CN112521928B - Fracturing propping agent taking power plant waste solids as raw materials and preparation method thereof - Google Patents
Fracturing propping agent taking power plant waste solids as raw materials and preparation method thereof Download PDFInfo
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Abstract
Hair brushDisclosed is a fracturing propping agent using power plant waste solids as raw materials and a preparation method thereof. A fracturing proppant taking power plant waste solids as raw materials comprises: 88 to 92 percent of power plant waste solids, 6 to 8 percent of adhesive and 2.5 to 3.5 percent of additive; wherein, the power plant waste solids adopt SiO 2 Fly ash and slag with the content of more than 70 percent. The invention also discloses a preparation method of the fracturing propping agent. According to the fracturing propping agent taking the power plant waste solids as the raw material and the preparation method thereof, the source of the production raw material of the fracturing propping agent is expanded, the spanning of the production raw material from high aluminum to high silicon is realized, and the low-cost and large-scale production of the fracturing propping agent becomes possible; meanwhile, the process technology is developed based on solid waste of a power plant, so that the environmental damage is reduced, and the process has good development prospect and popularization value.
Description
Technical Field
The invention belongs to the technical field of oilfield development, and particularly relates to a fracturing propping agent taking power plant waste solids as a raw material and a preparation method thereof.
Background
Along with the increasing development of oil and gas in China, especially the development and utilization of ultralow permeability oil and gas reservoirs such as shale oil, gas and the like, the fracturing completion adopted before production becomes a main technical means. Among them, fracturing proppant products have become indispensable important resources in the oil and gas development process. In recent years, the domestic demand is gradually increased and exceeds 600 million tons. The traditional proppant mainly comprises quartz sand and ceramsite sand.
The ceramsite proppant is produced by taking scarce high-alumina ore as a raw material. The aluminum ore resource in China is gradually exhausted, a large amount of high-aluminum propping agent needs to be imported every year to meet the domestic demand, and the production cost of the high-aluminum propping agent is high. With the increasingly strict requirements on the national environmental protection, the ceramsite proppant industry with high energy consumption and high pollution is particularly concerned.
The ceramsite proppant has insufficient capacity and high cost, so that petroleum development enterprises face huge development cost, and low-end quartz sand for fracturing (with the compressive strength of 28 and 35 MPa) has to be reused on a large scale as a ceramsite support (with the compressive strength of 52, 69 and 86 MPa) substitute product. Although the quartz sand has large yield and low cost, the quartz sand has low compressive strength grade and large limitation of application conditions; meanwhile, the development and processing processes of the fracturing propping agent have large influence on the surface environment, large water resource consumption and serious environmental influence, and comprehensive comments are not an ideal fracturing propping agent.
In Xinjiang, there are many thermal power plants, the power plants produce a great amount of solid wastes with high silicon content, such as fly ash, slag and the like, in the production process, the utilization approaches are few, a great amount of solid wastes can only be accumulated in an ash discharge site, and the solid wastes are accumulated year by year and have serious influence on the environment.
In view of the above, the invention provides a novel fracturing propping agent, which takes power plant waste solids as a raw material to replace the traditional high-alumina ore as a fracturing propping agent production raw material, and solves the problem that the production raw material in the propping agent industry is increasingly exhausted.
Disclosure of Invention
The invention aims to provide a fracturing propping agent taking waste solids of a power plant as raw materials, which realizes replacement of production raw materials of the fracturing propping agent from traditional high-alumina ore to high-silicon low-aluminum solid wastes, realizes innovation and breakthrough of industrial technology, solves the problem of increasing exhaustion of production raw materials in the propping agent industry, and explores a new way for recycling of the solid wastes of western thermal power plants.
In order to realize the purpose, the adopted technical scheme is as follows:
a fracturing propping agent taking power plant waste solids as raw materials comprises: 88-92 parts of power plant waste solids, 6-8 parts of adhesive and 2.5-3.5 parts of additive;
wherein the power plant waste solid adopts SiO 2 Fly ash and slag with the content of more than 70 percent.
Further, the fracturing proppant comprises: 90 parts of power plant waste solids, 7 parts of clay binder and 3 parts of additive.
Further, the adhesive is clay mineral.
Further, the additive is natural ore with the metal oxide content of more than 50%;
the metal oxide is one or more of manganese oxide, potassium oxide, magnesium oxide and calcium oxide.
The invention also aims to provide the preparation method of the fracturing propping agent, which utilizes the solid wastes of a power plant to replace the traditional propping agent for producing oil and gas field fracturing by using aluminum ore, has simple process and prepares the fracturing propping agent mainly containing high-strength mullite and microcrystal mixed structure crystalline phase.
In order to realize the purpose, the adopted technical scheme is as follows:
the preparation method of the fracturing propping agent comprises the following steps:
mixing the waste solids of the power plant with an additive, carrying out light burning at 900-1000 ℃, adding an adhesive, and grinding to obtain mixed powder;
the mixed powder is made into balls through a granulating machine, and semi-finished product particles are obtained after screening;
and drying the semi-finished product particles by hot air, then sending the semi-finished product particles into a rotary kiln for baking, and then cooling to obtain the fracturing propping agent.
Further, the size of the mixed powder is less than 19um;
the grain diameter of the semi-finished product is 0.106-0.9mm.
Further, the light burning temperature is 940 ℃;
the hot air drying temperature is 120-130 ℃.
Furthermore, the baking temperature is 1250 +/-20 ℃, and the time is 2-2.5h.
And further, the temperature of the rotary kiln is raised to 1250 +/-20 ℃ within 4 h.
And furthermore, the kiln speed of the rotary kiln is 5-7 min/circle.
Compared with the prior art, the invention has the beneficial effects that:
the technical scheme of the invention is based on the basis of the traditional feldspar ceramic process, and the crystallization environment of a crystalline phase is adjusted by changing the raw material ratio, controlling the aluminum-silicon ratio and the addition of calcium, magnesium, potassium, manganese, sodium and other elements; the proppant is prepared by controlling the environment of a firing kiln and firing the mixture by a low-kiln-speed firing method at the temperature of about 1250 ℃, so that the aim of changing the strength of the material and other corresponding mechanical properties is fulfilled, and an ideal proppant product of high-strength microcrystal sand is obtained.
The fracturing propping agent using the power plant waste solids as the raw material has various indexes meeting the requirements of industrial standards, has sufficient raw material supply and low production cost (lower than ceramsite sand and slightly higher than quartz sand), can realize large-scale industrial production, has the advantages of low density, low acid solubility, low water immersion intensity, high surface smoothness (enamel), good flow conductivity and the like, can well meet the production requirements of oilfield development, and is an ideal propping agent substitute product.
Drawings
FIG. 1 is a process flow diagram of example 1;
FIG. 2 is a SE (M) plot of the fracturing proppant obtained in example 4 under 1150, 1250, 1350 ℃ bake conditions; 1150, 1250 and 1350 ℃ are respectively arranged from left to right in the figure;
figure 3 is an XRD pattern of the frac proppant obtained in example 4 under 1150, 1250, 1350 ℃ bake conditions.
Detailed Description
In order to further illustrate the fracturing propping agent using power plant waste solids as a raw material and the preparation method thereof, and achieve the intended purpose of the invention, the following detailed description is provided with reference to the preferred embodiments for the fracturing propping agent using power plant waste solids as a raw material and the preparation method thereof, and the specific implementation manner, structure, characteristics and efficacy thereof. In the following description, different "one embodiment" or "an embodiment" refers to not necessarily the same embodiment. Furthermore, the particular features, structures, or characteristics may be combined in any suitable manner in one or more embodiments.
The fracturing propping agent using power plant waste solids as raw materials and the preparation method thereof are further described in detail by combining specific embodiments as follows:
the starting materials and processes not mentioned in detail in the present invention are those conventional in the art.
The traditional alumina product generally adopts corundum phase and mullite as main crystal phases, a small amount of glass phase, and the batching component points are generally positioned in a corundum-mullite batching area of a calcium-aluminum-silicon phase diagram. The solid wastes of the power plant have the characteristics of low alumina content and high silica content, the basic theory adopted by the product design belongs to liquid phase sintering, the generated mullite phase and glass phase are the main crystal phase, and the contents of other crystal phases such as corundum, spinel and the like are very little. The batching point is positioned in a strengthened feldspar ceramic area of a potassium-aluminum-silicon ternary phase diagram, and the product in the area is characterized by liquid phase sintering, and the finished product belongs to a low density range. The invention starts from the components and the process, and the specific technical scheme is as follows:
a fracturing propping agent taking power plant waste solids as raw materials comprises: 88-92 parts of power plant waste solids, 6-8 parts of adhesive and 2.5-3.5 parts of additive;
wherein the power plant waste solids adopt SiO in Xinjiang region 2 Fly ash and slag with the content of more than 70 percent.
Preferably, the fracturing proppant comprises: 90 parts of power plant waste solids, 7 parts of clay binder and 3 parts of additive.
Preferably, the binder is clay mineral. The clay mineral is the same as that used in the preparation of the ceramic.
Preferably, the additive is natural ore with metal oxide content more than 50%; the metal oxide is one or more of manganese oxide, potassium oxide, magnesium oxide and calcium oxide. The natural ore containing metal oxide is adopted, so that the natural ore can be ensured to be melted and changed into a liquid phase in the sintering process. The additive is used as a solid-liquid sintering fluxing additive, and the solid-liquid mass transfer of sintering is increased by regulating and controlling the dosage of the additive, so that the densification and the sintering strength are improved; and can regulate the crystal phase.
The preparation method of the fracturing propping agent comprises the following steps:
mixing the waste solid of the power plant and the additive, lightly burning at 900-1000 ℃, adding the adhesive, and grinding to obtain mixed powder.
And (3) granulating the mixed powder by a granulator to obtain balls, and screening to obtain semi-finished product granules.
And drying the semi-finished product particles by hot air, then sending the semi-finished product particles into a rotary kiln for baking, and then cooling to obtain the fracturing propping agent.
Preferably, the size of the mixed powder is less than 19um, so that the raw materials can be fully and uniformly mixed.
The particle size of the semi-finished product particles is 0.106-0.9mm, and the specification is the conventional specification of the fracturing propping agent.
Preferably, the light burning temperature is 940 ℃;
the hot air drying temperature is 120-130 ℃.
Preferably, the baking temperature is 1250 +/-20 ℃ and the baking time is 2-2.5h. Baking and sintering at low kiln speed and 1250 deg.C to change its internal crystal phase and form high-strength mullite and microcrystal mixed crystal phase. In the actual operation process, the temperature cannot be well and stably controlled to 1250 ℃, so the baking temperature can fluctuate by 20 ℃.
Further preferably, the temperature of the rotary kiln is raised to 1250 +/-20 ℃ within 4 h.
Further preferably, the kiln speed of the rotary kiln is 5-7 min/circle. Tests prove that the problems of easy powder removal and ring burning after the materials are hung on the wall exist when the materials are baked at the conventional kiln speed. Therefore, the invention determines to carry out baking at low speed through experiments, and can ensure the final yield.
The invention prepares series proppant products with controllable influence factors of crystal phases such as potassium aluminum silicon, magnesium aluminum silicon, manganese aluminum silicon and the like by regulating and controlling a sintering system by regulating and controlling factors such as sintering temperature, temperature rise program, sintering atmosphere and the like.
The process technology of the invention expands the source of the production raw materials of the fracturing propping agent, realizes the spanning of the production raw materials from high aluminum to high silicon, has wider raw material source and lower cost, enables the low-cost and large-scale production of the fracturing propping agent to be possible, solves the bottleneck restricting the development of the industry, and provides material guarantee for the low-cost development concept of oil gas in China; meanwhile, the process technology is developed based on the solid waste of the power plant, a new way is explored for the solid waste treatment of the power plant while the environmental damage is reduced, the national benefits and the people are benefited, the social benefits are huge, and the development prospect and the popularization value are good.
Example 1.
Raw materials: 90 parts of power plant waste solids, 7 parts of adhesive and 3 parts of additive.
Wherein the waste solids of the power plant adopt SiO in Xinjiang area 2 Fly ash and slag with the content of more than 70 percent. The binder is clay mineral. The additive is natural ore with metal oxide content more than 50%; the metal oxide is one or more of manganese oxide, potassium oxide, magnesium oxide and calcium oxide.
The process is shown in fig. 1, and the specific operation steps are as follows:
(1) Pretreatment and raw material refinement: firstly, the fly ash, the slag and the additive are roughly mixed according to the proportion, then the mixture is calcined for 1h at 900-1000 ℃ by a light-burning kiln, after carbon residue and harmful components are removed, the mixture is added with the adhesive and mixed evenly, and the mixture is sent to a ball mill to be ground to below 19um, so as to obtain the raw material, namely mixed powder required by production.
(2) And (3) granulating: and (3) pelletizing the mixed powder in a pelletizer to obtain pellets with the size of 0.106-0.9mm, and sieving to obtain the required semi-finished product particles.
(3) And (3) sintering: and drying the semi-finished product particles in a hot air drying kiln at 120 ℃, screening and feeding into a rotary kiln. Heating to 1250 + -20 deg.C within 4h, baking at low kiln speed of 5-7 min/circle and 1250 + -20 deg.C, and sintering for 2.5h to change the internal crystal phase to form high-strength mullite and microcrystal mixed crystal phase. And finally, cooling by a cooling kiln, and screening to obtain the corresponding high-strength microcrystalline sand proppant, namely the fracturing proppant taking the power plant waste solids as the raw material.
After the microcrystalline sand proppant product provided by the embodiment of the invention is put into industrial scale production, through strict detection, all indexes of the microcrystalline sand proppant product reach or are superior to design requirements, and the requirement of fracturing construction of an oil and gas field is completely met. The ratio of each index to the values of the conventional quartz sand and ceramsite sand is shown in Table 1.
TABLE 1
As can be seen from Table 1, the microcrystalline sand proppant produced by processing solid wastes of a power plant can meet the requirements of proppant industry standard of SY/T5108-2014 proppant performance test method for hydraulic fracturing and gravel filling operation, part of the indexes are superior to the industry standard, the compressive strength index (40-103 MPa) of the product is superior to that of a natural quartz sand proppant (14-35 MPa), the strength of the product is equivalent to that of ceramsite sand, the cost of the product is only about 65% of that of the traditional ceramsite proppant, the microcrystalline sand proppant is used for fracturing construction, the volume density (less than 1.4) of the microcrystalline sand proppant is lower than that of the traditional proppant (1.55-1.8), the dosage of the proppant and the sand carrying liquid proportioning ratio can be reduced, the comprehensive fracturing construction cost can be reduced by more than 30%, and the application prospect and the economic benefit can be in a long term.
Example 2.
Raw materials: 88 parts of power plant waste solids, 8 parts of a binder and 3.5 parts of an additive.
Wherein, the waste solids of the power plant adopt SiO 2 Fly ash and slag with content over 75 percent. The binder is clay mineral. The additive is natural ore with metal oxide content more than 50%; the metal oxide is one or more of manganese oxide, potassium oxide, magnesium oxide and calcium oxide.
The specific operation steps are as follows:
(1) Pretreatment and raw material refinement: firstly, the fly ash, the slag and the additive are coarsely mixed according to the proportion, then the mixture is calcined for about 1h at 940 ℃ in a light-burning kiln, the residual carbon and harmful components are removed, then the binder is added and mixed evenly, and the mixture is sent to a ball mill to be ground to below 19um, so that the raw material, namely mixed powder, required by production is obtained.
(2) And (3) granulating: and (3) pelletizing the mixed powder in a pelletizer (water can be sprayed in the pelletizing process to enable the raw materials to be pelletized), wherein the size is 0.3-0.6mm, and screening to obtain required semi-finished product particles.
(3) And (3) sintering: and (4) drying the semi-finished product particles with hot air in a kiln, screening, and feeding into a rotary kiln. (the hot air drying can use the residual heat of the rotary kiln, the temperature can reach 120-130 degree)
Heating to 1250 + -20 deg.C within 4h, baking at 1250 + -20 deg.C at 6 min/circle low kiln speed, and sintering for 2.5h to change the internal crystal phase to form high-strength mullite and microcrystal mixed crystal phase. And finally, performing forced cooling in a cooling kiln, cooling to room temperature within 2 hours, and screening to obtain the corresponding high-strength microcrystalline sand proppant, namely the fracturing proppant taking the waste solids of the power plant as the raw material.
Example 3.
Raw materials: 91.5 parts of power plant waste solids, 6 parts of adhesive and 2.5 parts of additive.
Wherein, the waste solids of the power plant adopt SiO 2 Fly ash and slag with the content of more than 70 percent. The binder is clay mineral. The additive is natural ore with metal oxide content more than 50%; the metal oxide is one or more of manganese oxide, potassium oxide, magnesium oxide and calcium oxide.
The specific operation steps are as follows:
(1) Pretreatment and raw material refinement: firstly, the fly ash, the slag and the additive are coarsely mixed according to the proportion, then the mixture is calcined for about 1h at 980 ℃ by a light-burning kiln, the residual carbon and harmful components are removed, then the binder is added and mixed evenly, and the mixture is sent to a ball mill to be ground to below 19um, thus obtaining the raw material, namely mixed powder required by production.
(2) And (3) granulating: and (3) pelletizing the mixed powder in a pelletizer (water can be sprayed in the pelletizing process to enable the raw materials to be pelletized), wherein the size of the raw materials is 0.425-0.212mm, and screening to obtain required semi-finished product particles.
(3) And (3) sintering: and drying the semi-finished product particles in a hot air drying kiln at 130 ℃, screening and feeding into a rotary kiln. After the temperature is raised to 1250 +/-20 ℃ within 4h, the mixture is baked at the low kiln speed of 7 min/circle and the temperature of 1250 +/-20 ℃ for 2.5h, so that the internal crystal phase is changed, and the high-strength mullite and microcrystal mixed structure crystal phase is formed. And finally, performing forced cooling in a cooling kiln, cooling to room temperature within 2 hours, and screening to obtain the corresponding high-strength microcrystalline sand proppant, namely the fracturing proppant taking the waste solids of the power plant as the raw material.
Example 4.
The operation procedure of example 4 is the same as that of example 1, except that in step (3), specifically:
(3) And (3) sintering: baking at 1100, 1150, 1200, 1250, 1300 and 1350 ℃ (the sintering temperature can fluctuate up and down by 20 ℃), sintering for 2.5h, cooling in a cooling kiln, and screening to obtain the fracturing propping agent taking the waste solids of the power plant as the raw material.
The physical properties of the fracturing proppant prepared in this example were measured and the results are shown in table 2.
TABLE 2
As can be seen from Table 2, the product obtained at 1250 ℃ has the highest bulk density and apparent density, and the lowest turbidity and breakage rate, i.e., the best product quality. Therefore, 1250 ℃. + -. 20 ℃ is the optimal sintering temperature range of the product.
SE (M) and XRD detection are carried out on the microcrystalline sand fracturing propping agent obtained under the baking conditions of 1150, 1250 and 1350 ℃, and the results are shown in figures 2-3. As can be seen from FIGS. 2-3, the diffraction peaks of the phases are calculated by fitting with Rietveld-Q software, and the detection of the relevant physical indexes can determine that the content of the mullite and glass phase mixed solid solution affecting the strength in the sample reaches the optimal value at 1250 ℃, and the optimal sintering temperature range of the product is 1250 +/-20 ℃.
Example 5.
The procedure of example 5 is the same as that of example 1 except for the mass ratio of the power plant solid waste, the binder and the additive in step (1), as shown in Table 3.
Physical properties of the fracturing proppant prepared in this example were measured, and the results are shown in table 3.
TABLE 3
As can be seen from table 3, in the power plant solid waste: adhesive: the mass ratio of the additive is 90. Therefore, the power plant is wasted in solid: adhesive: the mass ratio of the additive is 90.
The fracturing propping agent taking the waste solids of the power plant as the raw materials and the preparation method thereof are environment-friendly, can comprehensively utilize the resources of the waste solids of the power plant, have sufficient raw materials, can realize low-cost large-scale industrial production, have the cost which is about 30 percent lower than that of the ceramsite propping agent, can consume a large amount of waste solids and waste wastes and can save precious bauxite ore resources by replacing the ceramsite propping agent, have good economic and social benefits, and are ideal for replacing new materials.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and any simple modification, equivalent change and modification made to the above embodiments according to the technical spirit of the present invention are within the scope of the technical solution of the present invention.
Claims (8)
1. The fracturing propping agent taking the waste solids of the power plant as the raw materials is characterized by comprising the following components in parts by weight: 88-92 parts of power plant waste solids, 6-8 parts of adhesive and 2.5-3.5 parts of additive;
wherein, the power plant waste solids adopt SiO 2 Fly ash and slag with the content of more than 70 percent;
the additive is natural ore with metal oxide content more than 50%;
the metal oxide is one or more of manganese oxide, potassium oxide, magnesium oxide and calcium oxide;
the preparation method of the fracturing propping agent comprises the following steps:
mixing the waste solids of the power plant with an additive, carrying out light burning at 900-1000 ℃, adding an adhesive, and grinding to obtain mixed powder;
the mixed powder is made into balls by a granulating machine, and semi-finished product particles are obtained after screening;
and drying the semi-finished product particles by hot air, then sending the semi-finished product particles into a rotary kiln for baking, and then cooling to obtain the fracturing propping agent.
2. The fracturing proppant of claim 1, wherein the fracturing proppant comprises: 90 parts of power plant waste solids, 7 parts of clay binder and 3 parts of additive.
3. The fracturing proppant of claim 1,
the adhesive is clay mineral.
4. The fracturing proppant of claim 1,
the size of the mixed powder is less than 19um;
the grain diameter of the semi-finished product is 0.106-0.9mm.
5. The fracturing proppant of claim 1,
the light burning temperature is 940 ℃;
the hot air drying temperature is 120-130 ℃.
6. The fracturing proppant of claim 1,
the baking temperature is 1250 +/-20 ℃, and the baking time is 2-2.5h.
7. The fracturing proppant of claim 1,
the temperature of the rotary kiln is raised to 1250 +/-20 ℃ within 4 h.
8. The fracturing proppant of claim 1,
the kiln speed of the rotary kiln is 5-7 min/circle.
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| CN103288426A (en) * | 2013-05-28 | 2013-09-11 | 陕西科技大学 | Method for preparing special fracturing propping agent for shale gas by utilizing industrial waste |
| CN105358738A (en) * | 2013-08-20 | 2016-02-24 | 艾普罗普有限公司 | Proppant material incorporating fly ash and method of manufacture |
| CN106431349A (en) * | 2016-09-30 | 2017-02-22 | 洛阳赛罗帕陶瓷科技有限公司 | Ultralow-density cordierite petroleum fracturing propping agent and preparation method thereof |
| CN109626960A (en) * | 2019-01-25 | 2019-04-16 | 攀枝花秉扬科技股份有限公司 | A kind of coal gangue haydite proppant and preparation method thereof |
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