CN108946723A - Metal oxide-loaded spherical activated charcoal, preparation method and use - Google Patents
Metal oxide-loaded spherical activated charcoal, preparation method and use Download PDFInfo
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- CN108946723A CN108946723A CN201810797902.0A CN201810797902A CN108946723A CN 108946723 A CN108946723 A CN 108946723A CN 201810797902 A CN201810797902 A CN 201810797902A CN 108946723 A CN108946723 A CN 108946723A
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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
- C01B32/312—Preparation
- C01B32/318—Preparation characterised by the starting materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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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
- C01B32/312—Preparation
- C01B32/336—Preparation characterised by gaseous activating agents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/30—Sulfur compounds
- B01D2257/304—Hydrogen sulfide
Abstract
The present invention relates to metal oxide-loaded spherical activated charcoals, preparation method and use, belong to the technical field of absorbent charcoal material.Spherical activated charcoal area load metal oxide of the invention, with good absorption property, and to H2The selective absorption of the gases such as S is had excellent performance, and application range is very extensive.Preparation method of the invention is easy, realizes the in-situ treatment in carbonisation to polymer, without pre-processing using sulfuric acid to raw polymer before carburising step, significantly improves efficiency.
Description
Technical field
The present invention relates to metal oxide-loaded spherical activated charcoals, preparation method and use, belong to absorbent charcoal material
Technical field.
Background technique
Active carbon is through high temperature carbonization and to activate hydrophobic adsorbent obtained by making raw material containing the substance based on charcoal.It is living
Property charcoal contain a large amount of micropores, one of can have a biggish surface area, therefore become most widely used adsorbent.Currently, active
Charcoal is applied not only to removal coloration, stink, it may also be used for some organic pollutants and certain inorganic matters in water removal is removed, comprising certain
Toxic heavy metal.
Active carbon is usually prepared and carbonization to suitable carbon raw material and subsequent activation.The study found that former
The difference of material may influence property, such as its composition, porosity, hardness of activated carbon product etc..Usually used raw material includes
But it is not limited to cocoanut shell, waste wood, peat, bituminous coal, pitch and certain plastics.As needed, active carbon can have a variety of shapes
Formula, such as carbon dust, splint coal, carbon granules, molding carbon, and the spherical activated charcoal (Spherical risen from late 1970s
Active Carbon,SAC)。
Active carbon such as carbon dust, splint coal, carbon granules relative to aforementioned other forms etc., spherical activated charcoal is in mobility, resistance to
Mill property and hardness etc. have lot of advantages.However, leading to it since performance is single, derived product is few, preparation process is complicated
There is limitation in application range, and cost is high.
Summary of the invention
To improve problems of the prior art, the present invention provides a kind of spherical activated charcoal preparation method, comprising:
1) spherical polymer that load has metal oxide and/or metal ion is provided；
2) product for obtaining step 1) is carbonized；
3) product activation for obtaining step 2).
According to the present invention, in step 1), the metal can be selected from the transition of such as periodic table of chemical element period 5
In metallic element, such as Y, Zr, Nb, Mo, Tc, Ru, Rh and Pd any one or combinations thereof, be preferably selected from Y, Zr, Nb, Mo and
In Tc any one or combinations thereof, be more preferably selected from any one in Y, Zr, Nb and Mo or combinations thereof.
According to the present invention, the metal oxide is preferably the metal oxide for containing above-mentioned metal；
According to the present invention, the metal ion is preferably the inorganic salts for containing above-mentioned metal ion, for example, chlorate, nitre
Hydrochlorate, carbonate, sulfate；
According to the present invention, the polymer can be homopolymer or copolymer.Wherein, the homopolymer refers to by a kind of list
The polymer of polymerization reaction preparation occurs for body, and the copolymer, which refers to, occurs polymerization reaction preparation by the monomer of two or more
Polymer.
According to the present invention, the monomer, which can be selected from, has 2~60 carbon atoms, and has at least one carbon-carbon double bond
Compound, such as with 2~20 carbon atoms, and the compound at least one carbon-carbon double bond.For example, the monomer
Can be selected from following substance: ethylene, propylene, isopropyl alkene, butylene, isobutene, amylene, iso-amylene, new amylene, hexene, dissident's alkene,
Neohexene, styrene, methyl styrene, acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, butadiene,
Pentadiene, isoprene, pentadiene, dissident's diene, divinylbenzene, diethylene glycol divinyl ether.
Preferably, the polymer matrix of the copolymer is by the structural unit structure derived from the first monomer and second comonomer
At wherein first monomer has 2~10 carbon atoms and contains a carbon-carbon double bond, the second comonomer has 4~15
A carbon atom and contain at least two carbon-carbon double bonds.Preferably, in the polymer matrix of the copolymer, derived from described the
The structural unit of one monomer accounts for 75% to the 98% of the general construction unit of the polymer network, and preferably 80% to 90%；Spread out
Be born in the second comonomer structural unit account for the polymer network general construction unit 25% to 2%, preferably 20%
To 10%.
According to an embodiment of the invention, first monomer is selected from styrene, methyl styrene, acrylic acid, methyl-prop
One of monoolefine that olefin(e) acid, methyl acrylate, methyl methacrylate and carbon atom number are 2~6 or more, the carbon
Atomicity be 2~6 monoolefine be, for example, ethylene, propylene, isopropyl alkene, butylene, isobutene, amylene, iso-amylene, new amylene, oneself
Alkene, dissident's alkene, neohexene etc..
According to an embodiment of the invention, the second comonomer is selected from butadiene, pentadiene, isoprene, pentadiene, different
One of hexadiene, divinylbenzene and diethylene glycol divinyl ether or more.
Preferably, the load capacity of the ion of the metallic element or oxide is 0.1 weight % to 10 weight %, preferably
0.2 weight % to 5 weight %, more preferably 0.5 weight % is to 2 weight %, the total weight based on polymer.
According to the present invention, step 1) includes:
I) monomer, initiator, metallic compound (such as metal ion compound and/or metal oxide) are mixed and is gathered
Reaction is closed, the spherical polymer of loaded metal ion or metal oxide is obtained；
Alternatively,
Ii) spherical polymer, alkali are mixed with metallic compound (such as metal ion compound and/or metal oxide),
Temperature be 90 DEG C~110 DEG C under conditions of carry out it is metal-doped, preferably carried out under opposing steam flow metal-doped 2h~
10h obtains the spherical polymer of loaded metal ion.
The ionic compound of the metal can be nitrate, chloride or the sulfate of metal, preferably transition metal
Nitrate, chloride or sulfate.
Preferably, in step i), the polymerization reaction is preferably suspension polymerization；Preferably, polymerization reaction also exists
It is carried out in the presence of water, dispersing agent, dispersion aids.
For example, water: dispersing agent: the weight ratio of dispersion aids is 800~1000:0.5~3.0:0.05~0.2；If deposited
In the first monomer: second comonomer: the weight ratio of initiator is 0.75~0.98:0.02~0.25:0.003~0.01.
Preferably, water, dispersing agent, dispersion aids constitute water phase, and the first monomer, second comonomer constitute oily phase；The oil phase
Weight ratio with water phase can be 1:4~6.
Preferably, in step ii), metal compound solution is mixed with spherical polymer, alkali is added after 1~2h
Solution, then opposing steam flow is doped again.
According to an embodiment of the invention, the load of metal can be carried out for example, by following methods:
It is at 90~110 DEG C, spherical polymer is dry；Dry spherical shape is placed in the solution injection of metallic compound to gather
In the container for closing object, so that spherical polymer fully absorbs the solution of metallic compound；After 1~2h, inject 1-10%'s
NaOH solution；At 90-110 DEG C, 1~20h of opposing steam flow is carried out, Metal Supported is made；It is molten using the hydrochloric acid or sulfuric acid of 2-10%
Liquid adjusts pH, is finally cleaned using clear water.
According to an embodiment of the invention, suspension polymerization may include:
Each ingredient is added in reaction kettle, compressed air or nitrogen are passed through into reaction kettle, keeps pressure in reaction kettle
Under barotropic state of the gauge pressure less than or equal to 0.5MPa, 70 DEG C~90 DEG C are warming up to, keeps the temperature 2 hours~24 hours, then be warming up to
100 DEG C~150 DEG C, 4 hours~36 hours are kept the temperature, then washes, is dry, screening, obtaining spherical polymer.
In preferred embodiments, dispersing agent be inorganic dispersant or organic dispersing agent or combinations thereof, described inorganic point
Powder be, for example, silicate, carbonate or phosphate, or combinations thereof, the organic dispersing agent is, for example, polyvinyl alcohol, gelatin, carboxylic
Methylcellulose or polyacrylate, or combinations thereof.
In preferred embodiments, dispersion aids is lauryl sodium sulfate, calcium dodecyl benzene sulfonate, dodecyl
Benzene sulfonic acid sodium salt, calcium mahogany sulfonate, petroleum sodium sulfonate or barium stearate, or combinations thereof.
In preferred embodiments, the initiator is organic per-compounds, inorganic peroxy compounds or azo
Conjunction object, or combinations thereof.
In preferred embodiments, the initiator be peroxidating two acyl class, two alkanes of peroxidating, peroxyesters,
Azodiisobutyronitrile or persulfate, or combinations thereof.
Preferably, the polymerization reaction can also carry out in the presence of pore-foaming agent.The pore-foaming agent can selected from paraffin,
Magnesium sulfate, sodium carbonate, gelatin or glycerol, or combinations thereof.
According to the present invention, the preferably not sulfonated and not sulfuric acid-treated polymer of the polymer.
According to the present invention, the median particle diameter D of the spherical polymer50It can be 0.8-2.5mm, such as 1.0-2.3mm, such as
1.2-2.0mm is specifically as follows 1.3mm, 1.4mm, 1.5mm, 1.6mm, 1.7mm, 1.8mm, 1.9mm or 2.0mm.
Preferably, step 1) further includes having the spherical polymer of metal oxide and/or metal ion to do the load
Dry step.According to the present invention, drying can be carried out in fluidized bed, be preferably conducted batch-wise.In general, temperature when dry can be
100~400 DEG C, such as 100~200 DEG C.
According to the present invention, carbonization can carry out at least one rotation pipe, especially at least one rotary tube furnace
It carries out.Preferably, carbonization carries out in closed system and/or under an inert atmosphere.
The temperature of carburising step can change within a large range.In general, the temperature of carbonization can be 50~1200 DEG C,
Such as 100~1000 DEG C.Preferably, carbonization can successively be carried out in 2 or more temperature regions, such as 2 to 8 humidity provinces
Domain successively carries out.And preferably, the temperature of the temperature region is differing from each other.Alternatively, what carbonization can rise in gradient
At a temperature of carry out.
According to an embodiment of the invention, when carbonization is when 2 temperature regions successively carry out, first in the first temperature region
Carbonization is carbonized subsequently into second temperature region.For example, the temperature of the first temperature region can be 50~500 DEG C, such as 200
~450 DEG C；The temperature in second temperature region can be 800~1200 DEG C, such as 850~950 DEG C.
According to an embodiment of the invention, in carburising step, the mixture of water vapour or water vapour and inert gas can
By carbonization in sprinkling or injection inject.Injection preferably on entrance or processing flow direction carbonization technique or device it is upper
Trip.In the mixture of water vapour and inert gas, the ratio of water vapour can change in the larger context.In general, water steams
The ratio of vapour can be 1~30 volume %, such as 2~20 volume %, such as 5~15 volume %.
Preferably, carburising step carries out in the presence of oxygen.For example, oxygen or the mixture containing oxygen can be carbonized
Middle introducing or injection are preferably exporting or on processing flow direction in the downstream of carbonization technique or device.Oxygen contains aerobic
The volume flow rate of injection or the introducing of the mixture of gas can change in the larger context.In general, oxygen, particularly to have
The form of the preferred air of the oxygen mixture of at least one other gas exists, and introduces or the volumetric rate of injection can be in 10-
500L/min, especially in 25-250L/min, preferably in 50-100L/min.
Preferably, carburising step carries out in the presence of sulfuric acid and/or oleum.
Preferably, in carburising step, spherical polymer is contacted with sulfuric acid and/or oleum.Preferably, spherical polymerization
Object and sulfuric acid and/or oleum uniformly in contact with.For example, the sulfuric acid and/or oleum can be before carbonization starts, carbonizations
When beginning and/or carbonization starts to mix with spherical polymer afterwards.The sulfuric acid and/or oleum can be by spraying or spraying
Mode mixed with spherical polymer.
The weight ratio of spherical polymer and sulfuric acid and/or oleum can be 1:1~1:2.
Oleum is the sulfuric acid solution of sulfur trioxide, and wherein the weight percent of sulfur trioxide can be 5~40 weights
Measure %, such as 10~30 weight %, such as 20 weight %.
According to the present invention, activation step entirety or can be conducted batch-wise.
According to the present invention, it is more advantageous to, activation is carried out under closed system and/or inert environments, is especially existed
The beginning of activation and/or at the beginning of the heating period.
The temperature of activation can change in the larger context.In general, activation temperature is 300~1800 DEG C, such as 400~
1500 DEG C, such as 500~1250 DEG C.
Preferably, activation step can carry out in the presence of activated gas.The activated gas can selected from water vapour,
One of carbon dioxide, oxygen, ammonia are a variety of.Also, the activated gas can also include inert gas, to reduce
The content of activated gas.For example, the ratio of water vapour can be in the larger context in water vapour and noble gas mixtures
Variation.In general, the percent by volume of water vapour can be 5~70%, such as 10~50%, such as 15~40%.
When using two or more activated gas, they can while or be introduced into activation step simultaneously.
The introducing of activated gas can be carried out by injection, sprinkling and/or air blast mode.Activated gas can be in identical or different temperature
Lower introducing.For example, introducing the water vapour or water vapour that temperature is 500 DEG C or more by injection, sprinkling and/or air blast in activation
With the mixture of inert gas.For example, in activation can also by injection, sprinkling and/or air blast introduce temperature be 800 DEG C with
On carbon dioxide or carbon dioxide and inert gas mixture.
The present invention also provides spherical activated charcoal prepared by the above method, the spherical activated charcoal load has metal oxygen
Compound.
Preferably, on the spherical activated charcoal metal oxide load capacity based on the total weight of active carbon be 0.1 weight
Measure % to 10 weight %, preferably 0.2 weight % to 5 weight %, more preferably 0.5 weight % to 2 weight %.
According to the present invention, the median particle diameter D of the spherical activated charcoal50It can be 0.2-1.5mm, such as 0.5-1.3mm, such as
0.8-1.2mm is specifically as follows 0.9mm, 1.0mm, 1.1mm or 1.2mm.
According to the present invention, the specific surface area B of the spherical activated charcoal is higher than 850m2/g。
For example, 880m2/g≤B≤1300m2/g.As example, 900m2/g≤B≤1150m2/g。
Purposes the present invention also provides the spherical activated charcoal as adsorbent material.
Preferably, the spherical activated charcoal contains H for adsorbing2The gas of S.
The present invention also provides a kind of absorption H2The method of S gas, including by the spherical activated charcoal and contain H2The gas of S
Contact.
Beneficial effects of the present invention:
Spherical activated charcoal area load metal oxide of the invention, with good absorption property, and to H2S etc.
The selective absorption of gas is had excellent performance, and application range is very extensive.
Preparation method of the invention is easy, the in-situ treatment in carbonisation to polymer is realized, without in carbon
Raw polymer is pre-processed using sulfuric acid before changing step, significantly improves efficiency.
Specific embodiment
Technical solution of the present invention is described in detail below by way of illustrative specific embodiment.But it should not be by these
Embodiment is construed to limiting the scope of the invention.All technologies realized based on above content of the present invention are encompassed by this
Invention is intended in the range of protection.
Unless otherwise indicated, documented raw material and reagent are commercial product in embodiment, or can pass through known method
Acquisition is prepared in situ.
Embodiment 1
The preparation of the spherical polymer of 1.1 loaded metal ions:
In 50 liters of polymeric kettle be added 18 liters of water, be heated to 45 DEG C, be separately added under stirring 10g magnesium carbonate,
20g gelatin and 0.15g methylene blue are added after stirring evenly and are mixed by 3kg methyl styrene, 1kg dipentene and 20g benzoyl peroxide
Oil phase made of conjunction adds 1.0kg paraffin, closes polymeric kettle, and clean compressed air is passed through into polymeric kettle, keeps in kettle
Gaseous pressure is 0.02MPa.Then, stirring is opened, liquid pearl in kettle is adjusted to appropriate granularity, is warming up to 80 DEG C, keeps the temperature 12 hours,
It is warming up to 100 DEG C again, keeps the temperature 20 hours, is filtered, washed, dried and sieved, obtains the spherical shape that granularity is 0.5mm~0.8mm
Polymer 2.35kg.
Gained spherical polymer is 2 hours dry in 90 DEG C, it is then packed into 20 liters of round-bottomed flask, prepares 200 liters
The YCl of saturation3Solution, by the YCl3Solution injects in the round-bottomed flask, and spherical polymer ball is made to fully absorb YCl3Solution, 1
The NaOH solution that 50 milliliters of concentration are 4% is reinjected after hour, under the conditions of at a temperature of 90 °C, is carried out within opposing steam flow 8 hours
It is metal-doped.After finishing, product is washed with deionized water, then carries out pickling with the dilution heat of sulfuric acid that concentration is 5%, works as acid
After water outlet pH value is washed till between 5~6,5.25kg load YCl is obtained with clear water cleaning, drying3Spherical polymer SP1.
1.2 carbonization
The spherical polymer SP1 that the mass ratio that step 1.1 is obtained is 1:1 and the oleum for containing 20 weight % sulfur trioxides
Acid-mixed close, then feed the mixture into rotary tube furnace, 150~170 DEG C at a temperature of sulfonation 5 hours.
Continue to heat up with the heating speed of 3 DEG C/min, and in the mixed atmosphere that the percent by volume of oxygen is 3%, into
Row carbonization treatment:
350 DEG C are heated to, is stopped 360 minutes；
520 DEG C are heated to, is stopped 260 minutes.Cooling, obtains carbonized product.
1.3 activation
In rotary tube furnace, the carbonized product that step 1.2 obtains is heated to 925 DEG C with 200 DEG C/h of speed,
It is passed through the mixed gas of water vapour and nitrogen that volume ratio is 1:3 after constant temperature 30min, continues to activate 30min, cooling is born
Carry Y2O3Spherical activated charcoal SAC1.
Embodiment 2
The preparation of the spherical polymer of 2.1 loaded metal ions:
In 50 liters of polymeric kettle be added 18 liters of water, be heated to 45 DEG C, be separately added under stirring 10g magnesium carbonate,
20g gelatin and 0.15g methylene blue are added after stirring evenly and are mixed by 3kg methyl styrene, 1kg dipentene and 20g benzoyl peroxide
Oil phase made of conjunction adds 1.0kg paraffin, closes polymeric kettle, and clean compressed air is passed through into polymeric kettle, keeps in kettle
Gaseous pressure is 0.02MPa.Then, stirring is opened, liquid pearl in kettle is adjusted to appropriate granularity, is warming up to 80 DEG C, keeps the temperature 12 hours,
It is warming up to 100 DEG C again, keeps the temperature 20 hours, is filtered, washed, dried and sieved, obtains the spherical shape that granularity is 0.5mm~0.8mm
Polymer 2.35kg.
Using the spherical polymer 4kg being prepared, 100 DEG C drying 1 hour, be then packed into round-bottomed flask.It prepares
The ZrCl of 200 liters of saturations2Solution, by the ZrCl2Solution injects in round-bottomed flask, and spherical polymer is made to fully absorb ZrCl2It is molten
Liquid reinjects the NaOH solution that 50 milliliters of concentration are 4% after 1.5 hours, under conditions of temperature is 110 DEG C, steam reflux 6 is small
Shi Jinhang is metal-doped.After finishing, product is washed with deionized water, then carries out acid with the dilution heat of sulfuric acid that concentration is 5%
It washes, after pickling to water outlet pH value is between 5~6, obtains 5.10kg load ZrCl with clear water cleaning, drying2Spherical polymerization
Object SP2.
2.2 carbonization
The spherical polymer SP2 that the mass ratio that step 2.1 obtains is 1:1.2 is mixed with the concentrated sulfuric acid, then by mixture
Be added rotary tube furnace, 150~170 DEG C at a temperature of sulfonation 4 hours；
Continue to heat up with the heating speed of 3 DEG C/min, and in the mixed atmosphere that the percent by volume of oxygen is 3%, into
Row carbonization treatment:
320 DEG C are heated to, is stopped 250 minutes；
540 DEG C are heated to, is stopped 250 minutes, cooling obtains carbonized product.
2.3 activation
In rotary tube furnace, the carbonized product that step 2.2 obtains is heated to 850 DEG C with 200 DEG C/h of speed,
It is passed through the mixed gas of water vapour and nitrogen that volume ratio is 1:3 after constant temperature 30min, continues to activate 60min, cooling is born
Carry ZrO2Spherical activated charcoal SAC2.
Embodiment 3
The drying of 3.1 spherical polymers
The unsupported spherical polymer 4kg prepared using 1 step 1.1 first step of embodiment, 100 DEG C drying 1 hour, so
After be packed into round-bottomed flask, obtain spherical polymer SP3.
3.2 carbonization
The spherical polymer SP3 that the mass ratio that step 3.1 obtains is 1:1.5 is mixed with the concentrated sulfuric acid, stirs 4 at 100 DEG C
Hour, cool down, 200 liters of saturation MoCl are added in obtained solid by filtering2In solution, it is vigorously stirred 10 hours at 120 DEG C, then
Filtering, rotary tube furnace is added in obtained solid, 155~160 DEG C at a temperature of sulfonation 5 hours；
Continue to heat up with the heating speed of 3 DEG C/min, and in the mixed atmosphere that the percent by volume of oxygen is 3%, into
Row carbonization treatment:
300 DEG C are heated to, is stopped 200 minutes；
500 DEG C are heated to, is stopped 240 minutes, cooling obtains carbonized product.
3.3 activation
In rotary tube furnace, the carbonized product that step 3.2 obtains is heated to 850 DEG C with 200 DEG C/h of speed,
It is passed through the mixed gas of water vapour and nitrogen that volume ratio is 1:3 after constant temperature 30min, continues to activate 60min, cooling is born
Carry MoO2Spherical activated charcoal SAC3.
Embodiment 4
The drying of 4.1 spherical polymers
The unsupported spherical polymer 4kg prepared using 1 step 1.1 first step of embodiment, 110 DEG C drying 1 hour, so
After be packed into round-bottomed flask, obtain spherical polymer SP4.
4.2 carbonization
The spherical polymer SP4 that the mass ratio that step 3.1 obtains is 1:1.6 is mixed with the concentrated sulfuric acid, stirs 4 at 100 DEG C
Hour, cool down, 200 liters of saturation NbCl are added in obtained solid by filtering2In solution, it is vigorously stirred 10 hours at 120 DEG C, then
Filtering, rotary tube furnace is added in obtained solid, 170~175 DEG C at a temperature of be carbonized 5 hours, cooling, obtain carbonization produce
Object.
4.3 activation
In rotary tube furnace, the carbonized product that step 4.2 obtains is heated to 850 DEG C with 200 DEG C/h of speed,
It is passed through the mixed gas of water vapour and nitrogen that volume ratio is 1:3 after constant temperature 30min, continues to activate 60min, cooling is born
Carry Nb2O5Spherical activated charcoal SAC4.
5 performance test of embodiment
With natural gas and H2S is raw material, wherein H2S content is 5000mg/m3, in 20 DEG C of desulfurization temperature, pressure normal pressure, gas
Air speed 1000h-1And adsorbent loading amount investigates the desulphurizing ability of above-mentioned spherical activated charcoal SAC4 to be tested under conditions of 20ml
Energy.In desulfurization breakthrough experiment, reactor outlet desulphurised natural gas sulfur content is reached into 5mg/m3As the breakthrough point of sulphur, measurement with
Sulphur penetration capacity based on this.As a result as shown in the table.
| Embodiment | Working sulfur capacity (%) |
| Embodiment 1 | 5.48 |
| Embodiment 2 | 5.86 |
| Embodiment 3 | 5.97 |
| Embodiment 4 | 6.32 |
It can be seen from the results above that the metal oxide-loaded active carbon of the application has preferable adsorption of hydrogen sulfide
Ability.
Claims (10)
1. a kind of spherical activated charcoal preparation method, wherein include:
1) spherical polymer that load has metal oxide and/or metal ion is provided；
2) product for obtaining step 1) is carbonized；
3) product activation for obtaining step 2).
Preferably, in step 1), the metal can be selected from the transition metal element of such as periodic table of chemical element period 5,
Such as any one in Y, Zr, Nb, Mo, Tc, Ru, Rh and Pd or combinations thereof, it is preferably selected from appointing in Y, Zr, Nb, Mo and Tc
It anticipates one kind or combinations thereof, is more preferably selected from any one in Y, Zr, Nb and Mo or combinations thereof.
2. preparation method according to claim 1, wherein the metal oxide is preferably the metal for containing above-mentioned metal
Oxide；
Preferably, the metal ion is preferably the inorganic salts for containing above-mentioned metal ion, for example, chlorate, nitrate, carbon
Hydrochlorate, sulfate.
3. preparation method according to claim 1 or 2, wherein step 1) further includes that the load is had metal oxide
And/or the step of the spherical polymer drying of metal ion；
Preferably, drying can be carried out in fluidized bed, be preferably conducted batch-wise；Temperature when dry can be 100~400 DEG C, example
Such as 100~200 DEG C.
4. preparation method according to claim 1-3, wherein the temperature of carbonization can be 50~1200 DEG C, example
Such as 100~1000 DEG C；
Preferably, carbonization can successively be carried out in 2 or more temperature regions, and the temperature of the temperature region is differing from each other；
Preferably, it is successively carried out in 2 to 8 temperature regions, carbonization can carry out at a temperature of gradient rises；
Preferably, when carbonization is when 2 temperature regions successively carry out, first in the carbonization of the first temperature region, subsequently into second
Temperature region carbonization, the temperature of the first temperature region can be 50~500 DEG C, such as 200~450 DEG C；Second temperature region
Temperature can be 800~1200 DEG C, such as 850~950 DEG C.
5. preparation method according to claim 1-4, wherein in carburising step, water vapour or water vapour and
The mixture of inert gas can be injected by the sprinkling in being carbonized or injection；In the mixture of water vapour and inert gas,
The ratio of water vapour can be 1~30 volume %, such as 2~20 volume %, such as 5~15 volume %；
Preferably, carburising step carries out in the presence of oxygen；For example, oxygen or the mixture containing oxygen can draw in carbonization
Enter or injects；Oxygen, particularly the presence in the form of the preferred air of the oxygen mixture at least one other gas, draw
The volumetric rate for entering or injecting can be in 10-500L/min, especially in 25-250L/min, preferably in 50-100L/min.
6. preparation method according to claim 1-5, wherein carburising step is in sulfuric acid and/or oleum
In the presence of carry out；
Preferably, in carburising step, spherical polymer is contacted with sulfuric acid and/or oleum；
Preferably, spherical polymer and sulfuric acid and/or oleum uniformly in contact with；
Preferably, the sulfuric acid and/or oleum can before carbonization starts, when carbonization starts and/or carbonization start after with ball
Shape mixed with polymers；
Preferably, the sulfuric acid and/or oleum can be mixed by way of spraying or spraying with spherical polymer；
Preferably, the weight ratio of spherical polymer and sulfuric acid and/or oleum can be 1:1~1:2；
Preferably, oleum is the sulfuric acid solution of sulfur trioxide, and wherein the weight percent of sulfur trioxide can be 5~40 weights
Measure %, such as 10~30 weight %, such as 20 weight %.
7. preparation method according to claim 1-6, wherein activation step entirety or can be conducted batch-wise；
Preferably, activation is carried out under closed system and/or inert environments, especially in the beginning of activation and/or heating
At the beginning of stage.
Preferably, activation temperature is 300~1800 DEG C, such as 400~1500 DEG C, such as 500~1250 DEG C.
Preferably, activation step can carry out in the presence of activated gas；
The activated gas can be selected from one of water vapour, carbon dioxide, oxygen, ammonia or a variety of；
The activated gas can also include inert gas；
Preferably, in water vapour and noble gas mixtures, the percent by volume of water vapour can be 5~70%, such as 10
~50%, such as 15~40%.
Preferably, when using two or more activated gas, they can not be introduced into simultaneously or simultaneously activation step
In；
The introducing of activated gas can be carried out by injection, sprinkling and/or air blast mode；
Activated gas can introduce at the same or different temperatures；
The water vapour or water vapour and indifferent gas that temperature is 500 DEG C or more are introduced by injection, sprinkling and/or air blast in activation
The mixture of body；
Carbon dioxide or the titanium dioxide that temperature is 800 DEG C or more can also be introduced by injection, sprinkling and/or air blast in activation
The mixture of carbon and inert gas.
8. the spherical activated charcoal that the described in any item methods of claim 1-7 are prepared, the spherical activated charcoal load has gold
Belong to oxide；
Preferably, on the spherical activated charcoal metal oxide load capacity be 0.1 weight % to 10 weight %, preferably 0.2
Weight % to 5 weight %, more preferably 0.5 weight % is to 2 weight %, the total weight based on active carbon.
9. purposes of the spherical activated charcoal described in claim 8 as adsorbent material；
Preferably, the spherical activated charcoal contains H for adsorbing2The gas of S.
10. a kind of absorption H2The method of S gas, including by spherical activated charcoal described in claim 8 and contain H2The gas of S contacts.
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