CN114308373B - Method for utilizing graphite ore full resources - Google Patents

Method for utilizing graphite ore full resources Download PDF

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CN114308373B
CN114308373B CN202210007561.9A CN202210007561A CN114308373B CN 114308373 B CN114308373 B CN 114308373B CN 202210007561 A CN202210007561 A CN 202210007561A CN 114308373 B CN114308373 B CN 114308373B
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graphite
tailings
concentrate
ore
mass
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CN114308373A (en
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张以河
张娜
邸祥云
王新珂
张帅
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China University of Geosciences Beijing
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China University of Geosciences Beijing
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Priority to PCT/CN2022/124896 priority patent/WO2023130790A1/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03B—SEPARATING SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS
    • B03B7/00—Combinations of wet processes or apparatus with other processes or apparatus, e.g. for dressing ores or garbage
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03B—SEPARATING SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS
    • B03B9/00—General arrangement of separating plant, e.g. flow sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
    • 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
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
    • C04B28/04—Portland cements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06—Homopolymers or copolymers of vinyl chloride
    • 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
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/91—Use of waste materials as fillers for mortars or concrete

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Structural Engineering (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Composite Materials (AREA)
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Abstract

The invention provides a method for utilizing the whole resources of graphite ores, which comprises the steps of firstly carrying out primary separation on raw graphite ores to obtain crystalline graphite ores/cryptocrystalline graphite ores and low-grade graphite ores; respectively processing, wherein the low-grade graphite ore is subjected to stage grinding and stage flotation in sequence to obtain graphite concentrate and graphite tailings; then purifying and filtering the graphite concentrate in sequence to obtain crystalline graphite ore/aphanitic graphite ore; sequentially carrying out flotation and fine selection on the crystalline graphite ore to obtain graphite tailings and crystalline graphite concentrate; purifying the crystalline graphite concentrate to obtain crystalline graphite; or crushing, grinding and grading the aphanitic graphite ore in sequence to obtain graphite tailings and aphanitic graphite concentrate; purifying the aphanitic graphite concentrate to obtain aphanitic graphite; the obtained graphite tailings can be used as a raw material for preparing 3D printing building components, composite boards or mineral compound fertilizers, and the full resource utilization of graphite ores is realized.

Description

Method for utilizing graphite ore full resources
Technical Field
The invention relates to the technical field of recycling of solid waste resources, in particular to a method for utilizing graphite ore full resources.
Background
With the rise of new energy and new material industries, graphite products, particularly crystalline graphite and aphanitic graphite which are deep-processed products of graphite ores, attract more and more attention and gradually become important materials which cannot be replaced in the fields of national defense, aerospace, new materials and the like, however, graphite tailings generated after the deep processing of the graphite ores are usually discharged to a river ditch or thrown in a tailing pond of a dam near a mine as solid waste materials, and as the graphite tailings have fine particles, the tailings accumulated in the tailing pond form a dust storm source in the wind, a large amount of dust is generated in daily road transportation and production, and the dust becomes a main component part of environmental pollution. Therefore, how to realize the full resource utilization of the graphite ore becomes an urgent problem to be solved.
Disclosure of Invention
The invention aims to provide a method for utilizing the whole resources of graphite ores. The method provided by the invention can realize the full utilization of the graphite tailings, thereby realizing the full resource utilization of the graphite ores.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a method for utilizing graphite ore full resources, which comprises the following steps:
(1) Primarily selecting raw graphite ores to obtain crystalline graphite ores/cryptocrystalline graphite ores and low-grade graphite ores;
(2) Carrying out stage grinding and stage flotation on the low-grade graphite ore obtained in the step (1) in sequence to obtain graphite concentrate and graphite tailings;
(3) Sequentially carrying out first purification and filtration on the graphite concentrate obtained in the step (2) to obtain crystalline graphite ore/aphanitic graphite ore;
(4-1) sequentially carrying out flotation and fine selection on the crystalline graphite ore obtained in the step (1) and the step (3) to obtain graphite tailings and crystalline graphite concentrate;
(5-1) carrying out second purification on the crystalline graphite concentrate obtained in the step (4-1) to obtain crystalline graphite;
or: (4-2) sequentially crushing, grinding and grading the aphanitic graphite ore obtained in the step (1) and the step (3) to obtain graphite tailings and aphanitic graphite concentrate;
(5-2) carrying out third purification on the aphanitic graphite concentrate obtained in the step (4-2) to obtain aphanitic graphite;
(6) And (3) using the graphite tailings obtained in the step (2) and the graphite tailings obtained in the step (4-1)/(4-2) to prepare 3D printing building components, composite boards or mineral compound fertilizers.
Preferably, the 3D printed building component in the step (6) comprises the following raw materials: a main agent, a reinforcing material and an auxiliary agent;
the main agent is prepared from the following raw materials in percentage by mass: 20-30% of hydraulic cementing material, 10-20% of admixture, 40-60% of graphite tailings, 0-5% of copper tailings and 0-10% of construction sand;
the reinforcing material accounts for 0.2 to 0.5 percent of the mass of the main agent.
Preferably, the admixture comprises fly ash and/or mineral fines.
Preferably, the particle size of the graphite tailings, the copper tailings and the construction sand is independently 10-30 mm.
Preferably, the reinforcing material includes at least one of basalt fibers, polypropylene fibers, and glass fibers.
Preferably, the composite board in the step (6) is prepared from the following raw materials in percentage by mass: 40-70% of plastic, 10-40% of graphite tailings, 5-10% of graphite tailings, 10-40% of mineral addition powder and 1-10% of compatilizer.
Preferably, the composite board is prepared from the following raw materials in percentage by mass: 50-60% of plastic, 15-20% of graphite tailings, 5-10% of graphite tailings, 10-20% of mineral additive powder and 5-10% of compatilizer.
Preferably, the preparation method of the mineral compound fertilizer in the step (6) comprises the following steps:
1) Mixing the graphite tailings, the organic matters and the microbial agent to obtain a mixture;
2) Fermenting the mixture obtained in the step 1) to obtain the mineral compound fertilizer.
Preferably, the organic matter in step 1) comprises waste garden biomass and/or lignite humic acid.
Preferably, the temperature of the fermentation in the step 2) is 30-50 ℃, and the fermentation time is 5-8 days.
The invention provides a method for utilizing the whole resources of graphite ores, which comprises the steps of firstly carrying out primary separation on raw graphite ores to obtain crystalline graphite ores/cryptocrystalline graphite ores and low-grade graphite ores; respectively processing, wherein the low-grade graphite ore is subjected to stage grinding and stage flotation in sequence to obtain graphite concentrate and graphite tailings; then purifying and filtering the graphite concentrate in sequence to obtain crystalline graphite ore/aphanitic graphite ore; sequentially carrying out flotation and fine selection on the crystalline graphite ore to obtain graphite tailings and crystalline graphite concentrate; purifying the crystal graphite concentrate to obtain crystal graphite; or crushing, grinding and grading the aphanitic graphite ore in sequence to obtain graphite tailings and aphanitic graphite concentrate; purifying the aphanitic graphite concentrate to obtain aphanitic graphite; the obtained graphite tailings can be used as a raw material for preparing 3D printing building components, composite boards or mineral compound fertilizers, and the full resource utilization of graphite ores is realized. Experimental results show that the composite board prepared by taking the graphite tailings prepared by the method as raw materials has the electromagnetic shielding absorption peak strength of-13.24 to-21.45 dB and the heat conductivity of 0.1023 to 0.1452W/(m.k); the 28-day compressive strength of the prepared 3D printing building component is not lower than 45MPa; the organic matter content of the prepared mineral compound fertilizer can reach 36.50%, and the total nutrient content can reach 9.05%.
Drawings
Fig. 1 is a process flow diagram of a method for utilizing all resources of graphite ore provided in example 1.
Detailed Description
The invention provides a method for utilizing graphite ore full resources, which comprises the following steps:
(1) Carrying out primary separation on graphite raw ores to obtain crystalline graphite ores/aphanitic graphite ores and low-grade graphite ores;
(2) Sequentially carrying out stage grinding and stage flotation on the low-grade graphite ore obtained in the step (1) to obtain graphite concentrate and graphite tailings;
(3) Sequentially carrying out first purification and filtration on the graphite concentrate obtained in the step (2) to obtain crystalline graphite ore/aphanitic graphite ore;
(4-1) sequentially carrying out flotation and fine selection on the crystalline graphite ore obtained in the step (1) and the step (3) to obtain graphite tailings and crystalline graphite concentrate;
(5-1) carrying out second purification on the crystalline graphite concentrate obtained in the step (4-1) to obtain crystalline graphite;
or: (4-2) sequentially crushing, grinding and grading the aphanitic graphite ore obtained in the step (1) and the step (3) to obtain graphite tailings and aphanitic graphite concentrate;
(5-2) carrying out third purification on the aphanitic graphite concentrate obtained in the step (4-2) to obtain aphanitic graphite;
(6) And (3) using the graphite tailings obtained in the step (2) and the graphite tailings obtained in the step (4-1)/(4-2) to prepare 3D printing building components, composite boards or mineral compound fertilizers.
The invention carries out primary separation on the graphite raw ore to obtain crystalline graphite ore/crystalline graphite ore and low-grade graphite ore.
The process provided by the invention is applicable to any graphite raw ore, preferably to raw ore rich in crystalline graphite or raw ore rich in cryptocrystalline graphite.
In the invention, when the raw graphite ore is rich in crystalline graphite, the raw graphite ore is primarily selected to obtain crystalline graphite ore and low-grade graphite ore; and when the graphite raw ore is rich in aphanitic graphite, carrying out primary separation on the graphite raw ore to obtain aphanitic graphite ore and low-grade graphite ore.
The operation of the primary selection is not specially limited, and the conventional operation of the method is adopted to ensure that the graphite raw ore is processed to obtain the crystalline graphite ore/aphanitic graphite ore and the low-grade graphite ore.
After the low-grade graphite ore is obtained, the low-grade graphite ore is subjected to stage grinding and stage flotation in sequence to obtain graphite tailings and graphite concentrate.
In the present invention, the content of graphite in the low-grade graphite ore is preferably not more than 10wt%.
In the present invention, the staged milling is preferably wet milling; the mass content of the particles with the particle size of less than 0.074mm in the ore pulp obtained by stage grinding is preferably 60-80%; the mass percentage of the ore pulp is preferably 10-20%. The invention adopts stage grinding to crush the low-grade graphite ore so as to provide the material with the granularity meeting the requirement of the next ore dressing process.
In the present invention, the staged flotation preferably comprises the steps of:
I. performing roughing on the ore pulp obtained by stage grinding to obtain roughing tailings and roughing concentrate;
II. Grinding the rough concentrate obtained in the step I to obtain graphite concentrate;
and III, scavenging the rougher tailings obtained in the step I to obtain graphite concentrate and graphite tailings.
The invention preferably performs roughing on the ore pulp obtained by stage grinding to obtain roughed tailings and roughed concentrate.
In the invention, the collecting agent adopted by the rough concentration is preferably kerosene; the mass of the collecting agent is preferably 800-1000 g/t on the basis of ore pulp; the foaming agent adopted by the roughing is preferably pine oil; based on ore pulp, the mass of the foaming agent is preferably 50-100 g/t; the inhibitor adopted by the roughing is preferably water glass; the mass of the inhibitor is preferably 700-900 g/t based on the ore pulp.
After the rougher concentrate is obtained, the rougher concentrate is preferably ground by the invention to obtain the graphite concentrate.
In the present invention, the ore grinding is preferably wet grinding; the mass content of the particles with the particle size of less than 0.037mm in the concentrate is preferably 90-98%. The invention adopts ore grinding to crush the rough concentration so as to provide materials with granularity meeting the requirement of the next ore dressing process.
After the rougher tailings are obtained, the rougher tailings are preferably subjected to scavenging to obtain graphite concentrate and graphite tailings.
In the invention, the collecting agent adopted by scavenging is preferably kerosene; the mass of the collecting agent is preferably 300-350 g/t on the basis of the mass of the roughed tailings; the foaming agent adopted in the scavenging is preferably 2# oil; the mass of the foaming agent is preferably 30-60 g/t based on the mass of the roughed tailings.
After obtaining the graphite concentrate, the invention sequentially carries out first purification and filtration on the graphite concentrate to obtain the crystalline graphite ore/aphanitic graphite ore.
In the invention, when the graphite raw ore is raw ore rich in crystalline graphite, the graphite concentrate is subjected to first purification and filtration in sequence to obtain crystalline graphite ore; and when the graphite raw ore is rich in aphanitic graphite, sequentially carrying out first purification and filtration on the graphite concentrate to obtain the aphanitic graphite ore.
In the present invention, the first purification is preferably a chemical purification; the chemical purification preferably adopts dilute hydrochloric acid and hydrofluoric acid solution; the mass of the dilute hydrochloric acid is preferably 15-30 kg/t and the mass of the hydrofluoric acid solution is preferably 10-15 kg/t based on a dry graphite sample of graphite concentrate. The concentration of the dilute hydrochloric acid and hydrofluoric acid solution is not particularly limited in the present invention, and may be those known to those skilled in the art. In the present invention, the chemical purification is preferably performed under stirring. The stirring operation in the present invention is not particularly limited, and a stirring operation known to those skilled in the art may be employed. According to the invention, the first purification is adopted to remove impurities in the graphite concentrate, wherein hydrofluoric acid can react with the impurities in the graphite to generate water-soluble fluoride and volatile matters, so that the purpose of purification is achieved; the main chemical reactions are as follows:
Na 2 O+2HF＝2NaF+H 2 O
K 2 O+2HF＝2KF+H 2 O
Al 2 O 3 +6HF＝2AlF 3 +3H 2 O
SiO 2 +4HF＝SiF 4 ↑+2H 2 O
but the hydrofluoric acid reacts with CaO, mgO, etc. to obtain a precipitate,
CaO+2HF＝CaF 2 ↓+H 2 O
MgO+2HF＝MgF 2 ↓+H 2 O
in order to solve the problem of precipitation, a small amount of dilute hydrochloric acid is added into a hydrofluoric acid solution, so that the interference of impurity elements such as Ca, mg and the like can be removed.
The operation of the filtration is not particularly limited in the present invention, and a filtration operation known to those skilled in the art may be employed.
After the filtration is completed, the product obtained by the filtration is preferably dried to obtain the crystalline/cryptocrystalline graphite ore. The operation of the drying preferably used in the present invention is not particularly limited, and a drying operation known to those skilled in the art may be used.
After the crystalline graphite ore is obtained, the invention sequentially carries out flotation and concentration on the crystalline graphite ore to obtain graphite tailings and crystalline graphite concentrate.
In the present invention, the grain size of the crystalline graphite ore is preferably 100 mesh or more; when the particle size of the crystalline graphitic ore does not meet the above conditions, it is preferable in the present invention to perform coarse grinding on the crystalline graphitic ore. The present invention is not particularly limited to the specific operation of rough grinding of the crystalline graphite ore, and a rough grinding operation known to those skilled in the art may be employed.
In the present invention, the collector used in the flotation is preferably kerosene; the mass of the collecting agent is preferably 360-390 g/t based on the mass of the crystalline graphite ore; the foaming agent adopted by the flotation is preferably 2# oil; the mass of the foaming agent is preferably 40-79 g/t based on the mass of the crystalline graphite ore; the inhibitor adopted by the flotation is preferably water glass; the mass of the inhibitor is preferably 10-20 kg/t based on the mass of the crystalline graphite ore. The invention can further improve the quality of the crystalline graphite ore by controlling the type and the dosage of the medicament adopted by the flotation.
In the present invention, the number of selection is preferably two; the collecting agent adopted in each concentration is preferably kerosene; the mass of the collecting agent is preferably 300-350 g/t based on the mass of a dry sample of the selected graphite; the foaming agent adopted in each concentration is preferably 2# oil; the mass of the foaming agent is preferably 30-60 g/t based on the mass of a dry sample of the selected graphite; the inhibitor adopted for each concentration is preferably water glass; the mass of the inhibitor is preferably 1-10 kg/t based on the dry sample mass of the selected graphite. The invention can further improve the quality of the crystalline graphite ore by controlling the type and the dosage of the adopted medicament for concentration, thereby realizing the separation of the graphite tailings and the crystalline graphite concentrate.
After the crystalline graphite concentrate is obtained, the crystalline graphite concentrate is subjected to second purification to obtain crystalline graphite.
In the present invention, the second purification is preferably: mixing the crystal graphite concentrate with petroleum coke, and purifying at 2900-3100 ℃ for 9-12 h to obtain the crystal graphite. The invention can further improve the graphitization degree of the crystal graphite concentrate by controlling the temperature and time of the second purification, thereby obtaining high-quality crystal graphite.
In the invention, the mass of the petroleum coke is preferably 300-800 g/t based on the mass of the crystalline graphite concentrate. In the invention, petroleum coke is a graphitization carburant, and the graphitization degree of the crystalline graphite concentrate can be improved, so that high-quality crystalline graphite is obtained.
In the present invention, the mixing of the crystalline graphite concentrate with the petroleum coke is preferably carried out in a graphitization furnace. The source of the graphitization furnace is not particularly limited in the present invention, and any equipment known to those skilled in the art may be used.
After the cryptocrystalline graphite ore is obtained, the cryptocrystalline graphite ore is sequentially crushed, ground and classified to obtain graphite tailings and cryptocrystalline graphite concentrate.
In the present invention, the pulverization is preferably carried out by coarse pulverization and intermediate pulverization in this order. In the present invention, the particle size of the product obtained by the coarse crushing is preferably 0.5mm or less; the particle size of the product obtained by the medium crushing is preferably less than or equal to 0.074mm. The operation of the coarse crushing and the intermediate crushing is not particularly limited in the invention, as long as the particle size of the product obtained by the coarse crushing and the particle size of the product obtained by the intermediate crushing are ensured to meet the requirements.
After the pulverization is completed, the present invention preferably dries the product obtained by the pulverization. The present invention is not particularly limited to the above-mentioned drying, and the drying operation known to those skilled in the art may be employed.
In the present invention, the ore grinding is preferably wet grinding; the volume concentration of the ore pulp obtained by grinding is preferably 10-15%; the particle size of particles in the ore pulp obtained by grinding is less than 0.047mm. The ore grinding is adopted in the invention to crush the crushed product again so as to provide the material with the granularity meeting the requirement of the next ore dressing process.
In the present invention, the classification preferably comprises the steps of:
A. screening ore pulp obtained by grinding to obtain concentrate with the granularity of more than or equal to 200 meshes and concentrate with the granularity of less than 200 meshes;
B. grinding the concentrate with the granularity of less than 200 meshes obtained in the step A, and drying to obtain concentrate with the granularity of less than 100 meshes in a proportion of 68-72 wt%;
C. and B, mixing the concentrate with the granularity of less than 100 meshes and the proportion of 68-72 wt% obtained in the step B with the concentrate with the granularity of more than or equal to 200 meshes obtained in the step A, and then carrying out flotation to obtain graphite tailings and aphanitic graphite concentrate.
The ore pulp obtained by grinding is preferably screened to obtain the concentrate with the granularity of more than or equal to 200 meshes and the concentrate with the granularity of less than 200 meshes.
In the present invention, the sieving is preferably performed in a vibrating sieve. The present invention is not particularly limited as to the source of the vibrating screen, and a vibrating screen well known to those skilled in the art may be used.
After the concentrate with the granularity of less than 200 meshes is obtained, the concentrate with the granularity of less than 200 meshes is preferably ground, and the concentrate with the granularity of less than 100 meshes in a proportion of 68-72 wt% is obtained after drying. The operation of the ore grinding is not specially limited by the invention, as long as the ratio of 68-72 wt% of the final obtained concentrate with the granularity less than 100 is ensured.
After the concentrate with the granularity of less than 100 meshes and the proportion of 68-72 wt% and the concentrate with the granularity of more than or equal to 200 meshes are obtained, the concentrate with the granularity of less than 100 meshes and the proportion of 68-72 wt% and the concentrate with the granularity of more than or equal to 200 meshes are mixed and then subjected to flotation to obtain the graphite tailings and the aphanitic graphite concentrate.
The operation of the mixing is not particularly limited in the present invention, and the technical scheme for preparing the mixed material, which is well known to those skilled in the art, can be adopted.
In the invention, the collector used for the flotation is preferably coal tar; the mass of the collecting agent is preferably 360-390 g/t on the basis of the mass of the dry graphite sample; the foaming agent adopted by the flotation is preferably 2# oil and/or 4# oil; the mass of the foaming agent is preferably 40-60 g/t based on the mass of a dry graphite sample; the inhibitor adopted by the flotation is preferably water glass and sodium fluosilicate; the mass of the water glass is preferably 1-10 kg/t based on the mass of the dry graphite sample; the mass of the sodium fluosilicate is preferably 1-10 kg/t. The invention can further improve the quality of the aphanitic graphite ore by controlling the type and the dosage of the medicament adopted by the flotation.
After the aphanitic graphite concentrate is obtained, the aphanitic graphite concentrate is subjected to third purification to obtain aphanitic graphite.
In the present invention, the third purification is preferably: mixing the aphanitic graphite concentrate with petroleum coke, and purifying at 2900-3100 ℃ for 9-12 h to obtain aphanitic graphite. The invention can further improve the graphitization degree of the crystalline graphite concentrate by controlling the temperature and time of the third purification, thereby obtaining high-quality aphanitic graphite.
In the invention, the mass ratio of the petroleum coke is preferably 600-1000 g/t based on the mass of the aphanitic graphite concentrate. In the invention, the petroleum coke is a graphitization carburant, and the graphitization degree of the aphanitic graphite concentrate can be improved, so that high-quality aphanitic graphite is obtained.
In the present invention, the mixing of the aphanitic graphite concentrate with petroleum coke is preferably carried out in a graphitization furnace. The source of the graphitization furnace is not particularly limited in the present invention, and any equipment known to those skilled in the art may be used.
After the graphite tailings are obtained, the graphite tailings are used for preparing 3D printing building components, composite plates or mineral compound fertilizers.
In the present invention, the 3D printed building element preferably comprises the following raw materials: a main agent, a reinforcing material and an auxiliary agent;
the main agent is preferably prepared from the following raw materials in percentage by mass: 20-30% of hydraulic cementing material, 10-20% of admixture, 40-60% of graphite tailings, 0-5% of copper tailings and 0-10% of construction sand;
the reinforcing material is preferably 0.2 to 0.5% by mass of the main agent.
In the present invention, the raw material of the 3D printed construction element preferably comprises a base agent. In the present invention, the raw material of the main agent preferably includes 20 to 30%, more preferably 25%, of the hydraulic binder, in a percentage by mass of the main agent. In the present invention, the hydraulic binder is preferably portland cement (PO 42.5) and/or belite cement; when the hydraulic binder is portland cement and/or belite cement, the mass ratio of portland cement to belite cement is preferably 4:1. in the present invention, the hydraulic binder can bind other raw materials into a whole, and can be hardened in water more favorably, and has excellent strength.
In the invention, the raw materials of the main agent preferably further comprise 10-20% of admixture, and more preferably 15% of the main agent by mass percentage. In the present invention, the admixture preferably comprises fly ash and/or mineral powder; when the admixture is fly ash and mineral powder, the mass ratio of fly ash to mineral powder is preferably 1:3; the particle size of the admixture is preferably 8 to 12 μm. In the invention, the composition of the fly ash is preferably as follows by mass percent: al (Al) 2 O 3 15～35％，SiO 2 20～45％，Fe 2 O 3 2-20 percent of CaO and less than or equal to 25 percent of CaO. In the invention, the admixture can be matched with other components to improve the strength of the 3D printing building component.
In the invention, the raw materials of the main agent preferably also comprise 40-60% of graphite tailings by weight percentage, and more preferably 45-50% of the main agent. In the invention, the particle size of the graphite tailings is preferably 10-30 mm; the graphite tailings preferably have the following composition in percentage by mass: siO 2 2 30～60％，Al 2 O 3 5～20％，CaO 5～25％，Fe 2 O 3 3～15％，K 2 O<6% and MgO 1-3%. In the invention, the graphite tailings serving as the aggregate can be matched with other components to improve the strength of the 3D printing building componentAnd (4) degree.
In the invention, the raw material of the main agent preferably further comprises 0-5% of copper tailings by weight percent, and more preferably 2-3% by weight percent of the main agent. In the invention, the particle size of the copper tailings is preferably 10-30 mm. In the invention, the copper tailings serving as the aggregate can be matched with other components to improve the strength of the 3D printing building component.
In the invention, the raw material of the main agent preferably further comprises 0-10% of construction sand by mass percent of the main agent, and more preferably 5-10% of construction sand by mass percent of the main agent. In the present invention, the particle size of the construction sand is preferably 10 to 30mm. In the invention, the building sand is used as an aggregate, and can be matched with other components to improve the strength of the 3D printing building component.
In the present invention, the raw material of the 3D printed construction element preferably further comprises a reinforcing material; the reinforcing material is preferably 0.2 to 0.5% by mass of the main agent. In the present invention, the reinforcing material preferably includes at least one of basalt fiber, polypropylene fiber, and glass fiber; when the reinforcing materials are two of basalt fibers, polypropylene fibers and glass fibers, the mass ratio of the two reinforcing materials is preferably 1:1; when the reinforcing materials are basalt fibers, polypropylene fibers and glass fibers, the mass ratio of the basalt fibers to the polypropylene fibers to the glass fibers is preferably 1:1:1; the length of the reinforcing material is preferably 8 to 30mm, more preferably 18mm. In the invention, the reinforcing material can be matched with other components to improve the strength of the 3D printing building component.
In the present invention, the raw material of the 3D printed building element preferably further comprises an auxiliary agent. In the present invention, the auxiliary is preferably at least one of a water reducing agent, a volume stabilizer, and a defoaming agent.
In the invention, the mass of the water reducing agent is preferably 0.1-0.5 wt% of the mass of the main agent; the water reducing agent is preferably at least one of a naphthalene-based high-efficiency water reducing agent and a polycarboxylic acid high-efficiency water reducing agent.
In the invention, the volume stabilizer is preferably 0.1-0.5 wt% of the mass of the main agent; the volume stabilizer is preferably at least one of hydroxyethyl cellulose ether and hydroxymethyl cellulose ether.
In the invention, the mass of the defoaming agent is preferably 0.1 to 0.5wt% of the mass of the main agent; the defoaming agent is preferably an ether or an organic oil or fat.
The invention adopts the graphite tailings as the aggregate, and is matched with other components, so that the strength of the 3D printing building component is improved, the graphite tailings resource is fully utilized, the printed building is firmer and more durable, the environment-friendly, high-efficiency and energy-saving effects are realized, the building garbage and the building dust are reduced, the noise pollution is reduced, the labor intensity of workers is reduced, and the building material is saved.
In the present invention, the method for preparing the 3D printed building element preferably comprises the steps of:
a. mixing the main agent, the reinforcing material and the auxiliary agent to obtain a mixed material;
b. mixing the mixed material obtained in the step a with water to obtain slurry;
c. and c, performing 3D printing on the slurry obtained in the step b to obtain a 3D printing building component.
The invention preferably mixes the main agent, the reinforcing material and the auxiliary agent to obtain a mixed material. The operation of mixing the main agent, the reinforcing material and the auxiliary agent is not particularly limited in the invention, and the technical scheme for preparing the mixed material, which is well known to those skilled in the art, can be adopted.
After the mixed material is obtained, the invention preferably mixes the mixed material with water to obtain the slurry.
In the present invention, the amount of water is not particularly limited, and may be adjusted according to common knowledge.
The operation of mixing the mixed material with water is not particularly limited in the invention, and the technical scheme for preparing the mixed material, which is well known to those skilled in the art, can be adopted.
After the slurry is obtained, the slurry is subjected to 3D printing to obtain a 3D printing building component.
In the present invention, the 3D printing preferably employs contour printing. The operation of the outline printing is not particularly limited in the present invention, and may be an operation known to those skilled in the art.
The preparation method of the 3D printing building component has high precision, is suitable for printing 1-3 layers of low-rise buildings, has wide application area range, can save 30-60% of building materials and reduce 50-80% of labor.
In the invention, the composite board is preferably prepared from the following raw materials in percentage by mass: 40-70% of plastic, 10-40% of graphite tailings, 5-10% of graphite tailings, 10-40% of mineral addition powder and 1-10% of compatilizer.
In the present invention, the raw material of the composite board preferably includes 40 to 70% by mass of plastic, and more preferably 50 to 60% by mass of plastic. In the present invention, the plastic is preferably at least one of polyvinyl chloride, polypropylene, polyethylene, waste polyvinyl chloride, waste polypropylene, and waste polyethylene. In the present invention, the plastic is a base material.
In the invention, the raw material of the composite board preferably comprises 10-40% of graphite tailings by mass, and more preferably 15-20% of graphite tailings by mass. In the invention, the composition of the graphite tailings is preferably as follows: siO 2 2 30～60％，Al 2 O 3 5～20％，CaO 5～25％，Fe 2 O 3 3～15％，K 2 O<6 percent and 1 to 3 percent of MgO; the granularity of the graphite tailings is preferably 800-1200 meshes. In the invention, the graphite tailings can be uniformly dispersed in the plastic matrix, and the heat conduction and electromagnetic shielding performance of the composite board can be improved by matching with other raw materials.
In the invention, the raw materials of the composite board preferably comprise 5-10% of graphite tailings by mass percentage, and more preferably 7-8% of graphite tailings by mass percentage. In the invention, the granularity of the graphite tailing is 800-1000 meshes; the composition of the graphite tailings is preferably ultrafine graphite. In the invention, the graphite tailings can be matched with other raw materials to improve the heat conduction and electromagnetic shielding performance of the composite board together.
In the present invention, the raw material of the composite board preferably includes 10 to 40% by mass of mineral addition powder, and more preferably 10 to 20% by mass of mineral addition powder. In the present inventionIn the invention, the mineral addition powder preferably comprises at least one of red mud and fly ash; the granularity of the mineral addition powder is preferably 600-800 meshes. In the invention, the red mud preferably comprises the following components in percentage by mass: al (aluminum) 2 O 3 15～25％，SiO 2 30～45％，Fe 2 O 3 20～29％，Na 2 O is less than or equal to 5 percent and TiO 2 1 to 6 percent; the composition of the fly ash is preferably as follows by mass percent: by mass percentage, al 2 O 3 15～35％，SiO 2 20～45％，Fe 2 O 3 2-20% and CaO is less than or equal to 25%. In the invention, the mineral addition powder can be matched with other raw materials to jointly improve the heat conduction and electromagnetic shielding performance of the composite board.
In the present invention, the raw material of the composite board preferably includes 1 to 10% by mass of a compatibilizer, and more preferably 5 to 10% by mass. In the present invention, the compatibilizing agent is preferably at least one of a cyclic acid anhydride type and maleic anhydride. In the invention, the compatilizer can improve the compatibility of all raw materials, thereby further improving the heat conduction and electromagnetic shielding performance of the composite board.
When the graphite tailings are used as raw materials to prepare the composite board, the powder and the compatilizer are added in cooperation with the plastics, the graphite tailings and the minerals, so that the heat conduction performance and the electromagnetic shielding performance of the composite board are improved.
In the present invention, the method for preparing the composite board preferably includes the steps of:
(1) mixing graphite tailings, plastics, graphite tailings, mineral addition powder and a compatilizer to obtain a mixed material;
(2) and (2) carrying out compression molding on the mixed material obtained in the step (1) to obtain the composite board.
According to the invention, the graphite tailings, the plastic, the graphite tailings, the mineral addition powder and the compatilizer are preferably mixed to obtain the mixed material.
In the invention, the mixing of the graphite tailings, the plastics, the graphite tailings, the mineral addition powder and the compatilizer is preferably carried out in an internal mixer or an open mill; the mixing temperature is preferably 100-170 ℃; the mixing time is preferably 0.5 to 2 hours. The sources of the internal mixer and the open mill are not particularly limited by the present invention, and the equipment known to those skilled in the art can be used.
After the mixed material is obtained, the mixed material is preferably subjected to compression molding to obtain the composite board.
In the present invention, the press molding is preferably performed in a vulcanizer; the absolute pressure for compression molding is preferably 10-20 MPa; the compression molding temperature is preferably 100-170 ℃; the time for the compression molding is preferably 2 to 3min. The source of the vulcanizer of the present invention is not particularly limited, and any equipment known to those skilled in the art may be used.
The preparation method of the composite board provided by the invention is simple in process and is suitable for industrial production.
In the present invention, the preparation method of the mineral compound fertilizer preferably comprises the following steps:
1) Mixing the graphite tailings, the organic matters and the microbial agent to obtain a mixture;
2) Fermenting the mixture obtained in the step 1) to obtain the mineral compound fertilizer.
According to the invention, the graphite tailings, the organic matters and the microbial liquid are preferably mixed to obtain a mixture.
In the invention, the particle size of the graphite tailings is preferably 0.0004-5 mm; the composition of the graphite tailings is preferably as follows: siO 2 2 30～60％，Al 2 O 3 5～20％，CaO 5～25％，Fe 2 O 3 3～15％，K 2 O<6 percent and 1 to 3 percent of MgO. In the invention, the graphite tailings can improve the physicochemical property of soil.
In the invention, the organic matter preferably comprises waste garden biomass and/or lignite humic acid; the mass ratio of the waste garden biomass to the lignite humic acid is preferably 5:1. in the present invention, the mass of the organic matter is preferably 57 to 111% of the graphite tailings. In the invention, the organic matter is a main source of soil nutrients, promotes the growth and development of crops, promotes the formation of a soil structure, improves the physical properties of soil, improves the soil structure, improves the fertilizer retention capacity and the buffer performance of the soil, and improves the soil nutrient.
In the invention, the microbial liquid is preferably obtained by extracting a Natural microbial community by using a 'Wahua I' microbial agent and continuously culturing for more than 4 hours at 85 ℃ by using a Natural-Biotechnology Natural culture technology; the mass of the microbial liquid is preferably 2-3% of that of the graphite tailings, and more preferably 2.7%. In the present invention, the microbial solution is used for fermentation.
The operation of mixing the graphite tailings, the organic matters and the microbial liquid is not particularly limited, and the technical scheme for preparing the mixed material, which is well known by the technical personnel in the field, is adopted.
After the mixture is obtained, the mixture is preferably fermented to obtain the mineral compound fertilizer.
In the present invention, the temperature of the fermentation is preferably 30 to 50 ℃, more preferably 40 ℃; the fermentation time is preferably 5 to 8 days, and more preferably 7 days; the fermentation is preferably carried out in a fermenter.
According to the invention, the graphite tailings, the waste garden biomass and/or lignite humic acid are used as raw materials, and the mineral compound fertilizer is prepared by a microbial fermentation method, so that the problem of graphite tailing accumulation is solved, the comprehensive utilization of solid wastes is realized, and the prepared mineral compound fertilizer can be used as a product, so that a new way is provided for the comprehensive utilization of the graphite tailings.
The sources of the raw materials other than the graphite tailings are not particularly limited in the present invention, and commercially available products known to those skilled in the art may be used.
The invention provides a method for utilizing the whole resources of graphite ores, which comprises the steps of firstly carrying out primary separation on raw graphite ores to obtain crystalline graphite ores/cryptocrystalline graphite ores and low-grade graphite ores; respectively treating the low-grade graphite ores, wherein the low-grade graphite ores are subjected to stage grinding and stage flotation in sequence to obtain graphite concentrates and graphite tailings; then purifying and filtering the graphite concentrate in sequence to obtain crystalline graphite ore/aphanitic graphite ore; carrying out flotation and fine selection on the crystalline graphite ore in sequence to obtain graphite tailings and crystalline graphite concentrate; purifying the crystalline graphite concentrate to obtain crystalline graphite; or crushing, grinding and grading the aphanitic graphite ore in sequence to obtain graphite tailings and aphanitic graphite concentrate; purifying the aphanitic graphite concentrate to obtain aphanitic graphite; the obtained graphite tailings can be used as a raw material for preparing 3D printing building components, composite boards or mineral compound fertilizers, and the full resource utilization of graphite ores is realized.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
Example 1
A method for utilizing graphite ore full resources comprises the following steps:
(1) Carrying out primary separation on the graphite raw ore to obtain crystalline graphite ore and low-grade graphite ore; wherein, the content of graphite in the low-grade graphite ore is 10wt%;
(2) Carrying out stage grinding and stage flotation on the low-grade graphite ore obtained in the step (1) in sequence to obtain graphite concentrate and graphite tailings; wherein, the mass content of particles with the particle size of less than 0.074mm in the ore pulp obtained by stage grinding is 60 percent; the mass percentage of the ore pulp is 10 percent;
the stage flotation comprises the following steps:
I. roughly separating ore pulp obtained by stage grinding to obtain roughly separated tailings and roughly separated concentrate; wherein the collecting agent is kerosene with the mass of 900g/t; the foaming agent is terpineol oil with the mass of 80g/t; the inhibitor is water glass, and the mass of the inhibitor is 800g/t;
II. Grinding the rough concentrate obtained in the step I to obtain graphite concentrate; wherein, the ore grinding is wet grinding; the mass content of particles with the particle size of less than 0.037mm in the concentrate is 90-98%;
III, scavenging the rougher tailings obtained in the step I to obtain graphite concentrate and graphite tailings; wherein the collecting agent adopted by scavenging is kerosene with the mass of 330g/t; the foaming agent is 2# oil; the mass is 50g/t;
(3) Sequentially carrying out first purification, filtration and drying on the graphite concentrate obtained in the step (2) to obtain crystalline graphite ore; wherein the first purification is a chemical purification; the chemical purifying agent is dilute hydrochloric acid or hydrofluoric acid solution; the mass of the dilute hydrochloric acid is 20kg/t, and the mass of the hydrofluoric acid solution is 15kg/t;
(4-1) sequentially carrying out flotation and fine selection on the crystalline graphite ore obtained in the step (1) and the step (3) to obtain graphite tailings and crystalline graphite concentrate; wherein the granularity of the crystalline graphite ore is more than 100 meshes; the collecting agent is kerosene with the mass of 370g/t; the foaming agent is No. 2 oil with the mass of 60g/t; the inhibitor is water glass with the mass of 15kg/t; the selection times are two times; the collecting agent adopted in each fine concentration is kerosene, and the mass of the collecting agent is 300g/t; the foaming agent adopted in each selection is 2# oil, and the mass is 40g/t; the inhibitors adopted in each selection are all water glass, and the mass is 8kg/t;
(5) Mixing the crystalline graphite concentrate obtained in the step (4-1) with petroleum coke in a graphitization furnace, and purifying at 3000 ℃ for 10 hours to obtain crystalline graphite; wherein the mass of the petroleum coke is 800g/t on the basis of the mass of the crystalline graphite concentrate;
(6) Using the graphite tailings obtained in the steps (2) and (4-1) to prepare a composite board;
the graphite tailing consists of SiO 2 30～60％，Al 2 O 3 5～20％，CaO 5～25％，Fe 2 O 3 3～15％，K 2 O<6 percent and 1 to 3 percent of MgO;
the composite board is prepared from the following raw materials in percentage by mass: 60% of plastic, 15% of graphite tailings, 10% of mineral addition powder and 5% of compatilizer;
wherein the plastic is polyvinyl chloride; the particle size of the graphite tailings is 1200 meshes; the particle size of the graphite tailing is 1000 meshes; the graphite tailing comprises ultrafine graphite; the particle size of the mineral addition powder is 800Mesh; the mineral addition powder is red mud; the red mud comprises the following components in percentage by mass: al (Al) 2 O 3 15～25％，SiO 2 30～45％，Fe 2 O 3 20～29％，N a2 O is less than or equal to 5 percent and TiO 2 1 to 6 percent; the fly ash comprises the following components in percentage by mass: al (Al) 2 O 3 15～35％，SiO 2 20～45％，Fe 2 O 3 2-20 percent of CaO, less than or equal to 25 percent of CaO; the compatilizer is maleic anhydride;
the preparation method of the composite board comprises the following steps:
(1) mixing graphite tailings, plastics, graphite tailings, mineral addition powder and a compatilizer in an open mill to obtain a mixed material; wherein the mixing temperature is 105 ℃, and the mixing time is 0.5h;
(2) carrying out compression molding on the mixed material obtained in the step (1) in a vulcanizing machine to obtain a composite board with the thickness of 3 mm; wherein the absolute pressure of the compression molding is 20MPa, the temperature is 170 ℃, and the time is 3min.
The process flow diagram of the method for utilizing the graphite ore full resources provided by the embodiment 1 is shown in figure 1.
The composite board prepared in example 1 was subjected to a performance test to obtain an electromagnetic shielding absorption peak having a strength of-13.24 dB and a thermal conductivity of 0.1452W/(m.k).
Example 2
The formula content of the composite board in the example 1 is adjusted, and other steps are unchanged, namely the composite board is prepared from the following raw materials in percentage by mass: 65% of plastic, 15% of graphite tailings, 5% of graphite tailings, 10% of mineral addition powder and 5% of compatilizer;
the composite board prepared in example 2 was subjected to a performance test to obtain an electromagnetic shielding absorption peak having a strength of-19.24 dB and a thermal conductivity of 0.1023W/(m.k).
Example 3
The formula content of the composite board in the example 1 is adjusted, and other steps are unchanged, namely the composite board is prepared from the following raw materials in percentage by mass: 60% of plastic, 20% of graphite tailings, 5% of mineral addition powder and 10% of compatilizer;
the composite board prepared in the embodiment 3 is subjected to performance test, and the strength of the electromagnetic shielding absorption peak is-21.45 dB, and the thermal conductivity is 0.1235W/(m.k).
Example 4
Step (6) of example 1 was replaced with: the graphite tailings obtained in the steps (2) and (4-1) are used for preparing a 3D printing building component, and other steps are not changed;
the 3D printing building component is prepared from a main agent, a reinforcing material and an auxiliary agent;
the main agent is prepared from the following raw materials in percentage by mass: 30% of hydraulic cementing material, 20% of admixture, 40% of graphite tailings and 10% of construction sand;
the reinforcing material accounts for 0.2 percent of the mass of the main agent;
the auxiliary agent accounts for 0.21 percent of the mass of the main agent (0.2 percent of the water reducing agent and 0.1 thousandth of the volume stabilizer);
wherein the hydraulic cementing material is PO 42.5 and belite cement; the mass ratio of the portland cement to the belite cement is 4:1; the admixture is fly ash and mineral powder; the mass ratio of the fly ash to the mineral powder is 1:3, the grain diameter is 8-12 μm; the fly ash comprises the following components in percentage by mass: al (Al) 2 O 3 15～35％，SiO 2 20～45％，Fe 2 O 3 2-20 percent of CaO, less than or equal to 25 percent of CaO; the particle size of the graphite tailings is 10-30 mm; the graphite tailings comprise the following components in percentage by mass: siO 2 2 30～60％，Al 2 O 3 5～20％，CaO 5～25％，Fe 2 O 3 3～15％，K 2 O<6 percent and 1 to 3 percent of MgO; the grain size of the building sand is 10-30 mm; the reinforced material is basalt fiber, and the length of the reinforced material is 8-30 mm; the water reducing agent is a polycarboxylic acid high-efficiency water reducing agent; the volume stabilizer is hydroxymethyl cellulose ether;
the preparation method of the 3D printing building component comprises the following steps:
a. mixing a hydraulic cementing material, an admixture, graphite tailings, building sand, a reinforcing material and an auxiliary agent to obtain a mixed material;
b. mixing the mixed material obtained in the step a with water to obtain slurry; wherein the mass of the water is 0.12 of the mixed material;
c. and c, conveying the slurry obtained in the step b to a printing sprayer through a conveying system, and performing 3D printing by adopting a contour printing process to obtain a 3D printing building component.
After the 3D printing building component prepared in example 4 is cured and molded, a performance test is performed, and the compressive strength of the building component reaches 67MPa in 28 days.
Example 5
The formulation and preparation method of the 3D printed building element of example 4 was changed, with the other steps unchanged;
the 3D printing building component is prepared from a main agent, a reinforcing material and an auxiliary agent;
the main agent is prepared from the following raw materials in percentage by mass: 30% of hydraulic cementing material, 10% of admixture, 45% of graphite tailings, 5% of copper tailings and 10% of construction sand;
the reinforcing material accounts for 0.2 percent of the mass of the main agent;
the auxiliary agent accounts for 0.41 percent of the mass of the main agent (0.4 percent of water reducing agent and 0.1 thousandth of volume stabilizer);
wherein the hydraulic cementing material is PO 42.5 and belite cement; the mass ratio of the Portland cement to the belite cement is 4:1; the admixture is mineral powder; the particle size of the mineral powder is 8-12 mu m; the particle size of the graphite tailings is 10-30 mm; the graphite tailings comprise the following components in percentage by mass: siO 2 2 30～60％，Al 2 O 3 5～20％，CaO 5～25％，Fe 2 O 3 3～15％，K 2 O<6 percent and 1 to 3 percent of MgO; the grain diameters of the copper tailings and the construction sand are both 10-30 mm; the reinforced material is basalt fiber, and the length of the reinforced material is 8-30 mm; the water reducing agent is a polycarboxylic acid high-efficiency water reducing agent; the volume stabilizer is hydroxymethyl cellulose ether;
the preparation method of the 3D printing building component comprises the following steps:
a. mixing a hydraulic cementing material, an admixture, graphite tailings, copper tailings, construction sand, a reinforcing material and an auxiliary agent to obtain a mixed material;
b. mixing the mixed material obtained in the step a with water to obtain slurry; wherein the mass of the water is 0.14 of the mixed material;
c. and c, conveying the slurry obtained in the step b to a printing spray head through a conveying system, and performing 3D printing by adopting a contour printing process to obtain a 3D printing building component.
After the 3D printing building component prepared in example 5 is cured and molded, a performance test is performed, and the compressive strength of 60MPa in 28 days is obtained.
Example 6
The formulation and preparation method of the 3D printed building element of example 4 was changed, with the other steps unchanged;
the 3D printing building component is prepared from a main agent, a reinforcing material and an auxiliary agent;
the main agent is prepared from the following raw materials in percentage by mass: 30% of hydraulic cementing material, 20% of admixture and 50% of graphite tailings;
the reinforcing material accounts for 0.2 percent of the mass of the main agent;
the auxiliary agent accounts for 0.315 percent of the mass of the main agent (0.3 percent of water reducing agent and 0.15 thousandth of volume stabilizer);
wherein the hydraulic cementing material is PO 42.5 and belite cement; the mass ratio of the portland cement to the belite cement is 4:1; the admixture is fly ash and mineral powder; the mass ratio of the fly ash to the mineral powder is 1:3, the grain diameter is 8-12 mu m; the fly ash comprises the following components in percentage by mass: al (Al) 2 O 3 15～35％，SiO 2 20～45％，Fe 2 O 3 2-20% of CaO and less than or equal to 25%; the particle size of the graphite tailings is 10-30 mm; the graphite tailings comprise the following components in percentage by mass: siO 2 2 30～60％，Al 2 O 3 5～20％，CaO 5～25％，Fe 2 O 3 3～15％，K 2 O<6 percent and 1 to 3 percent of MgO; the reinforcing material is basalt fiber, and the length of the reinforcing material is 8-30 mm; the water reducing agent is a polycarboxylic acid high-efficiency water reducing agent; the volume stabilizer is hydroxymethyl cellulose ether;
the preparation method of the 3D printing building component comprises the following steps:
a. mixing a hydraulic cementing material, an admixture, graphite tailings, a reinforcing material and an auxiliary agent to obtain a mixed material;
b. mixing the mixed material obtained in the step a with water to obtain slurry; wherein the mass of the water is 0.14 of the mixed material;
c. and c, conveying the slurry obtained in the step b to a printing spray head through a conveying system, and performing 3D printing by adopting a contour printing process to obtain a 3D printing building component.
After the 3D printed building component prepared in example 6 was cured and molded, a performance test was performed to obtain a compressive strength of 61MPa after 28 days.
Example 7
Step (6) of example 1 was replaced with: the graphite tailings obtained in the steps (2) and (4-1) are used for preparing a mineral compound fertilizer, and other steps are unchanged;
the preparation method of the mineral compound fertilizer comprises the following steps:
1) Mixing the graphite tailings, the organic matters and the microbial liquid to obtain a mixture; wherein the organic matter is waste garden biomass and lignite humic acid; 46.8wt% of graphite tailings, 43.1wt% of waste garden biomass, 8.8wt% of lignite humic acid and 1.3wt% of microbial liquid; the particle size of the graphite tailings is 0.0004-5 mm; the graphite tailings comprise the following components: siO 2 2 30～60％，Al 2 O 3 5～20％，CaO 5～25％，Fe 2 O 3 3～15％，K 2 O<6 percent and 1 to 3 percent of MgO; the microbial agent solution is 'Waihua I' microbial agent extracted Natural microbial community, and is obtained by continuously culturing for more than 4h at 85 ℃ by Natural-Biotechnology Natural culture technology;
2) Fermenting the mixture obtained in the step 1) in a fermentation basin to obtain a mineral compound fertilizer; wherein the fermentation temperature is 40 deg.C, and the fermentation time is 7 days.
The performance test of the mineral compound fertilizer prepared in example 7 showed that the organic matter content of the mineral compound fertilizer was 36.50% and the total nutrient content was 9.05%.
Example 8
Step (6) of example 1 was replaced with: the graphite tailings obtained in the steps (2) and (4-1) are used for preparing a mineral compound fertilizer, and other steps are not changed;
the preparation method of the mineral compound fertilizer comprises the following steps:
1) Mixing the graphite tailings, the waste garden biomass and the microbial liquid to obtain a mixture; wherein the graphite tailings account for 62.6wt%, the waste garden biomass accounts for 35.7wt%, and the microbial liquid accounts for 1.7wt%; the particle size of the graphite tailings is 0.0004-5 mm; the graphite tailings comprise the following components: siO 2 2 30～60％，Al 2 O 3 5～20％，CaO 5～25％，Fe 2 O 3 3～15％，K 2 O<6 percent and 1 to 3 percent of MgO; the microbial liquid is obtained by extracting a Natural microbial community from 'Wahua I' microbial agent and continuously culturing for more than 4 hours at 85 ℃ by a Natural-Biotechnology Natural culture technology;
2) Fermenting the mixture obtained in the step 1) in a fermentation basin to obtain a mineral compound fertilizer; wherein the fermentation temperature is 40 deg.C, and the fermentation time is 7 days.
The performance test of the mineral compound fertilizer prepared in example 8 showed that the organic matter content of the mineral compound fertilizer was 27.83% and the total nutrient content was 7.34%.
Example 9
A method for utilizing graphite ore full resources comprises the following steps:
(1) Carrying out primary separation on the graphite raw ore to obtain aphanitic graphite ore and low-grade graphite ore; wherein, the content of graphite in the low-grade graphite ore is 10wt%;
(2) Sequentially carrying out stage grinding and stage flotation on the low-grade graphite ore obtained in the step (1) to obtain graphite concentrate and graphite tailings; wherein, the mass content of particles with the particle size of less than 0.074mm in the ore pulp obtained by stage grinding is 60 percent; the mass percentage of the ore pulp is 10 percent;
the stage flotation comprises the following steps:
I. roughly separating ore pulp obtained by stage grinding to obtain roughly separated tailings and roughly separated concentrate; wherein the collecting agent is kerosene with the mass of 900g/t; the foaming agent is terpineol oil with the mass of 80g/t; the inhibitor is water glass, and the mass of the inhibitor is 800g/t;
II. Grinding the rough concentrate obtained in the step I to obtain graphite concentrate; wherein, the ore grinding is wet grinding; the mass content of particles with the particle size of less than 0.037mm in the concentrate is 90-98%;
III, scavenging the rougher tailings obtained in the step I to obtain graphite concentrate and graphite tailings; the collecting agent adopted by scavenging is kerosene, and the mass of the collecting agent is 330g/t; the foaming agent is 2# oil; the mass is 50g/t;
(3) Sequentially carrying out first purification, filtration and drying on the graphite concentrate obtained in the step (2) to obtain aphanitic graphite ore; wherein the first purification is a chemical purification; the chemical purification adopts dilute hydrochloric acid and hydrofluoric acid solution as medicaments; the mass of the dilute hydrochloric acid is 20kg/t, and the mass of the hydrofluoric acid solution is 15kg/t;
(4-2) sequentially carrying out coarse crushing, intermediate crushing, drying, grinding and grading on the aphanitic graphite ore obtained in the step (1) and the step (3) to obtain graphite tailings and aphanitic graphite concentrate; wherein the particle size of the product obtained by coarse crushing is below 0.5 mm; the particle size of the product obtained by the medium crushing is 0.074mm; ore grinding is wet grinding; the volume concentration of ore pulp obtained by grinding is 10-15%;
the classification comprises the following steps:
A. screening ore pulp obtained by grinding in a vibrating screen to obtain concentrate with the granularity of more than or equal to 200 meshes and concentrate with the granularity of less than 200 meshes; wherein the fineness of the screen mesh of the vibrating screen is 200 meshes;
B. grinding the concentrate with the granularity of less than 200 meshes obtained in the step A, and drying to obtain concentrate with the granularity of less than 100 meshes in a proportion of 68-72 wt%;
C. mixing the concentrate with the granularity of less than 100 meshes and the proportion of 68-72 wt% obtained in the step B with the concentrate with the granularity of more than or equal to 200 meshes obtained in the step A, and then performing flotation to obtain graphite tailings and aphanitic graphite concentrate; wherein the collecting agent adopted by the flotation is coal tar, and the mass of the collecting agent is 380g/t; the foaming agent adopted by the flotation is 2# oil, and the mass is 50g/t; the inhibitor adopted by the flotation is water glass and sodium fluosilicate, and the mass of the water glass is 10kg/t; the mass of the sodium fluosilicate is 10kg/t;
(5-2) mixing the aphanitic graphite concentrate obtained in the step (4-2) with petroleum coke in a graphitization furnace, and purifying at 3000 ℃ for 10 hours to obtain aphanitic graphite; the quality of the aphanitic graphite concentrate is taken as a reference, and the quality of the petroleum coke is 800g/t;
(6) Using the graphite tailings obtained in the steps (2) and (4-2) to prepare a composite board;
the composition of the graphite tailings is SiO 2 30～60％，Al 2 O 3 5～20％，CaO 5～25％，Fe 2 O 3 3～15％，K 2 O<6 percent and 1 to 3 percent of MgO;
the composite board is prepared from the following raw materials in percentage by mass: 60% of plastic, 15% of graphite tailings, 10% of mineral addition powder and 5% of compatilizer;
wherein the plastic is polyvinyl chloride; the particle size of the graphite tailings is 1200 meshes; the particle size of the graphite tailing is 1000 meshes; the graphite tailing comprises ultrafine graphite; the grain size of the mineral addition powder is 800 meshes; the mineral addition powder is red mud; the red mud comprises the following components in percentage by mass: al (Al) 2 O 3 15～25％，SiO 2 30～45％，Fe 2 O 3 20～29％，N a2 O is less than or equal to 5 percent and TiO 2 1 to 6 percent; the fly ash comprises the following components in percentage by mass: al (aluminum) 2 O 3 15～35％，SiO 2 20～45％，Fe 2 O 3 2-20% of CaO and less than or equal to 25%; the compatilizer is maleic anhydride;
the preparation method of the composite board comprises the following steps:
(1) mixing graphite tailings, plastics, graphite tailings, mineral addition powder and a compatilizer in an open mill to obtain a mixed material; wherein the mixing temperature is 105 ℃, and the mixing time is 0.5h;
(2) carrying out compression molding on the mixed material obtained in the step (1) in a vulcanizing machine to obtain a composite board with the thickness of 3 mm; wherein the absolute pressure of the compression molding is 20MPa, the temperature is 170 ℃, and the time is 3min.
The composite board prepared in example 9 was subjected to a performance test, and the composite board had a tensile strength of 46MPa, a tensile modulus of 2200MPa, a flexural strength of 55MPa, a flexural modulus of 2300MPa, and an impact strength of 5.4KJ/m 2 The electromagnetic shielding absorption peak has the strength of-12.56 dB and the thermal conductivity of 0.1263W/(m.k).
From the above embodiments, it can be seen that the method provided by the invention can realize the full utilization of the graphite tailings, thereby realizing the full resource utilization of the graphite ores.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. A method for utilizing graphite ore full resources comprises the following steps:
(1) Carrying out primary separation on graphite raw ores to obtain crystalline graphite ores/aphanitic graphite ores and low-grade graphite ores;
(2) Carrying out stage grinding and stage flotation on the low-grade graphite ore obtained in the step (1) in sequence to obtain graphite concentrate and graphite tailings;
(3) Sequentially carrying out first purification and filtration on the graphite concentrate obtained in the step (2) to obtain crystalline graphite ore/aphanitic graphite ore;
(4-1) sequentially carrying out flotation and fine selection on the crystalline graphite ore obtained in the step (1) and the step (3) to obtain graphite tailings and crystalline graphite concentrate;
(5-1) carrying out second purification on the crystalline graphite concentrate obtained in the step (4-1) to obtain crystalline graphite;
or: (4-2) sequentially crushing, grinding and grading the aphanitic graphite ore obtained in the step (1) and the step (3) to obtain graphite tailings and aphanitic graphite concentrate;
(5-2) carrying out third purification on the aphanitic graphite concentrate obtained in the step (4-2) to obtain aphanitic graphite;
(6) And (3) using the graphite tailings obtained in the step (2) and the graphite tailings obtained in the step (4-1)/(4-2) to prepare 3D printing building components, composite boards or mineral compound fertilizers.
2. The method according to claim 1, wherein the 3D printed building element in step (6) comprises the following raw materials: a main agent, a reinforcing material and an auxiliary agent;
the main agent is prepared from the following raw materials in percentage by mass: 20-30% of hydraulic cementing material, 10-20% of admixture, 40-60% of graphite tailings, 0-5% of copper tailings and 0-10% of construction sand;
the reinforcing material accounts for 0.2-0.5% of the mass of the main agent.
3. The method of claim 2, wherein the admixture comprises fly ash and/or mineral fines.
4. The method of claim 2, wherein the graphite tailings, the copper tailings, and the construction sand independently have a particle size of 10 to 30mm.
5. The method of claim 2, wherein the reinforcement material comprises at least one of basalt fibers, polypropylene fibers, and glass fibers.
6. The method according to claim 1, wherein the composite board in the step (6) is prepared from the following raw materials in percentage by mass: 40-70% of plastic, 10-40% of graphite tailings, 5-10% of graphite tailings, 10-40% of mineral addition powder and 1-10% of compatilizer.
7. The method according to claim 6, wherein the composite board is prepared from the following raw materials in percentage by mass: 50-60% of plastic, 15-20% of graphite tailings, 5-10% of graphite tailings, 10-20% of mineral additive powder and 5-10% of compatilizer.
8. The method as claimed in claim 1, wherein the preparation method of the mineral compound fertilizer in the step (6) comprises the following steps:
1) Mixing the graphite tailings, the organic matters and the microbial agent to obtain a mixture;
2) Fermenting the mixture obtained in the step 1) to obtain the mineral compound fertilizer.
9. The method according to claim 8, wherein the organic matter of step 1) comprises waste landscape biomass and/or lignite humic acid.
10. The method as claimed in claim 8, wherein the temperature of the fermentation in the step 2) is 30-50 ℃ and the time of the fermentation is 5-8 days.
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