CN105694063A - Method for extraction of humic acid in high-concentration divalent-ion leachate MBR + NF concentrated liquid - Google Patents
Method for extraction of humic acid in high-concentration divalent-ion leachate MBR + NF concentrated liquid Download PDFInfo
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- CN105694063A CN105694063A CN201410689333.XA CN201410689333A CN105694063A CN 105694063 A CN105694063 A CN 105694063A CN 201410689333 A CN201410689333 A CN 201410689333A CN 105694063 A CN105694063 A CN 105694063A
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Abstract
The present invention discloses a method for extraction of humic acid, namely a method for two-stage ultrafiltration extraction of humic acid in a urban domestic waste sanitary landfill site and waste incineration power plant mixed leachate or a separate waste incineration power plant leachate MBR + NF membrane interception liquid, and the extraction method is advanced, practical, economic, simple in process and equipment, small in land occupation, free of secondary pollution, reliable and simple in operation, and suitable for extraction of humic acid in leachate MBR + NF membrane interception liquids with high salt content especially high divalent salt ion concentration.
Description
Technical field
The invention belongs to technical field of waste treatment, particularly to separating humic acids from municipal solid waste sanitary landfill and garbage incinerating power plant mixing percolate or independent garbage incinerating power plant percolate MBR+NF film trapped fluid and concentrating as the extracting method containing humic acid water-soluble fertilizer。
Background technology
Percolate is that a kind of pollution intensity is big, and is extremely difficult to the high concentrated organic wastewater processed, and is one of garbage sanitary filling field and the main secondary pollution of garbage incinerating power plant。Current percolate processes prevailing technology and is mainly MBR+NF+RO, wherein RO reaches the operation use of quality of reused water requirement as salt in process guarantee up to standard and further removal NF water outlet, the main process of percolate process up to standard is MBR+NF, this group technology reaches in " household refuse landfill sites Environmental capacity standard " (GB16889-2008) while limited value of discharge standard making process water outlet, it is inevitably generated the MBR+NF film trapped fluid accounting for stock solution volume 1/4-1/6, the method processing this trapped fluid at present recharges landfill yard, advanced oxidation, return spray incinerator and with flyash curing etc., but all there is cost intensive in these methods or impact processes defect or the deficiencies such as system stability, actually it is difficult to operation steady in a long-term。It is COD based on major pollutants in MBR+NF film trapped fluid, and in this COD, humic acids accounts for more than 60-70%, therefore it is contemplated that recycle the purpose reaching harmless treatment with resource, to obtain better environmental benefit and economic benefit。Patent of invention " percolation liquid of city life garbage landfill reuse method " and " extracting method of humic acids " disclose percolation liquid of city life garbage landfill stock solution and the method for resource of percolate MBR+NF film trapped fluid, although the former can obtain the organic liquid fertilizer that organic matter (humic acids) solid content is higher, but there is submerged combustion evaporation unit organic (humic acids) and inorganic salt inferior separating effect, the shortcoming such as energy resource consumption is big, operating cost is high, maintenance management is more complicated；Although the latter promotes with inorganic salt separating effect relative to the former humic acids, and energy consumption is greatly reduced, but the garbage sanitary filling field higher for divalent salts content and humic acids separation and recovery in garbage burning factory mixing percolate or independent garbage incinerating power plant percolate MBR+NF film trapped fluid, when high multiple separates concentration, easily occur that calcium and magnesium and sulfate radical reach supersaturation Precipitation, cause that serious fouling membrane, the operation stability of influential system occurs in its membranous system, even damage membranous system。Thus it is necessary that further research and development technology is more advanced, economy is more reasonable, operation maintenance is easier, the reliable extracting method of humic acids suitable in the percolate MBR+NF film trapped fluid that divalent salts content is higher。
Summary of the invention
It is an object of the invention to provide the extracting method of a kind of humic acids, i.e. municipal solid waste sanitary landfill and the two-stage ultrafiltration extracting method of humic acids in garbage incinerating power plant mixing percolate or independent garbage incinerating power plant percolate MBR+NF film trapped fluid, this extracting method is advanced, practical, economical, flow process and equipment are simple, take up an area few, non-secondary pollution, runs easy, reliable。
For achieving the above object, the present invention adopts the following technical scheme that
1) percolate MBR+NF film trapped fluid being pumped into one-level ultrafiltration system, operation pressure is 0.5 ~ 1.8MPa, and cycles of concentration is 5 ~ 12 times；In described one-level ultrafiltration concentration liquid, humic acids concentration reaches more than 7000mg/L, obtains one-level liquid and one-level ultrafiltration permeate are concentrated by ultrafiltration after membrance separation；Film used by one-level ultrafiltration filter system is a kind of antipollution height desalination rate ultrafilter membrane, and retaining relative molecular weight is 1000 ~ 2500。Owing to one-level ultrafiltration permeate COD exceedes limited value of discharge standard, need to process, nanofiltration system can be pumped into, operation pressure is 0.4 ~ 2Mpa, cycles of concentration is 2 ~ 5 times, it is 200 ~ 500 that NF membrane retains relative molecular weight, the NF membrane trapped fluid of formation supernatant after Fenton oxidation mix with percolate MBR+NF water outlet with corresponding proportion again after mixing with the nanofiltration permeate of formation after qualified discharge, after Fenton oxidation produce chemical sludge mechanical dehydration after return landfill yard dispose。
2) one-level of step 1) being concentrated by ultrafiltration liquid pump and enter two-stage ultrafiltering system, operate pressure 0.5 ~ 1.8MPa, cycles of concentration is 5 ~ 15 times；In described ultrafiltration concentration liquid, humic acids concentration reaches more than 30g/L；Two-stage ultrafiltering concentrated solution and two-stage ultrafiltering permeate is obtained after membrance separation；Namely two-stage ultrafiltering concentrated solution obtains containing humic acid water-soluble fertilizer through supplement nitrogen, phosphorus, these elements of potassium。Film used by two-stage ultrafiltering system is a kind of antipollution height desalination rate ultrafilter membrane, and retaining relative molecular weight is 1000 ~ 2500。Two-stage ultrafiltering permeate is back to the one-level ultrafiltration system described in step 1) and again separates concentration。
The present invention has the great advantage that
(1) two-stage ultrafiltration technology is taked to extract municipal solid waste sanitary landfill and humic acids in garbage incinerating power plant mixing percolate or independent garbage incinerating power plant percolate MBR+NF film trapped fluid, the humic acids concentration reclaimed can meet the index request of humic acids in agricultural industry criteria " containing humic acid water-soluble fertilizer " (NY1106-2010), can obtain containing humic acid water-soluble fertilizer through suitably augmenting the simply processing such as nitrogen, phosphorus, potassium。One-level ultrafiltration permeate adopts Fenton oxidation to process after nanofiltration concentrates, supernatants after precipitation mix with percolate MBR+NF water outlet with corresponding proportion again after mixing with the nanofiltration permeate of formation after qualified discharge, major part divalent salts ion in MBR+NF film trapped fluid is made to have a rational exhaust outlet, do not accumulate in the entire system, ensure that system longtime running is stable, and effectively reduce operating cost。
(2) advanced technology in the harmless treatment of MBR+NF film trapped fluid or resource utilization method, the ripe practical approach of economical rationality is little, especially the extracting method of humic acids suitable in the percolate MBR+NF film trapped fluid that divalent salts content is higher is lacked, utilize this extracting method with humic acids in garbage incinerating power plant mixing percolate or independent garbage incinerating power plant percolate MBR+NF film trapped fluid, built municipal solid waste sanitary landfill can be easily separated recovery, so both solve the Environmental capacity problem of film trapped fluid, realize again turning waste into wealth, reach environmental benefit, the unification of Social benefit and economic benefit。
(3) this extracting method is advanced, practical, economical, and flow process and equipment are simple, takes up an area few, non-secondary pollution, runs easy, reliable, is suitable in the percolate MBR+NF film trapped fluid that the particularly divalent salts ion concentration of high salinity is high the extraction of humic acids。
Accompanying drawing explanation
Accompanying drawing is the process chart of the present invention。
Detailed description of the invention
Below in conjunction with accompanying drawing, municipal solid waste sanitary landfill of the present invention is further described with the two-stage ultrafiltration extracting method of humic acids in garbage incinerating power plant mixing percolate or independent garbage incinerating power plant percolate MBR+NF film trapped fluid。
First the general thought of the present invention is set forth。Owing to the content of Organic substance and inorganic salt all compares high in municipal solid waste sanitary landfill and garbage incinerating power plant mixing percolate or individually garbage incinerating power plant percolate MBR+NF film trapped fluid, Organic substance is mainly difficult to biodegradable humic acids, inorganic salt then contains substantial amounts of divalent salts ion, cause it to be difficult to harmless treatment or processing cost is higher, and nano-filtration unit is low to the MBR+NF film trapped fluid separation cycles of concentration of this water quality characteristic because divalent salts ion almost all being retained so that it in patent of invention " extracting method of humic acids ", bad adaptability, and the enrichment rapidly of divalent salts ion may result in divalent salts ion supersaturation in whole system separation concentration process and precipitates out inorganic salt precipitation, film is caused to block, even damage membranous system。Therefore, the present invention adopts two-stage Ultra filtration membrane technique that with humic acids in garbage incinerating power plant mixing percolate or independent garbage incinerating power plant percolate MBR+NF, municipal solid waste sanitary landfill is carried out extraction and makes containing humic acid water-soluble fertilizer, thus solving its Environmental capacity problem。In addition, patent of invention " percolation liquid of city life garbage landfill reuse method " adopts two-stage ultrafiltration and evaporation group technology to make organic liquid fertilizer to separate humic acids in percolate stock solution, and the present invention adopts simple membrane separation process, and raw material sources, flow process and technological parameter are all different。The raw material MBR+NF film trapped fluid water quality of the present invention is more complicated, derive from municipal solid waste sanitary landfill and garbage incinerating power plant mixing percolate or independent garbage incinerating power plant percolate, and the raw material of patent of invention " reuse method of percolation liquid of city life garbage landfill " and " extracting method of humic acids " is from simple municipal solid waste sanitary landfill, the content of its inorganic salt, the particularly concentration of divalent salts ion, the raw material generally relative to the present invention is low。It is embodied in: (1) adopts two-stage ultra-filtration and separation concentration municipal solid waste sanitary landfill to make the method containing humic acid water-soluble fertilizer with humic acids in garbage incinerating power plant mixing percolate or independent garbage incinerating power plant percolate MBR+NF film trapped fluid；(2) in order to improve the transmitance of inorganic salt, particularly bivalent ions passing through, the relative molecular weight that retains used by one-level ultrafilter membrane is 1000 ~ 2500, and cycles of concentration is 5 ~ 12 times, makes the humic acids concentration that one-level is concentrated by ultrafiltration in liquid reach more than 7000mg/L。The transmitance of this grade of ultrafiltration inorganic salt is between 85% ~ 90%, and organic transmitance is 5% ~ 10%, and Organic substance is well separated with inorganic salt；(3) due in one-level ultrafiltration permeate organic content relatively low, mixed liquor COD is typically between 250 ~ 400mg/L, separation recovery efficiencies is low again, and for making whole system have individual divalent salts ion outlet, so discharging after one-level ultrafiltration permeate is carried out Fenton oxidation process。Processing the water yield for reducing Fenton, effectively reduce Fenton oxidation cost, first employing retains the NF membrane that relative molecular weight is 200 ~ 500 and one-level ultrafiltration permeate carries out 2 ~ 5 times of concentrations。After the nanofiltration concentrated solution formed mix with the nanofiltration permeate formed after Fenton oxidation processes, then qualified discharge after mixing with percolate MBR+NF water outlet with corresponding proportion, time landfill yard disposal after chemical sludge mechanical dehydration。(4) in order to improve the concentration of humic acids in one-level ultrafiltration concentration liquid further, adopting two-stage ultrafiltering to continue it is carried out concentration 5 ~ 15 times, the relative molecular weight that retains of film is 1000 ~ 2500, and the content of humic acids reaches more than 30g/L。The transmitance of this grade of ultrafiltration inorganic salt is 80% ~ 85%, and transmissivity of organic matter through is below 5%, and Organic substance and inorganic salt separating effect are still fine。(5) in order to improve the system response rate to humic acids, COD concentration is reached the two-stage ultrafiltering permeate of more than 1000mg/L and is back to one-level ultrafiltration system and re-starts separation concentration。(6) its humic acids content of two-stage ultrafiltering concentrated solution is more than 30g/L, meets the index request of humic acids in agricultural industry criteria " containing humic acid water-soluble fertilizer " (NY1106-2010)。Can obtain containing humic acid water-soluble fertilizer by simply adding a great number of elements such as nitrogen, phosphorus, potassium。
As shown in drawings, municipal solid waste sanitary landfill is divided into two parts with garbage incinerating power plant mixing percolate or independent garbage incinerating power plant percolate MBR+NF film trapped fluid after one-level ultrafiltration system: a part is film trapped fluid, its organic matter is mainly humic acids, concentration is significantly improved than charging, up to more than 7000mg/L, Organic substance 90% ~ 95% retains, and inorganic salt (representing with electrical conductivity) 85% ~ 90% is through ultrafilter membrane, namely major part inorganic ion can well pass through in one-level ultrafiltration system, inorganic matter can be good at separating with Organic substance, the film trapped fluid water yield obtained accounts for 8% ~ 20% into water；Another part is film permeate, the water yield accounts for 80% ~ 92% into water, mixed liquor COD concentration is generally less than 400mg/L, and be the Organic substance of molecular weight, Fenton oxidation is adopted to process after nanofiltration system concentrates 2 ~ 5 times, after supernatants after precipitation mixes with the nanofiltration permeate of formation, qualified discharge after mixing with percolate MBR+NF water outlet with corresponding proportion again, divalent salts ion is made to have individual floss hole, thus avoiding divalent salts ion cumulative effect membranous system in the entire system to run, it is ensured that the operation steady in a long-term of whole system。In one-level ultrafiltration concentration liquid, humic acids content does not also reach the index request of humic acids in " containing humic acid water-soluble fertilizer " (NY1106-2010), therefore, adopt two-stage ultrafiltering system that one-level is concentrated by ultrafiltration liquid and separate concentration further, separate through two-stage ultrafiltering system and be also divided into two parts after concentration: one is film trapped fluid, account for the 6% ~ 20% of charging liquid measure, wherein the content of humic acids is up to more than 30g/L, meet the index request of humic acids in " containing humic acid water-soluble fertilizer " (NY1106-2010), this grade of organic rejection is more than 95%, and the transmitance of inorganic salt is 80% ~ 85%, namely Organic substance and inorganic salt in one-level ultrafiltration concentration liquid are had good separating effect by two-stage ultrafiltering system；Another part is two-stage ultrafiltering permeate, accounts for the 80% ~ 94% of feeding liquid, and its COD concentration reaches more than 1000mg/L, is mainly composed of humic acids, is back to one-level ultrafiltration system and again separates concentration, improves the humic acids response rate of total system。
Embodiment 1
Municipal solid waste sanitary landfill of the present invention and humic acids extracting method technical parameter in garbage incinerating power plant mixing percolate or independent garbage incinerating power plant percolate MBR+NF film trapped fluid:
1, the condition of water quality of percolate MBR+NF film trapped fluid
pH6.0~7.5
COD1000~4500mg/L
Electrical conductivity 10 ~ 25ms/cm
Ca2+300~1500mg/L
Mg2+200~1000mg/L
SO4 2-600~3000mg/L
2, one-level ultrafiltration system
Operating pressure 0.5 ~ 1.8Mpa
Cycles of concentration 5 ~ 12 times
Molecular cut off 1000 ~ 2500Da
COD7000~13000mg/L
3, two-stage ultrafiltering system
Operating pressure 0.5 ~ 1.8MPa
Cycles of concentration 5 ~ 15 times
Molecular cut off 1000 ~ 2500Da
Humic acids >=30g/L
4, nanofiltration system
Operating pressure 0.4 ~ 2Mpa
Cycles of concentration 2 ~ 5 times
Molecular cut off 200 ~ 500Da
5, Fenton processes system
FeSO4·7H2O dosage 0.03 ~ 0.1mol/L
n(H2O2)/n(Fe2+) add ratio 3 ~ 5
Original ph 3-7.5
Response time 120min
Embodiment 2
This sanitary filling field first stage of the project brought into operation in nineteen ninety-five, the second stage of the project completes for use in 2012, garbage incinerating power plant first stage of the project brought into operation in 2008, sanitary filling field and garbage incinerating power plant day produce percolate respectively 1200 tons and 300 tons, and total percolate water yield is 1500 ton per days。The percolate that sanitary filling field and garbage incinerating power plant produce mixes at regulating reservoir, and after homogenizing is all measured, water quality is as follows: pH is 7 ~ 8.5, and COD is 6000 ~ 12000mg/L, BOD is 2000 ~ 6000mg/L, and electrical conductivity is 10 ~ 18ms/cm, and color is grey black。This percolate body processing system is MBR+NF technique, and stable water outlet reaches discharge standard。The water quality of this percolate MBR+NF film trapped fluid is: pH is 6.5 ~ 7.2, and COD is 1000 ~ 3000mg/L, and humic acids concentration (in COD) is about 600 ~ 2100mg/L, and electrical conductivity is 12 ~ 20ms/cm。Film trapped fluid directly can be lifted into one-level ultrafiltration system by pump, the relative molecular weight that retains of one-level ultrafilter membrane is 1000Da, operation pressure reduction is 0.8Mpa, cycles of concentration is 10 times, it is 7000 ~ 13000mg/L that membrance separation rear stage is concentrated by ultrafiltration liquid COD, electrical conductivity is 14 ~ 22ms/cm, and humic acids concentration is about 4500 ~ 10000mg/L, and color is bronzing darkly；One-level ultrafiltration permeate COD is 250 ~ 500mg/L, and electrical conductivity is 11 ~ 16ms/cm, and color is light yellow, enters nanofiltration system and separates concentration。It is 300 that nanofiltration retains relative molecular weight, and operation pressure reduction is 0.8Mpa, and cycles of concentration is 3 times, and after membrane separation concentration, trapped fluid COD is 800 ~ 1500mg/L, and electrical conductivity is 14 ~ 18ms/cm, and color is yellow；Nanofiltration permeate COD is 20 ~ 40mg/L, and color is colourless。Above-mentioned nanofiltration trapped fluid enters Fenton system, FeSO4·7H2O dosage is 0.08mol/L, n(H2O2)/n(Fe2+)=4, initial pH are 4, and response time 120min has reacted rear pH and adjusted back 7 ~ 8.5, after oxidized precipitation, water outlet COD is 200 ~ 500mg/L, and color is colourless or light yellow, after mixing with nanofiltration permeate, then press qualified discharge after corresponding proportion mixes with percolate MBR+NF water outlet；And precipitating sludge returns landfill yard after mechanical dehydration and disposes。Separate, through one-level ultrafiltration system of the present invention, the one-level ultrafiltration concentration liquid obtained after concentration and be lifted into two-stage ultrafiltering system by pump, the relative molecular weight that retains of ultrafilter membrane is 1000 ~ 2500, operation pressure reduction is 0.8Mpa, cycles of concentration is 6 times, after membrance separation, two-stage ultrafiltering concentrated solution COD reaches 50000 ~ 70000mg/L, electrical conductivity is 21 ~ 30ms/cm, humic acids concentration is about 30000 ~ 45000mg/L, color is black, show the satisfied index request containing humic acid water-soluble fertilizer product to humic acids of humic acids content in two-stage ultrafiltering concentrated solution, through adding N, P, the a great number of elements such as K can obtain containing humic acid water-soluble fertilizer。Two-stage ultrafiltering permeate is transparent, in yellow, passes back into one-level ultrafiltration system and again separates concentration。
The foregoing is only presently preferred embodiments of the present invention, all equalizations done according to the present patent application the scope of the claims change and modify, and all should belong to the covering scope of the present invention。
Claims (8)
1. the extracting method of humic acids, it is characterised in that: described humic acids is in municipal solid waste sanitary landfill and garbage incinerating power plant mixing percolate or independent garbage incinerating power plant percolate MBR+NF film trapped fluid；Described extracting method is one-level ultrafiltration and two-stage ultrafiltering。
2. humic acids extracting method according to claim 1, it is characterised in that: described method comprises the steps: 1) percolate MBR+NF film trapped fluid is pumped into one-level ultrafiltration system, obtain one-level after membrance separation and liquid and one-level ultrafiltration permeate are concentrated by ultrafiltration；One-level ultrafiltration permeate pumps into nanofiltration system again, obtains nanofiltration concentrated solution and nanofiltration permeate after membrance separation；2) one-level of step 1) is concentrated by ultrafiltration liquid pump and enters two-stage ultrafiltering system, after membrance separation, obtain two-stage ultrafiltering concentrated solution and two-stage ultrafiltering permeate；Namely two-stage ultrafiltering concentrated solution obtains containing humic acid water-soluble fertilizer through supplement nitrogen, phosphorus, these elements of potassium。
3. humic acids extracting method according to claim 1, it is characterised in that: the divalent salts content in percolate MBR+NF film trapped fluid is high, Ca2+> 300mg/L, Mg2+> 200mg/L, SO4 2->600mg/L。
4. humic acids extracting method according to claim 2, it is characterised in that: the operation pressure of the one-level ultrafiltration system described in step 1) is 0.5 ~ 1.8MPa, and cycles of concentration is 5 ~ 12 times；In described one-level ultrafiltration concentration liquid, humic acids concentration reaches more than 7000mg/L；Film used by described one-level ultrafiltration system is a kind of antipollution height desalination rate ultrafilter membrane, and retaining relative molecular weight is 1000 ~ 2500。
5. humic acids extracting method according to claim 2, it is characterised in that: step 2) described in the operation pressure 0.5 ~ 1.8MPa of two-stage ultrafiltering system, cycles of concentration is 5 ~ 15 times；In described two-stage ultrafiltering concentrated solution, humic acids concentration reaches more than 30g/L；Film used by described two-stage ultrafiltering system is a kind of antipollution height desalination rate ultrafilter membrane, and retaining relative molecular weight is 1000 ~ 2500。
6. humic acids extracting method according to claim 2, it is characterised in that: by step 2) described in the one-level ultrafiltration system that is back to described in step 1) of the permeate of two-stage ultrafiltering system again separate concentration。
7. humic acids extracting method according to claim 2, it is characterised in that: the operation pressure of the nanofiltration system described in step 1) is 0.4 ~ 2Mpa, and cycles of concentration is 2 ~ 5 times；Described NF membrane is a kind of high desalination rate NF membrane, and molecular cut off is 200 ~ 500。
8. humic acids extracting method according to claim 2, it is characterized in that: qualified discharge after mixing with percolate MBR+NF water outlet with corresponding proportion again after the supernatant after Fenton oxidation precipitates of the nanofiltration concentrated solution described in step 1) mix with described nanofiltration permeate, time landfill yard disposal after mechanical sludge dewatering。
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| CN110734162A (en) * | 2019-10-13 | 2020-01-31 | 麦王环境技术股份有限公司 | deep purification device and treatment process for concentrated salt water |
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