CN105555714A - Activated carbon for water purifier - Google Patents
Activated carbon for water purifier Download PDFInfo
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- CN105555714A CN105555714A CN201580001883.0A CN201580001883A CN105555714A CN 105555714 A CN105555714 A CN 105555714A CN 201580001883 A CN201580001883 A CN 201580001883A CN 105555714 A CN105555714 A CN 105555714A
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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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- 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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
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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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28064—Surface area, e.g. B.E.T specific surface area being in the range 500-1000 m2/g
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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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28066—Surface area, e.g. B.E.T specific surface area being more than 1000 m2/g
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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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28078—Pore diameter
- B01J20/28083—Pore diameter being in the range 2-50 nm, i.e. mesopores
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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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28088—Pore-size distribution
- B01J20/28092—Bimodal, polymodal, different types of pores or different pore size distributions in different parts of the sorbent
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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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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
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- 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
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- 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
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- 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
- C01P2006/16—Pore diameter
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
Abstract
The powdered or particulate activated carbon for a water purifier of the present invention is characterized in that the BET specific surface area of the activated carbon is 700 m2/g or greater and less than 1250 m2/g, that the ratio of the pore volume of pores with a diameter of 2 nm or less to the pore volume of pores with a diameter of 30nm or less is 50% or greater and less than 80%, and that the ratio of the pore volume of pores with a diameter of greater than 2 nm and less than or equal to 10 nm to the pore volume of pores with a diameter of 30 nm or less is greater than or equal to 10% and less than 40%.
Description
Technical field
The present invention relates to water purifier gac, be specifically related to the water purifier gac of the adsorptive power excellence to Organohalogen compounds.
Background technology
Former water for tap water must carry out chlorine process, containing a certain amount of residual chlorine in the tap water after process.On the other hand, residual chlorine, except having germicidal action, also has organic oxygenolysis, generates the Organohalogen compounds such as carcinogenic substance haloform class.Organohalogen compounds molecular weight residual in tap water is little, and concentration in tap water is extremely low.Therefore, it is very difficult for fully removing these type of Organohalogen compounds with traditional gac.
For such problem, propose the method for the pore size distribution optimizing gac.Consider the absorption improving medium pore volume ratio and contribute to improving Organohalogen compounds, propose kinds of schemes.
Such as patent documentation 1 propose Phenolic resin powder through carbonization, be combined the particulate state carbon molding formed with activated species, disclose the relation by regulating specific surface area, pore diameter and pore volume, particle volume density and tamped density, thus improve the technology to the adsorptivity of lower boiling organochlorine compound.
In addition, patent documentation 2 discloses by regulating relative to pore diameter
following pore volume, pore diameter
pore volume ratio and pore diameter
following pore volume ratio, improves the technology of the adsorptivity to haloform class.
Prior art document
Patent documentation
Patent documentation 1 Unexamined Patent 9-110409 publication
Patent documentation 2 JP 2006-247527 publication
Summary of the invention
In recent years, along with the increase of water demand, need to improve gac under water delivery condition to the absorption property of Organohalogen compounds.But gac does not in the past have sufficient absorption property under water delivery condition.
The present invention is conceived to above-mentioned situation, and its object is to provides a kind of water purifier gac, and this water purifier gac not only has the equilibrium adsorption capacity of excellent Organohalogen compounds, and under water delivery condition, also have excellent absorption property.
Solve the of the present invention Powdered of above-mentioned technical problem or granular water purifier gac, have following character, BET specific surface area is 700m
2/ more than g and 1250m
2/ below g, relative to the pore volume of below pore diameter 30nm, the pore volume ratio of below pore diameter 2nm is more than 50% and is less than 80%, and, relative to the pore volume of below pore diameter 30nm, pore diameter is greater than 2nm and the pore volume ratio of below 10nm is more than 10% and less than 40%.
Water purifier gac of the present invention has following embodiment, the average pore diameter of gac is preferably more than 2.0nm and below 4.0nm, and the pore volume of below the pore diameter 30nm relative to gac, the pore volume ratio of below 10nm is preferably more than 80%.
In addition, water purifier gac of the present invention is preferably and carries out activation treatment to the carbide of the stacked body of paper-resol and make BET specific surface area be gac in above-mentioned scope, and more preferably activation treatment is steam-activation treatment.
Water purifier gac of the present invention, because specific surface area and pore structure are optimised, can not only play the excellent equilibrium adsorption capacity to Organohalogen compounds, and under water delivery condition, also can play excellent absorption property.
Accompanying drawing explanation
Fig. 1 is the figure representing the relation of 1，1，1-trichloroethane equilibrium adsorption capacity and specific surface area in the balancing test of each gac of embodiment.
Fig. 2 is the figure of the relation representing 1，1，1-trichloroethane carrying capacity and specific surface area in the water delivery test of each gac of embodiment.
Fig. 3 is the figure of the pore size distribution of each gac representing embodiment.
Embodiment
Organohalogen compounds adsorb in the micropore of below pore diameter 2nm, in order to improve the absorption property to Organohalogen compounds under water delivery condition, need to improve the velocity of diffusion of Organohalogen compounds in particle.Thus must consider that the pore diameter increased as the input channel of leading to micropore is greater than 2nm and the medium hole of below 50nm.But the adjustment that the specific surface area of gac in the past and pore volume can not be strict, can not remove Organohalogen compounds efficiently under water delivery condition.
Such as, in patent documentation 1, improve the ratio of the pore volume of pore diameter 0.6-0.8nm in spherical resol.But in patent documentation 1, the larger pore contributing to improving the velocity of diffusion of Organohalogen compounds in pore is not taken into full account, thus can not improve the absorption property under water delivery condition.
In addition in patent documentation 2, expect by improve with soccerballene be raw material gac in the pore volume ratio of pore diameter 2-10nm improve absorption property to Organohalogen compounds under water delivery condition.But from taking into account the viewpoint of velocity of diffusion of higher adsorptive capacity and Organohalogen compounds under water delivery condition, still there is the leeway of the relation of research pore diameter and pore volume.Particularly use soccerballene as activated carbon raw material in patent documentation 2, preparation cost is high, and using soccerballene as the gac of raw material, with improve water delivery condition under there is the problem being difficult to regulate in specific surface area that the absorption property of Organohalogen compounds is adapted and pore volume.
The present inventor is for the equilibrium adsorption capacity not only with excellent Organohalogen compounds, and the gac also under water delivery condition with excellent absorption property is studied.It found that can take into account the pore diameter of the balance of the velocity of diffusion of adsorptive capacity and Organohalogen compounds and the relation of pore volume and specific surface area well.
I.e. Powdered or granular water purifier gac of the present invention, by strictly regulating in the medium hole of the velocity of diffusion contributing to raising Organohalogen compounds, pore diameter is greater than 2nm and the pore volume ratio of below 10nm (hereinafter also referred to " the pore volume ratio of 2-10nm "), and contribute to the pore volume ratio (hereinafter also referred to " the pore volume ratio of below 2nm ") of below pore diameter 2nm of the adsorptive capacity improving Organohalogen compounds, and then the strict specific surface area regulating gac, can improve Organohalogen compounds equilibrium adsorption capacity and the absorption property under water delivery condition.
The feature of water purifier gac of the present invention is, BET specific surface area is 700m
2/ more than g and be less than 1250m
2/ g, relative to the pore volume (hereinafter also referred to " total pore volume ") of below pore diameter 30nm, the pore volume ratio of below 2nm is more than 50% and is less than 80%, and relative to total pore volume, the pore volume ratio of 2-10nm is more than 10% and is less than 40%.
Have the water purifier gac of the present invention of above-mentioned formation, movement, the velocity of diffusion of the Organohalogen compounds in gac are accelerated, and be there is a large amount of adsorption site.Therefore, the absorption property of gac of the present invention under water delivery condition is excellent.
Below gac of the present invention is specifically described.
[BET specific surface area is 700m
2/ more than g and be less than 1250m
2/ g]
When the BET specific surface area of gac is too small, sufficient adsorptive capacity can not be obtained.Therefore, BET specific surface area is 700m
2/ more than g, is preferably 800m
2/ more than g, is more preferably 900m
2/ more than g.On the other hand, when BET specific surface area is excessive, while the tamped density reduction of gac, the balance of the pore volume ratio cannot guaranteeing below the 2nm contributing to raising adsorptive capacity well and the pore volume ratio contributing to the 2-10nm improving velocity of diffusion.Therefore, BET specific surface area is less than 1250m
2/ g, is preferably 1100m
2/ below g, is more preferably 1050m
2/ below g, is more preferably less than 1000m
2/ g.
[relative to total pore volume, the pore volume ratio of below pore diameter 2nm is more than 50% and is less than 80%]
In gac, the pore of below pore diameter 2nm is effective pore in the adsorptive capacity improving Organohalogen compounds, when the pore volume ratio of below 2nm is too small, can not guarantee sufficient adsorptive capacity.Therefore, relative to total pore volume, the pore volume ratio of below 2nm is more than 50%, is preferably more than 60%, is more preferably more than 70%.On the other hand, when the pore volume ratio of below 2nm is excessive, fully can not guarantee the pore volume ratio contributing to the 2-10nm improving velocity of diffusion, the absorption property under water delivery condition reduces.Therefore, relative to total pore volume, the pore volume ratio of below 2nm is less than 80%, is preferably less than 75%.
[relative to total pore volume, pore diameter is greater than 2nm and the pore volume ratio of below 10nm is more than 10% and is less than 40%]
In gac pore diameter be greater than 2nm and the pore of below 10nm improving the velocity of diffusion of Organohalogen compounds in gac inside thus absorption property under effectively improving water delivery condition is effective.When the pore volume ratio of 2-10nm is too small, velocity of diffusion slows down, and the absorption property under water delivery condition reduces.Therefore, relative to total pore volume, the pore volume ratio of 2-10nm is more than 10%, is preferably more than 15%, is more preferably more than 20%, more preferably more than 25%.On the other hand, when the pore volume ratio of 2-10nm is excessive, the pore volume ratio of below 2nm reduces, and adsorptive capacity reduces.Therefore, relative to total pore volume, the pore volume ratio of 2-10nm is less than 40%, is preferably less than 35%.
In order to improve the absorption property to Organohalogen compounds under water delivery condition further, preferably meet the following conditions.
[relative to total pore volume, the pore volume ratio of below 10nm]
As mentioned above, in gac, to be the pore of below 10nm be pore diameter contributes to the pore improving adsorptive capacity and velocity of diffusion, by guaranteeing that it is more than a certain amount of, can improve the absorption property of gac further.Therefore, relative to total pore volume of gac, the total volume fraction (hereinafter referred to as " the pore volume ratio of below 10nm ") of the pore volume ratio of described below 2nm and the pore volume ratio of 2-10nm is preferably more than 80%, be more preferably more than 85%, more preferably more than 90%.Although be not particularly limited the upper limit, when but the pore volume ratio of below 10nm is excessive, the pore diameter that can reduce as the input channel of Organohalogen compounds is greater than the medium hole with larger pore diameter or the micropore of 10nm, thus the movement of Organohalogen compounds in gac inside, rate of diffusion reduce, the absorption property under water delivery condition reduces.Therefore, relative to total pore volume, the pore volume ratio of below 10nm is preferably less than 98%, is more preferably less than 96%, and more preferably less than 95%.
[total pore volume of gac]
As long as gac of the present invention meets above-mentioned pore volume ratio, for the pore volume of below pore diameter 30nm, Zong namely pore volume does not limit.When total pore volume is too small, sufficient adsorptive capacity cannot be guaranteed.Therefore, total pore volume is preferably 0.30cm
3/ more than g, is more preferably 0.40cm
3/ more than g, more preferably 0.50cm
3/ more than g.The upper limit of total pore volume is not particularly limited, such as, be preferably 0.80cm
3/ below g, is more preferably 0.70cm
3/ below g.
[average pore diameter of gac]
Average pore diameter for gac is not particularly limited, from improving the viewpoint of Organohalogen compounds to the importing efficiency of gac inside, being preferably more than 2.0nm, being more preferably more than 2.1nm, more preferably more than 2.2nm, is further preferably more than 2.3nm.On the other hand, due to average pore diameter excessive time, tamped density can reduce, and therefore, the average pore diameter of gac is preferably below 4.0nm, is more preferably below 3.5nm, more preferably below 3.0nm.
[median size of gac]
Gac of the present invention can be Powdered or particulate state, is not particularly limited for median size, is preferably more than 20 μm, be more preferably more than 30 μm, more preferably more than 40 μm, be preferably less than 300 μm, be more preferably less than 150 μm, more preferably less than 100 μm.
Gac of the present invention is to the haloform class of trichloromethane, trifluoromethane, difluorochloromethane, two methyl chlorobromides, two bromochloromethanes, methenyl bromide etc., trichloroethane, the Organohalogen compounds of trieline etc. have excellent absorption property, preferably little to molecular weight and 1 of difficult absorption, 1,1-trichloroethane has excellent absorption property.
Gac of the present invention is applicable to remove the above-mentioned substance comprised in tap water or trade effluent.
Gac of the present invention, the equilibrium adsorption capacity based on the balancing test of aftermentioned embodiment preferably can reach more than 20mg/g, more preferably can reach more than 25mg/g.In addition gac of the present invention is suitable as the gac removing trihalid under water delivery condition, the Organohalogen compounds removal rate tested based on the water delivery of aftermentioned embodiment can maintain the carrying capacity of more than 80%, be preferably more than 52L/g, be more preferably more than 60L/g, more preferably more than carrying capacity 70L/g, is further preferably more than 80L/g.
Use the form of the water purifier of gac of the present invention to be not particularly limited, can use in various known water purifier.
Next, be specifically described the manufacture method of gac of the present invention, manufacture method of the present invention is not by the restriction of following preparation example, and can suitably change, these changes are also contained in scope of the present invention.
The gac of the invention described above can by carrying out the method preparation of activation treatment by activation raw material." activation treatment " forms pore on the surface of activation raw material, increases the process of specific surface area and pore volume.As activation treatment, preferably carry out steam activation.In addition, activation treatment can be carried out once, also can carry out repeatedly.Activated material can use the raw material of common gac, particularly preferably following raw material.
As activation raw material, be preferably the mixture of the activation raw material (hereinafter also referred to " medium hole formation raw material ") easily forming larger pore and the activation raw material (hereinafter also referred to " micropore formation raw material ") easily forming smaller pore.As activation raw material, use medium hole to be formed situation that raw material and micropore form the mixture of raw material, does not need to carry out repeatedly activation treatment, can obtain having the gac of the pore volume ratio of each pore diameter meeting afore mentioned rules by activation treatment.
Form raw material as medium hole, the cellulose-based raw materials such as such as paper, cotton fibre, wood materials can be enumerated.Form raw material as micropore, the such as synthetic resins such as resol, furane resin system raw material can be enumerated.These medium holes form raw material and micropore formation raw material at least uses more than one separately.Further, medium hole forms the proportioning of raw material and micropore formation raw material, suitably can change according to the physical properties of the gac expected.Form the mixture of raw material and micropore formation raw material as medium hole, such as, be preferably the stacked body of paper-resol.
The stacked body of paper-resol and the resol used in patent documentation 1 or patent documentation 2 or soccerballene etc. as raw material gac compared with, by regulating activation condition, strictly can control the formation of medium hole or micropore.Therefore, the accurate control of the specific surface area and pore volume ratio etc. of gac can be realized.Thus the gac that under obtaining water delivery condition, the absorption property of Organohalogen compounds is very excellent.
Medium hole forms mixture or the mixture of raw material and micropore formation raw material etc., preferably uses after carbonizing treatment.Described carbonizing treatment, usually can be under the inert gas atmospheres such as nitrogen, helium, argon gas, carries out heat treated with the incombustible temperature of carbon raw material, time.The temperature of this carbonizing treatment is preferably more than 500 DEG C, is more preferably more than 550 DEG C, is preferably less than 850 DEG C, is more preferably less than 800 DEG C.Hold-time is not particularly limited, at this carbonizing treatment temperature, keep more than about 5-10 minute.
Activation treatment is not particularly limited, as long as obtain BET specific surface area and the pore volume ratio of the gac of the invention described above.From easier and accurately control BET specific surface area and pore volume ratio viewpoint, be preferably steam activation.
In steam activation, after activating heating raw materials to specified temperature, carry out activation treatment by supply water vapour, and make BET specific surface area and pore volume ratio be the scope of afore mentioned rules.The heating of activation raw material is preferably carried out in the inert gas atmospheres such as nitrogen, argon gas, helium.
Temperature (in-furnace temperature) when carrying out activation treatment is preferably more than 400 DEG C, is more preferably more than 450 DEG C, is preferably less than 1500 DEG C, is more preferably less than 1300 DEG C.In addition, heat-up time when carrying out activation treatment is preferably more than 0.5 hour, is more preferably more than 1.0 hours, is preferably less than 10 hours, is more preferably less than 5 hours.
The water vapour total amount supplied in activation treatment is not particularly limited.
Supply form for water vapour is not particularly limited, such as, can be following any one, supply water vapour does not carry out the form that supplies dilutedly, carries out the form supplied with inert gas dilution water vapour as mixed gas.In order to make activation treatment effectively carry out, preferably carry out the form supplied with inert gas dilution.When water vapour inert gas dilution supplies, in this mixed gas (total pressure 101.3kPa), steam partial pressure is preferably more than 30kPa, is more preferably more than 40kPa.
Gac after steam activation, can carry out cleaning process, thermal treatment, pulverization process as required.Carry out cleaning process to the gac after steam activation by using the known solvents such as water, acid solution or alkaline solution.By cleaning gac, can except the impurity such as deashing.Thermal treatment is heated under inert gas atmosphere further by the gac after steam activation or after cleaning.By heat-treating gac, the water contained in gac can be removed.Pulverization process uses disc refiner, ball mill, ball mill etc. to carry out.In addition, the particle diameter of gac can suitably adjust as required.
The application advocates the interests of the right of priority of No. 2014-76685th, the Japanese invention patent application based on application on April 3rd, 2014.On April 3rd, 2014 application No. 2014-76685th, Japanese invention patent application specification sheets full content as the application reference and be cited.
Embodiment
Next, be described in detail the present invention by enumerating embodiment, but the present invention is not by the restriction of following embodiment, can carry out suitable change in the contextual teachings of adaptation and implement, these are all included in technical scope of the present invention.
(condition determination etc.)
1, specific surface area, total pore volume
After gac 0.2g carries out heating under vacuum at 250 DEG C, use nitrogen adsorption device (Micromeritics Inc. is standby, " ASAP-2400 "), obtain adsorption isothermal line, calculate specific surface area (m by BET method
2/ g), total pore volume (V of the pore of below pore diameter 30nm is calculated from adsorption isothermal line
total: cm
3/ g).
2, the pore volume of average pore diameter and each pore diameter
Average pore diameter is the shape of the pore that supposition gac is formed is cylindrical calculating.In addition, the pore volume of each pore diameter is undertaken analyzing by BJH method and is calculated the pore volume of each pore diameter.Based on the above-mentioned specific surface area that calculates and total pore volume, calculated by following formula (1)-(4).Further, pore size distribution as shown in Figure 3.
Average pore diameter (nm)=(4 × total pore volume (V
total: cm
3/ g))/specific surface area (m
2/ g) (1)
The pore volume (≤V of below pore diameter 2nm
2nm: cm
3/ g)=total pore volume (V
total: cm
3/ g)-(pore volume (V of 2-10nm
2-10nm: cm
3/ g)+be greater than the pore volume (V of 10nm
10nm<: cm
3/ g)) (2)
Pore diameter is greater than 2nm and the pore volume (V of below 10nm
2-10nm: cm
3/ g)=total pore volume (V
total: cm
3/ g)-(the pore volume (≤V of below 2nm
2nm: cm
3/ g)+be greater than the pore volume (V of 10nm
10nm<: cm
3/ g)) (3)
Be greater than the pore volume (V of 10nm
10nm<: cm
3/ g)=total pore volume (V
total: cm
3/ g)-(the pore volume (≤V of below 2nm
2nm: cm
3/ g) pore volume (V of+2-10nm
2-10nm: cm
3/ g)) (4)
3, relative to total pore volume (V
total), each pore diameter (≤V
2nm, V
2-10nm, V
10nm<) pore volume ratio
Above-mentioned each pore volume calculates the pore volume ratio (%) of each pore diameter divided by total pore volume.
4, water delivery test
Fill pillar (diameter 15mm) with the gac 2.0g that particle diameter is adjusted within the scope of 53-250 μm, carry out water delivery test according to JISS3201 (2010: Domestic water purifier test method).Particularly, 1，1，1-trichloroethane concentration is adjusted to the former water of 0.3 ± 0.06mg/L with air speed (SV) 500h
-1pass through pillar.Quantitative assay is carried out by the concentration headspace gas chromatography of the 1，1，1-trichloroethane before and after pillar.Flex point (Po Over point) for flowing out 1 of water, 1,1-trichloroethane relative concentration flows into 20% of water in pillar, calculate 1 when arriving flex point, 1,1-trichloroethane carrying capacity (=[the total filtration water yield (the L)/quality of activated carbon (g) to during flex point]), as filterability.The TurboMatrixHS that headspace gas chromatography sampler uses PerkinElmer Inc. standby, the QP2010 that gas chromatography mass spectrometer uses Shimadzu Seisakusho Ltd. to prepare.
5, balancing test
After being diluted with methyl alcohol 50mL by 1，1，1-trichloroethane 0.5g, modulate stoste with methanol dilution 10 times further.Stoste 5mL pure water is diluted, has modulated the 1，1，1-trichloroethane aqueous solution of concentration 5mg/L.In the brown triangular flask of capacity 100mL, insert stirrer and particle diameter be adjusted to gac within the scope of 53-250 μm, then fill the 1，1，1-trichloroethane aqueous solution and airtight.After this triangular flask is inserted in the thermostatic bath of maintenance 20 DEG C, stir 14 hours.After 14 hours, by the aqueous solution in triangular flask by syringe type strainer.The filtrate obtained obtains the equilibrium concentration (mg/L) of the 1，1，1-trichloroethane aqueous solution with headspace gas chromatography, and obtain 1 divided by quality of activated carbon, the equilibrium adsorption capacity (mg/g) of 1, the 1-trichloroethane aqueous solution, makes adsorption isothermal curve, calculate 1 when equilibrium concentration is 0.3mg/L, 1,1-trichloroethane equilibrium adsorption capacity, as to 1, the adsorptive capacity of 1,1-trichloroethane.
Gac No.1
Using the carbon dust that obtains through carbonization as the stacked body of paper-resol of carbon raw material 870 DEG C of heating, put into and be adjusted in the process furnace of inert atmosphere.While the stacked body of input paper-resol, in process furnace, supply water vapour (steam partial pressure: 40kPa), in inert gas atmosphere, carry out 2.0 hours steam-activation treatments obtain gac No.1.Further, relative to paper-resol stacked body 100 weight part dropped into, the feed rate of water vapour is 300 weight parts.
Gac No.2-4
Except soak time changes, prepare gac No.2-4 in the same manner as gac No.1.
Gac No.5
Prepare commercially available coconut husk steam activation gac (MCEvolveTechnologiesCorporation system) as gac No.5.
Gac No.6
The potassium hydroxide adding mass ratio 0.64 times in the stacked body 30g of paper-resol through carbonization as activator after, drop in process furnace, in nitrogen atmosphere, 800 DEG C are carried out 2 hours activation treatment.The activated carbon obtained is carried out water and is cleaned process in the warm water of 60 DEG C, then carries out hydrochloric acid and cleans process (concentration of hydrochloric acid 5.25 quality %), then carries out the clean process of water with the warm water of 60 DEG C.Afterwards, gac is placed in retort furnace, nitrogen circulation under (2L/ divides) in-furnace temperature is warming up to 750 DEG C (heat-up rates: 10 DEG C/minute), 750 DEG C of maintenances prepare gac No.6 in 2 hours.
Table 1
Fig. 1 represents the 1，1，1-trichloroethane equilibrium adsorption capacity of each gac in balancing test and the relation of specific surface area.In addition Fig. 2 represents the 1，1，1-trichloroethane carrying capacity of each gac in water delivery test and the relation of specific surface area.Fig. 3 represents the pore size distribution of gac No.1-6.
As shown in Figure 1, making the gac No.1-4 of the stacked body of paper using-resol, having in balancing test than using the absorption property that the gac No.5 of coconut husk is more excellent.In addition, as shown in Figure 2, in water delivery experiment, gac No.1-4 has the more excellent absorption property of specific activity charcoal No.6.
As shown in Figure 3, gac No.1-4 is compared with gac No.5,6, and the pore volume ratio of 2-10nm is larger.Therefore, as shown in Figure 1, 2, the gac No.1-4 meeting important document of the present invention, in balancing test and water delivery test, has all given play to the absorption property of the excellence to 1，1，1-trichloroethane.
Claims (5)
1. a Powdered or granular water purifier gac, is characterized in that,
BET specific surface area is 700m
2/ more than g and be less than 1250m
2/ g,
Relative to the pore volume of below pore diameter 30nm, the pore volume ratio of below pore diameter 2nm is more than 50% and is less than 80%, and,
Relative to the pore volume of below pore diameter 30nm, pore diameter is greater than 2nm and the pore capacity ratio of below 10nm is more than 10% and is less than 40%.
2. water purifier gac according to claim 1, wherein, the average pore diameter of described gac is more than 2.0nm and below 4.0nm.
3. water purifier gac according to claim 1 and 2, wherein, relative to the pore volume of below pore diameter 30nm in described gac, the pore volume ratio of below 10nm is more than 80%.
4. the water purifier gac according to any one in claim 1-3, wherein, described gac is carry out activation treatment to the carbide of the stacked body of paper-resol to make BET specific surface area be gac in described scope.
5. water purifier gac according to claim 4, wherein, described activation treatment is steam-activation treatment.
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| CN109012581A (en) * | 2018-07-24 | 2018-12-18 | 北海和荣活性炭科技有限责任公司 | The production method of water purification composite carbon rod filter core |
| CN111247097A (en) * | 2018-09-28 | 2020-06-05 | 关西热化学株式会社 | Activated carbon and preparation method thereof |
| CN112135794A (en) * | 2018-06-19 | 2020-12-25 | 株式会社安德如 | Activated carbon |
| TWI789802B (en) * | 2020-06-30 | 2023-01-11 | 日商可樂麗股份有限公司 | Carbonaceous material, method for producing same, filter for water purification, and water purifier |
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| US11865509B2 (en) * | 2018-01-04 | 2024-01-09 | Asahi Kasei Kabushiki Kaisha | Porous molding |
| JP6683968B1 (en) * | 2018-06-19 | 2020-04-22 | 株式会社アドール | Activated carbon |
| EP3812349A4 (en) * | 2018-06-19 | 2022-02-09 | Ad'All Co., Ltd. | Activated carbon |
| JP6542968B1 (en) * | 2018-09-28 | 2019-07-10 | 関西熱化学株式会社 | Activated carbon and method for producing the same |
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| WO2015152391A1 (en) | 2015-10-08 |
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| KR20160142275A (en) | 2016-12-12 |
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