CN105688866A - Preparation method of adsorbent based on crustacean waste - Google Patents
Preparation method of adsorbent based on crustacean waste Download PDFInfo
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- CN105688866A CN105688866A CN201610127845.6A CN201610127845A CN105688866A CN 105688866 A CN105688866 A CN 105688866A CN 201610127845 A CN201610127845 A CN 201610127845A CN 105688866 A CN105688866 A CN 105688866A
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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
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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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
- C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
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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
- B01J2220/4875—Sorbents characterised by the starting material used for their preparation the starting material being a waste, residue or of undefined composition
- B01J2220/4881—Residues from shells, e.g. eggshells, mollusk shells
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Abstract
A preparation method of an adsorbent based on crustacean waste comprises following steps: (1), the crustacean waste is soaked with water and then is dried and smashed; (2), the smashed crustacean waste is soaked in an HCl solution and dried into solids; (3), the solids are soaked in a citric acid solution and subjected to a stirring reaction; (4), after a mixed solution is filtered, solid particles are dried and subjected to heat treatment, cleaning and drying, and the adsorbent based on crustacean waste is obtained. According to the preparation method, the low-cost crustacean waste is taken as a raw material for preparation of the adsorbent, the technology is simple, and the prepared adsorbent based on crustacean waste has good adsorption performance on heavy metal, cannot produce second pollution, is environment-friendly and can be widely applied to treatment of heavy metal wastewater.
Description
Technical field
The present invention relates to a kind of method utilizing shell-fish garbage to prepare adsorbent, belong to shell-fish garbage absorbent preparation technical field。
Background technology
Along with industrial expansion, the exploitation of heavy metal, smelting, processing and business manufacture increasing, and many heavy metals enter water body such as lead, cadmium etc., can accumulate, cause serious environmental pollution in algae and bed mud；Concentration can be carried out by food chain and enter human body, health can be caused damage。In recent years, of common occurrence about heavy metal pollution event, Hunan children blood lead exceeds standard event, heavy metal pollution " vegetable basket " etc., it can be seen that, the improvement of heavy metal pollution is imperative。
Biosorption process is exactly use the part of the biomaterials self such as active microorganism, nonactive microorganism, agricultural product castoff, shell-fish garbage and natural organic matter or functional group and metal ion to form coordination compound, is then passed through solid-liquid separation and removes the metal ion in waste water。Select the method to process heavy metal wastewater thereby and have that raw material is easy to get, processing cost is low, environmental protection, clearance advantages of higher。Therefore, people are from economic and environment-friendly theory, and progressively popularizing selection biosorption process processes the heavy metal in water body。
The consumption that makes of marine product is all increasing every year, the garbage substantial amounts of its generation, one tuna can produce the garbage of about 25%, and Eriocheir sinensis probably can produce the marine product garbage of 60%, and the whole world can produce about 6～8,000,000 tons/year of discarded Eriocheir sinensiss, shrimp and lobster shell。In some developing countries, these discarded carapaces are usually simply poured onto in ocean or refuse landfill, and in developed country, for instance Australia, process the expense of discarded carapace per ton up to 150 dollars。
Containing the functional group such as hydroxyl, amino in these shell-fish garbages, stable chelate can be formed with metal ion in solution, can, as the raw material preparing adsorbent, be the pollution administration new approaches of a kind of " treatment of wastes with processes of wastes against one another ", moreover it is possible to reduce the processing cost of sewage。Therefore, how utilizing shell-fish garbage to prepare a kind of adsorbent economic and environment-friendly, that adsorption capacity is high is the application technical issues that need to address。
Summary of the invention
For the deficiency that existing shell-fish waste utilization technology exists, the present invention provides a kind of with low cost, technique simply based on the preparation method of the adsorbent of shell-fish garbage, and the method can prepare the shell-fish garbage adsorbent that heavy metal absorption property is good。
The preparation method of the adsorbent based on shell-fish garbage of the present invention, comprises the following steps:
(1) shell-fish garbage (Carapax Eriocheir sinensis, Crusta Penaeus seu Panulirus etc.) is soaked in water 15～24 hours, then cleans clean, dry to constant weight, be crushed to 70～100 orders；
(2) at 70 DEG C～80 DEG C, the shell-fish garbage of pulverizing is soaked in the HCl solution of concentration 0.5～1mol/L 1.5～3 hours, with distilled water flushing to pH value 6.5～7.0 after cooling, is dried into solid；
(3) solid of step (2) gained is dipped in the citric acid solution that concentration is 0.2～1.0mol/L, form mixed liquor, mixed liquor is placed in the water-bath of 80～90 DEG C, with the rotating speed stirring reaction 1.5 hours～2 hours of 80～100 revs/min；
(4) mixed liquor is cooled to room temperature, after filtration, solid particle is dried 26～32 hours at 60 DEG C～70 DEG C, subsequently heat-treated, finally clean with distilled water, dry, obtain shell-fish garbage adsorbent。
Drying temperature in described step (1) and step (4) is 65 DEG C-75 DEG C。
Described step (2) medium silt is soaked in HCl solution according to the ratio of 1g:20mL～25mL。
In described step (3) solid of gained in 1g:10mL～20mL ratio be dipped in citric acid solution。
Heat treatment in described step (4) refers under argon shield 130 DEG C～150 DEG C heat treatments 50 minutes～60 minutes, 100 DEG C in atmosphere～130 DEG C heat treatments 1.5 hours～2 hours。
The present invention prepares adsorbent with shell-fish garbage with low cost for raw material, and technique is simple, and the shell-fish garbage ABSORBENTS ABSORPTION metal adsorption performance of preparation is good, can be widely applied to the improvement of heavy metal wastewater thereby。The invention have the characteristics that:
(1) technique is simple, and raw material citric acid and shell-fish garbage have biodegradable, and what synthesis prepared will not produce secondary pollution based on shell-fish garbage adsorbent, has environment friendly, and can effectively reduce the processing cost of waste water。
(2) prepare based on shell-fish garbage adsorbent, compared with raw material, surface active composition content increases, and the advantages of good adsorption effect of heavy metal provides theoretical foundation for the industrial wastewater containing heavy metal and surface water treatment。
(3) the shell-fish garbage quantity used is big, with low cost, and utilizes it to prepare adsorbent can to provide new approach for the comprehensive utilization of shell-fish garbage。
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope diagram of shell-fish garbage adsorbent prepared by the present invention。
Detailed description of the invention
Embodiment 1
(1) it is soaked in water placed in the vessel for Carapax Eriocheir sinensis 15 hours, then cleans clean, dry to constant weight at 70 DEG C, put into crusher for crushing, cross 80 mesh sieves。
(2) at 70 DEG C, 40g Carapax Eriocheir sinensis is soaked in the HCl solution of 1000mL concentration 0.5mol/L 3 hours, with distilled water flushing to pH value 6.5 after cooling, is placed in 70 DEG C of baking ovens and dries。
(3) the solid 2g of gained is dipped in the citric acid solution that 40mL concentration is 0.2mol/L, is placed in the water-bath of 80 DEG C, to react 2 hours under the mixing speeds of 80 revs/min。
(4) above-mentioned mixed liquor is cooled to room temperature; filter; solid particle is placed in Constant Temp. Oven; temperature controls at 70 DEG C after dry 26 hours, 140 DEG C of heat treatments 55 minutes under argon shield, in atmosphere 130 DEG C of heat treatments 1.5 hours; cooling; clean with distilled water, be placed in 70 DEG C of baking ovens and dry, obtain Carapax Eriocheir sinensis adsorbent (CS1)。
Fig. 1 gives the scanning electron microscope diagram of Carapax Eriocheir sinensis adsorbent prepared by the present embodiment。
Being placed in by 0.2gCS1 in the lead waste water (pH value 5.0) that 100mL concentration is 10mg/L, be placed on shaking table and vibrate, rotating speed is 120rpm (rev/min)。After 36 hours, extracting 5mL supernatant, be passed through 0.45 μm of PTFE film and filter, measure residual lead ion concentration in filtrate with atomic absorption spectrophotometer, obtaining CS1 to plumbous adsorption capacity is 4.61mg/g。
Embodiment 2
(1) it is soaked in water placed in the vessel for Carapax Eriocheir sinensis 24 hours, then cleans clean, dry to constant weight at 65 DEG C, put into crusher for crushing, cross 100 mesh sieves。
(2) at 75 DEG C, 40g Carapax Eriocheir sinensis is soaked in the HCl solution of 800mL concentration 1mol/L 1.5 hours, with distilled water flushing to pH value 6.8 after cooling, is placed in 70 DEG C of baking ovens and dries。
(3) the solid 3g of gained is dipped in the citric acid solution that 45mL concentration is 0.5mol/L, is placed in the water-bath of 80 DEG C, to react 1.9 hours under the mixing speeds of 90 revs/min。
(4) above-mentioned mixed liquor is cooled to room temperature; filter; solid particle is placed in Constant Temp. Oven; temperature controls at 60 DEG C after dry 32 hours, 150 DEG C of heat treatments 50 minutes under argon shield, in atmosphere 120 DEG C of heat treatments 1.7 hours; cooling; clean with distilled water, be placed in 75 DEG C of baking ovens and dry, obtain Carapax Eriocheir sinensis adsorbent (CS2)。
Being placed in by 0.2gCS2 in the lead waste water (pH value 6.0) that 100mL concentration is 10mg/L, be placed on shaking table and vibrate, rotating speed is 120rpm。After 12 hours, extracting 5mL supernatant, be passed through 0.45 μm of PTFE film and filter, measure residual lead ion concentration in filtrate with atomic absorption spectrophotometer, obtaining CS2 to plumbous adsorption capacity is 4.42mg/g。
Embodiment 3
(1) it is soaked in water placed in the vessel for Carapax Eriocheir sinensis 20 hours, then cleans clean, dry to constant weight at 75 DEG C, put into crusher for crushing, cross 70 mesh sieves。
(2) at 70 DEG C, 40g Carapax Eriocheir sinensis is soaked in the HCl solution of 900mL concentration 0.7mol/L 2.5 hours, with distilled water flushing to pH value 6.8 after cooling, is placed in 70 DEG C of baking ovens and dries。
(3) the solid 2g of gained is dipped in the citric acid solution that 20mL concentration is 1mol/L, is placed in the water-bath of 90 DEG C, to react 1.5 hours under the mixing speed of 100rpm。
(4) above-mentioned mixed liquor is cooled to room temperature; filter; solid particle is placed in Constant Temp. Oven; temperature controls at 70 DEG C after dry 28 hours, 130 DEG C of heat treatments 1 hour under argon shield, in atmosphere 100 DEG C of heat treatments 2 hours; cooling; clean with distilled water, be placed in 70 DEG C of baking ovens and dry, obtain Carapax Eriocheir sinensis adsorbent (CS3)。
Being placed in by 0.1gCS3 in the lead waste water (pH is 5.0) that 100mL concentration is 10mg/L, be placed on shaking table and vibrate, rotating speed is 120rpm。After 24 hours, extracting 5mL supernatant, be passed through 0.45 μm of PTFE film and filter, measure residual lead ion concentration in filtrate with atomic absorption spectrophotometer, obtaining CS3 to plumbous adsorption capacity is 4.06mg/g。
Embodiment 4
(1) it is soaked in water placed in the vessel for fresh-water turtle shell 18 hours, then cleans clean, dry to constant weight at 70 DEG C, put into crusher for crushing, cross 90 mesh sieves。
(2) at 80 DEG C, 40g fresh-water turtle shell is soaked in the HCl solution of 1000mL concentration 0.9mol/L 2 hours, with distilled water flushing to pH value 7.0 after cooling, is placed in 70 DEG C of baking ovens and dries。
(3) the solid 2g of gained is dipped in the citric acid solution that 35mL concentration is 0.8mol/L, is placed in the water-bath of 85 DEG C, to react 1.8 hours under the mixing speed of 85rpm。
(4) above-mentioned mixed liquor is cooled to room temperature; filter; solid particle is placed in Constant Temp. Oven; temperature controls at 65 DEG C after dry 30 hours, 140 DEG C of heat treatments 50 minutes under argon shield, in atmosphere 110 DEG C of heat treatments 2 hours; cooling; clean with distilled water, be placed in 70 DEG C of baking ovens and dry, obtain fresh-water turtle shell adsorbent (CS4)。
Being placed in by 0.4gCS4 in the lead waste water (pH is 5.5) that 100mL concentration is 10mg/L, be placed on shaking table and vibrate, rotating speed is 120rpm。After 24 hours, extracting 5mL supernatant, be passed through 0.45 μm of PTFE film and filter, measure residual lead ion concentration in filtrate with atomic absorption spectrophotometer, obtaining CS4 to plumbous adsorption capacity is 4.96mg/g。
Embodiment 5
(1) it is soaked in water placed in the vessel for Crusta Penaeus seu Panulirus 22 hours, then cleans clean, dry to constant weight at 75 DEG C, put into crusher for crushing, cross 100 mesh sieves。
(2) at 75 DEG C, 40g Crusta Penaeus seu Panulirus is soaked in the HCl solution of 850mL concentration 0.8mol/L 1.8 hours, with distilled water flushing to pH value 7.0 after cooling, is placed in 70 DEG C of baking ovens and dries。
(3) the solid 2g of gained is dipped in the citric acid solution that 25mL concentration is 0.35mol/L, is placed in the water-bath of 85 DEG C, to react 1.7 hours under the mixing speed of 95rpm。
(4) above-mentioned mixed liquor is cooled to room temperature; filter; solid particle is placed in Constant Temp. Oven; temperature controls at 65 DEG C after dry 28 hours, 145 DEG C of heat treatments 55 minutes under argon shield, in atmosphere 120 DEG C of heat treatments 1.8 hours; cooling; clean with distilled water, be placed in 65 DEG C of baking ovens and dry, obtain Crusta Penaeus seu Panulirus adsorbent (CS5)。
Being placed in by 0.4gCS5 in the lead waste water (pH value is 6.0) that 100mL concentration is 10mg/L, be placed on shaking table and vibrate, rotating speed is 120rpm。After 36 hours, extracting 5mL supernatant, be passed through 0.45 μm of PTFE film and filter, measure residual lead ion concentration in filtrate with atomic absorption spectrophotometer, obtaining CS5 to plumbous adsorption capacity is 4.78mg/g。
Claims (5)
1. based on a preparation method for the adsorbent of shell-fish garbage, it is characterized in that, comprise the following steps:
(1) shell-fish garbage is soaked in water 15～24 hours, then cleans clean, dry to constant weight, be crushed to 70～100 orders；
(2) at 70 DEG C～80 DEG C, the shell-fish garbage of pulverizing is soaked in the HCl solution of concentration 0.5～1mol/L 1.5～3 hours, with distilled water flushing to pH value 6.5～7.0 after cooling, is dried into solid；
(3) solid of step (2) gained is dipped in the citric acid solution that concentration is 0.2～1.0mol/L, form mixed liquor, mixed liquor is placed in the water-bath of 80～90 DEG C, with the rotating speed stirring reaction 1.5 hours～2 hours of 80～100 revs/min；
(4) mixed liquor is cooled to room temperature, after filtration, solid particle is dried 26～32 hours at 60 DEG C～70 DEG C, subsequently heat-treated, finally clean with distilled water, dry, obtain shell-fish garbage adsorbent。
2. the preparation method of the adsorbent based on shell-fish garbage according to claim 1, is characterized in that, described step (1) and the drying temperature in step (4) are 65 DEG C-75 DEG C。
3. the preparation method of the adsorbent based on shell-fish garbage according to claim 1, is characterized in that, described step (2) medium silt is soaked in HCl solution according to the ratio of 1g:20mL～25mL。
4. the preparation method of the adsorbent based on shell-fish garbage according to claim 1, is characterized in that, in described step (3) solid of gained in 1g:10mL～20mL ratio be dipped in citric acid solution。
5. the preparation method of the adsorbent based on shell-fish garbage according to claim 1; it is characterized in that; heat treatment in described step (4) refers under argon shield 130 DEG C～150 DEG C heat treatments 50 minutes～60 minutes, 100 DEG C in atmosphere～130 DEG C heat treatments 1.5 hours～2 hours。
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109289791A (en) * | 2018-11-29 | 2019-02-01 | 运城学院 | A method of dephosphorization adsorbent is prepared using citric acid-modified |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109289791A (en) * | 2018-11-29 | 2019-02-01 | 运城学院 | A method of dephosphorization adsorbent is prepared using citric acid-modified |
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Application publication date: 20160622 |