CN101045591A - Comprehensive treatment method for recovered and used humic acid in garbage infiltration liquid - Google Patents
Comprehensive treatment method for recovered and used humic acid in garbage infiltration liquid Download PDFInfo
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Abstract
A process for reclaiming the humic acid in the percolated liquid of garbage includes such steps as filtering, regulating pH=1.0-5.5, adding flocculant, fast stirring, settling, depositing, separating to obtain humic acid, adsorbing and filtering supernatant, regulating pH=6-8, and reusing it to garbage burying field.
Description
Technical field
The present invention relates to field of environment protection, relate to a kind of improvement method of percolate, relate in particular to the comprehensive processing method that humic acid is recycled in a kind of percolate.
Background technology
Sanitary landfill is a main mode of disposing domestic waste, and this method processing cost is low, technology reliable, good operability, is widely adopted.Percolate is a garbage collecting and transferring, in processing and the disposal process one of modal " secondary pollution ", be that the pollution threat of generally acknowledging in the world is big, complicated component, the high concentrated organic wastewater that is difficult to handle, it contains and is difficult to biodegradable humic acid, naphthalene, non-chlorination aromatics such as phenanthrene, the chlorination aromatics, phosphoric acid ester, phthalic ester, phenolic compound and amino benzenes compounds and multiple metal ion etc., humic acid wherein can adsorb heavy metal and some toxic organic pollutants, surface water and underground water are constituted potential harm (wat.Res.1997,31 (7): 1609～1618).Therefore, all need the generation of percolate is control effectively, the percolate of discharging is dealt carefully with from the management that runs to after the closing of landfill yard.Owing to contain some toxicants (as polycyclic aromatic hydrocarbons, polychlorobiphenyl etc.) and biorefractory material (as humic acid, tensio-active agent etc.) in the percolate, make the application of biological process be subjected to restriction significantly; And physical method processing cost height such as air supporting, coagulating sedimentation, activated carbon adsorption, reverse osmosis are difficult to apply.
Owing to be subjected to the influence of the many-sided factor of technology and economic dispatch, China has 39% landfill yard not have the percolate treatment facility approximately at present; Though the percolate that 49% landfill yard produces is treated, but still can not be up to standard; The percolate that only has 12% landfill yard to produce is up to standard substantially after treatment, and the processing mode of back up to standard percolate is to enter municipal sewage pipe network (" environmental hygiene engineering ", 2006,14 (6): 17-19) basically.Therefore, the practical leachate treatment technology of searching cost performance the best is many environment sanitation facilities designs and builds a difficult problem that needs to be resolved hurrily.
Study and put into practice through for many years and show, adopt physics method, chemical method or biochemical process to carry out percolate merely and handle and often be difficult to reach processing requirements, and expense costliness (Environ Chem Lett (2006) 4:51-61).Though occurred some comparatively ripe, the reasonable percolate treating process of cost performance in recent years: as adjusting+ammonia-nitrogen desorption+A/SBR, adjusting+A
2/ O biological denitrification system+NF, adjusting+pH regulator+combination treatment technology such as the continuous nanofiltration+reverse osmosis of SBR+, but still have the problem of running cost height, the wasting of resources.
Summary of the invention
The purpose of this invention is to provide humic acid in a kind of percolate (humic substance) comprehensive utilization method, realize administering the Pollution abatement target of polluting and changing harmful to treasure, total clearance of TOC (being total organic carbon) and COD (being chemical oxygen demand (COD)) is reached respectively more than 97.5% and 99.7%.
Purpose of the present invention can realize by following measure:
The comprehensive processing method that humic acid is recycled in a kind of percolate of the present invention comprises the steps:
(1), removes impurity with the percolate coarse filtration;
(2) with acid for adjusting pH value to 1.0～5.5;
(3) add flocculation agent, stir fast and sedimentation 20～80min; Flocculation agent adds by the volume ratio of 0.01%～0.06% percolate;
(4) precipitation, separation; It is 6～8 that supernatant liquor filters back pH value with adsorbents adsorb;
(5) supernatant liquor after the processing recharges into refuse landfill or discharging after the high-level oxidation technology processing is up to standard.
The comprehensive processing method that humic acid is recycled in above-described a kind of percolate, the acid that is used for regulating the pH value in the described step (2) is organic acid: C1～C6 aliphatic or aromatic acid and mineral acid: nitric acid, phosphoric acid, sulfuric acid, hydrochloric acid, boric acid any.Acid can be SILVER REAGENT, technical grade or industrial waste acid (as the acid of alkyl plant sulfur waste).
The comprehensive processing method that humic acid is recycled in above-described a kind of percolate, the flocculation agent in the described step (3) are a kind of in yin, yang ion polyacrylamide, bodied ferric sulfate, the polymerize aluminum chloride.
The comprehensive processing method that humic acid is recycled in above-described a kind of percolate, precipitation, the separate mode in the described step (4) are meant a kind of in centrifugation, filtration, the press filtration mode.
The comprehensive processing method that humic acid is recycled in above-described a kind of percolate, the throw out in the described step (4) is a humic acid.
The comprehensive processing method that humic acid is recycled in above-described a kind of percolate, the sorbent material that is used for supernatant liquor in the described step (4) is a magnesium type modification slag, this sorbent material is to make with following method:
1. in the coal firing boiler slag, add 4mol/L NaOH solution, heat 4～6h down at 75 ℃～80 ℃; Adding concentrated hydrochloric acid after the cooling, to be neutralized to pH value of solution be 6～8; Through centrifugal, filter the back and dry down at 105 ℃～115 ℃ and obtain sodium type modification slag; The adding proportion of slag and NaOH solution is 1g: 3.0～3.5ml;
2. in sodium type modification slag, add 1mol/L MgCl
2Stir 3～3.5h under the solution, room temperature and carry out ion-exchange; It is centrifugal and with distilled water wash for several times to stop to stir the back, promptly gets magnesium type modification slag at 105 ℃～115 ℃ down dry 2～3h; Sodium type modification slag and MgCl
2The adding proportion of solution is 1g: 1.5～2.5ml.
The comprehensive processing method that humic acid is recycled in above-described a kind of percolate, it is characterized in that: the high-level oxidation technology in the described step (5) is to be in the photo catalysis reactor of light source with the ultraviolet lamp, add the ferrotitanium composite molecular sieve catalyst, the photocatalytic degradation technology of reaction 5～6h; The add-on of catalyzer is 0.5g/L～2.5g/L.
The comprehensive processing method that humic acid is recycled in above-described a kind of percolate, the every after treatment side's percolate of described humic acid can get humic acid 10～15kg (dry weight); Measure through potassium dichromate oxidation, its content is greater than 88% can directly pack.
The comprehensive processing method that humic acid is recycled in above-described a kind of percolate, described humic acid can be applicable to make organic fertilizer such as humic acids liquid fertilizer, humic acids compound fertilizer and (sees " rural science and technology exploitation ", 2003,7:36), industrial raw material (as the agent of store battery cathode expansion, humic acid tackiness agent etc.) or water conditioner (are seen " humic acid ", 2006,03:8～13; Application number be CN200410025618.X's " a kind of corrosion inhibiting and descaling agent "; The patent No. be CN03126702.5's " a kind of modifying agent and using method thereof of cultivating pool substrate ecotope ").
The present invention compared with prior art has the following advantages:
1, because percolate has been realized the comprehensive regulation, total clearance of its TOC and COD is reached respectively more than 97.5% and 99.7%, simultaneously again can be with throw out---humic acid is as commodity selling, be applied to organic fertilizer, industrial raw material or water conditioner, do not produce secondary pollution, realize both having administered waste water, fully utilized the target of resource again.
2, technology of the present invention is simple, equipment is few, investment is little, practicality is good, is particularly suitable for interior processing the in field of percolate.
3, have certain economic benefit, social benefit and environmental benefit.Produce 6000m per year for one
3The percolate landfill yard, by art breading of the present invention, running cost is 1,800,000 yuan, and the sales revenue of producing humic acid is 3,000,000 yuan, and selling pure profit is 1,200,000 yuan, thereby has reduced effluent charge and slowed down pollution to environment.
Description of drawings
Fig. 1 is a process flow sheet of the present invention.
Embodiment
Embodiment 1
2 liters of percolates, flocculation agent is selected cationic polyacrylamide for use, hydrochloric acid
Percolate: cationic polyacrylamide: hydrochloric acid=1: 0.0002: 0.01
The 2L percolate is removed impurity through coarse filtration, measure TOC and COD and be respectively 3402mg/L and 11500mg/L; Put into beaker, add the 20ml hcl acidifying under the room temperature, regulating pH is 4.0; The cationic polyacrylamide that adds 0.4ml 10% (by weight percentage), with the stirring velocity stirring 10min of 3000～4000r/min, sedimentation 80min, centrifugation can get humic acid 24g (dry weight); Measure its content 91.5% through potassium dichromate oxidation.Measure percolate TOC and COD and be respectively 527.3mg/L and 1311mg/L, clearance reaches 84.5% and 88.6% respectively.
Supernatant liquor is further removed pollutent in the percolate with the adsorption filtration of magnesium type modification slag, and filtering back percolate pH is 6.7, measures TOC and COD and is respectively 406mg/L and 970mg/L, and clearance reaches 48% and 52% respectively.
Get filtration back percolate 1L adding photo catalysis reactor and carry out photocatalytic degradation, with the mercury lamp of 30W as light source, add 1.0g ferrotitanium Y zeolite (Fe-Ti-HY) catalyzer, react after 6 hours, measure TOC and COD and be respectively 16.5mg/L and 19mg/L, clearance reaches 94% and 97% respectively, reaches " integrated wastewater discharge standard " primary standard (GB8978-1996).
Wherein the preparation method of magnesium type modification slag is: take by weighing the 120g slag, put in the 1000ml Erlenmeyer flask, add 4mol/L NaOH solution 400ml; Load onto prolong on Erlenmeyer flask top, heat 4h down at 75 ℃; Adding concentrated hydrochloric acid after the cooling, to be neutralized to pH value of solution be 7.2; 110 ℃ of oven dry down, obtain sodium type modification slag after 4000r/min is centrifugal, it is standby to bottle.Get 100g sodium type modification slag, put in the 500ml beaker, add 1mol/L MgCl
2Solution 200ml stirs 3h and carries out ion-exchange under the room temperature; It is centrifugal and with distilled water wash for several times to stop to stir the back, 110 ℃ down dry 2h promptly get magnesium type modification slag.
8 liters of embodiment 2 percolates, flocculation agent is selected bodied ferric sulfate for use, sulfuric acid
Percolate: bodied ferric sulfate: sulfuric acid=1: 0.0006: 0.004
The 8L percolate is removed impurity through coarse filtration, measure TOC and COD and be respectively 3402mg/L and 11500mg/L; Put into beaker, add the 32ml sulfuric acid acidation under the room temperature, regulating pH is 5.0; The bodied ferric sulfate that adds 4.8ml 10% (by weight percentage), with the stirring velocity stirring 10min of 3000～4000r/min, sedimentation 80min, centrifugation can get humic acid 99g (dry weight); Measure its content 91.5% through potassium dichromate oxidation.Measure percolate TOC and COD and be respectively 483.1mg/L and 1219mg/L, clearance reaches 85.8% and 89.4% respectively.
Supernatant liquor is further removed pollutent in the percolate with magnesium type modification slag (preparation method is with embodiment 1) adsorption filtration, and filtering back percolate pH is 6.7, measures TOC and COD and is respectively 256mg/L and 585mg/L, and clearance reaches 47% and 52% respectively.
Get filtration back percolate 1L adding photo catalysis reactor and carry out photocatalytic degradation, with the mercury lamp of 30W as light source, add 1.0g ferrotitanium Y zeolite (Fe-Ti-HY) catalyzer, react after 6 hours, measure TOC and COD and be respectively 12.8mg/L and 15mg/L, clearance reaches 95% and 97.5% respectively, reaches " integrated wastewater discharge standard " primary standard (GB8978-1996).
8 liters of embodiment 3 percolates, anionic polyacrylamide, phosphoric acid
Percolate: anionic polyacrylamide: phosphoric acid=1: 0.0004: 0.005
The 8L percolate is removed impurity through coarse filtration, measure TOC and COD and be respectively 3402mg/L and 11500mg/L; Put into beaker, add the acidifying of 40ml phosphoric acid under the room temperature, regulating pH is 5.5; The anionic polyacrylamide that adds 3.2ml 10% (by weight percentage), with the stirring velocity stirring 10min of 3000～4000r/min, sedimentation 80min, centrifugation can get humic acid 98g (dry weight); Measure its content 90.5% through potassium dichromate oxidation.Measure percolate TOC and COD and be respectively 571.5mg/L and 1415mg/L, clearance reaches 83.2% and 87.7% respectively.
Supernatant liquor magnesium type modification slag (preparation method is with embodiment 1) adsorption filtration, further remove pollutent in the percolate, filtering back percolate pH is 6.9, measures TOC and COD and is respectively 307.5mg/L and 686mg/L, and clearance reaches 46.2% and 51.5% respectively.
Get filtration back percolate 1L adding photo catalysis reactor and carry out photocatalytic degradation, with the mercury lamp of 30W as light source, add 1.0g ferrotitanium Y zeolite (Fe-Ti-HY) catalyzer, react after 6 hours, measure TOC and COD and be respectively 16.9mg/L and 19mg/L, clearance reaches 94.5% and 97.2% respectively, reaches " integrated wastewater discharge standard " primary standard (GB8978-1996).
8 liters of embodiment 4 percolates, polymerize aluminum chloride, acetate
Percolate: polymerize aluminum chloride: acetate=1: 0.0001: 0.008
The 8L percolate is removed impurity through coarse filtration, measure TOC and COD and be respectively 3402mg/L and 11500mg/L; Put into beaker, add the acidifying of 64ml acetate under the room temperature, regulating pH is 5.0; The polymerize aluminum chloride that adds 0.8ml 10% (by weight percentage), with the stirring velocity stirring 10min of 3000～4000r/min, sedimentation 80min, centrifugation can get humic acid 94g (dry weight); Measure its content 89.2% through potassium dichromate oxidation.Measure percolate TOC and COD and be respectively 503.5mg/L and 1265mg/L, clearance reaches 85.2% and 89.0% respectively.
Supernatant liquor is further removed pollutent in the percolate with magnesium type modification slag (preparation method is with embodiment 1) adsorption filtration, and filtering back percolate pH is 7.6, measures TOC and COD and is respectively 275.9mg/L and 633mg/L, and clearance reaches 45.2% and 50% respectively.
Get filtration back percolate 1L adding photo catalysis reactor and carry out photocatalytic degradation, with the mercury lamp of 30W as light source, add 1.0g ferrotitanium Y zeolite (Fe-Ti-HY) catalyzer, react after 6 hours, measure TOC and COD and be respectively 17.9mg/L and 19mg/L, clearance reaches 93.5% and 97% respectively, reaches " integrated wastewater discharge standard " primary standard (GB8978-1996).
2 liters of embodiment 5 percolates, anionic polyacrylamide, sulfuric acid
Percolate: anionic polyacrylamide: sulfuric acid=1: 0.0003: 0.08
The 2L percolate is removed impurity through coarse filtration, measure TOC and COD and be respectively 3402mg/L and 11500mg/L; Put into beaker, add the 160ml sulfuric acid acidation under the room temperature, regulating pH is 1.0; The anionic polyacrylamide that adds 0.6ml 10% (by weight percentage), with the stirring velocity stirring 10min of 3000～4000r/min, sedimentation 80min, centrifugation can get humic acid 20g (dry weight); Measure its content 92.3% through potassium dichromate oxidation.Measure percolate TOC and COD and be respectively 435.5mg/L and 1035mg/L, clearance reaches 87.2% and 91.0% respectively.
Supernatant liquor magnesium type modification slag (preparation method is with embodiment 1) adsorption filtration, further remove pollutent in the percolate, filtering back percolate pH is 6.4, measures TOC and COD and is respectively 234.3mg/L and 501mg/L, and clearance reaches 46.2% and 51.6% respectively.
Get filtration back percolate 1L adding photo catalysis reactor and carry out photocatalytic degradation, with the mercury lamp of 30W as light source, add 1.0g ferrotitanium Y zeolite (Fe-Ti-HY) catalyzer, react after 5 hours, measure TOC and COD and be respectively 17.6mg/L and 18mg/L, clearance reaches 92.5% and 96.4% respectively, reaches " integrated wastewater discharge standard " primary standard (GB8978-1996).
2 liters of embodiment 6 percolates, anionic polyacrylamide, waste sulfuric acid from alkylation
Percolate: anionic polyacrylamide: waste sulfuric acid from alkylation=1: 0.0003: 0.06
The 2L percolate is removed impurity through coarse filtration, measure TOC and COD and be respectively 3402mg/L and 11500mg/L; Put into beaker, add the acidifying of 120ml waste sulfuric acid from alkylation under the room temperature, regulating pH is 3.2; The anionic polyacrylamide that adds 0.6ml 10% (by weight percentage), with the stirring velocity stirring 10min of 3000～4000r/min, sedimentation 80min, centrifugation can get humic acid 27g (dry weight); Measure its content 89.7% through potassium dichromate oxidation.Measure percolate TOC and COD and be respectively 483.1mg/L and 1242mg/L, clearance reaches 85.8% and 89.2% respectively.
Supernatant liquor magnesium type modification slag (preparation method is with embodiment 1) adsorption filtration, further remove pollutent in the percolate, filtering back percolate pH is 6.8, measures TOC and COD and is respectively 257.0mg/L and 614mg/L, and clearance reaches 46.8% and 50.6% respectively.
Get filtration back percolate 1L adding photo catalysis reactor and carry out photocatalytic degradation, with the mercury lamp of 30W as light source, add 1.0g ferrotitanium Y zeolite (Fe-Ti-HY) catalyzer, react after 6 hours, measure TOC and COD and be respectively 16.7mg/L and 18mg/L, clearance reaches 93.5% and 97.2% respectively, reaches " integrated wastewater discharge standard " primary standard (GB8978-1996).
8 liters of embodiment 7 percolates, anionic polyacrylamide, hydrochloric acid
Percolate: anionic polyacrylamide: hydrochloric acid=1: 0.0001: 0.008
The 8L percolate is removed impurity through coarse filtration, measure TOC and COD and be respectively 3402mg/L and 11500mg/L; Put into beaker, add the 64ml hcl acidifying under the room temperature, regulating pH is 1.7; The anionic polyacrylamide that adds 0.8ml 10% (by weight percentage), with the stirring velocity stirring 10min of 3000～4000r/min, sedimentation 80min, centrifugation can get humic acid 97.2g (dry weight); Measure its content 90.1% through potassium dichromate oxidation.Measure percolate TOC and COD and be respectively 503.5mg/L and 1265mg/L, clearance reaches 85.2% and 89.0% respectively.
Supernatant liquor magnesium type modification slag (preparation method is with embodiment 1) adsorption filtration, further remove pollutent in the percolate, filtering back percolate pH is 6.6, measures TOC and COD and is respectively 271.4mg/L and 643mg/L, and clearance reaches 46.1% and 49.2% respectively.
Get filtration back percolate 1L adding photo catalysis reactor and carry out photocatalytic degradation, with the mercury lamp of 30W as light source, add 1.0g ferrotitanium Y zeolite (Fe-Ti-HY) catalyzer, react after 6 hours, measure TOC and COD and be respectively 14.9mg/L and 17mg/L, clearance reaches 94.5% and 97.4% respectively, reaches " integrated wastewater discharge standard " primary standard (GB8978-1996).
8 liters of embodiment 8 percolates, cationic polyacrylamide, phosphoric acid
Percolate: cationic polyacrylamide: phosphoric acid=1: 0.0004: 0.008
The 8L percolate is removed impurity through coarse filtration, measure TOC and COD and be respectively 3402mg/L and 11500mg/L; Put into beaker, add the acidifying of 64ml phosphoric acid under the room temperature, regulating pH is 2.8; The cationic polyacrylamide that adds 3.2ml 10% (by weight percentage), with the stirring velocity stirring 10min of 3000～4000r/min, sedimentation 80min, centrifugation can get humic acid 95g (dry weight); Measure its content 88.6% through potassium dichromate oxidation.Measure percolate TOC and COD and be respectively 493.3mg/L and 1242mg/L, clearance reaches 85.5% and 89.2% respectively.
Supernatant liquor magnesium type modification slag (preparation method is with embodiment 1) adsorption filtration, further remove pollutent in the percolate, filtering back percolate pH is 7.1, measures TOC and COD and is respectively 263.4mg/L and 625mg/L, and clearance reaches 46.6% and 49.7% respectively.
Get filtration back percolate 1L adding photo catalysis reactor and carry out photocatalytic degradation, with the mercury lamp of 30W as light source, add 1.0g ferrotitanium Y zeolite (Fe-Ti-HY) catalyzer, react after 6 hours, measure TOC and COD and be respectively 13.7mg/L and 17mg/L, clearance reaches 94.8% and 97.2% respectively, reaches " integrated wastewater discharge standard " primary standard (GB8978-1996).
Claims (7)
1, the comprehensive processing method that humic acid is recycled in a kind of percolate comprises the steps:
(1), removes impurity with the percolate coarse filtration;
(2) with acid for adjusting pH value to 1.0～5.5;
(3) add flocculation agent, stir fast and sedimentation 20～80min; Flocculation agent adds by the volume ratio of 0.01%～0.06% percolate;
(4) precipitation, separation; It is 6～8 that supernatant liquor filters back pH value with adsorbents adsorb;
(5) supernatant liquor after the processing recharges into refuse landfill or discharging after the high-level oxidation technology processing is up to standard.
2, the comprehensive processing method that humic acid is recycled in a kind of percolate as claimed in claim 1 is characterized in that: the acid that is used for regulating the pH value in the described step (2) is organic acid: C1～C6 aliphatic or aromatic acid and mineral acid: nitric acid, phosphoric acid, sulfuric acid, hydrochloric acid, boric acid any.
3, the comprehensive processing method that humic acid is recycled in a kind of percolate as claimed in claim 1 is characterized in that: the flocculation agent in the described step (3) is a kind of in yin, yang ion polyacrylamide, bodied ferric sulfate, the polymerize aluminum chloride.
4, the comprehensive processing method that humic acid is recycled in a kind of percolate as claimed in claim 1 is characterized in that: the precipitate and separate mode in the described step (4) is meant a kind of in centrifugation, filtration, the press filtration mode.
5, the comprehensive processing method that humic acid is recycled in a kind of percolate as claimed in claim 1, it is characterized in that: the throw out in the described step (4) is a humic acid.
6, the comprehensive processing method that humic acid is recycled in a kind of percolate as claimed in claim 1, it is characterized in that: the sorbent material that is used for supernatant liquor in the described step (4) is a magnesium type modification slag, and this sorbent material is to make with following method:
1. in the coal firing boiler slag, add 4mol/L NaOH solution, heat 4～6h down at 75 ℃～80 ℃; Adding concentrated hydrochloric acid after the cooling, to be neutralized to pH value of solution be 6～8; Through centrifugal, filter the back and dry down at 105 ℃～115 ℃ and obtain sodium type modification slag; The adding proportion of slag and NaOH solution is 1g: 3.0～3.5ml;
2. in sodium type modification slag, add 1mol/L MgCl
2Stir 3～3.5h under the solution, room temperature and carry out ion-exchange; It is centrifugal and with distilled water wash for several times to stop to stir the back, promptly gets magnesium type modification slag at 105 ℃～115 ℃ down dry 2～3h; Sodium type modification slag and MgCl
2The adding proportion of solution is 1g: 1.5～2.5ml.
7, the comprehensive processing method that humic acid is recycled in a kind of percolate as claimed in claim 1, it is characterized in that: the high-level oxidation technology in the described step (5) is to be in the photo catalysis reactor of light source with the ultraviolet lamp, add the ferrotitanium composite molecular sieve catalyst, the photocatalytic degradation technology of reaction 5～6h; The add-on of catalyzer is 0.5g/L～2.5g/L.
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- 2007-04-30 CN CNB200710017849XA patent/CN100513335C/en not_active Expired - Fee Related
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