CN104415735A - Modified coke for treating aged landfill leachate, preparation method of modified coke and treatment method of aged landfill leachate - Google Patents
Modified coke for treating aged landfill leachate, preparation method of modified coke and treatment method of aged landfill leachate Download PDFInfo
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- CN104415735A CN104415735A CN201310382119.5A CN201310382119A CN104415735A CN 104415735 A CN104415735 A CN 104415735A CN 201310382119 A CN201310382119 A CN 201310382119A CN 104415735 A CN104415735 A CN 104415735A
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- coke
- modified coke
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- modified
- landfill leachate
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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
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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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
- B01J20/305—Addition of material, later completely removed, e.g. as result of heat treatment, leaching or washing, e.g. for forming pores
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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
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
-
- 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
- B01J2220/42—Materials comprising a mixture of inorganic materials
Abstract
The invention relates to the fields of environmental chemistry and water treatment engineering, and in particular relates to a modified coke for treating aged landfill leachate, a preparation method of the modified coke and a treatment method of the aged landfill leachate. The industrial coke having porosity, adsorbability and flammability is taken as a carrier, and alkali/acid activation is combined with a surface chemical compound modification technology of Cu<2+> and dibutyl phthalate polycondensate, so that the modified coke material suitable for adsorbing, purifying and modifying the aged landfill leachate can be prepared. The modified coke not only has an obvious selective adsorption and desorption effect for organic pollutants and ammonia nitrogen molecules in sewage, but also can be stilled recycled as fuel after being used, so that the problem of aftertreatment of waste residue does not exist.
Description
Technical field
The present invention relates to Environmental Chemistry and engineering of water treatment field, particularly relate to rubbish aging percolate adsorption treatment technology and material, be specifically related to a kind of modified coke for the treatment of aging percolate and preparation method thereof and processing method.
Background technology
Common percolate is the very complicated high concentrated organic wastewater of a kind of composition, its CODcr, the concentration of the pollutant such as ammonia nitrogen and heavy metal ion is all significantly higher than general municipal sewage, common biochemical processing method is adopted to make it standard water discharge, must other physical-chemical processing method additional.
Sensu lato aging percolate is included in the chronic percolate of landfill yard garbage loading embeading, and common percolate in water treatment plant through the water outlet non-up to standard of biochemical degradation process, its common ground is all to live through relatively fully and microbial degradation process completely, even if extend the biochemical reaction time again or their CODcr of change condition no longer occurs to change significantly.According to current biochemical processing process, the CODcr of percolate is generally maximum can only be down to about 500 ~ 600mg/L.Its reason is, microbial metabolic products in percolate, the degradation product of organic pollutant molecule, ammonia nitrogen in high density, and C/N is than the inhibitory action that increases gradually microbial activity of lacking of proper care, and when BOD5/CODcr is less than 0.3, the biodegradability of water is close to the limit.
Process for aging percolate must adopt other method, comprises advanced oxidation (AOP) and reactive adsorption treatment technology etc.
Photochemical catalytic oxidation, CWO, Fenton oxidation, active carbon-H2O2 catalytic oxidation, electrochemical oxidation, and microwave, ultrasonic wave, the contaminant molecule degradation techniques such as plasma all belong to AOP method class, and the major defect of this method is processing cost, and all higher to equipment and technology conditional request.
For reactive adsorption technology, about the existing disclosed report of the patented technology processing common percolate, as CN1751992, " a kind of modified alta-mud for the treatment of percolate and manufacture method thereof " disclosed in 29 days March in 2006, CN1680016, " method that epidesmine removes organic matter ability in percolate is improved " disclosed in 12 days October in 2005, CN1730415, " garbage leachate treatment process being core with diatomite and UASB " disclosed in 8 days February in 2006, CN1607009, disclosed in 20 days April in 2005, " sodium humate/potassium is used for rubbish deodorizing as biochemical deodorant, deodorant preparation and deodorizing method " etc.But their ubiquitous problems are the how post processings of inefficacy absorption carrier, and even regeneration then will increase operation and processing cost, directly abandon or landfill if do not process, and pollutant is transferred winding border again.
About the open source literature report of reactive adsorption method treatment of aged percolate is comparatively rarely seen.
Summary of the invention
Object of the present invention is intended to the porous based on industrial coke, adsorptivity and flammable feature, by chemically composited modification technology, obtain a kind of efficient adsorption modified coke material that can be used in aging landfill leachate treatment, solve the post processing problem of traditional sorbing material simultaneously.
Another object of the present invention is the preparation method providing a kind of modified coke material of the present invention.
A further object of the invention is the processing method providing a kind of modified coke of the present invention for aging percolate.
In order to solve the problem of prior art, technical scheme of the present invention is as follows:
For the treatment of a preparation method for the modified coke of aging percolate, said method comprising the steps of:
(1) activation of coke: coke is ground into particulate powders shape, cross the sieve in 150 ~ 200 order apertures, the powder sig water that sieves boils, cooling, filters, being added under conventional temperature by the powder leached is dissolved with in the dilute nitric acid solution of mantoquita in advance, soak reaction, filter, the powder leached is washed to pH for neutral, drying, obtains activated charcoal.
(2) modification of activated charcoal: add activated charcoal, constant temperature in the solution of Butyl Phthalate condensation polymer, slowly stir, soaks reaction a period of time, filters, dry, obtains modified coke.
Preferably, the concentration of the sig water described in step 1 is 2 ~ 5%, and described boiling time is 15min, described in be dissolved with in the dilute nitric acid solution of mantoquita, concentration mantoquita is 3 ~ 8% by mass percentage, and dust technology is
3 ~ 10%, the described immersion reaction time is 2h, and described baking temperature is 105 DEG C.
Preferably, sig water is NaOH.
Preferably, the preparation method of the solution of the Butyl Phthalate condensation polymer described in step 2 is: by rate of charge, getting Butyl Phthalate (technical pure level) with the volume ratio of ethanol (technical pure level) is: 1:4.5 ~ 1:5.0, mixing, stirring at normal temperature is to dissolving, add appropriate ferric nitrate wherein again, adjust pH=2-3 with dust technology, stir 30 minutes under normal temperature.
Preferably, the thermostat temperature described in step 2 is 50 DEG C, and the reaction time is 4h, and baking temperature is 105 DEG C.
Preferably, the coke described in step 1 is the ature of coal coke of metallurgical industry.
Preferably, the mantoquita described in step 2 is can copper nitrate, copper chloride, the mixture of any one or several in copper sulphate.
Certainly, activation and the modification of described coke are not limited thereto, and those skilled in the art can according to actual conditions and needs, the process conditions of the reasonably activation of adjustment coke and modification, the temperature of such as constant temperature, reaction time, dry temperature etc.
A kind of modified coke, described modified coke is obtained by preparation method described above.
Modified coke, for the treatment of a method for aging percolate, adopts reactive adsorption bed method or reactor stirring and adsorbing method.
Described reactive adsorption bed method refers to that aging percolate flows out from the other end after flowing into from one end of adsorption bed again, the method that water will be controlled by flow pump according to the pollution level of water quality by the flow of adsorption bed and holdup time; Described reactor stirring and adsorbing method refers to that modified coke and aging percolate are in reaction vessel, the contact and promotion contaminant molecule and the adsorption process of particle on coke modification surface that increase the two is uniformly mixed, the method that its treatment effeciency will decide by controlling the factor such as mixing speed and reaction time according to the pollution level of water quality by continuous print.
Therefore the technical scheme of the application embodiment of the present invention, has following beneficial effect:
1) have employed alkali cementing and close acid-soluble multiplicity reactivation technology, eliminate the organic matter of coal tar, inorganic acid alkali DDGS impurity, greatly expanded the duct of coke and absorption specific surface, increased adsorption capacity and ability.
2) have employed Cu2+ and the chemically composited modification technology of Butyl Phthalate condensation polymer on activated charcoal surface, significantly enhance absorption carrier to the selective adsorption capacity of ammonia nitrogen and organic pollutant molecule and saturated extent of adsorption.
3) can be burnt together together with by the organic pollution of enrichment with the absorption carrier coke crossed, do not increase the cost of absorption carrier, resource is used appropriately, and solves the post processing problem of traditional absorption carrier simultaneously.
4) incinerate after industrially often directly being evaporated by aging percolate, energy consumption and disposal cost are very high, and the present invention can solve the large problem of aging landfill leachate treatment difficulty separately or in conjunction with other further treatment technique.
Detailed description of the invention
Describe the present invention in detail below in conjunction with specific embodiment, be used for explaining the present invention in this illustrative examples of the present invention and explanation, but not as a limitation of the invention.
Embodiment 1, the preparation of modified coke product
Get after industrial coke is ground into particulate powders shape and cross 200 mesh sieves, powder 1kg after screening is put in the 5% NaOH sig water heating kettle of 2L and boils 15 minutes, cooling, filter.
Being put into by coke powder after soda boiling being dissolved with concentration is in advance in the dilute nitric acid solution stirring enamel reaction still of 3 ~ 10% of 3 ~ 8% copper nitrates, soak under normal temperature after 2 hours and filter, be separated, wash with water to pH for neutral, drying box dry for standby at being placed in 105 DEG C.
Getting Butyl Phthalate (technical pure level) 1.7L joins in the reactor being loaded with 8L ethanol (technical pure level) in advance, stirring at normal temperature adds ferric nitrate 30g after dissolving, pH=2-3 is adjusted with dust technology, stir under normal temperature after 30 minutes and in reactant liquor, add activated charcoal 1kg again, at 50 DEG C, slow stirring reaction is after 4 hours, filter, dry at 105 DEG C and obtain modified coke product.
Embodiment 2, the process test of different aging percolate
It is in the Filter column of 20cm that the modified coke product 1kg obtained by above-mentioned steps is put into diameter, tamps.
The pH of 20L percolate in head tank is adjusted to about 8, and then it flowed into by upper catheter, flowed out by bottom conduit after slow transitting through coke gasification reaction adsorption column, flow velocity is controlled by flow valve, and flow is 0.8m/h.Percolate takes from the exit of refuse landfill and Refuse Leachate Treatment Plant biochemical treatment operation respectively.Experimental test the results are shown in Table 1.
Result shows, through the CODcr of modified coke to the aging percolate after different biological mode degraded, the water quality index such as NH+4-N and colourity all has a significant effect.Useless coke after saturated adsorption still can as fuel recovery, without post processing problem.
Table 1 modified coke adsorption column treatment of aged percolate result of the test
Above the technical scheme that the embodiment of the present invention provides is described in detail, apply specific case herein to set forth the principle of the embodiment of the present invention and embodiment, the explanation of above embodiment is only applicable to the principle helping to understand the embodiment of the present invention; Meanwhile, for one of ordinary skill in the art, according to the embodiment of the present invention, detailed description of the invention and range of application all will change, and in sum, this description should not be construed as limitation of the present invention.
Claims (10)
1. for the treatment of a preparation method for the modified coke of aging percolate, it is characterized in that: said method comprising the steps of:
(1) activation of coke: coke is ground into particulate powders shape, cross the sieve in 150 ~ 200 order apertures, the powder sig water that sieves boils, cooling, filters, being added under conventional temperature by the powder leached is dissolved with in the dilute nitric acid solution of mantoquita in advance, soak reaction, filter, the powder leached is washed to pH for neutral, drying, obtains activated charcoal.
(2) modification of activated charcoal: add activated charcoal in the solution of Butyl Phthalate condensation polymer, Slow Isothermal stirs, and soaks reaction a period of time, filters, dry, obtains modified coke.
2. the preparation method of modified coke according to claim 1, it is characterized in that: the concentration of the sig water described in step 1 is 2 ~ 5%, described boiling time is 15min, describedly be dissolved with in the dilute nitric acid solution of mantoquita, concentration mantoquita is 3 ~ 8% by mass percentage, dust technology is 3 ~ 10%, and the described immersion reaction time is 2h, and described baking temperature is 105 DEG C.
3. the preparation method of modified coke according to claim 2, is characterized in that: described sig water is NaOH.
4. the preparation method of modified coke according to claim 1, it is characterized in that: the preparation method of the solution of the Butyl Phthalate condensation polymer described in step 2 for getting Butyl Phthalate (technical pure level) with the volume ratio of ethanol (technical pure level) is: 1:4.5 ~ 1:5.0, mixing, stirring at normal temperature is to dissolving, add appropriate ferric nitrate wherein again, adjust pH=2-3 with dust technology, stir 30 minutes under normal temperature.
5. the preparation method of modified coke according to claim 1, is characterized in that: the thermostat temperature described in step 2 is 50 DEG C, and the reaction time is 4h, and baking temperature is 105 DEG C.
6. the preparation method of modified coke according to claim 1, is characterized in that: the coke described in step 1 is the ature of coal coke of metallurgical industry.
7. the preparation method of modified coke according to claim 1, is characterized in that: the mantoquita described in step 2 is the mixture of any one or several in copper nitrate, copper chloride, copper sulphate.
8. a modified coke, is characterized in that: described modified coke is obtained by the preparation method described in any one of claim 1 ~ 7.
9. modified coke is for the treatment of a method for aging percolate, it is characterized in that: adopt reactive adsorption bed method or reactor stirring and adsorbing method.
10. modified coke according to claim 9 is for the treatment of the method for aging percolate, it is characterized in that: described reactive adsorption bed method refers to that aging percolate flows out from the other end after flowing into from one end of adsorption bed again, the method that water will be controlled by flow pump according to the pollution level of water quality by the flow of adsorption bed and holdup time; Described reactor stirring and adsorbing method refers to that modified coke and aging percolate are in reaction vessel, the contact and promotion contaminant molecule and the adsorption process of particle on coke modification surface that increase the two is uniformly mixed, the method that its treatment effeciency will decide by controlling the factor such as mixing speed and reaction time according to the pollution level of water quality by continuous print.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310382119.5A CN104415735A (en) | 2013-08-28 | 2013-08-28 | Modified coke for treating aged landfill leachate, preparation method of modified coke and treatment method of aged landfill leachate |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201310382119.5A CN104415735A (en) | 2013-08-28 | 2013-08-28 | Modified coke for treating aged landfill leachate, preparation method of modified coke and treatment method of aged landfill leachate |
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| CN104415735A true CN104415735A (en) | 2015-03-18 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106512934A (en) * | 2016-11-09 | 2017-03-22 | 广州城辉环保科技有限公司 | Adsorbent for advanced treatment on landfill leachate and preparation method thereof |
| CN113731360A (en) * | 2021-09-03 | 2021-12-03 | 天津市政工程设计研究总院有限公司 | Zeolite-active coke porous wear-resistant adsorption material and preparation method thereof |
-
2013
- 2013-08-28 CN CN201310382119.5A patent/CN104415735A/en not_active Withdrawn
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106512934A (en) * | 2016-11-09 | 2017-03-22 | 广州城辉环保科技有限公司 | Adsorbent for advanced treatment on landfill leachate and preparation method thereof |
| CN113731360A (en) * | 2021-09-03 | 2021-12-03 | 天津市政工程设计研究总院有限公司 | Zeolite-active coke porous wear-resistant adsorption material and preparation method thereof |
| CN113731360B (en) * | 2021-09-03 | 2023-06-06 | 天津市政工程设计研究总院有限公司 | Zeolite-active Jiao Duokong wear-resistant adsorption material and preparation method thereof |
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Application publication date: 20150318 |