CN112174313A - Anaerobic granular sludge regulator and preparation method and application thereof - Google Patents
Anaerobic granular sludge regulator and preparation method and application thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/28—Anaerobic digestion processes
- C02F3/2833—Anaerobic digestion processes using fluidized bed reactors
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
- C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/04—Surfactants, used as part of a formulation or alone
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/06—Nutrients for stimulating the growth of microorganisms
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Abstract
The invention discloses an anaerobic granular sludge regulator and a preparation method and application thereof. The effects of the invention include: 1. regulating inorganic mineral deposition, regulating anaerobic granular sludge density, maintaining the fluidization mass transfer characteristic of an anaerobic granular sludge bed, and ensuring the activity of an anaerobic granular sludge reactor; 2. meanwhile, the growth of anaerobic microorganisms is promoted, and the activity of granular sludge is maintained. The invention effectively solves the problem of inactivation of the anaerobic granular sludge reactor caused by biological induction of carbonate deposition, and has obvious application value.
Description
Technical Field
The invention relates to the technical field of industrial water treatment, in particular to an anaerobic granular sludge regulator and a preparation method and application thereof.
Background
Anaerobic biotechnology is commonly used for the treatment of high-concentration industrial wastewater, but the fluidization characteristics and microbial metabolic activity of anaerobic granular sludge are affected by excessive mineral composition or lack of nutrient elements in the industrial wastewater. For example, anaerobic granular sludge calcification induced by high calcium wastewater leads to a sharp increase in anaerobic granular sludge density from the conventional range (ρ ═ 1.0-1.2g/ml) to the calcification range (ρ > 1.2 g/ml). The high-density sludge occupies microbial space due to the extrusion of inorganic minerals, is deposited at the bottom of a reactor and cannot be fluidized, so that the normal work of biological fluidized beds such as an upflow sludge blanket (UASB) reactor, an anaerobic expanded granular sludge blanket (GESB) reactor, an Internal Circulation (IC) reactor and the like is seriously influenced, and finally, the waste water treatment system is disabled.
Biologically induced carbonate deposition refers to the precipitation of carbonate from a supersaturated solution as a result of microbial cells and their biochemical activities, in the process, metabolites secreted by the microbes
With Ca in the environment2+、Mg2+A reaction occurs to precipitate the minerals. The content of divalent cations (such as calcium ions and magnesium ions) in the wastewater is higher than 300mg/L, thereby causing the density of anaerobic granular sludge to increase sharply, the fluidization property to decrease, and the total effective microorganism amount and mass transfer performance of the anaerobic reactor to decrease, and finally causing the failure and collapse of an anaerobic system.
Chinese patent No. CN201910701262.3 discloses a composite phosphorus-based calcification inhibitor for blocking anaerobic granular sludge calcification and an application method thereof, wherein the raw materials comprise the following components in parts by mass: 40-85 parts of phosphoric acid, 10-25 parts of sodium tripolyphosphate and 5-25 parts of sodium pyrophosphate; it is applied to the treatment of waste paper pulping, food processing, landfill leachate and fermented high calcium-containing waste water.
Chinese patent with application number CN202010453450.1 discloses a phosphorus-free scale inhibition and dispersion agent for sewage treatment, which is characterized in that: the composition comprises the following raw materials in parts by mass: 30-50 parts of polymaleic anhydride, 20-30 parts of benzotriazole, 40-50 parts of zinc nitrate, 5-15 parts of polyacrylic acid, 10-20 parts of polyepoxysuccinic acid, 1-5 parts of sodium gluconate and 0.8-1.2 parts of deionized water; the phosphorus-free scale inhibition and dispersion agent can effectively reduce the interception of calcium ions in the anaerobic reactor, and can fundamentally solve the problems of anaerobic reactor pipeline scaling and anaerobic granular sludge calcification in a high-calcium environment.
In addition, the waste water of paper making and petrochemical industry is usually lack of basic nutrient elements such as nitrogen and phosphorus and trace elements such as cobalt and nickel, so that anaerobic microorganisms grow badly due to lack of nutrient metabolism, and the waste water treatment efficiency is influenced. In order to improve the pollutant degrading activity of anaerobic microorganisms and ensure the efficient and stable operation of an anaerobic treatment system, a microbial nutrient is widely applied to provide a proper growth and propagation environment for the anaerobic microorganisms.
Chinese patent No. CN201110457552.1 discloses a nutrient for culturing microorganisms, which comprises the following components in percentage by weight: 80-120 parts of glucose, 15-20 parts of urea, 2-5 parts of disodium hydrogen phosphate, 2-5 parts of monopotassium phosphate and 0.1-0.3 part of magnesium sulfate. It is applied to promote the rapid proliferation of wastewater treatment microorganisms.
The microbial promoters or nutrients of the above-mentioned publications have the following disadvantages:
1. the medicament has single function, the medicament formula design is only designed from the aspects of blocking mineral deposition and supplementing microorganism nutrition, and the influence of the density of the granular sludge and the fluidization characteristic thereof on the anaerobic reactor is not considered;
2. the phosphorus-based calcification inhibitor has scaling risk, and excessive phosphate is added to generate secondary calcium scale (calcium phosphate or hydroxyapatite), so that the waste of phosphorus nutrient salt is caused.
3. The medicament residue has a secondary pollution risk. For example, the excessive addition of the main components such as phosphate causes the risk of overproof total phosphorus in effluent, and because the biodegradability of the surfactant is poor, the residual medicament is not beneficial to the control of the water quality at the tail end of the wastewater treatment system.
Disclosure of Invention
The invention aims to provide an anaerobic granular sludge regulator, which regulates the density of anaerobic granular sludge to be within a normal range of 1.0-1.2g/ml by regulating inorganic mineral deposition, maintains the fluidization mass transfer characteristic of an anaerobic granular sludge bed, promotes the growth of anaerobic microorganisms and maintains the activity of the granular sludge. The stable and efficient operation of the anaerobic granular sludge reactor is ensured by comprehensively adjusting the fluidization characteristics and the microbial activity of the anaerobic granular sludge.
In order to realize the technical purpose, the invention provides an anaerobic granular sludge regulator which comprises the following raw materials in percentage by mass: 20 to 30 percent of citric acid or citrate, 5 to 15 percent of humic acid, 0.5 to 1 percent of alkyl polyglycoside surfactant, 1 to 2 percent of trace elements, 1 to 2 percent of biological factor supplement and the balance of water.
Further, the citrate is selected from one or two of sodium citrate and potassium citrate.
Further, the type of cation in the citrate does not affect the citrate anaerobic granular sludge calcification inhibitor effect.
Further, the humic acid is selected from one or more of sodium humate, potassium humate and ammonium humate.
Further, the trace elements comprise the following components in parts by mass: NH (NH)4HCO340 parts of KH2PO320 portions of FeSO4·7H2O20 parts, MnSO4·H2O5 parts, Al2(SO4)3·18H2O5 parts, NiSO4·6H2O05 parts, CoSO4·7H2O2.5 parts and (NH)4)6MO7O24·4H2O1.5 parts, H3BO31 part.
Further, the biological factor supplement comprises the following components in parts by mass: 35 parts of amino acid, 20 parts of vitamin, 25 parts of purine and 20 parts of pyridine.
The invention also provides a preparation method of the anaerobic granular sludge regulator, which comprises the following steps:
mixing the raw materials, adding water, and stirring in a mixing kettle for 2 hours to obtain liquid, namely the anaerobic granular sludge microbial accelerant.
The invention also provides application of the anaerobic granular sludge regulator in treating high calcium-containing wastewater.
Further, the high-concentration organic wastewater is waste paper pulping wastewater, food processing wastewater, landfill leachate, petrochemical wastewater or fermentation wastewater.
Further, the application method comprises the step of adding the anaerobic granular sludge regulator into the inlet water of the anaerobic reactor according to the mass ratio of calcium in the wastewater to the anaerobic granular sludge regulator being 20-120:1 in a high-concentration organic wastewater system without regulating the initial pH value of the wastewater to be treated.
The technical principle of the invention is as follows:
first, the particle density is a key parameter for adjusting the fluidized state of the granular sludge blanket in fluidized reactors such as an upflow sludge blanket (UASB) reactor, an anaerobic expanded granular sludge blanket (GESB) reactor, and an Internal Circulation (IC) reactor. By adjusting the biological induction carbonate deposition process, the average density of the anaerobic granular sludge can be effectively controlled.
Secondly, on the basis of the characteristic that citrate can chelate calcium ions, the interface energy of calcium carbonate crystal nuclei is improved by utilizing citrate inside the anaerobic granular sludge, so that the calcium carbonate microcrystal nuclei are difficult to separate out and deposit; meanwhile, in the process of converting amorphous calcium carbonate into calcite through crystallization, the citrate adsorbs and occupies the lattice position of the normal growth of crystals, and inhibits the regular growth of the crystals, so that the regularity of the crystallization is damaged, even calcium carbonate is dissolved, and the deposition of a large amount of calcium scale in the granular sludge is blocked.
Furthermore, divalent cations such as calcium and magnesium are key components constituting the framework of the anaerobic granular sludge, and the calcium and magnesium loss caused by citrate can cause deflocculation loss of the anaerobic granular sludge. By strengthening and supplementing nutrition required by microorganism metabolism, the growth and propagation of anaerobic microorganisms are facilitated and the complete structure of anaerobic granular sludge is maintained. The microelement is an indispensable component for composing an anaerobic microorganism cell structure and a microbial enzyme system, and the supplement of the microelement biological factor can enhance the activity of the microorganism and ensure that the microorganism can grow and propagate in a large amount in high-concentration organic wastewater and even toxic wastewater. The alkyl polyglycoside surfactant can provide non-toxic surface activity, increase the bioavailability of nutrients and minerals, enable microorganisms to quickly proliferate in a severe environment, form granular sludge with a good structure, and remarkably improve the activity of the anaerobic granular sludge reactor.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention has the advantages of better granulation effect of the granular sludge, compact structure, good settling property, contribution to improving the anaerobic treatment efficiency and the load impact resistance, and difficult acidification phenomenon.
(2) The invention realizes the targeted release of citrate-containing ions in the anaerobic granular sludge by utilizing the degradability of organic acid, thereby inhibiting free calcium ions from forming calcium deposition in the granular sludge and further maintaining the activity of the anaerobic granular sludge.
(3) According to the invention, after the calcium scale is removed by directly adding the anaerobic granular sludge regulator into the water inlet of the anaerobic reactor, the citric acid can be degraded by microorganisms, so that secondary pollution is avoided.
(4) According to the invention, the anaerobic granular sludge regulator is directly added into the water inlet of the anaerobic reactor, and the anaerobic reactor can adjust the density of the anaerobic granular sludge on line without stopping, discharging sludge and removing scale, so that the problem of deposition and inactivation of the granular sludge caused by sludge mineral deposition in high-concentration wastewater treatment is effectively solved, the anaerobic granular sludge sewage treatment system can be used in the fields of waste paper pulping wastewater, food processing wastewater, garbage percolate, petrochemical wastewater, fermentation wastewater and the like, and has a remarkable application value.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention. It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
For numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The description and examples are intended to be illustrative only.
The calcium ion retention rate is used as a reference standard for blocking calcification of anaerobic granular sludge, and the calcium ion retention rate is calculated according to the inlet and outlet water concentration of the anaerobic reactor, and is shown as a formula I:
wherein r is the calcium ion retention rate,%;
CInand CAntitarnish OThe calcium ion concentration of the inlet water and the outlet water of the anaerobic reactor is mg/L.
Example 1:
(1) 1.5kg of trace elements (wherein: NH)4HCO30.6kg、KH2PO30.3kg、FeSO4·7H2O0.3kg、MnSO4·H2O0.075kg、Al2(SO4)3·18H2O0.075kg、NiSO4·6H2O0.075kg、CoSO4·7H2O0.0375kg、(NH4)6MO7O24·4H2O0.0225kg、H3BO30.015kg)；
(2) 1.5kg of biological factor supplement (wherein, 0.525kg of amino acid, 0.3kg of vitamin, 0.375kg of purine and 0.3kg of pyridine).
(3) 0.8kg of alkyl polyglycoside surfactant;
(1) 22kg of sodium citrate (industrial grade 98%);
(2) 10kg of sodium humate;
mixing the raw materials, supplementing water to 100kg, and stirring in a mixing kettle for 2 hours to obtain liquid, namely the anaerobic granular sludge regulator.
Example 2:
the raw materials used in this example:
(1) 1.5kg of trace elements (wherein: NH)4HCO30.6kg、KH2PO30.3kg、FeSO4·7H2O0.3kg、MnSO4·H2O0.075kg、Al2(SO4)3·18H2O0.075kg、NiSO4·6H2O0.075kg、CoSO4·7H2O0.0375kg、(NH4)6MO7O24·4H2O0.0225kg、H3BO30.015kg)；
(2) 1.5kg of biological factor supplement (wherein, 0.525kg of amino acid, 0.3kg of vitamin, 0.375kg of purine and 0.3kg of pyridine).
(3) 1kg of alkyl polyglycoside surfactant;
(1) 25kg of sodium citrate (technical grade 98%);
(2) 10kg of sodium humate;
mixing the raw materials, supplementing water to 100kg, and stirring in a mixing kettle for 2 hours to obtain liquid, namely the anaerobic granular sludge regulator.
Example 3:
the raw materials used in this example:
(1) 2kg of trace elements (wherein: NH)4HCO30.8kg、KH2PO30.4kg、FeSO4·7H2O0.4kg、MnSO4·H2O0.1kg、Al2(SO4)3·18H2O0.1kg、NiSO4·6H2O0.1kg、CoSO4·7H2O0.05kg、(NH4)6MO7O24·4H2O0.03kg、H3BO30.02kg)；
(2) 1.5kg of biological factor supplement (wherein, 0.525kg of amino acid, 0.3kg of vitamin, 0.375kg of purine and 0.3kg of pyridine).
(3) 0.5kg of alkyl polyglycoside surfactant;
(1) 30kg of sodium citrate (industrial grade 98%);
(2) 15kg of sodium humate;
mixing the raw materials, supplementing water to 100kg, and stirring in a mixing kettle for 2 hours to obtain liquid, namely the anaerobic granular sludge regulator.
Example 4:
the raw materials used in this example:
(1) 2kg of trace elements (wherein: NH)4HCO30.8kg、KH2PO30.4kg、FeSO4·7H2O0.4kg、MnSO4·H2O0.1kg、Al2(SO4)3·18H2O0.1kg、NiSO4·6H2O0.1kg、CoSO4·7H2O0.05kg、(NH4)6MO7O24·4H2O0.03kg、H3BO30.02kg)；
(2) 2kg of biological factor supplement (wherein, 0.7kg of amino acid, 0.4kg of vitamin, 0.5kg of purine and 0.4kg of pyridine).
(3) 1kg of alkyl polyglycoside surfactant;
(1) 30kg of sodium citrate (industrial grade 98%);
(2) 15kg of sodium humate;
mixing the raw materials, supplementing water to 100kg, and stirring in a mixing kettle for 2 hours to obtain liquid, namely the anaerobic granular sludge regulator.
Application example 1:
as can be seen from the above table, after the regulator is added, the COD removal rate is improved by 10 percent, and the specific methanogenic activity is increased by 22ml/gVS and Ca2+The rejection rate was reduced by 61%.
Application example 2:
the anaerobic granular sludge regulator obtained in the embodiment 2 is used in landfill leachate and petrochemical wastewater treatment plants, the typical inlet water quality of the landfill leachate and the petrochemical wastewater is COD 6000-12000 mg/L, Ca2+500-900 mg/L. According to the actual calcium ion concentration of the wastewater, according to calciumAdding the anaerobic granular sludge regulator into a water inlet regulating tank of the anaerobic reactor at a mass ratio of 20:1 to the anaerobic granular sludge regulator.
TABLE 2 comparison of the anaerobic treatment effect of landfill leachate before and after adding anaerobic granular sludge conditioner
As can be seen from the above table, after the regulator is added, the COD removal rate is improved by 9 percent, and the specific methanogenic activity is increased by 10ml/gVS and Ca2+The retention rate is reduced by 59%.
Application example 3:
the anaerobic granular sludge regulator obtained in the example 3 is used in bean product production wastewater, the typical inlet water quality is COD 2000-5000 mg/L, and Ca is2+150-300 mg/L. According to the actual calcium ion concentration of the wastewater, adding an anaerobic granular sludge regulator into a water inlet regulating tank of the anaerobic reactor according to the mass ratio of calcium to the anaerobic granular sludge regulator of 100: 1.
TABLE 3 comparison of the anaerobic treatment effect of bean product production wastewater before and after adding anaerobic granular sludge conditioner
As can be seen from the above table, after the regulator is added, the COD removal rate is improved by 10 percent, the specific methanogenic activity is increased by 32ml/gvs, and Ca is added2+The retention rate is reduced by 59%.
Application example 4:
the anaerobic granular sludge regulator obtained in the embodiment 4 is used in the anaerobic condition of molasses alcohol wastewater, the typical influent water quality of the molasses alcohol wastewater is COD 6000-10000 mg/L, Ca2+200-500 mg/L. According to the actual calcium ion concentration of the wastewater, adding an anaerobic granular sludge regulator into a water inlet regulating tank of the anaerobic reactor according to the mass ratio of calcium to the microbial accelerant of 120: 1.
TABLE 4 comparison of anaerobic treatment Effect of molasses alcohol wastewater before and after adding anaerobic granular sludge conditioner
As can be seen from the above table, after the regulator is added, the COD removal rate is improved by 10 percent, and the specific methanogenic activity is increased by 22ml/gVS and Ca2+The rejection rate was reduced by 65%.
It should be noted that the above examples are only for illustrating the technical idea and features of the present invention, and the purpose thereof is to enable others to understand the content of the present invention and to implement the present invention, and thus the protection scope of the present invention is not limited thereby. All equivalent changes or improvements made according to the spirit of the invention should be covered within the scope of the invention.
Claims (9)
1. The anaerobic granular sludge regulator is characterized by comprising the following raw materials in percentage by mass: 20 to 30 percent of citric acid or citrate, 5 to 15 percent of humic acid, 0.5 to 1 percent of alkyl polyglycoside surfactant, 1 to 2 percent of trace elements, 1 to 2 percent of biological factor supplement and the balance of water.
2. The anaerobic granular sludge regulator as claimed in claim 1, wherein said citrate is selected from one or two of sodium citrate and potassium citrate.
3. The anaerobic granular sludge conditioner as claimed in claim 1, wherein said humic acid is selected from one or more of sodium humate, potassium humate, ammonium humate.
4. The anaerobic granular sludge regulator as claimed in claim 1, wherein the trace elements comprise the following components in parts by weight: NH (NH)4HCO340 parts of KH2PO320 portions of FeSO4·7H2O20 parts and MnSO4·H2O5 parts, Al2(SO4)3·18H2O5 parts, NiSO4·6H2O05 part, CoSO4·7H2O2.5 parts and (NH)4)6MO7O24·4H2O1.5 parts, H3BO31 part.
5. The anaerobic granular sludge regulator as claimed in claim 1, wherein the biological factor supplement comprises the following components by weight: 35 parts of amino acid, 20 parts of vitamin, 25 parts of purine and 20 parts of pyridine.
6. A method of preparing an anaerobic granular sludge conditioner according to any one of claims 1 to 5, comprising the steps of: mixing the raw materials, adding water, and stirring in a mixing kettle for 2 hours to obtain liquid, namely the anaerobic granular sludge regulator.
7. Use of an anaerobic granular sludge conditioner according to any one of claims 1 to 5 for the treatment of high concentration organic wastewater.
8. The use according to claim 7, wherein the high concentration organic wastewater is wastepaper pulping wastewater, food processing wastewater, landfill leachate, petrochemical wastewater or fermentation wastewater.
9. The application of the anaerobic granular sludge regulator as claimed in claim 8, wherein the application method comprises the step of adding the anaerobic granular sludge regulator into the inlet water of the anaerobic reactor according to the mass ratio of calcium in the wastewater to the anaerobic granular sludge regulator being 20-120:1 in a high-concentration organic wastewater system.
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| CN112779147A (en) * | 2020-12-23 | 2021-05-11 | 广西大学 | Method and device for measuring micro mass transfer and biochemical reaction process of microorganism aggregate in fluidized state |
| CN113402023A (en) * | 2021-08-03 | 2021-09-17 | 知和环保科技有限公司 | Sludge granulation method |
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