CN105771922A - Preparation and application methods of copper ion adsorbent - Google Patents
Preparation and application methods of copper ion adsorbent Download PDFInfo
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- CN105771922A CN105771922A CN201610353658.XA CN201610353658A CN105771922A CN 105771922 A CN105771922 A CN 105771922A CN 201610353658 A CN201610353658 A CN 201610353658A CN 105771922 A CN105771922 A CN 105771922A
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- culture medium
- phosphoric acid
- absorption agent
- copper
- medium waste
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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
- B01J2220/4887—Residues, wastes, e.g. garbage, municipal or industrial sludges, compost, animal manure; fly-ashes
Abstract
The invention relates to preparation and application methods of a copper ion adsorbent, and belongs to the field of environment protection. The mode of modification with sodium hydroxide, phosphoric acid and microwaves is adopted in the preparation method, and the preparation method comprises the specific steps that firstly, lentinula edodes culture medium waste materials are air-dried and ground and then pass through a 20-mesh screen, and a screened-down product is taken and put into a dryer for use; secondly, the pretreated lentinula edodes culture medium waste material particles are put into a sodium hydroxide solution with the mass fraction of 10%, constant temperature oscillation is carried out for 2-3 h under the conditions of 30 DEG C and 100-200 r/min, filtering separation is carried out, and the modified culture medium waste materials are washed with clean water till washing liquor is approximately neutral, and then are dried to the constant weight at 80 DEG C; thirdly, then, a 0.5 mol.L-1 phosphoric acid solution is added according to the proportion of 1:(15-20), the mixture is heated for 2.5-5 min under the medium heat condition in microwaves and then taken out, excessive phosphoric acid is washed away with clean water, the product is dried to the constant weight at 80 DEG C, and the copper ion adsorbent is obtained. The raw material, namely, the lentinula edodes culture medium waste materials, used in the preparation method is low in cost, the modification method is simple and easy to implement, and the modified adsorbent has a good adsorbing effect.
Description
Technical field
The invention belongs to field of environment protection, relate to a kind of working in coordination with microwave modification mushroom culture medium waste material with chemical agent and preparing the preparation method of a kind of copper absorption agent, and be used for this adsorbent removing containing Cu2+Acid wastewater in mine processing method.
Background technology
Acid wastewater in mine is owing to the sulfide mineral in mine is under the effect of empty gas and water and microorganism, and a series of materialization and biochemical reaction occur, and progressively generate containing a large amount of metal ions, such as Fe2+、Cu2+、Mn2+、Zn2+、Cd2+、As3+Etc. yellowish-brown acid waste water.According to statistics, every day can be discharged the waste water of thousands of to tens thousand of cubic metres in many mines, these acid waste waters are owing to the fluctuation of its water quality and quantity is big, emission point dispersion is wayward, pH value is low and containing plurality of heavy metal ion, and become one of the severeest environmental problem that global mining faces.Therefore, seek economy, the technology of improvement acid wastewater in mine pollution effectively, it is ensured that the Sustainable Development and Utilization of mineral resources, become the major issue faced under existing situation, be also the focus of scholars's common concern.
In recent years, utilize industrial or agricultural waste biomass material, as the Adsorption of Heavy Metal Ions such as shell, sawdust, bark, rice husk, bagasse arouse great concern.Due to this method have that adsorbance is big, efficiency is high, simple to operate, adsorbent wide material sources, low cost, can the treatment of wastes with processes of wastes against one another, and can be enriched with by pyrolysis and can reclaim the many merits such as heavy metal, and become the acid wastewater in mine processing method with development prospect.
China is Lentnus edodes state maximum in the world, and the substantial amounts of mushroom culture medium waste material of annual generation, Common resources approach is used as the raw material of fertilizer, feedstuff, and economic value added is relatively low.Due to organic substances such as mushroom culture medium waste material cellulose, polysaccharide, protein, and these Organic substances contain the functional group such as hydroxyl, carboxyl, it is possible to combine heavy metal ion, therefore can be considered as biological adsorption agent to process heavy metal wastewater thereby.
But natural mushroom culture medium waste material adsorption capacity is relatively low, input water there is also organic dissolution and cause the rising of waste water COD, therefore natural mushroom culture medium waste material is modified, to improve its adsorption capacity and chemical stability.Chinese patent CN102658092A, with natural mushroom culture medium waste material as raw material, is that adsorbent heavy metal ion prepared by modifying agent with sulphuric acid and citric acid mixed solution or sodium hydroxide solution.It uses strong acid or strong base solution to be modified, then carries out calcining transformation, and modifying process will produce spent acid alkali liquor, need neutralisation treatment, and cause the wasting of resources and environmental pollution；Calcining link in its technique adds production cost.
Summary of the invention
The method that it is an object of the invention to use sodium hydroxide and phosphoric acid solution to work in coordination with microwave modification improves the ability of copper ion in natural mushroom culture medium waste material adsorbent solution, a kind of modified mushroom culture medium waste material copper absorption agent is provided, its heavy metal has good absorption property, can be used for containing heavy metal Cu2+The process of acid wastewater in mine.The method is simple to operate, with low cost, adsorbent material wide material sources, cheap and easy to get, and technique is simple, and cost is relatively low, the preferable and recyclable heavy metal of absorption property.
The preparation method of a kind of copper absorption agent, uses sodium hydroxide and phosphoric acid solution to work in coordination with microwave modification mode, specifically comprises the following steps that
(1) pretreatment of mushroom culture medium waste material: mushroom culture medium waste material, after air-drying, pulverizing, is crossed 20 mesh sieves, taken undersize and put in exsiccator standby.
(2) the mushroom culture medium waste granules through pretreatment is placed in the NaOH solution that mass fraction is 10%, vibration stirring 2～3h under the conditions of 30 DEG C, 100～200r/min；Filtering and separate, filtering residue clear water rinses to washing liquid weakly acidic pH, dries to constant weight at 80 DEG C；
(3) in 1:(15～20) ratio add 0.5mol L-1Phosphoric acid solution, takes out after jointly heating 2.5～5min under the conditions of microwave moderate heat, with clear water, unnecessary phosphoric acid is rinsed out；Dry at 80 DEG C to constant weight, cross 20 mesh sieves, prepare modified mushroom culture medium waste material copper absorption agent.
Copper absorption agent obtained as described above is for the adsorption treatment of the acid wastewater in mine containing heavy metal.Concrete processing method is: with 10g/L, copper absorption agent is joined initial Cu2+Concentration is in the mine simulation acid waste water of 150mg/L, and 30 DEG C, constant temperature oscillation stirring under conditions of 140r/min, it reaches to adsorb saturated, to Cu when 45min2+Clearance reach 91.3%, compared to natural mushroom culture medium waste material, improve 46.95%；Additionally, it can Adsorption of Cu at low ph values2+, when wastewater pH be about 0.7, remaining condition ibid time, adsorbance reaches 2.95mg/g.
Adsorbing saturated copper absorption agent and be pyrolyzed 1h under the air atmosphere of 450 DEG C, in residue, copper content is 92.48mg/g, is enriched 7.07 times, and solid residue stable in properties does not results in secondary pollution, it is also possible to reclaim copper resource.
The method of the present invention first uses pretreatment by strong alkali, processes by Phosphation, drying modified adsorbent, unnecessary phosphoric acid can neutralize the alkali of scraped surface residual, it is to avoid the secondary pollution caused due to adsorbing material modification, and is not required to carry out calcining transformation, Simplified flowsheet, reduces cost.Most of deliquescent pigment and Organic substance in the most adsorbable acid wastewater in mine of this adsorbent, removal effect significantly improves, and illustrates that adsorbing material prepared by this method has broad application prospects and market prospect in heavy metal field in removing sewage.
Accompanying drawing explanation
Fig. 1 (a) is the sodium hydroxide of the present invention and phosphoric acid solution works in coordination with microwave modification mushroom culture medium waste material adsorbent in Adsorption of Cu2+Front scanning electron microscope (SEM) photograph,
Sodium hydroxide and phosphoric acid solution that Fig. 1 (b) is invention work in coordination with microwave modification mushroom culture medium waste material adsorbent in Adsorption of Cu2+Front scanning electron microscope (SEM) photograph；
Fig. 2 is the sodium hydroxide of the present invention and phosphoric acid solution works in coordination with microwave modification mushroom culture medium waste material adsorbent in Adsorption of Cu2+Infrared spectrogram front and back.
Fig. 3 is the sodium hydroxide of the present invention and phosphoric acid solution works in coordination with microwave modification mushroom culture medium waste material adsorbent in Adsorption of Cu2+Zeta figure front and back.
Detailed description of the invention
Below in conjunction with detailed description of the invention, the present invention is further illustrated:
The preparation method of modified mushroom culture medium copper absorption agent: discarded mushroom culture medium is the obsolete fungus stick after the four batches of Lentinus Edodess of gathering provided by Beijing company；By discarded mushroom culture medium after air-drying, pulverizing, cross 20 mesh sieves, take the lower grain products of sieve；Lower for sieve grain products is placed in the NaOH solution that mass fraction is 10%, vibration 2～3h under the conditions of 30 DEG C, 100～200r/min；Filter and separate, filtering residue clear water is rinsed to washing liquid weakly acidic pH, dries to constant weight at 80 DEG C；Again in 1:(15～20) ratio add 0.5mol L-1Phosphoric acid solution, takes out after jointly heating 2.5～5min under the conditions of microwave moderate heat, with clear water, unnecessary phosphoric acid is rinsed out；Dry at 80 DEG C to constant weight, cross 20 mesh sieves, i.e. prepare modified discarded mushroom culture medium waste material copper absorption agent.
Absorption test case 1
Solution ph be 3, Cu2+Initial concentration is 150mg/l, modified mushroom culture medium waste material copper absorption agent dosage is 10g/l, 30 DEG C, vibrate under the conditions of 140r/min 2h, the modified mushroom culture medium waste material copper absorption agent before and after absorption is characterized.
Scanning electron microscope analysis
In the present embodiment, modified mushroom culture medium waste material copper absorption agent is in Adsorption of Cu2+Microstructure front and back is as shown in Figure 1.It will be seen from figure 1 that a notable change of the modified mushroom culture medium heavy metal absorbent after Xi Fu is that surface pore is occupied, this absolutely proves Cu2+There occurs that duct is adsorbed.
Infrared spectrum analysis
Copper absorption agent modified in the present embodiment is in Adsorption of Cu2+Infrared spectrogram front and back is as shown in Figure 2, it can be seen that the mushroom culture medium waste material copper absorption agent after sodium hydroxide and phosphoric acid solution work in coordination with microwave modification is in Adsorption of Cu2+Spectrogram front and back has obvious similarity, illustrates that this sorbent structure is stable.Modified mushroom culture medium waste material copper absorption agent is in Adsorption of Cu2+Infrared spectrum change front and back is shown in Table 1.
Table 1 adsorbent Cu2+Infrared band change front and back
As seen from Table 1, modified mushroom culture medium waste material copper absorption agent is in Adsorption of Cu2+During, hydroxyl, amide groups, phosphate-based there occurs change, show that these groups take part in Cu2+Absorption.
Zeta potential is analyzed
Modified mushroom culture medium waste material copper absorption agent Adsorption of Cu2+Zeta potential front and back is with the change of pH value, as shown in Figure 3.
Being found the Zeta potential before and after this adsorbent by Fig. 3, after absorption, the Zeta potential numerical value of this adsorbent reduces, and the absolute value of the two Zeta potential difference increases with the rising of pH.Cu2+Obligate absorption, adsorbed Cu is there occurs at this adsorbent surface2+The positive charge part carried is transferred to this adsorbent surface so that it is the numerical value of surface net negative charge reduces, thus causes Zeta potential numerical value to reduce.Additionally, pH value is the highest, obligate absorption is the biggest to the contribution of adsorbance.
Claims (8)
1. the preparation method of a copper absorption agent, it is characterised in that use sodium hydroxide+phosphoric acid+microwave
Being modified mode, it concretely comprises the following steps:
(1) pretreatment of mushroom culture medium waste material: mushroom culture medium waste material, after air-drying, pulverizing, crosses 20
Mesh sieve, takes undersize and puts in exsiccator standby；
(2) pretreated mushroom culture medium waste granules is placed in sodium hydroxide solution, 30 DEG C,
Constant temperature oscillation 2～3h under the conditions of 100～200r/min, filter and separate, and modified culture medium waste clear water rushes
It is washed till washing liquid weakly acidic pH, dries to constant weight at 80 DEG C；
(3) it is proportionally added into phosphoric acid solution, takes out after jointly heating 2.5～5min under the conditions of microwave moderate heat,
With clear water, unnecessary phosphoric acid is rinsed out, dry to constant weight at 80 DEG C, prepare copper absorption agent.
2. according to the preparation method of the copper absorption agent described in claim 1, it is characterised in that sodium hydroxide
The concentration of solution be mass fraction be 10%, phosphoric acid solution concentration is 0.5mol L-1。
3. according to the preparation method of the copper absorption agent described in claim 1, it is characterised in that Lentinus Edodes is cultivated
Base waste material with the consumption of phosphoric acid solution is: mushroom culture medium waste material weight and phosphoric acid solution volume ratio are 1:
(15～20), mushroom culture medium waste material weight g, phosphoric acid solution volume ml.
4. the application process of the copper absorption agent as described in claim 1-3, it is characterised in that use
Sodium hydroxide+phosphoric acid+microwave is modified copper absorption agent prepared by mode in acid wastewater in mine
Cu2+Adsorption.
5. the application process of copper absorption agent as claimed in claim 4, it is characterised in that by prepared suction
Attached dose joins in the waste water containing heavy metal, constant temperature oscillation stirring under conditions of 30 DEG C, 100～200r/min
2～3h, then filter after separating, i.e. obtain the waste water after removing heavy metals.
6. according to the application process of the copper absorption agent described in claim 4 or 5, it is characterised in that initial
Cu2+When concentration is 150mg/L, copper absorption agent dosage is 10g/L, it reaches absorption when 45min
Saturated, to Cu2+Clearance reach 91.3%, compared to natural mushroom culture medium waste material, improve 46.95%.
7. according to the application process of the copper absorption agent described in claim 5, it is characterised in that coexist from
In the acid wastewater in mine that son exists, coexisting ion is to copper absorption agent Adsorption of Cu2+Suppression order be:
Zn2+＜ Mg2+＜ Na+＜ ＜ Fe3+＜ Al3+。
8. according to the application process of the copper absorption agent described in claim 6, it is characterised in that copper ion
Carry out burning disposal after adsorbent is saturated, under the air atmosphere of 450 DEG C, copper ion saturated for absorption is inhaled
Attached dose of pyrolysis 1h, in residue, copper content is 92.48mg/g, is enriched 7.07 times, does not results in secondary pollution,
Copper resource can also be reclaimed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201610353658.XA CN105771922A (en) | 2016-05-25 | 2016-05-25 | Preparation and application methods of copper ion adsorbent |
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| CN201610353658.XA CN105771922A (en) | 2016-05-25 | 2016-05-25 | Preparation and application methods of copper ion adsorbent |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110773135A (en) * | 2019-10-08 | 2020-02-11 | 西安交通大学 | Adsorbent for adsorbing copper ions, and film protective agent and water treatment agent containing same |
| CN115364816A (en) * | 2022-09-22 | 2022-11-22 | 河北科技大学 | Modified wormcast and preparation method and application thereof |
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| CN102658092A (en) * | 2012-05-02 | 2012-09-12 | 北京科技大学 | Method for preparing and applying modified mushroom culture medium waste material heavy metal adsorbent |
| CN102935352A (en) * | 2012-01-20 | 2013-02-20 | 北京科技大学 | Method for absorbing and removing heavy metal and hexavalent chromium from waste liquid by using mangosteen slag |
| CN105198030A (en) * | 2014-06-13 | 2015-12-30 | 北京科技大学 | Method for removing chloride ions in water through garlic waste |
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2016
- 2016-05-25 CN CN201610353658.XA patent/CN105771922A/en active Pending
Patent Citations (4)
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| CN102557181A (en) * | 2012-01-20 | 2012-07-11 | 北京科技大学 | Method for adsorption and removal of heavy metals and dye of waste water by garlic waste |
| CN102935352A (en) * | 2012-01-20 | 2013-02-20 | 北京科技大学 | Method for absorbing and removing heavy metal and hexavalent chromium from waste liquid by using mangosteen slag |
| CN102658092A (en) * | 2012-05-02 | 2012-09-12 | 北京科技大学 | Method for preparing and applying modified mushroom culture medium waste material heavy metal adsorbent |
| CN105198030A (en) * | 2014-06-13 | 2015-12-30 | 北京科技大学 | Method for removing chloride ions in water through garlic waste |
Non-Patent Citations (1)
| Title |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110773135A (en) * | 2019-10-08 | 2020-02-11 | 西安交通大学 | Adsorbent for adsorbing copper ions, and film protective agent and water treatment agent containing same |
| CN115364816A (en) * | 2022-09-22 | 2022-11-22 | 河北科技大学 | Modified wormcast and preparation method and application thereof |
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