CN111762883A - Anaerobic granular sludge scale inhibitor and preparation method and application thereof - Google Patents
Anaerobic granular sludge scale inhibitor and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses an anaerobic granular sludge scale inhibitor and a preparation method and application thereof, belonging to the technical field of sewage treatment. The anaerobic granular sludge scale inhibitor comprises the following components in parts by mass: 0 to 50 parts of amino trimethylene phosphonic acid, 0 to 50 parts of hydroxyethylidene diphosphonic acid, 0 to 30 parts of hydrolyzed polymaleic anhydride, 0 to 50 parts of sodium polyacrylate, 0 to 30 parts of 1,2, 4-tricarboxylic acid-2-phosphonic butane and 0 to 25 parts of maleic acid-acrylic acid copolymer. The anaerobic granular sludge scale inhibitor provided by the embodiment of the invention can directly react with metal ions such as calcium, magnesium and the like in an anaerobic reactor, and the formed compounds can be uniformly dispersed in water and are easy to discharge, so that precipitated calcium salt can be avoided being formed, the granular sludge calcification is effectively relieved, and the growth and proliferation of sludge can be effectively promoted.
Description
Technical Field
The invention relates to the technical field of sewage treatment, in particular to an anaerobic granular sludge scale inhibitor and a preparation method and application thereof.
Background
Efficient Anaerobic reactors using Anaerobic Granular Sludge, such as IC reactors (IC), Expanded Granular Sludge Beds (EGSB), Upflow Anaerobic Sludge Beds (UASB), and the like, are common technologies for treating high-concentration organic wastewater in the industries of paper making, chemical engineering, printing and dyeing, starch, citric acid, and the like. Among them, calcification loss of anaerobic granular sludge is a common problem in the above treatment technologies, which can seriously affect the efficiency of the anaerobic treatment process.
Specifically, in the operation of the anaerobic reactor, if the concentration of calcium ions in wastewater is high, precipitated calcium salts are formed and enter the inner part of the reactor through the micropore channels of granular sludge to form scale and core, and after the reactor is operated for a long time, the granular sludge is touched by hands, so that the touch of small stones is generated, and the phenomenon is called anaerobic granular sludge calcification. The activity of the calcified granular sludge is lost, and the organic waste in the sewage can not be treated any more, so that the efficiency of the whole anaerobic treatment link of the sewage is greatly reduced.
The traditional method of controlling calcification of anaerobic granular sludge is to periodically remove calcified sludge from the anaerobic reactor and replenish fresh sludge, which is costly. Or a large amount of hydrochloric acid is added in the anaerobic treatment link to increase the solubility of calcium ions and inhibit calcium salt precipitation, but the method has high operation cost and low efficiency, and the high-concentration chloride ions can seriously corrode equipment and inhibit the microbial activity in the anaerobic granular sludge.
Disclosure of Invention
An object of an embodiment of the present invention is to provide an anaerobic granular sludge scale inhibitor to solve the above problems in the background art.
In order to achieve the above purpose, the embodiments of the present invention provide the following technical solutions:
an anaerobic granular sludge scale inhibitor comprises the following components in parts by mass: 0 to 50 parts of amino trimethylene phosphonic acid, 0 to 50 parts of hydroxyethylidene diphosphonic acid, 0 to 30 parts of hydrolyzed polymaleic anhydride, 0 to 50 parts of sodium polyacrylate, 0 to 30 parts of 1,2, 4-tricarboxylic acid-2-phosphonic butane and 0 to 25 parts of maleic acid-acrylic acid copolymer.
As a preferable scheme of the embodiment of the invention, the anaerobic granular sludge scale inhibitor comprises the following components in parts by mass: 5-25 parts of amino trimethylene phosphonic acid, 10-25 parts of hydroxyethylidene diphosphonic acid, 5-15 parts of hydrolyzed polymaleic anhydride, 5-15 parts of polyacrylic acid, 5-20 parts of 1,2, 4-tricarboxylic acid-2-phosphonic butane and 5-15 parts of maleic acid-acrylic acid copolymer.
Another object of an embodiment of the present invention is to provide a method for preparing the above anaerobic granular sludge scale inhibitor, which comprises the following steps:
weighing aminotrimethylene phosphonic acid, hydroxyethylidene diphosphonic acid, hydrolyzed polymaleic anhydride, polyacrylic acid, 1,2, 4-tricarboxylic acid-2-phosphonic butane and maleic acid-acrylic acid copolymer according to the mass parts for later use;
putting the weighed amino trimethylene phosphonic acid, hydroxyethylidene diphosphonic acid, hydrolyzed polymaleic anhydride, polyacrylic acid, 1,2, 4-tricarboxylic acid-2-phosphonic butane and maleic acid-acrylic acid copolymer into a chemical reaction kettle for reaction to obtain a chemical reaction product;
and mixing the chemical reaction product with water to obtain the anaerobic granular sludge scale inhibitor.
As another preferable scheme of the embodiment of the invention, in the step, the mass ratio of the chemical reaction product to the water is (13-53): (47-87).
As another preferable scheme of the embodiment of the invention, in the step, the mass ratio of the chemical reaction product to the water is (22-36): 64-78).
The embodiment of the invention also aims to provide the anaerobic granular sludge scale inhibitor prepared by the preparation method.
The embodiment of the invention also aims to provide the application of the anaerobic granular sludge scale inhibitor in sewage treatment.
As another preferable scheme of the embodiment of the present invention, the application comprises the following steps:
and adding the anaerobic granular sludge scale inhibitor into sewage at the suction inlet or upstream of the raw water pump of the anaerobic reactor.
As another preferable scheme of the embodiment of the invention, the addition amount of the anaerobic granular sludge scale inhibitor is 10-25 ppm.
Compared with the prior art, the embodiment of the invention has the beneficial effects that:
the anaerobic granular sludge scale inhibitor provided by the embodiment of the invention can directly react with metal ions such as calcium, magnesium and the like in an anaerobic reactor, and the formed compound can be uniformly dispersed in water and is easy to discharge, so that precipitated calcium salt can be avoided being formed, granular sludge calcification is effectively relieved, and the growth and proliferation of sludge can be effectively promoted.
In addition, the anaerobic granular sludge scale inhibitor provided by the embodiment of the invention is applied to sewage treatment, can completely replace the traditional method for inhibiting calcification of anaerobic granular sludge, and has the following better effects: the method has the advantages of small dosage, high economy, no toxic or side effect on equipment and activated sludge, environmental protection, and capability of finally realizing the calcification control and growth and proliferation of the anaerobic granular sludge, and obviously reducing the cost and improving the efficiency of the operation of each sewage station.
In particular, embodiments of the present invention provide anaerobic granular sludge scale inhibitors having an extremely high chelating capacity that results in the precipitation of calcium salt cations (e.g., Ca)2+，Mkg2+Etc.) to form stable chelates with them, thereby preventing them from precipitating calcium salt anions (e.g., CO)3 2-，SO3 2-And PO4 3-Etc.) so that the probability of generating precipitated calcium salt inside the granular sludge is greatly reduced;
the anaerobic granular sludge scale inhibitor provided by the embodiment of the invention also has a dispersing function, and after being dissolved in water, the anaerobic granular sludge scale inhibitor is adsorbed on the microcrystals of the precipitated calcium salt, so that the repulsion among particles is increased, the coalescence of the particles is hindered, the particles are in a good dispersed state, and the dispersing function of the anaerobic granular sludge scale inhibitor prevents the scale forming particles from contacting and agglomerating with each other, thereby preventing the scale or the precipitated calcium salt from further growing.
The anaerobic granular sludge scale inhibitor provided by the embodiment of the invention also has a lattice distortion effect, wherein partial functional groups in the anaerobic granular sludge scale inhibitor act on insoluble inorganic salt crystal nuclei or microcrystals to occupy a certain position, so that the normal growth of inorganic salt crystals is hindered and destroyed, the growth rate of the crystals is slowed down, and the formation of salt scale is reduced. Particularly, even the formed precipitated salt scale is loose, and is easy to be washed away under the washing of water flow.
The anaerobic granular sludge scale inhibitor provided by the embodiment of the invention also has the effect of promoting the production of granular sludge, and because the anaerobic granular sludge scale inhibitor contains trace nutrient salt components necessary for the growth of anaerobic granular sludge, the anaerobic granular sludge scale inhibitor can promote the growth of granular sludge microorganisms, ensure the activity of the microorganisms and prevent the granular sludge from being loosened.
Drawings
FIG. 1 is a schematic view of a sewage treatment process.
FIG. 2 is a graph showing the trend of improvement in calcium retention of anaerobic reactor during a statistical period in a section of paper mill in Jiangsu.
FIG. 3 is a graph showing the trend of improvement in calcium retention in column # 1 IC over a statistical time period in a paper mill section from Shandong.
FIG. 4 is a graph showing the trend of improvement in calcium retention in column 2# IC over a statistical time period in a paper mill section from Shandong.
FIG. 5 is a graph showing the trend of improvement in calcium retention in column 3# IC over a statistical time period in a paper mill section from Shandong.
FIG. 6 is a graph showing the trend of improvement in calcium retention in column 4# IC over a statistical time period in a paper mill section from Shandong.
FIG. 7 is a graph showing the trend of improvement in calcium retention in anaerobic reactors during a statistical time period in a section of a paper mill in Guangdong.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The embodiment provides an anaerobic granular sludge scale inhibitor, and the preparation method comprises the following steps:
(1) 50kg of hydroxyethylidene diphosphonic acid, 30kg of hydrolyzed polymaleic anhydride, 50kg of sodium polyacrylate, 30kg of 1,2, 4-tricarboxylic acid-2-phosphonic butane and 25kg of maleic acid-acrylic acid copolymer are weighed for later use.
(2) Putting the weighed hydroxyethylidene diphosphonic acid, hydrolyzed polymaleic anhydride, polyacrylic acid, 1,2, 4-tricarboxylic acid-2-phosphonic butane and maleic acid-acrylic acid copolymer into a chemical reaction kettle for reaction to obtain a chemical reaction product.
(3) And mixing the chemical reaction product with water according to the mass ratio of 13:87 to obtain the anaerobic granular sludge scale inhibitor.
Example 2
The embodiment provides an anaerobic granular sludge scale inhibitor, and the preparation method comprises the following steps:
(1) 50kg of aminotrimethylene phosphonic acid, 50kg of hydroxyethylidene diphosphonic acid, 30kg of hydrolyzed polymaleic anhydride, 50kg of sodium polyacrylate and 30kg of 1,2, 4-tricarboxylic acid-2-phosphonic butane are weighed for later use.
(2) And putting the weighed aminotrimethylene phosphonic acid, hydroxyethylidene diphosphonic acid, hydrolyzed polymaleic anhydride, polyacrylic acid and 1,2, 4-tricarboxylic acid-2-phosphonic butane into a chemical reaction kettle for reaction to obtain a chemical reaction product.
(3) And mixing the chemical reaction product with water according to the mass ratio of 53:47 to obtain the anaerobic granular sludge scale inhibitor.
Example 3
The embodiment provides an anaerobic granular sludge scale inhibitor, and the preparation method comprises the following steps:
(1) 5kg of aminotrimethylene phosphonic acid, 10kg of hydroxyethylidene diphosphonic acid, 5kg of hydrolyzed polymaleic anhydride, 15kg of polyacrylic acid, 20kg of 1,2, 4-tricarboxylic acid-2-phosphonic butane and 15kg of maleic acid-acrylic acid copolymer are weighed for later use.
(2) And putting the weighed amino trimethylene phosphonic acid, hydroxyethylidene diphosphonic acid, hydrolyzed polymaleic anhydride, polyacrylic acid, 1,2, 4-tricarboxylic acid-2-phosphonic butane and maleic acid-acrylic acid copolymer into a chemical reaction kettle for reaction to obtain a chemical reaction product.
(3) And mixing the chemical reaction product with water according to the mass ratio of 22:78 to obtain the anaerobic granular sludge scale inhibitor.
Example 4
The embodiment provides an anaerobic granular sludge scale inhibitor, and the preparation method comprises the following steps:
(1) 25kg of aminotrimethylene phosphonic acid, 25kg of hydroxyethylidene diphosphonic acid, 15kg of hydrolyzed polymaleic anhydride, 5kg of polyacrylic acid, 5kg of 1,2, 4-tricarboxylic acid-2-phosphonic butane and 5kg of maleic acid-acrylic acid copolymer are weighed for later use.
(2) And putting the weighed amino trimethylene phosphonic acid, hydroxyethylidene diphosphonic acid, hydrolyzed polymaleic anhydride, polyacrylic acid, 1,2, 4-tricarboxylic acid-2-phosphonic butane and maleic acid-acrylic acid copolymer into a chemical reaction kettle for reaction to obtain a chemical reaction product.
(3) And mixing the chemical reaction product with water according to the mass ratio of 36:64 to obtain the anaerobic granular sludge scale inhibitor.
Example 5
The embodiment provides an anaerobic granular sludge scale inhibitor, and the preparation method comprises the following steps:
(1) 15kg of aminotrimethylene phosphonic acid, 18kg of hydroxyethylidene diphosphonic acid, 10kg of hydrolyzed polymaleic anhydride, 10kg of polyacrylic acid, 12kg of 1,2, 4-tricarboxylic acid-2-phosphonic butane and 10kg of maleic acid-acrylic acid copolymer are weighed for later use.
(2) And putting the weighed amino trimethylene phosphonic acid, hydroxyethylidene diphosphonic acid, hydrolyzed polymaleic anhydride, polyacrylic acid, 1,2, 4-tricarboxylic acid-2-phosphonic butane and maleic acid-acrylic acid copolymer into a chemical reaction kettle for reaction to obtain a chemical reaction product.
(3) And mixing the chemical reaction product with water according to the mass ratio of 30:70 to obtain the anaerobic granular sludge scale inhibitor.
Example 6
The embodiment provides an anaerobic granular sludge scale inhibitor, and the preparation method comprises the following steps:
(1) 50kg of amino trimethylene phosphonic acid, 10kg of hydrolyzed polymaleic anhydride, 20kg of sodium polyacrylate, 10kg of 1,2, 4-tricarboxylic acid-2-phosphonic butane and 15kg of maleic acid-acrylic acid copolymer are weighed for later use.
(2) And putting the weighed aminotrimethylene phosphonic acid, hydrolyzed polymaleic anhydride, polyacrylic acid, 1,2, 4-tricarboxylic acid-2-phosphonic butane and maleic acid-acrylic acid copolymer into a chemical reaction kettle for reaction to obtain a chemical reaction product.
(3) And mixing the chemical reaction product with water according to the mass ratio of 13:87 to obtain the anaerobic granular sludge scale inhibitor.
Example 7
The embodiment provides an anaerobic granular sludge scale inhibitor, and the preparation method comprises the following steps:
(1) 30kg of aminotrimethylene phosphonic acid, 20kg of hydroxyethylidene diphosphonic acid, 20kg of sodium polyacrylate, 20kg of 1,2, 4-tricarboxylic acid-2-phosphonic butane and 5kg of maleic acid-acrylic acid copolymer are weighed for later use.
(2) And putting the weighed amino trimethylene phosphonic acid, hydroxyethylidene diphosphonic acid, polyacrylic acid, 1,2, 4-tricarboxylic acid-2-phosphonic butane and maleic acid-acrylic acid copolymer into a chemical reaction kettle for reaction to obtain a chemical reaction product.
(3) And mixing the chemical reaction product with water according to the mass ratio of 13:87 to obtain the anaerobic granular sludge scale inhibitor.
Example 8
The embodiment provides an anaerobic granular sludge scale inhibitor, and the preparation method comprises the following steps:
(1) 10kg of aminotrimethylene phosphonic acid, 30kg of hydroxyethylidene diphosphonic acid, 10kg of hydrolyzed polymaleic anhydride, 10kg of 1,2, 4-tricarboxylic acid-2-phosphonic butane and 12kg of maleic acid-acrylic acid copolymer are weighed for later use.
(2) And putting the weighed amino trimethylene phosphonic acid, hydroxyethylidene diphosphonic acid, hydrolyzed polymaleic anhydride, 1,2, 4-tricarboxylic acid-2-phosphonic butane and maleic acid-acrylic acid copolymer into a chemical reaction kettle for reaction to obtain a chemical reaction product.
(3) And mixing the chemical reaction product with water according to the mass ratio of 13:87 to obtain the anaerobic granular sludge scale inhibitor.
Example 9
The embodiment provides an anaerobic granular sludge scale inhibitor, and the preparation method comprises the following steps:
(1) 10kg of amino trimethylene phosphonic acid, 30kg of hydroxyethylidene diphosphonic acid, 20kg of hydrolyzed polymaleic anhydride, 20kg of sodium polyacrylate and 15kg of maleic acid-acrylic acid copolymer are weighed for later use.
(2) And putting the weighed amino trimethylene phosphonic acid, hydroxy ethylidene diphosphonic acid, hydrolyzed polymaleic anhydride, polyacrylic acid and maleic acid-acrylic acid copolymer into a chemical reaction kettle for reaction to obtain a chemical reaction product.
(3) And mixing the chemical reaction product with water according to the mass ratio of 13:87 to obtain the anaerobic granular sludge scale inhibitor.
Example 10
The embodiment provides a use method of the anaerobic granular sludge scale inhibitor, which comprises the following steps:
as shown in the attached figure 1, when the sewage station is transported to treat sewage, the solid equipment is not required to be changed, the anaerobic granular sludge scale inhibitor can be added into the anaerobic reactor through a metering pump at a suction inlet or upstream of a raw water pump of the anaerobic reactor (namely, on a pipeline between a raw water supply pump and a pre-acidification tank, and the part A in the figure 1), the addition amount of the anaerobic granular sludge scale inhibitor is controlled to be 10-25 ppm according to the sewage inflow of the anaerobic reactor, and the specific addition amount can be determined according to the treated water quality and the treated water quantity, and is not limited to the above.
The anaerobic granular sludge scale inhibitor provided in example 5 above was applied to the sewage treatment of paper mills in Shandong, Hubei, Jiangsu, Guangdong and Fujian according to the method provided in example 10 above. Among them, the sewage stations of these enterprises all have the problems of high concentration of calcium ions at the inlet of IC, serious calcification of sludge and need of frequent mud supplementation. By applying the anaerobic granular sludge scale inhibitor provided by the embodiment 5 of the invention, the calcium ion retention of the anaerobic reactors of the sewage stations of various enterprises is generally reduced to less than 100mkg/L from 200-300 mkg/L with a high value, namely the problem of anaerobic sludge calcification is now reversed, and sludge proliferation is realized from frequent sludge supplement, wherein the following cases are partially taken:
as shown in fig. 2, a graph of the improvement trend of calcium rejection of an anaerobic reactor in a statistical period of a certain paper mill part in jiangsu is shown, and after the anaerobic granular sludge scale inhibitor provided in example 5 is added in 2019, 6 and 25 days, the calcium rejection of the anaerobic reactor is remarkably reduced.
As shown in fig. 3 to 6, the graphs show the trend of improving calcium retention of each IC tower (1 # IC tower, 2# IC tower, 3# IC tower, 4# IC tower) in the statistical time of the paper mill part in shandong, the paper mill needs to supplement sludge every two months before using the anaerobic granular sludge scale inhibitor provided in the above example 5, and after using the anaerobic granular sludge scale inhibitor provided in the above example 5 from 2019 in 4 months, the VSS/TSS value of the sludge is maintained and not deteriorated, and the total amount of the sludge is steadily increased. Specifically, the statistical data of the sludge change of the 4# IC tower of the paper mill from 5 months to 11 months in 2019 are shown in table 1 below. Wherein TSS refers to the total suspended matter, namely the total mass of the granular sludge containing inorganic components; VSS refers to the volatile suspension, i.e. the content of available microorganisms.
TABLE 1
| Counting date | 5 month and 28 days | 6 month and 28 days | 10 month and 22 |
11 month and 10 days |
| Sludge TSS Total volume (kg) | 132444.0 | 137478.8 | 142540 | 150491.8 |
| Sludge VSS Total volume (kg) | 78928.2 | 81910.0 | 98637.0 | 109070.9 |
| VSS/TSS (%) | 59.59 | 60.81 | 69.20 | 72.48 |
From the above table 1, it is apparent that the total sludge amount and microorganism content of the IC tower are ensured and increased after the anaerobic granular sludge scale inhibitor provided in example 5 of the present invention is added.
As shown in fig. 7, which is a graph showing the improvement trend of calcium interception of an anaerobic reactor in a statistical period of a certain paper mill section in the guangdong, after the anaerobic granular sludge scale inhibitor provided in example 5 was added at noon of 9/10 in 2019, the calcium interception of the anaerobic reactor was significantly reduced.
In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.
Claims (9)
1. The anaerobic granular sludge scale inhibitor is characterized by comprising the following components in parts by mass: 0 to 50 parts of amino trimethylene phosphonic acid, 0 to 50 parts of hydroxyethylidene diphosphonic acid, 0 to 30 parts of hydrolyzed polymaleic anhydride, 0 to 50 parts of sodium polyacrylate, 0 to 30 parts of 1,2, 4-tricarboxylic acid-2-phosphonic butane and 0 to 25 parts of maleic acid-acrylic acid copolymer.
2. The anaerobic granular sludge scale inhibitor as claimed in claim 1, which comprises the following components in parts by mass: 5-25 parts of amino trimethylene phosphonic acid, 10-25 parts of hydroxyethylidene diphosphonic acid, 5-15 parts of hydrolyzed polymaleic anhydride, 5-15 parts of polyacrylic acid, 5-20 parts of 1,2, 4-tricarboxylic acid-2-phosphonic butane and 5-15 parts of maleic acid-acrylic acid copolymer.
3. A method of preparing the anaerobic granular sludge scale inhibitor as claimed in claim 1 or 2, comprising the steps of:
weighing aminotrimethylene phosphonic acid, hydroxyethylidene diphosphonic acid, hydrolyzed polymaleic anhydride, polyacrylic acid, 1,2, 4-tricarboxylic acid-2-phosphonic butane and maleic acid-acrylic acid copolymer according to the mass parts for later use;
putting the weighed amino trimethylene phosphonic acid, hydroxyethylidene diphosphonic acid, hydrolyzed polymaleic anhydride, polyacrylic acid, 1,2, 4-tricarboxylic acid-2-phosphonic butane and maleic acid-acrylic acid copolymer into a chemical reaction kettle for reaction to obtain a chemical reaction product;
and mixing the chemical reaction product with water to obtain the anaerobic granular sludge scale inhibitor.
4. The method as claimed in claim 1, wherein the mass ratio of the chemical reaction product to water is (15-100): (0-85).
5. The method for preparing the anaerobic granular sludge scale inhibitor as claimed in claim 2, wherein the mass ratio of the chemical reaction product to water in the step (20-60) to (40-80).
6. An anaerobic granular sludge scale inhibitor prepared by the preparation method of any one of claims 3 to 5.
7. Use of an anaerobic granular sludge scale inhibitor as claimed in any one of claims 1 to 2 and claim 6 in sewage treatment.
8. The use according to claim 7, characterized in that it comprises the following steps:
and adding the anaerobic granular sludge scale inhibitor into sewage at the suction inlet or upstream of the raw water pump of the anaerobic reactor.
9. The use of claim 8, wherein the anaerobic granular sludge scale inhibitor is added in an amount of 10 to 25 ppm.
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| CN115259409A (en) * | 2022-07-26 | 2022-11-01 | 上海净豚环保科技有限公司 | Calcification-preventing growth-promoting scale inhibitor for anaerobic granular sludge and preparation method thereof |
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Application publication date: 20201013 |