CN114291907A - Biological reduction method for sludge iron - Google Patents
Biological reduction method for sludge iron Download PDFInfo
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- CN114291907A CN114291907A CN202210031732.1A CN202210031732A CN114291907A CN 114291907 A CN114291907 A CN 114291907A CN 202210031732 A CN202210031732 A CN 202210031732A CN 114291907 A CN114291907 A CN 114291907A
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- sludge
- iron
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- biological reduction
- biological
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 173
- 239000010802 sludge Substances 0.000 title claims abstract description 98
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 85
- 230000009467 reduction Effects 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 44
- 238000003756 stirring Methods 0.000 claims abstract description 33
- 239000007787 solid Substances 0.000 claims abstract description 16
- 241000894006 Bacteria Species 0.000 claims abstract description 14
- 238000007599 discharging Methods 0.000 claims abstract description 10
- 238000012258 culturing Methods 0.000 claims abstract description 8
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 17
- 238000011946 reduction process Methods 0.000 claims description 3
- 238000005265 energy consumption Methods 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 5
- 230000008569 process Effects 0.000 description 22
- 239000000203 mixture Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 150000002505 iron Chemical class 0.000 description 5
- 238000004064 recycling Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005345 coagulation Methods 0.000 description 3
- 230000015271 coagulation Effects 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 3
- 239000010865 sewage Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000012840 feeding operation Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000000813 microbial effect Effects 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 2
- 230000035755 proliferation Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 239000000370 acceptor Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000001174 ascending effect Effects 0.000 description 1
- 230000031018 biological processes and functions Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 235000013980 iron oxide Nutrition 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a sludge iron biological reduction method, which comprises the following steps: s1, putting sludge to be treated and anaerobic sludge into an iron biological reduction reactor, and inoculating and culturing iron reducing bacteria; the ratio of the mass of solids in the sludge to be treated to the mass of solids in the anaerobic sludge is 1-4: 1; s2, adding sludge to be treated into the cultured iron biological reduction reactor, and carrying out intermittent stirring; s3, discharging when at least one of the pH value and the ORP in the iron biological reduction reactor is stable in the step S2; in steps S1 to S2, the ratio of the mass of solids to the mass of iron in the sludge to be treated is < 6. The sludge iron biological reduction method provided by the invention has the effects of improving iron reduction efficiency and reducing equipment operation energy consumption.
Description
Technical Field
The invention belongs to the technical field of sludge recycling, and particularly relates to a sludge iron biological reduction method.
Technical Field
The iron salt coagulation process and the fenton process produce a large amount of iron-containing sludge. The traditional sludge anaerobic reactor aims at realizing the stabilization, reduction and resource of sludge organic matters, and can only convert degradable organic matters into CH4And CO2. The chemical sludge (iron-containing sludge) mainly containing iron salt has low organic matter content, the reduction and recycling objects are mainly inorganic iron salt, and the traditional sludge anaerobic reactor and the biological process thereof cannot achieve the aim.
The biological reduction process of the iron can realize the aims of recycling and reducing the iron. In an anaerobic environment, the iron reducing bacteria take organic matters as electron donors and extracellular insoluble iron oxides as terminal electron acceptors, couple the reduction of Fe (III) through oxidizing the electron donors, and store energy required by life activities from the process. After the ferric oxide is converted into ferrous, the ferric oxide can be effectively separated and utilized, so that the recycling of iron is realized.
Different from the traditional anaerobic treatment process, in the anaerobic treatment process of the iron-rich sludge, CH is produced4The process is effectively blocked, and the organic acid generated by the hydrolysis of the organic matter is mainly utilized by the microorganisms such as iron reducing bacteria and the like. In addition, the growth environment requirements of iron reducing bacteria are also different from that of traditional anaerobic microbial populations. Therefore, the traditional sludge anaerobic treatment technology is not suitable for the anaerobic treatment of the iron-rich sludge from the aspects of sludge composition difference and microbial flora difference.
In conclusion, the creation of a growth environment suitable for iron reducing bacteria and the improvement of the biological reduction efficiency of iron are very important for realizing the biological reduction of sludge iron.
Disclosure of Invention
The invention provides a sludge iron biological reduction method, which utilizes iron reducing bacteria to realize biological reduction of iron, improves the reduction efficiency of iron in sludge through process control, and reduces the energy consumption of equipment at the same time.
The invention provides a sludge iron biological reduction method, which comprises the following steps:
s1, putting sludge to be treated and anaerobic sludge into an iron biological reduction reactor, and inoculating and culturing iron reducing bacteria; the mass ratio of the solids in the sludge to be treated to the solids in the anaerobic sludge is 1-4: 1;
s2, adding the sludge to be treated into the cultured iron biological reduction reactor, and carrying out intermittent stirring;
s3, discharging when at least one of the pH value and the ORP (oxidation-reduction potential) in the iron biological reduction reactor is stable in the step S2;
in steps S1 to S2, the ratio of the mass of solids to the mass of iron in the sludge to be treated is < 6.
The mechanism of the sludge iron biological reduction method is as follows:
since iron-reducing bacteria are ubiquitous in nature, particularly widely present in anaerobic sludge, in step S1, sludge to be treated and anaerobic sludge are mixed and cultured, and iron in the sludge to be treated creates a proliferation environment for the iron-reducing bacteria in the anaerobic sludge, thereby realizing culture;
when the step S1 realizes the culture and proliferation of the iron reducing bacteria, the biological reduction of iron in the sludge to be treated is started; monitoring pH and ORP in the iron biological reduction reactor during the process, and discharging when at least one of them is stable.
According to a preferred embodiment of the present invention, at least the following advantages are provided:
(1) according to the invention, researches show that when the ratio of the solid content (SS) to the iron content in the sludge is less than 6, the method is beneficial to the separation of ferrous and improves the recycling value of the ferrous.
(2) According to the invention, researches show that the intermittent stirring is more beneficial to the reduction of iron reducing bacteria, so that the reduction efficiency of iron is improved, and the operation energy consumption and the cost of the reactor are reduced compared with the traditional continuous stirring.
(3) According to the invention, the discharging time of the iron biological reduction reactor in the step S3 is determined through pH and ORP monitoring, so that the invalid reaction time is shortened, the processing capacity of the system is improved, and the energy consumption and the cost of the whole processing process are reduced.
In some embodiments of the invention, the sludge to be treated is an iron-containing sludge.
In some embodiments of the invention, the iron-containing sludge is from at least one of an iron salt coagulation process and a fenton process.
In some embodiments of the invention, in step S1, the anaerobic sludge is from a wastewater anaerobic treatment reactor.
In some embodiments of the invention, in step S1, the initial pH of the sludge to be treated after mixing with anaerobic sludge is 7.0 or more.
In some embodiments of the invention, in step S1, the initial pH of the sludge to be treated after mixing with the anaerobic sludge is 7.0-7.2.
In some embodiments of the invention, in step S1, the inoculating and culturing is performed under anaerobic conditions.
In some embodiments of the invention, in step S1, the culturing is terminated when the ferrous iron content in the iron bioreduction reactor no longer rises.
In the culture process, the ferrous content is subjected to the processes of ascending, descending and finally dynamic balance;
therefore, the non-rising time may be the highest point of the ferrous content or the time when the ferrous content starts to decrease.
In some embodiments of the invention, step S2 further includes adjusting the pH of the sludge to be treated to be 6.5 or more before the sludge to be treated is added.
In some embodiments of the invention, the concentration of iron in the sludge to be treated is greater than or equal to 5 g/L.
In some embodiments of the invention, the concentration of iron in the sludge to be treated is 10.3-15.2 g/L.
In some embodiments of the present invention, in step S2, the adding period is 1 to 5 days/time.
In some embodiments of the invention, in step S2, the volume of the sludge to be treated added each time is 10-50% of the volume of the iron biological reduction reactor.
In some embodiments of the invention, in step S2, the intermittent stirring is performed for a time period of 5-30 min, wherein the stirring time is greater than or equal to 3 times per day.
In some embodiments of the invention, in step S2, the intermittent stirring is performed under anaerobic conditions.
In some embodiments of the invention, in step S3, the pH is stabilized to a variation of 0.05 or less over 4 hours.
In some embodiments of the invention, in step S3, the ORP is stabilized to 5mV or less change over 4 hours.
In some embodiments of the invention, in step S3, the pH of the discharge is greater than the pH of the sludge to be treated.
In some embodiments of the invention, the sludge iron bioreduction process is performed at ambient conditions.
Drawings
The invention is further described with reference to the following figures and examples, in which:
fig. 1 is a statistical chart of the output ferrous iron yield in comparative example 1.
Detailed Description
The concept and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments to fully understand the objects, features and effects of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and those skilled in the art can obtain other embodiments without inventive effort based on the embodiments of the present invention, and all embodiments are within the protection scope of the present invention.
Example 1
In this embodiment, a sludge iron biological reduction is performed, and the specific process is as follows:
A1. selecting sludge to be treated: the basic parameters of the iron-containing sludge produced by the iron salt coagulation process are shown in table 1, and the ratio of the solid content (SS) to the iron content (Fe) is 2.46, so that the requirement of <6 is met;
A2. inoculating and culturing iron reducing bacteria: mixing and stirring the sludge to be treated obtained in the step A1 and anaerobic granular sludge (purchased from Guangzhou paper making group Co., Ltd., specifically, the anaerobic process of sewage treatment) according to the ratio of the mass of the solid in the sludge to be treated to the mass of the solid in the anaerobic granular sludge to be 4:1, putting the mixture into an iron biological reduction reactor, and mixing to obtain an initial pH value of 7.2;
after the mixture is mixed and stirred in the iron biological reduction reactor for 12 days, the content of ferrous iron in the mixture reaches the maximum value (5630 mg/L);
A3. feeding operation: as shown in Table 1, the sludge to be treated meets the feeding control requirements (pH is more than 6.5, Fe is more than 5g/L) without being adjusted, the sludge is fed/discharged once a day (batch reaction, feeding is carried out after discharging is finished), and the feeding amount of each time is 10 percent of the volume of the iron biological reduction reactor (namely 90 percent of bottom sludge is reserved);
after feeding, intermittent stirring is adopted, namely stirring is carried out for 0.5h, then standing is carried out for 7.5h, and the process is repeated continuously;
the pH value after the reactor is stabilized is about 7.6, the ORP value after the reactor is stabilized is about-420 mV, and the discharging is carried out after the pH value or the ORP value of the reactor reaches a stable value.
The energy saving of the present embodiment is calculated as follows: the reactor was stirred 24/(7.5+0.5) times a day for 3 hours each for 0.5h a day, and 3 × 0.5h for 1.5h a day, which saved the stirring time period by 93.75% compared to the continuous stirring time (24 h a day), i.e., the stirrer operation energy consumption was reduced by 93.75%.
Example 2
In this embodiment, a sludge iron biological reduction is performed, and the specific process is as follows:
A1. selecting sludge to be treated: the basic parameters of the iron-containing sludge (also called Fenton sludge) produced by the wastewater Fenton treatment process are shown in Table 1, and the ratio of the solid content (SS) to the iron content (Fe) is 1.97, so that the requirement of <6 is met;
A2. inoculating and culturing iron reducing bacteria: mixing the solid mass in the sludge obtained in the step A1 with the solid mass in hydrolysis acidification pool sludge (obtained from the Xiaohudao sewage treatment plant of the China center environmental Water affairs (Guangzhou) Co., Ltd.) and also from the anaerobic process of sewage treatment) in a ratio of 7:3, putting the mixture into an iron biological reduction reactor, and after mixing, setting the initial pH value to 6.1; adding liquid caustic soda (sodium hydroxide aqueous solution) to adjust the initial pH value to 7.0;
after the mixture is mixed and stirred in the iron biological reduction reactor for 10 days, the ferrous content in the mixture reaches the maximum value (6800 mg/L);
A3. feeding operation: adjusting the pH value of the sludge to be treated obtained in the step A1 from 5.6 to 7.0, feeding/discharging once every 2 days (batch reaction, feeding after discharging is finished), wherein the feeding amount is 20% of the volume of the iron biological reduction reactor each time (namely 80% of bottom sludge is reserved each time);
after feeding, intermittent stirring is adopted, namely stirring is carried out for 0.25h, and then standing is carried out for 3.75h, and the steps are repeated continuously;
the pH value after the reactor is stabilized is about 7.1, the ORP value after the reactor is stabilized is about-440 mV, and the discharging is carried out after the pH value or the ORP value of the reactor reaches a stable value.
The energy saving of the present embodiment is calculated as follows: the reactor was stirred 24/(3.75+0.25) times a day for 6 hours each time for 6 × 0.25 hours a day for 1.5 hours, which saved the stirring time period by 93.75% compared to the continuous stirring time (24 hours a day), i.e., the energy consumption for the stirrer was reduced by 93.75%.
TABLE 1 parameters relating to examples 1 to 2
Comparative example 1
The comparative example carries out biological reduction of sludge iron, and the specific process is different from that of the example 1:
in step A3, continuous stirring was carried out for 20 days, and then batch stirring was carried out for 20 days according to the method of example 1.
The comparative example also counts the values of ferrous iron and pH in the discharged material liquid in the processes of 20-day continuous stirring and 20-day intermittent stirring, and the specific results are shown in the result of figure 1. FIG. 1 shows: after the stirring mode is changed from continuous stirring to intermittent stirring, the ferrous content and the pH value of the discharged sludge are rapidly increased, the promotion effect of the intermittent stirring on iron reduction is shown, meanwhile, the running time of the stirrer is reduced by the intermittent stirring, and the energy consumption of the system is reduced.
The specific expression is that the concentration of the ferrous iron discharged from the reactor is 3.5-4.0 g/L during continuous stirring, and the concentration of the ferrous iron discharged is increased to 5.5-6.0 g/L after the stirring method is replaced by intermittent stirring. Compared with a continuous stirring method, the discharged ferrous iron concentration of the intermittent stirring method is increased by about 2g/L, namely, increased by about 50-60%, and the specific statistical result is shown in figure 1.
In conclusion, the invention finally improves the yield of ferrous iron and greatly reduces the energy consumption of the biological reduction method of the iron mud through the adjustment of each step.
The embodiments of the present invention have been described in detail with reference to the accompanying drawings, but the present invention is not limited to the above embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the gist of the present invention. Furthermore, the embodiments of the present invention and the features of the embodiments may be combined with each other without conflict.
Claims (10)
1. The biological reduction method for sludge iron is characterized by comprising the following steps:
s1, putting sludge to be treated and anaerobic sludge into an iron biological reduction reactor, and inoculating and culturing iron reducing bacteria; the mass ratio of the solids in the sludge to be treated to the solids in the anaerobic sludge is 1-4: 1;
s2, adding the sludge to be treated into the cultured iron biological reduction reactor, and carrying out intermittent stirring;
s3, discharging when at least one of the pH value and the ORP in the iron biological reduction reactor is stable in the step S2;
in steps S1 to S2, the ratio of the mass of solids to the mass of iron in the sludge to be treated is < 6.
2. The biological reduction method for sludge iron as claimed in claim 1, wherein in step S1, the initial pH of the sludge to be treated after mixing with anaerobic sludge is 7.0 or more.
3. The biological sludge iron reduction process according to claim 1, wherein the culturing is ended when the ferrous iron content in the biological iron reduction reactor does not rise any more in step S1.
4. The biological reduction method for the iron in the sludge as claimed in claim 1, wherein in step S2, before the sludge to be treated is added, the pH value of the sludge to be treated is adjusted to be more than or equal to 6.5.
5. The biological reduction method for sludge iron according to claim 1, characterized in that the concentration of iron in the sludge to be treated is not less than 5 g/L.
6. The biological reduction method for sludge iron according to claim 1, wherein in step S2, the adding period is 1-5 days/time; preferably, in the step S2, the volume of the sludge to be treated added each time is 10-50% of the volume of the iron biological reduction reactor.
7. The biological reduction method for sludge iron as claimed in claim 1, wherein in step S2, the intermittent stirring is performed for a time period of 5-30 min, and the stirring frequency is not less than 3 times per day.
8. The biological reduction method for sludge iron according to claim 1, wherein in step S3, the pH is stabilized to a variation of 0.05 or less within 4 hours.
9. The biological reduction method for sludge iron according to claim 1, wherein in step S3, the ORP is stabilized to 5mV or less in variation over 4 hours.
10. The biological sludge iron reduction process of claim 4, wherein in step S3, the pH value of the discharge is greater than the pH value of the sludge to be treated.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202210031732.1A CN114291907A (en) | 2022-01-12 | 2022-01-12 | Biological reduction method for sludge iron |
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| CN202210031732.1A CN114291907A (en) | 2022-01-12 | 2022-01-12 | Biological reduction method for sludge iron |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008068040A1 (en) * | 2006-12-04 | 2008-06-12 | Universiteit Gent | Process and apparatus for the biological treatment of waste water |
| CN110877956A (en) * | 2019-12-24 | 2020-03-13 | 北京城市排水集团有限责任公司 | Device and method for treating Fenton iron mud |
| CN113371849A (en) * | 2021-07-29 | 2021-09-10 | 江西师范大学 | Fenton iron mud separation and recycling method and device |
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- 2022-01-12 CN CN202210031732.1A patent/CN114291907A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008068040A1 (en) * | 2006-12-04 | 2008-06-12 | Universiteit Gent | Process and apparatus for the biological treatment of waste water |
| CN110877956A (en) * | 2019-12-24 | 2020-03-13 | 北京城市排水集团有限责任公司 | Device and method for treating Fenton iron mud |
| CN113371849A (en) * | 2021-07-29 | 2021-09-10 | 江西师范大学 | Fenton iron mud separation and recycling method and device |
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Application publication date: 20220408 |