CN107108232A - Activated carbon, hydro-thermal charcoal and preparation method thereof - Google Patents
Activated carbon, hydro-thermal charcoal and preparation method thereof Download PDFInfo
- Publication number
- CN107108232A CN107108232A CN201580059522.1A CN201580059522A CN107108232A CN 107108232 A CN107108232 A CN 107108232A CN 201580059522 A CN201580059522 A CN 201580059522A CN 107108232 A CN107108232 A CN 107108232A
- Authority
- CN
- China
- Prior art keywords
- hydro
- biomass
- thermal charcoal
- activated carbon
- preparing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- C01B32/342—Preparation characterised by non-gaseous activating agents
-
- 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
- C01B32/324—Preparation characterised by the starting materials from waste materials, e.g. tyres or spent sulfite pulp liquor
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/14—Pore volume
Abstract
There is provided activated carbon, hydro-thermal charcoal and preparation method thereof.Include providing (10) biomass and the biomass mixed into (14) with oxidant to form biomass oxidant mixture for preparing the method (10) of hydro-thermal charcoal and activated carbon.Make the biomass oxidant mixture be subjected to (16) hydrothermal carbonization process to form the hydro-thermal charcoal compared with the biomass with increased oxygen-containing functional group content.The hydro-thermal charcoal is mixed into (18) with activator to form hydro-thermal charcoal activating mixtures.The hydro-thermal charcoal activating mixtures are made to be subjected to (20) chemical activating process to form activated carbon.
Description
Technical field
The present invention relates to carbonaceous material, more specifically it relates to activated carbon, hydro-thermal charcoal (hydrochar) and preparation method thereof.
Background technology
As environmental problem is increasingly sharpened, sustainable and renewable resource such as biomass use causes many concerns.Grind
Study carefully and show, carbonaceous material has a wide range of applications such as the activated carbon and hydro-thermal charcoal from biomass, but by carbonaceous material
Characteristic limitation.Accordingly, it is desirable to provide with improved carbonaceous material of characteristic and preparation method thereof.
The content of the invention
Therefore, in a first aspect, the invention provides a kind of method for preparing activated carbon.Methods described includes providing
Biomass simultaneously mixes the biomass with oxidant to form biomass-oxidant mixture.Make the biomass-oxidant
Mixture is subjected to hydrothermal carbonization process to form the hydro-thermal charcoal compared with the biomass with increased oxygen-containing functional group content.
The hydro-thermal charcoal is mixed with activator to form hydro-thermal charcoal-activating mixtures.Make the hydro-thermal charcoal-activating mixtures warp
By chemical activating process to form activated carbon.
In second aspect, the invention provides a kind of activated carbon, the mesoporous surface area of the activated carbon is about 1300 squares
Rice/gram (m2/ g) to about 2000m2/ g, mesopore volume is about 1.9 cubic centimetre/gram (cm3/ g) to about 3.8cm3/ g, and it is mesoporous
Porosity is more than 70 (%).
In the third aspect, the invention provides a kind of method for preparing hydro-thermal charcoal.Methods described includes providing biological
Matter and the biomass is mixed with oxidant to form biomass-oxidant mixture.Mix the biomass-oxidant
Compound is subjected to hydrothermal carbonization process to form the hydro-thermal charcoal compared with the biomass with increased oxygen-containing functional group content.
In fourth aspect, the invention provides a kind of hydro-thermal charcoal, the hydro-thermal charcoal and the biomass for preparing the hydro-thermal charcoal
Compared to increased oxygen-containing functional group content.
By the detailed description for the principle for illustrating the present invention below in conjunction with accompanying drawing and by means of example, other aspects of the present invention
It will become apparent with advantage.
Brief description of the drawings
Embodiment of the present invention is described only by means of example now with reference to accompanying drawing, wherein：
Fig. 1 is to show the signal for being used to prepare the method for hydro-thermal charcoal and activated carbon according to one embodiment of the invention
Property flow chart；
Fig. 2 is the photo for the biomass for showing cocoanut shell；
Fig. 3 is the photograph for the hydro-thermal charcoal for showing the biomass preparation by cocoanut shell according to one embodiment of the invention
Piece；
Fig. 4 is the photo for showing to be mixed with Fig. 3 of activator hydro-thermal charcoal；
Fig. 5 is to show showing according to device (set-up) for chemical activating process of one embodiment of the invention
It is intended to；
Fig. 6 shows commercially available mesoporous carbon and in the case where carrying out and not carrying out pre- chemical activation processing by cocoanut shell
The figure of the N2 adsorption-desorption isotherm of activated carbon prepared by biomass under 77 Kelvins (K)；
Fig. 7 shows commercially available mesoporous carbon and in the case where carrying out and not carrying out pre- chemical activation processing by cocoanut shell
The figure of the pore-size distribution of activated carbon prepared by biomass；
Fig. 8 shows the activated carbon prepared in the case where carrying out and not carrying out pre- chemical activation processing by the biomass of sawdust
Pore-size distribution figure；
Fig. 9 is to show to be prepared by the biomass of palm kernel shell in the case where carrying out and not carrying out pre- chemical activation processing
The figure of the pore-size distribution of activated carbon；And
Figure 10 is to show commercially available mesoporous carbon and in the case where carrying out and not carrying out pre- chemical activation processing by cocoanut shell
Biomass prepare activated carbon rhodamine B (Rhodamine B) adsorption curve figure.
Embodiment
The detailed description proposed below in conjunction with accompanying drawing is intended to the description as presently preferred embodiments of the invention, not
Only form of the invention can be put into practice by being intended to indicate that.It should be understood that can be by being intended to difference reality within the scope of the invention
Scheme is applied to realize identical or identical functions.
Referring now to Fig. 1, the method 10 for preparing hydro-thermal charcoal and activated carbon will now be described.This method starts from providing
The step 12 of biomass.
Biomass may include gardening waste material.In the present embodiment, biomass can be following one or more：Coconut
Shell, palm kernel shell, sawdust, timber, shuck, pod, fruit stone, seed, skin, bagasse, peat, lignite and ub-bituminous coal, and can be with
Coarse grained form using particle diameter as about 0.5 millimeter (mm) to about 5mm is provided.In one embodiment, tool may be selected
There is the biomass of high rigidity to improve yield.
In step 14, biomass is mixed with oxidant to form biomass-oxidant mixture.
Oxidant can be following one or more：Hydrogen peroxide, carboxylic acid, peroxy acid, binary acid and humic acid.
Biomass-oxidant mixture can include about 60 mass % (weight %) to about 80 weight % biomass.
Make biomass-oxidant mixture be subjected to hydrothermal carbonization process to form hydro-thermal charcoal (after hydro-thermal process in step 16
The charcoal (char) of acquisition), the hydro-thermal charcoal is with compared with preparing the biomass of the hydro-thermal charcoal there is increased oxygen-containing functional group to contain
Amount.The formation for being incorporated to oxygen-containing functional group (OFG) on induction hydro-thermal charcoal of oxidant during the hydro-thermal process of biomass.
Can be at about 200 degrees Celsius (DEG C) to carrying out hydrothermal carbonization process about 20 minutes (min) at a temperature of about 300 DEG C to about
The time of 200 minutes.The hydrothermal carbonization of biomass is used to improve chemical characteristic (that is, the oxygen-containing official of high concentration of hydro-thermal product char
The aromatisation with low degree can be rolled into a ball), this makes hydro-thermal charcoal turn into effective precursor that subsequent chemistry is activated.
The hydro-thermal charcoal of formation can have the oxygen-containing functional group content of about 30 percentages (%) to about 70% more than biomass.
In one embodiment, hydro-thermal charcoal has the oxygen-containing functional group content of about 40% to about 60% more than biomass.Hydro-thermal charcoal contains
Oxygen functional group content can be about 1.2 milliequivalents/gram (meq/g) to about 1.6meq/g.In specific embodiments, oxygen-containing functional group
Content can be about 1.29meq/g, about 1.42meq/g or about 1.58meq/g.Oxygen-containing functional group content can include carboxyl, lactone group
With the one or more in phenolic group.
In step 18, hydro-thermal charcoal is mixed with activator to form hydro-thermal charcoal-activating mixtures.
Activator can be following one or more：Zinc chloride, phosphoric acid, metal chloride, inorganic acid, sodium phosphate and alkali.
Activator can be about 2 with respect to the ratio between hydro-thermal charcoal in hydro-thermal charcoal-activating mixtures:1 to about 10:1.
In step 20, hydro-thermal charcoal-activating mixtures are made to be subjected to chemical activating process to form activated carbon.
Chemical activating process about 0.5 hour (h) can be carried out under about 350 DEG C to about 650 DEG C for the treatment of temperature to about 3 hours
Time.Speed that can be with about 5 degrees celsius/minutes (DEG C/min) to about 15 DEG C/min is warming up to chemical activating process
(ramp to) treatment temperature.In one embodiment, can be in the ml/min of flow about 20 (ml/ minutes) to about 100ml/
The chemical activating process is carried out in the presence of the nitrogen of minute.
The mesoporous surface area of the activated carbon of formation can be about 1300 meters squared per gram (m2/ g) to about 2000m2/ g, mesopore volume
It can be about 1.9 cubic centimetre/gram (cm3/ g) to about 3.8cm3/ g, mesoporous porosity can be more than 70 (%), its intermediary hole porosity
For the mesoporous surface area (A of activated carbonme) relative Brunauer-Emmett-Teller (BET) surface areas (AtThe ratio between).At one
In embodiment, mesoporous surface area can be about 1331m2/ g, mesopore volume can be about 1.98cm3/ g, and mesoporous porosity can be
About 76%.In another embodiment, mesoporous surface area can be about 1780m2/ g, mesopore volume can be about 3.5cm3/ g, and
Mesoporous porosity can be about 100%.In still another embodiment, mesoporous surface area can be about 1815m2/ g, mesopore volume can
It is about 2.8cm3/ g, and mesoporous porosity can be about 98%.
By this method 10, can be obtained by abandoned biomass has high or increased mesoporous porosity and high or increase
Mesoporous surface area activated carbon.The raising of the porosity of activated carbon is high expectations, and by selecting biomass, selection
Oxidant, selects chemical activating agent, optimizes activation condition such as temperature, heating rate and gas flow, and selection pretreatment side
Method is obtained in method 10.
In method 10, carry out hydro-thermal process to biomass in the presence of an oxidizer has as pre-treatment step to produce
The precursor that the hydro-thermal charcoal of high or increased OFG contents is activated as subsequent chemistry.Pre-treatment step induction shape on hydro-thermal charcoal
Into more oxygen-containing functional groups, make hydro-thermal charcoal precursor more reactive during subsequent chemistry is activated.With high or increased
Thus the chemical activation of the hydro-thermal charcoal of OFG contents is produced with high or increased mesoporous porosity and high or increased Jie
The activated carbon of aperture surface area.
High mesoporous carbon is applied in immobilization (immobilization) field of biomolecule such as enzyme, vitamin etc..
For stored energy application, electro-catalysis, electrode material and environment remediation application, high mesoporous porosity is also high expectations.
Embodiment
Come using cocoanut shell (Cocoa Cortex cocois radicis (cocos nucifera)), palm kernel shell and sawdust as abandoned biomass
Source.Cocoanut shell (after trim fiber), palm kernel shell (removing after pulp) and sawdust are dried 24 hours at 105 DEG C, business is used
Industry laboratory blender (Waring) is crushed, and then grinds and sieve to produce the coarse granule of about 10 mesh to 20 mesh.Cocoanut shell
The photo of biomass is as shown in Figure 2.
Then biomass is mixed with oxidant to form biomass-oxidant mixture.Use hydrogen peroxide (30%
GR, Merck) as oxidant to be induced during the pretreatment of biomass starting material OFG is formed on charcoal.Carried out with hydrogen peroxide
Pretreatment assigns hydro-thermal charcoal precursor with more OFG contents, so that it is more reactive to subsequent chemistry activation.
Make biomass-hydrogen peroxide mixture (90mL H in the autoclaves of Parr 4848 at 200 DEG C2O2(10 weights
Amount %) in 15g biomass) be subjected to hydro-thermal process 20 minutes.Then reactor is cooled to room temperature, and by product at 105 DEG C
Dry 12 hours.The photo of the hydro-thermal charcoal prepared by the biomass of coconut husk is as shown in Figure 3.
Then using zinc chloride (ZnCI2, SILVER REAGENT (Scharlab)) and activated carbon is prepared by chemical activation.
More specifically, with 5:The ratio between 1 zinc chloride and shell are by hydro-thermal charcoal precursor and liquor zinci chloridi (equivalent to 15g raw materials
90mL water in the precursor of biomass) mixing, dried 12 hours at 105 DEG C.Show to be mixed with the photo of the hydro-thermal charcoal of activator
As shown in Figure 4.Addition zinc chloride shows as the form in two kinds of competition mechanisms as the effect of chemical activating agent：Micropore formation and
Hole expands.Under the ratio between low zinc chloride-raw material, micropore formation is main effect.Hole expand high zinc chloride-raw material it
Be formed as cost to sacrifice micropore than under and occur, therefore reduce micro content.In addition, the amount of the activator used is depended on
The desired characteristic of raw material, the surface functional group existed, treatment conditions and product such as aperture, surface area, hardness etc..
Referring now to Fig. 5, the schematic diagram of the device 50 for chemical activating process is shown.Device 50 includes and stove 54
(Carbolite) source nitrogen 52 being in fluid communication.Flowmeter 56 is provided to detect the air-flow from source nitrogen 52 to stove 54.Stove 54
Outlet is in fluid communication with washer 58.
Hydro-thermal charcoal-activating mixtures 60 are attached in the alumina boat in quartz ampoule, are subsequently placed in stove 54.In stream
Measure in the presence of the nitrogen for 50mL/ minutes, the temperature in stove 54 is warming up to 500 DEG C with 10 DEG C/min of speed and holding 2 is small
When.Then in the presence of flow is the nitrogen of 50mL/ minutes, the temperature in stove 54 is cooled to room temperature.In 250mL hydrochloric acid
Products therefrom is stirred 30 minutes in (37%, Panreac) (about 0.1mol/L), and with a large amount of distillation water washings until by rinsing
The pH that liquid is obtained is 6.Finally, activated carbon is dried 24 hours and for analyzing at 105 DEG C.
Using sodium hydroxide (Merck, EMSURE,>99%) OFG contents are measured.Boehm titration is carried out to assess usually
The oxygen-containing functional group of carboxyl, lactone group and phenolic group.More specifically, in nitrogen (N2) in the presence of inert atmosphere, by biomass and water
Hot charcoal is heated to up to 150 DEG C, continues 24 hours.It is cooled to after room temperature, by 1.5g samples and 50mL NaOH (0.05M)
Mixing, and mixture vibration is stirred 24 hours.Then sample is removed by filtration, and 10mL deciles are titrated with 0.05M HCl
Sample is to obtain OFG contents.
Adsorption-desorption isothermal is obtained by using gas absorption analyzer (Nova-3000 series, Quantachrome)
Line, Brunauer-Emmett-Teller (BET) surface areas (At) and adsorbent pore volume.Use NLDFT (non-localized density
Function theory) method acquisition pore-size distribution.In addition, determining mesoporous surface area (A using t figures methodme) and micro pore volume, wherein total hole
Volume is evaluated as the liquid volume of the nitrogen under about 0.98 relative pressure.Then by from total pore volume (Vt) in subtract it is micro-
Pore volume (Vmi) calculate mesopore volume (Vme).Selection rhodamine B assesses the energy of adsorption of activated carbon as model adsorption thing
Power.Adsorption experiment is carried out using balanced oscillator method (batch equilibration), and by using UV- visible spectrophotometers
(Shimadzu-3600) concentration of dyestuff is assessed.
Table 1 shows the OFG contents of biomass before and after hydrothermal carbonization process.
Table 1
| Sample | OFG contents (meq/g) |
| Cocoanut shell (CS) | 1.04 |
| CS hydro-thermal charcoals | 1.58 |
| Sawdust (SD) | 0.95 |
| SD hydro-thermal charcoals | 1.42 |
| Palm kernel shell (PKS) | 0.89 |
| PKS hydro-thermal charcoals | 1.29 |
As can be seen from the above Table 1, compared with preparing the biomass of hydro-thermal charcoal, the hydro-thermal charcoal of formation has increased contain
Oxygen functional group content.From experimental data it can also be seen that having as the hydro-thermal charcoal of the result formation of pre-treatment step than preparing
The oxygen-containing functional group content of about 40% to about 60% more than the biomass of hydro-thermal charcoal.
Table 2 below shows the characteristic of following a variety of different carbon samples：Commercially available mesoporous carbon (Sigma Aidrich), passes through
Activated carbon (CS-ZP) prepared by the direct chemical activation of raw material cocoanut shell, by being subjected to hydro-thermal in the presence of hydrogen peroxide in advance
Activated carbon (CS-HHTZP) prepared by the raw material cocoanut shell of reason, the activated carbon prepared by the direct chemical activation of palm kernel shell
(PKS-ZP) activated carbon (PKS-HHTZP), prepared by the palm kernel shell for being subjected to hydrothermal pretreatment in the presence of hydrogen peroxide,
The activated carbon (SD-ZP) prepared by the direct chemical activation of sawdust, and it is pre- by being subjected to hydro-thermal in the presence of hydrogen peroxide
Activated carbon (SD-HHTZP) prepared by the sawdust of processing.
Table 2
It is as living in as can be seen from the above Table 2, hydro-thermal process carried out by using hydrogen peroxide and carrying out chemistry using zinc chloride
The activated carbon changed and obtained has high mesoporous area, mesopore volume and mesoporous porosity.From upper table 2 it can also be seen that working as
When using hydrogen peroxide preprocessing biomass in thermal and hydric environment, it was observed that these attributes are dramatically increased.In fact, can from above-mentioned table 2
To find out, hydrogen peroxide is used to cause activated carbon that there is up to 100% high mesoporous porosity (mesoporous face in hydrothermal step
Product/BET areas), up to 1815m2/ g high mesoporous surface area, up to 3.5cm3/ g high mesopore volume.
As a result such deduction is determined, including oxidant preprocessing process improves the validity of activator and realized more
High mesoporous area and Geng Gao mesoporous porosity.High OFG contents on hydro-thermal charcoal, and subsequent zinc chloride activation so that with
Formation of the carbon phase prepared when being pre-processed in the absence of hydrogen peroxide than having promoted significantly high mesoporous porosity.Mesoporous surface area and
Dramatically increasing for volume is attributed to improved chemical activation, and the improved chemical activation is due to by hydrogen peroxide-induced
Functionalisation of surfaces and the formation for adding OFG on hydro-thermal charcoal.
Referring now to Fig. 6, show under 77 Kelvins (K) commercially available mesoporous carbon and carrying out and do not carrying out pre- chemical activation
The figure of N2 adsorption-desorption isotherm of the activated carbon prepared in the case of processing by the biomass of cocoanut shell.Continuous lines represent to inhale
Attached, symbol represents desorption.Hysteresis confirms mesoporous presence.From Fig. 6, it is apparent that with the direct chemistry by biomass
Activated carbon (CS-ZP) prepared by activation is compared with commercially available mesoporous carbon, by being subjected to hydrothermal pretreatment in the presence of hydrogen peroxide
The adsorption volume of activated carbon (CS-HHTZP) prepared by biomass is higher.This shows before chemical activation, in depositing for oxidant
In the importance of the hydrothermal pretreatment of lower progress biomass.
Referring now to shown in Fig. 7,8 and 9, Fig. 7 commercially available mesoporous carbon and carry out and do not carry out at pre- chemical activation
The figure of the pore-size distribution of the activated carbon prepared in the case of reason by the biomass of cocoanut shell, Fig. 8, which is shown, to carry out and is not carrying out
The figure of the pore-size distribution of the activated carbon prepared in the case of pre- chemical activation processing by the biomass of sawdust, Fig. 9, which is shown, to be entered
Row and do not carry out the activated carbon prepared by the biomass of palm kernel shell in the case of pre- chemical activation processing pore-size distribution figure.
These results indicate that compared with the activated carbon prepared by the direct chemical activation of biomass, being carried out in the presence of oxidant
Activated carbon prepared by hydrothermal pretreatment provides preferably mesoporous porosity and bigger mesopore volume, is 50 angstromsExtremely
Referring now to Figure 10, show commercially available mesoporous carbon and carry out and in the case of not carrying out pre- chemical activation processing by
The figure of the rhodamine B adsorption curve of activated carbon prepared by the biomass of cocoanut shell.The figure shows in liquid phase (Ce) in absorption
Amount (the q of the dyestuff of every gram of charcoal absorption under the different equilibrium concentrations of thinge).Balance concussion result of study shown in Figure 10 is true
Compared with having determined the activated carbon (CS-ZP) and commercially available mesoporous carbon with being prepared by the direct chemical activation of biomass, by peroxidating
The adsorption capacity that the activated carbon (CS-HHTZP) of the biomass preparation of hydrothermal pretreatment is subjected in the presence of hydrogen is higher.Can also be from
Observed in Figure 10, the saturated capacity of CS-HHTZP, CS-ZP and commercially available mesoporous carbon be respectively 913mg/g, 715mg/g and
176mg/g.It is worth noting that, mesoporous carbon, CS-HHTZP saturated capacity are high by 28% than CS-ZP.This increase of absorption
Again show that the contribution for the higher mesoporous porosity realized before chemical activation by the hydro-thermal process containing hydrogen peroxide.
As a result the notable beneficial effect of hydrothermal pretreatment step in the presence of hydrogen peroxide is shown and its dramatically increasing
Obtain the effect in terms of the mesoporous area of activated carbon.More oxygen-containing functional groups are produced using the hydrothermal carbonization of hydrogen peroxide, are promoted
Easily realize chemical activation.Oxygen-containing functional group (carboxyl, lactone group and phenolic group) content in precursor is to control the reaction of chemical activation
The important instruction of property, therefore may be used as the prediction thing of activated carbon porosity.Research indicates the table of biomass starting material discarded object
The importance of the face modification precursor with increased OFG (oxygen-containing functional group) content excellent to formation, increased OFG is (oxygen-containing
Functional group) content is conducive to chemical activation, and therefore in the mesoporous area of carbon obtained by preparation with strong Beneficial Effect.It is situated between
Dramatically increasing for hole area supplements chemical activating agent to realize by using oxidant.
It is aobvious for those skilled in the art although specific composition and parameter are described in detail in the above-described embodiments
And be clear to, without departing from the scope of the invention, wherein can modify and change.
From discussion above, it is apparent that the invention provides for having increased oxygen-containing official by abandoned biomass production
The method of the hydro-thermal charcoal of energy mass contg and the activated carbon with high or increased mesoporous porosity and surface area.Advantageously,
Formation of the oxidant induction of the oxygen-containing functional group (OFG) on gained hydro-thermal charcoal is incorporated to during the hydro-thermal process of biomass.Water
High or increased OFG contents promote to form the significantly high charcoal of mesoporous porosity after chemical activation on hot charcoal.
Mesoporous carbon produced by the invention is suitably applied many fields, such as energy storage, water process, gas separation
With purifying and electro-catalysis.
Although having been shown and describing the preferred embodiments of the invention, it should be clear that the present invention is not limited only to institute
The embodiment of description.It is many to change, change in the case where not departing from the scope as described in the claims of the present invention
Become, change, substitute and equivalent will will be apparent from for those skilled in the art.
In addition, be distinctly claimed unless the context otherwise, otherwise in entire disclosure and claims, word " bag
Include ", "comprising" etc. should be interpreted (opposite with exclusive or exhaustive meaning) of pardon, that is to say, that " including but not limit
In " meaning.
Claims (35)
1. a kind of method for preparing activated carbon, including：
Biomass is provided；
The biomass is mixed with oxidant to form biomass-oxidant mixture；
Make the biomass-oxidant mixture be subjected to hydrothermal carbonization process to be formed compared with the biomass with increased
The hydro-thermal charcoal of oxygen-containing functional group content；
The hydro-thermal charcoal is mixed with activator to form hydro-thermal charcoal-activating mixtures；And
Hydro-thermal charcoal-the activating mixtures are made to be subjected to chemical activating process to form activated carbon.
2. the method according to claim 1 for preparing activated carbon, wherein the biomass is comprising following one kind or more
It is a variety of：Cocoanut shell, palm kernel shell, sawdust, timber, shuck, pod, fruit stone, seed, skin, bagasse, peat, lignite and ub-bituminous coal.
3. the method according to claim 1 for preparing activated carbon, wherein using particle diameter as about 0.5 millimeter (mm) extremely
About 5mm coarse grained form provides the biomass.
4. the method according to claim 1 for preparing activated carbon, wherein the oxidant is comprising following one kind or more
It is a variety of：Hydrogen peroxide, carboxylic acid, peroxy acid, binary acid and humic acid.
5. the method according to claim 1 for preparing activated carbon the, wherein biomass-oxidant mixture is included
About 60 mass % (weight %) to the about 80 weight % biomass.
6. the method according to claim 1 for preparing activated carbon, wherein at about 200 degrees Celsius (DEG C) to about 300 DEG C
At a temperature of carry out time of the hydrothermal carbonization process about 20 minutes (min) to about 200 minutes.
7. the method according to claim 1 for preparing activated carbon, wherein the hydro-thermal charcoal has than the biomass
The oxygen-containing functional group content of many about 30 percentages (%) to about 70%.
8. the method according to claim 7 for preparing activated carbon, wherein the hydro-thermal charcoal has than the biomass
The oxygen-containing functional group content of many about 40% to about 60%.
9. the method according to claim 1 for preparing activated carbon, wherein the oxygen-containing functional group content of the hydro-thermal charcoal
It is about 1.2 milliequivalents/gram (meq/g) to about 1.6meq/g.
10. the method according to claim 9 for preparing activated carbon, wherein the oxygen-containing functional group content is about
1.29meq/g, about 1.42meq/g or about 1.58meq/g.
11. the method according to claim 9 for preparing activated carbon, wherein the oxygen-containing functional group content is comprising following
It is one or more of：Carboxyl, lactone group and phenolic group.
12. the method according to claim 1 for preparing activated carbon, wherein the activator is following one or more
Kind：Zinc chloride, phosphoric acid, metal chloride, inorganic acid, sodium phosphate and alkali.
13. the method according to claim 1 for preparing activated carbon, wherein in the hydro-thermal charcoal-activating mixtures
Described in the ratio between the relatively described hydro-thermal charcoal of activator be about 2:1 to about 10:1.
14. the method according to claim 1 for preparing activated carbon, wherein in about 350 DEG C to about 650 DEG C of processing temperature
The degree lower time for carrying out chemical activating process about 0.5 hour (h) to about 3 hours.
15. the method according to claim 13 for preparing activated carbon, wherein with about 5 degrees celsius/minutes (DEG C/min) to about
15 DEG C/min of speed makes the chemical activating process be warming up to the treatment temperature.
16. the method according to claim 1 for preparing activated carbon, wherein being about 20 ml/min (ml/ in flow
Minute) to carrying out the chemical activating process in the presence of the nitrogen of about 100ml/ minutes.
17. a kind of activated carbon, it has about 1300 meters squared per gram (m2/ g) to about 2000m2/ g mesoporous surface area, about 1.9 stand
Square centimetre/gram (cm3/ g) to about 3.8cm3/ g mesopore volume, and more than 70 (%) mesoporous porosity.
18. activated carbon according to claim 17, wherein：
The mesoporous surface area is about 1331m2/ g, the mesopore volume is about 1.98cm3/ g, and the mesoporous porosity is
About 76%；
The mesoporous surface area is about 1780m2/ g, the mesopore volume is about 3.5cm3/ g, and the mesoporous porosity is about
100%；Or
The mesoporous surface area is about 1815m2/ g, the mesopore volume is about 2.8cm3/ g, and the mesoporous porosity is about
98%.
19. a kind of method for preparing hydro-thermal charcoal, including：
Biomass is provided；
The biomass is mixed with oxidant to form biomass-oxidant mixture；And
Make the biomass-oxidant mixture be subjected to hydrothermal carbonization process to be formed compared with the biomass with increased
The hydro-thermal charcoal of oxygen-containing functional group content.
20. the method according to claim 19 for preparing hydro-thermal charcoal, wherein the biomass comprising following a kind of or
It is more kinds of：Cocoanut shell, palm kernel shell, sawdust, timber, shuck, pod, fruit stone, seed, skin, bagasse, peat, lignite and secondary cigarette
Coal.
21. the method according to claim 19 for preparing hydro-thermal charcoal, wherein using particle diameter as about 0.5 millimeter (mm)
Coarse grained form to about 5mm provides the biomass.
22. the method according to claim 19 for preparing hydro-thermal charcoal, wherein the oxidant comprising following a kind of or
It is more kinds of：Hydrogen peroxide, carboxylic acid, peroxy acid, binary acid and humic acid.
23. the method according to claim 19 for preparing hydro-thermal charcoal, wherein the biomass-oxidant mixture bag
The biomass containing about 60 mass % (weight %) to about 80 weight %.
24. the method according to claim 19 for preparing hydro-thermal charcoal, wherein at about 200 degrees Celsius (DEG C) to about 300
The time of the hydrothermal carbonization process about 20 minutes (min) to about 200 minutes is carried out at a temperature of DEG C.
25. the method according to claim 19 for preparing hydro-thermal charcoal, wherein the hydro-thermal charcoal has than the biology
The oxygen-containing functional group content of about 30 percentages (%) to about 70% more than matter.
26. the method according to claim 25 for preparing hydro-thermal charcoal, wherein the hydro-thermal charcoal has than the biology
The oxygen-containing functional group content of about 40% to about 60% more than matter.
27. the method according to claim 19 for preparing hydro-thermal charcoal, wherein the oxygen-containing functional group of the hydro-thermal charcoal contains
Amount is about 1.2 milliequivalents/gram (meq/g) to about 1.6meq/g.
28. the method according to claim 27 for preparing hydro-thermal charcoal, wherein the oxygen-containing functional group content is about
1.29meq/g, about 1.42meq/g or about 1.58meq/g.
29. the method according to claim 27 for preparing hydro-thermal charcoal, wherein the oxygen-containing functional group content include with
Lower one or more：Carboxyl, lactone group and phenolic group.
30. a kind of hydro-thermal charcoal, it is with having increased oxygen-containing functional group content compared with preparing the biomass of the hydro-thermal charcoal.
31. hydro-thermal charcoal according to claim 30, wherein the hydro-thermal charcoal has about 30 percentage more than the biomass
(%) to about 70% oxygen-containing functional group content.
32. hydro-thermal charcoal according to claim 31, wherein the hydro-thermal charcoal has more than the biomass about 40% to about
60% oxygen-containing functional group content.
33. hydro-thermal charcoal according to claim 30, works as wherein the oxygen-containing functional group content of the hydro-thermal charcoal is about 1.2 millis
Amount/gram (meq/g) to about 1.6meq/g.
34. hydro-thermal charcoal according to claim 33, wherein the oxygen-containing functional group content is about 1.29meq/g, about
1.42meq/g or about 1.58meq/g.
35. hydro-thermal charcoal according to claim 33, wherein the oxygen-containing functional group content includes following one or more：
Carboxyl, lactone group and phenolic group.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| SG10201407219Q | 2014-11-04 | ||
| SG10201407219Q | 2014-11-04 | ||
| PCT/SG2015/050406 WO2016072932A1 (en) | 2014-11-04 | 2015-10-22 | Activated carbon, hydrochar and processes for making same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107108232A true CN107108232A (en) | 2017-08-29 |
| CN107108232B CN107108232B (en) | 2020-11-10 |
Family
ID=55909511
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201580059522.1A Active CN107108232B (en) | 2014-11-04 | 2015-10-22 | Activated carbon, hydrothermal carbon and preparation method thereof |
Country Status (3)
| Country | Link |
|---|---|
| CN (1) | CN107108232B (en) |
| SG (1) | SG11201703235YA (en) |
| WO (1) | WO2016072932A1 (en) |
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106753501A (en) * | 2017-01-16 | 2017-05-31 | 上海理工大学 | A kind of method that hydro-thermal biomass directly prepare pyrolkigneous liquid |
| CN107364859A (en) * | 2017-07-24 | 2017-11-21 | 广西柳城县成霖农业科技有限公司 | A kind of method that activated carbon is produced using bagasse |
| CN107555424A (en) * | 2017-08-31 | 2018-01-09 | 西南大学 | A kind of preparation method of porous class graphene active carbon material and products thereof and application |
| CN108516549A (en) * | 2018-04-19 | 2018-09-11 | 句容市盛达环保净化材料有限公司 | A kind of preparation method of activated carbon |
| CN108640112A (en) * | 2018-03-08 | 2018-10-12 | 哈尔滨工程大学 | A kind of preparation method of high activity active fruit shell carbon anode fuel for indirect carbon consuming cell |
| CN108689407A (en) * | 2018-06-26 | 2018-10-23 | 中国科学院生态环境研究中心 | A kind of technique that binder pressed active carbon is exempted from abandoned biomass preparation |
| CN108751194A (en) * | 2018-04-19 | 2018-11-06 | 句容市盛达环保净化材料有限公司 | A kind of preparation method of activated carbon |
| CN109809405A (en) * | 2019-03-15 | 2019-05-28 | 合肥学院 | A kind of preparation method of honey peach peach-pit matrix activated carbon |
| CN109809402A (en) * | 2019-01-14 | 2019-05-28 | 陕西科技大学 | A kind of preparation method being used for sodium-ion battery material with three-dimensional hollow porous carbon made of pomace |
| CN110364369A (en) * | 2019-06-05 | 2019-10-22 | 华东理工大学 | It is a kind of using shredded coconut meat as active carbon capacitor electrode material of carbon source and preparation method thereof |
| CN110371971A (en) * | 2019-06-21 | 2019-10-25 | 广东广垦畜牧工程研究院有限公司 | A kind of preparation method and application of the biogas residue hydro-thermal carbon of activation |
| CN110898805A (en) * | 2019-11-28 | 2020-03-24 | 广东省生态环境技术研究所 | Preparation method and application of graphene-like structure biochar loaded nano zero-valent iron composite material |
| CN110902680A (en) * | 2019-12-18 | 2020-03-24 | 浙江科技学院 | Method for preparing mesoporous carbon material by organic potassium catalytic activation of sodium lignosulfonate |
| CN111530413A (en) * | 2020-04-15 | 2020-08-14 | 广东省微生物研究所（广东省微生物分析检测中心） | Biochar for enhancing soil self-repair and preparation method and application thereof |
| CN112028071A (en) * | 2020-09-17 | 2020-12-04 | 常州大学 | Waste mango kernel biochar and preparation method thereof |
| CN112456488A (en) * | 2020-11-25 | 2021-03-09 | 四川大学 | Hierarchical pore biochar and preparation method and application thereof |
| CN113149006A (en) * | 2021-05-12 | 2021-07-23 | 广西科学院 | Method for preparing capacitance carbon by using biomass rich in lignin as raw material |
| CN113683090A (en) * | 2021-09-23 | 2021-11-23 | 湖南省格林森炭业股份有限公司 | Activated carbon multi-element composite activating agent |
| CN116443849A (en) * | 2023-04-27 | 2023-07-18 | 安徽建筑大学 | Porous carbon material with high specific surface area and preparation method and application thereof |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106276899A (en) * | 2016-08-19 | 2017-01-04 | 湖南农业大学 | Ultracapacitor carbon material prepared by a kind of fast-growing grass and production method thereof |
| CN106587055A (en) * | 2016-11-17 | 2017-04-26 | 华南理工大学 | Biomass-based porous carbon material, preparation method thereof, and application thereof in supercapacitor |
| CN108117074B (en) * | 2016-11-28 | 2020-04-28 | 北京化工大学 | Preparation method of super activated carbon and method for recycling produced waste liquid and producing by-product carbonate |
| CN108821287A (en) * | 2018-06-26 | 2018-11-16 | 中国科学院生态环境研究中心 | A kind of preparation and its application of biomass-based powdered carbon binder |
| US10557098B1 (en) | 2019-03-21 | 2020-02-11 | King Saud University | Synthesis of hydrochar from jackfruit |
| CN110562978A (en) * | 2019-09-20 | 2019-12-13 | 安徽大学 | Method for modifying active carbon electrode material by composite aerobic acid hydrothermal method |
| CN110577222B (en) * | 2019-10-21 | 2021-04-09 | 中国矿业大学 | Activated carbon and preparation method and application thereof |
| WO2022130351A1 (en) * | 2020-12-19 | 2022-06-23 | Cancrie Inc. | Process for obtaining high surface area mesoporous carbons from biomass waste for energy storage |
| CN114057279B (en) * | 2021-11-09 | 2023-12-26 | 广东石油化工学院 | Method for accelerating iron circulation by utilizing hydrothermal carbon to promote catalytic degradation of organic pollutants |
| CN114272942A (en) * | 2021-11-12 | 2022-04-05 | 南昌航空大学 | Phosphoric acid modified hydrothermal carbon and preparation method and application thereof |
| CN114433227B (en) * | 2022-01-24 | 2022-12-27 | 中国科学院广州地球化学研究所 | Modified peat-magnetite composite magnetic Fenton material and preparation method and application thereof |
| US11891312B1 (en) | 2023-03-10 | 2024-02-06 | King Saud University | Magnetic hydrochar synthesized from microalgal biomass |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1593744A (en) * | 2004-06-24 | 2005-03-16 | 中国海洋大学 | Method for preparing active carbon materials SO#-[2] absorbent by medicament activation method |
| CN101439857A (en) * | 2008-12-11 | 2009-05-27 | 武汉科技大学 | Mesoporous activated carbon and preparation process thereof |
| CN103962097A (en) * | 2014-04-02 | 2014-08-06 | 中国石油大学(华东) | Method for preparing CO2 carbon-based absorbent on basis ofenteromorpha |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6057262A (en) * | 1995-05-19 | 2000-05-02 | University Of Kentucky Research Foundation | Activated carbon and process for making same |
| CN101759181A (en) * | 2009-12-15 | 2010-06-30 | 李广朝 | Method for producing activated carbon for super capacitors |
| CN102205963A (en) * | 2011-03-16 | 2011-10-05 | 吉林大学 | Method for preparing activated carbon for biomass-based super capacitor |
-
2015
- 2015-10-22 CN CN201580059522.1A patent/CN107108232B/en active Active
- 2015-10-22 WO PCT/SG2015/050406 patent/WO2016072932A1/en active Application Filing
- 2015-10-22 SG SG11201703235YA patent/SG11201703235YA/en unknown
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1593744A (en) * | 2004-06-24 | 2005-03-16 | 中国海洋大学 | Method for preparing active carbon materials SO#-[2] absorbent by medicament activation method |
| CN101439857A (en) * | 2008-12-11 | 2009-05-27 | 武汉科技大学 | Mesoporous activated carbon and preparation process thereof |
| CN103962097A (en) * | 2014-04-02 | 2014-08-06 | 中国石油大学(华东) | Method for preparing CO2 carbon-based absorbent on basis ofenteromorpha |
Non-Patent Citations (3)
| Title |
|---|
| AKSHAY JAIN: "HYDROTHERMAL PRE-TREATMENT OF BIOMASS WASTE FOR HIGH SURFACE AREA MESOPOROUS ACTIVATED CARBONS", 《NUS PH.D THESES》 * |
| JING WANG等: "Mesoporous carbon with large pore volume and high surface area prepared by a co-assembling route for Lithium-Sulfur Batteries", 《ELECTROCHIMICA ACTA》 * |
| YINGWEN XUE等: "Hydrogen peroxide modification enhances the ability of biochar (hydrochar) produced from hydrothermal carbonization of peanut hull to remove aqueous heavy metals: Batch and column tests", 《》 * |
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106753501A (en) * | 2017-01-16 | 2017-05-31 | 上海理工大学 | A kind of method that hydro-thermal biomass directly prepare pyrolkigneous liquid |
| CN107364859A (en) * | 2017-07-24 | 2017-11-21 | 广西柳城县成霖农业科技有限公司 | A kind of method that activated carbon is produced using bagasse |
| CN107555424A (en) * | 2017-08-31 | 2018-01-09 | 西南大学 | A kind of preparation method of porous class graphene active carbon material and products thereof and application |
| CN108640112A (en) * | 2018-03-08 | 2018-10-12 | 哈尔滨工程大学 | A kind of preparation method of high activity active fruit shell carbon anode fuel for indirect carbon consuming cell |
| CN108516549A (en) * | 2018-04-19 | 2018-09-11 | 句容市盛达环保净化材料有限公司 | A kind of preparation method of activated carbon |
| CN108751194A (en) * | 2018-04-19 | 2018-11-06 | 句容市盛达环保净化材料有限公司 | A kind of preparation method of activated carbon |
| CN108689407A (en) * | 2018-06-26 | 2018-10-23 | 中国科学院生态环境研究中心 | A kind of technique that binder pressed active carbon is exempted from abandoned biomass preparation |
| CN109809402A (en) * | 2019-01-14 | 2019-05-28 | 陕西科技大学 | A kind of preparation method being used for sodium-ion battery material with three-dimensional hollow porous carbon made of pomace |
| CN109809405A (en) * | 2019-03-15 | 2019-05-28 | 合肥学院 | A kind of preparation method of honey peach peach-pit matrix activated carbon |
| CN110364369A (en) * | 2019-06-05 | 2019-10-22 | 华东理工大学 | It is a kind of using shredded coconut meat as active carbon capacitor electrode material of carbon source and preparation method thereof |
| CN110371971A (en) * | 2019-06-21 | 2019-10-25 | 广东广垦畜牧工程研究院有限公司 | A kind of preparation method and application of the biogas residue hydro-thermal carbon of activation |
| CN110898805A (en) * | 2019-11-28 | 2020-03-24 | 广东省生态环境技术研究所 | Preparation method and application of graphene-like structure biochar loaded nano zero-valent iron composite material |
| CN110902680A (en) * | 2019-12-18 | 2020-03-24 | 浙江科技学院 | Method for preparing mesoporous carbon material by organic potassium catalytic activation of sodium lignosulfonate |
| CN111530413A (en) * | 2020-04-15 | 2020-08-14 | 广东省微生物研究所（广东省微生物分析检测中心） | Biochar for enhancing soil self-repair and preparation method and application thereof |
| CN112028071A (en) * | 2020-09-17 | 2020-12-04 | 常州大学 | Waste mango kernel biochar and preparation method thereof |
| CN112456488A (en) * | 2020-11-25 | 2021-03-09 | 四川大学 | Hierarchical pore biochar and preparation method and application thereof |
| CN112456488B (en) * | 2020-11-25 | 2022-06-21 | 四川大学 | Hierarchical pore biochar and preparation method and application thereof |
| CN113149006A (en) * | 2021-05-12 | 2021-07-23 | 广西科学院 | Method for preparing capacitance carbon by using biomass rich in lignin as raw material |
| CN113149006B (en) * | 2021-05-12 | 2021-11-02 | 广西科学院 | Method for preparing capacitance carbon by using biomass rich in lignin as raw material |
| CN113683090A (en) * | 2021-09-23 | 2021-11-23 | 湖南省格林森炭业股份有限公司 | Activated carbon multi-element composite activating agent |
| CN116443849A (en) * | 2023-04-27 | 2023-07-18 | 安徽建筑大学 | Porous carbon material with high specific surface area and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2016072932A1 (en) | 2016-05-12 |
| SG11201703235YA (en) | 2017-05-30 |
| CN107108232B (en) | 2020-11-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107108232A (en) | Activated carbon, hydro-thermal charcoal and preparation method thereof | |
| Leng et al. | An overview on engineering the surface area and porosity of biochar | |
| Lv et al. | A functional activated carbon for efficient adsorption of phenol derived from pyrolysis of rice husk, KOH-activation and EDTA-4Na-modification | |
| Reddy et al. | A comparison of microstructure and adsorption characteristics of activated carbons by CO2 and H3PO4 activation from date palm pits | |
| Romero-Anaya et al. | Spherical carbons: Synthesis, characterization and activation processes | |
| Mahmoudi et al. | Adsorption of methyl orange using activated carbon prepared from lignin by ZnCl2 treatment | |
| Ahmad et al. | Equilibrium, kinetics, and thermodynamics of remazol brilliant blue R dye adsorption onto activated carbon prepared from pinang frond | |
| Zeng et al. | Sorption of ammonium and phosphate from aqueous solution by biochar derived from phytoremediation plants | |
| Bouchelta et al. | Effects of pyrolysis conditions on the porous structure development of date pits activated carbon | |
| Li et al. | Efficient removal of cationic dyes via activated carbon with ultrahigh specific surface derived from vinasse wastes | |
| Hao et al. | Activated carbons for water treatment prepared by phosphoric acid activation of hydrothermally treated beer waste | |
| Chen et al. | Effective removal of methyl orange and rhodamine B from aqueous solution using furfural industrial processing waste: Furfural residue as an eco-friendly biosorbent | |
| US20140162873A1 (en) | Materials and methods for production of activated carbons | |
| CN101708842A (en) | Method for preparing high specific surface area active carbon by using polyvinyl chloride wastes | |
| Chung et al. | Synthesis and characterization of activated hollow carbon fibers from Ceiba pentandra (L.) Gaertn.(kapok) | |
| CN110064367A (en) | A kind of biomass-based activated carbon microballon and its preparation method and application | |
| Yahya et al. | Preparation of activated carbon from desiccated coconut residue by chemical activation with NaOH | |
| Dos Santos et al. | Syagrus oleracea–activated carbon prepared by vacuum pyrolysis for methylene blue adsorption | |
| Khalil et al. | High surface area nanostructured activated carbons derived from sustainable sorghum stalk | |
| Qin et al. | Efficient decolorization of citric acid fermentation broth using carbon materials prepared from phosphoric acid activation of hydrothermally treated corncob | |
| CN102424383B (en) | Method for preparing mesoporous carbon material for electrochemical capacitor | |
| Arslanoğlu et al. | Fabrication, characterization, and adsorption applications of low-cost hybride activated carbons from peanut shell-vinasse mixtures by one-step pyrolysis | |
| Özsin | Production and characterization of activated carbon from pistachio-nut shell | |
| Fathy et al. | Utilization of cotton stalks-biomass waste in the production of carbon adsorbents by KOH activation for removal of dye-contaminated water | |
| Buah et al. | Granular activated carbons from palm nut shells for gold di-cyanide adsorption |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |