CN109689201A - Adsorbent containing layered double-hydroxide and active carbon - Google Patents

Adsorbent containing layered double-hydroxide and active carbon Download PDF

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Publication number
CN109689201A
CN109689201A CN201780054566.4A CN201780054566A CN109689201A CN 109689201 A CN109689201 A CN 109689201A CN 201780054566 A CN201780054566 A CN 201780054566A CN 109689201 A CN109689201 A CN 109689201A
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Prior art keywords
ldh
activated carbon
compound
powdered activated
dispersion
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A·普拉马尼克
S·达斯
P·萨卡尔
S·阿帕沃
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Unilever NV
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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
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • 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
    • B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
    • B01J20/041—Oxides or hydroxides
    • 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
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
    • 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
    • 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
    • B01J20/28002—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 physical properties
    • B01J20/28004—Sorbent size or size distribution, e.g. particle size
    • 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
    • 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
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3071—Washing or leaching
    • 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
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
    • B01J20/3204—Inorganic carriers, supports or substrates
    • 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
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3234—Inorganic material layers
    • B01J20/3236—Inorganic material layers containing metal, other than zeolites, e.g. oxides, hydroxides, sulphides or salts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/25—Coated, impregnated or composite adsorbents
    • 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
    • B01D2257/306—Organic sulfur compounds, e.g. mercaptans

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  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

The present invention relates to a kind of materials of absorption volatile compound especially sulfur-containing compound.It has been found that the adsorbent of the high surface area suitable for high volatility compound can be obtained by growing the nano particle of layered double-hydroxide (LDH) on the surface of Powdered Activated Carbon (PAC).The invention discloses a kind of compound adsorbents, are [M it includes general formula2+ 1‑xM3+ x(OH)2]q+(Xn‑)q/n·yH2The nano particle and Powdered Activated Carbon (PAC) of the layered double-hydroxide (LDH) of O, wherein M2+=Ca2+、Mg2+、Mn2+、Fe2+、Co2+、Ni2+、Cu2+Or Zn2+；M3+=Al3+Or Fe3+；X=[M3+]/[M3++M2+]；Q=x；N=1 to 4；With y=LDH present on moisture subnumber；X=is selected from halide, sulfate, nitrate, the anion of carbonate or the anion part from organic source；Wherein, the composite material can be obtained by hydro-thermal method, and the hydro-thermal method is successively the following steps are included: (a) is by Powdered Activated Carbon and M2+Water soluble salt and M3+Water soluble salt contact and mixing；(b) alkali is added into the dispersion of step (a)；(c) by the way that the dispersion of step (b) is heated to 80 to 100 DEG C so that its aging；(d) water phase and dispersed phase of dispersion are separated in any manner；And the dispersed phase is washed with water (e) to remove excessive alkali, obtain compound adsorbent, wherein the amount of the nano particle of layered double-hydroxide (LDH) is 10-30 weight %, and wherein, the partial size of the Powdered Activated Carbon is 50 μm to 500 μm.

Description

Adsorbent containing layered double-hydroxide and active carbon
Technical field
The present invention relates to adsorbents.Particularly, the present invention relates to the compound suctions for being suitable for adsorbing volatile sulfur compound Attached dose.
Background technique
Active carbon and layered double-hydroxide (LDH) (layered double hydroxide) are widely used as adsorbent, Although for adsorbing different types of material.The dynamics for controlling absorption and the release of high volatility compound is that a technology is asked Topic.Carbon as one of high surface area material is well-known with the ability of its absorption and release volatile compound.However, carbon and gold The mixture for belonging to hydroxide/oxide or other inorganic adsorbents does not show the characterization of adsorption significantly increased.It is difficult to lead to Cross chemical benign pathways and synthesize these compounds, and templated synthesis typically result in product higher cost and yield it is lower.
Layered double-hydroxide (LDH) is usually synthesized by coprecipitation method.In this approach, under stiring by metal The aqueous solution and alkali of ion mix in pond.Sometimes it is reacted at elevated temperatures to improve the crystallinity of particle and ruler It is very little.However, there is significant bigger size, usually micron-scale by the particle that this method synthesizes.
US 4458030A (KYOWA KAGAKU KOGYO KK, 1984) discloses a kind of adsorbent composition, it includes The combination of hydrotalcite and active carbon.The composition adsorbs many kinds of substance.Adsorption capacity is not the additive effect of each ingredient capacity.It is living Property charcoal can be powdered or graininess.However, by by powder and suitable binder such as water and polyvinyl alcohol, by Mixture is mediated and is molded to prepare composite material by the mixture divided.Mixture can be molded as to any desired shape Shape, such as hollow cylinder, sphere, solid cylinder or polygon-prism that diameter is 1 to 50mm, are then dried and forge It burns.
2013/0316898 AA of US (THE UNIVERSITY OF SURREY) discloses a kind of composite adsorbing material, and And it is a kind of for adsorbing and the porous C-base composte material of height of stable inorganic substance in particular.Composite adsorbing material includes porous Carbon carrier matrix and adsorbent material, wherein adsorbent material is formed sediment in the inner hole deposition of carrier matrix.The invention expands to this suction The various uses of attached agent material, such as recycle metal for Water warfare, from waste stream and repair application, and by adsorbent material Material improvement destroys pollutant-receptor connection purpose into soil.But the absorption of volatile compound is not disclosed.
It is special for volatile compound although cited article discloses the adsorbent for various types material It is not the adsorbent still unmet demand of sulfur-containing compound.
Therefore, it is an object of the present invention to provide a kind of adsorbents for volatile compound.
Another purpose is to provide the adsorbent with very high surface area.
, it is surprising that the present invention has been determined by hydro-thermal method grown layer on the surface of Powdered Activated Carbon (PAC) The nano particle of shape double-hydroxide (LDH) can obtain the suction for being suitable for volatile compound with very high surface area Attached dose.
Summary of the invention
Therefore, in a first aspect, being [M it includes general formula the invention discloses a kind of compound adsorbent2+ 1-xM3+ x(OH)2]q+ (Xn-)q/n·yH2The nano particle and Powdered Activated Carbon (PAC) of the layered double-hydroxide (LDH) of O, wherein
M2+=Ca2+、Mg2+、Mn2+、Fe2+、Co2+、Ni2+、Cu2+Or Zn2+；
M3+=Al3+Or Fe3+；
X=[M3+]/[M3++M2+]；
Q=x
N=1 to 4；And
Moisture subnumber present on y=LDH；
X=is selected from halide, sulfate, nitrate, the anion of carbonate or the anion part from organic source；
Wherein, the composite material can be obtained by hydro-thermal method, the hydro-thermal method successively the following steps are included:
(a) by Powdered Activated Carbon and M2+Water soluble salt and M3+Water soluble salt contact and mixing；
(b) alkali is added into the dispersion of step (a)；
(c) by the way that the dispersion of step (b) is heated to 80 to 100 DEG C so that its aging；
(d) water phase and dispersed phase of dispersion are separated in any manner；And
(e) dispersed phase is washed with water to remove excessive alkali, obtains compound adsorbent, wherein layered double hydrogen The amount of the nano particle of oxide (LDH) is 10-30 weight %, and wherein, the partial size of the Powdered Activated Carbon be 50 μm extremely 500μm。
In second aspect, the invention discloses a kind of hydro-thermal method for being used to prepare compound adsorbent, the compound adsorbents It is [M comprising general formula2+ 1-xM3+ x(OH)2]q+(Xn-)q/n·yH2The nano particle and powder of the layered double-hydroxide (LDH) of O are living Property charcoal (PAC), wherein
M2+=Ca2+、Mg2+、Mn2+、Fe2+、Co2+、Ni2+、Cu2+Or Zn2+；
M3+=Al3+Or Fe3+；
X=[M3+]/[M3++M2+]；
Q=x
N=1 to 4；And
Moisture subnumber present on y=LDH；
X=is selected from halide, sulfate, nitrate, the anion of carbonate or the anion part from organic source；
In order the following steps are included:
(a) by Powdered Activated Carbon and M2+Water soluble salt and M3+Water soluble salt contact and mixing；
(b) alkali is added into the dispersion of step (a)；
(c) by the way that the dispersion of step (b) is heated to 80 to 100 DEG C so that its aging；
(d) water phase and dispersed phase of dispersion are separated in any manner；And
(e) dispersed phase is washed with water to remove excessive alkali, obtains compound adsorbent, wherein layered double hydrogen The amount of the nano particle of oxide (LDH) is 10-30 weight %, and wherein, the partial size of the Powdered Activated Carbon be 50 μm extremely 500μm。
According to the third aspect, the invention discloses a kind of compound adsorbents, are made up of:
Layered double-hydroxide (LDH) nano particle of 5-30 weight % and the Powdered Activated Carbon of 70-95 weight % (PAC), wherein the general formula of the LDH are as follows:
[M2+ 1-xM3+ x(OH)2]q+(Xn-)q/n·yH2O, in which:
M2+=Ca2+、Mg2+、Mn2+、Fe2+、Co2+、Ni2+、Cu2+Or Zn2+；
M3+=Al3+Or Fe3+；
X=[M3+]/[M3++M2+]；
Q=x
N=1 to 4；
Moisture subnumber present on y=LDH；
X=is selected from halide, sulfate, nitrate, the anion of carbonate or the anion part from organic source；
Wherein, the amount of the nano particle of layered double-hydroxide (LDH) is 10-30 weight %, and wherein, described The partial size of Powdered Activated Carbon is 50 μm to 500 μm.
By reading described in detail below and appended claims, these and other aspects, feature and advantage are for ability Domain those of ordinary skill will be apparent.To avoid doubt, any feature of one aspect of the present invention can be used for the present invention Any other aspect.Word " comprising " be intended to indicate that " containing " but be not necessarily " consist of " or " by ... constitute ".It changes Sentence is talked about, and listed step or option need not be exhaustion.It should be noted that the embodiment provided in being described below is intended to illustrate this Invention, rather than to limit the invention to those embodiments itself.Similarly, unless otherwise stated, all percentages It is w/w percentage.In addition in operation and comparative example, or in the case where in addition explicitly pointing out, this specification All numerical value of the middle amount for indicating material or reaction condition, the physical property of material and/or purposes are interpreted as being modified by " about ". X and y are understood to include with the numberical range that the format of " from x to y " indicates.When for special characteristic with the format of " from x to y " When describing multiple preferred scopes, it should be understood that it is also contemplated that combining all ranges of different endpoints.
Specific embodiment
Method
According in a first aspect, it includes receiving for layered double-hydroxide (LDH) the present invention provides a kind of compound adsorbent Rice grain and Powdered Activated Carbon (PAC), can be obtained by hydro-thermal method.
Hydro-thermal method is related to water and pressure to the combined effect for obtaining synthetic crystal function.Therefore, it is carried out using Aquo System This synthesis is appropriate.There is the material of high-crystallinity and purity for obtaining, this method is typically superior to other standards technology.
In the present invention, hydro-thermal method ensures that partial size is significantly lower (nano-grade size).However, no any spacer/ In the case where carrier, nano particle LDH is easily formed cluster aggregation, may finally influence the effective surface area of material.Powder Active carbon (PAC) serves as carrier/spacer, passes through the LDH particle of Hydrothermal Growth nano-scale on it.Which ensure that aggregation Body is formed with minimum.This method ensures uniform fold LDH on carbon particles, to obtain being especially odorous compound Sulfur-containing compound has the composite material of high-affinity.
Hydrothermal synthesis starts from making Powdered Activated Carbon and M2+Water soluble salt and M3+Water soluble salt contact and mix.It is excellent PAC is immersed in the mixture solution of the salt containing trivalent metal ion and the salt containing bivalent metal ion and continues by selection of land At least 4 hours, to ensure that metal ion almost adsorbs in carbon matrix, and further to continue at least two small for hybrid dispersions When, it is preferable to use ultrasonoscope.The trivalent metal ion of layered double-hydroxide and the molar ratio of bivalent metal ion are preferably 1:2 to 1:4, more preferably 1:3.
Relatively low-ratio between the amount of liquid (i.e. water) and the amount of carbon ensures effectively adsorbing and reduce for metal ion The chance of bulk solution ion-losses.
In step (b), alkali is added in the dispersion of step (a).
Aqueous slkali is added into dispersion until the pH of dispersion increases to 10, and then in blender, preferably magnetic force It is vigorously stirred about 15 minutes with 800 to 1000RPM until mixture is changed into powder point in water from gel state in blender Granular media.Alkali is preferably the mixture of sodium hydroxide and sodium carbonate.The molar concentration of further preferred sodium hydroxide is about 4M, and The molar concentration of sodium carbonate is 15M.
In the next step, about 24 hours are preferably lasted for come old by the way that the dispersion of step (b) is heated to 80-100 DEG C Change.It is preferred that the total volume of aqueous mixture is maintained at 70ml between 150ml.Some remaining headspaces for generate by Stressed water vapour is applied in limit environment to be necessary.In general, in the case where not using any sealing gas such as nitrogen, by this The pressure that vapor in kind system applies at about 100 DEG C is between 1-2 bars.
When reacting completion, for example using filter medium such as cloth or filter paper, simple filtration is come under vacuum by any method The water phase of dispersion is separated with dispersed phase；And dispersed phase is thoroughly washed with water, is preferably distilled, to remove excessive alkali, with Obtain compound adsorbent.It is preferred that dispersion is cooled to room temperature (about 25 DEG C) before using any separation method.It will thus obtain The composite material obtained is dry in air -oven, such as drying 24 hours at 80 DEG C.
It can optionally calcined composite material.
The property of LDH, carbon and composite material
The divalent metal of LDH is preferably Mg2+、Cu2+Or Zn2+, more preferably Mg2+Or Zn2+。
It is preferred that the amount of the nano particle of layered double-hydroxide (LDH) is the 10-20 weight % of composite material, more preferably 10 weight % of composite material.Similarly, the amount of PAC is the 70-90 weight %, the preferably 80- of composite material of composite material 90 weight %, and 90 weight % of most preferably composite material.
The aperture of Powdered Activated Carbon (PAC) is preferablyExtremely
The partial size of Powdered Activated Carbon is 50 μm to 500 μm, more preferably 50 μm to 300 μm.
The surface area of composite material is preferably 750m2/ g to 1000m2/g.Term surface area refers to BET surface area, can be with It is determined by any standard assay techniques known in the art.
It is particularly preferred that the powder of layered double-hydroxide and 90 weight % that composite adsorbing material contains 10 weight % is lived Property charcoal.
It is further illustrated by the following non-limitative examples the present invention now.
Embodiment
Material
All reagents used are the A.R. grade purchased from Sigma Aldrich.Zinc nitrate hexahydrate [Zn (NO3)2.6H2O], aluminum nitrate nonahydrate [Al (NO3)3.9H2O], sodium hydroxide, natrium carbonicum calcinatum, Powdered Activated Carbon (supply Quotient: Active Carbon Ltd, Inida；Partial size be 50 μm to 300 μm) and deionized water be used for synthesize.
Method
The preparation of compound adsorbent according to the present invention:
It is the mixing of 3:1 by the PAC molar ratio for being immersed in 50ml aluminum nitrate (0.033 mole) and zinc nitrate (0.1 mole) In the aqueous solution of object, it is ultrasonically treated 4 hours and stands overnight.This results in dispersions.
Dispersion is transferred in bottle of the 250ml with plug, and be added sodium hydroxide and sodium carbonate (4M sodium hydroxide and 1.5M sodium carbonate) mixture alkaline aqueous solution, until pH reaches 10.It will be dispersed with 800-1000RPM under magnetic stirring Body is vigorously mixed 15 minutes.
Bottle is stoppered, to avoid air leakage, and bottle is kept for 24 hours in the air -oven for being set as 85 DEG C. 250ml is maintained at 70ml with the total volume of the aqueous mixture in plug bottle and is used for enough headspaces between 150ml, are left Stressed vapor is applied in generation in constrained environment.
When reacting completion, the content in bottle is cooled to room temperature (25 DEG C) and is used under vacuum The filtering of 42 filter paper.(dispersed phase) particle is thoroughly washed with distilled water.Thus obtained composite material is air-dried 24 at 80 DEG C Hour.
Ratio by changing PAC and LDH has synthesized some other composite adsorbing materials.To all materials thus synthesized Material is tested, wherein using HS-GC technology measurement material to the affinity of volatile malodorous gas.
The preparation of mixture:
Some mixtures (i.e. simple physical mixture) of LDH and PAC are prepared in typical reaction system, wherein The LDH of general ' x'g synthesis is mixed with (100-x) g Powdered Activated Carbon.The value of x is 10 to 40.Rotation mixing is assisted by blender Then the two is vortexed about 5 minutes.
Mixture is used to also test, wherein measuring their parents to volatile malodorous gas using HS-GC technology And power.
HS-GC technology:
The mixture of dimethyl disulphide, diethyl disulfide, isovaleric acid and valeric acid (each 2 μ L) is added to 8 μ L In ethyl alcohol, and entire mixture is transferred in 22mLGC headspace vial, is sealed immediately.This is used as reference standard.
By the correct mixture of same concentrations in 50mg adsorbent material of the present invention prepared in accordance with the present invention (and in range Except mixture) on adsorb in advance, and seal relevant bottle immediately.
All bottles are continued 10 minutes in 40 DEG C of incubations, and analyze these active matters using the GC with headspace sampler Headspace concentration.Use following head space condition:
Capillary column: CPWAX52CB (long 30mx0.25mmID)
Oven program: 40 DEG C -10 DEG C/min to 250 DEG C are kept for 10 minutes
Carrier gas: helium (1mL/ minutes)
Constant temperature: 40 DEG C of temperature；Incubative time 10 minutes
Needle temperature: 70 DEG C
Transmission line temperature: 110 DEG C
Embodiment 1: the effect comparison of composite material and mixture
One purpose of the experiment is determining composite material prepared in accordance with the present invention to sulfenyl volatile malodorous compounds The affinity of (passing through absorption).Another purpose be the simple mixtures by affinity Yu ingredient (LDH and PAC) affinity into Row compares.Volatile compound is dimethyl disulphide (CH3)2S and diethyl disulfide (C2H5)2S.They are that lavatory is disliked The main reason for smelly and halitosis.
HS GC technology (HS-GC) is used to measure the concentration of these volatile compounds, is by determining peak Lower area (peak area) discovery.
There is the material of more high-affinity (adsorptivity) will adsorb more volatile compounds malodorous compound.This meeting The headspace concentration of malodorous compound is reduced, this can be showed in the form of area under lower peak in turn.On the contrary, for disliking There is smelly compound the material compared with low-affinity (adsorptivity) will adsorb less volatile compound.This will increase stench chemical combination The headspace concentration of object, this can be showed in the form of area under higher peak in turn.
The result of embodiment 1 is shown in Table 1 in a tabular form.
Table 1
Data in table 1 clearly illustrate that composite material is substantially better than its corresponding mixture.
The adsorption capacity of embodiment 2:LDH-PAC composite material and LDH-GAC composite material
In this embodiment, by the adsorption capacity of LDH-PAC prepared in accordance with the present invention (Powdered Activated Carbon) composite material It is compared with the comparative composite made of LDH-GAC (granular activated carbon).
It is replaced during the composite material of LDH and GAC under the method title in embodiment part by describing with GAC It is prepared by PAC.
The process of embodiment 1 (HS-GC) is followed to determine and compare the adsorptivity of two kinds of composite materials.
The result of embodiment 2 is shown in a tabular form in table 2.
Table 2
Data in table 2 clearly illustrate, composite material made according to the present invention be substantially better than comprising GAC (supplier: Active Carbon Ltd,India；500 μm to 1000 μm of partial size) and LDH composite material.
Influence of embodiment 3:LDH and the PAC concentration to porosity
In this embodiment, using the various composite materials in the previously described method preparation scope of the invention.
Composite material contains different amounts of LDH and PAC.The porosity of all composite materials passes through mercury porosity analyzer It (is manufactured by U.S. MicromeriticsIV it) measures.
Data are listed in Table 3 below in a tabular form.
Table 3
Porosity is the measurement for the degree that substance adsorbs another substance.Porosity shows to can be used for adsorbing other objects more greatly The Kong Yue of matter is more.In other words, it means that the material with more macroporosity is more likely to than the material with more low porosity As better adsorbent.
It is in table 3 statistics indicate that composite A and the porosity of B are high.

Claims (8)

1. compound adsorbent is [M it includes general formula2+ 1-xM3+ x(OH)2]q+(Xn-)q/n·yH2The layered double-hydroxide (LDH) of O Nano particle and Powdered Activated Carbon (PAC), wherein
M2+=Ca2+、Mg2+、Mn2+、Fe2+、Co2+、Ni2+、Cu2+Or Zn2+；
M3+=Al3+Or Fe3+；
X=[M3+]/[M3++M2+]；
Q=x
N=1 to 4；And
Moisture subnumber present on y=LDH；
X=is selected from halide, sulfate, nitrate, the anion of carbonate or the anion part from organic source；
Wherein, the composite material can be obtained by hydro-thermal method, the hydro-thermal method in order the following steps are included:
(a) by Powdered Activated Carbon and M2+Water soluble salt and M3+Water soluble salt contact and mixing；
(b) alkali is added into the dispersion of step (a)；
(c) by the way that the dispersion of step (b) is heated to 80-100 DEG C so that its aging；
(d) water phase and dispersed phase of dispersion are separated in any manner；And
(e) dispersed phase is washed with water to remove excessive alkali, obtains compound adsorbent, wherein layered double hydroxides The amount of the nano particle of object (LDH) is 10-30 weight %, and wherein, and the partial size of the Powdered Activated Carbon is 50 μm to 500 μ m。
2. compound as described in claim 1, wherein the partial size of the Powdered Activated Carbon is 50 μm to 300 μm.
3. such as the described in any item compounds of claim 1 to 2, wherein the amount of the Powdered Activated Carbon is 70-90 weight %.
4. compound as described in any one of claims 1 to 3, wherein the surface area of the compound is 750-1000m2/g。
5. such as the described in any item compounds of Claims 1-4, wherein M3+With M2+Molar ratio be 1:2 to 1:4.
6. compound as claimed in claim 5, wherein the ratio is 1:3.
7. such as compound as claimed in any one of claims 1 to 6, wherein M2+For Mg2+、Cu2+Or Zn2+。
8. being used to prepare the hydro-thermal method of compound adsorbent, the compound adsorbent includes that general formula is [M2+ 1-xM3+ x(OH)2]q+ (Xn-)q/n·yH2The nano particle and Powdered Activated Carbon (PAC) of the layered double-hydroxide (LDH) of O, wherein
M2+=Ca2+、Mg2+、Mn2+、Fe2+、Co2+、Ni2+、Cu2+Or Zn2+；
M3+=Al3+Or Fe3+；
X=[M3+]/[M3++M2+]；
Q=x
N=1 to 4；And
Moisture subnumber present on y=LDH；
X=is selected from halide, sulfate, nitrate, the anion of carbonate or the anion part from organic source；
The method in order the following steps are included:
(a) by Powdered Activated Carbon and M2+Water soluble salt and M3+Water soluble salt contact and mixing；
(b) alkali is added into the dispersion of step (a)；
(c) by the way that the dispersion of step (b) is heated to 80-100 DEG C so that its aging；
(d) water phase and dispersed phase of dispersion are separated in any manner；And
(e) dispersed phase is washed with water to remove excessive alkali, obtains compound adsorbent, wherein layered double-hydroxide (LDH) amount of nano particle is 10-30 weight %, and wherein, and the partial size of the Powdered Activated Carbon is 50 μm to 500 μm.
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