CN109071349A - 用于纯化水的颗粒组合物和过滤器 - Google Patents
用于纯化水的颗粒组合物和过滤器 Download PDFInfo
- Publication number
- CN109071349A CN109071349A CN201780024232.2A CN201780024232A CN109071349A CN 109071349 A CN109071349 A CN 109071349A CN 201780024232 A CN201780024232 A CN 201780024232A CN 109071349 A CN109071349 A CN 109071349A
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- composition
- weight
- ldh
- particles
- cement
- Prior art date
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- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 60
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 45
- 239000008213 purified water Substances 0.000 title description 2
- 239000002245 particle Substances 0.000 claims abstract description 53
- 239000004568 cement Substances 0.000 claims abstract description 25
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 24
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- 239000000440 bentonite Substances 0.000 claims abstract description 7
- 229910000278 bentonite Inorganic materials 0.000 claims abstract description 7
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000010440 gypsum Substances 0.000 claims abstract description 7
- 229910052602 gypsum Inorganic materials 0.000 claims abstract description 7
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- 238000000354 decomposition reaction Methods 0.000 claims abstract description 6
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- 108010010803 Gelatin Proteins 0.000 claims abstract description 5
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- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 5
- 239000004115 Sodium Silicate Substances 0.000 claims abstract description 5
- 229920002125 Sokalan® Polymers 0.000 claims abstract description 5
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- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 5
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- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 12
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- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 7
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 claims description 6
- 239000010881 fly ash Substances 0.000 claims description 6
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 claims description 4
- 229940023476 agar Drugs 0.000 claims description 4
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- 239000007900 aqueous suspension Substances 0.000 claims description 4
- 239000010426 asphalt Substances 0.000 claims description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 4
- 239000000920 calcium hydroxide Substances 0.000 claims description 4
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 4
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- 229910052570 clay Inorganic materials 0.000 claims description 4
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- 229910020038 Mg6Al2 Inorganic materials 0.000 claims 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 abstract 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 abstract 1
- 235000011941 Tilia x europaea Nutrition 0.000 abstract 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 1
- 239000000428 dust Substances 0.000 abstract 1
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- 229910018084 Al-Fe Inorganic materials 0.000 description 5
- 229910018192 Al—Fe Inorganic materials 0.000 description 5
- 229910003023 Mg-Al Inorganic materials 0.000 description 5
- 239000008188 pellet Substances 0.000 description 5
- 150000001768 cations Chemical class 0.000 description 4
- 238000005469 granulation Methods 0.000 description 4
- 230000003179 granulation Effects 0.000 description 4
- 239000010797 grey water Substances 0.000 description 4
- -1 hydrotalcite compound Chemical class 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 3
- 229910052901 montmorillonite Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
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- 229910017767 Cu—Al Inorganic materials 0.000 description 2
- 229910007570 Zn-Al Inorganic materials 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 150000001339 alkali metal compounds Chemical class 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000000378 calcium silicate Substances 0.000 description 2
- 229910052918 calcium silicate Inorganic materials 0.000 description 2
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 101150026107 ldh1 gene Proteins 0.000 description 2
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- 238000002360 preparation method Methods 0.000 description 2
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- 239000005995 Aluminium silicate Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910017827 Cu—Fe Inorganic materials 0.000 description 1
- 229910019089 Mg-Fe Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229910052586 apatite Inorganic materials 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- 238000011001 backwashing Methods 0.000 description 1
- UREZNYTWGJKWBI-UHFFFAOYSA-M benzethonium chloride Chemical compound [Cl-].C1=CC(C(C)(C)CC(C)(C)C)=CC=C1OCCOCC[N+](C)(C)CC1=CC=CC=C1 UREZNYTWGJKWBI-UHFFFAOYSA-M 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
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- 238000009477 fluid bed granulation Methods 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 description 1
- 229910000271 hectorite Inorganic materials 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000007909 melt granulation Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
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- 235000005985 organic acids Nutrition 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[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 VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 1
- 230000002572 peristaltic effect Effects 0.000 description 1
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- 238000003825 pressing Methods 0.000 description 1
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- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- 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
- C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
- C04B20/0016—Granular materials, e.g. microballoons
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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
- B01J20/04—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
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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
- B01J20/28014—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 form
- B01J20/2803—Sorbents comprising a binder, e.g. for forming aggregated, agglomerated or granulated products
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3028—Granulating, agglomerating or aggregating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3042—Use of binding agents; addition of materials ameliorating the mechanical properties of the produced sorbent
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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
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- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
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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
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- C—CHEMISTRY; METALLURGY
- 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
- C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B18/02—Agglomerated materials, e.g. artificial aggregates
- C04B18/021—Agglomerated materials, e.g. artificial aggregates agglomerated by a mineral binder, e.g. cement
-
- C—CHEMISTRY; METALLURGY
- 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
- C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B18/02—Agglomerated materials, e.g. artificial aggregates
- C04B18/027—Lightweight materials
-
- 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
- C02F2101/301—Detergents, surfactants
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/002—Grey water, e.g. from clothes washers, showers or dishwashers
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Ceramic Engineering (AREA)
- Civil Engineering (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
- Water Treatment By Sorption (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
本发明公开了一种颗粒形式的组合物，其包含：(i)95至98重量％的分子式[M2+ 1‑xM3+ x(OH)2]q+(Xn‑)q/n·yH2O的层状双氢氧化物(LDH)；其中，M2+是Ca2+，Mg2+，Mn2+，Fe2+，Co2+，Ni2+，Cu2+或Zn2+中的至少一种；M3+是Al3+，Fe3+，Cr3+，Ga3+或V3+中的至少一种，X是层间阴离子，其是Cl‑，Br‑，NO3 ‑，CO3 2‑，SO4 2‑或SeO4 2‑中的至少一种；并且“x”是0.1至0.33的摩尔金属比；(ii)0.3至2重量％的无机粘合剂，其是水泥，白水泥，石膏，石灰石，白垩，硅酸铝，飞灰，膨润土，沥青，铝酸钙，粘土，熟石灰或硅酸钠中的至少一种；和，0.2至1.5重量％的分子量为1000至500,000道尔顿且分解温度≤400℃的有机粘合剂，其是聚乙烯醇，聚乙二醇，聚乙烯吡咯烷酮，聚丙烯酸，淀粉，纤维素，藻酸盐，琼脂，明胶或瓜尔胶中的至少一种。
Description
技术领域
本发明涉及用于纯化水的过滤器，所述水被表面活性剂污染，特别是涉及具有较长寿命的过滤器。
背景技术
灰水(也拼写为灰水)通常含有一定量的表面活性剂。通常使用由活性炭制成的过滤器来纯化这样的水。预期这样的过滤器应该具有长寿命并且它们具有长期功效。但是，这并不是在所有情况下的观察结果。通常的过滤器或者寿命很短，或者它们的功效达不到标准。有些过滤器倾向于很早就“突破(breakthrough)”。突破时间是经纯化的水中的污染物的浓度超过处理要求时的时间。有关突破时间的更多信息在网站https://iaspub.epa.gov/tdb/pages/treatment/treatmentOverview.do？treatmentProcessId＝2074826383中呈现。
层状双氢氧化物(缩写为LDH)代表一类矿物，其中一种是水滑石。
水滑石可用于纯化被砷污染的水。关于这样的用途见于例如Ind.Eng.Chem.Res.2005，第44卷，第6804至6815页。一些参考书，百科全书以及无机化学和水纯化方面的文章表明含有二价和三价阳离子的水滑石的改性变体(除了通常的那些之外)优于天然形式。
WO2009010376A1(Unilever)公开了一种用于纯化水的组合物，其具有作为层状双氢氧化物(LDH)的第一组分。
WO15193087A1(Unilever)公开了一种用于纯化水的组合物，所述水含有包括砷的重金属。在这种情况下，仅由LDH制成的颗粒用于水的纯化，但在测试时，颗粒化LDH与活性炭颗粒以及有机粘合剂组合使用以形成用于纯化水的结合过滤块。
US5846430B1(Crosfield Ltd)公开了LDH类材料用于纯化含染料水的用途。
US4642193B(Kyowa Kagaku Kogyo，1984)公开了通过使水与水滑石化合物的颗粒或其煅烧的形式接触来纯化核反应堆中使用的冷却水。通过使用粘合剂如聚乙烯醇，磷灰石，膨润土，水辉石，蒙脱石(montmorillonite)和蒙脱石(smectite)制备颗粒。将相当于水滑石的1至20重量％的量的粘合剂与其混合，并加入合适的量例如基于水滑石化合物的重量的10至约50％的水。将混合物捏合10至60分钟直至混合物变成粘稠的湿物质，然后将其模塑成各种形状。
US2011/0038775A1(Takahashi Shinji等)公开了一种用于分解和除去烃的多孔模塑催化剂。该催化剂由层状双氢氧化物(LDH)制成。示例性组合物具有约48重量％的LDH，40重量％的丙二醇，4重量％的无机粘合剂和4重量％的有机粘合剂。
et.al.Ind.Eng.Chem.Res.2015，第54卷，第1123-1130页公开了水滑石颗粒用于来自水溶液的有机酸的离子交换的用途。将85份水滑石与15份膨润土混合以得到均匀混合物。将水(61份)加入混合物中以形成糊状物，将其挤出并切成直径为1.3mm，长度为2-3mm的颗粒。将颗粒在马弗炉中煅烧。
MURAYAMA et.al.Resources Processing,2013，第60卷，第131-137页公开了使用造粒机制备LDH粒料。该粒料含有5％的聚乙烯醇(PVA)溶液作为粘合剂。将LDH加入旋转盘式造粒机中，并用LDH:PVA(溶液)重量比为100g:30g的溶液喷雾。粒料化的产物在343K的温度下干燥24小时。将干燥的粒料过筛以收集尺寸在0.85至1.40mm之间的粒料，将其用于测试。该粒料可用于从废水中除去阴离子物质As(V)，Se(IV)和Cr(VI)。
CN101049953(Beijing University of Chemical Technology)公开了由聚乙烯醇结合的LDH制成的颗粒作为催化剂。
WO15052036A1(Unilever)公开了一种用于纯化灰水(即，含有表面活性剂的水)的装置和方法，这通过连续通气，泡沫破碎和分离来实现。可以过滤经处理的水以回收淡水，其可以重新用于辅助应用。
WO15101768A1(Johnson Mathey PLC)公开了一种制备吸附剂的方法，该方法包括将颗粒硅酸钙水泥和颗粒碱金属化合物混合在一起，并用水处理该混合物以水合硅酸钙水泥的步骤，其中颗粒碱金属化合物包含氧化物，氢氧化物，碳酸盐或碳酸氢盐，并且在用水处理之前和/或之后使吸附剂成形。
WO06053402A1(Nubian Water Systems Pty Ltd)公开了一种水纯化方法，其中活性炭用于纯化灰水。
因此，已知LDH可以纯化污染的水，包括含有一定量表面活性剂的水。然而，由LDH制成的过滤器，包括现有技术中公开的结合过滤器，具有较短的寿命。在使用颗粒介质进行水纯化的背景下，介质的突破需要干预，例如更换或反洗。任何干预对于过滤器用户都是技术问题，并且每次干预都导致过滤器的一些性能损失。
发明内容
我们已经确定，由根据本发明的LDH颗粒制成的过滤器具有更长的寿命，并且它们花费更长时间达到其突破时间。
根据第一方面，公开了一种颗粒形式的组合物，其包含：
(i)95至96重量％的分子式[M2+ 1-xM3+ x(OH)2]q+(Xn-)q/n·yH2O的层状双氢氧化物(LDH)；
其中，
M2+是Ca2+，Mg2+，Mn2+，Fe2+，Co2+，Ni2+，Cu2+或Zn2+中的至少一种；
M3+是Al3+，Fe3+，Cr3+，Ga3+或V3+中的至少一种，
X是层间阴离子(interlayer anion)，其是Cl-，Br-，NO3 -，CO3 2-，SO4 2-或SeO4 2-中的至少一种；并且，
“x”是0.1至0.33的摩尔金属比；
(ii)0.3至2重量％的无机粘合剂，其是水泥，白水泥，石膏，石灰石，白垩，硅酸铝，飞灰(fly ash)，膨润土，沥青，铝酸钙，粘土，熟石灰或硅酸钠中的至少一种；和，
(iii)0.2至1.5重量％的分子量为1000至500,000道尔顿且分解温度≤400℃的有机粘合剂，其是聚乙烯醇，聚乙二醇，聚乙烯吡咯烷酮，聚丙烯酸，糖，淀粉，纤维素，藻酸盐，琼脂，明胶或瓜尔胶中的至少一种。
根据第二方面，公开了一种用于纯化水的过滤器，其包含第一方面的组合物。
根据第三方面，公开了第一方面的组合物用于纯化水的用途，所述水包含1至100ppm的表面活性剂。
根据第三方面，公开了制备根据第一方面的组合物的方法。
具体实施方式
除非另有说明，否则本文所有份均为重量份。
本发明提供一种颗粒形式的组合物。所述颗粒包含三种成分：
(i)如下所述的层状双氢氧化物；
(ii)如下所述的有机粘合剂；和，
(iii)如下所述的无机粘合剂
根据本发明的组合物是颗粒的，即，是颗粒形式，其可以通过本领域已知的任何方法制备。一些方法的详情包括在说明书中。
层状双氢氧化物(LDH)
层状双氢氧化物的分子式为[M2+ 1-xM3+ x(OH)2]q+(Xn-)q/n·yH2O；其中，M2+是Ca2+，Mg2 +，Mn2+，Fe2+，Co2+，Ni2+，Cu2+或Zn2+中的至少一种；M3+是Al3+，Fe3+，Cr3+，Ga3+或V3+中的至少一种，X是层间阴离子，其是Cl-，Br-，NO3 -，CO3 2-，SO4 2-或SeO4 2-中的至少一种；并且，“x”是0.1至0.33的摩尔金属比。
当LDH含有两种或三种阳离子时，优选组合如下：
Mg-Al，Cu-Al，Zn-Al，Zn-Fe，Cu-Fe，Mg-Fe，Mg-Al-Fe，Zn-Al-Fe，Cu-Al-Fe，Cu-Mg-Fe，Zn-Mg-Fe，Zn-Cu-Fe，Zn-Cu-Al，Zn-Mg-Al，Cu-Mg-Al，Zn-Cu-Al-Fe，Mg-Cu-Al-Fe或Mg-Zn-Al-Fe。
优选的层间阴离子是Cl-，Br-，NO3 -和CO3 2-。特别优选LDH包含至少一种选自Mg，Zn或Cu的二价阳离子和至少一种Fe或Al的三价阳离子。
因此，根据本发明，一些最优选的LDH是Mg6Al2CO3(OH)16·4(H2O)，Zn6Fe2(OH)16(CO3)·4H2O或Cu6Fe2(OH)16(CO3)·4H2O或Zn6AlFe(OH)16(CO3)·4H2O或Cu6AlFe(OH)16(CO3)·4H2O。
特别优选LDH是水滑石，其是Mg6Al2CO3(OH)16·4(H2O)。
无机粘合剂：
根据本发明的组合物的颗粒包含0.3至2重量％的无机粘合剂，其是水泥，白水泥，石膏，石灰石，白垩，硅酸铝，飞灰，膨润土，沥青，铝酸钙，粘土，熟石灰或硅酸钠中的至少一种。优选无机粘合剂是水泥，白水泥，石膏，石灰石，白垩，硅酸铝，飞灰中的至少一种。特别优选的无机粘合剂是水泥。或者，另一种特别优选的无机粘合剂是白水泥。
有机粘合剂：
根据本发明的组合物的颗粒包含0.2至1.5重量％的分子量为1000至500,000道尔顿且分解温度≤400℃的有机粘合剂，其是聚乙烯醇，聚乙二醇，聚乙烯吡咯烷酮，聚丙烯酸，淀粉，纤维素，海藻酸盐，琼脂，明胶或瓜尔胶中的至少一种。聚乙烯醇是优选的粘合剂。
进一步优选聚乙烯醇部分水解并且水解为70至80％。在聚乙烯醇的情况下，优选分子量为1000至500,000道尔顿，更优选5000至50000道尔顿，最优选8000至25000道尔顿。
特别优选的是，在根据本发明的颗粒形式的组合物中，LDH是水滑石，无机粘合剂是水泥，并且有机粘合剂是聚乙烯醇。
造粒
根据本发明的组合物是颗粒的，即，是颗粒形式。通过造粒制备颗粒。
可以使用任何适当的造粒方法将成分造粒。例如，造粒可以通过干法压制或湿法造粒方法进行，例如挤出，翻滚，压制，流化，流化床造粒，熔融造粒，喷雾造粒，或粒料化。可适当选择颗粒的形状和大小。颗粒可以是任何期望的形状，例如球形，实心圆柱形，中空圆柱形或金字塔形，并且它们的尺寸范围可以如下文所述。可以使用任何合适的压制机，例如压片机，辊压机，chilsonator，滚圆机(spheronizer)或其组合，而湿法造粒技术包括湿剪切机如快速混合造粒机，犁剪切混合机，行星式混合机或其组合的非详尽列表。
本发明提供了一种颗粒组合物，其可以原样用于水纯化，而不必使颗粒进行制备总是含有另外的有机粘合剂的结合嵌段的进一步加工。
煅烧：
颗粒可以以煅烧以及未煅烧的形式使用。然而，优选颗粒是煅烧的形式。通过将相应的未煅烧的颗粒加热至≤400℃可获得该形式。
优选地，煅烧颗粒的孔径为5nm至200nm，更优选20至150nm，最优选25至100nm。优选地，煅烧颗粒的堆积密度为0.2g/ml至0.9g/ml，更优选0.25至0.8g/ml，最优选0.4至0.6g/ml。优选地，煅烧颗粒的孔隙率百分比为90％至60％，更优选为85％至75％，最优选为80％至70％。优选地，煅烧颗粒的表面积为10m2/g至250m2/g，更优选50至250m2/g，最优选100至250m2/g。
进一步优选颗粒的粒度为500至1000μm。
用于水纯化的过滤器和组合物的用途：
根据第二方面，公开了一种用于纯化水的过滤器，其包含第一方面的组合物。该过滤器可用于纯化被表面活性剂污染的水。组合物的颗粒可以是结合的(用粘合剂如聚乙烯)，或者它们可以是未结合的。优选颗粒是未结合的。
优选过滤器是填充床过滤器，更优选路径长度为5至7cm。
根据另一方面，公开了如第一方面所述的组合物用于纯化包含1至100ppm表面活性剂的水的用途。
优选10克的根据本发明的组合物的突破时间在30至80ml/分钟的流速下为至少10分钟。该流速是待纯化的水通过过滤器的流速。
进一步优选在用于填充床过滤器之前，将颗粒在其TDS不超过50ppm的水中浸泡24至48小时。
将在非限制性实施例的帮助下详细解释本发明。
实施例
实施例-1：Mg-Al水滑石颗粒的制备
Mg-Al LDH(水滑石)粉末得自Taurus Chemicals，Hyderabad，India。平均粒度为小于50μm，堆积密度为0.26g/ml。
对于一些对比实验，颗粒活性炭(GAC)购自Active Carbon，Hyderabad，India。其粒度为500至1000μm。使用商业白水泥作为无机粘合剂(作为pH为6.5且TDS为80ppm的在水中的2％水性悬浮液)。分子量为8000至25000道尔顿的商业聚乙烯醇(80％水解)是有机粘合剂。
使用刮刀将56g LDH与84ml的(2％)水性白水泥悬浮液在容器中混合以形成湿混合物。此后，将另外的14g LDH加入到湿混合物中。用刮刀使其混合以得到几乎自由流动的聚集物。将聚集物与另外的28g LDH一起添加到滚圆机(spheroniser)中以减少进一步的聚集。将滚圆机设定为以200至500RPM旋转2至5分钟，之后将球形颗粒在80℃下在烘箱中干燥5小时。将其在350至400℃下煅烧3至4小时。在某些情况下，添加聚乙烯醇(PVA)水溶液。干燥后，将颗粒过筛以分离500至1000μm的颗粒，将其用于如下所述的填充床实验。
制备了一些更多的组合物用于对其进行实验，并对前述方法进行适当的修改。
所有颗粒的组成示于表1中。
表1
水的纯化
制备含有10g实施例-1的组合物(颗粒)的过滤器并用于实验。内直径为2cm的60cm长的丙烯酸柱用作过滤器的主体。颗粒的粒度为500至1000μm。使用前，将颗粒在水中浸泡24小时。
使已知浓度的表面活性剂(十二烷基苯磺酸钠)的水溶液以50ml/分钟的受控流速通过该柱。通过使用蠕动泵维持该流。不时地收集流出塔(经处理的)的水，并通过Hyamine滴定法测量表面活性剂的浓度。目标是确定在其时在输出水中发现明显量的表面活性剂的时间点。换句话说，目标是确定每种组合物的突破时间；值越高，组合物越好且越有效。
对表1的每种组合物进行相同的实验，观察结果列于表2中。
表2
注：称为LDH 2，3和4的颗粒是根据本发明的。
表2中的数据表明，与不含PVA的颗粒相比，含有白水泥和PVA的颗粒具有显著更长的突破时间。数据还清楚地表明煅烧增加了突破时间。在350℃下煅烧的颗粒的突破时间更长，这反过来高于在250℃下煅烧的颗粒。根据本发明的颗粒具有比商业GAC长得多的突破时间(几乎一个数量级)。标记为LDH 1的颗粒(其缺乏有机粘合剂)具有非常短的突破时间，或者当突破时间为16分钟时，表面活性剂在水中的浓度为14ppm，LDH 1颗粒未暴露于高表面活性剂负荷，但是颗粒仍然没有表现出更长的使用寿命。
表3中列出了本发明组合物和对比组合物的一些重要物理性质。
表3
表3表明煅烧颗粒的平均表面积大于未煅烧的颗粒。平均孔径不受甚至高达1.4重量％的PVA的包含所影响，而在具有0.3％和1.7％的颗粒的平均BET表面积之间观察到显著差异。
实施例-2：Zn-Al水滑石颗粒的制备
Zn-Al LDH粉末购自Priti Industries，Gujarat，India。平均粒度为小于63μm，平均堆积密度为0.28g/ml。
使用商业白水泥作为无机粘合剂(作为pH为6.5且TDS为80ppm的在水中的2％水性悬浮液)。分子量为8000至9000道尔顿的商业聚乙烯醇(80％水解)是有机粘合剂。使用刮刀将60克Zn LDH与40ml的(2％)白水泥水性悬浮液在容器中混合以形成湿混合物。此后，将另外的15g Zn LDH加入到湿混合物中。然后加入20ml的(2.5％)PVA并混合。然后加入9g ZnLDH粉末并用刮刀使其混合以得到自由流动的聚集物。将聚集物与另外的16g Zn LDH一起加入到滚圆机中以减少进一步的聚集。将滚圆机设定为以约300RPM旋转约3分钟，之后将球形颗粒在80℃下在烘箱中干燥5小时。将它们在350℃下煅烧3小时。干燥后，将颗粒过筛以分离500至1000μm的颗粒，将其用于如下所述的填充床实验。
颗粒的组成示于表4中。
表4
| 成分 | 成分重量/g |
| 总LDH | 98.7 |
| 白水泥 | 0.8 |
| PVA | 0.5 |
| 颗粒组合物的总重量 | 100 |
水的纯化
表4的颗粒组合物用于纯化水的实验中。该程序如下表1所述。观察结果总结在表5中。
表5
实施例2的颗粒组合物具有4分钟的突破时间，但初始表面活性剂浓度非常高。
Claims (14)
1.一种颗粒形式的组合物，其包含：
(i)95至98重量％的分子式[M2+ 1-xM3+ x(OH)2]q+(Xn-)q/n·yH2O的层状双氢氧化物(LDH)；
其中，
M2+是Ca2+，Mg2+，Mn2+，Fe2+，Co2+，Ni2+，Cu2+或Zn2+中的至少一种；
M3+是Al3+，Fe3+，Cr3+，Ga3+或V3+中的至少一种，
X是层间阴离子，其是Cl-，Br-，NO3 -，CO3 2-，SO4 2-或SeO4 2-中的至少一种；并且“x”是0.1至0.33的摩尔金属比；
(ii)0.3至2重量％的无机粘合剂，其是水泥，白水泥，石膏，石灰石，白垩，硅酸铝，飞灰，膨润土，沥青，铝酸钙，粘土，熟石灰或硅酸钠中的至少一种；和，
(iii)0.2至1.5重量％的分子量为1000至500,000道尔顿且分解温度≤400℃的有机粘合剂，其是聚乙烯醇，聚乙二醇，聚乙烯吡咯烷酮，聚丙烯酸，淀粉，纤维素，藻酸盐，琼脂，明胶或瓜尔胶中的至少一种。
2.如权利要求1所述的组合物，其中所述颗粒是煅烧的形式，可通过将相应的未煅烧颗粒加热至≤400℃而获得。
3.如权利要求1或2所述的组合物，其中所述LDH是水滑石，Mg6Al2CO3(OH)164H2O。
4.如权利要求1至3中任一项所述的组合物，其中所述无机粘合剂是水泥，白水泥，石膏，石灰石，白垩，硅酸铝或飞灰中的至少一种。
5.如权利要求1至4中任一项所述的组合物，其中所述有机粘合剂是聚乙烯醇。
6.如权利要求5所述的组合物，其中所述聚乙烯醇的分子量为8000道尔顿至10000道尔顿。
7.如权利要求2至6中任一项所述的组合物，其中煅烧颗粒的孔径为5nm至200nm。
8.如权利要求2至7中任一项所述的组合物，其中煅烧颗粒的堆积密度为0.2g/ml至0.9g/ml。
9.如权利要求2至8中任一项所述的组合物，其中煅烧颗粒的孔隙率百分比为90％至60％。
10.如权利要求2至9中任一项所述的组合物，其中煅烧颗粒的表面积为10m2/g至250m2/g。
11.一种用于纯化水的过滤器，其包含如前述权利要求1至10中任一项所述的组合物。
12.前述权利要求1至10中任一项所述的组合物用于纯化水的用途，所述水包含1至100ppm的表面活性剂。
13.如权利要求12所述的组合物的用途，其中所述表面活性剂是阴离子的。
14.一种制备如权利要求1所述的颗粒形式的组合物的方法，其包括以下步骤：
(i)混合95至98重量份的煅烧或未煅烧的形式的层状双氢氧化物(LDH)与0.3至2.0重量份的无机粘合剂的水性悬浮液，所述层状双氢氧化物的分子式为
[M2+ 1-xM3+ x(OH)2]q+(Xn-)q/n·yH2O；
其中，
M2+是Ca2+，Mg2+，Mn2+，Fe2+，Co2+，Ni2+，Cu2+或Zn2+中的至少一种；
M3+是Al3+，Fe3+，Cr3+，Ga3+或V3+中的至少一种；X是层间阴离子，其是Cl-，Br-，NO3 -，CO3 2-，SO4 2-或SeO4 2-中的至少一种；并且x是0.1至0.33的摩尔金属比，并且其中煅烧的形式定义为通过将未煅烧的LDH加热至≤400℃而获得的形式，所述无机粘合剂为水泥，白水泥，石膏，石灰石，白垩，硅酸铝，飞灰，膨润土，沥青，铝酸钙，粘土，熟石灰或硅酸钠中的至少一种；和，
(i)向步骤(i)的混合物中添加0.2至1.5重量份的分子量为1000至500,000道尔顿且分解温度≤400℃的有机粘合剂，其为聚乙二醇，聚乙烯吡咯烷酮，聚丙烯酸，糖，淀粉，纤维素，藻酸盐，琼脂，明胶或瓜尔胶中的至少一种，并进一步混合所有成分；
(ii)使步骤(ii)的所述混合物通过造粒机以得到颗粒形式的所述组合物。
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| WO2021230760A1 (en) * | 2020-05-15 | 2021-11-18 | Qatar Foundation For Education, Science And Community Development | An adsorbent material, synthesis thereof, and use thereof |
| CN116444210B (zh) * | 2023-04-07 | 2024-10-15 | 广西大学 | 一种单组分抗腐蚀地聚物水泥材料及制备方法 |
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| PH12018502216A1 (en) | 2019-08-05 |
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