A kind of petroleum fracturing proppant and preparation method thereof

Abstract

The present invention relates to the technical field of fracturing proppants, and provides a petroleum fracturing proppant and a preparation method thereof, wherein the components of the petroleum fracturing proppant include waste FCC catalyst, high-aluminum slag and a binder. The present invention adopts waste FCC catalyst and high-aluminum slag from waste hydrogenation catalyst as the main raw materials for preparing the petroleum fracturing proppant, and on the basis of realizing the comprehensive utilization of waste FCC catalyst and high-aluminum slag, by adopting waste FCC catalyst and high-aluminum slag to replace bauxite conventionally used for preparing petroleum fracturing proppants, the manufacturing cost of the petroleum fracturing proppant is reduced, and the prepared petroleum fracturing proppant has good performance, and provides a new idea and method for the comprehensive utilization of waste FCC catalyst and high-aluminum slag.

Description

Technical Field

[0001] The present invention relates to the technical field of fracturing proppants, and in particular to a petroleum fracturing proppant and a preparation method thereof. Background Art

[0002] The contents in this section merely provide background information related to the present invention and may not constitute prior art.

[0003] FCC (fluidized catalytic cracking) is an important part of modern crude oil refining process. After being used in the FCC unit, the FCC catalyst will be deactivated and become waste FCC catalyst. Since the waste FCC catalyst contains a variety of toxic heavy metals, if the waste FCC catalyst is disposed of by landfill, it will seriously pollute the environment.

[0004] At the same time, in addition to the waste FCC catalyst, the current crude oil refining process will also produce a large amount of waste hydrogenation catalyst. For the waste hydrogenation catalyst, the known comprehensive utilization method is to extract vanadium (i.e. ammonium metavanadate) and molybdenum (sodium molybdate) from the waste hydrogenation catalyst. After the waste hydrogenation catalyst is extracted with vanadium and molybdenum, high-aluminum slag will be produced. High-aluminum slag is mainly used in the production of glazes, coatings or plastics. However, as the amount of waste hydrogenation catalyst continues to increase, the output of high-aluminum slag is also increasing. Therefore, it is necessary to consider new comprehensive utilization methods for high-aluminum slag, rather than just limiting the use of high-aluminum slag in the production of glazes, coatings or plastics.

[0005] On the other hand, as a ceramic particle product, oil fracturing proppant is mainly used as downhole support in the process of shale oil or shale gas exploitation, so as to increase the production of shale oil or shale gas. In the related art, the known oil fracturing proppant is usually prepared with bauxite as the main raw material. Due to the high price of bauxite, the manufacturing cost of oil fracturing proppant is virtually increased. Summary of the invention

[0006] The inventors of the present invention have found that the aluminum-silicon ratio of the waste FCC catalyst is close to 1:1, which is conducive to the growth of mullite phase crystals under high temperature conditions, and the reliable growth of mullite phase crystals is expected to improve the performance of oil fracturing proppants. At the same time, the inventors of the present invention have further found that the high-aluminum slag obtained after extracting vanadium and molybdenum from the waste hydrogenation catalyst has a high aluminum oxide content, and the phase crystals of the high-aluminum slag are α or β crystal phases. If the high-aluminum slag is mixed with the waste FCC catalyst, the aluminum-silicon ratio in the waste FCC catalyst can be adjusted, and it can be phased into mullite phase crystals in the later stage, which is expected to further improve the performance of the oil fracturing proppants.

[0007] To this end, the purpose of the present invention is to provide a petroleum fracturing proppant and a preparation method thereof. The present invention adopts waste FCC catalyst and high-aluminum slag to replace bauxite for preparing the petroleum fracturing proppant, thereby reducing the manufacturing cost of the petroleum fracturing proppant on the basis of realizing the comprehensive utilization of the waste FCC catalyst and the high-aluminum slag, and the prepared petroleum fracturing proppant has good performance, and provides a new idea and method for the comprehensive utilization of the waste FCC catalyst and the high-aluminum slag.

[0008] The purpose of the present invention is achieved through the following technical solutions:

[0009] In one aspect, the present invention provides a petroleum fracturing proppant, wherein the components of the petroleum fracturing proppant include a waste FCC catalyst, high-aluminum slag and a binder.

[0010] In some possible embodiments, by weight percentage, the waste FCC catalyst, the high-aluminum slag and the binder account for 83%, 11% and 6% respectively.

[0011] In another aspect, the present invention provides a method for preparing a petroleum fracturing proppant, comprising the following steps:

[0012] S1. Adding high-aluminum slag and a binder to the spent FCC catalyst and mixing the mixture to obtain a mixed material;

[0013] S2. Add water to the mixture obtained in step S1 and granulate to obtain embryo balls;

[0014] S3. calcining the embryo balls obtained in step S2, and cooling after calcination to obtain an oil fracturing proppant;

[0015] In step S3, the calcination time of the embryo ball is 3 hours, the calcination temperature is increased from 200°C to 1310-1350°C in the first 1.5 hours, the calcination temperature is maintained at 1310-1350°C for 1.5-2.5 hours, and the calcination temperature is reduced from 1310-1350°C to 1100°C for 2.5-3 hours.

[0016] In some possible embodiments, in step S1, by weight percentage, the waste FCC catalyst, the high-aluminum slag and the binder in the mixture account for 83%, 11% and 6% respectively.

[0017] In some possible embodiments, in step S1, the waste FCC catalyst is a waste FCC catalyst having a particle size less than 300 mesh obtained after powder selection, and a dry powder selector is used for the powder selection.

[0018] In some possible embodiments, in step S1, the high-aluminum slag comes from spent hydrogenation catalyst.

[0019] In some possible embodiments, in step S3, the particle size of the embryo balls is 30-45 mesh.

[0020] In some possible embodiments, in step S2, water is added to the mixed material and granulation is performed in an automatic granulator.

[0021] In some possible embodiments, in step S3, the embryo balls need to be cooled to a temperature less than 80°C after calcination.

[0022] In some possible embodiments, the preparation method further comprises the steps of:

[0023] S4. Screening the petroleum fracturing proppant obtained in step S3 to screen out finished petroleum fracturing proppant with a particle size of 40-70 mesh.

[0024] The technical solution of the embodiment of the present invention has at least the following advantages and beneficial effects:

[0025] The invention adopts waste FCC catalyst and high-aluminum slag from waste hydrogenation catalyst as main raw materials for preparing petroleum fracturing proppant, and on the basis of realizing comprehensive utilization of waste FCC catalyst and high-aluminum slag, adopts waste FCC catalyst and high-aluminum slag to replace bauxite conventionally used for preparing petroleum fracturing proppant, thereby reducing the manufacturing cost of petroleum fracturing proppant, and the prepared petroleum fracturing proppant has good performance, and provides a new idea and method for comprehensive utilization of waste FCC catalyst and high-aluminum slag. DETAILED DESCRIPTION

[0026] In order to make the purpose, technical solution and advantages of the present invention more clear, the technical solution of the present invention will be clearly and completely described below in conjunction with specific implementation methods.

[0027] The first aspect of the present invention provides an oil fracturing proppant. Furthermore, the oil fracturing proppant is a low-density 40 / 70 oil pressure proppant, that is, an oil fracturing proppant with low density and a particle size of 40-70 mesh.

[0028] Specifically, the components of the petroleum fracturing proppant include waste FCC catalyst, high-aluminum slag and binder. Furthermore, by weight percentage, the waste FCC catalyst, high-aluminum slag and binder in the petroleum fracturing proppant account for 83%, 11% and 6% respectively.

[0029] In the present invention, the waste FCC catalyst may be, but is not limited to, the waste FCC catalyst produced in the crude oil refining process, wherein the chemical composition of the waste FCC catalyst mainly includes: Al2O3 63-68%, SiO2 18-20%, Fe2O3 4-7%, K2O 0.5-1.5%, CaO 1-3% and MgO 0.5-2%, etc. The inventors of the present invention have found that the aluminum-silicon ratio of the waste FCC catalyst is close to 1:1, which is conducive to the growth of mullite phase crystals under high temperature conditions, and the reliable growth of mullite phase crystals is expected to improve the performance of petroleum fracturing proppants. For this reason, it is considered to use the waste FCC catalyst as one of the main raw materials for preparing petroleum fracturing proppants.

[0030] High-aluminum slag can be, but is not limited to, derived from waste hydrogenation catalysts. Specifically, high-aluminum slag can be obtained by extracting vanadium and molybdenum from waste hydrogenation catalysts produced during crude oil refining. The high-aluminum slag is a white or brown powdery structure with a particle size of generally 40-200 meshes and an alumina content of not less than 90%. The inventors of the present invention have found that due to the high alumina content in the high-aluminum slag and the phase crystals of the high-aluminum slag being α or β crystal phases, if the high-aluminum slag is mixed with waste FCC catalysts, the aluminum-silicon ratio in the waste FCC catalysts can be adjusted, and the phase can be formed into mullite phase crystals in the later stage, thereby hopefully further improving the performance of the oil fracturing proppant. For this reason, the inventors of the present invention consider using high-aluminum slag from waste hydrogenation catalysts as another main raw material for preparing oil fracturing proppant.

[0031] As for the binder, the binder may be, but is not limited to, starch.

[0032] The invention adopts waste FCC catalyst and high-aluminum slag from waste hydrogenation catalyst as main raw materials for preparing petroleum fracturing proppant, and on the basis of realizing comprehensive utilization of waste FCC catalyst and high-aluminum slag, adopts waste FCC catalyst and high-aluminum slag to replace bauxite conventionally used for preparing petroleum fracturing proppant, thereby reducing the manufacturing cost of petroleum fracturing proppant, and the prepared petroleum fracturing proppant has good performance, and provides a new idea and method for comprehensive utilization of waste FCC catalyst and high-aluminum slag.

[0033] The second object of the present invention is to provide a method for preparing a petroleum fracturing proppant, by which a low-density 40 / 70 petroleum fracturing proppant can be prepared, thereby achieving the above-mentioned technical effect.

[0034] Specifically, the preparation method comprises the following steps:

[0035] S1. Adding high-aluminum slag and a binder to the spent FCC catalyst and mixing the mixture to obtain a mixed material.

[0036] In combination with the above, in step S1, the high-aluminum slag comes from the waste hydrogenation catalyst, and by weight percentage, the waste FCC catalyst, high-aluminum slag and binder in the mixed material account for 83%, 11% and 6% respectively.

[0037] Furthermore, before mixing, the waste FCC catalyst should be powdered so as to select the waste FCC catalyst of the target particle size as the raw material for preparing the oil fracturing proppant, thereby improving the quality of the finally prepared oil fracturing proppant. Furthermore, in step S1, the waste FCC catalyst is a waste FCC catalyst with a particle size of less than 300 mesh obtained after powder selection, that is, the particle size of the waste FCC catalyst used as the raw material for preparing the oil fracturing proppant should be less than 300 mesh.

[0038] It should be noted that the above-mentioned powder selection of the waste FCC catalyst can be but is not limited to the following method: the waste FCC catalyst is transported to the waste FCC catalyst silo by a vacuum loader, the waste FCC catalyst silo is connected to a quantitative feeder, the quantitative feeder transports the waste FCC catalyst to a powder selector through an elevator for powder selection, and then the waste FCC catalyst with a particle size less than 300 mesh is obtained, and the waste FCC catalyst obtained after the powder selection is stored in a powder silo.

[0039] In the above operation, the powder classifier used for powder selection is a dry powder classifier. It is worth noting that compared with the use of a known wet mill for powder selection, the use of a dry powder classifier for powder selection has lower costs and higher output, so it is expected to batch process waste FCC catalysts and improve production efficiency.

[0040] Secondly, the above-mentioned mixing of the waste FCC catalyst, high-aluminum slag and starch can be carried out in, but not limited to, the following manner: a certain amount of waste FCC catalyst in the powder bin is transported to the granulation bin of the granulator by a hoist, and at the same time, a certain amount of high-aluminum slag and a binder are added to the granulation bin to complete the mixing through the granulator, thereby obtaining a mixed material.

[0041] S2. After completing the mixing operation of step S1 to obtain a mixed material, water is added to the mixed material obtained in step S1 and granulation is performed to obtain embryo balls.

[0042] It should be noted that in step S2, adding water to the mixed material and granulating the mixed material may be performed in, but is not limited to, the following manner: adding water to a granulation bin of a granulator, and then granulating the mixed material using the granulator to obtain embryo balls.

[0043] In the above operation, water is added to the mixed material and granulation is completed in an automatic granulator. It is worth noting that, compared with the known disc granulator, the use of an automatic granulator for granulation can achieve granulation of large quantities of mixed materials, and the strength of the embryo balls obtained by granulation is better, which is expected to further improve production efficiency and improve the quality of the embryo balls obtained by granulation.

[0044] S3. calcining the embryo balls obtained in step S2, and cooling after calcination to obtain an oil fracturing proppant.

[0045] In step S3, the calcination time of the embryo ball is 3 hours, wherein the calcination temperature is increased from 200°C to 1310-1350°C in the first 1.5 hours, maintained at 1310-1350°C for 1.5-2.5 hours, and reduced from 1310-1350°C to 1100°C for 2.5-3 hours.

[0046] It should be noted that the present invention realizes the calcination of the embryo balls by adopting three-stage temperature control. Specifically, the first stage is to increase the calcination temperature from 200°C to 1310-1350°C in the first 1.5 hours, which is the preheating stage for the embryo balls. The second stage is to maintain the calcination temperature at 1310-1350°C for 1.5-2.5 hours, which is the insulation stage. The third stage is to reduce the calcination temperature from 1310-1350°C to 1100°C for 2.5-3 hours, which is the cooling stage.

[0047] It is worth noting that since the calcination process of the embryo balls directly affects the quality of the finally produced petroleum fracturing proppant, the present invention adopts a specific calcination process to calcine the embryo balls. Specifically, by adopting a calcination process of first preheating, then heat preservation, and finally cooling, the mullite phase crystals in the waste FCC catalyst and the high-aluminum slag can be effectively grown reliably, thereby hopefully improving the quality of the finally produced petroleum fracturing proppant.

[0048] Moreover, in step S3, the particle size of the embryo balls used for calcination is 30-45 mesh, that is, after the granulation is completed in the aforementioned step S2 to obtain the embryo balls, the obtained embryo balls can also be screened so as to screen out the embryo balls with a particle size of 30-45 mesh, and the embryo balls with a particle size of 30-45 mesh can be used as raw materials for subsequent calcination.

[0049] It should be noted that the above-mentioned screening of the embryo balls obtained by granulation and the subsequent calcination and cooling of the screened embryo balls can be carried out but is not limited to the following method: after the granulator completes granulation to obtain the embryo balls, the lower belt conveyor of the granulator can be used in conjunction with the elevator to transport the embryo balls to the screening machine for screening, so as to obtain embryo balls with a particle size of 30-45 mesh, and the embryo balls with a particle size of 30-45 mesh can be stored in the kiln head bin, and then the embryo balls in the kiln head bin are transported to the rotary kiln for calcination. After the calcination is completed, the embryo balls are transported to the cooler for cooling, thereby obtaining oil fracturing proppants, and the obtained oil pressure proppants can be stored in the calcination silo.

[0050] Furthermore, in step S3, the embryo balls need to be cooled to a temperature less than 80°C after calcination.

[0051] In addition, considering that the particle size of the petroleum fracturing proppant obtained in step S3 may not be within the range of 40-70 meshes, the preparation method provided by the present invention may further include the steps of:

[0052] S4. Screening the petroleum fracturing proppant obtained in step S3 to screen out the finished petroleum fracturing proppant with a particle size of 40-70 mesh.

[0053] It should be noted that the above-mentioned screening of the petroleum fracturing proppant can be but is not limited to the following method: the petroleum fracturing proppant in the calcined material bin is transported to the screening machine for screening by a hoist, so as to obtain the petroleum fracturing proppant with a particle size of 40-70 mesh and store it in the qualified product bin, after which the low-density 40 / 70 petroleum fracturing proppant in the qualified product bin can be directly packaged and sold or used.

[0054] In order to understand the present invention more clearly and intuitively, the present invention will be further described below in conjunction with specific embodiments. It should be understood that these embodiments are only used to illustrate the present invention and are not used to limit the scope of the present invention. Any product identical or similar to the present invention obtained by anyone under the inspiration of the present invention or by combining the features of the present invention with other prior arts falls within the protection scope of the present invention.

[0055] Example 1

[0056] The components of the oil fracturing proppant by weight include: 450 kg of spent FCC catalyst, 60 kg of high-alumina slag and 34 kg of binder.

[0057] The preparation method of the petroleum fracturing proppant comprises the following steps:

[0058] S1. Add 60 kg of high-aluminum slag and 34 kg of binder to 450 kg of spent FCC catalyst and mix them to obtain a mixed material.

[0059] Among them, the particle size of the spent FCC catalyst is less than 300 mesh, and the high-aluminum slag comes from the spent hydrogenation catalyst.

[0060] S2. Add water to the mixture obtained in step S1 and granulate to obtain embryo balls; after obtaining the embryo balls, screen the embryo balls to select embryo balls with a particle size of 30-45 mesh.

[0061] Among them, the roundness of the embryo balls obtained after granulation was 0.82, and the sphericity was 0.86.

[0062] S3. calcining the embryo balls with a particle size of 30-45 mesh obtained in step S2, and cooling to a temperature less than 80° C. after calcination to obtain an oil fracturing proppant.

[0063] In step S3, the calcination time of the embryo balls is 3 hours, wherein the calcination temperature is increased from 200°C to 1310°C in the first 1.5 hours, maintained at 1310°C for 1.5-2.5 hours, and decreased from 1310°C to 1100°C for 2.5-3 hours.

[0064] S4. Screening the petroleum fracturing proppant obtained in step S3 to screen out the finished petroleum fracturing proppant with a particle size of 40-70 mesh.

[0065] Example 2

[0066] The components of the oil fracturing proppant by weight include: 450 kg of spent FCC catalyst, 60 kg of high-alumina slag and 34 kg of binder.

[0067] The preparation method of the petroleum fracturing proppant comprises the following steps:

[0068] S1. Add 60 kg of high-aluminum slag and 34 kg of binder to 450 kg of spent FCC catalyst and mix them to obtain a mixed material.

[0069] Among them, the particle size of the spent FCC catalyst is less than 300 mesh, and the high-aluminum slag comes from the spent hydrogenation catalyst.

[0070] S2. Add water to the mixture obtained in step S1 and granulate to obtain embryo balls; after obtaining the embryo balls, screen the embryo balls to select embryo balls with a particle size of 30-45 mesh.

[0071] Among them, the roundness of the embryo balls obtained after granulation was 0.88, and the sphericity was 0.84.

[0072] S3. calcining the embryo balls with a particle size of 30-45 mesh obtained in step S2, and cooling to a temperature less than 80° C. after calcination to obtain an oil fracturing proppant.

[0073] In step S3, the calcination time for calcining the embryo balls is 3 hours, wherein the calcination temperature is increased from 200°C to 1325°C in the first 1.5 hours, maintained at 1325°C for 1.5-2.5 hours, and decreased from 1325°C to 1100°C for 2.5-3 hours.

[0074] S4. Screening the petroleum fracturing proppant obtained in step S3 to screen out the finished petroleum fracturing proppant with a particle size of 40-70 mesh.

[0075] Example 3

[0076] The components of the oil fracturing proppant by weight include: 450 kg of spent FCC catalyst, 60 kg of high-alumina slag and 34 kg of binder.

[0077] The preparation method of the petroleum fracturing proppant comprises the following steps:

[0078] S1. Add 60 kg of high-aluminum slag and 34 kg of binder to 450 kg of spent FCC catalyst and mix them to obtain a mixed material.

[0079] Among them, the particle size of the spent FCC catalyst is less than 300 mesh, and the high-aluminum slag comes from the spent hydrogenation catalyst.

[0080] S2. Add water to the mixture obtained in step S1 and granulate to obtain embryo balls; after obtaining the embryo balls, screen the embryo balls to select embryo balls with a particle size of 30-45 mesh.

[0081] Among them, the roundness of the embryo balls obtained after granulation was 0.85 and the sphericity was 0.90.

[0082] S3. calcining the embryo balls with a particle size of 30-45 mesh obtained in step S2, and cooling to a temperature less than 80° C. after calcination to obtain an oil fracturing proppant.

[0083] In step S3, the calcination time of the embryo balls is 3 hours, wherein the calcination temperature is increased from 200°C to 1350°C in the first 1.5 hours, maintained at 1350°C for 1.5-2.5 hours, and decreased from 1350°C to 1100°C for 2.5-3 hours.

[0084] S4. Screening the petroleum fracturing proppant obtained in step S3 to screen out the finished petroleum fracturing proppant with a particle size of 40-70 mesh.

[0085] According to the standard SY / T5108-2014 "Proppant Performance Test Method for Hydraulic Fracturing and Gravel Packing Operations", the low-density 40 / 70 petroleum fracturing proppant prepared in the above Examples 1-3 was tested for performance, and the results are shown in Table 1 below.

[0086] It should be noted that in the standard SY / T5108-2014 "Test Method for Proppant Performance for Hydraulic Fracturing and Gravel Packing Operations", the standard for the crushing rate of low-density 40 / 70 petroleum fracturing proppants is: under the pressure level of 52MPa, the crushing rate of petroleum fracturing proppants should be ≤10%.

[0087] Table 1 Performance test results of low-density 40 / 70 petroleum fracturing proppants prepared in Examples 1-3

[0088]

[0089] As can be seen from Table 1, the low-density 40 / 70 petroleum fracturing proppants prepared in Examples 1-3 all have good bulk density and apparent density, and can meet the use requirements of relevant units (such as China National Petroleum Corporation). At the same time, the low-density 40 / 70 petroleum fracturing proppants prepared in each embodiment have a crushing rate of less than 10% when the pressure level is 52 MPa, and therefore also meet the crushing rate requirements of the low-density 40 / 70 petroleum fracturing proppants in the relevant standards.

[0090] It can be seen that the present invention uses waste FCC catalyst and high-aluminum slag from waste hydrogenation catalyst as the main raw materials for preparing oil fracturing proppant, thereby realizing the comprehensive utilization of waste FCC catalyst and high-aluminum slag, and is expected to provide a new idea and method for the comprehensive utilization of waste FCC catalyst and high-aluminum slag. At the same time, the oil fracturing proppant prepared by adopting a specific preparation method has good bulk density, apparent density and crushing rate, and can meet relevant use requirements and standards.

[0091] The above are only preferred embodiments of the present invention and are not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A petroleum fracturing proppant, characterized in that: The components of the petroleum fracturing proppant include waste FCC catalyst, high-aluminum slag and binder, and by weight percentage, the waste FCC catalyst, the high-aluminum slag and the binder account for 83%, 11% and 6% respectively; Wherein, the high-aluminum slag comes from waste hydrogenation catalyst.

2. A method for preparing a petroleum fracturing proppant, characterized in that: The following steps are involved: S1. Adding high-aluminum slag and a binder to the waste FCC catalyst and mixing them to obtain a mixture; in terms of weight percentage, the waste FCC catalyst, the high-aluminum slag and the binder in the mixture account for 83%, 11% and 6% respectively; the high-aluminum slag comes from the waste hydrogenation catalyst; S2. adding water to the mixture obtained in step S1 and granulating the mixture to obtain embryo balls; S3. calcining the embryo balls obtained in step S2, and cooling after calcination to obtain an oil fracturing proppant; In step S3, the calcination time of the embryo ball is 3 hours, the calcination temperature is increased from 200°C to 1310-1350°C in the first 1.5 hours, the calcination temperature is maintained at 1310-1350°C for 1.5-2.5 hours, and the calcination temperature is reduced from 1310-1350°C to 1100°C for 2.5-3 hours.

3. The method for preparing a petroleum fracturing proppant according to claim 2, characterized in that: In step S1, the waste FCC catalyst is a waste FCC catalyst with a particle size of less than 300 mesh obtained after powder selection, and a dry powder selector is used for the powder selection.

4. The method for preparing a petroleum fracturing proppant according to claim 2, characterized in that: In step S3, the particle size of the embryo balls is 30-45 mesh.

5. The method for preparing a petroleum fracturing proppant according to claim 2, characterized in that: In step S2, water is added to the mixed material and granulation is performed in an automatic granulator.

6. The method for preparing a petroleum fracturing proppant according to claim 2, characterized in that: In step S3, the embryo balls need to be cooled to a temperature less than 80°C after calcination.

7. The method for preparing a petroleum fracturing proppant according to claim 2, characterized in that: Also includes the steps: S4. Screening the petroleum fracturing proppant obtained in step S3 to screen out finished petroleum fracturing proppant with a particle size of 40-70 mesh.

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