss rate and oil production rate of each application example are summarized in Table 2, and the thermogravimetric curves of each application example are shown in Figure 1 shown.

[0067] The present invention can achieve a good oil generation effect in a short time by simulating underground in-situ conditions with the help of a high-pressure reactor, and the oil generation rate of oil shale during the reaction process can be calculated through thermogravimetric data. Compared with the direct addition of Ni(NO3)2·6H2O (i.e., comparative application example 1), the addition of 0.01 mol of the active component Ni can only achieve an oil generation rate of 43.603%. By adding the emulsion catalyst prepared in the present invention, the maximum oil generation rate of 48.136% can be achieved in 48 hours of extraction time.

[0068] Table 2

[0069]

[0070] The parts not mentioned in the above methods can be realized by adopting or drawing on existing technologies.

[0071] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. An emulsion catalyst for in-situ oil generation from oil shale, characterized in that: The emulsion catalyst is prepared from the following raw materials in the following weight proportions: 1.01%-18.12% active metal component, 0.10%-0.18% dispersant, 0.02%-0.15% surfactant, 0.01%-0.06% auxiliary agent, and the balance is water.

2. The emulsion catalyst for in-situ oil generation from oil shale according to claim 1, characterized in that: The active metal component adopts an organic metal salt; the carbon number of a single organic group in the organic metal salt is selected from 4-6, 8-12, and 17-21, and the active metal in the organic metal salt is at least one of Cr, Mn, Fe, Co, Ni, Cu, and Zn.

3. An emulsion catalyst for in-situ oil generation from oil shale according to claim 1 or 2, characterized in that: The active metal component content is calculated by: calibrating through the active metal concentration, and calculating the amount of the active metal component according to the relative molecular mass of the specific organic metal salt; the active metal concentration is 0.001~0.12mol / L.

4. The emulsion catalyst for in-situ oil generation from oil shale according to claim 1, characterized in that: The dispersant is at least one of monoglyceride and fatty acid amide; the monoglyceride is at least one of monostearate glyceryl and monostearate laurate; the fatty acid amide is at least one of oleamide and erucamide.

5. The emulsion catalyst for in-situ oil generation from oil shale according to claim 1, characterized in that: The surfactant is fatty amine polyoxyethylene ether; the fatty amine polyoxyethylene ether is at least one of laurylamine polyoxyethylene ether and octadecylamine polyoxyethylene ether.

6. The emulsion catalyst for in-situ oil generation from oil shale according to claim 1, characterized in that: The auxiliary agent is an isomeric alcohol ether; the isomeric alcohol ether is at least one of isomeric decanol polyoxyethylene ether and isomeric tridecanol polyoxyethylene ether.

7. The emulsion catalyst for in-situ oil generation from oil shale according to claim 1, characterized in that: The interfacial tension range of the emulsion catalyst is: 0.006~0.254 mN / m.

8. A method for preparing an emulsion catalyst for in-situ oil generation from oil shale as claimed in any one of claims 1 to 7, characterized in that The steps are as follows: adding active metal components, dispersants, surfactants and additives into water, and stirring and dispersing them under heating conditions until an emulsion is formed; the heating temperature is 40-60°C.

9. The use of an emulsion catalyst for in-situ oil generation from oil shale as claimed in any one of claims 1 to 7, characterized in that: The emulsion catalyst can be injected into the formation together with water when injecting water into the formation, effectively promoting the oil shale cracking and oil production process.

10. The use of an emulsion catalyst for in-situ oil generation from oil shale as claimed in claim 9, characterized in that: The oil shale is mixed with the emulsion catalyst, and cracked to produce oil in a high-pressure reactor under simulated underground in-situ conditions; the cracking oil production temperature is 280-360°C, and the cracking oil production time is 12-96h; the mass ratio of the oil shale to the emulsion catalyst is 50-100:1, and the mass ratio of the oil shale to water is 1:1-3.

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