CN109529789A - Absorbent particles and preparation method thereof for removing heavy metal - Google Patents
Absorbent particles and preparation method thereof for removing heavy metal Download PDFInfo
- Publication number
- CN109529789A CN109529789A CN201710866948.9A CN201710866948A CN109529789A CN 109529789 A CN109529789 A CN 109529789A CN 201710866948 A CN201710866948 A CN 201710866948A CN 109529789 A CN109529789 A CN 109529789A
- Authority
- CN
- China
- Prior art keywords
- absorbent particles
- water
- hydraulic binder
- composition
- metal
- 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.)
- Pending
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- 239000002245 particle Substances 0.000 title claims abstract description 114
- 239000002250 absorbent Substances 0.000 title claims abstract description 102
- 230000002745 absorbent Effects 0.000 title claims abstract description 102
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title description 4
- 239000000463 material Substances 0.000 claims abstract description 181
- 238000001914 filtration Methods 0.000 claims abstract description 59
- 239000011230 binding agent Substances 0.000 claims abstract description 55
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 55
- 239000000203 mixture Substances 0.000 claims abstract description 32
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 31
- 239000011572 manganese Substances 0.000 claims abstract description 31
- 229910021518 metal oxyhydroxide Inorganic materials 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 24
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 20
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 20
- 230000003647 oxidation Effects 0.000 claims abstract description 19
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 19
- 239000003463 adsorbent Substances 0.000 claims abstract description 14
- -1 poly(ethylene glycol) Polymers 0.000 claims description 26
- 229920001223 polyethylene glycol Polymers 0.000 claims description 24
- 239000011148 porous material Substances 0.000 claims description 21
- 239000004568 cement Substances 0.000 claims description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 13
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
- 239000002562 thickening agent Substances 0.000 claims description 11
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 10
- 229910002588 FeOOH Inorganic materials 0.000 claims description 10
- 239000004576 sand Substances 0.000 claims description 7
- 150000002894 organic compounds Chemical class 0.000 claims description 6
- 239000004408 titanium dioxide Substances 0.000 claims description 6
- 239000011398 Portland cement Substances 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 5
- 239000004411 aluminium Substances 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 239000001506 calcium phosphate Substances 0.000 claims description 5
- 229910021653 sulphate ion Inorganic materials 0.000 claims description 5
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims description 5
- 229940078499 tricalcium phosphate Drugs 0.000 claims description 5
- 229910000391 tricalcium phosphate Inorganic materials 0.000 claims description 5
- 235000019731 tricalcium phosphate Nutrition 0.000 claims description 5
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims description 3
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 2
- 229910052791 calcium Inorganic materials 0.000 claims 2
- 239000011575 calcium Substances 0.000 claims 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 abstract description 14
- 239000000843 powder Substances 0.000 description 29
- 239000000853 adhesive Substances 0.000 description 18
- 230000001070 adhesive effect Effects 0.000 description 18
- 229910052785 arsenic Inorganic materials 0.000 description 13
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 13
- 239000004927 clay Substances 0.000 description 13
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 6
- 238000005469 granulation Methods 0.000 description 6
- 230000003179 granulation Effects 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000005245 sintering Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229910021536 Zeolite Inorganic materials 0.000 description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 239000012085 test solution Substances 0.000 description 4
- 239000010457 zeolite Substances 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 3
- 238000005453 pelletization Methods 0.000 description 3
- 235000019738 Limestone Nutrition 0.000 description 2
- DMGNFLJBACZMRM-UHFFFAOYSA-N O[P] Chemical compound O[P] DMGNFLJBACZMRM-UHFFFAOYSA-N 0.000 description 2
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000006028 limestone Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 150000002927 oxygen compounds Chemical class 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002594 sorbent Substances 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- MTJGVAJYTOXFJH-UHFFFAOYSA-N 3-aminonaphthalene-1,5-disulfonic acid Chemical compound C1=CC=C(S(O)(=O)=O)C2=CC(N)=CC(S(O)(=O)=O)=C21 MTJGVAJYTOXFJH-UHFFFAOYSA-N 0.000 description 1
- HKDXPUPTIQCIPH-UHFFFAOYSA-L [O--].[O--].[O--].O[Ti+3].O[Ti+3] Chemical compound [O--].[O--].[O--].O[Ti+3].O[Ti+3] HKDXPUPTIQCIPH-UHFFFAOYSA-L 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005842 biochemical reaction Methods 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 239000002384 drinking water standard Substances 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 238000000918 plasma mass spectrometry Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000011885 synergistic combination Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
Classifications
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- B01J20/16—Alumino-silicates
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00793—Uses not provided for elsewhere in C04B2111/00 as filters or diaphragms
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Abstract
Combine adsorbent particles object for removing heavy metal from water includes metal oxyhydroxides material, metal oxide materials, oxidation manganese material and hydraulic binder.Absorbent particles may include the residue of organic pore-forming agents.The method for preparing multiple absorbent particles includes by the mixture pelleting of filtering material, hydraulic binder and water, 18 DEG C to 30 DEG C at a temperature of the multiple absorbent particles are kept being glued the period in a sealed container, and the multiple absorbent particles are washed in additional water.Filtering material includes metal oxyhydroxides material, metal oxide materials and oxidation manganese material.The method may include before by mixture pelleting, water-soluble organic pore-forming agents are dissolved in water.
Description
Technical field
The present invention relates to the adsorbents for Water warfare.More particularly, the present invention relate to heavy metal is removed from water
Adsorbent and be used to prepare from water remove heavy metal adsorbent method.
Background technique
There may be the heavy metals of harmful concentration, such as arsenic (As), lead (Pb), cadmium (Cd) and mercury in some drinking water
(Hg).The source of heavy metal can be naturally occurring or as caused by industrial pollution.Many technologies, including reverse osmosis can be passed through
Thoroughly or it is distilled off heavy metal.However, these technologies may be expensive, because they can be energy and resource-intensive.
The less expensive method for removing heavy metal can be by containing the granulated adsorbent designed for removing heavy metal
The cylinder of agent carried out drainage.However, such granulated sorbent cannot efficiently remove heavy metal, lead to bigger and more expensive filter
Cylinder.
Summary of the invention
Combine adsorbent particles object for removing heavy metal from water includes metal oxyhydroxides material, metal oxidation
Object material, oxidation manganese material and hydraulic binder.Absorbent particles may include organic pore-forming agents.Prepare multiple adsorbents
The method of grain includes mixing filtering material and hydraulic binder, by the mixing of filtering material and hydraulic binder
Object is combined with water to form thickener, and thickener is granulated to form multiple absorbent particles, additional water is applied to multiple absorption
The respective surface of agent particle, 18 DEG C to 30 DEG C at a temperature of in a sealed container by multiple absorbent particles keep be glued the time
Section simultaneously washs multiple absorbent particles in additional water.Filtering material includes metal oxyhydroxides material, metal oxide
Material and oxidation manganese material.This method may include combining by the mixture of filtering material and hydraulic binder with water with shape
Pore creating material is dissolved in water at before thickener.Pore creating material includes water-soluble or water miscibility organic compound.
Various embodiments are related to the combine adsorbent particles object for removing heavy metal from water.Multiple absorbent particles
Respectively contain metal oxyhydroxides material, metal oxide materials, oxidation manganese material and hydraulic binder.In some implementations
In scheme, hydraulic binder includes following at least one: Portland cement, aluminous cement, sulphate aluminium cement, hydroxyl phosphorus
Lime stone, tricalcium phosphate and fluoroaluminate cement.In some embodiments, hydraulic binder is 5 wt% to 20 of composition
wt%.In some embodiments, hydraulic binder is 10 wt% to 12 wt% of composition.In some embodiments, more
A absorbent particles respectively also include molecular screen material.In some embodiments, metal oxyhydroxides material and metal oxygen
Compound material and oxidation the ratio between manganese material and molecular screen material are 0.5-2:0.5-2:0.5-2:0.01-1.In some embodiments
In, multiple absorbent particles respectively also include the residue of pore creating material, and pore creating material includes water-soluble or water miscibility organic compound
Object.In some specific embodiments, pore creating material includes following at least one: poly(ethylene glycol), glycerol, ethylene glycol, dimethyl
Formamide and dimethyl sulfoxide.In some specific embodiments, it is 100 grams/mol to 4000 that pore creating material, which includes weight average molecular weight,
Gram/mol poly(ethylene glycol).In some embodiments, metal oxyhydroxides material includes FeOOH, metal oxygen
Compound material includes titanium dioxide, and aoxidizing manganese material includes manganese sand.
Various embodiments are related to the method for preparing multiple absorbent particles.The method includes by filtering material and hydraulic
Property adhesive mixes, and combines the mixture of filtering material and hydraulic binder to form thickener with water, by thickener
It is granulated to form multiple absorbent particles, additional water is applied to the respective surface of multiple absorbent particles, at 18 DEG C to 30
In a sealed container multiple absorbent particles are kept being glued the period at a temperature of DEG C and washs multiple suctions in additional water
Attached dose of particle.Filtering material includes metal oxyhydroxides material, metal oxide materials and oxidation manganese material.In some implementations
In scheme, hydraulic binder includes following at least one: Portland cement, aluminous cement, sulphate aluminium cement, hydroxyl phosphorus
Lime stone, tricalcium phosphate and fluoroaluminate cement.In some embodiments, hydraulic binder is that filtering material and the hydraulicity are viscous
5 wt% to 20 wt% of mixture total weight.In some specific embodiments, hydraulic binder is filtering material and the hydraulicity
10 wt% to 12 wt% of adhesive gross weight.In some embodiments, metal oxyhydroxides material includes hydroxyl oxidation
Iron, metal oxide materials include titanium dioxide, and aoxidizing manganese material includes manganese sand.In some embodiments, filtering material
It also include molecular screen material.In some specific embodiments, metal oxyhydroxides material and metal oxide materials and oxygen
Changing the ratio between manganese material and molecular screen material is 0.5-2:0.5-2:0.5-2:0.01-1.In some embodiments, this method is also
Including combining the mixture of filtering material and hydraulic binder with water pore creating material is dissolved in water before forming thickener
In, pore creating material includes water-soluble or water miscibility organic compound.In some specific embodiments, pore creating material include with down toward
Few one kind: poly(ethylene glycol), glycerol, ethylene glycol, dimethylformamide and dimethyl sulfoxide.In some specific embodiments, it makes
Hole agent includes the poly(ethylene glycol) that weight average molecular weight is 100 grams/mol to 4000 grams/mol.
It being described below, above and other feature of the invention and obtaining with reference to embodiment of the present invention in conjunction with the accompanying drawings
Their mode will become more apparent and present invention itself is best understood from.
Detailed description of the invention
Fig. 1 is the sample for the 4th comprising the clay adhesive group absorbent particles for illustrating and needing high temperature sintering
Crushing strength is compared, from according to the crushing strength of the sample of each groups of three groups of absorbent particles of the embodiment of the disclosure
Figure.
Fig. 2 is each group for the other two groups of absorbent particles comprising clay adhesive for illustrating and needing high temperature sintering
The specific surface area of sample compare, from the ratio according to the sample of each groups of two groups of absorbent particles of the embodiment of the disclosure
The figure of surface area (Brunauer-Emmett-Teller surface area).
Fig. 3 is the figure for illustrating the arsenic removal efficiency of the absorbent particles of the embodiment according to the disclosure.
Detailed description
For adsorbing the absorbent particles of heavy metal from water usually by the filtering material that is kept together with clay adhesive
Combination is made.Filtering material powder can be turned into fine powder, be mixed with adhesive, be then shaped to its size and be used for
Such as the absorbent particles of household filter cylinder.In terms of removing at least some heavy metals, the synergistic combination of adjacent filtering material can
To lead to the efficiency greater than 90%.Filtering material may include metal oxyhydroxides, such as FeOOH (FeOOH),
Absorption heavy metal, such as arsenic aspect are highly effective.
Adhesive keeps together filtering material to provide the adsorbent of the crushing strength at least 7 newton (N)
Grain, to be able to bear the strict demand of relevant to filter cylinder is manufactured and used manufacture and processing.It is high-caliber in this way in order to develop
Crushing strength, it is necessary to up to 400 DEG C to 800 DEG C at a temperature of be sintered or calcining use clay adhesive absorbent particles.
However, FeOOH thermally labile and according to its thermogravimetric analysis (TGA) curve, by tend to higher than 150 DEG C at a temperature of convert
For iron oxide (Fe2O3).The removal efficiency of filtering material can be reduced to down to 60%, because of Fe by the conversion2O3In an absorption huge sum of money
It is effective unlike FeOOH to belong to aspect.
Hydraulic binder is used according to the absorbent particles of the embodiment of the disclosure.Hydraulic binder is sent out with water
Material of the biochemical reaction to solidify and harden.Hydraulic binder can be in room temperature or close to being at room temperature glued filtering material
Or it is bonded together.Hydraulic binder does not need high temperature so that absorbent particles are assigned with required intensity.It is glued with comprising clay
The absorbent particles (it is necessarily exposed to high temperature) of mixture are compared, and the absorbent particles comprising hydraulic binder can be shown
Higher removal efficiency.It is not intended to be bound by any theory, it is believed that since the absorbent particles comprising hydraulic binder are not sudden and violent
It is exposed to high temperature, retains more metal oxyhydroxides for the filtering heavy metal from water.In some embodiments, by making
It is further increased heavy metal to be improved the specific surface area of absorbent particles with water-soluble or water miscibility organic pore-forming agents and removed
Efficiency.Such absorbent particles can further include the residue of organic pore creating material.
The embodiment of the disclosure includes the method for preparing absorbent particles comprising is applied to water and glues comprising the hydraulicity
Absorbent particles of mixture and in room temperature or close at room temperature being kept in a sealed container to allow adhesive by filter material
Expect the period being glued together.The method forms the absorbent particles with enough crushing strengths to burn without the use of high temperature
Knot.In some embodiments, by the way that water-soluble or water miscibility organic pore-forming agents are added to absorbent particles come further
Improve heavy metal removal efficiency.Pore creating material exists during the granulation and splicing of absorbent particles, then after splicing, big portion
Divide and be rinsed, leaves the open-celled structure by most each absorbent particles, improve the specific surface area of absorbent particles.
In some embodiments, it then can will be mixed by mixing filtering material and hydraulic binder
Conjunction object is combined with water forms absorbent particles to form thickener.Thickener can be granulated to form absorbent particles.For making
Some technologies of grain include extrusion granulation, centrifugal granulating, melt pelletization, mist projection granulating and extruding pelletization as known in the art.
Filtering material may include metal oxyhydroxides material, metal oxide materials and oxidation manganese material.Metal hydroxyl
Base oxide material may include such as FeOOH (FeO (OH)) or hydroxyl titanium oxide (TiO (OH)).Metal oxide material
Material may include such as titanium dioxide (TiO2), ferrous oxide (FeO) or iron oxide (Fe2O3).Manganese oxide (MnO) material can be with
It is the form of such as manganese sand material material.In some embodiments, filtering material powder can further include molecular screen material, example
Such as activated alumina or zeolite, such as zeolite 13X.
In some embodiments, metal oxyhydroxides material and metal oxide materials and oxidation manganese material and molecule
The weight ratio for sieving material can be 0.5-2:0.5-2:0.5-2:0.01-1.In some embodiments, metal oxyhydroxides
The weight ratio of material and metal oxide materials and oxidation manganese material and molecular screen material can be 1 to 1 to 1 to 0.6, or indicate
For 1:1:1:0.6.
In some embodiments, the weight relative to the metal oxyhydroxides material of the total weight of filtering material powder
Percentage can be down to 2 wt%, 5 wt% or 10 wt%, or up to 30 wt%, 60 wt% or 90 wt% or above-mentioned weight percent
Any weight percent between any two of ratio.For example, in some embodiments, relative to the total of filtering material powder
The weight percent of the metal oxyhydroxides material of weight can be 2 wt% to 90 wt%, 5 wt% to 60 wt% or 10 wt%
To 30 wt%.
In some embodiments, the weight percent relative to the metal oxide materials of the total weight of filtering material powder
Than can be down to 2 wt%, 5 wt% or 10 wt%, or up to 30 wt%, 60 wt% or 90 wt% or above-mentioned weight percent
Any weight percent between any two.For example, in some embodiments, the total weight relative to filtering material powder
The weight percent of metal oxide materials can be 2 wt% to 90 wt%, 5 wt% to 60 wt% or 10 wt% to 30
wt%。
In some embodiments, the weight percent relative to the oxidation manganese material of the total weight of filtering material powder can
With down to 2 wt%, 5 wt% or 10 wt%, or up to 30 wt%, 60 wt% or 90 wt% or above-mentioned weight percent is any
Any weight percent between two.For example, in some embodiments, the oxygen of the total weight relative to filtering material powder
The weight percent for changing manganese material can be 2 wt% to 90 wt%, 5 wt% to 60 wt% or 10 wt% to 30 wt%.
In some embodiments, the weight percent relative to the molecular screen material of the total weight of filtering material powder can
With down to 0.5 wt%, 2 wt% or 5 wt%, or up to 10 wt%, 20 wt% or 30 wt% or above-mentioned weight percent are appointed
Any weight percent between what two.For example, in some embodiments, total weight relative to filtering material powder
The weight percent of molecular screen material can be 0.5 wt% to 30 wt%, 2 wt% to 20 wt% or 5 wt% to 10 wt%.
It can be by metal oxyhydroxides material, metal oxide materials, oxidation manganese material and the respective powder of molecular screen material
Endization is to form filtering material.Filtering material can be with as low as 0.05 micron (μm), 0.1 μm, 0.2 μm, 0.3 μm,
0.5 μm, 1 μm or 2 μm, or greatly to 3 μm, 5 μm, 10 μm, 20 μm, 30 μm, 50 μm or 100 μm or any two
The fine powder form of intermediate value powder size between above-mentioned value.For example, in some embodiments, intermediate value powder size can be
0.05 μm to 100 μm, 0.05 μm to 2 μm, 0.3 μm to 30 μm, 1 μm to 50 μm, 3 μm to 50 μm or 10 μm extremely
20 µm.In some embodiments, intermediate value powder size can be about 10 μm.As known in the art, intermediate value powder size
It can be for example, by dynamic light scattering system measurement.It in some embodiments, can be by metal oxyhydroxides material, metal
The respective individually powdered of oxide material, oxidation manganese material and molecular screen material, is then combined to form filtering material.One
It, can be by metal oxyhydroxides material, metal oxide materials, oxidation manganese material and molecular sieve material in a little other embodiments
Material combination, then together powdered to form filtering material.
Hydraulic binder may include following at least one: Portland cement, aluminous cement, sulphate aluminium cement,
Hydroxyapatite, tricalcium phosphate and fluoroaluminate cement.
After the pelletizing, additional water can be applied to the surface of each absorbent particles, it then can be in a reservoir by profit
The period is glued in wet absorbent particles sealing.In some embodiments, during being glued the period, absorbent particles can be with
In room temperature or close at room temperature.As defined herein, in room temperature or close to being 18 DEG C to 30 DEG C at room temperature.In some embodiments
In, the temperature being glued during the period can be down to 18 DEG C, 19 DEG C, 20 DEG C, 21 DEG C, 22 DEG C or 23 DEG C, or up to 25 DEG C, 26
DEG C, 27 DEG C, 28 DEG C, 29 DEG C or any temperature between 30 DEG C or the above-mentioned temperature of any two.For example, in some embodiments
In, the temperature during being glued the period can be 18 DEG C to 30 DEG C, 19 DEG C to 29 DEG C, 20 DEG C to 28 DEG C, 21 DEG C to 27 DEG C, 22 DEG C
To 26 DEG C or 23 DEG C to 25 DEG C.
During being glued the period, chemical reaction occurs for water and hydraulic binder to form inorganic hydrate, incited somebody to action
Filter material material is bonded together, and forms the absorbent particles of hardening.Absorbent particles form enough crushing strengths during it
Being glued the period may be as little to 3 days, 5 days, 7 days, 9 days, 11 days or 13 days, or long to 17 days, 19 days, 21 days, 23 days or 25 days
Or any splicing period between any two above-mentioned splicing period.For example, in some embodiments, being glued the period
It can be 3 days to 25 days, 7 days to 23 days, 9 days to 21 days, 11 days to 19 days, 13 days to 17 days, 5 days to 9 days, 5 days to 11 days
Or 7 days to 17 days.After being glued the period, absorbent particles can be removed from sealing container.In some embodiments, exist
Additional water washing absorbent particles can be used later by being glued the period.
Fig. 1 is the sample for the 4th comprising the clay adhesive group absorbent particles for illustrating and needing high temperature sintering
Crushing strength is compared, from according to the crushing strength of the sample of each groups of three groups of absorbent particles of the embodiment of the disclosure
Figure.All four groups of absorbent particles include identical filtering material as described above.As described above according to the embodiment party of the disclosure
Three groups of absorbent particles of case preparation respectively contain aluminous cement as hydraulic binder.For two groups in three groups, phase
Weight percent for the hydraulic binder that filtering material and hydraulic binder amount to is 16.7 wt%.For in three groups
Third group, the weight percent of the hydraulic binder amounted to relative to filtering material and hydraulic binder is 11.1
wt%.Three groups of splicing period is 11 days to 25 days at room temperature.4th group of absorbent particles include filtering material and concave convex rod
The Concave-convex clay rod adhesive of 11 wt% of stone clay adhesive is simultaneously sintered at 500 DEG C.Absorbent particles be it is spherical and
Diameter is about 2 millimeters.
Test the crushing strength of 20 absorbent particles of each group in four groups.Using from Dalian Panghui
The granule strength tester of Keji, Ltd. measure crushing strength and measure arithmetic mean of instantaneous value to each group.As a result shown in Figure 1.
As shown in Figure 1, the absorbent particles comprising hydraulic binder according to the embodiment of the disclosure are shown than comprising clay
The significantly bigger crushing strength of the absorbent particles of adhesive.
Therefore, in some embodiments, the hydraulicity relative to the total weight of filtering material and hydraulic binder is viscous
The weight percent of mixture can down to 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt% or 10 wt. %, or up to 12 wt%,
13 wt%, 14 wt%, 16 wt%, 18 wt% or 20 wt%, or between the above-mentioned weight percent of any two.For example, one
In a little embodiments, the weight percent of the hydraulic binder of the total weight relative to filtering material and hydraulic binder can
Think 5 wt% to 20 wt%, 6 wt% to 18 wt%, 7 wt% to 16 wt%, 8 wt% to 14 wt%, 9 wt% to 13 wt% or 10
Wt% to 12 wt%.
In some embodiments, absorbent particles can further include organic pore creating material (PFA).PFA is water-soluble
Or water miscibility organic compound.In some embodiments, PFA may include following at least one: poly(ethylene glycol), sweet
Oil, ethylene glycol, dimethylformamide and dimethyl sulfoxide.In some embodiments, it is 100 that PFA, which may include weight average molecular weight,
Gram/mol to 4000 grams/mol of poly(ethylene glycol) (PEG).In some embodiments, PFA may include weight average molecular weight
For 100 grams/mol to 800 grams/mol of compatibility poly(ethylene glycol) (PEG).For example, in some embodiments, PFA can be with
The PEG-400 for being about 400 grams/mol comprising average molecular weight.PEG-400 is liquid at room temperature and miscible with water.?
In other embodiments, PFA may include PEG-2000.PEG-2000 is solid at room temperature and water-soluble.
In some embodiments, the concentration of PFA in water can be down to 5 wt%, 8 wt%, 11 wt%, 14 wt%, 17
Wt. % or 20 wt%, or up to 26 wt%, 32 wt%, 38 wt%, 44 wt% or 50 wt% or the above-mentioned concentration of any two it
Between any concentration.For example, in some embodiments, the concentration of PFA in water can be for 5 wt% to 50 wt%, 8 wt% extremely
44 wt%, 11 wt% are to 38 wt%, 14 wt% to 32 wt%, 17 wt% to 26 wt% or 20 wt% to 26 wt%.
As set forth above, it is possible to before combining water with the mixture of filtering material and hydraulic binder, by PFA and water
Combination.Therefore, there are PFA during the granulation of absorbent particles and splicing.After being glued the period, suction can be thoroughly washed
Attached dose of particle rinses out most of PFA and leaves the open-celled structure by most each absorbent particles.Open-celled structure is available
In the specific surface area for improving absorbent particles.In some embodiments, and not all PFA is rinsed, therefore, PFA
Residue will be left in absorbent particles.
Fig. 2 is each group for the other two groups of absorbent particles comprising clay adhesive for illustrating and needing high temperature sintering
The specific surface area of sample compare, from the ratio according to the sample of each groups of two groups of absorbent particles of the embodiment of the disclosure
The figure of surface area (Brunauer-Emmett-Teller surface area).First group of absorbent particles include clay adhesive and
It is sintered at 500 DEG C.Second group of absorbent particles also includes clay adhesive and further includes inorganic PFA.Second group at 500 DEG C
Acid elution is also carried out after lower sintering to be formed with the hole improved on sorbent particle surfaces.According to the embodiment of disclosure preparation the
Three groups of absorbent particles and it includes hydraulic binders.Also the 4th group of adsorbent is prepared according to the embodiment of the disclosure
Grain and in addition to hydraulic binder, also include organic pore-forming agents.In all four groups, adhesive is filtering material and bonding
11 wt% of the total weight of agent.
According to 9277 Determination of the Specific Surface Area of Solids by of ISO
The absorbent particles of Gas Adsorption measurement each group in four groups are to measure its specific surface area.As a result shown in Figure 2.Such as
Shown in Fig. 2, produced using the absorbent particles ratio of hydraulic binder using clay adhesive according to the embodiment of the disclosure
Those of there is significant bigger specific surface area.In addition, being had according to the embodiment of the disclosure using the absorbent particles of PFA
Highest specific surface area in four groups.It is not intended to be bound by any theory, it is believed that when compared with inorganic pore creating material, in granulation stage
Between, organic pore-forming agents can be more equally distributed in absorbent particles.Distribution of the PFA in absorbent particles more evenly can be with
More effective hole path is generated in absorbent particles after the washing being glued after the period.
Specific embodiment
Embodiment 1
By the 64g filter material that will include FeOOH, titanium dioxide that weight ratio is 1:1:1:0.6, manganese sand and zeolite 13X
Mix powder is expected to prepare absorbent particles.By the intermediate value powder size of filtering material mix powder to 10 μm with
Form filtering material powder.Centrifugal mixer at 3000 RPM (comes from FlacTek Inc., Landrum, South
150.1 FVZ-K of Speedmixer DAC of Carolina, U.S.) in by 8g aluminous cement (CA-70,70 wt%
Al2O3, 30 wt% CaO) hydraulic binder and filtering material powder be mixed together 1 minute.100g is had about 2000
Gram/mol the PFA of poly(ethylene glycol) (PEG-2000) form of average molecular weight be dissolved in 400g water to form 20 wt%
Solution.By the PEG-2000 spray solution of 20 wt% of the amount of 0.5g to 2g in filtering material powder and hydraulic binder
Centrifugal mixer on mixture, and at 3000 RPM (comes from FlacTek Inc., Landrum, South
150.1 FVZ-K of Speedmixer DAC of Carolina, U.S.) middle granulation 30 seconds.It repeats the PEG- of 20 wt%
2000 spray solutions 30 seconds processes are granulated on the mixture and in centrifugal mixer until added 10.8g 20 wt%
PEG-2000 solution to form spherical adsorbent paricles.Absorbent particles are placed in the vessel and are sprayed with the water of 2g to 5g.
Container is sealed.Absorbent particles stay 7 days in a sealed container splicing periods.
After being glued the period, absorbent particles are washed thoroughly with water to remove most of PFA in absorbent particles
Upper formation open-celled structure.Resulting absorbent particles diameter is about 0.4 mm to 0.8 mm, and contains the water of about 11.1 wt%
Hydraulic binder.The specific surface area of absorbent particles is measured as described above and is measured as 157 m2/g.Test absorption as described above
The crushing strength of agent particle.It was found that absorbent particles have the crushing strength of about 7.8 N.
The also efficiency of test absorbent particles removing arsenic.Absorbent particles sample with 310 milliliters of volumes is placed on 550
In milliliter filter cylinder.Make the test solution of the arsenic for containing about 100/1000000000ths parts (ppb) more than 1320 liters with 6 ls/h of speed
Rate passes through the filter cylinder.Absorbent particles remove about 90% arsenic.
Embodiment 2
By the 64g filter material that will include FeOOH, titanium dioxide that weight ratio is 1:1:1:0.6, manganese sand and zeolite 13X
Mix powder is expected to prepare absorbent particles.By the intermediate value powder size of filtering material mix powder to 10 μm with
Form filtering material powder.Centrifugal mixer at 3000 RPM (comes from FlacTek Inc., Landrum, South
150.1 FVZ-K of Speedmixer DAC of Carolina, U.S.) in by 8g aluminous cement (CA-70,70 wt%
Al2O3, 30 wt% CaO) hydraulic binder and filtering material powder be mixed together 1 minute.By 100g have about 600 grams/
Mole average molecular weight poly(ethylene glycol) (PEG-600) form PFA be dissolved in 400g water with formed 20 wt% it is molten
Liquid.By the PEG-600 spray solution of 20 wt% of the amount of 0.5g to 2g filtering material powder and hydraulic binder mixing
On object, and at 3000 RPM centrifugal mixer (come from FlacTek Inc., Landrum, South Carolina,
U.S. 150.1 FVZ-K of Speedmixer DAC) middle granulation 30 seconds.Repetition exists the PEG-600 spray solution of 20 wt%
30 seconds processes are granulated on mixture and in centrifugal mixer until 20 wt% of added 10.8g PEG-600 solution
To form spherical adsorbent paricles.Absorbent particles are placed in the vessel and are sprayed with the water of 2g to 5g.Container is sealed.Absorption
Agent particle stays 7 days in a sealed container splicing periods.
After being glued the period, absorbent particles are washed thoroughly with water to remove most of PFA in absorbent particles
Upper formation open-celled structure.Resulting absorbent particles diameter is about 0.4 mm to 0.8 mm, and contains the water of about 11.1 wt%
Hydraulic binder.The specific surface area of absorbent particles is measured as described above and is measured as 181 m2/g.Test absorption as described above
The crushing strength of agent particle.It was found that absorbent particles have the crushing strength of about 12.5 N.
The also efficiency of test absorbent particles removing arsenic.Absorbent particles sample with 300 milliliters of volumes is placed on 550
In milliliter filter cylinder.Make the test solution of the arsenic for containing about 100/1000000000ths parts (ppb) more than 1400 liters with 5 ls/h of speed
Rate passes through the filter cylinder.Pass through adsorbent by remaining arsenic in inductivity coupled plasma mass spectrometry measurement test solution to measure
The percentage for the arsenic that particle removes.As a result shown in Figure 3.Fig. 3 shows the outlet arsenic concentration in terms of ppb in left axle and in right axle
Upper display removal efficiency respectively changes with the volume of the test solution by filter cylinder.As shown in figure 3, absorbent particles are from water
The middle arsenic removed greater than 90%, and export arsenic concentration and keep below 10 ppb, meet World Health Organization's drinking water standard.
Although being associated with exemplary design describes the present invention, can further be repaired in spirit and scope of the present disclosure
Change the present invention.In addition, this application is intended to cover within the scope of of the art known or conventional practice with the disclosure
It is such to deviate from.
Claims (20)
1. the combine adsorbent particles object for removing heavy metal from water, multiple absorbent particles respectively contain:
Metal oxyhydroxides material；
Metal oxide materials；
Aoxidize manganese material；With
Hydraulic binder.
2. the composition of claim 1, wherein the hydraulic binder includes following at least one: Portland cement, aluminic acid
Calcium cement, sulphate aluminium cement, hydroxyapatite, tricalcium phosphate and fluoroaluminate cement.
3. the composition of claim 1, wherein the hydraulic binder is 5 wt% to 20 wt% of the composition.
4. the composition of claim 3, wherein the hydraulic binder is 10 wt% to 12 wt% of the composition.
5. the composition of claim 1, wherein the multiple absorbent particles respectively further include molecular screen material.
6. the composition of claim 5, wherein metal oxyhydroxides material and metal oxide materials and oxidation manganese material with
The ratio between molecular screen material is 0.5-2:0.5-2:0.5-2:0.01-1.
7. the composition of claim 1, wherein the multiple absorbent particles respectively further include the residue of pore creating material, institute
Stating pore creating material includes water-soluble or water miscibility organic compound.
8. the composition of claim 7, wherein the pore creating material includes following at least one: poly(ethylene glycol), glycerol, second two
Alcohol, dimethylformamide and dimethyl sulfoxide.
9. the composition of claim 8, wherein it is 100 grams/mol to 4000 grams/mol that the pore creating material, which includes weight average molecular weight,
Poly(ethylene glycol).
10. the composition of claim 1, wherein the metal oxyhydroxides material includes FeOOH, metal oxide
Material includes titanium dioxide, and aoxidizing manganese material includes manganese sand.
11. the method for preparing multiple absorbent particles, which comprises
Filtering material and hydraulic binder are mixed, the filtering material includes metal oxyhydroxides material, gold
Belong to oxide material and oxidation manganese material；
It combines the mixture of filtering material and hydraulic binder to form thickener with water；
Thickener is granulated to form multiple absorbent particles；
Additional water is applied to the respective surface of the multiple absorbent particles；
18 DEG C to 30 DEG C at a temperature of in a sealed container by the multiple absorbent particles keep be glued the period；With
The multiple absorbent particles are washed in additional water.
12. the method for claim 11, wherein the hydraulic binder includes following at least one: Portland cement, aluminic acid
Calcium cement, sulphate aluminium cement, hydroxyapatite, tricalcium phosphate and fluoroaluminate cement.
13. the method for claim 11, wherein the hydraulic binder is the total of the filtering material and hydraulic binder
5 wt% to 20 wt% of weight.
14. the method for claim 13, wherein the hydraulic binder is the total of the filtering material and hydraulic binder
10 wt% to 12 wt% of weight.
15. the method for claim 14, wherein the metal oxyhydroxides material includes FeOOH, metal oxide material
Material includes titanium dioxide, and aoxidizing manganese material includes manganese sand.
16. the method for claim 14, wherein the filtering material further includes molecular screen material.
17. the method for claim 16, wherein metal oxyhydroxides material and metal oxide materials and oxidation manganese material with
The ratio between molecular screen material is 0.5-2:0.5-2:0.5-2:0.01-1.
It further comprise by the mixture of filtering material and hydraulic binder and water group 18. the method for claim 11
Before closing to form thickener, pore creating material is dissolved in water, the pore creating material includes water-soluble or water miscibility organic compound.
19. the method for claim 18, wherein the pore creating material includes following at least one: poly(ethylene glycol), glycerol, second two
Alcohol, dimethylformamide and dimethyl sulfoxide.
20. the method for claim 19, wherein it is 100 grams/mol to 4000 grams/mol that the pore creating material, which includes weight average molecular weight,
Poly(ethylene glycol).
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| CN201710866948.9A CN109529789A (en) | 2017-09-22 | 2017-09-22 | Absorbent particles and preparation method thereof for removing heavy metal |
| PCT/US2018/051654 WO2019060358A1 (en) | 2017-09-22 | 2018-09-19 | Adsorbent granules for removal of heavy metals and method of making |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110314644A (en) * | 2019-07-24 | 2019-10-11 | 西安建筑科技大学 | A kind of sulphate aluminium cement-bentonite composite material and its preparation method and application for adsorbing heavy metal ion |
| CN110452703A (en) * | 2019-08-28 | 2019-11-15 | 孙毅 | One heavy metal species normal temperature cure agent and the method for using heavy metal in its curing heavy metal pollutant |
| CN111804269A (en) * | 2020-05-09 | 2020-10-23 | 南京云香纳米技术有限公司 | A filter for removing harmful gases |
| CN112107992A (en) * | 2019-06-21 | 2020-12-22 | 南京云香纳米技术有限公司 | Harmful gas removing medium and preparation method thereof |
| KR20230095211A (en) * | 2021-12-22 | 2023-06-29 | 한국광해광업공단 | Manufacturing method of bead-type arsenic adsorbent using iron hydroxide-based waste |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111921496A (en) * | 2020-07-10 | 2020-11-13 | 广东石油化工学院 | Composite adsorbent and preparation method and application thereof |
| CN115647002B (en) * | 2022-10-20 | 2025-07-22 | 湖北聚海环境科技有限公司 | Biomass phosphogypsum reclaimed material, solid waste cooperative reclaiming process and application thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997017307A2 (en) * | 1995-11-06 | 1997-05-15 | Aeci Limited | Method for preparing hardened granules from a particulate material |
| WO2001097965A1 (en) * | 2000-06-19 | 2001-12-27 | Bridgestone Corporation | Adsorbent, process for producing the same, and applications thereof |
| DE10210786A1 (en) * | 2002-03-12 | 2003-10-02 | Bayer Ag | Mixtures of adsorber materials |
| CN103649349B (en) * | 2011-05-10 | 2016-09-07 | 凯米罗总公司 | For the method removing pollutant from water-based system |
| CN102580701B (en) * | 2012-01-18 | 2014-12-24 | 西安蓝晓科技新材料股份有限公司 | Preparation method of arsenic removal resin |
-
2017
- 2017-09-22 CN CN201710866948.9A patent/CN109529789A/en active Pending
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112107992A (en) * | 2019-06-21 | 2020-12-22 | 南京云香纳米技术有限公司 | Harmful gas removing medium and preparation method thereof |
| CN110314644A (en) * | 2019-07-24 | 2019-10-11 | 西安建筑科技大学 | A kind of sulphate aluminium cement-bentonite composite material and its preparation method and application for adsorbing heavy metal ion |
| CN110452703A (en) * | 2019-08-28 | 2019-11-15 | 孙毅 | One heavy metal species normal temperature cure agent and the method for using heavy metal in its curing heavy metal pollutant |
| CN111804269A (en) * | 2020-05-09 | 2020-10-23 | 南京云香纳米技术有限公司 | A filter for removing harmful gases |
| KR20230095211A (en) * | 2021-12-22 | 2023-06-29 | 한국광해광업공단 | Manufacturing method of bead-type arsenic adsorbent using iron hydroxide-based waste |
| KR102653354B1 (en) | 2021-12-22 | 2024-03-29 | 한국광해광업공단 | Manufacturing method of bead-type arsenic adsorbent using iron hydroxide-based waste |
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| WO2019060358A1 (en) | 2019-03-28 |
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