CN119349841B - Sludge dewatering deodorant and preparation method thereof - Google Patents
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Abstract
本发明属于污泥处理领域，公开了一种污泥脱水除臭剂及其制备方法。一种污泥脱水除臭剂，包括如下重量份原料：季铵化单宁‑戊二醛5~20份，阳离子聚丙烯酰胺1~10份，碳酸钙20~50份，改性沸石10~30份；其中，所述改性沸石是通过使用十六烷基三甲基溴化铵改性沸石再接枝对苯二酚得到，表面有酚羟基和硅羟基基团；所述季铵化单宁‑戊二醛是季铵化单宁与戊二醛进行偶联反应得到。本发明提供的污泥脱水除臭剂原料中，季铵化单宁‑戊二醛和改性沸石在空间结构和化学作用两个层面形成协同效应，空间上形成的微孔‑大孔多级通道网络显著提升了脱水效率；化学上季铵基团与酚羟基的互补作用实现了全方位的除臭效果。The present invention belongs to the field of sludge treatment, and discloses a sludge dehydration deodorant and a preparation method thereof. A sludge dehydration deodorant comprises the following raw materials in parts by weight: 5 to 20 parts of quaternized tannin-glutaraldehyde, 1 to 10 parts of cationic polyacrylamide, 20 to 50 parts of calcium carbonate, and 10 to 30 parts of modified zeolite; wherein the modified zeolite is obtained by using hexadecyltrimethylammonium bromide to modify zeolite and then grafting hydroquinone, and has phenolic hydroxyl and silicon hydroxyl groups on the surface; the quaternized tannin-glutaraldehyde is obtained by coupling reaction of quaternized tannin and glutaraldehyde. In the sludge dehydration deodorant raw materials provided by the present invention, quaternized tannin-glutaraldehyde and modified zeolite form a synergistic effect at two levels of spatial structure and chemical action, and the micropore-macropore multi-level channel network formed in space significantly improves the dehydration efficiency; the complementary effect of quaternary ammonium groups and phenolic hydroxyl groups in chemistry realizes a full range of deodorization effects.
Description
Technical Field
The invention relates to the field of sludge treatment, in particular to a sludge dewatering deodorant and a preparation method thereof.
Background
In the field of sludge treatment, malodor control and dewatering efficiency have long been two key technical problems puzzling industry development, which directly affect the effect and economy of treatment process and are also closely related to environmental protection and public health.
The sludge malodor mainly originates from the anaerobic decomposition process of organic matters, and the generated gases such as hydrogen sulfide, ammonia gas, methyl mercaptan and the like are bad in smell and possibly cause harm to human health. Traditional malodor control methods include chemical deodorization, biological deodorization, physical adsorption, masking methods and the like, but the methods have the problems of unstable effect, high cost, possibility of secondary pollution and the like. On the other hand, sludge dewatering is also facing a great challenge as a key link for reducing the volume of sludge and the cost of subsequent treatment. Common dehydration methods such as mechanical dehydration, natural dehydration, chemical conditioning and the like are often limited by factors such as large equipment investment, high running cost, low efficiency, environmental influence and the like in practical application. Particularly, the hydration layer formed by colloidal substances and bacterial Extracellular Polymers (EPS) in the sludge seriously affects the dewatering effect, and the conventional method is difficult to effectively destroy the structures.
More particularly, the prior art is often focused on only a single problem, or on malodor control or on improving dehydration efficiency, and the separation type treatment method not only increases overall treatment cost, but also may lead to complicated process and increased operation difficulty. In some cases, a solution to one problem may exacerbate another problem, as some chemical deodorants may reduce the dewatering performance of the sludge, which further increases technical difficulties.
Disclosure of Invention
The invention aims to provide a sludge dewatering deodorant and a preparation method thereof, which are used for solving the problem of malodor and the difficult problem of dewatering in the sludge treatment process, accord with the principle of sustainable development and provide a safe and environment-friendly solution for sludge treatment and resource utilization.
In order to achieve the aim, in one aspect, the invention provides a sludge dewatering deodorant which comprises the following raw materials, by weight, 5-20 parts of quaternized tannin-glutaraldehyde, 1-10 parts of cationic polyacrylamide, 20-50 parts of calcium carbonate and 10-30 parts of modified zeolite;
Wherein, the modified zeolite is modified zeolite by cetyl trimethyl ammonium bromide and is grafted with hydroquinone, and the surface of the modified zeolite is provided with phenolic hydroxyl groups and silicon hydroxyl groups;
The quaternized tannin-glutaraldehyde is obtained by coupling reaction of quaternized tannin and glutaraldehyde.
Preferably, the tannin in the quaternized tannin-glutaraldehyde is selected from any one of tannin extract, gallotannin, catechin.
Preferably, the quaternized tannin-glutaraldehyde is prepared by dissolving quaternized tannin in deionized water, adding glutaraldehyde, and reacting at room temperature for 1.5-2.5h at pH 7.5-8.5.
Preferably, the molar ratio of glutaraldehyde to quaternized tannin is (0.5-2): 1.
Preferably, the preparation method of the modified zeolite comprises the steps of reacting hexadecyl trimethyl ammonium bromide modified zeolite with hydroquinone methanol solution at 65-75 ℃ and pH of 7.5-8.5 under nitrogen atmosphere for 3-5 hours, cooling to room temperature, carrying out suction filtration, collecting a solid product, washing, drying, roasting, grinding and sieving.
Preferably, the mass ratio of the cetyl trimethyl ammonium bromide modified zeolite to the hydroquinone is 1 (0.1-0.5).
Preferably, the calcination is carried out at 540-560 ℃ for 5-7 hours.
On the other hand, the invention provides a preparation method of the sludge dewatering deodorant, which comprises the steps of mixing the raw materials, granulating, drying and sieving.
Preferably, the granulation speed is 30-40rpm and the time is 15-20min.
Preferably, the drying is vacuum drying at 50-60 ℃ for 4-5 hours.
Compared with the prior art, the invention has the beneficial effects that:
1. in the raw material of the sludge dewatering deodorant provided by the invention, quaternized tannin-glutaraldehyde and modified zeolite form a synergistic effect on two layers of space structure and chemical action. The microporous-macroporous multistage channel network formed in space obviously improves the dehydration efficiency, and the complementary effect of the chemical quaternary ammonium group and the phenolic hydroxyl group realizes the omnibearing deodorization effect.
2. The sludge dewatering deodorant provided by the invention ensures stable dispersion of modified zeolite in floccules through a double fixing mechanism of physical coating and chemical bonding, and effectively solves the problems of easy agglomeration and poor dispersibility of functional components in the prior art. Meanwhile, the multipoint crosslinking effect of glutaraldehyde groups forms a stable three-dimensional network structure, so that the mechanical strength and stability of the flocs are greatly improved.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a sludge dewatering deodorant which comprises, by weight, 5-20 parts of quaternized tannin-glutaraldehyde, 1-10 parts of cationic polyacrylamide, 20-50 parts of calcium carbonate and 10-30 parts of modified zeolite, wherein the modified zeolite is obtained by grafting hydroquinone onto hexadecyl trimethyl ammonium bromide modified zeolite, phenolic hydroxyl groups and silicon hydroxyl groups are present on the surface, and the quaternized tannin-glutaraldehyde is obtained by coupling reaction of quaternized tannin and glutaraldehyde.
The action mechanism of the sludge dewatering deodorant provided by the invention is as follows:
The core action mechanism of the sludge dewatering deodorant is mainly characterized by the synergistic combination of two major functional components of quaternized tannin-glutaraldehyde and modified zeolite. Quaternized tannin glutaraldehyde is a structurally complex organic compound whose molecule contains three key structural units with specific functions. The quaternary ammonium group can perform ion exchange with negative charge groups on the surfaces of sludge particles through electrostatic attraction and selectively adsorb odor molecules with negative charges such as hydrogen sulfide, mercaptan and the like, the glutaraldehyde group can perform cross-linking reaction with nitrogen-containing compounds such as proteins, amino acids and the like in the sludge to form a stable covalent bond network structure and react with nitrogen-containing odor such as ammonia, amines and the like to generate a stable Schiff base compound, and the polyphenol structure in the tannin molecules not only enhances the stability of flocs through hydrogen bonding, but also can adsorb various polar odor molecules.
The modified zeolite is another key functional component, and after being modified by cetyl trimethyl ammonium bromide and connected with hydroquinone, the modified zeolite forms a unique composite structure. The three-dimensional pore structure of the zeolite provides sufficient space for physical adsorption, the introduction of hexadecyl long chain remarkably improves the adsorption capacity of malodorous gas, and grafted hydroquinone not only increases the quantity of surface phenolic hydroxyl groups, but also forms synergistic effect with silicon hydroxyl groups on the surface of the zeolite, thus constructing a unique difunctional active site. In the deodorizing process, the phenolic hydroxyl group mainly removes alkaline odor such as ammonia gas through acid-base neutralization, while the silicon hydroxyl group provides additional polar adsorption sites, and various malodorous gases are removed through the dual functions of physical adsorption and chemical reaction.
The synergistic effect between quaternized tannin glutaraldehyde and modified zeolite is mainly represented at two levels of steric structure and chemical action. In terms of space structure, glutaraldehyde groups in quaternized tannin-glutaraldehyde molecules contain two aldehyde groups (-CHO) which can undergo a crosslinking reaction with amino groups (-NH 2) of nitrogen-containing compounds such as proteins, amino acids, and the like in sludge. Since a plurality of reaction sites exist on each molecule, a net-shaped three-dimensional structure is formed. When such a network is formed, modified zeolite particles having a regular porous framework structure will be "embedded" therein naturally. This intercalation is achieved both by physical coating of the zeolite particles with the network and by chemical bonding of the zeolite surface active groups to the network. The dual immobilization mechanism of physical coating and chemical bonding effectively ensures that zeolite particles can be stably dispersed without agglomeration.
In terms of pore structure, the system forms a unique double-layer channel, wherein zeolite provides a regular microporous structure, and the network structure of quaternized tannin-glutaraldehyde forms a mesoporous channel. The multi-stage pore canal system combining the micropores and the macropores can more efficiently lead out the moisture in the sludge, and remarkably improves the dehydration efficiency. Meanwhile, in the aspect of chemical action, the quaternary ammonium group and the phenolic hydroxyl group form a complementary deodorizing system, and the deodorizing system can be aimed at odor molecules of different types at the same time, so that the deodorizing effect is comprehensively improved.
To further optimize system performance, the sludge dewatering deodorant also contains other important auxiliary components. The cationic polyacrylamide and the quaternized tannin-glutaraldehyde are matched for use, so that the flocculation effect can be remarkably enhanced.
Through the multicomponent synergistic design, the sludge dewatering deodorant has excellent comprehensive performance in practical application, not only has high-efficiency dewatering capacity, but also can realize lasting and stable deodorizing effect.
In some preferred embodiments, the quaternized tannin glutaraldehyde is prepared by dissolving quaternized tannin in deionized water, adding glutaraldehyde, and reacting at room temperature for 1.5-2.5 hours at pH 7.5-8.5, wherein the molar ratio of glutaraldehyde to quaternized tannin is (0.5-2): 1.
In some preferred embodiments, the preparation method of the modified zeolite comprises the steps of reacting hexadecyl trimethyl ammonium bromide modified zeolite with hydroquinone methanol solution at 65-75 ℃ and pH 7.5-8.5 under nitrogen atmosphere for 3-5 hours, cooling to room temperature, carrying out suction filtration, collecting solid products, washing, drying, roasting, grinding and sieving, wherein the mass ratio of hexadecyl trimethyl ammonium bromide modified zeolite to hydroquinone is 1 (0.1-0.5).
The preparation method of quaternized tannin and hexadecyl trimethyl ammonium bromide modified zeolite is disclosed in the prior art, and the invention is to carry out coupling reaction with glutaraldehyde on the basis of quaternized tannin obtained in the prior art, graft hydroquinone on the basis of hexadecyl trimethyl ammonium bromide modified zeolite, and realize dehydration and deodorization of sludge.
The tannin in quaternized tannin-glutaraldehyde can be selected from tannin extract, gallotannin, and catechin.
The second aspect of the invention provides a preparation method of the sludge dewatering deodorant, which comprises the steps of mixing raw materials, granulating, drying and sieving.
The particular method of granulation, drying and sieving used in the present invention is generally known in the art and the final particle size can be determined by one skilled in the art based on the environment in which the sludge dewatering deodorant is used.
Illustratively, the granulation speed is 30-40rpm for 15-20min and the drying is vacuum dried at 50-60deg.C for 4-5 hr.
In order to make the technical scheme of the invention clearer, the sludge dewatering deodorant and the performance are described in detail by a plurality of specific examples.
In the following examples, "parts" are "parts by weight".
The source information for some of the chemicals and reagents used in the examples described below are as follows:
pentanediol, cationic polyacrylamide, and calcium carbonate were purchased from Shanghai Meilin Biochemical technologies Co., ltd.
Example 1
The sludge dewatering deodorant comprises 18 parts of quaternized tannin extract-glutaraldehyde, 6 parts of cationic polyacrylamide, 30 parts of calcium carbonate and 22 parts of modified zeolite.
The preparation method of the quaternized tannin extract-glutaraldehyde comprises the steps of dissolving the quaternized tannin extract in deionized water, adjusting the pH value to 8.0, slowly dropwise adding glutaraldehyde solution, stirring at room temperature for reacting for 2 hours after dropwise adding, dialyzing with deionized water as a dialysis medium for 48 hours, and freeze-drying to obtain the quaternized tannin extract-glutaraldehyde, wherein the molar ratio of the glutaraldehyde to the quaternized tannin extract is 1:1.
The preparation method of the modified zeolite comprises the steps of dissolving hydroquinone in absolute methanol to obtain a hydroquinone methanol solution, mixing the hexadecyl trimethyl ammonium bromide modified zeolite and the hydroquinone methanol solution, adjusting the pH value to 8.0, heating to 70 ℃, controlling the stirring speed to 300rpm, reacting for 4 hours under the protection of nitrogen, cooling to room temperature, filtering, collecting a solid product, washing with absolute methanol, drying in vacuum at 60 ℃ for 12 hours, heating to 550 ℃ at the heating rate of 2 ℃ per minute, roasting for 6 hours at 550 ℃, naturally cooling to room temperature, grinding the roasted sample into fine powder, sieving with a 100-mesh sieve to obtain the hexadecyl trimethyl ammonium bromide modified zeolite grafted hydroquinone, wherein the mass ratio of the hexadecyl trimethyl ammonium bromide modified zeolite to the hydroquinone is 1:0.4.
The preparation method of the sludge dewatering deodorant comprises the steps of mixing all raw materials, granulating at a rotating speed of 30-40 rpm for 15-20 min, vacuum drying the granulated product at 50-60 ℃ for 4-5 h, sieving with a 60-mesh sieve, removing oversized particles, sieving with a 200-mesh sieve, and removing fine powder.
Example 2
The sludge dewatering deodorant comprises 5 parts of quaternized tannin extract-glutaraldehyde, 1 part of cationic polyacrylamide, 20 parts of calcium carbonate and 10 parts of modified zeolite.
The preparation method of the quaternized tannin extract-glutaraldehyde, the modified zeolite and the sludge dewatering deodorant of the embodiment refers to the embodiment 1, wherein the molar ratio of glutaraldehyde to quaternized tannin in the preparation process of the quaternized tannin extract-glutaraldehyde is 0.5:1, and the mass ratio of hexadecyl trimethyl ammonium bromide modified zeolite to hydroquinone in the preparation process of the modified zeolite is 1:0.1.
Example 3
The sludge dewatering deodorant comprises 20 parts of quaternized tannin extract-glutaraldehyde, 10 parts of cationic polyacrylamide, 50 parts of calcium carbonate and 30 parts of modified zeolite.
The preparation method of the quaternized tannin extract-glutaraldehyde, the modified zeolite and the sludge dewatering deodorant of the embodiment refers to the embodiment 1, wherein the molar ratio of glutaraldehyde to quaternized tannin extract in the preparation process of the quaternized tannin extract-glutaraldehyde is 2:1, and the mass ratio of cetyl trimethyl ammonium bromide modified zeolite to hydroquinone in the preparation process of the modified zeolite is 1:0.5.
Example 4
The sludge dewatering deodorant comprises 12.5 parts of quaternized tannin extract-glutaraldehyde, 5.5 parts of cationic polyacrylamide, 35 parts of calcium carbonate and 20 parts of modified zeolite.
The preparation methods of the quaternized tannin extract-glutaraldehyde, the modified zeolite and the sludge dewatering deodorant of the present example refer to example 1, in which the molar ratio of glutaraldehyde to quaternized tannin extract in the preparation process of quaternized tannin extract-glutaraldehyde is 1.25:1, and the mass ratio of hexadecyl trimethyl ammonium bromide modified zeolite to hydroquinone in the preparation process of modified zeolite is 1:0.3.
Example 5
The sludge dewatering deodorant comprises 18 parts of quaternized gallotannin-glutaraldehyde, 6 parts of cationic polyacrylamide, 30 parts of calcium carbonate and 22 parts of modified zeolite.
The preparation methods of the quaternized gallotannin-glutaraldehyde, the modified zeolite and the sludge dewatering deodorant of the present example refer to example 1, in which the molar ratio of glutaraldehyde to quaternized gallotannin in the preparation process of quaternized gallotannin-glutaraldehyde is 1:1, and the mass ratio of cetyl trimethylammonium bromide modified zeolite to hydroquinone in the preparation process of modified zeolite is 1:0.4.
Example 6
The sludge dewatering deodorant comprises 18 parts of quaternized catechin-glutaraldehyde, 6 parts of cationic polyacrylamide, 30 parts of calcium carbonate and 22 parts of modified zeolite.
The preparation methods of quaternized catechin-glutaraldehyde, modified zeolite and sludge dewatering deodorant of this example refer to example 1, in which the molar ratio of glutaraldehyde to quaternized catechin in the preparation of quaternized catechin-glutaraldehyde is 1:1, and in which the mass ratio of cetyltrimethylammonium bromide modified zeolite to hydroquinone in the preparation of modified zeolite is 1:0.4.
Comparative example 1
The difference compared with example 1 is that quaternized tannin glutaraldehyde is not used in the raw material of the sludge dewatering deodorant, and the other raw materials and the preparation method are the same as in example 1.
Comparative example 2
The difference compared with example 1 is that modified zeolite is not used in the raw material of the sludge dewatering deodorant, and the rest of raw materials and the preparation method are the same as in example 1.
Comparative example 3
The difference compared with example 1 is that quaternized tannin glutaraldehyde and modified zeolite are not used in the raw material of the sludge dewatering deodorant, and the other raw materials and preparation methods are the same as in example 1.
Comparative example 4
The only difference compared to example 1 is that quaternized tannin glutaraldehyde was replaced with equivalent amount of quaternized tannin in the raw material of the sludge dewatering deodorant, and the rest of raw material and preparation method were the same as example 1.
Comparative example 5
The difference compared with example 1 is that the modified zeolite is replaced with the equivalent amount of cetyltrimethylammonium bromide modified zeolite in the raw material of the sludge dewatering deodorant, and the rest of the raw materials and the preparation method are the same as example 1.
Test examples
The sludge dewatering deodorant prepared in the above examples and comparative examples was subjected to performance test, the sludge to be treated used in the test was from a sewage treatment plant, the water content was 95-98%, and the solid content was 2-5%. The specific test method is as follows:
1. Dehydration effect test
(1) Testing a control group, namely taking 1000mL of sludge to be treated, directly transferring the sludge into a plate-and-frame filter press, and measuring the water content of a filter cake under the filter pressing condition that the pressure is 0.6MPa and the time is 30 min;
(2) Testing in an experimental group, namely taking 1000mL of sludge to be treated, respectively adding 1% of the dehydration deodorant of each example and the dehydration deodorant of each comparative example, stirring for 2min at a speed of 200r/min under a condition of rapid stirring for 50r/min under a condition of slow stirring for 10min, transferring into a plate-and-frame filter press, and measuring the water content of a filter cake under a condition of pressure of 0.6MPa for 30min under a condition of filter pressing;
(3) The method for measuring the water content comprises the steps of drying an aluminum box at 105 ℃ to constant weight (m 1), weighing a sludge sample in the aluminum box (m 2), drying at 105 ℃ for 24 hours to constant weight (m 3), and calculating a formula of water content (%) = [ (m 2-m3)/(m2-m1) ] -100%.
2. Deodorant effect test
(1) Sensory evaluation, namely organizing 5 people in an evaluation group, wherein the odor intensity is graded to be 0 grade, namely odorless, 1 grade, namely slightly odorous and can be perceived only by deliberate smell, 2 grade, namely odorous but not obvious, 3 grade, namely obvious odorous, and 4 grade, namely strong odorous. The raw sludge and the sludge treated with the dehydrated deodorant were evaluated, respectively.
(2) And (3) gas phase component analysis, namely respectively placing equal amount of sludge into two standard sealed containers with the same specification, wherein a control group is sludge without dehydration deodorant, an experimental group is sludge treated by dehydration deodorant of each example and comparative example with the mass percent of 1%, standing for 2 hours under the same condition after sealing, respectively measuring the concentration of ammonia gas and hydrogen sulfide in the two containers by adopting a gas chromatography, and calculating the removal rate, namely the removal rate (%) = [ (C 0-C)/C0 ]. Times.100%, wherein C 0 is the concentration of the control group and C is the concentration of the experimental group.
The specific method for measuring the concentration of ammonia and hydrogen sulfide comprises the steps of analyzing hydrogen sulfide by using a gas chromatograph provided with a Flame Photometric Detector (FPD), wherein carrier gas is nitrogen, the detector temperature is 90 ℃, the column box temperature is 50 ℃, and the carrier gas flow is 30mL/min. Ammonia gas was analyzed using a thermal conductivity detector with TCD, the carrier gas was hydrogen, carrier gas flow was 25mL/min, detector temperature 250 ℃, and column box temperature 70 ℃.
The experimental results are shown in tables 1-2.
Table 1 example, comparative example dewatering effect
。
Table 2 deodorizing effect of examples, comparative examples
。
From the above results, it can be seen that the water content of examples 1 to 6 was reduced by 30% or more in terms of the dewatering effect, with example 1 being most remarkable in terms of the reduction of 34.2%. In contrast, the comparative examples had a water cut-off of only 12.7-24.2% which is significantly lower than the examples, indicating that the absence of quaternized tannin glutaraldehyde or modified zeolite significantly affected the dewatering effect.
Examples 1 to 6 exhibited excellent gas removal ability in terms of deodorizing effect, and the removal rates of ammonia gas and hydrogen sulfide were each more than 88%. The effect of example 1 is most ideal, the ammonia removal rate is up to 94.8%, and the hydrogen sulfide removal rate is up to 96.7%. The comparative example shows that the removal rate is reduced by about 40-50% in the absence of quaternized tannin glutaraldehyde, about 30-40% in the absence of modified zeolite, and only 30-40% if both are absent.
For comparison of the effects of different tannins, it was found that tannin extract tannins (example 1) exhibited excellent overall properties, with the effect of gallotannins (example 5) being similar thereto, while catechins (example 6) remained at a higher level, albeit slightly less effective. This shows that tannins from different sources can achieve good treatment effects, wherein the difference of the water content reduction ranges is within 3%, and the difference of the deodorizing effects is within 5%.
From the data presentation of comparative examples 4 and 5, the degree of modification has a significant effect on the sludge treatment effect. In comparative example 4, when only quaternized tannin was used without glutaraldehyde crosslinking, the decrease in the water content of the sludge was reduced to about 18.5%, and the removal rates of ammonia gas and hydrogen sulfide were reduced to about 55% and 58%, respectively, indicating that the lack of glutaraldehyde crosslinking significantly impaired the treatment effect. In comparative example 5, when zeolite modified by cetyl trimethyl ammonium bromide is used and hydroquinone grafting is not performed, the water content of the sludge is reduced by about 20.3%, and the gas removal rate is reduced to about 60% and 63% respectively, which shows that the lack of active phenolic hydroxyl groups provided by hydroquinone on the zeolite surface reduces the performance. The decrease in performance of these two sets of data compared with the optimal examples is evident, fully confirming the necessity of two modification steps of glutaraldehyde crosslinking and hydroquinone grafting, which play a key role in improving the dewatering and deodorizing effects of the whole system. The experimental results of comparative examples 4 and 5 further demonstrate the importance of the complete modification process to achieve good handling results, indicating that simplifying any modification step results in a significant decrease in performance.
Finally, it should be noted that although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications may be made to the technical solutions described in the foregoing embodiments, or equivalents may be substituted for some of the technical features thereof, and any modifications, equivalents, improvements or changes may be made without departing from the spirit and principle of the present invention.
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| US6020422A (en) * | 1996-11-15 | 2000-02-01 | Betzdearborn Inc. | Aqueous dispersion polymers |
| US20070227971A1 (en) * | 2004-05-18 | 2007-10-04 | Biomass Processing Technology, Inc. | Flocculation Method and Flocculated Organism |
| CN1868576B (en) * | 2005-05-24 | 2010-10-27 | 黄亮 | Biological modification infusorial earth adsorbent, and its prepn. method |
| JP2007237026A (en) * | 2006-03-06 | 2007-09-20 | Kenjiro Makino | Method for manufacturing functional product using biomass |
| CN111423053A (en) * | 2020-03-15 | 2020-07-17 | 河海大学 | An in-situ treatment method for black and odorous water bodies in rivers based on modified plant tannins |
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