CN118206260B - A method for promoting methanogenesis by anaerobic digestion of sludge using β-cyclodextrin - Google Patents
A method for promoting methanogenesis by anaerobic digestion of sludge using β-cyclodextrin Download PDFInfo
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- 239000010802 sludge Substances 0.000 title claims abstract description 99
- 229920000858 Cyclodextrin Polymers 0.000 title claims abstract description 56
- 239000001116 FEMA 4028 Substances 0.000 title claims abstract description 56
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 title claims abstract description 56
- 235000011175 beta-cyclodextrine Nutrition 0.000 title claims abstract description 56
- 229960004853 betadex Drugs 0.000 title claims abstract description 56
- 230000029087 digestion Effects 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 33
- 230000001737 promoting effect Effects 0.000 title claims abstract description 21
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 92
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 230000001965 increasing effect Effects 0.000 claims abstract description 11
- 239000010865 sewage Substances 0.000 claims description 22
- 239000007787 solid Substances 0.000 claims description 19
- 239000007853 buffer solution Substances 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 8
- 239000004576 sand Substances 0.000 claims description 8
- 238000004062 sedimentation Methods 0.000 claims description 8
- 239000004575 stone Substances 0.000 claims description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 230000001105 regulatory effect Effects 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 238000011010 flushing procedure Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 4
- 238000007873 sieving Methods 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 3
- 238000005273 aeration Methods 0.000 claims description 2
- 239000010801 sewage sludge Substances 0.000 claims description 2
- 239000000872 buffer Substances 0.000 claims 2
- 238000012216 screening Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 11
- 230000007062 hydrolysis Effects 0.000 abstract description 7
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 7
- 230000001186 cumulative effect Effects 0.000 description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 4
- 238000004064 recycling Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000020477 pH reduction Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000002154 agricultural waste Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 239000010871 livestock manure Substances 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000009790 rate-determining step (RDS) Methods 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/02—Biological treatment
- C02F11/04—Anaerobic treatment; Production of methane by such processes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
-
- 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
- C02F2101/30—Organic compounds
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Water Supply & Treatment (AREA)
- Environmental & Geological Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
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Abstract
A method for promoting anaerobic digestion of sludge to produce methane by using beta-cyclodextrin belongs to the technical field of anaerobic digestion. The invention aims to solve the problems of low hydrolysis efficiency of refractory organic matters and low yield of energy-type product methane in the anaerobic digestion process of excess sludge. The invention provides a method for promoting anaerobic digestion of sludge to produce methane by using beta-cyclodextrin, which strengthens the production of biological methane in the anaerobic digestion process of excess sludge by using beta-cyclodextrin. The efficiency of beta-cyclodextrin for promoting the conversion of organic matters in sludge into methane gradually increases along with the increase of the beta-cyclodextrin dosage from 50mg/g to 300mg/g, and when the beta-cyclodextrin dosage is 300mg/g, the accumulated methane yield of an experimental group is increased by more than 60% compared with a control group. The invention can obtain a method for promoting anaerobic digestion of sludge to produce methane by using beta-cyclodextrin.
Description
Technical Field
The invention belongs to the technical field of anaerobic digestion, and particularly relates to a method for promoting sludge anaerobic digestion to produce methane by using beta-cyclodextrin.
Background
Conventional biological sewage treatment processes, such as activated sludge process, produce a large amount of excess sludge when treating municipal sewage. Future research on sludge treatment should be focused on harmless treatment and recycling. Anaerobic digestion technology is one of the most economical and effective methods for utilizing biomass energy, and is widely used for treating and disposing organic solid wastes such as livestock manure, agricultural wastes, excess sludge and the like. Anaerobic digestion of excess sludge can promote recycling of waste, and realize synergistic effects of pollution reduction and carbon reduction.
Anaerobic digestion can be divided into four stages of hydrolysis, acidification, hydrogen production, acetic acid production and methane production, wherein hydrolysis of refractory organics is the rate limiting step of anaerobic digestion. In order to enhance the hydrolysis of excess sludge, researchers have developed various pretreatment techniques to enhance the release of soluble organics in the sludge, thereby enhancing the recovery of energy-derived products. However, the increase of the sludge pretreatment process increases the operation complexity of the whole sludge treatment process and increases the operation cost of the sludge treatment process, so that the efficiency of directly adopting physical, chemical and biological means to promote the conversion of organic matters in the residual sludge into methane during the sludge digestion period can effectively solve the problems. Compared with physical and biological treatment technologies, the chemical treatment technology has the advantages of simple and convenient operation, short treatment period, effective reduction of running cost and the like, and becomes a research hot spot and a focus in recent years. Therefore, development of an effective sludge chemical treatment method is an effective method for promoting reduction of excess sludge and recycling of energy.
Disclosure of Invention
The invention aims to solve the problems of low hydrolysis efficiency of refractory organic matters and low yield of energy-type product methane in the anaerobic digestion process of excess sludge, and provides a method for promoting anaerobic digestion of sludge to produce methane by using beta-cyclodextrin.
The method for promoting anaerobic digestion of sludge to produce methane by using beta-cyclodextrin is specifically completed by the following steps:
1. Sieving the sewage and sludge mixture obtained from the secondary sedimentation tank of the sewage treatment plant to remove large-particle sand stone, placing the large-particle sand stone in a thermostatic chamber to settle until the interface between the sewage and the sludge is layered, and removing upper-layer sewage to obtain residual sludge A;
2. firstly, flushing anaerobic sludge by using PBS buffer solution, and then re-suspending the anaerobic sludge by using PBS buffer solution to obtain inoculated sludge B;
3. Firstly, adding excess sludge A into an anaerobic bottle, then adding beta-cyclodextrin, then adding inoculated sludge B, and uniformly mixing to obtain a reaction system, regulating the pH value of the reaction system to be neutral, removing oxygen in the anaerobic bottle by utilizing nitrogen, sealing the anaerobic bottle from which the oxygen is removed, transferring the sealed anaerobic bottle into a constant-temperature oscillating table for anaerobic digestion to produce methane, and stopping the reaction when the methane yield is not increased any more;
The volume ratio of the excess sludge A to the inoculated sludge B in the step three is 10:1;
the dosage of the beta-cyclodextrin in the third step is 50 mg/g-300 mg/g, and the dosage of the beta-cyclodextrin is the mass ratio of the beta-cyclodextrin to the volatile solid of the residual sludge A.
The principle of the invention is as follows:
anaerobic digestion can be divided into four stages of hydrolysis, acidification, hydrogen production, acetic acid production and methane production. The invention discovers that the beta-cyclodextrin promotes the release of organic matters in the sludge, the hydrolysis of polysaccharide and protein, the acidogenesis process and the methanogenesis process, thereby strengthening the anaerobic digestion efficiency of the residual sludge.
The invention has the following beneficial effects:
The invention provides a method for promoting anaerobic digestion of sludge to produce methane by using beta-cyclodextrin, which strengthens the production of biological methane in the anaerobic digestion process of excess sludge by using beta-cyclodextrin. The efficiency of beta-cyclodextrin for promoting the conversion of organic matters in sludge into methane gradually increases along with the increase of the beta-cyclodextrin dosage from 50mg/g to 300mg/g, and when the beta-cyclodextrin dosage is 300mg/g, the accumulated methane yield of an experimental group is increased by more than 60% compared with a control group.
Drawings
FIG. 1 is a graph of cumulative methane production.
Detailed Description
The method for promoting anaerobic digestion of sludge to produce methane by utilizing beta-cyclodextrin in the first embodiment is specifically completed by the following steps:
1. Sieving the sewage and sludge mixture obtained from the secondary sedimentation tank of the sewage treatment plant to remove large-particle sand stone, placing the large-particle sand stone in a thermostatic chamber to settle until the interface between the sewage and the sludge is layered, and removing upper-layer sewage to obtain residual sludge A;
2. firstly, flushing anaerobic sludge by using PBS buffer solution, and then re-suspending the anaerobic sludge by using PBS buffer solution to obtain inoculated sludge B;
3. Firstly, adding excess sludge A into an anaerobic bottle, then adding beta-cyclodextrin, then adding inoculated sludge B, and uniformly mixing to obtain a reaction system, regulating the pH value of the reaction system to be neutral, removing oxygen in the anaerobic bottle by utilizing nitrogen, sealing the anaerobic bottle from which the oxygen is removed, transferring the sealed anaerobic bottle into a constant-temperature oscillating table for anaerobic digestion to produce methane, and stopping the reaction when the methane yield is not increased any more;
The volume ratio of the excess sludge A to the inoculated sludge B in the step three is 10:1;
the dosage of the beta-cyclodextrin in the third step is 50 mg/g-300 mg/g, and the dosage of the beta-cyclodextrin is the mass ratio of the beta-cyclodextrin to the volatile solid of the residual sludge A.
In the second embodiment, the difference between the first embodiment and the second embodiment is that the sewage sludge mixture obtained from the secondary sedimentation tank of the sewage treatment plant is sieved by a 20-mesh sieve in the first step. The other steps are the same as in the first embodiment.
In the third embodiment, the difference between the first embodiment and the second embodiment is that the temperature of the thermostatic chamber in the first step is 4 ℃. The other steps are the same as those of the first or second embodiment.
In the fourth embodiment, the difference between the present embodiment and the first to third embodiments is that the total solid TS value of the excess sludge A in the first step is 29.6+ -1.3 g/L and the volatile solid VS value is 17.9+ -0.5 g/L. The other steps are the same as those of the first to third embodiments.
In a fifth embodiment, the difference between the first embodiment and the fourth embodiment is that the PBS buffer solution in the second step is 1×PBS buffer solution, and the pH value is 7.4. Other steps are the same as those of the first to fourth embodiments.
In the sixth embodiment, the difference between the first embodiment and the fifth embodiment is that the total solid TS value of the inoculated sludge B in the second step is 35.8+ -0.9 g/L, and the volatile solid VS value is 25.8+ -0.5 g/L. Other steps are the same as those of the first to fifth embodiments.
In the seventh embodiment, the difference between the first embodiment and the sixth embodiment is that the anaerobic sludge is rinsed 3 times by using the PBS buffer solution in the second step. Other steps are the same as those of embodiments one to six.
In the eighth embodiment, the difference between the present embodiment and one to seven embodiments is that in the third step, the pH of the reaction system is adjusted to 7.0.+ -. 0.1 by using 1mol/L hydrochloric acid or 1mol/L sodium hydroxide. The other steps are the same as those of embodiments one to seven.
The eighth embodiment is different from the first embodiment in that the oxygen in the anaerobic bottle is removed by aerating with nitrogen for 20min in the third embodiment. Other steps are the same as those of embodiments one to eight.
The tenth embodiment is different from one of the first to ninth embodiments in that the temperature of the constant temperature shaking table in the third step is 35 ℃ and the rotation speed is 150rpm. The other steps are the same as those of embodiments one to nine.
The following examples are used to verify the benefits of the present invention:
The experimental methods used in the following examples are conventional methods unless otherwise specified.
Beta-cyclodextrin as referred to in the following examples is purchased at Macklin. The secondary sedimentation tank of the sewage treatment plant is Harbin secondary sedimentation tank of Wenchang sewage treatment plant. Anaerobic sludge is taken from an upflow anaerobic sludge blanket reactor operating for a long period of time.
Example 1A method for promoting anaerobic digestion of sludge to produce methane by using beta-cyclodextrin comprises the following steps:
1. Sieving a sewage and sludge mixture obtained from a secondary sedimentation tank of a sewage treatment plant by a 20-mesh sieve to remove large-particle sand and stone, placing the large-particle sand and stone in a constant temperature chamber at 4 ℃ to settle to the interface layering of sewage and sludge, and removing upper-layer sewage to obtain residual sludge A;
The total solid TS value of the residual sludge A in the first step is 29.6+/-1.3 g/L, and the volatile solid VS value is 17.9+/-0.5 g/L;
2. firstly, flushing anaerobic sludge for 3 times by using PBS buffer solution, and then re-suspending the anaerobic sludge by using the PBS buffer solution to obtain inoculated sludge B;
The PBS buffer solution in the second step is 1X PBS buffer solution, and the pH value is 7.4;
The total solid TS value of the inoculated sludge B in the second step is 35.8+/-0.9 g/L, and the volatile solid VS value is 25.8+/-0.5 g/L;
3. Firstly, adding 200mL of excess sludge A into an anaerobic bottle, then adding beta-cyclodextrin, then adding 20mL of inoculated sludge B, and uniformly mixing to obtain a reaction system, regulating the pH value of the reaction system to 7.0+/-0.1, removing oxygen in the anaerobic bottle by using nitrogen aeration for 20min, sealing the anaerobic bottle from which the oxygen is removed, transferring the sealed anaerobic bottle into a constant-temperature shaking table at 35 ℃ for anaerobic digestion and methane production, and stopping the reaction when the accumulated methane yield is not increased any more;
The volume ratio of the excess sludge A to the inoculated sludge B in the step three is 10:1;
the dosage of the beta-cyclodextrin in the step three is 50mg/g, and the dosage of the beta-cyclodextrin is the mass ratio of the beta-cyclodextrin to the volatile solid of the residual sludge A;
and step three, the rotating speed of the constant temperature shaking table is 150rpm.
In example 1, step three, the cumulative methane yield was 249mL when the cumulative methane yield was no longer increased and the reaction terminated.
Example 2 the difference between this example and example 1 is that the amount of beta-cyclodextrin added in step three was 100mg/g and the amount of beta-cyclodextrin added was the mass ratio of beta-cyclodextrin to the volatile solids of excess sludge A. Other steps and parameters were the same as in example 1.
In example 2, step three, the cumulative methane yield was 294mL when the cumulative methane yield was no longer increased and the reaction terminated.
Example 3 the difference between this example and example 1 is that the amount of beta-cyclodextrin added in step three was 300mg/g and the amount of beta-cyclodextrin added was the mass ratio of beta-cyclodextrin to the volatile solids of excess sludge A. Other steps and parameters were the same as in example 1.
In example 3, step three, the cumulative methane yield was 382mL when the cumulative methane yield was no longer increasing.
Comparative example 1 the difference between this example and example 1 is that the amount of beta-cyclodextrin added in the third step was 0mg/g, and the amount of beta-cyclodextrin added was the mass ratio of beta-cyclodextrin to the volatile solids of excess sludge A. Other steps and parameters were the same as in example 1.
In the third step of comparative example 1, the cumulative methane yield was 236mL when the cumulative methane yield was no longer increased and the reaction was terminated.
In conclusion, the beta-cyclodextrin is directly put into an anaerobic digestion system of excess sludge, so that the process of converting organic matters in the sludge into methane can be effectively promoted, and the promotion effect of the beta-cyclodextrin on the methane production efficiency is concentration-dependent. When the dosage of the beta-cyclodextrin is 300mg/g, the accumulated methane yield of the experimental group is highest, and the accumulated methane yield is increased by about 62% compared with the control group. The invention has important significance for promoting the anaerobic biological treatment of the excess sludge and the practical application of the energy resource recovery technology by utilizing the beta-cyclodextrin.
Claims (6)
1. A method for promoting anaerobic digestion of sludge to produce methane by using beta-cyclodextrin is characterized by comprising the following steps:
1. Sieving the sewage and sludge mixture obtained from the secondary sedimentation tank of the sewage treatment plant to remove large-particle sand stone, placing the large-particle sand stone in a thermostatic chamber to settle until the interface between the sewage and the sludge is layered, and removing upper-layer sewage to obtain residual sludge A;
Step one, screening a sewage sludge mixture obtained from a secondary sedimentation tank of a sewage treatment plant by a 20-mesh sieve;
The total solid TS value of the residual sludge A in the first step is 29.6+/-1.3 g/L, and the volatile solid VS value is 17.9+/-0.5 g/L;
2. firstly, flushing anaerobic sludge by using PBS buffer solution, and then re-suspending the anaerobic sludge by using PBS buffer solution to obtain inoculated sludge B;
The total solid TS value of the inoculated sludge B in the second step is 35.8+/-0.9 g/L, and the volatile solid VS value is 25.8+/-0.5 g/L;
3. Firstly, adding excess sludge A into an anaerobic bottle, then adding beta-cyclodextrin, then adding inoculated sludge B, and uniformly mixing to obtain a reaction system, regulating the pH value of the reaction system to be neutral, removing oxygen in the anaerobic bottle by utilizing nitrogen, sealing the anaerobic bottle from which the oxygen is removed, transferring the sealed anaerobic bottle into a constant-temperature oscillating table for anaerobic digestion to produce methane, and stopping the reaction when the methane yield is not increased any more;
The temperature of the constant-temperature oscillating table in the third step is 35 ℃, and the rotating speed is 150rpm;
The volume ratio of the excess sludge A to the inoculated sludge B in the step three is 10:1;
the dosage of the beta-cyclodextrin in the third step is 50 mg/g-300 mg/g, and the dosage of the beta-cyclodextrin is the mass ratio of the beta-cyclodextrin to the volatile solid of the residual sludge A.
2. A method for promoting anaerobic sludge digestion to produce methane by utilizing beta-cyclodextrin according to claim 1, wherein the temperature of the thermostatic chamber in the first step is 4 ℃.
3. The method for promoting methanogenesis by sludge anaerobic digestion with beta-cyclodextrin according to claim 1, wherein the PBS buffer in the second step is1×PBS buffer with pH of 7.4.
4. The method for promoting anaerobic sludge digestion to produce methane by utilizing beta-cyclodextrin according to claim 1, wherein in the second step, the anaerobic sludge is firstly washed 3 times by utilizing PBS buffer solution.
5. The method for promoting sludge anaerobic digestion to produce methane by using beta-cyclodextrin as claimed in claim 1, wherein in the third step, the pH value of the reaction system is regulated to 7.0+/-0.1 by using hydrochloric acid with the concentration of 1mol/L or sodium hydroxide with the concentration of 1 mol/L.
6. The method for promoting anaerobic digestion and methanogenesis of sludge by utilizing beta-cyclodextrin according to claim 1, wherein in the third step, oxygen in an anaerobic bottle is removed by utilizing nitrogen aeration for 20 min.
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| JP2006026534A (en) * | 2004-07-15 | 2006-02-02 | Cyclochem:Kk | Cyclodextrin-containing methane fermentation promoter |
| CN101784722A (en) * | 2007-06-28 | 2010-07-21 | 巴科曼实验室国际公司 | Use of cyclodextrins for odor control in papermaking sludges, and deodorized sludge and products |
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