CN111470850A - Ceramsite proppant prepared from industrial waste copper smelting slag and preparation process - Google Patents
Ceramsite proppant prepared from industrial waste copper smelting slag and preparation process Download PDFInfo
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- CN111470850A CN111470850A CN202010363768.0A CN202010363768A CN111470850A CN 111470850 A CN111470850 A CN 111470850A CN 202010363768 A CN202010363768 A CN 202010363768A CN 111470850 A CN111470850 A CN 111470850A
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
- C04B38/009—Porous or hollow ceramic granular materials, e.g. microballoons
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B33/00—Clay-wares
- C04B33/02—Preparing or treating the raw materials individually or as batches
- C04B33/13—Compounding ingredients
- C04B33/1305—Organic additives
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B33/00—Clay-wares
- C04B33/02—Preparing or treating the raw materials individually or as batches
- C04B33/13—Compounding ingredients
- C04B33/132—Waste materials; Refuse; Residues
- C04B33/138—Waste materials; Refuse; Residues from metallurgical processes, e.g. slag, furnace dust, galvanic waste
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B33/00—Clay-wares
- C04B33/32—Burning methods
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
- C04B38/06—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by burning-out added substances by burning natural expanding materials or by sublimating or melting out added substances
- C04B38/063—Preparing or treating the raw materials individually or as batches
- C04B38/0635—Compounding ingredients
- C04B38/0645—Burnable, meltable, sublimable materials
- C04B38/067—Macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/80—Compositions for reinforcing fractures, e.g. compositions of proppants used to keep the fractures open
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/60—Production of ceramic materials or ceramic elements, e.g. substitution of clay or shale by alternative raw materials, e.g. ashes
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Structural Engineering (AREA)
- Dispersion Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention belongs to the field of ceramic materials, and mainly relates to a ceramsite proppant prepared from industrial waste copper smelting slag and a preparation process thereof. The ceramsite proppant is prepared from the following raw materials: copper slag, clay and shale, wherein the copper slag is industrial waste copper smelting slag. The copper slag is prepared from the following raw materials in percentage by mass: 10% -50%, clay: 20% -50%, shale: 30-50 percent of the total weight of the copper slag, the clay and the shale is 100 percent. The performance of the ceramsite proppant prepared by the invention meets the SY/T5108-2014 industrial standard, the copper smelting slag is added into the raw materials, the utilization rate of solid wastes is increased, the additional value of the copper slag is improved, the raw material cost is low, the preparation method is simple, the resource circulation and the environmental protection are facilitated, and a new idea is provided for the comprehensive utilization of the copper slag.
Description
Technical Field
The invention belongs to the field of ceramic materials, and particularly relates to a ceramsite proppant prepared from industrial waste copper smelting slag and a preparation process thereof.
Background
Copper slag is slag generated in the copper smelting process, the yield of the copper slag is high in the copper production mainly by a pyrogenic process at present, and the utilization of low-grade copper ore leads to further sharp increase of the amount of the copper slag due to the gradual depletion of copper ore resources, so that the sharp contradiction and the tension situation of resource tension and resource over consumption are formed. Therefore, under the condition that the existing resources in China are seriously deficient, the resource comprehensive utilization technology of the copper-containing slag is developed, and the method has important strategic and practical significance for promoting the circular economy, the sustainable development and the environmental protection. The ceramic proppant is a high-strength ceramic particle which has different specifications, can meet certain performance indexes and can be used for deep supporting operation in the petroleum industry. For the development of the ceramsite, the main raw material adopted by China is high-grade mineral resources, and the ceramsite is prepared by adding a sintering aid and adopting a sintering method. The traditional ceramsite preparation is mainly prepared by processing non-renewable natural resources such as bauxite, shale, clay and the like serving as raw materials, and with the implementation of policies of environmental protection and comprehensive utilization of resources, the search for suitable raw materials for preparing the ceramsite by replacing the non-renewable natural resources becomes an important task. So far, no report of using copper slag as a raw material for preparing the ceramsite proppant is found.
Disclosure of Invention
The invention provides a ceramsite proppant prepared from industrial waste copper smelting slag and a preparation process thereof. The ceramsite proppant meets the service performance required by the industrial standard, simultaneously uses waste residues generated in the copper smelting process as raw materials, solves the problems of resource shortage, environmental pollution and sustainable development, and has the advantages of low preparation process cost and simple process.
In order to realize the task, the invention adopts the following technical scheme:
a ceramsite proppant prepared from industrial waste copper smelting slag is prepared from the following raw materials: copper slag, clay and shale, wherein the copper slag is industrial waste copper smelting slag.
Specifically, the copper slag is prepared from the following raw materials in percentage by mass: 10% -50%, clay: 20% -50%, shale: 30-50 percent of the total weight of the copper slag, the clay and the shale is 100 percent.
Specifically, the copper slag-shale composite material is prepared from the following raw materials, by mass, 20% of copper slag, 30% of clay and 50% of shale.
Furthermore, the volume density of the ceramsite proppant is less than or equal to 1.7g/cm3Apparent density is less than or equal to 3g/cm3The breaking rate is less than or equal to 9 percent under the stress condition of 52MPa, the roundness and the sphericity are more than or equal to 0.8, the acid solubility is less than or equal to 5 weight percent, and the turbidity is less than or equal to 100 FTU.
The preparation process of the ceramsite proppant prepared from the blast furnace copper slag comprises the following steps:
the method comprises the following steps: crushing the copper slag and the shale, and respectively grinding the copper slag, the clay and the shale;
step two: respectively weighing copper slag, clay and shale according to the following mass fractions, and mixing; then adding a bonding agent into the granulator to mix the raw materials into balls;
step three: respectively drying, screening and sintering the spherulites to obtain the composite material;
the copper slag: 10% -50%, clay: 20% -50%, shale: 30-50 percent of the total weight of the copper slag, the clay and the shale is 100 percent.
Specifically, the copper slag comprises 20-40% of silicon oxide by mass and 30-50% of iron oxide by mass.
Furthermore, the raw materials are ground and then pass through a 200-mesh sieve, and the particle size of the powder is smaller than 0.074 mm.
Further, the binding agent is a solution prepared from single components or composite components of polyvinyl alcohol, dextrin and carboxymethyl cellulose, and the total mass of the polyvinyl alcohol, the dextrin and the carboxymethyl cellulose in the solution accounts for 0-5% of the total mass of the solution.
Specifically, the copper slag: 20%, clay: 30%, shale: 50 percent, the sum of the mass percentages of the copper slag, the clay and the shale is 100 percent;
the binding agent is a single component of polyvinyl alcohol, and the polyvinyl alcohol in the solution accounts for 1% of the total mass of the solution.
Further, the drying temperature is 80-120 ℃, the sintering temperature is 1100-1300 ℃, and the heat preservation time is 1.0-3.0 h.
Compared with the prior art, the invention has the following advantages:
(1) the invention provides a ceramsite proppant which uses waste copper slag as a raw material, and realizes resource recycling and environmental protection; the added value of the copper slag is improved, and the preparation cost is reduced; the preparation process is simple, economic, rapid and energy-saving; the performance of the prepared ceramsite proppant can meet the requirements of industrial standards, and the preparation process is low in cost.
(2) The invention provides a preparation process of a ceramsite proppant, which is simple in process, economic and energy-saving.
Drawings
The accompanying drawings, which are included to provide a further understanding of the disclosure and are incorporated in and constitute a part of this specification, illustrate embodiments of the disclosure and together with the description serve to explain the disclosure without limiting the disclosure.
In the drawings:
FIG. 1 is a flow chart of the manufacturing process of the present invention;
the present invention will be described in further detail with reference to the following drawings and examples.
Detailed Description
The present invention is described below with reference to specific examples, but the present invention is not limited to the following examples, and it should be understood by those skilled in the art that the invention can be implemented by making several simple deductions or substitutions to prepare satisfactory ceramsite proppant without departing from the spirit of the present invention, and all such alternatives are within the scope of the present invention. The amounts of the substances are given in mass% unless otherwise specified below.
The copper slag in the invention is industrial waste copper smelting slag which can be obtained from pyrometallurgical copper smelting plants, and other reagents are commercially available.
The ceramsite proppant is prepared from the following raw materials in percentage by mass: 10% -50%, clay: 20% -50%, shale: 30-50 percent of the total weight of the copper slag, the clay and the shale is 100 percent.
The preparation process of the ceramsite proppant prepared from the blast furnace slag comprises the following steps: crushing the raw materials; weighing raw materials according to mass percentage and mixing the raw materials by using a ball mill; spraying water to the uniformly mixed powder in a sugar coating machine, mixing and granulating; drying the spherulites; finally sintering in a high-temperature furnace; and (4) screening and detecting the sintered spherical particles to finally obtain the ceramsite proppant meeting the standard.
The method specifically comprises the following steps:
the method comprises the following steps: crushing the copper slag and the shale, and respectively grinding the copper slag, the clay and the shale;
step two: weighing copper slag, clay and shale according to the following mass fractions respectively, and mixing; then adding a bonding agent into the granulator to mix the raw materials into balls;
step three: respectively drying, screening and sintering the spherulites to obtain the composite material;
the copper slag: 10% -50%, clay: 20% -50%, shale: 30-50 percent of the total weight of the copper slag, the clay and the shale is 100 percent.
The drying temperature is 80-120 ℃, the sintering temperature is 1100-1300 ℃, and the heat preservation time is 1.0-3.0 h.
The binding agent is a solution prepared from single components or composite components of polyvinyl alcohol, dextrin and carboxymethyl cellulose, and the total mass of the polyvinyl alcohol, the dextrin and the carboxymethyl cellulose in the solution accounts for 0-5% of the total mass of the solution.
Example 1
The embodiment provides a ceramsite proppant prepared from industrial waste copper smelting slag. The ceramsite proppant is prepared from the following raw materials: copper slag, clay and shale, wherein the copper slag is industrial waste copper smelting slag.
The ceramsite proppant is prepared from the following raw materials in percentage by mass: 20%, clay: 30%, shale: 50 percent, and the sum of the mass percentages of the copper slag, the clay and the shale is 100 percent.
The embodiment also discloses a preparation process for preparing the ceramsite proppant from the industrial waste copper smelting slag, which comprises the following steps:
the method comprises the following steps: crushing the copper slag and the shale, and respectively grinding the copper slag, the clay and the shale; the raw materials are ground and then are sieved by a 200-mesh sieve, namely the granularity of the powder is less than 0.074 mm.
Step two: weighing copper slag, clay and shale according to the following mass fractions respectively, and mixing; then, taking polyvinyl alcohol solution as a bonding agent, and mixing the raw materials into balls;
step three: respectively drying, screening and sintering the spherulites to obtain the composite material;
the method comprises the following steps: drying the spherical particles, and performing primary screening on the dried spherical particles by using a standard screen; finally sintering in a high-temperature furnace;
screening and detecting: and (3) carrying out secondary screening on the sintered ceramsite, and then detecting the performance to finally obtain the ceramsite proppant with the performance meeting the SY/T5108-2014 industry standard.
The binding agent is a single component of polyvinyl alcohol, and the polyvinyl alcohol in the solution accounts for 1% of the total mass of the solution.
The drying temperature of the ceramsite green body is 80 ℃, the sintering temperature is 1200 ℃, and the heat preservation time is 1.5 h.
The sintered ceramsite proppant has the volume density of 1.53g/cm3Apparent density of 2.90g/cm3The fracture rate is 7.3 percent under the stress condition of 52MPa, the roundness and the sphericity are 0.8, the acid solubility is 4.1wt percent, the turbidity is 90FTU, the performance of the material meets the requirement of the industry standard, and the material can be used for fracturing operation.
Example 2:
the ceramsite proppant is prepared from 25 mass percent of copper slag, 35 mass percent of clay, 40 mass percent of shale and 100 mass percent of the total of the copper slag, the clay and the shale in the raw material, which are the same as the ceramsite proppant in the example 1 and are different from the ceramsite proppant in the example 1.
The total mass of the polyvinyl alcohol, the dextrin and the carboxymethyl cellulose in the binding agent solution accounts for 0 percent of the solution in percentage by mass.
The drying temperature of the ceramsite green body is 100 ℃, the sintering temperature is 1150 ℃, and the heat preservation time is 2 hours.
The sintered ceramsite proppant has the volume density of 1.58g/cm3Apparent density 2.92g/cm3The fracture rate is 7.6 percent under the stress condition of 52MPa, the roundness and the sphericity are 0.8, the acid solubility is 4.5wt percent, the turbidity is 90FTU, the performance of the material meets the requirement of the industry standard, and the material can be used for fracturing operation.
Example 3:
the ceramsite proppant is prepared from the raw materials, wherein the mass fraction of copper slag in the raw materials is 40%, the mass fraction of clay in the raw materials is 30%, the mass fraction of shale in the raw materials is 30%, and the sum of the mass percentages of the copper slag, the clay and the shale is 100%, which is the same as that of example 1, but is different from that of example 1.
The bonding agent is prepared from dextrin serving as a single component and serves as a bonding agent, and the dextrin in the bonding agent solution accounts for 4% of the total mass of the solution in percentage by mass.
The drying temperature of the ceramsite green body is 90 ℃, the sintering temperature is 1200 ℃, and the heat preservation time is 2 hours.
The sintered ceramsite proppant has the volume density of 1.55g/cm3Apparent density 2.95g/cm3The fracture rate is 7.5 percent under the stress condition of 52MPa, the roundness and the sphericity are 0.8, the acid solubility is 4.6wt percent, the turbidity is 85FTU, the performance of the material meets the requirement of the industry standard, and the material can be used for fracturing operation.
Example 4:
the ceramsite proppant is prepared from the raw materials, wherein the mass fraction of copper slag in the raw materials is 45%, the mass fraction of clay in the raw materials is 15%, the mass fraction of shale in the raw materials is 40%, and the sum of the mass percentages of the copper slag, the clay and the shale is 100%, which is the same as that in example 1, but is different from that in example 1.
The binding agent is prepared from carboxymethyl cellulose as a single component by mass percent to prepare a solution as the binding agent, and the carboxymethyl cellulose in the binding agent solution accounts for 2 percent of the total mass of the solution by mass percent.
The drying temperature of the ceramsite green body is 90 ℃, the sintering temperature is 1100 ℃, and the heat preservation time is 2 hours.
The sintered ceramsite proppant has the volume density of 1.56g/cm3Apparent density 2.96g/cm3The fracture rate is 7.8 percent under the stress condition of 52MPa, the roundness and the sphericity are 0.8 percent, the acid solubility is 4.3 percent by weight, the turbidity is 90FTU, the performance of the material meets the requirement of the industry standard, and the material can be used for fracturing operation.
Claims (10)
1. The ceramsite proppant is characterized by being prepared from industrial waste copper smelting slag and prepared from the following raw materials: copper slag, clay and shale, wherein the copper slag is industrial waste copper smelting slag.
2. The ceramsite proppant prepared from the blast furnace copper slag according to claim 1 is prepared from the following raw materials in percentage by mass: 10% -50%, clay: 20% -50%, shale: 30-50 percent of the total weight of the copper slag, the clay and the shale is 100 percent.
3. The ceramsite proppant prepared from the blast furnace copper slag according to claim 1, is prepared from the following raw materials in percentage by mass, wherein the percentage by mass of the copper slag is 20%, the percentage by mass of the clay is 30%, and the percentage by mass of the shale is 50%.
4. The ceramsite proppant prepared from blast furnace copper slag according to claim 1, wherein the ceramsite proppant has a bulk density of not more than 1.7g/cm3Apparent density is less than or equal to 3g/cm3The breaking rate is less than or equal to 9 percent under the stress condition of 52MPa, the roundness and the sphericity are more than or equal to 0.8, the acid solubility is less than or equal to 5 weight percent, and the turbidity is less than or equal to 100 FTU.
5. The preparation process of the ceramsite proppant prepared from the blast furnace copper slag as set forth in any one of claims 1 to 4, is characterized by comprising the following steps:
the method comprises the following steps: crushing the copper slag and the shale, and respectively grinding the copper slag, the clay and the shale;
step two: respectively weighing copper slag, clay and shale according to the following mass fractions, and mixing; then adding a bonding agent into the granulator to mix the raw materials into balls;
step three: respectively drying, screening and sintering the spherulites to obtain the composite material;
the copper slag: 10% -50%, clay: 20% -50%, shale: 30-50 percent of the total weight of the copper slag, the clay and the shale is 100 percent.
6. The process for preparing ceramic proppant from blast furnace copper slag as set forth in claim 5, wherein said copper slag contains 20-40% by weight of silicon oxide and 30-50% by weight of iron oxide.
7. The preparation process of the ceramsite proppant prepared from the blast furnace copper slag according to claim 5, wherein the raw materials are ground and then pass through a 200-mesh sieve, and the particle size of the powder is less than 0.074 mm.
8. The preparation process of the ceramsite proppant prepared from the blast furnace copper slag as claimed in claim 5, wherein the binder is a solution prepared from a single component or a composite component of polyvinyl alcohol, dextrin and carboxymethyl cellulose, and the total mass of the polyvinyl alcohol, the dextrin and the carboxymethyl cellulose in the solution accounts for 0-5% of the total mass of the solution.
9. The preparation process of the ceramsite proppant prepared from the blast furnace copper slag as recited in claim 5, is characterized in that the copper slag: 20%, clay: 30%, shale: 50 percent, the sum of the mass percentages of the copper slag, the clay and the shale is 100 percent;
the binding agent is a single component of polyvinyl alcohol, and the polyvinyl alcohol in the solution accounts for 1% of the total mass of the solution.
10. The process for preparing ceramic proppant from blast furnace copper slag according to claim 5, wherein the drying temperature is 80-120 ℃, the sintering temperature is 1100-1300 ℃, and the holding time is 1.0-3.0 h.
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| CN202010363768.0A CN111470850A (en) | 2020-04-30 | 2020-04-30 | Ceramsite proppant prepared from industrial waste copper smelting slag and preparation process |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112851169A (en) * | 2021-02-18 | 2021-05-28 | 北京建筑材料科学研究总院有限公司 | Method for solidifying heavy metal elements in copper slag |
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2020
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112851169A (en) * | 2021-02-18 | 2021-05-28 | 北京建筑材料科学研究总院有限公司 | Method for solidifying heavy metal elements in copper slag |
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