CN104437341B - The preparation method of a kind of Treatment of Zinc-containing Wastewater adsorbent and application - Google Patents
The preparation method of a kind of Treatment of Zinc-containing Wastewater adsorbent and application Download PDFInfo
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- CN104437341B CN104437341B CN201410690082.7A CN201410690082A CN104437341B CN 104437341 B CN104437341 B CN 104437341B CN 201410690082 A CN201410690082 A CN 201410690082A CN 104437341 B CN104437341 B CN 104437341B
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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
- B01J20/048—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 containing phosphorus, e.g. phosphates, apatites, hydroxyapatites
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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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
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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
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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
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
- C02F1/62—Heavy metal compounds
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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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
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- Environmental & Geological Engineering (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Water Treatment By Sorption (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The preparation method of a kind of Treatment of Zinc-containing Wastewater adsorbent of disclosure and application, belong to technical field of heavy metal wastewater treatment；The method of the invention adopts aluminum sulfate modification technology that ardealite is modified after ardealite is carried out sodium chloride pretreatment, produces and obtains aluminium base modified ardealite adsorbent, Al3+Ardealite interlayer is entered into by ion-exchange reactions, and make interlayer strut to add large interlamellar spacing and aperture, the microcellular structure of this adsorbent increases further, thus improving porosity and the specific surface area of ardealite, there is good absorption property, ardealite after processing further has higher adsorption capacity, enables to become a kind of good adsorbent material removing zinc ion。
Description
Technical field
The present invention relates to the preparation method of a kind of Treatment of Zinc-containing Wastewater adsorbent and application, belong to technical field of heavy metal wastewater treatment。
Background technology
Zinc is a kind of reserves on earth heavy metal resources compared with horn of plenty。China's zinc resource reserves occupy second place of the world, and zinc resource is also widely used in modern industry production as among smelting, pharmacy and food service industry。Zinc is the indispensable element of health, and it is widely present in human muscle and skeleton, but content is very micro-, if serious consequence will occur excess。The main source of zinc-containing water is that health and industrial or agricultural activity are had serious harm by its discharge of electroplating wastewater, there is the harm such as persistency, toxicity are big, seriously polluted, once can not be biodegradable after entered environment, great majority participate in food chain circulation, and finally accumulate in vivo, destroy organism normal physiological metabolic activity, be detrimental to health。Making a general survey of the treatment technology electroplating zinc-containing water both at home and abroad at present, applying technique more, relatively mature and reliable mainly has: the sedimentation method, ion exchange, electrolysis, absorption method, bioanalysis, membrane separation process etc.。But there is capital cost height, run complexity in these methods, it is impossible to recycles the shortcomings such as the mud after absorption。Therefore, finding the way of a kind of fine solution zinc pollution, for the maintenance of good ecological environment, the urban ecological environment that especially industry is flourishing is critically important。
Ardealite is the solid waste produced in Wet-process phosphoric acid (WPPA) technical process, and its main component is CaSO4·2H2O, in May, 2006, State Environmental Protection Administration was with (2006) No. 176 civilian forms of ring letter, by qualitative for ardealite be dangerous solid waste, be classified as the controlling object of country's noxious waste pollution environment。Therefore one of the harmless treatment and the comprehensive utilization focus becoming Resource Recovery of Industrial Solid Waste research field of ardealite。
The recycling of ardealite has become phosphate fertilizer industry and has realized the key of sustainable development。Therefore, how to comprehensively utilize ardealite, control pollution, the treatment of wastes with processes of wastes against one another that ardealite produces, improve the value of ardealite, create good social benefit and environmental benefit just seems and is even more important。Ardealite may be used for Treatment of Zinc-containing Wastewater on utilizing, it it is a kind of method for the treatment of of wastes with processes of wastes against one another, but the ardealite adsorption capacity of non-modified and specific surface area are on the low side, it are used directly to Treatment of Zinc-containing Wastewater and can not reach in country " integrated wastewater discharge standard " (GB8978-1996) the emission request of zinc (< 2mg/L)。
The processing method of a kind of zinc-containing water disclosed in the patent that publication number is CN102464398A。The method utilizes flocculence Treatment of Zinc-containing Wastewater。Its processing step is be the powdered substance prepared with the mass ratio of 1:1～1:5 by ferrum aluminocopiapite and amorphous silica, then this material is joined in zinc-containing water processes。Although the method dezincification effect is high, but the preparation process of raw material is comparatively complicated, is unfavorable for large-scale industrial production。
It is be the composite zinc removing agent method of a kind of Treatment of Zinc-containing Wastewater disclosed in the patent of CN102464397A at publication number。The method utilizes By Bubble-floating Method Treatment of Zinc-containing Wastewater。Its processing step is for be re-dubbed composite zinc removing agent by Organic substance and inorganic matter, join when pH value is 4.0～6.0 in zinc-containing water, after stirring 10～30min, the waste water of gained carries out air-flotation process again, finally the one layer of residue Slag Scraping Device floating over wastewater surface being struck off, water outlet can lower than national grade one discharge standard。The method is higher in the preparation of composite zinc removing agent and operating cost equally, is unfavorable for the comprehensive utilization of resources of garbage。
Foreign study proves, the ardealite not being modified has certain characterization of adsorption, and zinc has good absorption property under appropriate conditions。Ardealite after absorption can utilize again as building materials after dried simultaneously, it is achieved thereby that the process of ardealite comprehensive utilization of resources。
Summary of the invention
The technical problem to be solved is to provide the method utilizing additive agent modified ardealite to process plating zinc-containing water, ardealite specific surface area after additive agent modified is big, adsorption capacity is high, and use modified ardealite Treatment of Zinc-containing Wastewater can reach the emission request in country " integrated wastewater discharge standard " (GB8978-1996) to zinc。
Technical scheme is as follows, through following each step:
(1) by ardealite sample broke to 120 ~ 180 orders, purification ardealite is obtained with removing impurity in ardealite after deionized water wash 3 ~ 5 times, in saturated nacl aqueous solution, purification ardealite is added in the ratio of 32 ~ 48g/L, it is configured to suspension, after stirring 3-7h under 30-40 DEG C of condition, decompression sucking filtration, with deionized water wash to neutral, room temperature is dried to water content and is obtained sodium ardealite sample less than or equal to 0.5%；
(2) in the ratio of 32 ~ 48g/L, sodium ardealite sample being added mass concentration is the Al of 1-5%2(SO4)3In solution, after stirring 4-8h under 30-40 DEG C of condition, reduce pressure sucking filtration, with deionized water wash to neutral, dries to water content less than or equal to 0.5% in 120-160 DEG C, crosses 120-180 mesh sieve, obtain aluminum modified ardealite adsorbent after being then ground。
The adsorbent that the preparation method of Treatment of Zinc-containing Wastewater adsorbent of the present invention prepares is for Treatment of Zinc-containing Wastewater, comprise the following steps: the adsorbent prepared is joined in zinc-containing water with the ratio of 8～12g/L, in waste water, the concentration of zinc ion is 50-90mg/L, and it is sufficiently stirred for mixing, muddy water filtration is carried out after contacting concussion 90 ~ 120min at 15～20 DEG C, discard filtering residue, and measure the content of zinc ion in the filtrate after process。
The present invention adopts sodium chloride and aluminum sulfate as additive, is modified producing to ardealite and obtains aluminium base modified ardealite adsorbent, Al3+Ardealite interlayer is entered into by ion-exchange reactions, and make interlayer strut to add large interlamellar spacing and aperture, the microcellular structure of this adsorbent increases further, thus improving porosity and the specific surface area of ardealite, there is good absorption property, make the ardealite after process have higher adsorption capacity further, enable to become a kind of good adsorbent material removing zinc ion；Compared with prior art, it is an advantage of the current invention that:
(1) present invention utilizes sodium chloride and aluminum sulfate modified ardealite, increases the specific surface area of ardealite so that it is have better adsorption function；
(3) present invention is capable of the removal of zinc in waste water, and overall adsorption amount is higher, under best theoretical condition, the adsorbance of zinc up to 69.8mg/g, thus is had important practical significance to containing the improvement of Zn Cr coating waste water and the improvement of water environment by aluminium base modified ardealite；
(4) present invention produces the raw material phosphor Gypsum Fibrosum of adsorbent is trade waste, will provide new thinking for the treatment of wastes with processes of wastes against one another。
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in further detail, but protection scope of the present invention is not limited to described content。
Embodiment 1
(1) by ardealite sample broke to 120 orders, wash magazins' layout in 3 removal ardealites with deionized water and obtain purification ardealite, 8g purification ardealite is dissolved in 250mL saturated nacl aqueous solution, it is configured to suspension, after stirring 3h under 30 DEG C of conditions, decompression sucking filtration, with deionized water wash to neutral, room temperature is dried to water content and is obtained sodium ardealite sample less than or equal to 0.5%；
(2) 8g sodium ardealite sample being added 250mL mass concentration is the Al of 1%2(SO4)3In solution, after stirring 4h under 30 DEG C of conditions, reduce pressure sucking filtration, with deionized water wash to neutral, dries to water content less than or equal to 0.5% in 120 DEG C, crosses 120 mesh sieves, obtain aluminum modified ardealite adsorbent after being then ground；
(3) step (2) gained adsorbent is added in zinc-containing water with the amount of 8g/L, in waste water, the concentration of zinc ion is 50mg/L, and is sufficiently stirred for mixing, and at 15 DEG C, contact concussion carried out muddy water filtration after 90 minutes, discarding filtering residue, in the filtrate after process, the content of zinc is 1.2mg/L。
Embodiment 2
(1) by ardealite sample broke to 160 orders, wash magazins' layout in 4 removal ardealites with deionized water and obtain purification ardealite, 10g purification ardealite is dissolved in 250mL saturated nacl aqueous solution, it is configured to suspension, after stirring 5h under 35 DEG C of conditions, decompression sucking filtration, with deionized water wash to neutral, room temperature is dried to water content and is obtained sodium ardealite sample less than or equal to 0.5%；
(2) 10g sodium ardealite sample being added 250mL mass concentration is the Al of 3%2(SO4)3In solution, after stirring 6h under 35 DEG C of conditions, reduce pressure sucking filtration, with deionized water wash to neutral, dries to water content less than or equal to 0.5% in 140 DEG C, crosses 160 mesh sieves, obtain aluminum modified ardealite adsorbent after being then ground；
(3) step (2) gained adsorbent is added in zinc-containing water with the amount of 10g/L, in waste water, the concentration of zinc ion is 70mg/L, and is sufficiently stirred for mixing, and at 18 DEG C, contact concussion carried out muddy water filtration after 100 minutes, discarding filtering residue, in the filtrate after process, the content of zinc is 0.8mg/L。
Embodiment 3
(1) by ardealite sample broke to 180 orders, wash magazins' layout in 5 removal ardealites with deionized water and obtain purification ardealite, 12g purification ardealite is dissolved in 250mL saturated nacl aqueous solution, it is configured to suspension, after stirring 7h under 40 DEG C of conditions, decompression sucking filtration, with deionized water wash to neutral, room temperature is dried to water content and is obtained sodium ardealite sample less than or equal to 0.5%；
(2) 12g sodium ardealite sample being added 250mL mass concentration is the Al of 5%2(SO4)3In solution, after stirring 8h under 40 DEG C of conditions, reduce pressure sucking filtration, with deionized water wash to neutral, dries to water content less than or equal to 0.5% in 160 DEG C, crosses 180 mesh sieves, obtain aluminum modified ardealite adsorbent after being then ground；
(3) step (2) gained adsorbent is added in zinc-containing water with the amount of 12g/L, in waste water, the concentration of zinc ion is 90mg/L, and is sufficiently stirred for mixing, and at 20 DEG C, contact concussion carried out muddy water filtration after 120 minutes, discarding filtering residue, in the filtrate after process, the content of zinc is 0.4mg/L。
Comparative example 1
(1) by ardealite sample broke to 120 orders, wash magazins' layout in 3 removal ardealites with deionized water and obtain purification ardealite sample；
(2) step (1) gained adsorbent is added in zinc-containing water with the amount of 8g/L, in waste water, the concentration of zinc ion is 50mg/L, and is sufficiently stirred for mixing, and at 15 DEG C, contact concussion carried out muddy water filtration after 90 minutes, discarding filtering residue, in the filtrate after process, the content of zinc is 23.8mg/L。
Comparative example 2
(1) by ardealite sample broke to 160 orders, wash magazins' layout in 4 removal ardealites with deionized water and obtain purification ardealite；
(2) step (1) gained adsorbent is added in zinc-containing water with the amount of 10g/L, in waste water, the concentration of zinc ion is 70mg/L, and is sufficiently stirred for mixing, and at 18 DEG C, contact concussion carried out muddy water filtration after 100 minutes, discarding filtering residue, in the filtrate after process, the content of zinc is 29.8mg/L。
Comparative example 3
(1) by ardealite sample broke to 180 orders, wash magazins' layout in 5 removal ardealites with deionized water and obtain purification ardealite；
(2) step (1) gained adsorbent is added in zinc-containing water with the amount of 12g/L, in waste water, the concentration of zinc ion is 90mg/L, and is sufficiently stirred for mixing, and at 20 DEG C, contact concussion carried out muddy water filtration after 120 minutes, discarding filtering residue, in the filtrate after process, the content of zinc is 36.3mg/L。
Claims (2)
1. the preparation method of a Treatment of Zinc-containing Wastewater adsorbent, it is characterised in that specifically include following steps:
(1) by ardealite sample broke to 120 ~ 180 orders, purification ardealite is obtained with removing impurity in ardealite after deionized water wash 3 ~ 5 times, in saturated nacl aqueous solution, purification ardealite is added in the ratio of 32 ~ 48g/L, it is configured to suspension, after stirring 3-7h under 30-40 DEG C of condition, decompression sucking filtration, with deionized water wash to neutral, room temperature is dried to water content and is obtained sodium ardealite sample less than or equal to 0.5%；
(2) in the ratio of 32 ~ 48g/L, sodium ardealite sample being added mass concentration is the Al of 1-5%2(SO4)3In solution, after stirring 4-8h under 30-40 DEG C of condition, reduce pressure sucking filtration, with deionized water wash to neutral, dries to water content less than or equal to 0.5% in 120-160 DEG C, crosses 120-180 mesh sieve, obtain aluminum modified ardealite adsorbent after being then ground。
2. the adsorbent that the preparation method of the Treatment of Zinc-containing Wastewater adsorbent described in claim 1 prepares is for Treatment of Zinc-containing Wastewater, it is characterized in that: the adsorbent prepared is joined in zinc-containing water with the ratio of 8～12g/L, in waste water, the concentration of zinc ion is 50-90mg/L, and it is sufficiently stirred for mixing, muddy water filtration is carried out after contacting vibration 90 ~ 120min at 15～20 DEG C, discard filtering residue, and measure the content of zinc ion in the filtrate after process。
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| CN107827504A (en) * | 2017-12-18 | 2018-03-23 | 寿光菌禾生物科技有限公司 | A kind of biological organic fertilizer with prevention and control root knot nematode disease function and preparation method thereof |
| CN113481348B (en) * | 2021-06-30 | 2022-07-26 | 广东牧人王电器有限公司 | Adsorption treatment process for harmful substances in cooking pot |
| CN113996265A (en) * | 2021-11-02 | 2022-02-01 | 南京理工大学 | Preparation method and application of iron-modified phosphogypsum |
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| CN1394823A (en) * | 2002-08-09 | 2003-02-05 | 孙国庆 | Modified phosphogypsum and its preparation |
| CN101973619A (en) * | 2010-09-17 | 2011-02-16 | 昆明理工大学 | Method for treating waste water from copper smelting by using modified ardealite |
| CN102633347A (en) * | 2012-04-27 | 2012-08-15 | 昆明理工大学 | Method for treating cadmium-containing wastewater by utilizing microwave modified ardealite |
| CN102674509A (en) * | 2011-10-20 | 2012-09-19 | 常州亚环环保科技有限公司 | Method for removing heavy metal ions from electroplating wastewater |
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Patent Citations (4)
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|---|---|---|---|---|
| CN1394823A (en) * | 2002-08-09 | 2003-02-05 | 孙国庆 | Modified phosphogypsum and its preparation |
| CN101973619A (en) * | 2010-09-17 | 2011-02-16 | 昆明理工大学 | Method for treating waste water from copper smelting by using modified ardealite |
| CN102674509A (en) * | 2011-10-20 | 2012-09-19 | 常州亚环环保科技有限公司 | Method for removing heavy metal ions from electroplating wastewater |
| CN102633347A (en) * | 2012-04-27 | 2012-08-15 | 昆明理工大学 | Method for treating cadmium-containing wastewater by utilizing microwave modified ardealite |
Non-Patent Citations (2)
| Title |
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