CN109923066A - Spheric active carbon and its manufacturing method - Google Patents
Spheric active carbon and its manufacturing method Download PDFInfo
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- CN109923066A CN109923066A CN201780068885.0A CN201780068885A CN109923066A CN 109923066 A CN109923066 A CN 109923066A CN 201780068885 A CN201780068885 A CN 201780068885A CN 109923066 A CN109923066 A CN 109923066A
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- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
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- C01B32/318—Preparation characterised by the starting materials
- C01B32/33—Preparation characterised by the starting materials from distillation residues of coal or petroleum; from petroleum acid sludge
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Abstract
The spheric active carbon that spheric active carbon of the invention is integrally formed.The average grain diameter of the spheric active carbon is 1.5mm or more 4.0mm hereinafter, the fine pore in the spheric active carbon be pore volume under 50nm or more 10000nm range below is 0.01ml/g or more 0.24ml/g range below.
Description
Technical field
The present invention relates to the manufacturing methods of a kind of spheric active carbon and the spheric active carbon.
Background technique
In chemical industry, active carbon is used in separating technology, purification, catalyst or solvent recovery, in turn, wide
It is general to be used in drainage sunk well relevant to earth environment pollution problem, public hazards countermeasure or medical application.
Such as non-patent literature 1 discloses a kind of granular work that powdered active carbon and average grain diameter are number mm or so
Property charcoal.
Additionally, it is known that have using the heavy hydrocarbon oil such as petroleum tar or ethylene bottom oil as the active carbon (patent document 1) of raw material, with
And using resin as the active carbon (patent document 2) of raw material.
Existing technical literature
Patent document
Patent document 1: Japanese Laid-Open Patent Publication " Japanese Unexamined Patent Publication 2005-119947 bulletin "
Patent document 2: Japanese Laid-Open Patent Publication " Japanese Unexamined Patent Publication 2000-233916 bulletin " non-patent literature
Non-patent literature 1: true Tian Xiongsan, other 2 " new edition active carbon basis and application ", talk society, Co., Ltd.,
On March 1st, 1992
Summary of the invention
Problems to be solved by the invention
Furthermore using active carbon, it is desirable that reduce the pressure loss and inhibit dust.
Active carbon is being filled in the devices such as column, so that fluid containing certain density target substance is circulated and the feelings that use
Under condition, in order to maximize the effect for the per unit volume of target substance, need densely to fill activated carbon particles.
But in the case where the partial size of active carbon is small, or the situation more than the dust yield caused by because of active carbon
Under, the inter-particle voids of active carbon can be blocked.In addition, in these cases, because the blocking of device filter etc. leads to pressure
Loss becomes larger, as a result, it is believed that for device, the load becomes large.In addition, in the fluid using active carbon processing big flow
In the case where, the dust of the small active carbon of partial size or generation can probably disperse.
In addition, after contacting active carbon with the fluid (gas or liquid) containing target substance, respectively by active carbon
And in the case that target substance separates, need to handle such as filtering.But, if the particle of active carbon is small or dust yield
It is more, then in order to separate them, effort, cost can be spent.
Especially, it can be said that being filled in device since the granularity of above-mentioned powdered active carbon is substantially smaller
It carries out in use, the pressure loss can become larger, and fluid treating capacity is also restrained.
In addition, when handling the fluid of big flow, powder I'm afraid meeting in the case where so using powdered active carbon
It disperses.
In contrast, it is also contemplated that being the granular active carbon for counting mm or so if average grain diameter, then when can reduce filling
The pressure loss, can carry out big flow fluid processing.
But in the past, it in the manufacturing method of granular active carbon, generally uses and dust active carbon is mixed with binder and made
The mode that grain granulates.That is not being integrally formed activity by the granular active carbon that previous manufacturing method obtains
Charcoal.As a result, it can be said that since the intensity of previous granular active carbon is weak, if such granular active carbon is filled in dress
It sets and carries out using then a large amount of to generate dust, it is difficult to carry out the separation with fluid.
In addition, it can be said that since previous granular active carbon generally utilizes coconut husk charcoal etc., also there is that impurity is more, powder
The problems such as impurity other than dirt is eluted out.
From the viewpoint, it is desirable that develop a kind of active carbon that can inhibit the pressure loss and dust.
Technical solution
The inventors of the present invention have made intensive studies in order to solve the above problems, as a result, have found following fact, from
And complete the present invention, that is, the integrally formed spheric active carbon for being number mm or so according to partial size, be able to suppress the pressure loss with
And dust.
It is average grain diameter is 1.5mm or more 4.0mm hereinafter, being integrally formed that is, the present invention provides a kind of spheric active carbon
Spheric active carbon, be pore volume under 50nm or more 10000nm range below in fine pore be 0.01ml/g or more
0.24ml/g range below.
In turn, the present invention provides a kind of manufacturing method of spheric active carbon with above-mentioned feature.
Beneficial effect
According to the present invention, it is possible to provide a kind of active carbon for being able to suppress the pressure loss and dust.
Specific embodiment
Hereinafter, the embodiment to spheric active carbon of the invention is specifically described.
(spheric active carbon)
The average grain diameter of the spheric active carbon (hereinafter also referred to as " spheric active carbon ") of present embodiment is 1.5mm or more
4.0mm is hereinafter, be pore volume under 50nm or more 10000nm range below in fine pore be 0.01ml/g or more
0.24ml/g or less.It should be noted that the detailed description of fine pore and pore volume describes below.
In the present specification, spheric active carbon means spherical active carbon.The spherical degree of spheric active carbon is not special
It limiting, draw ratio is preferably 0.7 or more, and more preferably 0.8 or more, further preferably 0.9 or more.Draw ratio is minor axis and length
The ratio between diameter.Major diameter and minor axis by well known method, such as in the projection image of spheric active carbon maximum length and
The average value of minimum length and find out.Draw ratio is closer to 1, and spheric active carbon is closer to real sphere.It should be noted that
If the draw ratio of spheric active carbon is 0.7 or more, when using spheric active carbon, can be further reduced because of spheric active carbon
Abrasion caused by the mutual collision of particle, therefore the generation of dust can be adequately suppressed.
The spheric active carbon that the spheric active carbon of present embodiment is integrally formed." integrally formed spheric active carbon " meaning
Refer to, formed as primary particle, and there is spherical active carbon.The spheric active carbon of present embodiment has aftermentioned
Fine pore and pore volume, therefore the also referred to as active carbon with porosity and spherical primary particle.Such as with agglutination
Previous spheric active carbon as the sintered body of particle is compared, the mechanical strength of the spheric active carbon of present embodiment.
For example, the spheric active carbon of present embodiment has high crushing strength, or has low compared with previous spheric active carbon
Water in vibrate rate of wear.
(average grain diameter)
From the viewpoint of the rising of the pressure loss for the filled layer for inhibiting spheric active carbon, the spherical work of present embodiment
Property charcoal average grain diameter lower limit value be 1.5mm or more, preferably 1.7mm or more, more preferably 1.8mm, further preferably
More than 2.0mm.In addition, from the viewpoint of the sufficient above-mentioned contact of the spheric active carbon and fluid realized in filled layer,
The upper limit value is 4.0mm hereinafter, preferably 3.5mm is hereinafter, more preferably 3.0mm or less.By making average grain diameter in the range
It is interior, it can fully increase the inter-particle voids of spheric active carbon.Therefore, if such spheric active carbon, then by spherical work
When property charcoal is filled in the devices such as column, knockout tower and contacts with the fluid containing target substance, it can fully reduce the pressure loss.
In the present embodiment, the average grain diameter of spheric active carbon can be evaluated according to JIS K 1474.That is, according to by
It is that the operation of JIS K 1474 obtains as a result, production spheric active carbon granularity add up line chart.By horizontal axis 50% point hang down
Straight line and granularity add up the intersection point of line chart, draw horizontal line in the longitudinal axis and find out the mesh (mm) of sieve shown in intersection point.It should
The value of mesh is set as the average grain diameter of spheric active carbon.
(fine pore)
In the present specification, fine pore it is meant that pore possessed by spheric active carbon pore diameter.In present embodiment
In, fine pore and pore volume can be measured by for example well known mercury penetration method.In addition, fine pore and pore volume
It according to the character of for example aftermentioned crosslinking heaviness pitch, the type for the additive being crosslinked in heaviness pitch or can utilize molten
The condition etc. that the additive is extracted in agent is adjusted.
(pore volume)
In the present specification, pore volume it is meant that the pore within the scope of the specific fine pore of active carbon volume.
From the viewpoint of the reduction of the productivity for the aftermentioned manufacturing method for inhibiting spheric active carbon, present embodiment
The lower limit value of pore volume in the range for being 50nm or more 10000nm or less in fine pore of spheric active carbon is 0.01ml/g
More than, preferably 0.02ml/g or more, more preferably 0.03ml/g or more, further preferably 0.05g/ml or more.In addition, from
From the viewpoint of preventing the crushing strength of spheric active carbon from reducing, which is 0.24ml/g hereinafter, preferably 0.22ml/g
Hereinafter, more preferably 0.20ml/g is hereinafter, further preferably 0.18ml/g or less.
In addition, from the viewpoint of the reduction of productivity for inhibiting spheric active carbon, the spheric active carbon of present embodiment
The range for being 10nm or more 10000nm or less in fine pore in the lower limit value of pore volume be 0.01ml/g or more, preferably
For 0.02ml/g or more, more preferably 0.03ml/g or more, further preferably 0.04ml/ or more.In addition, from spherical work is prevented
Property charcoal crushing strength reduce from the viewpoint of, the upper limit value be 0.28ml/g hereinafter, preferably 0.27ml/g hereinafter, more preferably
For 0.26ml/g hereinafter, further preferably 0.25ml/g, most preferably 0.24ml/g or less.
It according to the present embodiment, can be abundant when aftermentioned non-fusible by making spheric active carbon meet above-mentioned range
Ground forms necessary hole, therefore, can efficiently carry out non-fusible, can manufacture spherical active carbon.It is difficult to and ball in addition, can inhibit
The increase of the relevant pore volume of the adsorption capacity of shaped activated carbon, therefore, the density of spheric active carbon is got higher, spheric active carbon
The performance of per unit volume improves.
In the present embodiment, pore volume can be evaluated by for example well known mercury penetration method.(crushing strength)
Due to present embodiment spheric active carbon be primary particle, with obtained by the sintering of agglutination particle it is previous
Spheric active carbon compare, have high mechanical strength.The crushing strength of the spheric active carbon of present embodiment is preferably
1.20kg/ or more, more preferably 1.25kg/ or more, further preferably 1.30kg/.Crushing strength is for example according to ball
The purposes of shaped activated carbon and have enough sizes, may be, for example, 10.0kg/ or less.
Crushing strength can be measured by the following method.That is, optionally extracting the sample particle (example of spheric active carbon
Such as 32), using simple plastochondria hardometer (cylinder well Physicochemical instrument Co. Ltd. system), measure the moment of sample particle crushing
Hardness.Then, maximum value, the minimum value in the measured value of hardness are excluded, (such as 30 measurements of remaining measured value are calculated
Value) average value, as the crushing strength of the spheric active carbon.
(Dust Capacity)
In the present specification, dust is it is meant that the micro mist contained in spheric active carbon.In addition, Dust Capacity is it is meant that the dust
Amount, the amount calculated specifically by the tester of aftermentioned Dust Capacity.
In the present embodiment, from inhibit spheric active carbon filled layer in the pressure loss rising viewpoint and
From the viewpoint of the separating capacity for fully embodying spheric active carbon, the Dust Capacity contained in every 1g spheric active carbon is preferably
2000 μ g hereinafter, more preferably 1500 μ g hereinafter, further preferably 1200 μ g hereinafter, most preferably 1000 μ g or less.Dust
The amount the few the more preferred, and lower limit value can be 0 μ g or more.
The Dust Capacity of the spheric active carbon of present embodiment can be measured by aftermentioned specific method.Example can be passed through
Such as reduce Dust Capacity by being integrally formed the manufacturing method realized.
(rate of wear is vibrated in water)
If spheric active carbon is vibrated into the water and in water, because spheric active carbon is impinging one another, lead to ball
Shaped activated carbon is peeled off by shaving.In the present embodiment, it is calculated in water and is shaken according to the meter of the spheric active carbon peeled off at this time
Dynamic rate of wear.Specifically, vibrating rate of wear in water can calculate according to following formula.
Rate of wear (%)=(A-B)/A × 100 (%) (formula 1) is vibrated in water
A: the quality (g) of the spheric active carbon before being vibrated in water
B: the quality (g) of the spheric active carbon after being vibrated in water
In the water of the spheric active carbon of present embodiment vibrate rate of wear be preferably 5% hereinafter, more preferably 4.5% with
Under.It should be noted that in water vibrate rate of wear it is lower, then the intensity of spheric active carbon is bigger, thus because spheric active carbon that
This Dust Capacity for colliding and generating tails off.
(specific surface area)
For specific surface area, make evaluated substance adsorption gas molecule, according to the amount of adsorbed gas molecule
It is found out with the ratio between the absorption sectional area of gas molecule.Specifically, calculating N2 adsorption amount by BET method, the absorption of nitrogen molecular is cut
Area is set as 0.162nm2And find out specific surface area.It should be noted that specific surface area is also sometimes referred to as specific
surface area(SSA)。
The specific surface area of present embodiment is that gas molecule uses nitrogen, makes N2 adsorption in spheric active carbon under liquid nitrogen temperature
When specific surface area.Specific surface area can be adjusted according to the degree of for example aftermentioned activation.
From the viewpoint of the adsorption function for playing spheric active carbon, the specific surface area of the spheric active carbon of present embodiment
Preferably 100m2/ g or more, more preferably 300m2/ g or more, further preferably 400m2/ g or more., it can be said that if specific surface
Product is 100m2/ g or more then can fully play the adsorption function realized by spheric active carbon.From the viewpoint of above-mentioned, than
The surface area the big the more preferred, as long as but can fully obtain the range of the desired adsorption function of spheric active carbon i.e.
Can, it may be, for example, 4000m2/ g or less.
The spheric active carbon of present embodiment, which can add, is loaded with other substances.As other substances, for example, can enumerate acid, alkali,
And metal etc. can add the well known substance for being loaded in active carbon.As acid, specifically, such as can enumerate phosphoric acid, sulfuric acid not
Volatile acid, organic acids such as citric acid, malic acid etc..In addition, as alkali, specifically, can for example enumerate potassium carbonate, carbonic acid
Sodium, potassium hydroxide, sodium hydroxide etc..In addition, as metal, specifically, the transition elements such as can enumerate platinum, silver, iron, cobalt
And its compound etc..
In this way, the Dust Capacity contained in every 1g spheric active carbon is excellent for the spheric active carbon of present embodiment
It is selected as 2000 μ g or less.
In turn, rate of wear is vibrated in the water of the spheric active carbon of present embodiment is preferably 5% or less.
In turn, the draw ratio of the spheric active carbon of present embodiment is preferably 0.7 or more.
In turn, the spheric active carbon of present embodiment, which preferably adds, is loaded with alkali or acid.
Spheric active carbon according to the present embodiment can inhibit the pressure loss and Dust Capacity.It as a result, can be by such ball
Shaped activated carbon is used for multiple use.In addition, compared with previous active carbon, the spheric active carbon of present embodiment it is resistance to anti-thread breakage
Also good.
As long as the manufacturing method of the spheric active carbon of present embodiment can obtain the spherical activity for the feature for having above-mentioned
The method of charcoal, is just not particularly limited.Hereinafter, (hereinafter also referred to as to the manufacturing method of the spheric active carbon of present embodiment
" this manufacturing method ") an embodiment be illustrated.(manufacturing method of spheric active carbon)
(raw material)
In this manufacturing method, as the raw material of spheric active carbon, heavy hydrocarbon oil is used.As heavy hydrocarbon oil, such as can
It enumerates selected from by one or more of groups constituted such as petroleum tar, coal tar or ethylene bottom oil.
It wherein, then can be by the light composition of the Residual oil generated when ethylene manufactures (bottom oil) if ethylene bottom oil
It is evaporated under reduced pressure and is obtained.
In addition, fossil fuel or plant-derived resin can be originated from as spherical using contain furane resins or phenolic resin
The raw material of active carbon.
Specifically, this manufacturing method includes the manufacture of (1) crosslinking heaviness pitch, (2) into crosslinking heaviness pitch
Add that additive, (3) crosslinking molding of heaviness pitch, the extraction of (4) additive, (5) are non-fusible and (6) firing/activation
This six processes.Hereinafter, being successively illustrated to each process.
(1) it is crosslinked the manufacture of heaviness pitch
In this manufacturing method, manufacture is crosslinked heaviness pitch first.As described later, the manufacture of the crosslinking heaviness pitch
Process are as follows: ensure the non-compatibility with the appropriateness of the viscosity adjustment additive comprising aromatic compound, and then in additive
Abstraction process in, the necessary process for the porous of pelletted pitch.
For being crosslinked heaviness pitch, for example, at normal temperature to the heaviness hydrocarbon ils of liquid carry out crosslinking Treatment and
Heat treatment.It can obtain solid crosslinking heaviness pitch at normal temperature as a result,.It is crosslinked the specific manufacture of heaviness pitch
Method is for example recorded in No. 4349627 bulletins of Japanese Patent No..
(2) additive is added into crosslinking heaviness pitch
Then, by by additive make an addition to it is resulting be crosslinked in heaviness pitch, adjustment crosslinking heaviness pitch it is viscous
Degree makes to be crosslinked heaviness pitch as the viscosity suitable for spheroidizing.
As additive, such as the viscosity adjustment additive etc. such as can enumerate aftermentioned naphthalene.
Additive is made an addition in crosslinking heaviness pitch and after carrying out heating mixing, it can be by the way that heaviness drip will be crosslinked
Blueness molding obtains pelletted pitch.
In this manufacturing method, the additive made an addition in the crosslinking heaviness pitch from heavy hydrocarbon oil is preferably boiling point
200 DEG C or more, preferably 205 DEG C or more, more preferably 210 DEG C or more of two rings or tricyclic or its mixing
Object.
As the concrete example of such preferred additive, such as can enumerate selected from by naphthalene, methyl naphthalene, phenylnaphthalene, benzyl
One or more of groups of compositions such as naphthalene, methyl anthracene, phenanthrene, biphenyl.Wherein, additive is preferably naphthalene.
In the case where the total amount for being crosslinked the mixture of heaviness pitch and additive is set as 100 mass %, additive
The lower limit value of additive amount relative to crosslinking heaviness pitch is preferably 26 mass % or more, more preferably 27 mass % or more,
Further preferably 28 mass %.Additive additive amount be lower limit value situation below under, relative to resulting porosity
Pelletted pitch can not form sufficient hole sometimes.In addition, the upper limit value of the additive amount of additive be preferably 50 mass % hereinafter,
More preferably 45 mass % are hereinafter, further preferably 40 mass % or less.It is upper limit value or more in the additive amount of additive
In the case of, since heaviness pitch is opposite with the crosslinking heaviness pitch amount in the mixture of additive tails off for crosslinking, system
Make efficiency reduces sometimes.In addition, being formed in aftermentioned process, it is necessary to above drawing holes, therefore, resulting spherical activity
The intensity of charcoal becomes inadequate sometimes.It, can be from pelletted pitch in aftermentioned process by the way that the amount of additive is set as the range
In efficiently extract additive, for resulting porosity pelletted pitch, sufficient hole can be formed.It should be noted that
If the hole of porosity pitch is abundant, in aftermentioned non-fusible process, may proceed to by the cross-linking reaction that oxidation reaction is realized
The inside of porosity pelletted pitch can keep the spherical of porosity pelletted pitch, while be carbonized.It should be noted that if
Such as naphthalene additive amount is set as 25 mass %, then the hole of porosity pitch becomes inadequate and melts sometimes.
It should be noted that being contained in by the hole that above-mentioned additive is formed in fine pore is 50nm or more 10000nm or less
In the range of spheric active carbon pore volume a part.
(3) it is crosslinked the molding of heaviness pitch
Then, the crosslinking heaviness asphalt moulding of additive will be added to.At this time, it is preferred that make to be crosslinked heavy in advance
The mixture for changing pitch and additive homogenizes.The mixture of crosslinking heaviness pitch and additive is preferably made up of heating
Molten mixture.
The molding of crosslinking heaviness pitch can carry out in the state of molten mixture, alternatively, can be by by melting mixing
It is crushed after object is cooling, is stirred etc. and carries out in the hot water.It should be noted that in order to make mentioning for subsequent additive
It takes process to be easier to carry out, heaviness asphalt moulding will be crosslinked preferably in a manner of partial size 6.0mm pelletted pitch below is made.
Such as can be by the way that the water of suspending agent will be contained as decentralized medium, it, will crosslinking heaviness drip under normal pressure or pressurization
The green homogeneous mixture with additive, which melts, to be dispersed, and pelletted pitch is obtained.
In addition to this, the method as pelletted pitch in order to obtain, can also will such as Japanese Patent Publication 59-10930 public affairs
Report disclosed method as reference.Specifically, can mixing to heaviness pitch Yu viscosity adjustment additive will be crosslinked
Object squeezes out in the molten state and rodlike pitch is made, or cools and solidifies to pitch made of stretching the pitch,
It is made after the ratio between length/diameter is 5 rodlike pitches below, resulting rodlike pitch pressure break in the softening point of rodlike pitch
At a temperature of above, it is stirred and is shaped to spherical in the hot water containing suspending agent.
In the present embodiment, the size of above-mentioned rodlike pitch determines the average grain diameter of spheric active carbon.Therefore, in order to
Make the above 4.0mm of average grain diameter 1.5mm of spheric active carbon hereinafter, the long dimension direction of rodlike pitch is preferably dimensioned to be
1.5mm~10mm or so.In addition, the bore of the die orifice when squeezing out rodlike pitch is preferably 1.5mm~10mm or so.
It is heated to being crosslinked the mixed of heaviness pitch and additive by the way that the rodlike pitch obtained as described above to be added to
In the hot water for closing the softening point of object or more, pelletted pitch is made in rodlike pitch softening transform.
In addition, crushed after the molten mixture that will be crosslinked heaviness pitch and additive is cooling, in the hot water into
The temperature (hereinafter, the temperature is known as " spheroidizing temperature ") of hot water when row stirring is according to crosslinking heaviness pitch and additive
Molten mixture viscosity and suitably set.
In the present embodiment, the lower limit value of spheroidizing temperature is preferably 95 DEG C or more, and more preferably 97 DEG C or more, into one
Preferably 98 DEG C or more of step.In addition, the upper limit value of spheroidizing temperature be preferably 120 DEG C hereinafter, more preferably 115 DEG C hereinafter, into
One step is preferably 110 DEG C or less.By the way that spheroidizing temperature is set as the range, pelletted pitch can be efficiently obtained.It needs
Bright, if spheroidizing temperature is low, the mixture for being crosslinked heaviness pitch and additive will not be deformed, and therefore, probably can not
Efficiently make rodlike pitch spheroidizing.On the other hand, if spheroidizing temperature is excessively high, it is crosslinked the molten of heaviness pitch and additive
Melting mixture becomes bag-shaped or molten mixture tearing, and therefore, the partial size of final resulting spheric active carbon can probably become
It is small.
It should be noted that being preferably stirred when making rodlike pitch spheroidizing in the hot water.At this point, if mixing power
Weak, then pelletted pitch can probably settle, and pelletted pitch each other probably can welding.On the other hand, if mixing power is excessively high, fear
Fearness can generate the tearing of pelletted pitch because of shearing force.From the viewpoint, preferably properly select pelletted pitch in heat
Most suitable rabbling mechanism and speed of agitator as water float/flowing.It should be noted that as pelletted pitch stream is made
Dynamic mode is not limited to stir, other methods appropriate can also be used.
In turn, in the present embodiment, it is further preferred that make in the presence of suspending agent above-mentioned crosslinking heaviness pitch with
The mixture melting suspended dispersed of above-mentioned additive is in hot water.That is, when making rodlike pitch spheroidizing, it is further preferred that will
Suspending agent makes an addition in hot water.Hot water containing suspending agent has the dispersibility for improving pelletted pitch, and prevents pelletted pitch
The effect of welding each other.From the viewpoint, in the present embodiment, it is preferred that make to be crosslinked heaviness pitch
Mixture melting suspended dispersed with additive is in hot water, to obtain pelletted pitch.
In the present embodiment, it as suspending agent, such as can enumerate: polyvinyl alcohol (hereinafter also referred to " PVA "), xanthan
Glue, partly-hydrolysed polyvinyl acetate, methylcellulose, carboxymethyl cellulose, polyacrylic acid and its esters, polyethylene glycol and
Water-soluble high-molecular compounds such as its ether derivant, ester derivant starch, gelatin etc..
At this point, suitably setting the concentration of suspending agent.It should be noted that the concentration of suspending agent is higher, then spherical drip
Green sinking speed more reduces, and accordingly, pelletted pitch can be made to disperse by smaller mixing power, and can inhibit because shearing force is led
The tearing etc. of the pelletted pitch of cause.
In the present embodiment, in the case where PVA is used as suspending agent, content of the PVA relative to above-mentioned hot water
Lower limit value be 0.1 mass % or more, preferably 0.15 mass % or more, more preferably 0.23 mass % or more, further preferably
For 0.3 mass % or more.In addition, the upper limit value of the content be preferably 20 mass % hereinafter, more preferably 15 mass % hereinafter, into
One step is preferably 10 mass % or less.
The lower limit value of the temperature of hot water is preferably 95 DEG C or more, more preferably 97 DEG C or more, further preferably 98 DEG C with
On.In addition, the upper limit value of the temperature of hot water be preferably 120 DEG C hereinafter, more preferably 115 DEG C hereinafter, further preferably 110 DEG C
Below.
In turn, in the present embodiment, can be together with suspending agent and with tackifier, or tackifier are only used alone.
When carrying out spheroidizing, for the amount ratio of rodlike pitch and the hot water containing suspending agent, preferably liquor ratio is high.By
This, because rodlike pitch it is mutual collision etc. caused by small particle, heteromorphosis influence reduce.
(4) extraction of additive
Then, the additive contained in resulting pelletted pitch is removed, in subsequent non-fusible process, is formed for supplying
Oxidizing gas diffuses to the hole of the inside of pelletted pitch.
In the present embodiment, since crosslinking heaviness pitch has the non-compatibility with additive, speculate spherical
The inside of pitch forms the island structure of crosslinking heaviness pitch and additive.From the viewpoint, in this manufacturing method
In, it is preferred that the additive part contained in pelletted pitch is removed by using solvent, in subsequent non-fusible process
In, it is formed into hole of the oxygen relative to the channel of pelletted pitch.
The mass ratio of the slurry of solvent and pelletted pitch is preferably 7 or more, more preferably 9 or more, further preferably 13.
If the mass ratio of the slurry of solvent and pelletted pitch less than 7, extracts the additive of inside particles with being unable to fully sometimes, with
In non-fusible process afterwards, it can not be formed into hole of the oxygen relative to the channel of pelletted pitch sometimes.
As the solvent for additive to be extracted and removed from pelletted pitch, aliphatic compound can be enumerated.In the rouge
In fat compounds of group, such as the aliphatic hydrocarbons such as butane, pentane, hexane, heptane, naphtha, kerosene can be enumerated etc. with aliphatic hydrocarbon
Based on the aliphatic alcohols such as mixture, methanol, ethyl alcohol, propyl alcohol, butanol etc., wherein being suitble to use n-hexane.
At this point, the mass ratio of the slurry of n-hexane and pelletted pitch is preferably 7 or more, more preferably 9 or more, it is further excellent
It is selected as 13 or more.If the mass ratio of the slurry of n-hexane and pelletted pitch less than 7, extracts inside particles with being unable to fully sometimes
Additive can not be formed into hole of the oxygen relative to the channel of pelletted pitch sometimes in subsequent non-fusible process.
In the present embodiment, it is preferred that oxygen when being adequately formed for making non-fusible diffuses to internal hole.By
This, is preferably fully added agent from the extraction in pelletted pitch.
Solvent is used if so, then can maintain the shape of pelletted pitch, while efficiently only removing additive.
If removing additive from pelletted pitch in this manufacturing method, it is formed in pelletted pitch because extracting additive
And the through-hole generated, this makes it possible to obtain have uniform porous porosity pelletted pitch.
In the present embodiment, the softening point for being crosslinked heaviness pitch can largely effect on the softening of porosity pelletted pitch
Point.It should be noted that if softening point is too low, then when carrying out for aftermentioned infusible heat treatment, the spherical drip of porosity
Blueness probably can soften or melt, and it is not preferable.
In the present embodiment, the softening point of porosity pelletted pitch the high the more preferred.In order to improve the spherical drip of porosity
Green softening point preferably carries out the heaviness of cross-linked bitumen.If the softening point of porosity pelletted pitch is excessively high, in cross-linked bitumen
Middle generation anisotropy ingredient is probably crosslinked the spheroidizing of heaviness pitch, the extraction and aftermentioned uniform work of additive
Change processing etc. becomes difficult.
From the viewpoint, in the present embodiment, the softening point of porosity pelletted pitch is preferably 150 DEG C or more
350 DEG C hereinafter, more preferably 200 DEG C or more 300 DEG C, further preferably 220 DEG C or more 280 DEG C or less.
Furthermore the toluene insolubles of porosity pelletted pitch and the carbonization yield of pitch have good relevance, and toluene is not
The molten object the high, and being carbonized yield more tends to get higher.Therefore, toluene insolubles are preferably 40% or more, and more preferably 50% or more.
Above-mentioned toluene insolubles can be measured by well known method, for example, can the method as described in the 0030th section of patent document 1 into
Row measurement.
(5) non-fusible
Then, the spherical non-fusible pitch of porosity for heat for infusibility is formed by porosity pelletted pitch.In this system
It makes in method, as a result, by the hole formed using additive is extracted from pelletted pitch, spreads oxidizing gas equably
To the inside of porosity pelletted pitch, implement crosslinking Treatment.The spherical non-fusible pitch of porosity can be formed as a result,.It is more specific and
Speech, for example, gas phase flows porosity pelletted pitch in fluidized bed, with 100 DEG C or more 350 DEG C or less, preferably
120 DEG C or more 320 DEG C or less, more preferable 130 DEG C or more 300 DEG C or less are heated.
As oxidizing gas, O can be used2、O3、SO3、NO2, oxidizing gas such as air or with nitrogen, titanium dioxide
The inert gases such as carbon, vapor dilute mixed gas made of these oxidizing gas.
In addition, the degree of crosslinking Treatment can be according to the porosity pitch after the oxidation processes for example found out by elemental analysis
The oxygen content that elemental analysis obtains is judged.At this time, it is preferred that with oxygen content for 5 mass % or more, preferably 8
25 mass % of quality % or more hereinafter, more preferably 10 mass % or more, 23 mass % hereinafter, further preferably 11 mass %
Above 21 mass % mode below carries out oxidation processes.
(6) firing/activation
Finally, the spherical non-fusible pitch of porosity is burnt into and carbon is made, pore is formed on the carbon.It needs to illustrate
It is that the hole of the spheric active carbon formed in non-fusible process is the hole for spreading oxygen when non-fusible.It has passed through the burning
At after/activation procedure, the pore for influencing final adsorption capacity is formed in spheric active carbon.For example, by non-oxidizable
In atmosphere gas, 600 DEG C or more, preferably 650 DEG C or more, be more preferably 700 DEG C or more non-fusible pitches spherical to porosity
It is heat-treated, Spherical Carbon formed body can be obtained.
Then, by conventional method, by the firing of Spherical Carbon formed body, activation.At this point, with carbon dioxide and vapor
It is to be activated to Spherical Carbon formed body in the reactivity gas atmosphere of principal component etc. mild oxidizing gas.As a result,
The spheric active carbon of present embodiment can be obtained.
In the present embodiment, for Spherical Carbon formed body, to be preferably 600 DEG C or more, more preferably 650 DEG C or more,
Further preferably 700 DEG C or more make reactivity gas play a role.It can also make the carbonization and work of Spherical Carbon formed body as a result,
Change while carrying out, is preferred from the viewpoint of process economics therefore.
In the present embodiment, for the spheric active carbon obtained as described above, can also further add load acid, alkali or
Other substances such as metal.Other substances use well known method relative to the load that adds of spheric active carbon.If such as making metal
Add load or support in spheric active carbon, then the spheric active carbon can be used as catalyst etc..
Embodiment
Then, embodiment is shown on one side, the present invention will be described in more detail on one side, but the present invention is not limited to these
Embodiment.
[average grain diameter]
The average grain diameter of active carbon is evaluated according to JIS K 1474.Specifically, being made granularity according to JIS K1474
Accumulative line chart, is added up the intersection point of line chart by the vertical line and granularity of 50% point of horizontal axis, draws horizontal line in the longitudinal axis and find out
The mesh (mm) of sieve shown in intersection point, is set as average grain diameter for the value of the mesh.
[fine pore and pore volume]
For the fine pore and pore volume of active carbon, the pore volume mercury porisimetry based on mercury penetration method is used
(MICROMERITICS corporation " AUTOPORE 9200 ") measures the fine pore and pore volume of active carbon.It is specific and
Speech, active carbon is put into sample container, carries out deaerating for 30 minutes under 2.67Pa pressure below.Then, mercury is imported
In sample container, slowly pressurizes and mercury is pressed into the pore of active carbon.Then, according to the indentation of pressure and mercury at this time
The relationship of amount calculates the pore volume distribution of active carbon using each calculating formula below.
The calculating of pore diameter are as follows: when by mercury in the cylinder-shaped pore of pressure (P) indentation diameter (D), by mercury
Surface tension be set as " γ ", when the contact angle of mercury and porous wall is set as " θ ", according to surface tension and act on pore cut
The balance of the pressure in face, following relational expressions are set up:
- π D γ cos θ=π (D/2)2P (formula 2).
Therefore, become D=(- 4 γ cos θ)/P (formula 3).
In this specification, the surface tension of mercury is 484dyne/cn, and the contact angle of mercury and carbon is 130 degree, pressure P use
MPa indicates, and pore diameter D has found out the relationship of pressure P Yu pore diameter D using following formula with μm indicating.
D=1.24/P (formula 4)
It should be noted that the pore volume of the range of the 50~10000nm of pore diameter of the present embodiment is equivalent to right
The volume for the mercury that the range for the mercury indentation pressure answered is pressed into.
[evaluation of Dust Capacity]
The Dust Capacity of active carbon is evaluated according to following step.
1) after in advance that molecular filter (ADVANTEC diameter 47mm, 1 μm of mesh) is 1 hour dry at 110 DEG C, dry
It lets cool in dry device, then, is weighed with exact science balance to 0.1mg.
2) it takes the dry sample of 5g into the conical flask of 100ml, is weighed with exact science balance to 0.1mg.
3) pure water 100ml is added in conical flask, uses supersonic wave cleaning machine (Emerson Japan, Ltd. system
The desk-top ultrasonic cleaner 1510J-MT of Bransonic) 3 minutes.
4) it with the suspension after 106 μm of mesh of screen filtration ultrasonic wave, is filled with the suction of Millipore filter is set to
The membrane filter filtrate set.The conical flask wall surface pure water rinsing of above-mentioned process 3), also uses membrane filter to it.
5) sample remained on sieve in above-mentioned process 4) is put back in conical flask, addition pure water 100ml it
Afterwards, repeat it is total three times it is above-mentioned 3) and above-mentioned operation 4).
6) it after filtered molecular filter is 1 hour dry at 110 DEG C, lets cool in drier 30 minutes, then, uses
Exact science balance is weighed to 0.1mg.
7) carbon dust amount is calculated by following formula.
Carbon dust amount=(B-A)/S (formula 5)
A: the quality (g) of the molecular filter before filtering
B: the quality (g) of filtered molecular filter
S: the quality (g) of sample
[rate of wear is vibrated in water]
Rate of wear is vibrated in the water of active carbon to be evaluated according to the following method.
1) 1 hour dry molecular filter (0.3 μm of mesh) will have been carried out at 110 DEG C in advance and has let cool it in drier
Afterwards, it is weighed with exact science balance to 0.1mg.
2) the position grade for weighing dry sample about 10g to 0.1mg, moves into 200ml separatory funnel, addition pure water 50ml it
Afterwards, with bobbing machine (IWAKI INDUSTRY CO., LTD KM-SHAKER model V-S amplitude 40mm, vibration number 250 be reciprocal/point
Clock) vibrate within 120 minutes.
3) the screen filtration suspension for using 150 μm of mesh, carrys out suction strainer filtrate using molecular filter.Point in above-mentioned process 2)
Liquid funnel wall surface pure water rinsing, also uses membrane filter to it.
4) it after molecular filter is 30 minutes dry at 110 DEG C, is let cool in drier 30 minutes, the quality of molecular filter is quasi-
It really measures to 0.1mg.
5) rate of wear is vibrated in water to calculate according to the following formula.
Rate of wear (%)=(b-a)/s × 100 (formula 6) is vibrated in water
A: the quality (g) of the molecular filter before filtering
B: the quality (g) of filtered molecular filter
S: the quality (g) of sample
[specific surface area]
Use the specific area measuring device (MICROMERITICS based on gas adsorption method of specific surface area continuous flow general formula
Corporation " FLOWSORB III "), the gas absorption amount of sample (carbonaceous material) is measured, according to BET equation calculation specific surface area.
Specifically, sample is filled in coupon, the helium containing nitrogen 30vol% is passed through into the coupon on one side
It performs the following operation on one side, finds out the N2 adsorption amount for sample.That is, coupon is cooled to -196 DEG C, make sample adsorption of nitrogen.
Then, restore coupon to room temperature.At this point, desorbed using thermal conductivity detector (TCD) measurement from the spherical carbonaceous material sample of porosity
Nitrogen quantity, as the adsorbed gas scale of construction (v).Then, using the approximate formula by BET equation inference:
Vm=1/ (v (1-x)) (formula 7),
Using the one point method (relative pressure x=0.3) realized by N2 adsorption, the Vm under liquid nitrogen temperature is found out, and under passing through
The specific surface area of formula calculating sample:
Specific surface area=4.35 × Vm (m2/g) (formula 8).
It should be noted that v is the adsorbance (cm of actual measurement in each calculating formula3/ g), x is opposite pressure
Power.
[packed density]
Packed density is measured according to JIS K1474-1991 method.
[draw ratio]
The draw ratio of sample is calculated using digit microscope (KEYENCE corporation " VHX-700F ").
Specifically, culture dish is interspersed among by 30, sample particle to realize average extraction, by digit microscope
Measure the long axis of 1 particle and the length of short axle.Then, it in a manner of being up to 1, is calculated according to the length of long axis and short axle ratio
Draw ratio.In embodiment below etc., the average value of the draw ratio of 30 particles is set as draw ratio.
[crushing strength]
Crushing strength can be found out by the following method.That is, optionally extracting 32, sample particle of spheric active carbon, make
With simple plastochondria hardometer (cylinder well Physicochemical instrument Co. Ltd. system), the hardness of the moment of sample particle crushing is measured.From hard
Its maximum value and minimum value are excluded in the measured value of degree, calculate the average value of the measured value of the hardness of 30 sample particles
And the crushing strength as the sample particle.
[embodiment 1]
By the ethylene system of specific gravity (mass ratio of isometric pure water when the quality of sample at 15 DEG C is with 4 DEG C) 1.08
Residual oil (ethylene bottom oil) 10.0kg generated when making charges into 25 liters of internal volume of stainless steel pressure vessel.From reaction vessel
Lower part air is blown into 3.7L/min, under the pressurization of 0.4MPa, at 230 DEG C to 250 DEG C, carry out air blowing reaction (air
Blowing reaction) 20 minutes 4 hours.In this way, obtain the air blowing tar (air blowing tar) of 9.5kg.
By the hot heaviness of resulting air blowing tar 3.0kg at 385 DEG C, then further light composition is evaporated under reduced pressure and is removed, is obtained
Blown asphalt 1.4kg.The softening point of resulting pitch is 203 DEG C, toluene insolubles 58%.
Above-mentioned blown asphalt 0.72kg, naphthalene 0.28kg are charged to the pressure vessel of the internal volume 1.5L with stirring blade
In, after carrying out melting mixing at 200 DEG C, it is cooled to 140 DEG C~160 DEG C and is squeezed out, obtained the rodlike molding of diameter 2mm
Body.It then, is about 2.0mm to 2.8mm at length by the rodlike formed body pressure break.To dissolved with 1.2 weights as suspending agent
It measures the polyvinyl alcohol (saponification degree=88%) of % and is heated to putting into the pressure break object about 450ml in 100 DEG C of aqueous solution 1L.
Make to be cooled down after the spheroidizing of pressure break object by being dispersed with stirring, it is spherical to obtain with the water displacement polyvinyl alcohol water solution
Asphalt moulding somaplasm material.After removing most water by filtering, pass through the n-hexane of 7 times of weight of pelletted pitch slurry
Naphthalene in pelletted pitch slurry is extracted into removal, has obtained porosity pelletted pitch.Using thermopnore, it is passed through hot-air on one side,
On one side with 1 hour by the obtained porosity pelletted pitch from room temperature to 150 DEG C, then with the heating rate of 20 DEG C/h
From 150 DEG C be warming up to 260 DEG C after, with 260 DEG C keep 1 hour and aoxidized.In this way, which having obtained is not melt for heat
The spherical non-fusible pitch of porosity of property.Then, using thermopnore, in the nitrogen atmosphere of the vapor containing 50vol%,
At 850 DEG C, non-fusible pitch spherical to porosity carry out be activated until packed density be 0.79g/ml, obtained spherical work
Property charcoal.To in the average grain diameter of resulting spheric active carbon, fine pore distribution, Dust Capacity, water vibrate rate of wear, specific surface area,
Draw ratio and crushing strength are evaluated.
[embodiment 2~8]
As shown in table 1 and table 2, changed respectively by blown asphalt and the pitch amount naphthalene amount, spherical when naphthalene melting mixing
Rodlike formed body charge, spheroidizing temperature, polyvinyl alcohol concentration when change, after n-hexane amount and activation when extracting naphthalene
Packed density by operation same as Example 1, has obtained the active carbon of embodiment 2~8 in addition to this.
[embodiment 9]
As shown in table 1, adjust by blown asphalt and pitch amount when naphthalene melting mixing, naphthalene amount, rodlike formed body size,
Rodlike formed body charge, spheroidizing temperature, polyvinyl alcohol concentration when spheroidizing, n-hexane amount when extracting naphthalene, except this with
Outside, by operation same as Example 1, porosity pelletted pitch has been obtained.
In standing layer, be passed through hot-air on one side, on one side with 1 hour by resulting porosity pelletted pitch from room temperature to
150 DEG C, then with the heating rate of 20 DEG C/h from 150 DEG C be warming up to 260 DEG C after, with 260 DEG C keep 1 hour and carry out oxygen
Change.In this way, obtain the spherical non-fusible pitch of porosity for heat for infusibility.Then, in standing layer, containing
In the nitrogen atmosphere of the vapor of 50vol%, at 850 DEG C, non-fusible pitch spherical to porosity be activated until filling out
Filling density is 0.70g/ml, has obtained active carbon.
[embodiment 10]
As shown in table 1, adjust by blown asphalt and pitch amount when naphthalene melting mixing, naphthalene amount, rodlike formed body size,
Rodlike formed body charge, spheroidizing temperature, polyvinyl alcohol concentration when spheroidizing, n-hexane amount when extracting naphthalene, except this with
Outside, by operation same as Example 1, porosity pelletted pitch has been obtained.
In standing layer, be passed through hot-air on one side, on one side with 1 hour by resulting porosity pelletted pitch from room temperature to
150 DEG C, then with the heating rate of 20 DEG C/h from 150 DEG C be warming up to 300 DEG C after, with 300 DEG C keep 1 hour and carry out oxygen
Change.In this way, obtain the spherical non-fusible pitch of porosity for heat for infusibility.Then, in standing layer, containing
In the nitrogen atmosphere of the vapor of 50vol%, at 850 DEG C, non-fusible pitch spherical to porosity be activated until filling out
Filling density is 0.68g/ml, has obtained active carbon.
[embodiment 11]
Xanthan gum is used as suspending agent, as shown in table 1, adjust by blown asphalt and pitch amount when naphthalene melting mixing,
Rodlike formed body charge, spheroidizing temperature, xanthan gum concentration when naphthalene amount, rodlike formed body size, spheroidizing, when extracting naphthalene
N-hexane amount by operation same as Example 1, obtained porosity pelletted pitch in addition to this.
In standing layer, be passed through hot-air on one side, on one side with 1 hour by resulting porosity pelletted pitch from room temperature to
150 DEG C, then with the heating rate of 20 DEG C/h from 150 DEG C be warming up to 300 DEG C after, with 300 DEG C keep 1 hour and carry out oxygen
Change.In this way, obtain the spherical non-fusible pitch of porosity for heat for infusibility.Then, in standing layer, containing
In the nitrogen atmosphere of the vapor of 50vol%, at 850 DEG C, non-fusible pitch spherical to porosity be activated until filling out
Filling density is 0.70g/ml, has obtained active carbon.
[comparative example 1]
Pitch is set as 0.75kg, naphthalene amount is set as 0.25kg, in addition to this, is made by operation same as Example 1
At active carbon, in firing/activation process, the spherical non-fusible asphalt moulding of porosity knows from experience melting, is unable to maintain that its shape
Shape (spherical).
[comparative example 2]
As shown in table 1, amount, spheroidizing temperature, polyvinyl alcohol concentration and the hexane amount of blown asphalt and naphthalene are adjusted, this is removed
In addition, active carbon has been made by operation same as Example 1, in firing/activation process, the spherical infusibility of porosity
Asphalt moulding knows from experience melting, is unable to maintain that its shape (spherical).
[comparative example 3]
As shown in table 1, amount, spheroidizing temperature and the polyvinyl alcohol concentration of blown asphalt and naphthalene are adjusted, in addition to this, is led to
It crosses operation same as Example 1 and has been made active carbon.As a result, crosslinking heaviness pitch molding procedure obtained in
The shape of asphalt moulding body is ellipticity.
[comparative example 4]
It at length is about 1.0mm to 1.5mm by the rodlike formed body pressure break of diameter 1.0mm, and as shown in table 1, adjustment
The amount of blown asphalt and naphthalene, spheroidizing temperature, polyvinyl alcohol concentration and hexane amount, in addition to this, by same as Example 1
Operation, obtained active carbon.
[comparative example 5]
For spherical egression X7000H (Osaka Gas Chemical Co., Ltd.), carry out same as Example 1
Evaluation.
[comparative example 6]
For KURARAY COAL SW (Kuraray Chemical Co., Ltd.), carry out same as Example 1
Evaluation.
The result of above-mentioned each embodiment and comparative example is summarized in table 1 and table 2.
In table 1, " size " means the size of rodlike formed body, and " charge " means the charge of rodlike formed body.In addition,
" suspending agent " is, for example, PVA.In addition, " Rhex " means hexane mass ratio when extracting, more specifically, it is intended that n-hexane and ball
The mass ratio (n-hexane amount/pelletted pitch amount of slurry) of shape asphalt grout.
In table 2, " D1 " means to melt, and " D2 " means to be ellipticity.In addition, " Vp1 " means the range of 10~10000nm
Interior pore volume, " Vp2 " mean the pore volume in the range of 50~10000nm.In addition, " Asw " means vibromill in water
Consumption rate, " Rasp " mean draw ratio, and " Sp " means crushing strength.
[table 1]
[table 2]
Industrial utilizability
The present invention can be suitable as the active carbon for such as separating technology, purification, catalyst or solvent recovery etc..
Claims (11)
1. a kind of spheric active carbon, which is characterized in that the spheric active carbon be average grain diameter be 1.5mm or more 4.0mm hereinafter,
Integrally formed spheric active carbon,
It is pore volume under 50nm or more 10000nm range below in fine pore is 0.01ml/g or more 0.24ml/g or less
Range.
2. spheric active carbon according to claim 1, which is characterized in that
Crushing strength is 1.20kg/ or more.
3. spheric active carbon according to claim 1 or 2, which is characterized in that
The Dust Capacity contained in spheric active carbon described in every 1g is 2000 μ g or less.
4. spheric active carbon described in any one of claim 1 to 3, which is characterized in that
It is 5% or less that rate of wear is vibrated in water.
5. spheric active carbon according to any one of claims 1 to 4, which is characterized in that
Draw ratio is 0.7 or more.
6. spheric active carbon according to any one of claims 1 to 5, which is characterized in that
Add and is loaded with alkali or acid.
7. a kind of manufacturing method of spheric active carbon, which is characterized in that spherical described in any one of manufacturing claims 1~6
Active carbon, the manufacturing method include:
Relative to be originated from heavy hydrocarbon oil crosslinking heaviness pitch, as additive addition boiling point be 200 DEG C or more two rings or
The process of tricyclic；
Make the mixture of the crosslinking heaviness pitch and additive melting suspended dispersed in hot water, from thus obtained
Solvent extraction additive, the process for obtaining porosity pelletted pitch are used in pelletted pitch；And
Keep the porosity pelletted pitch non-fusible and firing/activation process,
The heavy hydrocarbon oil be selected from one of group being made of petroleum tar, coal tar and ethylene bottom oil or it is a kind of with
On,
The temperature of the hot water be 95 DEG C or more 120 DEG C hereinafter,
The solvent is aliphatic compound,
The mass ratio of the solvent and the pelletted pitch is 7 or more.
8. the manufacturing method of spheric active carbon according to claim 7, which is characterized in that
In the case where the total amount of the crosslinking heaviness pitch and the mixture of the additive is set as 100 mass %, institute
The additive amount for stating additive is 26 mass % or more, 50 mass % or less.
9. the manufacturing method of spheric active carbon according to claim 7 or 8, which is characterized in that
The additive is naphthalene.
10. the manufacturing method of the spheric active carbon according to any one of claim 7~9, which is characterized in that
Make the mixture of the crosslinking heaviness pitch and additive melting suspended dispersed in heat in the presence of suspending agent
In water.
11. the manufacturing method of spheric active carbon according to claim 10, which is characterized in that
The suspending agent is polyvinyl alcohol and a side or two sides in xanthan gum.
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| PCT/JP2017/044861 WO2018116947A1 (en) | 2016-12-21 | 2017-12-14 | Spherical activated carbon and method for producing same |
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| CN111039417A (en) * | 2019-12-26 | 2020-04-21 | 南京公诚节能新材料研究院有限公司 | Bio-based artificial aquatic weed |
| CN116323497A (en) * | 2020-09-23 | 2023-06-23 | 株式会社可乐丽 | Activated carbon and water treatment method using the same |
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| JP7191766B2 (en) * | 2019-05-24 | 2022-12-19 | Ｊｆｅケミカル株式会社 | Method for producing non-graphitizable carbon material |
| KR102379199B1 (en) * | 2021-07-16 | 2022-03-25 | 주식회사 퓨어스피어 | Filter for water treatment comprising spherical activated carbon |
| KR102595632B1 (en) * | 2021-11-12 | 2023-10-27 | 한국화학연구원 | Method of preparing ultra-high specific surface area spherical activated carbon and the activated carbon thereby |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111039417A (en) * | 2019-12-26 | 2020-04-21 | 南京公诚节能新材料研究院有限公司 | Bio-based artificial aquatic weed |
| CN116323497A (en) * | 2020-09-23 | 2023-06-23 | 株式会社可乐丽 | Activated carbon and water treatment method using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2018116947A1 (en) | 2018-06-28 |
| TWI651266B (en) | 2019-02-21 |
| TW201823158A (en) | 2018-07-01 |
| CN109923066B (en) | 2022-06-28 |
| JP6803398B2 (en) | 2020-12-23 |
| JPWO2018116947A1 (en) | 2019-10-24 |
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