CN102992478B - Method for relieving acidic suppression of methanogenic phase during anaerobic digestion of organic wastewater - Google Patents
Method for relieving acidic suppression of methanogenic phase during anaerobic digestion of organic wastewater Download PDFInfo
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- CN102992478B CN102992478B CN201210490706.1A CN201210490706A CN102992478B CN 102992478 B CN102992478 B CN 102992478B CN 201210490706 A CN201210490706 A CN 201210490706A CN 102992478 B CN102992478 B CN 102992478B
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- 230000029087 digestion Effects 0.000 title claims abstract description 83
- 238000000034 method Methods 0.000 title claims abstract description 36
- 239000002351 wastewater Substances 0.000 title claims abstract description 21
- 230000000696 methanogenic effect Effects 0.000 title claims abstract description 20
- 230000002378 acidificating effect Effects 0.000 title claims abstract 3
- 230000001629 suppression Effects 0.000 title claims 5
- 239000010802 sludge Substances 0.000 claims abstract description 30
- 239000002253 acid Substances 0.000 claims abstract description 17
- 239000011347 resin Substances 0.000 claims abstract description 15
- 229920005989 resin Polymers 0.000 claims abstract description 15
- 230000005764 inhibitory process Effects 0.000 claims abstract description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 239000010815 organic waste Substances 0.000 claims description 21
- 239000003957 anion exchange resin Substances 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 9
- 238000005273 aeration Methods 0.000 claims description 7
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 5
- 239000008103 glucose Substances 0.000 claims description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 239000000725 suspension Substances 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
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- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims 1
- 229920005372 Plexiglas® Polymers 0.000 claims 1
- 239000003513 alkali Substances 0.000 claims 1
- 150000001450 anions Chemical class 0.000 claims 1
- 229910021641 deionized water Inorganic materials 0.000 claims 1
- 238000005342 ion exchange Methods 0.000 claims 1
- 238000012163 sequencing technique Methods 0.000 claims 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims 1
- 150000007524 organic acids Chemical class 0.000 abstract description 26
- 230000008569 process Effects 0.000 abstract description 14
- 230000000694 effects Effects 0.000 abstract description 7
- 150000002500 ions Chemical class 0.000 abstract description 5
- 238000009825 accumulation Methods 0.000 abstract description 4
- 239000000872 buffer Substances 0.000 abstract description 4
- 235000005985 organic acids Nutrition 0.000 abstract description 3
- 230000002411 adverse Effects 0.000 abstract 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 14
- 239000000243 solution Substances 0.000 description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 7
- 239000003456 ion exchange resin Substances 0.000 description 7
- 229920003303 ion-exchange polymer Polymers 0.000 description 7
- 239000007789 gas Substances 0.000 description 6
- 230000004087 circulation Effects 0.000 description 5
- 238000010790 dilution Methods 0.000 description 5
- 239000012895 dilution Substances 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 241000370738 Chlorion Species 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 235000002595 Solanum tuberosum Nutrition 0.000 description 1
- 244000061456 Solanum tuberosum Species 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 235000013405 beer Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
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- 238000011161 development Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
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- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
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- 229920001778 nylon Polymers 0.000 description 1
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- 239000012466 permeate Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000000452 restraining effect Effects 0.000 description 1
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- 239000010865 sewage Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
Landscapes
- Purification Treatments By Anaerobic Or Anaerobic And Aerobic Bacteria Or Animals (AREA)
Abstract
本发明涉及高浓度有机废水的厌氧消化处理方法，具体的说是一种缓解有机废水厌氧消化产甲烷相的酸性抑制的方法。首先是利用TiO2改善厌氧活性污泥的沉降特性，提高产甲烷活性污泥的浓度，减少产甲烷活性污泥的流失；其次是在厌氧消化装置中使用碳酸氢根型强碱性离子交换树脂，即便在厌氧消化液碱度偏低的情况下，降低分子态有机酸的存在比例，总体上缓冲由于有机酸累积而造成的pH酸性环境对产甲烷过程的不利影响。The invention relates to an anaerobic digestion treatment method of high-concentration organic wastewater, in particular to a method for alleviating the acid inhibition of the anaerobic digestion of organic wastewater in the methanogenic phase. The first is to use TiO2 to improve the settling characteristics of anaerobic activated sludge, increase the concentration of methanogenic activated sludge, and reduce the loss of methanogenic activated sludge; secondly, use bicarbonate-type strong alkaline ions in the anaerobic digestion unit The exchange resin, even when the alkalinity of the anaerobic digestion solution is low, reduces the proportion of molecular organic acids, and generally buffers the adverse effects of the acidic pH environment caused by the accumulation of organic acids on the methanogenic process.
Description
Technical field
The present invention relates to the anaerobic digestion handling method of high concentrated organic wastewater, a kind of method that acidity of alleviating organic waste water anaerobic digestion methanogenic phase suppresses specifically.
Background technology
Along with expanding economy, environmental pollution and energy starved increase the weight of day by day, from the anaerobic digestion techniques at the end of the sixties in last century, just have started to be subject to people's favor, are widely used subduing aspect organic pollutant.Adopt the mode of anaerobic digestion to process organic waste water, particularly high concentrated organic wastewater, can, when subduing pollutent, recycle bioenergy.
The anaerobic digestion process of organic waste water is mainly divided into hydrolysis, produces acid, produces methane three phases.At hydrolysis stage, cyto-hydrolase is hydrolyzed to small molecules by larger molecular organics; Producing acid phase, it is main small molecular organic acid that microorganism is converted into acetic acid by the organism producing on last stage; Producing methane phase, methanogen is converted into methane and carbon dioxide by organic acid.In the anaerobic digestion process of high concentrated organic wastewater, after hydrolysis of organic matter, can form a large amount of voltaile fatty acids, if methanogen can not utilize these organic acids in time, will cause the pH of anaerobic digestion environment to reduce, thereby active generation of the methanogen of acid pH sensitivity suppressed, make acid process and produce unbalance between methane process just to become serious all the more, finally may cause the acid collapse of whole anaerobic digester system.
The waste water that the processes such as beer production, potato processing produce can classify as high concentrated organic wastewater, be applicable to very much Anaerobic Digestion, but very easily there is acidification rate, be greater than the situation of producing methane speed, thereby cause organic acid accumulation to cause the poor stability of anaerobic digestion.For this class problem, the method generally adopting is to occur when organic acid suppresses to add the alkaline matters such as lime, sodium hydroxide, sodium carbonate in anaerobic digestion device, be intended to increase system basicity, regulating pH to normal range, be beneficial to methanogen activity recovery, the system that maintains is normally moved.But this method, is not only improving requirement aspect system control, has also increased the cost of sewage disposal, has improved the salinity of anaerobic effluent, has reduced effluent quality.
TPAD technique generally can not drop in alkaline matter situation in anaerobic digestion device, solves the problem that in anaerobic digestion process, organic acid suppresses.This technique stage that mainly organic acid of anaerobic digestion produced physically separates with product methane phase, their independent operatings in different reactors are independent of each other, and relatively increase the reaction volume of methanogenic phase, reduce the organic acid load of methanogen, thereby reduce the restraining effect of organic acid to methanogen.This TPAD technique, controlling unit increases, and to having relatively high expectations of operator, its practical application is also among development.
In fact, the acetic acid of take of anaerobic digestion generation is that main organic acid is essentially monobasic weak acid, and ionization constant pK is generally between 4.7-4.8.Organic acid is that organic acid permeates cell membranes by molecular state realizes to the disadvantageous effect of methanogen substantially.When anaerobic digester system, because organic acid is accumulated while causing pH on the low side, the ratio that organic acid exists with molecular state form increases.Although use water miscible alkaline matter can improve pH, reduce molecular state organic acid and have ratio, water miscible alkaline matter is not recyclable and reuse.If can cushion with the material that certain solid-state form exists the acid pH environment that organic acid accumulation causes, can reuse again, can, when improving anaerobic digestion stability, reduce processing cost.
In addition; methanogen poor growth in anaerobic activated sludge; generally the settleability of anaerobically digested sludge is so not good, easily causes the loss of methanogen, and the good granulating anaerobic activated sludge of settleability needs the time more than some months could form under given conditions.If can improve by certain approach the settling property of anaerobic activated sludge within the relatively short time, and then improve the concentration of anaerobic activated sludge, be conducive to improve in anaerobic activated sludge methanogen to organic acid tolerance.
Summary of the invention
A kind of method that provides acidity of alleviating organic waste water anaerobic digestion methanogenic phase to suppress is provided the object of the invention.
For achieving the above object, the technical solution used in the present invention is:
A method of alleviating the acidity inhibition of organic waste water anaerobic digestion methanogenic phase adds pending organic waste water to utilize TiO in anaerobic digestion reaction system
2the anaerobic activated sludge of modification, and strongly basic anion exchange resin carries out digestion process and then make the acidity of organic waste water anaerobic digestion methanogenic phase suppress to be eased.
Described TiO
2modification anaerobic activated sludge is by progressively adding TiO to conventional anaerobic activated sludge
2and under sequence batch (condition, be cultured to that sludge volume index (SVI) obtains below 40mL/g; TiO in active sludge
2massfraction be 30-60%.
TiO in described anaerobic digestion reaction vessel
2the TS concentration of modification anaerobic activated sludge is 15-30g/L, and strongly basic anion exchange resin is filled in the anaerobic digestion reaction vessel first half; Described pending organic waste water is carried out to Anaerobic Digestion with intermittent type anoxic aeration agitation form in anaerobic digestion reaction vessel.
Described anaerobic digestion reaction vessel carries out anaerobism aeration 1-5min with the interval of every 30-360min.Described strongly basic anion exchange resin is bicarbonate radical type.
The addition of strongly basic anion exchange resin in described anaerobic digestion reaction vessel:
10mM < organic waste water basicity < 30mM, chlorine ion concentration < 6mM, during BOD < 3000mg/L, the addition (weight in wet base) of bicarbonate radical type negatively charged ion strongly basic anion exchange resin accounts for the mass ratio 2%-6% of anaerobic digestion solution;
10mM < organic waste water basicity < 30mM, chlorine ion concentration < 6mM, 3000mg/L < BOD < 6000mg/L, the addition (weight in wet base) of bicarbonate radical type negatively charged ion strongly basic anion exchange resin accounts for the mass ratio 4%-8% of anaerobic digestion solution;
10mM < organic waste water basicity < 30mM, chlorine ion concentration < 6mM, 6000mg/L < BOD < 9000mg/L, the addition (weight in wet base) of bicarbonate radical type negatively charged ion strongly basic anion exchange resin accounts for the mass ratio 8-12% of anaerobic digestion solution.
Described strongly basic anion exchange resin is filled in the ion exchange resin bag that is positioned at the anaerobic digestion reaction vessel first half.
The gaseous pressure carrying out in the anaerobic digestion reaction vessel of digestion process is controlled gaseous pressure at 0.102-0.11MPa by anaerobic digestion gaseous pressure by-pass cock.
The present invention utilizes TiO
2improve the settling character of anaerobic activated sludge, improve the concentration of methanogenesis activity mud, reduce the loss of methanogenesis activity mud; Next is in anaerobic digestion device, to use bicarbonate radical type strong basic ion exchange resin, even if in the situation that anaerobic digestion solution basicity is on the low side, reduce molecular state organic acid and have ratio, cushion generally the pH sour environment that causes due to organic acid accumulation to producing the disadvantageous effect of methane process.
Advantage of the present invention is:
1. treatment process of the present invention institute spent ion exchange resin can reuse, and economy is easy to promote in actual applications simultaneously
2. adopt the inventive method to reduce anaerobic activated sludge and run off, improve effluent characteristics.
3. adopt the inventive method can slow down the acid inhibition of methanogenic phase, improve anaerobic digestion efficiency.
Accompanying drawing explanation
The acid device suppressing of alleviation organic waste water anaerobic digestion methanogenic phase that Fig. 1 provides for the embodiment of the present invention.
Embodiment
Embodiment 1
As shown in Figure 1, device mainly comprises: anaerobic digestion reaction vessel 1, ion exchange resin bag 2, anaerobism aeration unit 3, anaerobic digestion gaseous pressure by-pass cock 4, anaerobic gas buffer unit 5, water-in 6 and water port 7.
Gaseous pressure in anaerobic digestion reaction vessel 1 is controlled between 0.102-0.11MPa; When pressure surpasses 0.11Mpa, by anaerobic digestion gaseous pressure by-pass cock 4 initiative exhausts, enter anaerobic gas buffer unit 5; While causing its gaseous pressure lower than 0.102Mpa during anaerobic digestion reaction vessel 1 draining, by anaerobic digestion gaseous pressure by-pass cock 4, initiatively from anaerobic gas buffer unit 5, to anaerobic digestion reaction vessel 1, shift anaerobic gas.
Concrete processing mode:
First utilize TiO
2improve the settling character of anaerobic activated sludge.
Two anaerobic reactor A and B form by the synthetic glass post of internal diameter 10cm, high 60cm.In two anaerobic reactors, inoculate anaerobic activated sludge suspension 4L respectively, the TS of mud and VS concentration are respectively 12g/L, 8.5g/L, and the basicity of mud suspension is 20mM left and right, chlorine ion concentration 4mM left and right.Then, take every 4 days be one-period, in each cycle, in two anaerobic reactors, add the glucose of 12g and the TiO of 12g respectively
2, and stir 1min every 6 hours anaerobism, when in reactor, gaseous pressure is greater than 0.11MPa, by air pressure adjustment switch 4 initiative exhausts, close to 0.102Mpa.Continue 4 cycles altogether, anaerobic activated sludge TS concentration 22/L left and right during end, anaerobic activated sludge bulk index (SVI) is 28ml/g left and right.
Then in anaerobic digestion reaction vessel, add strongly basic anionic resin 717.The strong alkaline quaternary ammonium group that this resin contains, can be at the negatively charged ion of very large pH scope internal adsorption solution, particularly more close to the exchange capacity of absorption of bicarbonate radical and organic acid.Based on this feature, in anaerobic digestion process, utilize bicarbonate radical type anionite-exchange resin 717 regulate on ion exchange resin with anaerobic digestion solution in the dynamic change of organic acid and bicarbonate radical, reduce generally molecular state organic acid ratio in anaerobic System, thereby reduce the disadvantageous effect of organic acid to methanogen.
First the sodium hydrogen carbonate solution of common chlorion type anionite-exchange resin 717 being put into 2M is translated into bicarbonate radical type and uses washed with de-ionized water.Then claim the bicarbonate radical type anionite-exchange resin 717 of 160g (weight in wet base) to pack in nylon cloth bag, cloth bag is hung on to the top of the pending waste water of upper reactor A, and utilize the gas producing in reactor to carry out timing anaerobism aeration agitation to reactor, strengthen the top of anaerobic activated sludge and processing waste water, the exchange interaction of organic acid between the top of processing waste water and resin.In reactor B, do not add anionite-exchange resin, process in contrast, checking ion exchange resin is to the acid mitigation suppressing of anaerobic digestion.
Finally compare the difference of anaerobic reactor A and B Anaerobic Digestion organic waste water.The simulative organic wastewater adding in two reactors is all acetic acid solutions that after dilution, final BOD concentration is 960mg/L, then under 35 ℃ of conditions, carry out Anaerobic Digestion, every 6h anaerobism stirs 1min, and initiative exhaust when gaseous pressure is greater than 0.11MPa in reactor is closed to 0.102Mpa.Treat that anaerobic digestion gas production stops and pH returns to and more than 6.5 is considered as anaerobic digestion reaction and finishes.So three circulations of operation, the average used time 20.1h of reactor A, the average used time 30.6h of reactor B, adds after 4% anionite-exchange resin, and the anaerobic digestion cycle has shortened 34.3%.
Embodiment 2
Difference from Example 1 is: the simulative organic wastewater adding in A and B reactor is all glucose solutions that after dilution, final BOD concentration is 1280mg/L, and other operational conditionss are constant.So three circulations of operation, the average used time 12.8h of reactor A, the average used time 24.7h of reactor B, adds after 4% anionite-exchange resin, and the anaerobic digestion cycle has shortened 47.4%.
Embodiment 3
Difference from Example 1 is: the simulative organic wastewater adding in A and B reactor is all acetic acid solutions that after dilution, final BOD concentration is 1920mg/L, and other operational conditionss are constant.So three circulations of operation, the average used time 43.9h of reactor A, the average used time 53.1h of reactor B, adds after 4% anionite-exchange resin, and the anaerobic digestion cycle has shortened 17.1%.
Embodiment 4
Difference from Example 1 is, the simulative organic wastewater adding in A and B reactor is all glucose solutions that after dilution, final BOD concentration is 2560mg/L, and other operational conditionss are constant.So three circulations of operation, the average used time 25.2h of reactor A, the average used time 34.8h of reactor B, adds after 4% strongly basic anionic resin, and the anaerobic digestion cycle has shortened 26.7%.
Embodiment 5
Difference from Example 1 is, the addition of anaerobic reactor A intermediate ion exchange resin 717 is increased to 6% (240g from 4%, weight in wet base), the simulative organic wastewater adding in A and B reactor is all glucose solutions that after dilution, final BOD concentration is 5000mg/L, every 2 hours anaerobism aeration agitation 1min, other operational conditionss were constant.So three circulations of operation, reactor A used time 96.7h, the average used time 191.4h of reactor B, adds after 6% anionite-exchange resin, and the anaerobic digestion cycle has shortened 49.5%.
Claims (6)
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|---|---|---|---|---|
| US5449467A (en) * | 1992-11-20 | 1995-09-12 | Director General Of Agency Of Industrial Science And Technology | Process for purifying water |
| EP1346954A1 (en) * | 2000-12-28 | 2003-09-24 | Takaaki Maekawa | Apparatus for purifying water containing dissolved organic matters and trace harmful substances |
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Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0576877A (en) * | 1991-09-25 | 1993-03-30 | Agency Of Ind Science & Technol | Water treatment method |
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2012
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| CN102259032A (en) * | 2011-05-31 | 2011-11-30 | 厦门大学嘉庚学院 | Method for preparing activated sludge / titanium dioxide composite material |
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