CN104961123A - Natural graphite ore stripping and purifying method - Google Patents
Natural graphite ore stripping and purifying method Download PDFInfo
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- CN104961123A CN104961123A CN201510338603.7A CN201510338603A CN104961123A CN 104961123 A CN104961123 A CN 104961123A CN 201510338603 A CN201510338603 A CN 201510338603A CN 104961123 A CN104961123 A CN 104961123A
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Abstract
The invention discloses a natural graphite ore stripping and purifying method. The method includes: mixing, by mass, 30-50% of graphite ore powder, 1-5% of oxidant, 0.2-5% of organic intercalator and the balance water, and standing for soaking for 2-10h; stirring while illuminating for 1-2h; press-filtering, washing and drying; feeding 10-50% of graphite ore filter cake, 0.5-40% of organic intercalator and the balance water into a reaction kettle, and mixing and standing; heating for 2-8h at temperature of 50-200 DEG C, and cooling for 3-5 times; press-filtering, washing, drying, mashing and feeding into an ultrasonic device for ultrasonic stripping for 0.5-12h; adding water for stirring, centrifuging and separating upper-layer suspension to obtain graphene and graphene nanosheets, and subjecting lower-layer precipitate to flotation to obtain high-carbon-content graphite; repeating the above steps to obtain high-purity graphite. By the method, the problem that natural graphite ore, especially aphanitic graphite is high in purifying technology difficulty, high in cost, severe in pollution and serious in resource waste in the prior art is solved.
Description
Technical field
The invention belongs to mineral products processing technique field, relate to a kind of natural graphite ore deposit and peel off method of purification.
Background technology
Graphite grade mainly contains electrographite and natural graphite, and synthetic graphite purity is high, but its production process needs to consume the high energy, and make its cost significantly increase, natural graphite is impure more, and purify loaded down with trivial details, Application and Development is restricted.Graphite resource is the superior resources mineral of China, and China's graphite resource enriches, first of reserves and the volume of production and marketing Dou Ju world.Graphite ore is mainly divided into crystalloid (flakey) graphite ore and phanerocrystalline-adiagnostic (earthy) graphite ore two type, the flotation flowsheet that crystalline flake graphite ore deposit is selected by adopting coarse concentrate regrinding again, reaches the object of purification crystalline flake graphite.The closed circuit flow process that flotation process is generally multistage grinding, multistage sorts, chats order (or concentrating) returns, to select flaky graphite as early as possible.Namely first carry out roughly grinding, roughly selecting, obtain the low-grade concentrate (grade is 40% ~ 50%) based on intergrowth, then by low-grade concentrate regrinding, select to obtain final concentrate again.Therefore multistage flow process has three kinds of forms, i.e. concentrate regrinding, middling ore regrinding and tailing regrind.Number of times of regrinding is 3 ~ 7 times, general 3 ~ 4 times.Because need through repeatedly grinding flowsheet, flaky graphite be very easily damaged and diminishes.The ore-dressing practice rate of recovery is under normal circumstances generally between 85% ~ 89%.To obtain the high-carbon graphite of carbon content about 99%, chemical method or pyroprocess purification graphite must be adopted.
Natural cryptocrystal graphite is one of Dominant Mineral Resources of China, is mainly used in the aspects such as casting, Graphite Electrodes, carbon rod of battery, refractory materials, pencil and carburelant.Aphanitic graphite crystal is minimum, and graphite granule is embedded in clay, is difficult to be separated.Due to aphanitic graphite head grade high (general carbon containing 60%-80%), part can reach 95%, median size 0.01-0.1 μm, is with the naked eye difficult to distinguish, therefore claims aphanitic graphite, is commonly called as amorphous graphite.Compared with crystalline flake graphite, amorphous graphite carbon content is high, and ash content is many, and crystal grain is little, and purification techniques difficulty is large, and its range of application is extremely restricted.In China, be usually all by exploitation graphite ore out after simple picking, be directly ground into product and sell.Therefore natural cryptocrystal graphite resource can not get sufficient utilization, and even blindly outlet, causes the waste of resource.In view of the technology content of natural cryptocrystal graphite and added value extremely low, high pure and ultra-fine graphite then most dependence on import that China market needs, the New Method of Purification of carrying out natural cryptocrystal graphite is particularly urgent.
At present, the technology of natural flake graphite is much still used for reference in the purification of aphanitic graphite, and the method for domestic and international purification aphanitic graphite can be divided into physical method and the large class of chemical process two.Physical method mainly contains flotation process and pyroprocess, and chemical process comprises alkali acid system, hydrogen fluoride, chlorinating roasting and hydrofluoric acid-salt (sulphur) acid system etc.The hydrofluoric acid wherein used in hydrogen fluoride and hydrofluoric acid-salt (sulphur) acid system has severe toxicity, generally industrially prohibit the use, chlorinating roasting can produce a large amount of hydrogen chloride emission, tail gas is difficult, seriously polluted, and, chlorine high in cost of production shortcoming serious to equipment corrosion limits applying of the method.Flotation process energy consumption and reagent consumes least, cost are minimum, but flotation process is only applicable to crystalloid crystalline flake graphite, is not suitable for aphanitic graphite, and when using this method purification graphite, graphite grade can only reach certain scope, is generally 85%-90%.And it is very difficult to upgrade further, and the rate of recovery of graphite is very low, and thus its range of application is restricted.To obtain the high-carbon graphite of carbon content about 99%, chemical method purification graphite must be adopted.Alkali acid system is method the most frequently used at present, has the advantage that product chemical purity is high, but soda acid consumption is large, and cost is high, and environmental pollution is serious.Pyroprocess requires high to material purity, specialized designs must build High Temperature Furnaces Heating Apparatus (2300-3000 DEG C), apparatus expensive, invests huge, and electric-heating technology requires strict.The purification of aphanitic graphite mainly contains two developing directions at present: (1) adopts continuous high temperature purification process, to reduce energy consumption and production costs, but develop the ultrahigh-temperature continuous processing apparatus that life-time service temperature reaches 3000 DEG C, need the problem of solution a lot, current state of the art is still difficult to reach.(2) by preferred chemical purification system, reduce the impact on environment as far as possible, take strict and scientific and reasonable pollution prevention measure to realize zero release and few discharge in process of production simultaneously.
Natural graphite by retrofit, not only can improve its added value, and can also provide the novel material of excellent performance for the high-tech industry of new development, therefore, the purification process of natural graphite is the only way of improving its added value, has become the common recognition of current people.Existing purification technique exists again that production cost is high, environmental pollution is serious and the shortcoming such as energy consumption is high, is difficult to apply, and needs the problem that solves a lot.
Summary of the invention
The object of this invention is to provide a kind of natural graphite ore deposit and peel off method of purification, solve natural graphite ore deposit in prior art, particularly Purification of Aphanitic Graphite technical difficulty is large, cost is high, pollution is large, the problem of serious waste of resources, be applicable to the purification of natural graphite of different taste, different mineral, and cost is low, environmental pollution is little, less energy-consumption, simple, be with a wide range of applications.
The technical solution adopted in the present invention is, method of purification is peeled off in a kind of natural graphite ore deposit, carries out according to following steps:
Step 1, according to mass percent, by the graphite breeze of 30 ~ 50%, 1% ~ 5% oxygenant, 0.2 ~ 5% organic intercalation agent, all the other mix furnishing pulp slurry for water, static dipping 2-10h in reaction tank;
Step 2, by the illumination 1-2h under constantly stirring of pulp slurry in step 1;
Step 3, pumps into press filtration in pressure filter, washing, drying by illumination pulp slurry, the graphite ore filter cake obtained;
Step 4, according to mass percent, by the graphite ore filter cake of 10-50%, inorganic intercalated dose of 0.5-40%, all the other are that water sends into reactor, mix furnishing pulp slurry, static dipping 5 ~ 48h;
Step 5, heats 2 ~ 8h by the reactor that pulp slurry is housed, is cooled to room temperature under 50-200 DEG C of condition, Repeat-heating, cooling 3 ~ 5 times;
Step 6, sends pulp slurry in reactor into press filtration in pressure filter, washing, drying, and subsequent processing sent into by the graphite ore filter cake obtained, and in filtrate, intercalator reclaims or recycles;
Step 7, smashs to pieces the graphite ore filter cake of step 6 and sends in Vltrasonic device, add water, and the water yield is 3-5 times of the water yield in step 4, ultrasonic stripping 0.5 ~ 12h;
Step 8, adds water by the pulp slurry of ultrasonic stripping, and the water yield is 2 times of step 7 water yield, and stir 0.5h, static 2 ~ 10h, upper strata suspension obtains Graphene and graphene nanometer sheet through centrifugation, and lower sediment, through flotation, obtains high-carbon graphite;
Step 9, high-carbon graphite flotation obtained repeats above-mentioned steps 1-8 after replacing the graphite breeze in step 1, obtains high purity graphite.
Preferably, graphite breeze is one or more mixtures in aphanitic graphite ore deposit, crystalline flake graphite or thin scale-phanerocrystalline-adiagnostic mixed type graphite ore.
Preferably, oxygenant is H
2o
2, (NH
4)
2s
2o
8, HNO
3one or more mixtures.
Preferably, organic intercalation agent is ammonium formiate, methane amide, ammonium acetate, ethanamide, ammonium benzoate, benzamide, phthalic acid ammonium, benzenedicarboxamide, phthalic imidine, CO (NH
2)
2, biuret, thiocarbamide one or more mixtures.
Preferably, phthalic acid ammonium is one or more mixtures of ammonium phthalate, m-phthalic acid ammonium, terephthalic acid ammonium.
Preferably, benzenedicarboxamide is one or more mixtures of O-phthalic acid amide, m-phthalic acid acid amides, terephthalic acid acid amides.
Preferably, the light source of illumination in step 2 adopts UV light, visible ray or sunlight.
Preferably, inorganic intercalated dose is NH
4cl, NH
4nO
3, (NH
4)
2sO
4, (NH
4)
3pO
4, (NH
4)
2hPO
4(NH
4)
2cO
3, NH
4hCO
3one or more mixtures.
Preferably, in step 5, during reactor heating, reactor is airtight or pour in inert gas system and heat.
The invention has the beneficial effects as follows:
1. the intercalator cost of material that adopts of the technology of the present invention is low, can be recycled or recycle.
2. the technology of the present invention is to graphite-structure without obvious destruction, also can not produce open defect, has provide protection to large size crystalline flake graphite.
3. the technology of the present invention product diversification (high-carbon graphite, high purity graphite, Graphene and graphene nanometer sheet) of producing, can adjust the product mix according to the market requirement.
4. the technology of the present invention can increase certain processing unit and implements on existing graphite flotation production line, and technique is simple, and equipment requirements is low, mild condition, and cost is low.
5. the technology of the present invention does not use bronsted lowry acids and bases bronsted lowry, and pollutent produces few, environmentally friendly.
6. the technology of the present invention is applicable to the natural graphite ore deposit of different fixed carbon content, also can be used for purifying with the stripping of molybdenum glance.
Accompanying drawing explanation
Fig. 1 schemes with the big size graphene AFM that the inventive method is prepared by crystalline flake graphite ore deposit.
Fig. 2 schemes with the Graphene AFM that the inventive method is prepared by aphanitic graphite ore deposit.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
Method of purification is peeled off in a kind of natural graphite ore deposit, comprises that natural graphite ore deposit is peeled off, purifying technology is divided into first time organic intercalation, inorganic intercalated, the ultrasonic stripping of second time and flotation;
Organic intercalation for the first time: natural graphite breeze, oxygenant, organic intercalation agent and water are mixed by a certain percentage, obtains graphite ore slurries, static dipping certain hour, by the graphite ore pulp illumination certain hour flooded, then filter, wash;
Second time is inorganic intercalated: mixed by a certain percentage with inorganic intercalated dose and water by gained graphite ore filter cake, obtain graphite ore slurries, static soak certain hour, the graphite ore pulp flooded is heated certain hour in a kettle., then filters, wash;
Ultrasonic stripping and flotation: be scattered in water by the graphite ore of twice intercalation, through ultrasonic stripping, flotation, reach the object of graphite and magazins' layout.
Specifically carry out according to following steps:
Step 1, according to mass percent, by the graphite breeze of 30 ~ 50%, 1% ~ 5% oxygenant, 0.2 ~ 5% organic intercalation agent, all the other mix furnishing pulp slurry for water, static dipping 2-10h in reaction tank;
Wherein, natural graphite breeze is one or more mixtures in aphanitic graphite ore deposit, crystalline flake graphite or thin scale-phanerocrystalline-adiagnostic mixed type graphite ore.
Oxygenant is H
2o
2, (NH
4)
2s
2o
8, HNO
3one or more mixtures.
Organic intercalation agent is ammonium formiate, methane amide, ammonium acetate, ethanamide, ammonium benzoate, benzamide, phthalic acid ammonium, benzenedicarboxamide, phthalic imidine, CO (NH
2)
2, biuret, thiocarbamide one or more mixtures; Again specifically, phthalic acid ammonium is one or more mixtures of ammonium phthalate, m-phthalic acid ammonium, terephthalic acid ammonium, and benzenedicarboxamide can be one or more mixtures of O-phthalic acid amide, m-phthalic acid acid amides, terephthalic acid acid amides.
Step 2, by the illumination 1-2h under constantly stirring of pulp slurry in step 1;
Wherein, the light source of illumination adopts UV light, visible ray or sunlight;
Step 3, pumps into press filtration in pressure filter, washing, drying by illumination pulp slurry, the graphite ore filter cake obtained;
Step 4, according to mass percent, by the graphite ore filter cake of 10-50%, inorganic intercalated dose of 0.5-40%, all the other are that water sends into reactor, mix furnishing pulp slurry, static dipping 5 ~ 48h;
Inorganic intercalated dose is NH
4cl, NH
4nO
3, (NH
4)
2sO
4, (NH
4)
3pO
4, (NH
4)
2hPO
4(NH
4)
2cO
3, NH
4hCO
3one or more mixtures;
Step 5, heats 2 ~ 8h by the reactor that pulp slurry is housed, is cooled to room temperature under 50-200 DEG C of condition, Repeat-heating, cooling 3 ~ 5 times;
Wherein, during reactor heating, reactor can, airtight or pour in inert gas system and heat, also can be normal heating or hyperbaric heating.
Step 6, sends pulp slurry in reactor into press filtration in pressure filter, washing, drying, and subsequent processing sent into by the graphite ore filter cake obtained, and in filtrate, intercalator reclaims or recycles;
Step 7, smashs to pieces the graphite ore filter cake of step 6 and sends in Vltrasonic device, add water, and the water yield is 3-5 times of the water yield in step 4, ultrasonic stripping 0.5 ~ 12h;
Step 8, adds water by the pulp slurry of ultrasonic stripping, and the water yield is 2 times of step 7 water yield, and stir 0.5h, static 2 ~ 10h, upper strata suspension obtains Graphene and graphene nanometer sheet through centrifugation, and lower sediment, through flotation, obtains high-carbon graphite;
Step 9, high-carbon graphite flotation obtained repeats above-mentioned steps 1-8 after replacing the graphite breeze in step 1, obtains high purity graphite.
As can be seen from Figure 1: graphene film layer thickness is about 2nm, single-layer graphene theoretic throat is that 0.35nm, AFM measured value is generally about 1nm, and about 2nm Graphene should be less than 5 layers Graphenes.Be of a size of about 5 μm (these are big size graphenes prepared by crystalline flake graphite)
As can be seen from Figure 2: graphene film layer thickness is about 0.5-1nm, single-layer graphene theoretic throat is that 0.35nm, AFM measured value is generally about 1nm, and prepared Graphene should be single-layer graphene.Be of a size of about 200-300nm (this is small size Graphene prepared by aphanitic graphite)
Embodiment one
By aphanitic graphite breeze 10kg (fixed carbon content is 43.2%, 200 orders), H
2o
2(1.0kg), ammonium formiate (0.3kg) and H
2o (30kg) mixing and stirring loads reaction tank, static soak 5h, and stir lower UV illumination 1h, press filtration in pressure filter sent into by graphite ore slurry; By filter cake and 1.0kg (NH
4)
2cO
3, 20L H
2o mixing and stirring, loads 50L closed reactor, static soak 32h.Start reactor heating installation, be heated to 80 DEG C of insulation 5h, circulating-heating, cooling 5 times.The graphite ore slurry heated is sent into press filtration in pressure filter, filter cake is smashed to pieces, is transferred in Vltrasonic device, add 30L water ultrasonic stripping 12h, ultrasonic graphite ore slurries are proceeded in 100L container, adds 50L water, stir 0.5h, static 6h.
By upper strata dispersion liquid centrifugation, obtain Graphene and graphene nanometer sheet (yield 25%); Collect lower sediment, add suitable quantity of water and stir, then add the stirrings such as collecting agent kerosene, inhibitor, pore forming material and adjusting agent, flotation separation, obtains high-carbon graphite 95.5%, recycling graphite rate 67%.
Embodiment two
By aphanitic graphite breeze 10kg (fixed carbon content is 65.3%, 300 orders), (NH
4)
2s
2o
8(0.5kg), ethanamide (0.1kg) and H
2o (20kg) mixing and stirring loads reaction tank, static soak 12h, and stir lower visible ray illumination 1.5h, press filtration in pressure filter sent into by graphite ore slurry; By filter cake and 3.0kg NH
4hCO
3, 20L H
2o mixing and stirring, loads 50L closed reactor, static soak 24h.Start reactor heating installation, be heated to 100 DEG C of insulation 4h, circulating-heating, cooling 3 times.The graphite ore slurry heated is sent into press filtration in pressure filter, filter cake is smashed to pieces, is transferred in Vltrasonic device, add 40L water ultrasonic stripping 6h, ultrasonic graphite ore slurries are proceeded in 100L container, adds 50L water, stir 0.5h, static 6h.
By upper strata dispersion liquid centrifugation, obtain Graphene and graphene nanometer sheet (yield 20%); Collect lower sediment, add suitable quantity of water and stir, then add the stirrings such as collecting agent kerosene, inhibitor, pore forming material and adjusting agent, flotation separation, obtains high-carbon graphite (carbon content 95.7%), recycling graphite rate 64%.
Embodiment three
By aphanitic graphite breeze 10kg (fixed carbon content is 78.3%, 200 orders), HNO
3(0.8kg), phthalic imidine (1.5kg) and H
2o (20kg) mixing and stirring loads reaction tank, static soak 5h, and stir lower visible ray illumination 2h, press filtration in pressure filter sent into by graphite ore slurry; By filter cake and 5kg (NH
4)
2cO
3, 30L H
2o mixing and stirring, loads 50L reactor (opening wide), static soak 30h.Start reactor heating installation, be heated to 90 DEG C of insulation 5h, circulating-heating, cooling 4 times.The graphite ore slurry heated is sent into press filtration in pressure filter, filter cake is smashed to pieces, is transferred in Vltrasonic device, add 30L water ultrasonic stripping 6h, ultrasonic graphite ore slurries are proceeded in 100L container, adds 50L water, stir 0.5h, static 6h.
By upper strata dispersion liquid centrifugation, obtain Graphene and graphene nanometer sheet (yield 18%); Collect lower sediment, add suitable quantity of water and stir, then add the stirrings such as collecting agent kerosene, inhibitor, pore forming material and adjusting agent, flotation separation, obtains high-carbon graphite (carbon content 96.3%), recycling graphite rate 65%,
Embodiment four
By crystalline flake graphite breeze 10kg (fixed carbon content is 12.3%, 250 orders), H
2o
2(2.0kg), ammonium phthalate (0.8kg) and H
2o (20kg) mixing and stirring loads reaction tank, static soak 10h, and stir lower UV illumination 1h, press filtration in pressure filter sent into by graphite ore slurry; By filter cake and 2.5kg (NH
4)
2hPO
4, 30L H
2o mixing and stirring, loads 50L closed reactor (being filled with nitrogen), static soak 30h.Start reactor heating installation, be heated to 180 DEG C of insulation 6h, circulating-heating, cooling 5 times.The graphite ore slurry heated is sent into press filtration in pressure filter, filter cake is smashed to pieces, is transferred in Vltrasonic device, add 30L water ultrasonic stripping 4h, ultrasonic graphite ore slurries are proceeded in 100L container, adds 50L water, stir 0.5h, static 6h.
By upper strata dispersion liquid centrifugation, obtain Graphene and graphene nanometer sheet (yield 16%); Collect lower sediment, add suitable quantity of water and stir, then add the stirrings such as collecting agent kerosene, inhibitor, pore forming material and adjusting agent, carry out flotation separation.Obtain high-carbon graphite (carbon content 97.5%), recycling graphite rate 77%.
Embodiment five
By thin scale-phanerocrystalline-adiagnostic mixed type graphite breeze 10kg (fixed carbon content is 33.2%, 250 orders), H
2o
2(1.5kg), terephthaldehyde's acid amide (0.5kg) and H
2o (30kg) mixing and stirring loads reaction tank, static soak 24h, and stir lower UV illumination 2h, press filtration in pressure filter sent into by graphite ore slurry; By filter cake and 8.0kg (NH
4)
2sO
4, 20L H
2o mixing and stirring, loads 50L closed reactor, static soak 24h.Start reactor heating installation, be heated to 120 DEG C of insulation 6h, circulating-heating, cooling 3 times.The graphite ore slurry heated is sent into press filtration in pressure filter, and filtrate is sent preceding processes back to and is recycled, and is smashed to pieces by filter cake, be transferred in Vltrasonic device, add 30L water ultrasonic stripping 8h, ultrasonic graphite ore slurries are proceeded in 100L container, add 50L water, stir 0.5h, static 6h.
By upper strata dispersion liquid centrifugation, obtain Graphene and graphene nanometer sheet (yield 21%); Collect lower sediment, add suitable quantity of water and stir, then add the stirrings such as collecting agent kerosene, inhibitor, pore forming material and adjusting agent, flotation separation, obtains high-carbon graphite (carbon content 96.8%), recycling graphite rate 71%.
Embodiment six
By crystalline flake graphite breeze 10kg (fixed carbon content is 65.3%, 300 orders), (NH
4)
2s
2o
8(0.8kg), NH4OAc (0.1kg) and H
2o (20kg) mixing and stirring loads reaction tank, static soak 3h, and stir lower visible ray illumination 1.5h, press filtration in pressure filter sent into by graphite ore slurry; By filter cake and 3kg (NH
4)
2hPO
4, 20L H
2o mixing and stirring, loads 50L closed reactor, static soak 20h.Start reactor heating installation, be heated to 100 DEG C of insulation 4h, circulating-heating, cooling 3 times.The graphite ore slurry heated is sent into press filtration in pressure filter, and filtrate is sent preceding processes back to and is recycled, and is smashed to pieces by filter cake, be transferred in Vltrasonic device, add 40L water ultrasonic stripping 10h, ultrasonic graphite ore slurries are proceeded in 100L container, add 50L water, stir 0.5h, static 6h.
By upper strata dispersion liquid centrifugation, obtain Graphene and graphene nanometer sheet (yield 20%); Collect lower sediment, add suitable quantity of water and stir, then add the stirrings such as collecting agent kerosene, inhibitor, pore forming material and adjusting agent, flotation separation, obtains high-carbon graphite (carbon content 97.3%), recycling graphite rate 75%.
Embodiment seven
By aphanitic graphite breeze 10kg (fixed carbon content is 65.3%, 250 orders), H
2o
2(2.0kg), ammonium phthalate (0.5kg) and H
2o (25kg) mixing and stirring loads reaction tank, static soak 10h, and stir lower UV illumination 1h, press filtration in pressure filter sent into by graphite ore slurry; By filter cake and 2kgNH
4cl, 30L H
2o mixing and stirring, loads 50L closed reactor (being filled with nitrogen), static soak 30h.Start reactor heating installation, be heated to 80 DEG C of insulation 5h, circulating-heating, cooling 5 times.The graphite ore slurry heated is sent into press filtration in pressure filter, filter cake is smashed to pieces, is transferred in Vltrasonic device, add 30L water ultrasonic stripping 2h, ultrasonic graphite ore slurries are proceeded in 100L container, adds 50L water, stir 0.5h, static 6h.
By upper strata dispersion liquid centrifugation, obtain Graphene and graphene nanometer sheet (yield 13%); Collect lower sediment, add suitable quantity of water and stir, then add the stirrings such as collecting agent kerosene, inhibitor, pore forming material and adjusting agent, carry out flotation separation.Obtain high-carbon graphite (carbon content 96.5%), recycling graphite rate 69%.
Embodiment eight
By aphanitic graphite breeze 10kg (fixed carbon content is 65.3%, 300 orders), HNO
3(1.8kg), benzamide (0.6kg) and H
2o (30kg) mixing and stirring loads reaction tank, static soak 8h, and stir lower UV illumination 2h, press filtration in pressure filter sent into by graphite ore slurry; By filter cake and 1.5kgNH
4nO
3, 30L H
2o mixing and stirring, loads 50L closed reactor, static soak 20h.Start reactor heating installation, be heated to 180 DEG C of insulation 8h, circulating-heating, cooling 5 times.The graphite ore slurry heated is sent into press filtration in pressure filter, filter cake is smashed to pieces, is transferred in Vltrasonic device, add 30L water ultrasonic stripping 8h, ultrasonic graphite ore slurries are proceeded in 100L container, adds 50L water, stir 0.5h, static 8h.
By upper strata dispersion liquid centrifugation, obtain Graphene and graphene nanometer sheet (yield 21%); Collect lower sediment, add the stirrings such as collecting agent kerosene, inhibitor, pore forming material and adjusting agent, carry out flotation separation, obtain high-carbon graphite (carbon content 96.9%), recycling graphite rate 70%.
Embodiment nine
By aphanitic graphite breeze 10kg (fixed carbon content is 65.3%, 200 orders), (NH
4)
2s
2o
8(1.0kg), ethanamide (0.3kg) and H
2o (20kg) mixing and stirring loads reaction tank, static soak 12h, and stir lower visible ray illumination 1.5h, press filtration in pressure filter sent into by graphite ore slurry; By filter cake and 5kg NH
4nO
3, 20L H
2o mixing and stirring, loads 50L closed reactor, static soak 32h.Start reactor heating installation, be heated to 60 DEG C of insulation 4h, circulating-heating, cooling 3 times.The graphite ore slurry heated is sent into press filtration in pressure filter, and filtrate is sent preceding processes back to and is recycled, and is smashed to pieces by filter cake, be transferred in Vltrasonic device, add 40L water ultrasonic stripping 12h, ultrasonic graphite ore slurries are proceeded in 100L container, add 50L water, stir 0.5h, static 5h.
By upper strata dispersion liquid centrifugation, obtain Graphene and graphene nanometer sheet (yield 28%); Collect lower sediment, add suitable quantity of water and stir, then add the stirrings such as collecting agent kerosene, inhibitor, pore forming material and adjusting agent, flotation separation, obtains high-carbon graphite (carbon content 96.3%), recycling graphite rate 64%.
Embodiment ten
By crystalline flake graphite breeze 10kg (fixed carbon content is 84.3%, 200 orders), HNO
3(0.8kg), terephthalamide (0.5kg) and H
2o (20kg) mixing and stirring loads reaction tank, static soak 24h, and stir lower UV illumination 2h, press filtration in pressure filter sent into by graphite ore slurry; By filter cake and 3kg (NH
4)
3pO
4, 30L H
2o mixing and stirring, loads 50L reactor (opening wide), static soak 36h.Start reactor heating installation, be heated to 120 DEG C of insulation 6h, circulating-heating, cooling 4 times.The graphite ore slurry heated is sent into press filtration in pressure filter, filter cake is smashed to pieces, is transferred in Vltrasonic device, add 30L water ultrasonic stripping 6h, ultrasonic graphite ore slurries are proceeded in 100L container, adds 50L water, stir 0.5h, static 6h.
By upper strata dispersion liquid centrifugation, obtain Graphene and graphene nanometer sheet (yield 20%); Collect lower sediment, add suitable quantity of water and stir, then add the stirrings such as collecting agent kerosene, inhibitor, pore forming material and adjusting agent, flotation separation, obtains high-carbon graphite (carbon content 97.3%), recycling graphite rate 78%.
Embodiment 11
By crystalline flake graphite breeze 10kg (fixed carbon content is 43.2%, 200 orders), H
2o
2(1.2kg), ammonium formiate (0.5kg) and H
2o (30kg) mixing and stirring loads reaction tank, static soak 5h, and stir lower visible ray illumination 1h, press filtration in pressure filter sent into by graphite ore slurry; By filter cake and 1kg NH
4cl, 20L H
2o mixing and stirring, loads 50L closed reactor, static soak 30h.Start reactor heating installation, be heated to 200 DEG C of insulation 5h, circulating-heating, cooling 5 times.The graphite ore slurry heated is sent into press filtration in pressure filter, filter cake is smashed to pieces, is transferred in Vltrasonic device, add 30L water ultrasonic stripping 2h, ultrasonic graphite ore slurries are proceeded in 100L container, adds 50L water, stir 0.5h, static 6h.
By upper strata dispersion liquid centrifugation, obtain Graphene and graphene nanometer sheet (yield 15%); Collect lower sediment, add suitable quantity of water and stir, then add the stirrings such as collecting agent kerosene, inhibitor, pore forming material and adjusting agent, flotation separation, obtains high-carbon graphite 95.8%, recycling graphite rate 77%.
Embodiment 12
By embodiment one gained high-carbon aphanitic graphite powder 3kg (fixed carbon content is 43.2%200 orders), H
2o
2(1.0kg), phthalic imidine (0.4kg) and H
2o (30kg) mixing and stirring loads reaction tank, static soak 5h, and stir lower visible ray illumination 1.5h, press filtration in pressure filter sent into by graphite ore slurry; By filter cake and 2kg NH
4cl, 20L H
2o mixing and stirring, loads 50L closed reactor, static soak 24h.Start reactor heating installation, be heated to 200 DEG C of insulation 6h, circulating-heating, cooling 5 times.The graphite ore slurry heated is sent into press filtration in pressure filter, filter cake is smashed to pieces, is transferred in Vltrasonic device, add 30L water ultrasonic stripping 12h, ultrasonic graphite ore slurries are proceeded in 100L container, adds 50L water, stir 0.5h, static 6h.
By upper strata dispersion liquid centrifugation, obtain Graphene and graphene nanometer sheet (yield 42%); Collect lower sediment, add the stirrings such as collecting agent kerosene, inhibitor, pore forming material and adjusting agent, carry out flotation separation, obtain high purity graphite (carbon content 99.90%), recycling graphite rate 65%.
Embodiment 13
By embodiment two gained high-carbon aphanitic graphite powder 3kg (fixed carbon content is 43.2%200 orders), HNO
3(1.2kg), ammonium formate (0.5kg) and H
2o (30kg) mixing and stirring loads reaction tank, static soak 24h, and stir lower visible ray illumination 1h, press filtration in pressure filter sent into by graphite ore slurry; By filter cake and 8.0kg (NH
4)
2hPO
4, 20L H
2o mixing and stirring, loads 50L closed reactor, static soak 30h.Start reactor heating installation, be heated to 120 DEG C of insulation 8h, circulating-heating, cooling 5 times.The graphite ore slurry heated is sent into press filtration in pressure filter, filter cake is smashed to pieces, is transferred in Vltrasonic device, add 30L water ultrasonic stripping 8h, ultrasonic graphite ore slurries are proceeded in 100L container, adds 50L water, stir 0.5h, static 6h.
By upper strata dispersion liquid centrifugation, obtain Graphene and graphene nanometer sheet (yield 38%); Collect lower sediment, add the stirrings such as collecting agent kerosene, inhibitor, pore forming material and adjusting agent, carry out flotation separation, obtain high purity graphite (carbon content 99.98%), recycling graphite rate 70%.
Embodiment 14
By embodiment three gained high-carbon aphanitic graphite powder 3kg (fixed carbon content is 43.2%200 orders), H
2o
2(1.2kg), ammonium acetate (0.5kg) and H
2o (30kg) mixing and stirring loads reaction tank, static soak 24h, and stir lower visible ray illumination 1h, press filtration in pressure filter sent into by graphite ore slurry; By filter cake and 5.0kg NH
4cl, 20L H
2o mixing and stirring, loads 50L closed reactor, static soak 30h.Start reactor heating installation, be heated to 180 DEG C of insulation 5h, circulating-heating, cooling 5 times.The graphite ore slurry heated is sent into press filtration in pressure filter, filter cake is smashed to pieces, is transferred in Vltrasonic device, add 30L water ultrasonic stripping 12h, ultrasonic graphite ore slurries are proceeded in 100L container, adds 50L water, stir 0.5h, static 6h.
By upper strata dispersion liquid centrifugation, obtain Graphene and graphene nanometer sheet (yield 40%); Collect lower sediment, add the stirrings such as collecting agent kerosene, inhibitor, pore forming material and adjusting agent, carry out flotation separation, obtain high purity graphite (carbon content 99.95%), recycling graphite rate 72%.
Embodiment 15
By embodiment one gained high-carbon aphanitic graphite powder 3kg (fixed carbon content is 43.2%200 orders), (NH
4)
2s
2o
8(1.2kg), m-phthalic acid ammonium (0.5kg) and H
2o (30kg) mixing and stirring loads reaction tank, static soak 24h, and stir lower visible ray illumination 1h, press filtration in pressure filter sent into by graphite ore slurry; By filter cake and 12kg NH
4cl, 20L H
2o mixing and stirring, loads 50L closed reactor, static soak 30h.Start reactor heating installation, be heated to 100 DEG C of insulation 2h, circulating-heating, cooling 5 times.The graphite ore slurry heated is sent into press filtration in pressure filter, filter cake is smashed to pieces, is transferred in Vltrasonic device, add 30L water ultrasonic stripping 5h, ultrasonic graphite ore slurries are proceeded in 100L container, adds 50L water, stir 0.5h, static 6h.
By upper strata dispersion liquid centrifugation, obtain Graphene and graphene nanometer sheet (yield 28%); Collect lower sediment, add the stirrings such as collecting agent kerosene, inhibitor, pore forming material and adjusting agent, carry out flotation separation, obtain high purity graphite (carbon content 99.96%), recycling graphite rate 65%.
Claims (9)
1. a method of purification is peeled off in natural graphite ore deposit, it is characterized in that, carries out according to following steps:
Step 1, according to mass percent, by the graphite breeze of 30 ~ 50%, 1% ~ 5% oxygenant, 0.2 ~ 5% organic intercalation agent, all the other mix furnishing pulp slurry for water, static dipping 2-10h in reaction tank;
Step 2, by the illumination 1-2h under constantly stirring of pulp slurry in step 1;
Step 3, pumps into press filtration in pressure filter, washing, drying by illumination pulp slurry, the graphite ore filter cake obtained;
Step 4, according to mass percent, by the graphite ore filter cake of 10-50%, inorganic intercalated dose of 0.5-40%, all the other are that water sends into reactor, mix furnishing pulp slurry, static dipping 5 ~ 48h;
Step 5, heats 2 ~ 8h by the reactor that pulp slurry is housed, is cooled to room temperature under 50-200 DEG C of condition, Repeat-heating, cooling 3 ~ 5 times;
Step 6, sends pulp slurry in reactor into press filtration in pressure filter, washing, drying, and subsequent processing sent into by the graphite ore filter cake obtained, and in filtrate, intercalator reclaims or recycles;
Step 7, smashs to pieces the graphite ore filter cake of step 6 and sends in Vltrasonic device, add water, and the water yield is 3-5 times of the water yield in step 4, ultrasonic stripping 0.5 ~ 12h;
Step 8, adds water by the pulp slurry of ultrasonic stripping, and the water yield is 2 times of step 7 water yield, and stir 0.5h, static 2 ~ 10h, upper strata suspension obtains Graphene and graphene nanometer sheet through centrifugation, and lower sediment, through flotation, obtains high-carbon graphite;
Step 9, high-carbon graphite flotation obtained repeats above-mentioned steps 1-8 after replacing the graphite breeze in step 1, obtains high purity graphite.
2. method of purification is peeled off in a kind of natural graphite ore deposit according to claim 1, it is characterized in that, described graphite breeze is one or more mixtures in aphanitic graphite ore deposit, crystalline flake graphite or thin scale-phanerocrystalline-adiagnostic mixed type graphite ore.
3. method of purification is peeled off in a kind of natural graphite ore deposit according to claim 1, and it is characterized in that, described oxygenant is H
2o
2, (NH
4)
2s
2o
8, HNO
3one or more mixtures.
4. method of purification is peeled off in a kind of natural graphite ore deposit according to claim 1, it is characterized in that, described organic intercalation agent is ammonium formiate, methane amide, ammonium acetate, ethanamide, ammonium benzoate, benzamide, phthalic acid ammonium, benzenedicarboxamide, phthalic imidine, CO (NH
2)
2, biuret, thiocarbamide one or more mixtures.
5. method of purification is peeled off in a kind of natural graphite ore deposit according to claim 4, and it is characterized in that, described phthalic acid ammonium is one or more mixtures of ammonium phthalate, m-phthalic acid ammonium, terephthalic acid ammonium.
6. method of purification is peeled off in a kind of natural graphite ore deposit according to claim 4, and it is characterized in that, described benzenedicarboxamide is one or more mixtures of O-phthalic acid amide, m-phthalic acid acid amides, terephthalic acid acid amides.
7. method of purification is peeled off in a kind of natural graphite ore deposit according to claim 1, it is characterized in that, the light source of illumination in step 2 adopts UV light, visible ray or sunlight.
8. method of purification is peeled off in a kind of natural graphite ore deposit according to claim 1, and it is characterized in that, described inorganic intercalated dose is NH
4cl, NH
4nO
3, (NH
4)
2sO
4, (NH
4)
3pO
4, (NH
4)
2hPO
4(NH
4)
2cO
3, NH
4hCO
3one or more mixtures.
9. method of purification is peeled off in a kind of natural graphite ore deposit according to claim 1, it is characterized in that, in described step 5, during reactor heating, reactor is airtight or pour in inert gas system and heat.
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