CN104961123B - A kind of native graphite ore deposit peels off method of purification - Google Patents
A kind of native graphite ore deposit peels off method of purification Download PDFInfo
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Abstract
The invention discloses a kind of native graphite ore deposit to peel off method of purification, according to mass percent, by 30~50% graphite miberal powder, 1%~5% oxidant, 0.2~5% organic intercalation agent, remaining be water mixing, 2 10h of static dipping；The lower 2h of illumination 1 of stirring；Press filtration, washing, drying；By 10 50% graphite ore filter cake, inorganic intercalated dose of 0.5 40%, remaining be water be sent into reactor, mixing it is static；2~8h is heated under the conditions of 50 200 DEG C, is cooled down 3~5 times；Press filtration, washing, drying, smash to pieces and be sent into Vltrasonic device, ultrasound peels off 0.5~12h；Water is added to stir, upper strata suspension is centrifuged obtaining graphene and graphene nanometer sheet, and lower sediment obtains high-carbon graphite through flotation；Repeat step obtains high purity graphite.Solve the problems, such as that particularly Purification of Aphanitic Graphite technical difficulty is big, cost is high, pollution is big, serious waste of resources for native graphite ore deposit in the prior art.
Description
Technical field
The invention belongs to mineral products processing technique field, is related to a kind of native graphite ore deposit and peels off method of purification.
Background technology
Graphite grade mainly has electrographite and native graphite, and artificial synthesized graphite purity is high, but its production process needs
The high energy is consumed, is substantially increased its cost, native graphite is impure more, and purification is cumbersome, and development and application are restricted.
Graphite resource is the superior resources mineral in China, and China's graphite resource enriches, first of reserves and the volume of production and marketing Dou Ju worlds.Graphite ore
Stone is broadly divided into crystalloid (flakey) graphite ore and cryptocrystalline (earthy) graphite ore two types, and crystalline flake graphite ore deposit is by adopting
The flotation flowsheet selected again with coarse concentrate regrinding, reach the purpose of purification crystalline flake graphite.Flotation process be generally multistage grinding,
The closed circuit flow that multistage sorts, chats order (or concentration) returns, to select flaky graphite as early as possible.First roughly ground,
Roughing, the low-grade concentrate (grade is 40%~50%) based on intergrowth is obtained, then by low-grade concentrate regrinding, select again
Obtain final concentrate.Therefore multistage flow has three kinds of forms, i.e. concentrate regrinding, middling ore regrinding and mine tailing is regrinded.Regrind number for 3~
7 times, general 3~4 times.Because need to pass through multiple grinding flowsheet, flaky graphite is highly prone to destroy and diminish.Under normal circumstances
The ore-dressing practice rate of recovery is typically between 85%~89%.High-carbon graphite to obtain phosphorus content 99% or so, must be using change
Method or high temperature method purification graphite.
Natural cryptocrystal graphite is one of the Dominant Mineral Resources in China, is mainly used in casting, graphite electrode, battery carbon
Rod, refractory material, pencil and carburant etc..Aphanitic graphite crystal is minimum, and graphite particle is embedded in clay, it is difficult to point
From.Because aphanitic graphite head grade is high (general carbon containing 60%-80%), partly up to 95%, average grain diameter 0.01-0.1 μ
M, it is difficult with the naked eye to distinguish, therefore claims aphanitic graphite, is commonly called as amorphous graphite.Compared with crystalline flake graphite, amorphous graphite carbon content is high,
Ash content is more, and crystal grain is small, and purification technique difficulty is big, is extremely restricted its application.Generally all it is to produce in China
The graphite ore come is directly ground to product sale after simple picking.Therefore natural cryptocrystal graphite resource cannot fill
The utilization divided, or even blindly export, cause the waste of resource.In view of technology content and the added value pole of natural cryptocrystal graphite
It is low, and the high pure and ultra-fine graphite that China market needs then most dependence imports, the New Method of Purification of development natural cryptocrystal graphite
It is particularly urgent.
At present, the purification of aphanitic graphite is many or uses for reference the technology of natural flake graphite, purifies cryptocrystalline both at home and abroad
The method of graphite can be divided into physical method and the major class of chemical method two.Physical method mainly has floatation and high temperature method, chemistry side
Method includes alkali acid system, hydrogen fluoride, chlorinating roasting and hydrofluoric acid-salt (sulphur) acid system etc..Wherein hydrogen fluoride and hydrofluoric acid-salt
Hydrofluoric acid used in (sulphur) acid system has severe toxicity, typically industrially prohibits the use of, and chlorinating roasting can produce a large amount of chlorinations
Hydrogen waste gas, tail gas is difficult, seriously polluted, it is serious to equipment corrosion, chlorine cost is high the shortcomings of limit the popularization of this method
Using.Floatation energy consumption and reagent consumption is minimum, cost is minimum, but floatation is only applicable to crystalloid crystalline flake graphite, is not suitable for
Aphanitic graphite, graphite grade can only achieve certain scope when purifying graphite using this method, usually 85%-90%.And enter
One step is upgrade extremely difficult, and the rate of recovery of graphite is very low, thus its application is restricted.It is carbon containing to obtain
The high-carbon graphite of amount 99% or so, it is necessary to which graphite is purified using chemical method.Alkali acid system is method the most frequently used at present, has product
The high advantage of chemical purity, but soda acid consumption is big, and cost is high, and environmental pollution is serious.High temperature method requires high to material purity,
The special design-build high temperature furnace (2300-3000 DEG C) of palpus, equipment is expensive, investment is huge, and electric-heating technology requirement is strictly.Cryptocrystalline
The purification of graphite mainly has two developing directions at present：(1) continuous high temperature purification process is used, to reduce energy consumption and be produced into
This, but to develop long-term use of temperature up to 3000 DEG C superhigh temperature continuous processing apparatus, it is necessary to solve the problems, such as it is a lot, it is current
Technical merit is still difficult to reach.(2) by preferred chemical purification system, the influence to environment is reduced as far as possible, while producing
During take strict and scientific and reasonable pollution prevention measure to realize zero-emission and few discharge.
Native graphite can not only improve its added value, can also be the high-tech industry of new development by retrofit
The new material of excellent performance is provided, therefore, the purification process of native graphite is to improve the only way of its added value, it has also become when
The common recognition of preceding people.Existing purification technique has that production cost is high, environmental pollution is serious and the shortcomings of high energy consumption again, it is difficult to pushes away
Extensively apply, it is necessary to solve the problems, such as a lot.
The content of the invention
It is an object of the invention to provide a kind of native graphite ore deposit to peel off method of purification, solves native graphite in the prior art
Ore deposit, the problem of particularly Purification of Aphanitic Graphite technical difficulty is big, cost is high, pollution is big, serious waste of resources, suitable for difference
Sample, the purification of the native graphite of different minerals, and cost is low, environmental pollution is small, low energy consumption, simple and easy, has extensive
Application prospect.
The technical solution adopted in the present invention is that a kind of native graphite ore deposit peels off method of purification, follows the steps below：
Step 1, according to mass percent, by by 30~50% graphite miberal powder, 1%~5% oxidant, 0.2~5%
Organic intercalation agent and remaining be water composition raw material in reaction tank be well mixed be tuned into pulp slurry, static dipping 2-
10h；
Step 2, pulp slurry in step 1 is being stirred continuously lower illumination 1-2h；
Step 3, illumination pulp slurry is pumped into press filtration in filter press, washing, drying, obtained graphite ore filter cake；
Step 4, according to mass percent, by by 10-50% graphite ore filter cake, inorganic intercalated dose of 0.5-40% and
Remaining is that the raw material of water composition are sent into reactor, well mixed to be tuned into pulp slurry, 5~48h of static dipping；
Step 5, the reactor equipped with pulp slurry is heated into 2~8h under the conditions of 50-200 DEG C, is cooled to room temperature, repeat to add
Heat, cooling 3~5 times；
Step 6, pulp slurry in reactor is sent into press filtration, washing, drying in filter press, obtained graphite ore filter cake is sent into
Subsequent processing, intercalator recovery or recycle in filtrate；
Step 7, the graphite ore filter cake of step 6 is smashed to pieces and be sent into Vltrasonic device, add water, water is water in step 4
3-5 times, ultrasound peel off 0.5~12h；
Step 8, the pulp slurry that ultrasound is peeled off being added into water, water is 2 times of step 7 water, stirs 0.5h, static 2
~10h, upper strata suspension are centrifuged obtaining graphene and graphene nanometer sheet, and lower sediment obtains high-carbon stone through flotation
Ink；
Step 9, high-carbon graphite flotation obtained obtains instead of the 1-8 that repeated the above steps after the graphite miberal powder in step 1
High purity graphite.
Preferably, graphite miberal powder is in aphanitic graphite ore deposit, crystalline flake graphite or thin scale-cryptocrystalline mixed type graphite ore
One or more kinds of mixtures.
Preferably, oxidant H2O2、(NH4)2S2O8、HNO3One or more kinds of mixtures.
Preferably, organic intercalation agent is ammonium formate, formamide, ammonium acetate, acetamide, ammonium benzoate, benzamide, benzene two
Ammonium formate, benzenedicarboxamide, phthalimide, CO (NH2)2, biuret, one or more kinds of mixtures of thiocarbamide.
Preferably, phthalic acid ammonium is ammonium phthalate, M-phthalic acid ammonium, the one or two of terephthalic acid (TPA) ammonium
Thing mixed above.
Preferably, benzenedicarboxamide is the one or two of phthalic amide, isophtalamide, terephthalamide
Thing mixed above.
Preferably, the light source of illumination uses UV light, visible ray or sunshine in step 2.Preferably, inorganic intercalated dose is
NH4Cl、NH4NO3、(NH4)2SO4、(NH4)3PO4、(NH4)2HPO4(NH4)2CO3And NH4HCO3At least one of.
Preferably, in step 5, when reactor heats, reactor is closed or pour in inert gas system and heat.
The beneficial effects of the invention are as follows：
1. intercalator cost of material is low used by the technology of the present invention, it can be recycled or recycle.
2. the technology of the present invention is destroyed to graphite-structure without obvious, open defect will not be also produced, to large scale crystalline flake graphite
With protective effect.
3. product diversification (high-carbon graphite, high purity graphite, graphene and graphene nano that the technology of the present invention is produced
Piece), it can be adjusted the product mix according to the market demand.
4. the technology of the present invention can increase certain process equipment on existing graphite flotation production line and be implemented, technique letter
Single, equipment requirement is low, mild condition, and cost is low.
5. the technology of the present invention, without using bronsted lowry acids and bases bronsted lowry, pollutant produces less, environmentally friendly.
6. the technology of the present invention is applied to the native graphite ore deposit of different fixation carbon contents, it can also be used to the stripping with molybdenite
Purification.
Brief description of the drawings
Fig. 1 is that the big size graphene AFM prepared with the inventive method by crystalline flake graphite ore deposit schemes.
Fig. 2 is that the graphene AFM prepared with the inventive method by aphanitic graphite ore deposit schemes.
Embodiment
The present invention is described in detail with reference to the accompanying drawings and detailed description.
A kind of native graphite ore deposit peels off method of purification, including native graphite ore deposit is peeled off, purifying technology is divided into for the first time
Organic intercalation, second inorganic intercalated, ultrasonic stripping and flotation；
First time organic intercalation：Native graphite miberal powder, oxidant, organic intercalation agent and water are mixed by a certain percentage
It is even, graphite pulp slurry, static dipping certain time are obtained, the graphite ore pulp illumination certain time that will have been impregnated, then filters, wash
Wash；
Second inorganic intercalated：Gained graphite ore filter cake is well mixed by a certain percentage with inorganic intercalated dose and water, obtained
To graphite pulp slurry, static soak certain time, the graphite ore pulp impregnated is heated certain time in a kettle, then mistake
Filter, washing；
Ultrasound is peeled off and flotation：The graphite ore of intercalation twice is dispersed in water, is peeled off through ultrasound, flotation, reaches graphite
The purpose separated with impurity.
Specifically follow the steps below：
Step 1, according to mass percent, by 30~50% graphite miberal powder, 1%~5% oxidant, 0.2~5%
Organic intercalation agent, remaining be water in reaction tank be well mixed be tuned into pulp slurry, static dipping 2-10h；
Wherein, native graphite miberal powder is in aphanitic graphite ore deposit, crystalline flake graphite or thin scale-cryptocrystalline mixed type graphite ore
One or more kinds of mixtures.
Oxidant is H2O2、(NH4)2S2O8、HNO3One or more kinds of mixtures.
Organic intercalation agent be ammonium formate, formamide, ammonium acetate, acetamide, ammonium benzoate, benzamide, phthalic acid ammonium,
Benzenedicarboxamide, phthalimide, CO (NH2)2, biuret, one or more kinds of mixtures of thiocarbamide；It is specific again
To say, phthalic acid ammonium is ammonium phthalate, M-phthalic acid ammonium, one or more kinds of mixtures of terephthalic acid (TPA) ammonium,
Benzenedicarboxamide can be one or more kinds of mixtures of phthalic amide, isophtalamide, terephthalamide.
Step 2, pulp slurry in step 1 is being stirred continuously lower illumination 1-2h；
Wherein, the light source of illumination uses UV light, visible ray or sunshine；
Step 3, illumination pulp slurry is pumped into press filtration in filter press, washing, drying, obtained graphite ore filter cake；
Step 4, according to mass percent, by 10-50% graphite ore filter cake, inorganic intercalated dose of 0.5-40%, remaining
Reactor is sent into for water, it is well mixed to be tuned into pulp slurry, 5~48h of static dipping；
Inorganic intercalated dose is NH4Cl、NH4NO3、(NH4)2SO4、(NH4)3PO4、(NH4)2HPO4(NH4)2CO3、NH4HCO3's
One or more kinds of mixtures；
Step 5, the reactor equipped with pulp slurry is heated into 2~8h under the conditions of 50-200 DEG C, is cooled to room temperature, repeat to add
Heat, cooling 3~5 times；
Wherein, when reactor heats, reactor can be closed or pour in inert gas system heating or often
Pressure heating or hyperbaric heating.
Step 6, pulp slurry in reactor is sent into press filtration, washing, drying in filter press, obtained graphite ore filter cake is sent into
Subsequent processing, intercalator recovery or recycle in filtrate；
Step 7, the graphite ore filter cake of step 6 is smashed to pieces and be sent into Vltrasonic device, add water, water is water in step 4
3-5 times, ultrasound peel off 0.5~12h；
Step 8, the pulp slurry that ultrasound is peeled off being added into water, water is 2 times of step 7 water, stirs 0.5h, static 2
~10h, upper strata suspension are centrifuged obtaining graphene and graphene nanometer sheet, and lower sediment obtains high-carbon stone through flotation
Ink；
Step 9, high-carbon graphite flotation obtained obtains instead of the 1-8 that repeated the above steps after the graphite miberal powder in step 1
High purity graphite.
As can be seen from Figure 1：Graphene sheet layer thickness is 2nm or so, and single-layer graphene theoretic throat is 0.35nm,
AFM measured values are usually that 1nm or so, 2nm or so graphenes should be less than 5 layers graphenes.Size is 5 μm or so, and (this is scale
Big size graphene prepared by graphite)
As can be seen from Figure 2：Graphene sheet layer thickness is 0.5-1nm or so, and single-layer graphene theoretic throat is
0.35nm, AFM measured value are usually 1nm or so, and prepared graphene should be single-layer graphene.Size is 200-300nm left
Right (this is small size graphene prepared by aphanitic graphite)
Embodiment one
By aphanitic graphite miberal powder 10kg (fixed carbon content is 43.2%, 200 mesh), H2O2(1.0kg), ammonium formate
(0.3kg) and H2Loading reaction tank is mixed evenly in O (30kg), static soak 5h, stirs lower UV illumination 1h, graphite ore slurry
It is sent into press filtration in filter press；By filter cake and 1.0kg (NH4)2CO3、20LH2O is mixed evenly, and loads 50L closed reactors,
Static soak 32h.Start reactor firing equipment, be heated to 80 DEG C of insulation 5h, circulating-heating, cooling 5 times.The stone that will have been heated
Black ore pulp material is sent into press filtration in filter press, and filter cake is smashed to pieces, is transferred in Vltrasonic device, adds 30L water ultrasound and peels off 12h, will
Ultrasonic graphite pulp slurry is transferred in 100L containers, adds 50L water, stirs 0.5h, static 6h.
Upper strata dispersion liquid is centrifuged, obtains graphene and graphene nanometer sheet (yield 25%)；Collect lower sediment,
Add suitable quantity of water to stir, add the stirring such as collecting agent kerosene, inhibitor, foaming agent and regulator, FLOTATION SEPARATION, obtain
High-carbon graphite 95.5%, recycling graphite rate 67%.
Embodiment two
By aphanitic graphite miberal powder 10kg (fixed carbon content is 65.3%, 300 mesh), (NH4)2S2O8(0.5kg), acetyl
Amine (0.1kg) and H2Loading reaction tank is mixed evenly in O (20kg), static soak 12h, stirs lower visible ray illumination 1.5h,
Graphite ore slurry is sent into press filtration in filter press；By filter cake and 3.0kg NH4HCO3、20L H2O is mixed evenly, and it is close to load 50L
Close reactor, static soak 24h.Start reactor firing equipment, be heated to 100 DEG C of insulation 4h, circulating-heating, cooling 3 times.Will
The graphite ore slurry heated is sent into press filtration in filter press, and filter cake is smashed to pieces, is transferred in Vltrasonic device, adds 40L water ultrasound
6h is peeled off, ultrasonic graphite pulp slurry is transferred in 100L containers, adds 50L water, stirs 0.5h, static 6h.
Upper strata dispersion liquid is centrifuged, obtains graphene and graphene nanometer sheet (yield 20%)；Collect lower sediment,
Add suitable quantity of water to stir, add the stirring such as collecting agent kerosene, inhibitor, foaming agent and regulator, FLOTATION SEPARATION, obtain
High-carbon graphite (carbon content 95.7%), recycling graphite rate 64%.
Embodiment three
By aphanitic graphite miberal powder 10kg (fixed carbon content is 78.3%, 200 mesh), HNO3(0.8kg), phthalyl
Imines (1.5kg) and H2Loading reaction tank is mixed evenly in O (20kg), static soak 5h, stirs lower visible ray illumination 2h, stone
Black ore pulp material is sent into press filtration in filter press；By filter cake and 5kg (NH4)2CO3、30L H2O is mixed evenly, and loads 50L reactions
Kettle (unlimited), static soak 30h.Start reactor firing equipment, be heated to 90 DEG C of insulation 5h, circulating-heating, cooling 4 times.Will
The graphite ore slurry heated is sent into press filtration in filter press, and filter cake is smashed to pieces, is transferred in Vltrasonic device, adds 30L water ultrasound
6h is peeled off, ultrasonic graphite pulp slurry is transferred in 100L containers, adds 50L water, stirs 0.5h, static 6h.
Upper strata dispersion liquid is centrifuged, obtains graphene and graphene nanometer sheet (yield 18%)；Collect lower sediment,
Add suitable quantity of water to stir, add the stirring such as collecting agent kerosene, inhibitor, foaming agent and regulator, FLOTATION SEPARATION, obtain
High-carbon graphite (carbon content 96.3%), recycling graphite rate 65%,
Example IV
By crystalline flake graphite miberal powder 10kg (fixed carbon content is 12.3%, 250 mesh), H2O2(2.0kg), ammonium phthalate
(0.8kg) and H2Loading reaction tank is mixed evenly in O (20kg), static soak 10h, stirs lower UV illumination 1h, graphite ore pulp
Material is sent into press filtration in filter press；By filter cake and 2.5kg (NH4)2HPO4、30L H2O is mixed evenly, and loads 50L confined reactions
Kettle (is filled with nitrogen), static soak 30h.Start reactor firing equipment, be heated to 180 DEG C of insulation 6h, circulating-heating, cooling 5
It is secondary.The graphite ore slurry heated is sent into press filtration in filter press, filter cake is smashed to pieces, is transferred in Vltrasonic device, adds 30L water
Ultrasound peels off 4h, and ultrasonic graphite pulp slurry is transferred in 100L containers, adds 50L water, stirs 0.5h, static 6h.
Upper strata dispersion liquid is centrifuged, obtains graphene and graphene nanometer sheet (yield 16%)；Collect lower sediment,
Add suitable quantity of water to stir, add the stirring such as collecting agent kerosene, inhibitor, foaming agent and regulator, carry out FLOTATION SEPARATION.
Obtain high-carbon graphite (carbon content 97.5%), recycling graphite rate 77%.
Embodiment five
By thin scale-cryptocrystalline mixed type graphite miberal powder 10kg (fixed carbon content is 33.2%, 250 mesh), H2O2
(1.5kg), terephthaldehyde's acid amide (0.5kg) and H2Loading reaction tank, static soak 24h, stirring is mixed evenly in O (30kg)
Lower UV illumination 2h, graphite ore slurry are sent into press filtration in filter press；By filter cake and 8.0kg (NH4)2SO4、20L H2O mixes equal
It is even, load 50L closed reactors, static soak 24h.Start reactor firing equipment, be heated to 120 DEG C of insulation 6h, circulation adds
Heat, cooling 3 times.The graphite ore slurry heated is sent into press filtration in filter press, filtrate is sent preceding processes recycling back to, will filtered
Cake is smashed to pieces, is transferred in Vltrasonic device, is added 30L water ultrasound and is peeled off 8h, ultrasonic graphite pulp slurry is transferred in 100L containers,
50L water is added, stirs 0.5h, static 6h.
Upper strata dispersion liquid is centrifuged, obtains graphene and graphene nanometer sheet (yield 21%)；Collect lower sediment,
Add suitable quantity of water to stir, add the stirring such as collecting agent kerosene, inhibitor, foaming agent and regulator, FLOTATION SEPARATION, obtain
High-carbon graphite (carbon content 96.8%), recycling graphite rate 71%.
Embodiment six
By crystalline flake graphite miberal powder 10kg (fixed carbon content is 65.3%, 300 mesh), (NH4)2S2O8(0.8kg), NH4OAc
(0.1kg) and H2Loading reaction tank is mixed evenly in O (20kg), static soak 3h, stirs lower visible ray illumination 1.5h, graphite
Ore pulp material is sent into press filtration in filter press；By filter cake and 3kg (NH4)2HPO4、20L H2O is mixed evenly, and it is closed anti-to load 50L
Answer kettle, static soak 20h.Start reactor firing equipment, be heated to 100 DEG C of insulation 4h, circulating-heating, cooling 3 times.Will heating
Complete graphite ore slurry is sent into press filtration in filter press, and filtrate sends preceding processes recycling back to, filter cake is smashed to pieces, is transferred to ultrasound
In device, add 40L water ultrasound and peel off 10h, ultrasonic graphite pulp slurry is transferred in 100L containers, add 50L water, stirring
0.5h, static 6h.
Upper strata dispersion liquid is centrifuged, obtains graphene and graphene nanometer sheet (yield 20%)；Collect lower sediment,
Add suitable quantity of water to stir, add the stirring such as collecting agent kerosene, inhibitor, foaming agent and regulator, FLOTATION SEPARATION, obtain
High-carbon graphite (carbon content 97.3%), recycling graphite rate 75%.
Embodiment seven
By aphanitic graphite miberal powder 10kg (fixed carbon content is 65.3%, 250 mesh), H2O2(2.0kg), phthalic acid
Ammonium (0.5kg) and H2Loading reaction tank is mixed evenly in O (25kg), static soak 10h, stirs lower UV illumination 1h, graphite ore
Slurry is sent into press filtration in filter press；By filter cake and 2kgNH4Cl、30L H2O is mixed evenly, and loads 50L closed reactors and (fills
Enter nitrogen), static soak 30h.Start reactor firing equipment, be heated to 80 DEG C of insulation 5h, circulating-heating, cooling 5 times.It will add
The complete graphite ore slurry of heat is sent into press filtration in filter press, and filter cake is smashed to pieces, is transferred in Vltrasonic device, adds the ultrasound stripping of 30L water
From 2h, ultrasonic graphite pulp slurry is transferred in 100L containers, adds 50L water, stirs 0.5h, static 6h.
Upper strata dispersion liquid is centrifuged, obtains graphene and graphene nanometer sheet (yield 13%)；Collect lower sediment,
Add suitable quantity of water to stir, add the stirring such as collecting agent kerosene, inhibitor, foaming agent and regulator, carry out FLOTATION SEPARATION.
Obtain high-carbon graphite (carbon content 96.5%), recycling graphite rate 69%.
Embodiment eight
By aphanitic graphite miberal powder 10kg (fixed carbon content is 65.3%, 300 mesh), HNO3(1.8kg), benzamide
(0.6kg) and H2Loading reaction tank is mixed evenly in O (30kg), static soak 8h, stirs lower UV illumination 2h, graphite ore slurry
It is sent into press filtration in filter press；By filter cake and 1.5kg NH4NO3、30L H2O is mixed evenly, and loads 50L closed reactors, quiet
Only soak 20h.Start reactor firing equipment, be heated to 180 DEG C of insulation 8h, circulating-heating, cooling 5 times.The stone that will have been heated
Black ore pulp material is sent into press filtration in filter press, and filter cake is smashed to pieces, is transferred in Vltrasonic device, adds 30L water ultrasound and peels off 8h, by
Ultrasonic graphite pulp slurry is transferred in 100L containers, adds 50L water, stirs 0.5h, static 8h.Upper strata dispersion liquid is centrifuged,
Obtain graphene and graphene nanometer sheet (yield 21%)；Lower sediment is collected, adds collecting agent kerosene, inhibitor, foaming agent
Stirred with regulator etc., carry out FLOTATION SEPARATION, obtain high-carbon graphite (carbon content 96.9%), recycling graphite rate 70%.
Embodiment nine
By aphanitic graphite miberal powder 10kg (fixed carbon content is 65.3%, 200 mesh), (NH4)2S2O8(1.0kg), acetyl
Amine (0.3kg) and H2Loading reaction tank is mixed evenly in O (20kg), static soak 12h, stirs lower visible ray illumination 1.5h,
Graphite ore slurry is sent into press filtration in filter press；By filter cake and 5kg NH4NO3、20L H2O is mixed evenly, and it is closed to load 50L
Reactor, static soak 32h.Start reactor firing equipment, be heated to 60 DEG C of insulation 4h, circulating-heating, cooling 3 times.It will add
The complete graphite ore slurry of heat is sent into press filtration in filter press, and filtrate sends preceding processes recycling back to, filter cake is smashed to pieces, is transferred to super
In acoustic device, add 40L water ultrasound and peel off 12h, ultrasonic graphite pulp slurry is transferred in 100L containers, add 50L water, stirring
0.5h, static 5h.
Upper strata dispersion liquid is centrifuged, obtains graphene and graphene nanometer sheet (yield 28%)；Collect lower sediment,
Add suitable quantity of water to stir, add the stirring such as collecting agent kerosene, inhibitor, foaming agent and regulator, FLOTATION SEPARATION, obtain
High-carbon graphite (carbon content 96.3%), recycling graphite rate 64%.
Embodiment ten
By crystalline flake graphite miberal powder 10kg (fixed carbon content is 84.3%, 200 mesh), HNO3(0.8kg), terephthalamide
(0.5kg) and H2Loading reaction tank is mixed evenly in O (20kg), static soak 24h, stirs lower UV illumination 2h, graphite ore pulp
Material is sent into press filtration in filter press；By filter cake and 3kg (NH4)3PO4, 30L H2O be mixed evenly, it is (spacious to load 50L reactors
Open), static soak 36h.Start reactor firing equipment, be heated to 120 DEG C of insulation 6h, circulating-heating, cooling 4 times.Will heating
Complete graphite ore slurry is sent into press filtration in filter press, and filter cake is smashed to pieces, is transferred in Vltrasonic device, adds 30L water ultrasound and peels off
6h, ultrasonic graphite pulp slurry is transferred in 100L containers, adds 50L water, stir 0.5h, static 6h.
Upper strata dispersion liquid is centrifuged, obtains graphene and graphene nanometer sheet (yield 20%)；Collect lower sediment,
Add suitable quantity of water to stir, add the stirring such as collecting agent kerosene, inhibitor, foaming agent and regulator, FLOTATION SEPARATION, obtain
High-carbon graphite (carbon content 97.3%), recycling graphite rate 78%.
Embodiment 11
By crystalline flake graphite miberal powder 10kg (fixed carbon content is 43.2%, 200 mesh), H2O2(1.2kg), ammonium formate (0.5kg)
And H2Loading reaction tank is mixed evenly in O (30kg), and static soak 5h stirs lower visible ray illumination 1h, and graphite ore slurry is sent
Enter press filtration in filter press；By filter cake and 1kg NH4Cl、20L H2O is mixed evenly, and loads 50L closed reactors, static leaching
Steep 30h.Start reactor firing equipment, be heated to 200 DEG C of insulation 5h, circulating-heating, cooling 5 times.The graphite ore that will have been heated
Slurry is sent into press filtration in filter press, and filter cake is smashed to pieces, is transferred in Vltrasonic device, adds 30L water ultrasound and peels off 2h, will be ultrasonic
Graphite pulp slurry is transferred in 100L containers, adds 50L water, stirs 0.5h, static 6h.
Upper strata dispersion liquid is centrifuged, obtains graphene and graphene nanometer sheet (yield 15%)；Collect lower sediment,
Add suitable quantity of water to stir, add the stirring such as collecting agent kerosene, inhibitor, foaming agent and regulator, FLOTATION SEPARATION, obtain
High-carbon graphite 95.8%, recycling graphite rate 77%.
Embodiment 12
By the gained high-carbon aphanitic graphite powder 3kg of embodiment one (fixed carbon content is 43.2%200 mesh), H2O2
(1.0kg), phthalimide (0.4kg) and H2Loading reaction tank is mixed evenly in O (30kg), static soak 5h, stirs
Lower visible ray illumination 1.5h is mixed, graphite ore slurry is sent into press filtration in filter press；By filter cake and 2kg NH4Cl、20L H2O mixing is stirred
Mix uniformly, load 50L closed reactors, static soak 24h.Start reactor firing equipment, be heated to 200 DEG C of insulation 6h, follow
Ring heating, cooling 5 times.The graphite ore slurry heated is sent into press filtration in filter press, filter cake is smashed to pieces, is transferred to Vltrasonic device
In, add 30L water ultrasound and peel off 12h, ultrasonic graphite pulp slurry is transferred in 100L containers, adds 50L water, stirs 0.5h,
Static 6h.
Upper strata dispersion liquid is centrifuged, obtains graphene and graphene nanometer sheet (yield 42%)；Collect lower sediment,
The stirring such as collecting agent kerosene, inhibitor, foaming agent and regulator is added, FLOTATION SEPARATION is carried out, obtains high purity graphite (carbon content
99.90%), recycling graphite rate 65%.
Embodiment 13
By the gained high-carbon aphanitic graphite powder 3kg of embodiment two (fixed carbon content is 43.2%200 mesh), HNO3
(1.2kg), ammonium formate (0.5kg) and H2O (30kg) is mixed evenly loading reaction tank, static soak 24h, visible under stirring
Light illumination 1h, graphite ore slurry are sent into press filtration in filter press；By filter cake and 8.0kg (NH4)2HPO4、20L H2O mixes equal
It is even, load 50L closed reactors, static soak 30h.Start reactor firing equipment, be heated to 120 DEG C of insulation 8h, circulation adds
Heat, cooling 5 times.The graphite ore slurry heated is sent into press filtration in filter press, filter cake is smashed to pieces, is transferred in Vltrasonic device,
Add 30L water ultrasound and peel off 8h, ultrasonic graphite pulp slurry is transferred in 100L containers, adds 50L water, stir 0.5h, it is static
6h。
Upper strata dispersion liquid is centrifuged, obtains graphene and graphene nanometer sheet (yield 38%)；Collect lower sediment,
The stirring such as collecting agent kerosene, inhibitor, foaming agent and regulator is added, FLOTATION SEPARATION is carried out, obtains high purity graphite (carbon content
99.98%), recycling graphite rate 70%.
Embodiment 14
By the gained high-carbon aphanitic graphite powder 3kg of embodiment three (fixed carbon content is 43.2%200 mesh), H2O2
(1.2kg), ammonium acetate (0.5kg) and H2O (30kg) is mixed evenly loading reaction tank, static soak 24h, visible under stirring
Light illumination 1h, graphite ore slurry are sent into press filtration in filter press；By filter cake and 5.0kg NH4Cl、20L H2O is mixed evenly, dress
Enter 50L closed reactors, static soak 30h.Start reactor firing equipment, be heated to 180 DEG C of insulation 5h, it is circulating-heating, cold
But 5 times.The graphite ore slurry heated is sent into press filtration in filter press, filter cake is smashed to pieces, is transferred in Vltrasonic device, is added
30L water ultrasound peels off 12h, and ultrasonic graphite pulp slurry is transferred in 100L containers, adds 50L water, stirs 0.5h, static 6h.
Upper strata dispersion liquid is centrifuged, obtains graphene and graphene nanometer sheet (yield 40%)；Collect lower sediment,
The stirring such as collecting agent kerosene, inhibitor, foaming agent and regulator is added, FLOTATION SEPARATION is carried out, obtains high purity graphite (carbon content
99.95%), recycling graphite rate 72%.
Embodiment 15
By the gained high-carbon aphanitic graphite powder 3kg of embodiment one (fixed carbon content is 43.2%200 mesh), (NH4)2S2O8
(1.2kg), M-phthalic acid ammonium (0.5kg) and H2Loading reaction tank is mixed evenly in O (30kg), static soak 24h, stirs
Lower visible ray illumination 1h is mixed, graphite ore slurry is sent into press filtration in filter press；By filter cake and 12kg NH4Cl、20L H2O is mixed
Uniformly, 50L closed reactors, static soak 30h are loaded.Start reactor firing equipment, be heated to 100 DEG C of insulation 2h, circulation
Heating, cooling 5 times.The graphite ore slurry heated is sent into press filtration in filter press, filter cake is smashed to pieces, is transferred to Vltrasonic device
In, add 30L water ultrasound and peel off 5h, ultrasonic graphite pulp slurry is transferred in 100L containers, adds 50L water, stir 0.5h, it is quiet
Only 6h.
Upper strata dispersion liquid is centrifuged, obtains graphene and graphene nanometer sheet (yield 28%)；Collect lower sediment,
The stirring such as collecting agent kerosene, inhibitor, foaming agent and regulator is added, FLOTATION SEPARATION is carried out, obtains high purity graphite (carbon content
99.96%), recycling graphite rate 65%.
Claims (7)
1. a kind of native graphite ore deposit peels off method of purification, it is characterised in that follows the steps below：
Step 1, according to mass percent, will be had by 30~50% graphite miberal powder, 1%~5% oxidant, 0.2~5%
Machine intercalator and the raw material that remaining is water composition are well mixed in reaction tank and are tuned into pulp slurry, static dipping 2-10h；
Step 2, pulp slurry in step 1 is being stirred continuously lower illumination 1-2h；
Step 3, illumination pulp slurry is pumped into press filtration in filter press, washing, drying, obtained graphite ore filter cake；
Step 4, according to mass percent, by by 10-50% graphite ore filter cake, inorganic intercalated dose of 0.5-40% and remaining
Reactor is sent into for the raw material of water composition, it is well mixed to be tuned into pulp slurry, 5~48h of static dipping；
Step 5, the reactor equipped with pulp slurry is heated into 2~8h under the conditions of 50-200 DEG C, is cooled to room temperature, Repeat-heating,
Cooling 3~5 times；
Step 6, pulp slurry in reactor is sent into press filtration, washing, drying in filter press, obtained graphite ore filter cake is sent into next
Process, intercalator recovery or recycle in filtrate；
Step 7, the graphite ore filter cake of step 6 is smashed to pieces and be sent into Vltrasonic device, add water, water is the 3-5 of water in step 4
Times, ultrasound peels off 0.5~12h；
Step 8, the pulp slurry that ultrasound is peeled off being added into water, water is 2 times of step 7 water, stirs 0.5h, static 2~
10h, upper strata suspension are centrifuged obtaining graphene and graphene nanometer sheet, and lower sediment obtains high-carbon graphite through flotation；
Step 9, high-carbon graphite flotation obtained obtains high-purity instead of the 1-8 that repeated the above steps after the graphite miberal powder in step 1
Graphite.
2. a kind of native graphite ore deposit according to claim 1 peels off method of purification, it is characterised in that the graphite miberal powder is
One or both of aphanitic graphite ore deposit, crystalline flake graphite or thin scale-cryptocrystalline mixed type graphite ore thing mixed above.
3. a kind of native graphite ore deposit according to claim 1 peels off method of purification, it is characterised in that the oxidant is
H2O2、(NH4)2S2O8、HNO3One or more kinds of mixtures.
4. a kind of native graphite ore deposit according to claim 1 peels off method of purification, it is characterised in that the organic intercalation agent
For ammonium formate, formamide, ammonium acetate, acetamide, ammonium benzoate, benzamide, ammonium phthalate, M-phthalic acid ammonium, right
Phthalic acid ammonium, phthalic amide, isophtalamide, to benzene phthalic amide, phthalimide, CO (NH2)2、
One or more kinds of mixtures of biuret, thiocarbamide.
5. a kind of native graphite ore deposit according to claim 1 peels off method of purification, it is characterised in that illumination in step 2
Light source uses UV light, visible ray or sunshine.
6. a kind of native graphite ore deposit according to claim 1 peels off method of purification, it is characterised in that described inorganic intercalated dose
For NH4Cl、NH4NO3、(NH4)2SO4、(NH4)3PO4、(NH4)2HPO4、 (NH4)2CO3And NH4HCO3At least one of.
7. a kind of native graphite ore deposit according to claim 1 peels off method of purification, it is characterised in that in the step 5, instead
When answering the kettle to heat, reactor is closed or pour in inert gas system and heat.
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