CN100402141C - Preparation method of modified turf adsorbent - Google Patents
Preparation method of modified turf adsorbent Download PDFInfo
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- CN100402141C CN100402141C CNB2006100457489A CN200610045748A CN100402141C CN 100402141 C CN100402141 C CN 100402141C CN B2006100457489 A CNB2006100457489 A CN B2006100457489A CN 200610045748 A CN200610045748 A CN 200610045748A CN 100402141 C CN100402141 C CN 100402141C
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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Abstract
The invention involves heavy metal wastewater treatment, specifically a preparation method based on a modified adsorbent of peat. It uses natural peat as the main raw material and alkaline solution to neutralize peat,regulates the pH of mixed solution to 10-12, then adjust the solid-liquid ratio to 1:1-1:100 with alkali solution, stirs, stews, separates the sediments from the supernatant, dries and disintegrates said sediments then prepares the modified peat adsorbent. The adsorption capacity of original peat is improve d, while the stability and the anti-hostile environment environmental capacity are strengthened. And the preparation method using the invention can prepare humic acid as absorbent which further enhance the industrial added value of peat. The raw materials using by the invention is cheap, the source is extensive, the modification process is simple, the technology is stable and reliable; the adsorptive capacity of the prepared modified adsorbent is high and it has features of high efficiency, wide applicability, pollution-free and environmentally friendly,etc.
Description
Technical field
The present invention relates to the processing of industrial wastewater, specifically a kind of preparation method of modified turf adsorbent.
Background technology
Heavy metal wastewater thereby is mainly derived from the industrial trade of mine metallurgy industry, machining industrial wastewater and other heavy metal-containing waste waters.All there is heavy metal pollution in the waste water of many factories, as mining factory, smelting factory, hardware processing factory, plating factory, tannery etc., soil around some military base is also contaminated, even the concentration of heavy metal ion of some refuse landfill subsurface infiltration liquid exceeds standard.Along with rapid economy development, containing heavy metal (as cadmium, lead, copper, zinc, chromium (trivalent and sexavalence), nickel, mercury, arsenic, gold and silver etc.) waste water discharges in a large number, these heavy metal ion enter in the surrounding environment by water body in a large number, and, make underground water and surface water that contaminated by heavy metals danger be arranged in the medium-term and long-term accumulation of environment.These heavy metals can not be decomposed by biology, accumulate in environment easily, if enter food chain, will accumulate in biologic artifact (comprising plant, animal, microorganism and the mankind), have the danger that causes various diseases; The economic worth of some heavy metal own is very high simultaneously, need recycle from waste water.Therefore, imperative for the processing of the heavy metal wastewater thereby in the various industrial trades.
The traditional handicraft of removing heavy metal ion in the industrial wastewater is a chemical precipitation method.By adding NaOH, lime or Na
2CO
3Regulate the pH of waste water, make the heavy metal ion in the waste water form precipitation, adopt subsequent techniques such as precipitation or filtration that sediment is separated with waste water then, thereby reach clean-up effect.Adopting alkaline precipitation is wherein modal technology, and the shortcoming of traditional handicraft is: need device for dehydrating sladge waste; Floor space is big, complicated operation.The mud that traditional precipitation method produce is meeting stripping once again under the situation that pH changes, and causes secondary pollution.In addition, all there is certain defective in some process for treating heavy-metal waste water in practical operation, as for the heavy metal wastewater thereby with a large amount of complexing agents, can't handle with chemical precipitation method; Be impracticable or need the expense of great number for lower these methods of heavy metal wastewater thereby of concentration.
From technical feasibility, economical and efficient and environmental safety angle, research and develop a kind of environmental friendliness, capital construction, the novel process that operation and maintenance cost is low are handled above-mentioned waste water and are seemed particularly important, reducing or eliminating the accumulation of heavy metal in environment, and satisfy the environmental requirement of increasingly stringent.
Absorption method is a kind of method that is commonly used to handle heavy metal wastewater thereby, compares with additive method, and this method technology is simple, easy to operate, and capital construction, operation and maintenance cost are lower.With regard to expense, adsorbent price decision absorption method is handled the heavy metal wastewater thereby expense.Existing adsorbent such as adsorbents such as active carbon, humic acid resin have stronger adsorption capacity, the heavy metal removing rate height, but need to extract and preparation the cost height through industry.Seek focus cheap, that new adsorbent that adsorption activity is high (cost performance height) is just becoming heavy metal containing wastewater treatment.
Peat is the soil resource that a kind of suitable cheapness easily obtains.The peat soil aboundresources in China the Northeast, particularly Jilin Province and Heilungkiang, the development and use of peat resource in recent years also come into one's own, but most of ways be with peat soil as raw material, carry out transporting to after the preliminary working other places and sell, with low content of technology, serious to environmental disruption, economic benefit is little.In world wide, peat about 70% is used for agricultural, wherein mainly is to produce various peat fertilizers.China's peat product has begun to move towards market, is forming scale exploitation and production, also is main as agricultural fertilizer, and the added value of industry is low.
Peat has stronger absorption heavy metal ability.Be rich in organic matter and be one of key character that peat soil distinguishes other type soil.The peat organic composition is based on humic acid, and the content of humic acid in the peat organic matter is higher, generally accounts for peat dry 20%-40%, and some is up to more than 50%.The influence that the height of humic acid content is formed by plant residue of peat is bigger.Under the identical condition of the content of organic matter, the humic acid content of general woody peat is the highest, is generally 40%, and meadow peat takes second place, and its content is between 20%-40%, and the moss peat content is minimum, less than 20%.In addition, humic acid content is relevant with the resolution of peat; Particularly initial period of being decomposed of the residual body of dead plants, humic acid content increases very fast, and along with increasing of decomposing, it is slow that its growth rate becomes.These organic matters are rich in polar functionalities group, as organic acid, ketone, phenol and hydroxyl; Make peat soil have very high-cation exchange and diadochy.For the research that peat soil is used for the heavy metal wastewater thereby adsorbent with use seldom, a little less than Chinese peat soil adsorbed heavy metal basic research, supporting with it treatment process does not almost have, and in a word the peat soil industrial applications is needed systematization in heavy metal containing wastewater treatment research.
Cheap, be easy to get and the adsorption capacity height, make peat become very promising heavy metal absorbent.Because the natural peat self characteristics: mechanical strength is low, strongly hydrophilic, poor chemical stability and the trend of shrinking and/or expanding is arranged, and makes that the treatment effeciency to sewage descends, thereby makes it be not suitable for directly carrying out the processing of sewage.Therefore, when peat is carried out suitable preliminary treatment, can improve the scope of application of peat, be applied in the heavy metal containing wastewater treatment better as adsorbent.Majority studies show that, by suitable pre-treatment such as heating and Chemical Pretreatment, immobilization technology, grain forming, can also make active carbon etc. and make peat have strong and more stable adsorption capacity.Wherein, by chemical method peat is carried out modification and be considered to very effective and feasible.The chemical modification of peat is more with the acid treatment report, and way is after peat is carried out acid treatment, to introduce functional groups such as sulfanilamide (SN) group, carboxylic acid, amine or vinylamine more usually, and the cation of peat or anion exchange capacity are increased substantially.So far, Shang Weijian is based on the report of the adsorbent of alkali treatment modifying peat.
Summary of the invention
The object of the present invention is to provide a kind of adsorption capacity and stability that can improve peat, can obtain the method for preparing modified turf adsorbent of byproduct humic acid simultaneously heavy metal.
To achieve these goals, the technical solution used in the present invention is as follows:
The preparation of modified turf adsorbent:
Peat soil pre-treatment: adopt raw material to be: natural peat.The natural peat drying is dried or air-dry, and go-on-go goes out foreign material, and it is standby to be ground into 1-100 purpose particle.
Preparation method: with arriving pH=10-12 with peat samples in the aqueous slkali, regulating solid-to-liquid ratio with aqueous slkali then is 1: 1-1: 100, the stirring at room certain hour, leave standstill, centrifugal, sediment and supernatant are separated, described drying precipitate, pulverizing, the peat sediment that is the modification processing is the alkali treatment modifying peat absorbent.
The preparation of another kind of modified turf adsorbent:
With arriving pH=10-12 with peat samples in the aqueous slkali, regulating solid-to-liquid ratio with aqueous slkali then is 1: 1-1: 100, the stirring at room certain hour, leave standstill, centrifugal, sediment and supernatant are separated described supernatant, regulate its pH with acid solution, make its pH=1-4, leave standstill behind the certain hour centrifugally, sediment is the adsorbent humic acid.
Wherein: described aqueous slkali is NaOH, KOH, soda lime; Described acid solution is HCl, H
2SO
4, HNO
3, phosphoric acid; Described aqueous slkali or acid solution can be spent acid or salkali waste.
The present invention has following advantage:
The new modified adsorbent of the present invention's preparation is because preparation process is simple, actual operation is strong, the gained modified adsorbent to various heavy metal ion adsorbed capacity further increase, applied widely, can obtain byproduct simultaneously, be the good method of peat absorbent being carried out performance reinforcement and improved properties, specific as follows:
1. to the adsorption capacity height of heavy metal ion.The peat absorbent counterweight metal adsorption that adopts modification of the present invention to handle, its adsorption capacity is the peat height of equal in quality quite.
2. preparation technology is simple, actual operation is strong.Adopt the present invention to strengthen through the mechanical strength and the stability of the modified turf adsorbent after the alkali treatment, it is simple to operate to need not to increase process matched therewith, the scope of application is wider, and natural peat is also very high for the adsorption efficiency of heavy metal, but because mechanical strength own or stability are not high, expand easily in the suction back, adsorption time can not be long, and needing to add corresponding process matched therewith could use.
3. the byproduct humic acid that obtains of the present invention can bring the added value of industry.Usually the content of humic acid of peat itself is very high,
It is the important source material of preparation humic acid, and comprises the part preparation process of humic acid in preparation technology of the present invention, both can obtain modification
Peat can obtain high-quality byproduct humic acid simultaneously, increases on explained hereafter and economic interests.
4. avoid secondary pollution.After adopting modified turf adsorbent of the present invention to dispose of sewage, can be in water residual a large amount of humic acid, make the water variable color, need not simultaneously further to dispose of sewage just can reach discharge standard.
5. the present invention is less demanding to equipment, and technical process is simple, can implement industrialization, has vast market prospect.
6. environmentally friendly, requiring of subsequent treatment is low.Modified turf adsorbent preparation method of the present invention only adds conventional soda acid from natural peat in the preparation process, can not work the mischief to environment; Because residual sewage reaches emission standards, need not subsequent treatment.
Description of drawings
Figure 1A natural peat morphosis figure.
Figure 1B alkali treatment post-modification of the present invention peat morphosis figure.
The specific embodiment
The present invention is described in more detail below by embodiment.
Embodiment 1
The preparation of modified turf adsorbent:
Peat soil pre-treatment: adopt raw material to be: natural peat.The natural peat drying is dried or air-dry, and go-on-go goes out foreign material, and it is standby to be ground into 40 purpose particles.
The preparation method: with among the 1mol/L NaOH and peat (PS) sample to pH=10.0, regulating liquid-solid ratio with 0.1mol/L NaOH then is 1: 1, stirring at room 24h, centrifugation, sediment are surplus materials after the peat extracting for the first time, promptly obtain alkali treatment modifying peat absorbent (APS1), after the APS1 drying, 60 mesh sieves of milling, standby, handle the heavy metal wastewater thereby test under continuous stirring state with 60 order peat.And the microstructure of PS, APS1 absorption behind the heavy metal observed with ESEM.
Simulation heavy metal wastewater thereby initial concentration: Cd:5.6mg/L, Pb:41.4mg/L, Cu:12.8mg/L; Zn:13mg/L.
The preparation of another kind of modified turf adsorbent:
With among the 1mol/L NaOH and peat (PS) sample to pH=10.0, regulating liquid-solid ratio with 0.1mol/L NaOH then is 1: 1, stirring at room 24h, centrifugation, separated liquid supernatant is regulated its pH with 6mol/LHCl, makes its pH=1, place centrifugally after 24 hours, sediment is the adsorbent humic acid.
The result compares:
1. adsorption effect and adsorption capacity change
Relatively PS and APS1 are to being subjected to test mass metal adsorption effect (referring to table 1), PS is more or less the same to the adsorption rate of similar heavy metal with APS1, and peat is by the extract after the NaOH basification, and it is to being subjected to the adsorption capacity of test mass metal ion, compare with original peat, not decline clearly.The adsorption effect of extract is relevant with the heavy metal type, and APS1 is to Cd, and the adsorption effect of Cu and Pb ion is suitable with the peat of identical dosage, but the adsorption effect of Zn slightly is better than peat under the equal conditions.After this shows that peat is by alkali treatment, absorption property to heavy metal changes little, do not influence its result of use in heavy metal containing wastewater treatment, but the byproduct humic acid that in preparation process, obtains, it is industrial of many uses, expanded the purposes of peat, improved the added value of peat, for the industrialized utilization of peat provides good approach.
Peat shows that to the Cd simulated wastewater treatment effect of higher concentration the treatment effect of APS1 has clear superiority than PS, no matter is water outlet effect or adsorption rate and adsorbance (referring to table 2).
Table 1 peat and extract counterweight metal simulated wastewater adsorption rate thereof are relatively
* dosage is 1.0g/L.
Table 2 peat and extract thereof are to high concentrations of Cd simulated wastewater adsorption effect
2. the morphosis of alkali treatment post-modification peat and original peat changes
Figure 1A result shows that have a large amount of laminar structured and undefined structures in the natural peat, institutional framework is loose, has a large amount of spaces, and laminar structured is incomplete humified plant residue, and the cell tissue structure is obvious.
Through APS1 surface topography such as the Fig. 2 (B) that obtains after the alkali treatment.Compare with peat, significant change has taken place in form.What account for key component in the peat is lignin and cellulose, also plays main effect in absorption heavy metal process.After alkali modification is handled, the densification of APS1 surface topography, mechanical strength increases.
Although through the peat microscopic appearance after the suitable alkali treatment certain variation has taken place, but the counterweight Adsorption Properties for Metal Ions does not have much affect, the adsorption effect that is subjected to the test mass metal is compared with natural peat, increasing. alkali treatment peat can obtain humic acid to increase the added value of industry of peat, on the other hand, the compact structure of peat after the alkali treatment, the shortcoming of having avoided original peat suction back volume to expand easily, after also having avoided original peat directly to adsorb, the weakness of the easy variable color of incipient stage water outlet.
Embodiment 2
Difference from Example 1 is:
The preparation of modified turf adsorbent:
The peat soil pre-treatment: it is standby that peat dust is broken into 60 purpose particles.
The preparation method: with arriving pH=11 with peat samples among the 1mol/L KOH, regulating liquid-solid ratio with 0.1mol/L NaOH then is 10: 1.
The preparation of another kind of modified turf adsorbent: with arriving pH=11 with peat samples among the 1mol/L KOH, regulating liquid-solid ratio with 0.1mol/L NaOH then is 10: 1, static separation, and separated liquid supernatant is used 6mol/LH
2SO
4Regulate its pH value, make its pH=3.
Embodiment 3
Difference from Example 1 is:
The preparation of modified turf adsorbent:
The peat soil pre-treatment: it is standby that peat dust is broken into 80 purpose particles.
The preparation method: with arriving pH=11 with peat samples in the 1mol/L soda lime, regulating liquid-solid ratio with 0.1mol/LNaOH then is 50: 1.
The preparation of another kind of modified turf adsorbent: with arriving pH=11 with peat samples in the 1mol/L soda lime, regulating liquid-solid ratio with 0.1mol/L NaOH then is 50: 1, static separation, and separated liquid supernatant is used 6mol/LHNO
3Regulate its pH, make its pH=3.
Embodiment 4
Difference from Example 1 is:
The preparation of modified turf adsorbent:
The peat soil pre-treatment: it is standby that peat dust is broken into 100 purpose particles.
The preparation method: with arriving pH=12 with peat samples among the 1mol/L NaOH, regulating liquid-solid ratio with 0.1mol/LNaOH then is 100: 1.
The preparation of another kind of modified turf adsorbent: with arriving pH=12 with peat samples among the 1mol/L NaOH, regulating liquid-solid ratio with 0.1mol/L NaOH then is static separation in 100: 1, and separated liquid supernatant is used 6mol/LH
3PO
4Regulate its pH, make its pH=4.
Claims (5)
1. the preparation method of a modified turf adsorbent is characterized in that: with the natural peat of removing floating thing and particle is raw material,
With in the aqueous slkali and peat, the pH value of regulating mixed solution is to 10-12, and regulating solid-to-liquid ratio with aqueous slkali then is 1: 1-1: 100, stir, and after leaving standstill, sediment and supernatant to be separated, described drying precipitate, pulverizing are modified turf adsorbent.
2. according to the preparation method of the described modified turf adsorbent of claim 1, it is characterized in that: described separated liquid supernatant, regulate its pH with acid solution, make its pH=1-4, occur sediment and supernatant after leaving standstill, remove supernatant, obtaining sediment is humic acid.
3. according to the preparation method of the described modified turf adsorbent of claim 1, it is characterized in that: described aqueous slkali is NaOH, KOH, soda lime.
4. according to the preparation method of the described modified turf adsorbent of claim 2, it is characterized in that: described acid solution is HCl, H
2SO
4, HNO
3, phosphoric acid.
5. according to the preparation method of claim 3 or 4 described modified turf adsorbents, it is characterized in that: described aqueous slkali or acid solution can be spent acid or salkali waste.
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| CN101973619B (en) * | 2010-09-17 | 2012-05-30 | 昆明理工大学 | Method for treating waste water from copper smelting by using modified ardealite |
| CN102336915B (en) * | 2011-08-12 | 2013-05-22 | 祁长喜 | Method for producing humate from base alkaline waste liquid |
| RU2497759C2 (en) * | 2011-09-26 | 2013-11-10 | Учреждение Российской академии наук Институт геологии и минералогии им. В.С. Соболева Сибирского отделения РАН (Институт геологии и минералогии СО РАН, ИГМ СО РАН) | Method of purifying industrial sewages from heavy metals |
| EP2742996A1 (en) | 2012-12-17 | 2014-06-18 | Latvijas Universitate | Sorbents and method for synthesis of sorbents intended for removal of radionuclides and toxic trace elements from water |
| CN104888734A (en) * | 2015-05-21 | 2015-09-09 | 安徽凤凰滤清器股份有限公司 | Green environmentally-friendly modified volcanic rock adsorbent |
| CN105419804B (en) * | 2015-10-30 | 2018-09-25 | 深圳市铁汉生态环境股份有限公司 | The renovation agent and a kind of restorative procedure of fluoride pollution soil of a kind of fluoride pollution soil |
| CN105885854A (en) * | 2016-04-12 | 2016-08-24 | 太原师范学院 | Remediation agent for heavy metal contaminated soil |
| CN106345431A (en) * | 2016-08-26 | 2017-01-25 | 夏百庆 | Soil heavy mental absorbing agent |
| CN107189790A (en) * | 2017-07-25 | 2017-09-22 | 舒城县舒茶九六茶场 | A kind of alkaline soil improver |
| CN112011066B (en) * | 2019-05-29 | 2022-04-01 | 三通生物工程（潍坊）有限公司 | Production process of high-purity humic acid |
| CN110746613B (en) * | 2019-10-25 | 2021-08-24 | 郑州大学 | Functionalized ore source organic medicament and use method thereof |
| CN118179446B (en) * | 2024-05-15 | 2024-07-16 | 四川大学 | Method for simultaneously preparing humic acid liquid fertilizer and heavy metal adsorbent by using furfural residues |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS49129686A (en) * | 1973-04-18 | 1974-12-12 | ||
| WO1994022768A1 (en) * | 1993-04-02 | 1994-10-13 | Archaeus Technology Group Limited | Removal of manganese from water |
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2006
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS49129686A (en) * | 1973-04-18 | 1974-12-12 | ||
| WO1994022768A1 (en) * | 1993-04-02 | 1994-10-13 | Archaeus Technology Group Limited | Removal of manganese from water |
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