CN110229544A - The method of natural gas acetylene association carbon black synthesis nanometer carbon black - Google Patents
The method of natural gas acetylene association carbon black synthesis nanometer carbon black Download PDFInfo
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- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
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- C09C1/48—Carbon black
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Abstract
The invention belongs to active carbon preparation technical fields, a kind of method for specifically disclosing natural gas acetylene association carbon black synthesis nanometer carbon black, accompanying natural gas carbon black slurry is put into a large amount of pure water solutions equipped with polyacrylamide (PAM) and is dispersed, the ionization environment that inorganic acid forms C+ is added under the conditions of -20 DEG C~+25 DEG C of temperature.Then carbon ion is captured using atoms mode, forms complex Cn +Ox ‑, while the metal ion etc. that the low molecule organic group and process pipelines that are bonded on carbon black ion in association carbon black generating process are detached from, it is oxidized to metal nitrate and unsaturated aromatic hydrocarbon；Then virtue freed by reduction dehydration, alcohol, obtain nano active Carbon Materials.Using the technical program, using gas acetylene by-product solid waste carbon black as raw material basis, low energy consumption, no pollution manufacturing condition under, complete the resource circulation utilization of product carbon, manufacture the nano active carbon product of high-quality.
Description
Technical field
The invention belongs to active carbon preparation technical fields more particularly to a kind of natural gas acetylene association carbon black to synthesize nanometer
The method of carbon black.
Background technique
Currently, active carbon is widely used to food, beverage, medicine, water process, fertilizer coating, chemical industry, smelting
The every aspect of the production and living such as refining, national defence, agricultural, active carbon will have fabulous development prospect and wide sale in future
Market.And grain diameter≤30nm active carbon nanoparticles are the basic material of science and industrial circle focus, Yin Qibiao all the time
Reveal many excellent physicochemical properties, such as the specific surface area of super large, microcellular structure, low-density, high electron mobility rate, good
Good chemical plasticity, excellent thermal conductivity, high elasticity modulus and mechanical strength etc..Active carbon nanoparticles are because excellent in its structure
More property can directly or indirectly convert the products such as fullerene, nanotube, graphene, nano-graphite by physical chemistry means, tool
Space is extremely widely applied to have in standby good secondary workability.
But active carbon nanoparticles (Li Jing≤13nm of current high-quality) still by the limitation of raw material and manufacturing process technology,
It is all made of the high carbon black products of high-temperature cracking method production degree of graphitization.The active carbon product of natural gas preparation, can especially use
In the electrical conductive activities nano-carbon material of power battery, domestic production producer is rare.And the by-product solid waste carbon black of natural gas acetylene
Be each manufacturing enterprise be difficult to handle, effect on environment greatly, have the characteristics that the chemical hazard solid waste of low temperature spontaneous combustion.It is logical
Chang Qiye using bury natural degradation, be added in coal mix burning, high temperature sintering processing etc. measures processing solid waste effect be not obvious,
And the condition of physical structure and generation that inventor has according to this solid waste carbon black carries out exploratory development, solid waste charcoal blacking, which is given up, is
Treasured realizes recycling for solid waste carbon black.
Summary of the invention
The purpose of the present invention is to provide a kind of method of natural gas acetylene association carbon black synthesis nanometer carbon black, realizations pair
The by-product solid waste carbon black of natural gas acetylene recycles, and generates the nano active carbon product of high-quality.
In order to achieve the above object, a kind of base case of the invention are as follows: natural gas acetylene association carbon black synthesis nanometer
The method of carbon black, comprising the following steps:
Step 1: weighing raw material respectively and guaranteeing the mass ratio of raw material are as follows: inorganic acid: acetylene product carbon (C+/Re/
Hx): desalted water (H2O): polyacrylamide (PAM)=0.1~10:0.25~30:70~100:0.1~100PPm, it will be above-mentioned
Raw material is added in stainless steel cooling cycle disperser, under -20 DEG C~30 DEG C cryogenic conditions, to be not less than the machinery of 600r/min
Mixing speed stirs 1h, obtains ± 0.5 ionization solution a of pH value=1.5；
Step 2: oxidant is added in solution a, and C+/ Re/Hx: the mass ratio of oxidant be 1:15, temperature be-
20 DEG C~30 DEG C, pressure P2Under conditions of=0.005~0.5MPa, solution b is obtained after carrying out closed oxidation reaction 2h；
Step 3: reducing agent is added into solution b, the pH value of solution b is adjusted are as follows: 6.5~7.5, carbon blacksurface is micro
Organic group H+\CH\CH2\C2H2\C2H4\C4H8Deng abjection, C is eliminatedn +OxBetween organic adhesion object, restore association carbon black on work
The residue of pipeline adc obtains solution d；
Step 4: solution d is transferred to stratification in extraction tower, the black colloidal solution of solution d higher slice, which enters to take off, washes tower,
It is filtered using the vacuum filter in the aperture 1000nm to vacuum meter and is zeroed, take out colloidal-carbon；
Step 5: alcoholysis is washed: colloidal-carbon is placed in take off and wash in tower, to the de- concentration for washing 10 times of colloidal-carbon volume of addition in tower
It for 99.5% refined methanol, is stirred with the speed not less than 500r/min, obtains solution e after stirring 30min, solution e is put into
In the vacuum filtration machine of 100nm, drains methanol and obtain de- fragrant nano active carbon black；
Step 6: de- virtue nano active carbon black is baked by heating, abjection methanol, unsaturated aromatic hydrocarbon and hydrazine hydrate are left
Object obtains nano active carbon black；
Step 7: nano active carbon black is sintered, high-specific area nano electrical conductive activities carbon black is obtained；
Step 8: high-specific area nano electrical conductive activities carbon black enters planetary ball mill crushing, counted after product testing
Amount packaging.
The working principle and beneficial effect of this base case are: accompanying natural gas carbon black is put into equipped with organic-flocculation
Disperse in a large amount of pure water solutions of agent -- polyacrylamide (PAM), nitric acid is added under the conditions of -20 DEG C~30 DEG C of temperature and forms C+
Ionization environment.Then carbon ion is captured using atoms mode, forms complex Cn +Ox -, association carbon black is generated
It is bonded in low molecule organic group on carbon black ion in the process such as: H+\CH\CH2\C2H2\C2H4\C4H8Deng and process pipelines
The metal cations Fe of disengaging+\Ni+\Cr+Deng being oxidized to metal nitrate and unsaturated aromatic hydrocarbon.It is freed by reduction dehydration, alcohol
Virtue obtains nano active Carbon Materials.
Active carbon nanoparticles are prepared using accompanying natural gas carbon black, realize the resource circulation utilization of solid waste carbon black, reduce resource
Waste avoids solid waste carbon pollution environment, and environmental protection needed for reducing manufacturer's cleaning solid waste carbon black is paid wages, and increases production
The type of the raw material of active carbon nanoparticles, and the limited source of the raw material of the prior art keep the yield of active carbon nanoparticles not high,
In this way compared with existing raw material, using the technical program make the solid waste carbon black of accompanying natural gas as new raw material come
Source, solves the problems, such as the insufficient raw material of the prior art, while improving the yield of active carbon nanoparticles to meet the market demand, reduces city
Field price, more conducively people, which are bought, to be used.
The average molecular mass of polyacrylamide (PAM) is above from thousands of to millions of to have several officials along key-like molecule
Energy group, can largely ionize in water, belong to polyelectrolyte, provide ionization for the carbon ion protonation in solid waste carbon black
Environment.And polyacrylamide (PAM) is used as flocculant, the collection for ultra-fine (1nm~5nm) solid carbon provides substance item
Part.Nitric acid is strong oxidizer, and nitric acid oxidation metal ion can destroy the catalytic action of organic group and metal, reduces ion carbon
With the coordination binding force of metal.Oxidant has the function of strong atoms, is carbon ion C+With oxygen atom O-Quantum coordination is provided
Feasibility, while organic group is oxidized to unsaturated aromatic hydrocarbon.Reducing agent is that amino is inserted between carbon ion, and carbon ion is isolated
Polymerizable functional, realize the separation of metal ion and ion carbon, the nanometer carbon ion for obtaining minimum partial size (can theoretically obtain
The single carbon works of the full state of the outer shell of atomic diameter, harvests the single carbon of a large amount of 1nm~5nm in the actual production process).
Further, de- virtue nano active carbon black is placed in 130 DEG C of rotation cellar dryer in step 6, baking time 4h.
Proper temperature can achieve the effect that preferably to deviate from foreign matter, while completely cut off external environment to the shadow of de- fragrant nano active carbon black
It rings, prevents other side reactions from occurring.
Further, nano active carbon black is put into 1250 DEG C of pipe type sintering furnaces, sintering time 2h in step 7.Guarantee nanometer
Activated carbon black sintering is abundant.
Further, the time of repose of step 4 is 2h, and solution d is automatically separated as upper layer and lower layer, and the lower leaf of solution d is from extracting
The bottom valve of tower is taken to be discharged.Time of repose is abundant in this way, guarantees to stand effect, while avoiding time of repose too long and slowing down production effect
The lower leaf of rate, solution d is discharged from the bottom valve of extraction tower, and cleaning is convenient.
Further, the oxidant of step 2 is the H that concentration is 50%2O2.The H of suitable concentration2O2, guarantee that oxidation reaction is filled
Point, while excessive oxidant is avoided, it results in waste of resources.
Further, the inorganic acid of step 1 is nitric acid (HNO3).Nitric acid has strong oxidation, can destroy carbon black
Structure, so that metal ion in carbon black is detached from constraint, be dissolved in acid solution, and nitric acid is unstable, easy decomposition, such nitric acid
It is separated more easily with other substances.
Further, inorganic acid in step 1: acetylene product carbon (C+/ Re/Hx): desalted water (H2O): polyacrylamide
(PAM)=1:3:97:2PPm.
Detailed description of the invention
Fig. 1 is the production system signal for the embodiment of the method that natural gas acetylene association carbon black of the present invention synthesizes nanometer carbon black
Figure.
Specific embodiment
Combined with specific embodiments below and attached drawing come present invention be described in more detail:
The basic reason that the product carbon of natural gas acetylene generates aggregation is charcoal ion and organic group in trace meter
Louis acid catalysis under existence condition synthesizes coordinate bond accumulation process.Metal ion (especially Ni, Cr, Fe inherently) is very
Good organic catalyst, (80 DEG C~120 DEG C) achieve that the electrochemistry formated ion of carbon ion in a certain temperature conditions
Coordinate bond+organic covalent polymerization object, this is the physical chemical factor that solid waste carbon black is difficult to degrade.According to the formation of solid waste carbon black
Condition purposefully solves the electron coordinate binding ability of solid waste carbon black, to obtain this embodiment scheme.
A kind of embodiment method of natural gas acetylene association carbon black synthesis nanometer carbon black, including following step as shown in Figure 1:
It is rapid:
Step 1: weighing raw material respectively and guaranteeing the mass ratio of raw material are as follows: nitric acid (HNO3): acetylene product carbon (C+/Re/
Hx): desalted water (H2O): the dispersion of stainless steel cooling cycle is added in above-mentioned raw materials by polyacrylamide (PAM)=1:3:97:2PPm
In device, under -20 DEG C~25 DEG C cryogenic conditions, dissolve to obtain pH value=1.5 with the mechanical stirring speed stirring 1h of 600r/min
± 0.5 ionization solution a,
Re: refer to each metal ion species Hx such as Fe Ni Cr: referring to H CH CH2 C2H2 C2H4 C4H8 organic group；
Step 2: the H that concentration is 50% is added in solution a2O2, and carbon black: H2O2Mass ratio be 1:15, in temperature
For -20 DEG C~30 DEG C, pressure P2Under conditions of=0.005~0.5MPa, solution b is obtained after carrying out closed oxidation reaction 2h；Step
Two chemical equation is as follows:
Step 3: hydrazine hydrate (H is added into solution b6N2O), the pH value of solution b is adjusted are as follows: 6.5-7.5, carbon blacksurface are micro-
The organic group H of amount+\CH\CH2\C2H2\C2H4\C4H8Deng abjection, C is eliminatedn +OxBetween organic adhesion object, restore association carbon black on
Process pipelines residue, obtain solution d；The chemical equation of step 3 is as follows:
Step 4: solution d is transferred to stratification in extraction tower, the black colloidal solution of solution d higher slice, which enters to take off, washes tower,
It is filtered using the vacuum filter in the aperture 1000nm to vacuum meter and is zeroed, take out colloidal-carbon；
Step 5: alcoholysis is washed: colloidal-carbon is placed in take off and wash in tower, to the de- concentration for washing 10 times of colloidal-carbon volume of addition in tower
It for 99.5% refined methanol, is stirred with the speed of 500r/min, obtains solution e after stirring 30min, solution e is put into 100nm's
In vacuum filtration machine, drains methanol and obtain de- fragrant nano active carbon black；
Step 6: de- virtue nano active carbon black is baked by heating, abjection methanol, unsaturated aromatic hydrocarbon and hydrazine hydrate are left
Object obtains nano active carbon black；
Step 7: nano active carbon black is sintered, high-specific area nano electrical conductive activities carbon black is obtained；
Step 8: high-specific area nano electrical conductive activities carbon black, which enters planetary ball mill, is crushed to 100nm, after product testing
Carry out metering packing.
Material and facility needed for the present embodiment is as follows:
Raw material: solid waste carbon black C+/ Re/Hx is indicated；C+: refer to ion carbon；Re: refer to each metal ion species such as Fe Ni Cr；
Hx: refer to H+\CH\CH2\C2H2\C2H4\C4H8Equal organic groups；
Auxiliary material: nitric acid, hydrogen peroxide, hydrazine hydrate (HNO3、H2O2、H6N2O)；
Ionizer: polyacrylamide (PAM)；
Inorganic salt solvent: deionized water (H2O)；
Unsaturated aromatic hydrocarbon solvent: alcohols (CH3OH)；
Production equipment: stainless steel cooling cycle disperser, extraction tower, it is de- wash tower, vacuum filtration unit, vacuum drier,
Rotary kiln dryer, tubular type are sintered device, nano material ball mill pulverizer；
All devices are required to electrostatic grounding.
The product testing data of the present embodiment:
What has been described above is only an embodiment of the present invention, and the common sense such as well known specific structure and characteristic are not made herein in scheme
Excessive description.It should be pointed out that for those skilled in the art, under the premise of not departing from the utility model structure, also
Several modifications and improvements can be made, these also should be considered as the protection scope of the utility model, these all will not influence this reality
With the effect and patent practicability of novel implementation.This application claims protection scope should be with the content of its claim
Standard, the records such as specific embodiment in specification can be used for explaining the content of claim.
Claims (7)
1. a kind of method of natural gas acetylene association carbon black synthesis nanometer carbon black, which comprises the following steps:
Step 1: weighing raw material respectively and guaranteeing the mass ratio of raw material are as follows: inorganic acid: acetylene product carbon (C+/ Re/Hx): desalination
Water (H2O): above-mentioned raw materials are added polyacrylamide (PAM)=0.1~10:0.25~30:70~100:0.1~100PPm
In stainless steel cooling cycle disperser, under -20 DEG C~30 DEG C cryogenic conditions, to be not less than the mechanical stirring speed of 600r/min
1h is stirred, ± 0.5 ionization solution a of pH value=1.5 is obtained；
Step 2: oxidant is added in solution a, and C+/ Re/Hx: the mass ratio of oxidant be 1:15, temperature be -20 DEG C~
30 DEG C, pressure P2Under conditions of=0.005~0.5MPa, solution b is obtained after carrying out closed oxidation reaction 2h；
Step 3: reducing agent is added into solution b, the pH value of solution b is adjusted are as follows: 6.5~7.5, micro organic of carbon blacksurface
Group H+\CH\CH2\C2H2\C2H4\C4H8Deng abjection, C is eliminatedn +OxBetween organic adhesion object, restore association carbon black on process duct
The residue of line obtains solution d；
Step 4: solution d is transferred to stratification in extraction tower, the black colloidal solution of solution d higher slice, which enters to take off, washes tower, uses
The vacuum filter in the aperture 1000nm is filtered to vacuum meter and is zeroed, and takes out colloidal-carbon；
Step 5: alcoholysis is washed: colloidal-carbon is placed in take off and wash in tower, is to the de- concentration for washing 10 times of colloidal-carbon volume of addition in tower
99.5% refined methanol is stirred with the speed not less than 500r/min, obtains solution e after stirring 30min, solution e is put into
In the vacuum filtration machine of 100nm, drains methanol and obtain de- fragrant nano active carbon black；
Step 6: de- virtue nano active carbon black is baked by heating, abjection methanol, unsaturated aromatic hydrocarbon and hydrazine hydrate residue are obtained
To nano active carbon black；
Step 7: nano active carbon black is sintered, high-specific area nano electrical conductive activities carbon black is obtained；
Step 8: high-specific area nano electrical conductive activities carbon black enters planetary ball mill crushing, metering packet is carried out after product testing
Dress.
2. the method for natural gas acetylene association carbon black synthesis nanometer carbon black according to claim 1, which is characterized in that step
It takes off virtue nano active carbon black in rapid six to be placed in the dryer of the cellar of the rotation not less than 130 DEG C, baking time 4h.
3. the method for natural gas acetylene association carbon black synthesis nanometer carbon black according to claim 1, which is characterized in that step
Nano active carbon black is put into not less than 1250 DEG C pipe type sintering furnaces, sintering time 2h in rapid seven.
4. the method for natural gas acetylene association carbon black synthesis nanometer carbon black according to claim 1, which is characterized in that step
Rapid four time of repose is 2h, and solution d is automatically separated as upper layer and lower layer, and the bottom of extraction tower is equipped with bottom valve, solution d lower leaf from
The bottom valve of extraction tower is discharged.
5. the method for natural gas acetylene association carbon black synthesis nanometer carbon black according to claim 1, which is characterized in that step
Rapid two oxidant is the H that concentration is 50%2O2。
6. the method for natural gas acetylene association carbon black synthesis nanometer carbon black according to claim 1, which is characterized in that step
Rapid one inorganic acid is nitric acid (HNO3)。
7. the method for natural gas acetylene association carbon black synthesis nanometer carbon black according to claim 1, which is characterized in that step
Inorganic acid in rapid one: acetylene product carbon (C+/ Re/Hx): desalted water (H2O): polyacrylamide (PAM)=1:3:97:2PPm.
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