CN109200998A - It discarded active carbon, preparation method in biological activated carbon method advanced water treatment technique and reapplies - Google Patents

It discarded active carbon, preparation method in biological activated carbon method advanced water treatment technique and reapplies Download PDF

Info

Publication number
CN109200998A
CN109200998A CN201811047088.7A CN201811047088A CN109200998A CN 109200998 A CN109200998 A CN 109200998A CN 201811047088 A CN201811047088 A CN 201811047088A CN 109200998 A CN109200998 A CN 109200998A
Authority
CN
China
Prior art keywords
water
active carbon
discarded
activated carbon
technique
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201811047088.7A
Other languages
Chinese (zh)
Other versions
CN109200998B (en
Inventor
董丽华
刘婧
侯立安
顾平
张光辉
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tianjin University
Original Assignee
Tianjin University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Tianjin University filed Critical Tianjin University
Priority to CN201811047088.7A priority Critical patent/CN109200998B/en
Publication of CN109200998A publication Critical patent/CN109200998A/en
Application granted granted Critical
Publication of CN109200998B publication Critical patent/CN109200998B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • 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
    • 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
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/102—Carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/60—Heavy metals or heavy metal compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/06—Polluted air
    • 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
    • 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

Abstract

The present invention discloses a kind of discarded active carbon in biological activated carbon method advanced water treatment technique, preparation method and reapplies.Waste biomass active carbon directly to reapply method include sampling and testing, sample characterization, adsorption test, dissolution test and practical application step.The discarded activated carbon application is in water process or air cleaning.The present invention is not required to save the renewable sources of energy to discarded regenerating active carbon or pretreatment, realize resource utilization；Direct reuse can make BAC technique have both absorption, biodegrade and removing heavy metals function in sampling water factory；The direct of discarded active carbon recycles the practical factor for being able to fully consider water process, achievees the purpose that make the best use of everything and economize on resources to the greatest extent.Compared with activated carbon modified, the product cost is low, environmental-friendly, good in economic efficiency and economize on resources, to pushing social sustainable development to have positive meaning.

Description

Discarded active carbon, preparation method in biological activated carbon method advanced water treatment technique And it reapplies
Technical field
The present invention relates to the recycling fields of discarded active carbon, are related to biological activated carbon (BAC) method advanced water treatment work The removing heavy metals that active carbon is discarded in skill reapply field, and in particular in biological activated carbon method advanced water treatment technique It discards active carbon, preparation method and reapplies.
Background technique
With the promulgation and implementation of " ten, water " and new national standard " standards for drinking water quality " (GB5749-2006), Country is increasingly stringenter the water standard of drinking water.Traditional common process is difficult to effectively remove chemical oxygen consumption (COC) (CODMn)、 Ammonia nitrogen, micro-content organism, cause a disease the pollutants such as protozoon, can not solve the contradiction between pollution of waterhead and water standard raising, more It is difficult to successfully manage sudden pollution of waterhead event.Due to BAC process (BAC or O3/ GAC) can effectively remove it is above-mentioned Pollutant, therefore become particularly significant and practicable advanced water treatment technique.BAC is for the odor in water[1], it is micro- Pollutant[2], natural organic matter[3], ammonia nitrogen[4], disinfection by-products formation potential[5], emerging pollutant[6], it is incretion interferent, anti- The organic pollutants such as raw element, humic acid[7,8]There is preferable removal effect.Korotta-Gamage and Sathasivan[8]It is right BAC technique since 2016 is summarized, and thinks that BAC technique is one of most promising water treatment technology.Change technique Water treatment efficiency is improved by the synergistic effect of biodegrade and activated carbon adsorption, the service life for extending active carbon, is reduced Cost of water treatment is rapidly developed in Water purification industry[9].It is widely applied in developed countries and regions such as Europe, America and Japan at present And tend to be mature[10,11], can be by active carbon service life from 3 using BAC Technology (BAC) according to the experience of Germany It extends within~6 months 2~3 years；If using permanganate index as major pollutants in raw water, in the situation that influent quality is suitable Under, active carbon can be used 6 years or more[12]。
China begins one's study BAC technique from the 1980s, and the technology is also in the advanced water treatment in China at present It is applied widely in the process and obtains good result[13-16].The domestic water factory's throughput for using BAC technique at present Have been approached 25,000,000 m3/ d accounts for about surface water factory processing capacity 20%, as the ground such as Shanghai, Jiangsu are carried out in an all-round way to water depth Processing, scale will all suffer from trend is continued growing, especially using surface water as the water treatment plant at water source and increase active carbon suction The urgent need of attached technique.While water treatment plant large-scale use BAC technique, discarded active carbon (" danger will be brought It is useless ") replacement or regeneration issues, ground however, being concentrated mainly on the mechanism such as absorption, biodegrade to the research of BAC technique at present In terms of studying carefully with application study, and for discarding research that active carbon rationally reapplies then rarely found report in BAC.Currently, state Interior earliest a batch uses the advanced water treatment factory of the technique, is faced with this problem, and is directed to what water factory's charcoal was proposed " Drinking Water water purification station-service coaly activated carbon " CJ/T345-2010 standard makes any regulation not to this, therefore, also compels Being essential will revise, that is, need to indicate an outlet to used discarded active carbon: rationally reapplying or become " dangerous waste ".
University Of Tianjin as CJ/T345-2010 standard revision editorial member in November, 2017 to Jiangsu, Shanghai, Zhejiang It is investigated etc. several representational water factories using BAC technique, wherein only only a few water factory has carried out active carbon again Raw reuse, the discarded active carbon of other water factories are not recycled reasonably.Undoubtedly, it discards active carbon and (is considered as " danger It is useless ") random disposition and use will cause serious environmental problems and secondary pollution risk, while and resource huge wave Take.
For this problem in the urgent need to address, discarded active carbon sample of the project applicant to part BAC technique water factory Product have carried out reapplying research, and undoubtedly this will continue to be back to water factory or reasonably reapply to provide new thinking for it, and will Theory and technology support is provided for the further development of BAC technique.
Summary of the invention
It is an object of the invention to overcome above-mentioned the deficiencies in the prior art, propose a kind of biological activated carbon method to water depth It discarded active carbon, preparation method in treatment process and reapplies, is ground by discarding reapplying for active carbon to BAC technique Study carefully, effectively solve the problems, such as the random disposition of discarded active carbon (" dangerous waste ") and use, realizes sustainable, the recycling of resource.
First technical solution of the invention is the discarded active carbon in biological activated carbon method advanced water treatment technique, The surface characteristic of used biological activated carbon becomes alkalinity by acidity；The used biological activated carbon be it is to be replaced or Regeneration.
PH < 7 or Zeta potential≤0 of the discarded active carbon of the present invention or the content of its surface acidity functional group are higher than surface The content of basic functionality.
Second technical solution of the invention is the discarded active carbon system in biological activated carbon method advanced water treatment technique Preparation Method includes the following steps:
(1) acquire representational discarded activated carbon sample: its source include in the activated carbon adsorption tank of BAC technique or The place for storing discarded active carbon is taken out；
(2) using new active carbon as reference, surface characteristic characterization is carried out to discarded activated carbon sample, using two or more sides The characterization that method is verified each other；
(3) pH of active carbon is discarded less than 7 or content >=surface alkalinty of current potential≤0 zeta or surface acidity functional group The content of functional group；
(4) discard the research that reapplies of activated carbon sample: direct reuse is in sampling water factory or is back to using same water Source, same process water supply plant；If going the occasion of removing heavy metals for other, need to carry out organic matter dissolution to water body to be measured Test.
Step (1) acquisition strategies of the present invention specifically:
(a) active carbon is discarded still in charcoal pond, then collects active carbon according to the method for the Appendix B of AWWA B605-2007 Representational used AC sample in pond；
(b) active carbon takes out from charcoal pond and is stored in elsewhere, then according to " Drinking Water water purification station-service coal quality Active carbon " method as defined in (CJT 345-2010) is sampled.
The original activity charcoal or use same technique that new active carbon is loaded for the water factory in step (2) of the present invention The active carbon of same batch production.
Step (2) characterizing method of the present invention includes: pH test, zeta current potential, surface polarity component, surface acidity With at least two in basic functionality (FT-IR analysis, Boehm titration) measurement and XPS elemental analysis.
It is back to sampling water factory in step (4) of the present invention or is back to the water supply using same water source, same process Factory is using reuse two ways after direct reuse or taking-up natural air drying.
The dissolution test of organic matter is dissolved in water body front and back DOC to be measured by discarded active carbon in step (4) of the present invention Or TOC difference characterizes；Specific value regard the property (recycled water, waste water etc.) of water body to be measured according to corresponding discharge standard and It is fixed.
Third technical solution of the invention is the discarded active carbon in biological activated carbon method advanced water treatment technique It reapplies, is applied to water process or air cleaning.
The present invention have compared with the existing technology it is following the utility model has the advantages that
1, the present invention is that the active carbon that water factory discards has found new outlet, is directly used in the removal of heavy metal in water, saves Regeneration cost, the secondary pollution problem for avoiding discarded active carbon, economize on resources, sustainable development.
2, the waste biomass active carbon direct reuse in the present invention in sampling water factory or is back to using same water source, phase With the water supply plant of technique, regeneration or other re-treating process are not needed not only but also do not introduce any other chemical substance.
3, the discarded active carbon in the present invention is used in BAC technique, so that BAC technique be made to have both adsorption function, biology drop Solve and go removing heavy metals function；This is of great significance for further understanding the development of BAC mechanism and BAC technique；With going The BAC water treatment technology of removing heavy metals function provides standby guarantee for the emergency processing of water factory, gives full play to active carbon to the greatest extent Function and the purpose that economizes on resources.
4, result of the present invention will be for using active carbon new and old in the water factory of BAC technique collocation use and discarded active carbon Reapplying for (dangerous waste) provides theory and technology support.
5, the present invention is at low cost, environment friendly, good in economic efficiency and economize on resources, to pushing social sustainable development With positive meaning.
Detailed description of the invention
Fig. 1 is the adsorption capacity of SBAC-5, SBAC-6 and SBAC-7 to Pb (II):
(a) initial concentration (4.45mg/L) and ultimate density detect SBAC-5, SBAC-6 and SBAC-7 to absorption Pb (II) ability；
(b) SBAC-5, SBAC-6 and SBAC-7 are carried out under different initial concentrations (2.45-8.08mg/L) to Pb (II) Adsorption experiment；
Fig. 2 is the FT-IR atlas analysis of SBACs sample before and after adsorbing Pb (II):
(a) FT-IR atlas analysis before active carbon and three kinds of waste biomass activated carbon adsorptions is not used
(b) tri- kinds of SBAC-5, SBAC-6 and SBAC-7 discarded activated carbon adsorption Pb (II) FT-IR atlas analysis afterwards
Fig. 3 adsorbs the O1s map swarming analysis of SBACs sample before and after Pb (II).
Specific embodiment
Below by specific embodiments and the drawings, the present invention is further illustrated.The embodiment of the present invention be in order to So that those skilled in the art is more fully understood the present invention, any limitation is not made to the present invention.
BAC(O3/ GAC) technique will be in some months or interior completion for more time is from new GAC to biological activated carbon (BAC) Transformation, since it integrates ozone oxidation, absorption and biological degradation function, BAC technique has become most promising water process One of.Although BAC technique effectively extends the service life of active carbon compared to individual activated carbon adsorption, BAC also has Service life, when its effluent quality does not reach requirement, it is still desirable to regeneration be carried out to used active carbon or more renewed Active carbon, that is, face the discarded active carbon of BAC technique reapplies problem.
BAC technique is famous with its excellent absorption and biological degradation function, but it goes removing heavy metals function seldom to be reported Road.This is because active carbon, which can be divided into, activates two classes under low temperature (200-400 DEG C) and higher temperatures (800-1000 DEG C), the former It usually will form acidic surface site, alkali mainly adsorbed from solution, there is hydrophily, and there is negative zeta current potential；The latter The surface site of alkalinity will be formed, and positive zeta current potential is presented[17].That is, one piece of coin has two sides, although in BAC technique The AC used shows the superior absorption property to organic pollutant, but determines its requirement to high-temperature activation, and then cause The development in its basic surface site, thus its to the adsorption capacity of metal ion from generally to down to nothing[18].Due to absorption Efficiency depends on the chemical property of adsorbate and sorbent material, specific surface area, aperture structure etc.[19], many is about activity Charcoal removes the research of metal from aqueous solution, is all the acidic surface function by modification to increase its carbon surface Group[20], wherein the oxidation processes of AC are very beneficial for improving the absorption of metal ion, this is the skill of most study so far Art[21]Although specific processing is conducive to enhance its ability for absorbing metal ion, the cost of water treatment system will increase, And the significant absorption for damaging organic matter in aqueous solution[22,23]。
Although the AC used in BAC technique due to lacking acidic surface functional groups without going removing heavy metals ability, But three main process occurred in BAC technique: ozone oxidation, absorption and biodegrade[24], it is directed to complicated object Reason, chemistry and biological effect[25-29].The technique of above-mentioned long-term complexity will have an impact the surface nature of AC, to change Its surface nature, i.e. BAC technical process will increase its acidic surface functional groups, to assign used active carbon removal weight The new function of metal.
Present invention employs following committed steps:
(1) in operating parameter (influent quality, water, the O for collecting BAC technique3Dosage etc.) on the basis of, to using The active carbon (SBAC) crossed is sampled；
(2) using new AC as reference, at least two kinds of surfaces characteristic verified each other is carried out to samples taken and are characterized, including pH Value, zeta current potential, surface functional group (FTIR or Boehm titration), surface polarity component analysis, element composition and its chemical shape State analysis etc.；
(3) as used AC its pH less than 7 or content >=surface alkali of current potential≤0 zeta or surface acidity functional group When property functional group content, which both has the function of removing heavy metals；
(4) the used AC in part can continue to stay in for removing removing heavy metals in active carbon charcoal adsorption tank, to make BAC Technique has both absorption, biodegrade and goes removing heavy metals function, or the processing of the heavy metal as other occasions.
Result of the invention will be for using active carbon new and old in the water factory of BAC technique collocation use and discarded active carbon Reapplying for (dangerous waste) provides theory and technology support.The undoubtedly active carbon that this new application direction will be discarded for water factory It reapplies and finds new outlet, be directly used in the removal of heavy metal in water, save regeneration cost, avoid discarded active carbon Secondary pollution problem economizes on resources, sustainable development.
Discarded active carbon in biological activated carbon method advanced water treatment technique, the surface of used biological activated carbon Characteristic becomes alkalinity by acidity；The used biological activated carbon is to be replaced or regeneration.
The present invention discards pH < 7 of active carbon or Zeta potential is less than 0 or the content of its surface acidity functional group is higher than table The content of face basic functionality.
And the discarded method for preparation of active carbon in biological activated carbon method advanced water treatment technique, include the following steps:
(1) acquire representational discarded activated carbon sample: its source include in the activated carbon adsorption tank of BAC technique or The place for storing discarded active carbon is taken out；
Acquisition strategies specifically:
(a), active carbon is discarded still in charcoal pond, then collects active carbon according to the method for the Appendix B of AWWA B605-2007 Representational used AC sample in pond；
(b), active carbon takes out from charcoal pond and is stored in elsewhere, then according to " Drinking Water water purification station-service coal quality Active carbon " method as defined in (CJT 345-2010) is sampled.
(2) using new active carbon as reference, surface characteristic characterization is carried out to discarded activated carbon sample, using two or more sides The characterization that method is verified each other:
New active carbon is the water factory original activity charcoal loaded or the activity of the same batch production of the same technique of use Charcoal；
Characterizing method includes: pH test, zeta current potential, surface polarity component, surface acidity and basic functionality (FT-IR Analysis, Boehm titration) it measures and at least two in XPS elemental analysis；
Using new active carbon as reference, to index such as pH relevant to absorption heavy metal, isoelectric point, surface polarity component (GC-MS), surface functional group (FT-IR, Boehm titration), elemental analysis etc. are characterized: at least using above-mentioned characterizing method In two methods characterization that active carbon is verified each other；Wherein pH refers to the pH of discarded active carbon, according to GB/T 7702.16-1997 or ASTM D3838-05 (2017) the method is tested；Isoelectric point refers to discarded activated carbon surface electricity PH when lotus is zero；Surface functional group can be measured by FT-IR or Boehm titration；Elemental analysis passes through XPS photoelectricity Sub- energy spectrum analysis carries out.
(3) pH of active carbon is discarded less than 7 or content >=surface alkalinty of current potential≤0 zeta or surface acidity functional group The content of functional group；
(4) discard the research that reapplies of activated carbon sample: direct reuse is in sampling water factory or is back to using same water Source, same process water supply plant；If going the occasion of removing heavy metals for other, need to carry out organic matter dissolution to water body to be measured Test: be back to sampling water factory or be back to using same water source, same process water supply plant using direct reuse or take out from Reuse two ways after so air-drying；The dissolution test of organic matter is dissolved in water body front and back DOC or TOC to be measured by discarded active carbon Difference characterizes；Specific value is depending on the property (recycled water, waste water etc.) of water body to be measured is according to corresponding discharge standard.
Embodiment 1: using 5 years discarded activated carbon samples, it is derived from certain water factory for using BAC advanced water treatment technique Activated carbon adsorption tank.The factory uses " coagulation+precipitating+BAC (O3/ GAC)+filtering " combination water treatment technological process, life Production capacity power is (200,000m3/ d), AC air-land combat EBCT are 14 minutes, and AC height are 2.0 meters, ozone Dosage is 2.0-2.5mg/L, and time of contact is 24 minutes.The water source of water factory comes from the river HP, and the average effluent quality of water factory is better than Chinese water quality standard for drinking water, average turbidity < 0.15NTU, CODMn< 1.50mg/L, NH3-N<0.02mg/L。
Embodiment 2: using 6 years discarded activated carbon samples, it is derived from certain water factory for using BAC advanced water treatment technique Activated carbon adsorption tank.The factory uses " coagulation+precipitating+filtering+BAC (O3/ GAC) " combination water treatment technological process, life Production capacity power is (260,000m3/ d), AC air-land combat EBCT are 14 minutes, and AC height are 1.8 meters, ozone Dosage is 1.8-2.0mg/L, and time of contact is 20 minutes.The water source of water factory comes from the river CJ, and the average effluent quality of water factory is better than Chinese water quality standard for drinking water.
Embodiment 3: being the water factory that certain uses BAC advanced water treatment technique using 7 years discarded activated carbon samples, and For the waste sample for having taken out and having air-dried.The water factory uses " coagulation+precipitating+filtering+BAC (O3/ GAC) " combination water at Process flow is managed, production capacity is (100,000m3/ d), AC air-land combat EBCT are 14 minutes, AC height Degree is 2.0 meters, ozone dosage 2.0-2.5mg/L, and time of contact is 22 minutes.The water source of water factory comes from the river HP, and water factory puts down Equal effluent quality is better than Chinese water quality standard for drinking water.
Embodiment 4: using 3 years discarded activated carbon samples, being derived from south, certain used BAC advanced water treatment technique Water supply plant.The factory uses " coagulation+precipitating+filtering+BAC (O3/ GAC)+ultrafiltration " combination water treatment technological process, life Production capacity power is (150,000m3/ d), AC air-land combat EBCT are 12 minutes, and AC height are 1.8 meters, ozone Dosage is 2.0-2.5mg/L, and time of contact is 20 minutes.The water source of water factory comes from certain lake water, and the average effluent quality of water factory is excellent In Chinese water quality standard for drinking water.
Embodiment 5: using 2 years discarded activated carbon samples, certain is derived from using BAC advanced water treatment technique water factory Activated carbon adsorption tank.The factory uses " coagulation+precipitating+filtering+BAC (O3/ GAC) " combination water treatment technological process, life Production capacity power is (500,000m3/ d), AC air-land combat EBCT are 14 minutes, and AC height are 2.0 meters, ozone Dosage is 2.0-2.5mg/L, and time of contact is 26 minutes.The water source of water factory comes from river water, and the average effluent quality of water factory is better than Chinese water quality standard for drinking water.
Embodiment 6: being that certain BAC advanced water treatment factory has taken out and air-dried using 7 years discarded activated carbon samples Waste sample.The factory uses " coagulation+precipitating+filtering+BAC (O3/ GAC) " combination water treatment technological process, produce energy Power is (250,000m3/ d), AC air-land combat EBCT are 14 minutes, and AC height are 2.0 meters, ozone dosage For 2.0-2.5mg/L, time of contact is 22 minutes.The water source of water factory comes from reservoir water, during the average effluent quality of water factory is better than State's water quality standard for drinking water.
The discarded active carbon of above-described embodiment 1,2 and 3 characterizes and application result is as follows:
Three kinds of discarded active carbons are denoted as SBAC-5, SBAC-6 and SBAC-7 respectively.
1.pH value
Embodiment 1, embodiment 2, collected discarded activated carbon sample SBAC-5, SBAC-6 and SBAC-7 in embodiment 3 PH be respectively 6.0,6.5 and 5.8, and the pH of new activated carbon sample employed in three kinds of embodiments is respectively 10.0,9.8 With 9.6, i.e., pH test result shows that the discarded activated carbon sample surface in three kinds of embodiments has become acid by alkalinity, It is provided with ion exchanging function.
2. surface acidity and basic functionality
The surface functional group of taken activated carbon sample is tested using Boehm titration, the results are shown in Table 1.
Table 1 discards the surface acidity and basic functionality of active carbon, mmol/g
The quantity of discarded activated carbon sample surface acidity functional group in three kinds of embodiments is above basic functionality Number, that is, demonstrate pH test result.
3. discarded active carbon in three kinds of embodiments is to the adsorption capacity of Pb (II)
SBAC-5 is detected by the initial concentration (4.45mg/L) and ultimate density of Pb (II) in test sequence batch test, SBAC-6 and SBAC-7 is to the ability for adsorbing Pb (II), shown in result figure 1a.It is research initial concentration to the shadow of removal Pb (II) It rings, keeping the dosage of discarded active carbon is 0.20mg/L, carries out SBAC- under different initial concentrations (2.45-8.08mg/L) 5, SBAC-6 and SBAC-7 is to the adsorption experiment of Pb (II), as a result as shown in Figure 1 b.
It can be seen that from FIG. 1 a that all SBAC samples are all shown to Pb when the dosage of SBACs reaches 0.10g/L (II) surprising adsorption capacity, with the increase of SBAC dosage, equilibrium concentration is gradually decreased, and three kinds of SBAC have reached absorption Balance.I.e. under the initial concentration of 4.45mg/L, all SBAC samples can effectively adsorb Pb (II), and maximum material removal rate is more than 99.0%, and for the 10-15% of new AC, this is a surprising result.That is, BAC process reform AC Surface nature and produce new product (SBAC), this make BAC technique in addition to adsorb and biodegrade other than can also remove Heavy metal.Compared with artificial modification AC, wherein not introducing chemical reagent, secondary pollution not will cause.Importantly, it is not It will increase the cost of system, the absorption of organic matter in aqueous solution will not be damaged.In addition, above-mentioned discovery will also for new AC and The thinking of SBAC being applied in combination or the recycling offer of SBAC (hazardous waste) is new, this can not only extend the longevity of AC again Life, and resource can be saved.
4. adsorbing the FT-IR analysis of SBACs sample before and after Pb (II)
Using new AC as control, SBAC-5, SBAC-6 and SBAC-7 are carried out using Fourier-870FT-IR (U.S.) The FT-IR analysis of Pb (II) absorption front and back, as a result as shown in Figure 2.
For Pb (II) adsorbs front and back FT-IR map, there is 1385cm in all samples-1Characteristic peak, and Pb (II) absorption front and back is unchanged, this should be attributed to NO3-Adsorption peak (Motta etc., 2008), water treatment procedure may be passed through It introduces.Absorption front and back is in 3200 and 3600cm-1Between, all SBACs have a wide absorption band, show adsorbent table There is free and Hydrogenbond OH group in face, wherein 3400cm after absorption-1The characteristic peak at place is as caused by the water adsorbed (Dong et al., 2014), 1100-1030cm-1Between another broadband should belong to straight chain C-OH stretching, extension (Abou- Mesalam, 2003).All SBAC samples are in absorption Pb (II) afterwards in 1665-1565cm-1There is visible adsorption peak in place, this Belong in the asymmetric stretching vibration (Ganesh etc., 2012) of carboxylate, it was confirmed that the appearance of SBACs surface carboxylic's root.And In SBAC-5 sample, 1665-1565cm there is before absorption-1Adsorption peak shows SBAC-5 during BAC process operation It has been already engaged in relevant chemical reaction.
5. adsorbing the XPS analysis of SBACs sample before and after Pb (II)
XPS analysis is carried out respectively to SBACs before and after Pb (II) absorption, element is formed as shown in table 2.By table 2 The element composition that table can be seen that absorption Pb (II) front and back SBACs is mainly made of carbon and oxygen, and impurity content is smaller (< 7%), And the variation of absorption front and back is little.Apparent difference is to adsorb the oxygen content difference of Pb (II) SBAC-5, SBAC-6 and SBAC-7 afterwards 2.1%, 2.46 and 2.42% is increased, and detects Pb 4f really in each SABC sample.
Table 2SABCs sample adsorbs the element composition variation before and after Pb (II)
Adsorption mechanism in order to facilitate understanding is right respectively using XPS peak41 software before and after adsorbing Pb (II) The peak O1s of SBAC-5, SBAC-6 and SBAC-7 have carried out swarming analysis, and are decomposed into the contribution of different surfaces oxygen-containing functional group (Kim etc. 2006), as a result as shown in figure 3, there is shown their peak area values.
As seen from Figure 3, three kinds of major surfaces are observed in the O 1s spectrum of SBAC-5, SBAC-6 and SBAC-7 Oxygen-containing functional group, content are highest for positioned at C-OH the or C-O-C functional group of 532.4eV；And it is located at 533.8eV and 530.8eV The high energy Asia peak at place corresponds respectively to carboxyl (H) O-C=O and C=O group, this is consistent with FT-IR spectrum.Wherein, SBAC-6 Carboxyl and hydroxyl with highest content, followed by BAC-7 and SBAC-5.Although after Pb (II) absorption, SBAC-5, SBAC- 6, SBAC-7 there is also C-OH or C-O-C, (H) O-C=O and C=O groups, but significant variation has occurred in its peak area, especially It is that (H) O-C=O group reduces 38.2%, 11.09% and 7.14% respectively, and C-OH or C-O-C group increases separately 4.07%, 11.62% and 10.34%, but for C=O group, SBAC-5 and SBAC-6 almost without observe variation.That is (H) O-C=O and C-OH group take part in Pb in solution (II) absorption (Tao etc., 2015；Deng 2017).Although metal from The adsorption process of son is extremely complex, in conjunction with above-mentioned characterization and correlation analysis it is found that metal and these ionization oxygen-containing functional groups Complexing is considered the main mechanism of SBAC adsorbing metal.
Bibliography
[1]Guo,Q.,et al.,2016.Simultaneous removal of multiple odorants from source water suffering from septic and musty odors:verification in a full- scale water treatment plant with ozonation.Water Res.100,1-6.
[2]Knopp,G.,et al.,2016.Elimination of micropollutants and transformation products from a wastewater treatment plant effluent through pilot scale ozonation followed by various activated carbon and biological filters.Water Res.100,580-592.
[3]Fu,J.et al.,2017.Pilot investigation of two-stage biofiltration for removal of natural organic matter in drinking water treatment.Chemosphere 166,311-322.
[4]Chung,Y.C.et al.,2005.Removal of high concentration of NH3and coexistent H2S by
biological activated carbon(BAC)biotrickling filter.Bioresour.Technol.96,1812-1820.
[5]Zha,X.S.,et al.,2016.The removal of organic precursors of DBPs during three advanced water treatment processes including ultrafiltration, biofiltration,and ozonation.Environ.Sci.Pollut.R.23, 1-12.
[6]Ahmed,M.B.,et al.2017.Progress in the biological and chemical treatment technologies for emerging contaminant removal from wastewater:a critical review,Journal of Hazardous Materials, 323(Pt A),274-298.
[7]Simpson D.R.Biofilm processes in biologically active carbon water purification.Water Research,2008,42(12):2839-2848.
[8]Korotta-Gamage S.M.,A.A review:Potential and challenges of biologically activated carbon Sathasivan to remove natural organic matter in drinking water purification process.Chemosphere, 2017,167:120-138.
[9] Wang Zhansheng, Liu Wenjun, Zhang Xihui are Beijing polluted source drinking water treatment: China Construction Industry Press, 2016.
[10]Umar M.,Roddick F.,Fan L.H.Impact of coagulation as a pre- treatment for UVC/H2O2-biological activated carbon treatment of a municipal wastewater reverse osmosis concentrate.Water Research,2016,88:12-19.
[11]Kaarela O.E.,Harkki H.A.,Palmroth M.R.T.,et al.Bacterial diversity and active biomass in full-scale granular activated carbon filters operated at low water temperatures.Environmental Technology,2015,36(6):681- 692.
[12] Liu Jianguang, Zhang Chunyang look into people's light, and the drinking water advanced treatment process activity charcoal cycle of operation is waited to inquire into water supply Draining, 2011,37 (5): 35-40.
[13] China Civil Engineering Society's water and wastewater industry branch advanced water treatment research association advanced water treatment technical principle With the Beijing Engineering Projects: China Construction Industry Press, 2013.
[14]Gao J.L.,Oloibiri V.,Chys M.,et al.Integration of autotrophic nitrogen removal,ozonation and activated carbon filtration for treatment of landfill leachate.Chemical engineering journal,2015, 275:281-287.
[16] the national water supply and drainage technology of Lu Zedong, Liu Wen monarch's ozone-biological active carbon Research progress .2016 Information Network nd Annual Meeting collection, 158-163.
[16] Feng Jun, Tao Ming, Xu Jianping advanced treating modification scheme and purifying water effect water purification technology, 2011,30 (3): 72-77.
[17]D.,Mohan,S.Chander,Single component and multi-component adsorption of metal ions by activated carbons,Colloid Surf.A:Phys.Eng.Asp.177 (2001),183-196
[18]Z.,Li,X.,Chang,Z.,Hu,X.,Huang,X.,Zou,Q.,Wu,R.,Nie,Zincon-modified activated carbon for solid-phase extraction and preconcentration of trace lead and chromium from environmental samples,J.Hazard.Mater.166(1)(2009)133- 7.
[19]J.Trujillo-Reyes,J.R.,Peralta-Videa,J.L.,Gardea-Torresdey, Supported and unsupported nanomaterials for water and soil remediation:are They a useful solution for worldwide pollution?, J. Hazard.Mater.280 (2014) 487- 503.
[20]A.,Benettayeb,E.,Guibal,A.,Morsli,R,Kessas,Chemical modification of alginate for enhanced sorption of Cd(II),Cu(II)and Pb(II),Chem.Eng.J.316 (2017)704-714.
[21]H.C.,Tao,H.R.,Zhang,J.B.,Li,W.Y.,Ding,Biomass based activated carbon obtained from sludge and sugarcane bagasse for removing lead ion from wastewater,Bioresour.Technol.192 (2015)611-617.
[22]L.,Hadjittofi,M.,Prodromou,I.,Pashalidis,Activated biochar derived from cactus fibres--preparation,characterization and application on Cu(II)removal from aqueous solutions, Bioresour.Technol.159(2014)460- 464.ACCEPTED MANUSCRIPT 30
[23]R.W.,Coughlin,F.S.,Ezra,Role of surface acidity in the adsorption of organicpollutants on the surface of carbon,Environ.Sci.Technol.2(1968)291- 297.
[24]Knopp,G.,et al.,2016.Elimination of micropollutants and transformation products from a wastewater treatment plant effluent through pilot scale ozonation followed by various activated carbon and biological filters.Water Res.100,580-592.
[25]V.,Abromaitis,V.,Racys,P.V.D.,Marel,G.,Ni,M.,Dopson,A.L., Wolthuizen,R.J.W., Meulepas,Effect of shear stress and carbon surface roughness on bioregeneration and performance of suspended versus attached biomass in metoprolol-loaded biological activated carbon systems, Chem.Eng.J.317(1)(2017),503-511.
[26]K.,Yapsakli,F.,Effect of type of granular activated carbon on DOC biodegradation in biological activated carbon filters,Process Biochem.45(2010)355-362.
[27]A O,F.,Cometabolicbioregeneration of activated carbons loaded with 2-chlorophenol,Bioresour.Technol.100(20)(2009)4604-4610.
[28]S.L.,Ng,C.E.,Seng,P.E.,Lim,Bioregeneration of activated carbon and activated rice husk loaded with phenolic compounds:kinetic modeling, Chemosphere 78(2010)510-516.
[29]W D.,Oh,P.E.,Lim,C.E.,Seng,A.N.,Sujari,Bioregeneration of granular activated carbon in simultaneous adsorption and biodegradation of chlorophenols,Bioresour.Technol.102(20) (2011)9497-9502.

Claims (9)

1. the discarded active carbon in biological activated carbon method advanced water treatment technique, which is characterized in that used bioactivity The surface characteristic of charcoal becomes alkalinity by acidity；
The used biological activated carbon is to be replaced or regeneration.
2. waste biomass active carbon according to claim 1, which is characterized in that pH < 7 of discarded active carbon or Zeta potential ≤ 0 or its surface acidity functional group content be higher than surface alkalinty functional group content.
3. a kind of discarded activity according to claim 1, in 2 described in any item biological activated carbon method advanced water treatment techniques Charcoal preparation method, which comprises the steps of:
(1) acquire representational discarded activated carbon sample: its source includes in the activated carbon adsorption tank of BAC technique or having taken out Store the place of discarded active carbon；
(2) using new active carbon as reference, surface characteristic characterization is carried out to discarded activated carbon sample, is carried out using two or more methods The characterization verified each other；
(3) pH of active carbon is discarded less than 7 or content >=surface alkalinty functional group of current potential≤0 zeta or surface acidity functional group Content；
(4) that discards activated carbon sample reapplies research: direct reuse is in sampling water factory or is back to the same water source of use, identical The water supply plant of technique；If going the occasion of removing heavy metals for other, need to carry out organic matter dissolution test to water body to be measured.
4. preparation method according to claim 3, which is characterized in that step (1) acquisition strategies specifically:
(a) active carbon is discarded still in charcoal pond, then collecting in active carbon pond according to the method for the Appendix B of AWWA B605-2007 has Representative used AC sample；
(b) active carbon takes out from charcoal pond and is stored in elsewhere, then according to " Drinking Water water purification station-service coal quality activity Charcoal " method as defined in (CJT 345-2010) is sampled.
5. preparation method according to claim 3, which is characterized in that new active carbon is the institute of water factory in the step (2) The original activity charcoal of filling or the active carbon produced using the same batch of same technique.
6. preparation method according to claim 3, which is characterized in that step (2) characterizing method include: pH test, Zeta current potential, surface polarity component, surface acidity and basic functionality (FT-IR analysis, Boehm titration) measurement and XPS element At least two in analysis.
7. preparation method according to claim 3, which is characterized in that be back to sampling water factory in the step (4) or return For the water supply plant using same water source, same process using reuse two ways after direct reuse or taking-up natural air drying.
8. preparation method according to claim 3, which is characterized in that the dissolution test of organic matter is logical in the step (4) It crosses discarded active carbon and is dissolved in water body front and back DOC or TOC difference to be measured to characterize；Specific value regards the property (regeneration of water body to be measured Water, waste water etc.) according to corresponding discharge standard depending on.
9. discarded active carbon in biological activated carbon method advanced water treatment technique reapplies, which is characterized in that be applied to water Processing or air cleaning.
CN201811047088.7A 2018-09-08 2018-09-08 Waste activated carbon in advanced treatment process of water supply by biological activated carbon method, preparation method and re-application Active CN109200998B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811047088.7A CN109200998B (en) 2018-09-08 2018-09-08 Waste activated carbon in advanced treatment process of water supply by biological activated carbon method, preparation method and re-application

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811047088.7A CN109200998B (en) 2018-09-08 2018-09-08 Waste activated carbon in advanced treatment process of water supply by biological activated carbon method, preparation method and re-application

Publications (2)

Publication Number Publication Date
CN109200998A true CN109200998A (en) 2019-01-15
CN109200998B CN109200998B (en) 2021-05-04

Family

ID=64987861

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811047088.7A Active CN109200998B (en) 2018-09-08 2018-09-08 Waste activated carbon in advanced treatment process of water supply by biological activated carbon method, preparation method and re-application

Country Status (1)

Country Link
CN (1) CN109200998B (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111063469A (en) * 2019-12-23 2020-04-24 天津大学 Method for removing radionuclide strontium in water
CN115010205A (en) * 2022-05-11 2022-09-06 天津大学 Method for removing heavy metal by biological activated carbon BAC process, determination method of heavy metal capacity and application

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN2250352Y (en) * 1996-04-19 1997-03-26 同济大学 Biological film purifying device
CN1421400A (en) * 2001-11-26 2003-06-04 财团法人工业技术研究院 Oxygen-containing water reflux and bioactive carbon waste water treating method and equipment
CN202046965U (en) * 2011-02-25 2011-11-23 兰州交通大学 Rainwater collection cellar water purification device with slow biological filter
CN103449598A (en) * 2013-08-12 2013-12-18 上海电力学院 Treatment method of ethylene diamine tetraacetic acid (EDTA) boiler cleaning wastewater of power plant
CN109110858A (en) * 2018-08-31 2019-01-01 天津大学 Integrate Adsorption of Organic, biodegrade, active carbon purifying reactor, design method and the application of removing heavy metals function

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN2250352Y (en) * 1996-04-19 1997-03-26 同济大学 Biological film purifying device
CN1421400A (en) * 2001-11-26 2003-06-04 财团法人工业技术研究院 Oxygen-containing water reflux and bioactive carbon waste water treating method and equipment
CN202046965U (en) * 2011-02-25 2011-11-23 兰州交通大学 Rainwater collection cellar water purification device with slow biological filter
CN103449598A (en) * 2013-08-12 2013-12-18 上海电力学院 Treatment method of ethylene diamine tetraacetic acid (EDTA) boiler cleaning wastewater of power plant
CN109110858A (en) * 2018-08-31 2019-01-01 天津大学 Integrate Adsorption of Organic, biodegrade, active carbon purifying reactor, design method and the application of removing heavy metals function

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
YASUSHI TAKEUCHI，ET AL: ""Biological Activated Carbon Treatment of Waste Water Containing Organics and Heavy Metal Ions"", 《FUNDAMENTALS OF ADSORPTION》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111063469A (en) * 2019-12-23 2020-04-24 天津大学 Method for removing radionuclide strontium in water
CN115010205A (en) * 2022-05-11 2022-09-06 天津大学 Method for removing heavy metal by biological activated carbon BAC process, determination method of heavy metal capacity and application

Also Published As

Publication number Publication date
CN109200998B (en) 2021-05-04

Similar Documents

Publication Publication Date Title
Cui et al. Removal of nitrate and phosphate by chitosan composited beads derived from crude oil refinery waste: Sorption and cost-benefit analysis
Erabee et al. Adsorptive treatment of landfill leachate using activated carbon modified with three different methods
CN103880245B (en) A kind for the treatment of process of percolate
CN110508243B (en) Preparation method and application of biomass-based porous carbon loaded iron floc adsorption material
CN111807453A (en) Modified biochar for adsorbing phosphorus in water body and preparation method and application thereof
CN112569900B (en) Preparation method and application of municipal sludge biochar
Dong et al. Physicochemical and porosity characteristics of thermally regenerated activated carbon polluted with biological activated carbon process
CN112340830B (en) Application of catalyst taking waste adsorbent after adsorption-desorption as raw material in treating high-salt organic wastewater by activating persulfate
CN105293771A (en) Rubbish penetrating fluid treatment method
CN110801814A (en) Preparation method of magnetic amino walnut shell biochar novel adsorbent
CN102580666B (en) Modified pumice for purifying heavy metal sewage and preparation method and application of modified pumice
CN109200998A (en) It discarded active carbon, preparation method in biological activated carbon method advanced water treatment technique and reapplies
CN111729654A (en) Preparation method and application of modified pagodatree leaf biochar
CN103449623A (en) Method for preparing metal nanometer material by recovering from industrial waste water
CN101444719B (en) Biosorption agent and application method thereof
CN101497032A (en) Method for preparing biological sorbent and method of use thereof
CN113003648A (en) Method for treating heavy metal/organic matter composite polluted wastewater by solid waste biomass carbonized material
KR101055661B1 (en) Heavy metal adsorption removal agent containing yulpi and heavy metal adsorption removal method using the same
CN106268618A (en) A kind of preparation method and applications of active adsorbing material
CN113083216B (en) Two-dimensional nickel-based composite metal oxide adsorbent, preparation method and application of adsorbent in removing phosphate radical
Jia et al. Variation characteristics of different fractions of dissolved organic matter in landfill leachate during UV-TiO2 photocatalytic degradation
CN102765777A (en) Method for removing cadmium ion from wastewater utilizing wild duckweed biomass
CN112371085A (en) Steel pickling sludge modified sludge activated carbon for rainwater treatment
Hunge The Efficacy of Newly Developed Activated Carbon from Bark of Butea monosperma For Removal of Hexavalent Chromium
CN113559617B (en) Preparation method and application of active alumina particle loaded manganese oxide composite material

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant