CN114195235B - Flocculant, raw material composition thereof, and preparation method and application thereof - Google Patents
Flocculant, raw material composition thereof, and preparation method and application thereof Download PDFInfo
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- CN114195235B CN114195235B CN202010909838.8A CN202010909838A CN114195235B CN 114195235 B CN114195235 B CN 114195235B CN 202010909838 A CN202010909838 A CN 202010909838A CN 114195235 B CN114195235 B CN 114195235B
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- flocculant
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- 239000000203 mixture Substances 0.000 title claims abstract description 34
- 239000002994 raw material Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000002699 waste material Substances 0.000 claims abstract description 66
- 239000007788 liquid Substances 0.000 claims abstract description 65
- 239000003999 initiator Substances 0.000 claims abstract description 64
- 238000004537 pulping Methods 0.000 claims abstract description 64
- 229920002401 polyacrylamide Polymers 0.000 claims abstract description 57
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims abstract description 19
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims abstract description 18
- 239000000126 substance Substances 0.000 claims abstract description 13
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 11
- 230000008569 process Effects 0.000 claims abstract description 8
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims abstract description 7
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims description 50
- 238000006243 chemical reaction Methods 0.000 claims description 37
- 238000002156 mixing Methods 0.000 claims description 31
- 239000007864 aqueous solution Substances 0.000 claims description 25
- 239000000706 filtrate Substances 0.000 claims description 20
- 230000000977 initiatory effect Effects 0.000 claims description 14
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 13
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 claims description 9
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 claims description 7
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 claims description 7
- 229920002678 cellulose Polymers 0.000 claims description 7
- 239000001913 cellulose Substances 0.000 claims description 7
- -1 salt compound Chemical class 0.000 claims description 7
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 claims description 6
- 229920005610 lignin Polymers 0.000 claims description 6
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 5
- 239000001632 sodium acetate Substances 0.000 claims description 5
- 235000017281 sodium acetate Nutrition 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 125000002091 cationic group Chemical group 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 229940015043 glyoxal Drugs 0.000 claims description 3
- 239000010865 sewage Substances 0.000 claims description 3
- WSMYVTOQOOLQHP-UHFFFAOYSA-N Malondialdehyde Chemical compound O=CCC=O WSMYVTOQOOLQHP-UHFFFAOYSA-N 0.000 claims description 2
- PCSMJKASWLYICJ-UHFFFAOYSA-N Succinic aldehyde Chemical compound O=CCCC=O PCSMJKASWLYICJ-UHFFFAOYSA-N 0.000 claims description 2
- WQZGKKKJIJFFOK-PHYPRBDBSA-N alpha-D-galactose Chemical compound OC[C@H]1O[C@H](O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-PHYPRBDBSA-N 0.000 claims description 2
- PYMYPHUHKUWMLA-WDCZJNDASA-N arabinose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)C=O PYMYPHUHKUWMLA-WDCZJNDASA-N 0.000 claims description 2
- 238000007865 diluting Methods 0.000 claims description 2
- 229930182830 galactose Natural products 0.000 claims description 2
- 229940118019 malondialdehyde Drugs 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 230000009467 reduction Effects 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 229960004279 formaldehyde Drugs 0.000 claims 1
- 125000000969 xylosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)CO1)* 0.000 claims 1
- 238000005189 flocculation Methods 0.000 abstract description 14
- 230000016615 flocculation Effects 0.000 abstract description 14
- 239000002351 wastewater Substances 0.000 abstract description 12
- 239000012028 Fenton's reagent Substances 0.000 abstract description 2
- 238000003756 stirring Methods 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 239000008394 flocculating agent Substances 0.000 description 10
- 238000007792 addition Methods 0.000 description 5
- 229920001131 Pulp (paper) Polymers 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 2
- 125000003172 aldehyde group Chemical group 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 231100000086 high toxicity Toxicity 0.000 description 2
- 231100000956 nontoxicity Toxicity 0.000 description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- UMHJEEQLYBKSAN-UHFFFAOYSA-N Adipaldehyde Chemical compound O=CCCCCC=O UMHJEEQLYBKSAN-UHFFFAOYSA-N 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- 241000219000 Populus Species 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 150000002016 disaccharides Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000007863 gel particle Substances 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002772 monosaccharides Chemical class 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5263—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using natural chemical compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
The invention discloses a flocculant, a raw material composition thereof, a preparation method and application thereof. The raw material composition comprises the following components in parts by weight: 1 part of pulping waste liquid, 0.1 to 0.2 part of polyacrylamide, 0.05 to 0.1 part of initiator and 0.1 to 0.2 part of cross-linking agent; the initiator comprises an initiator A and an initiator B, wherein the initiator A and the initiator B are one or more of sodium persulfate, potassium persulfate, ammonium persulfate, fenton reagent and azo initiators independently, and the initiator A and the initiator B are different substances; the pulping waste liquid is waste liquid generated in the process of preparing high-yield pulp. The flocculant prepared by the invention has high flocculation efficiency, can improve the settleability of various substances in water, greatly reduces the COD value in wastewater, has complete flocculation and low cost, and does not produce secondary pollution.
Description
Technical Field
The invention relates to a flocculant, a raw material composition thereof, a preparation method and application thereof.
Background
The chemical flocculants commonly used at present are divided into two major types, one is an inorganic flocculant represented by ferric salt and aluminum salt, and the other is a polymeric flocculant represented by polyacrylamide. Although chemical flocculants have long been used, there are also some drawbacks, such as unsatisfactory flocculation effect of inorganic flocculants, high toxicity of polymeric flocculants typified by polyacrylamide, and susceptibility to secondary pollution.
The high-yield pulping technology has good development prospect due to the characteristics of high pulp yield and environmental friendliness. The utilization rate of the high-yield pulp prepared by the high-yield pulping technology to the natural fiber is almost twice that of the chemical pulp, the pollution discharge is only 1/3-1/6 of that of the chemical pulp, the production investment is saved by half compared with that of a chemical pulp factory, and the high-yield pulp is greatly developed and produced based on the advantages. However, the post-treatment of the waste liquid generated by the high-yield pulping technology also becomes a main factor for restricting the development of the waste liquid, and most of organic matters in the waste liquid are cellulose, hemicellulose and lignin.
Therefore, the art needs to develop a flocculant which has the advantages of wide raw material source, low cost, high flocculation efficiency, complete flocculation, no toxicity and no secondary pollution, and realizes the efficient utilization of resources.
Disclosure of Invention
The invention aims to solve the technical problems that chemical flocculant in the prior art has high toxicity and is easy to cause secondary pollution; and the flocculant, the raw material composition and the preparation method and application thereof are provided by adopting the defects of low utilization rate of waste liquid generated in the pulping process, high post-treatment difficulty and the like of the high-yield pulping technology. The flocculant prepared by the invention has high flocculation efficiency, can improve the settleability of various substances in water, greatly reduces the COD value in wastewater, has complete flocculation and low cost, and does not produce secondary pollution.
The invention adopts the following technical scheme to solve the technical problems:
the invention provides a raw material composition which comprises the following components in parts by weight: 1 part of pulping waste liquid, 0.1 to 0.2 part of polyacrylamide, 0.05 to 0.1 part of initiator and 0.1 to 0.2 part of cross-linking agent;
the initiator comprises an initiator A and an initiator B, wherein the initiator A and the initiator B are one or more of sodium persulfate, potassium persulfate, ammonium persulfate, fenton reagent and azo-type initiator respectively and are different substances; the pulping waste liquid is waste liquid generated in the process of preparing high-yield pulp.
In the present invention, the preparation method of the high-yield pulp may be a PRC-APMP method or an APMP method, which are conventionally used by those skilled in the art, and preferably a PRC-APMP method.
In the present invention, the solid content of the pulping waste liquid can be the conventional solid content of the substances in the field, and is generally 50% -60%, preferably 57% -60%. In the field, the solid content of the pulping waste liquid is that the pulping waste liquid is subjected to solvent removal, and the residual materials after drying account for the mass percent of the pulping waste liquid.
In the invention, the pulping waste liquid generally comprises the following components in parts by weight: 45-55 parts of cellulose, 10-15 parts of lignin, 0.1-0.2 part of reducing sugar and 30-35 parts of salt compounds.
The reducing sugar may be a monosaccharide having a free aldehyde group or ketone group in the molecule or a disaccharide having a free aldehyde group in the molecule, generally one or more of xylose, arabinose and galactose, preferably xylose, as conventionally known to those skilled in the art.
Wherein the salt compound is a salt product conventionally produced in pulping process or an added salt raw material, for example, one or more of sodium acetate, sodium carbonate and potassium carbonate, preferably sodium acetate.
Wherein, the weight part of the cellulose is preferably 50-53 parts.
Wherein, the weight part of the lignin is preferably 13-15 parts.
Wherein, the weight part of the reducing sugar is preferably 0.15-0.18 part.
Wherein, the weight part of the salt compound is preferably 32-35 parts.
In the present invention, the polyacrylamide may be a cationic polyacrylamide conventionally used in the field of flocculants, preferably a cationic polyacrylamide.
In the present invention, the number average molecular weight of the polyacrylamide may be 7×10 6 ～9×10 6 Preferably 9X 10 6 。
In the present invention, the initiator A is preferably ammonium persulfate and/or sodium persulfate.
In the present invention, the initiator B is preferably potassium persulfate.
In a preferred embodiment, when the initiator B is potassium persulfate, the initiator A is ammonium persulfate or sodium persulfate.
In the present invention, the initiator is generally added in the form of an aqueous initiator solution. The mass percent of the initiator in the aqueous initiator solution may be conventional in the art, preferably from 8% to 15%, more preferably 10%.
In the present invention, the crosslinking agent may be a crosslinking agent conventionally used in the field of flocculants, preferably one or more of formaldehyde, glyoxal, malondialdehyde, succinaldehyde, glutaraldehyde and hexanedial, more preferably glutaraldehyde and/or formaldehyde.
In the present invention, water may be further included in the raw material composition.
Wherein the water may be 3 to 6.5 parts by weight, preferably 4 to 6.5 parts by weight.
In the present invention, the weight portion of the polyacrylamide is preferably 0.1 to 0.15 portion.
In the present invention, the initiator is preferably 0.05 to 0.08 parts by weight.
In the present invention, the weight ratio of the initiator a to the initiator B may be (0.6 to 1): 1, preferably (0.67 to 0.8): 1.
in the present invention, the crosslinking agent is preferably 0.14 to 0.2 parts by weight.
The invention also provides a preparation method of the flocculant, wherein the raw materials of the flocculant comprise the raw material composition; the preparation method of the flocculant comprises the following steps:
(1) The mixture of the pulping waste liquid and the polyacrylamide and the initiator A undergo an initiation reaction to prepare a material A;
(2) The material A and the initiator B are subjected to an initiation reaction to prepare a material B;
(3) And (3) reacting the material B with the cross-linking agent to obtain the modified polyurethane.
In the step (1), the mixture of the pulping waste liquid and the polyacrylamide is obtained by mixing the pulping waste liquid and the polyacrylamide.
Wherein, the polyacrylamide can be added in a batch mode conventionally used in the field.
Wherein the batch addition is generally based on the fact that the system does not form gel particles each time polyacrylamide is added. The number of batch additions is generally 3 or more.
Wherein the mixing time may be a time conventional in the art for such operations, preferably 10 to 15 minutes.
In the step (1), the pulping waste liquid can further comprise the operations of diluting, filtering and collecting filtrate before use.
Wherein the solids content of the diluted system may be 7% to 15%, preferably 7.6% to 10%.
Wherein the number of the screen meshes for filtering can be 80-100 meshes.
In the step (1), the initiator A may be added dropwise as conventionally used in the art.
The dripping time of the initiator A can be the time which is conventional in the operation in the field, and is generally 10 to 30 minutes, preferably 10 to 20 minutes.
In step (1), the temperature at which the reaction is initiated may be a temperature conventional in the art for such reactions, preferably 40 to 60 ℃, more preferably 50 to 60 ℃.
In step (1), the time for initiating the reaction may be a time conventional in the art for such reactions, preferably 25 to 70 minutes, more preferably 30 to 70 minutes.
In the step (2), the initiator B may be added dropwise as conventionally used in the art.
The dripping time of the initiator B can be the time which is conventional in the operation in the field, and is generally 10 to 30 minutes, preferably 15 to 30 minutes.
In step (2), the temperature at which the reaction is initiated may be conventional in the art, preferably from 40 to 60 ℃, more preferably from 50 to 60 ℃.
In step (2), the time for initiating the reaction may be a time conventional in the art for such reactions, preferably 25 to 60 minutes, more preferably 30 to 60 minutes.
In the step (3), the temperature of the system is reduced to the room temperature along with the temperature reduction operation in the reaction process.
Wherein the room temperature may be 10 to 30℃as conventionally considered by those skilled in the art.
The invention also provides a flocculant prepared by the preparation method of the flocculant.
The invention also provides an application of the flocculant in sewage treatment.
On the basis of conforming to the common knowledge in the field, the above preferred conditions can be arbitrarily combined to obtain the preferred examples of the invention.
The reagents and materials used in the present invention are commercially available.
The invention has the positive progress effects that: the flocculant prepared by the invention takes pulping waste liquid as a main raw material, can realize the efficient utilization of resources, and changes waste into valuable; the pulping waste liquid is cheap and easy to obtain, and has sufficient supply and no toxicity; the flocculant prepared by combining pulping waste liquid with other raw materials has the advantages of relatively simple raw material formula, simple and easy operation of preparation steps, small consumption in wastewater treatment, high flocculation efficiency, capability of improving the settleability of various substances in water, greatly reducing the COD value in wastewater, complete flocculation, low cost, no secondary pollution and the like.
Detailed Description
The invention is further illustrated by means of the following examples, which are not intended to limit the scope of the invention. The experimental methods, in which specific conditions are not noted in the following examples, were selected according to conventional methods and conditions, or according to the commercial specifications.
In the following examples and comparative examples; the preparation method of the pulping waste liquid comprises the following steps: the poplar is used as raw material, pulp is prepared by PRC-APMP pulping, the residual material after pulp removal is pulping waste liquid, and the solid content of the pulping waste liquid is 57%.
The pulping waste liquid comprises the following components in parts by weight: 50 parts of cellulose, 15 parts of lignin, 0.15 part of xylose and 32 parts of sodium acetate.
In the following examples, the polyacrylamide was a cationic polyacrylamide having a number average molecular weight of 9X 10 6 Left and right.
Example 1
(1) 50g of pulping waste liquid and 325g of deionized water are added into a 500mL beaker, stirred for 5min, and filtered through a 80-mesh screen, and the filtrate is collected;
adding the filtrate into a four-neck flask with a condenser pipe and a stirring rotor, adding 7.5g of polyacrylamide into the four-neck flask for three times at room temperature, and mixing for 10min to obtain a mixture of pulping waste liquid and polyacrylamide;
dropwise adding 10g of ammonium persulfate aqueous solution with the mass percent of 10% into a mixture of pulping waste liquid and polyacrylamide at the temperature of 50 ℃ for 10min; after the dripping is finished, continuing to carry out mixing reaction for 30min to obtain a material A;
(2) Dropwise adding 15g of 10% potassium persulfate aqueous solution into the material A prepared in the step (1) at the temperature of 50 ℃ for 15min; after the dripping is finished, continuing to carry out mixing reaction for 30min to obtain a material B;
(3) And (3) adding 5g of glutaraldehyde into the material B prepared in the step (2), and stirring to cool the system to room temperature to obtain the flocculant.
Example 2
(1) 50g of pulping waste liquid and 325g of deionized water are added into a 500mL beaker, stirred for 5min, and filtered through a 80-mesh screen, and the filtrate is collected;
adding the filtrate into a four-neck flask with a condensing tube and a stirring rotor, adding 5g polyacrylamide into the four-neck flask for six times at room temperature, and mixing for 10min to obtain a mixture of pulping waste liquid and polyacrylamide;
dropwise adding 10g of ammonium persulfate aqueous solution with the mass percent of 10% into a mixture of pulping waste liquid and polyacrylamide at the temperature of 50 ℃ for 10min; after the dripping is finished, continuing to carry out mixing reaction for 30min to obtain a material A;
(2) Dropwise adding 15g of 10% potassium persulfate aqueous solution into the material A prepared in the step (1) at the temperature of 50 ℃ for 15min; after the dripping is finished, continuing to carry out mixing reaction for 30min to obtain a material B;
(3) And (3) adding 5g of glutaraldehyde into the material B prepared in the step (2), and stirring to cool the system to room temperature to obtain the flocculant.
Example 3
(1) 50g of pulping waste liquid and 325g of deionized water are added into a 500mL beaker, stirred for 5min, and filtered through a 80-mesh screen, and the filtrate is collected;
adding the filtrate into a four-neck flask with a condenser pipe and a stirring rotor, adding 5g polyacrylamide into the four-neck flask for three times at room temperature, and mixing for 10min to obtain a mixture of pulping waste liquid and polyacrylamide;
dropwise adding 10g of ammonium persulfate aqueous solution with the mass percent of 10% into a mixture of pulping waste liquid and polyacrylamide at the temperature of 60 ℃ for 10min; after the dripping is finished, continuing to carry out mixing reaction for 30min to obtain a material A;
(2) Dropwise adding 15g of 10% potassium persulfate aqueous solution into the material A prepared in the step (1) at the temperature of 60 ℃ for 15min; after the dripping is finished, continuing to carry out mixing reaction for 30min to obtain a material B;
(3) And (3) adding 5g of glutaraldehyde into the material B prepared in the step (2), and stirring to cool the system to room temperature to obtain the flocculant.
Example 4
(1) 50g of pulping waste liquid and 200g of deionized water are added into a 500mL beaker, stirred for 5min, and filtered through a 80-mesh screen, and filtrate is collected;
adding the filtrate into a four-neck flask with a condenser pipe and a stirring rotor, adding 5g polyacrylamide into the four-neck flask for three times at room temperature, and mixing for 10min to obtain a mixture of pulping waste liquid and polyacrylamide;
dropwise adding 10g of ammonium persulfate aqueous solution with the mass percent of 10% into a mixture of pulping waste liquid and polyacrylamide at the temperature of 50 ℃ for 10min; after the dripping is finished, continuing to carry out mixing reaction for 30min to obtain a material A;
(2) Dropwise adding 15g of 10% potassium persulfate aqueous solution into the material A prepared in the step (21) at the temperature of 50 ℃ for 15min; after the dripping is finished, continuing to carry out mixing reaction for 30min to obtain a material B;
(3) And (3) adding 5g of glutaraldehyde into the material B prepared in the step (2), and stirring to cool the system to room temperature to obtain the flocculant.
Example 5
(1) 50g of pulping waste liquid and 325g of deionized water are added into a 500mL beaker, stirred for 5min, and filtered through a 80-mesh screen, and the filtrate is collected;
adding the filtrate into a four-neck flask with a condenser pipe and a stirring rotor, adding 5g polyacrylamide into the four-neck flask for three times at room temperature, and mixing for 10min to obtain a mixture of pulping waste liquid and polyacrylamide;
dropwise adding 20g of ammonium persulfate aqueous solution with the mass percent of 10% into a mixture of pulping waste liquid and polyacrylamide at the temperature of 50 ℃ for 20min; after the dripping is finished, continuing to carry out mixing reaction for 30min to obtain a material A;
(2) Dropwise adding 30g of 10% potassium persulfate aqueous solution into the material A prepared in the step (1) at the temperature of 50 ℃ for 30min; after the dripping is finished, continuing to carry out mixing reaction for 30min to obtain a material B;
(3) And (3) adding 5g of glutaraldehyde into the material B prepared in the step (2), and stirring to cool the system to room temperature to obtain the flocculant.
Example 6
(1) 50g of pulping waste liquid and 325g of deionized water are added into a 500mL beaker, stirred for 5min, and filtered through a 80-mesh screen, and the filtrate is collected;
adding the filtrate into a four-neck flask with a condenser pipe and a stirring rotor, adding 5g polyacrylamide into the four-neck flask for three times at room temperature, and mixing for 10min to obtain a mixture of pulping waste liquid and polyacrylamide;
dropwise adding 10g of 10 mass percent sodium persulfate aqueous solution into a mixture of pulping waste liquid and polyacrylamide at the temperature of 50 ℃ for 10min; after the dripping is finished, continuing to carry out mixing reaction for 30min to obtain a material A;
(2) Dropwise adding 15g of 10% potassium persulfate aqueous solution into the material A prepared in the step (1) at the temperature of 50 ℃ for 15min; after the dripping is finished, continuing to carry out mixing reaction for 30min to obtain a material B;
(3) And (3) adding 5g of glutaraldehyde into the material B prepared in the step (2), and stirring to cool the system to room temperature to obtain the flocculant.
Example 7
(1) 50g of pulping waste liquid and 325g of deionized water are added into a 500mL beaker, stirred for 5min, and filtered through a 80-mesh screen, and the filtrate is collected;
adding the filtrate into a four-neck flask with a condenser pipe and a stirring rotor, adding 5g polyacrylamide into the four-neck flask for three times at room temperature, and mixing for 10min to obtain a mixture of pulping waste liquid and polyacrylamide;
dropwise adding 10g of ammonium persulfate aqueous solution with the mass percent of 10% into a mixture of pulping waste liquid and polyacrylamide at the temperature of 50 ℃ for 10min; after the dripping is finished, continuing to carry out mixing reaction for 30min to obtain a material A;
(2) Dropwise adding 15g of 10% potassium persulfate aqueous solution into the material A prepared in the step (1) at the temperature of 50 ℃ for 15min; after the dripping is finished, continuing to carry out mixing reaction for 30min to obtain a material B;
(3) And (3) adding 10g of formaldehyde into the material B prepared in the step (2), and stirring to cool the system to room temperature to obtain the flocculant.
Example 8
(1) 50g of pulping waste liquid and 325g of deionized water are added into a 500mL beaker, stirred for 5min, and filtered through a 80-mesh screen, and the filtrate is collected;
adding the filtrate into a four-neck flask with a condenser pipe and a stirring rotor, adding 5g polyacrylamide into the four-neck flask for three times at room temperature, and mixing for 10min to obtain a mixture of pulping waste liquid and polyacrylamide;
dropwise adding 10g of ammonium persulfate aqueous solution with the mass percent of 10% into a mixture of pulping waste liquid and polyacrylamide at the temperature of 50 ℃ for 10min; after the dripping is finished, continuing to carry out mixing reaction for 60min to obtain a material A;
(2) Dropwise adding 15g of 10% potassium persulfate aqueous solution into the material A prepared in the step (1) at the temperature of 50 ℃ for 15min; continuously mixing and reacting for 60min after the dripping is finished to obtain a material B;
(1) And (3) adding 5g of glutaraldehyde into the material B prepared in the step (2), and stirring to cool the system to room temperature to obtain the flocculant.
Example 9
(1) 50g of the slurry waste liquid and 325g of deionized water are added into a 500mL beaker, stirred for 5min, and filtered through a 80-mesh screen, and the filtrate is collected;
adding the filtrate into a four-neck flask with a condenser pipe and a stirring rotor, adding 5g polyacrylamide into the four-neck flask for three times at room temperature, and mixing for 10min to obtain a mixture of pulping waste liquid and polyacrylamide;
dropwise adding 10g of ammonium persulfate aqueous solution with the mass percent of 10% into a mixture of pulping waste liquid and polyacrylamide at the temperature of 50 ℃ for 10min; after the dripping is finished, continuing to carry out mixing reaction for 30min to obtain a material A;
(2) Dropwise adding 15g of 10% potassium persulfate aqueous solution into the material A prepared in the step (1) at the temperature of 50 ℃ for 15min; after the dripping is finished, continuing to carry out mixing reaction for 30min to obtain a material B;
(3) And (3) adding 2g of glutaraldehyde and 5g of formaldehyde into the material B prepared in the step (2), and stirring to cool the system to room temperature to obtain the flocculant.
Comparative example 1
The difference from example 1 is that no pulping waste liquid was added in step (1), and other condition parameters were the same as in example 1.
Comparative example 2
In comparison with example 1, the difference is that no polyacrylamide is added in step (1), and other conditions are the same as in example 1.
Comparative example 3
In comparison with example 1, the difference is that in the step (1), the addition amount of the ammonium persulfate aqueous solution is adjusted from 10g to 5g and the dropping time is adjusted to 5min; the amount of potassium persulfate aqueous solution added in step (2) was adjusted from 15g to 10g, and the dropping time was adjusted to 10min, and other conditions were the same as in example 1.
Comparative example 4
In comparison with example 1, the difference is that in the step (1), the addition amount of the ammonium persulfate aqueous solution is adjusted from 10g to 30g and the dropping time is adjusted to 30min; the amount of potassium persulfate aqueous solution added in step (2) was adjusted from 15g to 30g, and the dropping time was adjusted to 30min, and other conditions were the same as in example 1.
Comparative example 5
In comparison with example 1, the difference is that glutaraldehyde is not added in step (3), and other condition parameters are the same as in example 1.
Comparative example 6
The difference from example 1 is that in step (2), the aqueous potassium persulfate solution is replaced with an aqueous ammonium persulfate solution of equal mass, and other conditions and parameters are the same as those in example 1.
Comparative example 7
The difference compared with example 1 is that in step (1), the pulping waste liquid is replaced by the same mass of cellulose aqueous solution with 57% solid content, and other condition parameters are the same as in example 1.
Effect examples
Preparing flocculant solution: the flocculants prepared in examples 1 to 9 and comparative examples 1 to 7 and the purchased polyacrylamide flocculant (PAM) were mixed with deionized water to prepare 17 parts of a flocculant solution with a mass percentage of 0.2% for use.
The flocculant solution prepared as described above was used to treat wastewater from different batches of a chemical plant, and the floc settling rate (results shown in Table 1), COD removal rate (results shown in Table 2) and turbidity removal rate (results shown in Table 3) were calculated. The dosage is calculated by the weight of the flocculant in the flocculant solution, namely 20mg of flocculant is added into each liter of wastewater. And a blank group is set, namely no flocculant is added.
Pouring a waste water sample obtained from a sewage treatment center of a chemical plant into a measuring cylinder with a plug with an inner diameter of 3cm and a volume of 100mL, adding a certain amount of prepared flocculant solution, reversing the measuring cylinder filled with the water sample upside down for a plurality of times, standing the measuring cylinder on a horizontal table top, starting timing, standing for 1min, and calculating a sedimentation rate; taking supernatant to measure COD and turbidity, wherein the COD is tested by adopting a potassium dichromate method according to the national standard HJ-T399-2007, and the testing equipment comprises a 6B-24 type double-temperature-zone intelligent digestion instrument and a 6B-2000 type water quality rapid measurement instrument; the turbidity of the wastewater was measured using a EFZ-200P turbidity meter.
The sedimentation rate is the distance of the flocs falling in unit time, and the unit is cm/min.
Turbidity removal = (turbidity Waste water as such Turbidity (turbidity) After treatment ) Turbidity/turbidity Waste water as such ×100％。
COD removal Rate= (COD Waste water as such -COD After treatment )/COD Waste water as such ×100％。
TABLE 1
TABLE 2
TABLE 3 Table 3
When the flocculant prepared by the embodiment is used for flocculation treatment, the addition amount of the flocculant is 1/3-1/2 of that of the flocculant sold in the market at present.
As can be seen from the data in tables 1 to 3, the flocculants prepared in examples 1 to 9 can effectively improve the settling rate, turbidity removal rate and COD removal rate of the flocs compared with the flocculants prepared in comparative examples 1 to 6; and the sedimentation rate, COD removal rate and turbidity removal rate of the flocculant prepared by the invention are equivalent to or even better than those of PAM. When the flocculant prepared in the comparative example 7 is used for flocculation treatment, the stability of the flocculation is poor, the flocculation is easy to scatter in the filter pressing process, and harmful substances in the wastewater are increased, so that the flocculant is not beneficial to industrialized large-scale use; and when the flocculating agent prepared in the examples 1-9 is used for flocculation treatment, the stability of the flocculated material is good, and the flocculated material is not scattered in the filter pressing process.
The above is only a preferred embodiment of the present invention, and it should be understood by those skilled in the art that the present invention is not limited by these embodiments, but the above embodiments and the description are merely illustrative of the principles of the present invention, and any modifications, equivalent substitutions, improvements, etc. within the spirit and principles of the present invention should be included in the scope of the present invention.
Claims (20)
1. A method for preparing a flocculant, comprising the steps of:
(1) The mixture of pulping waste liquid and polyacrylamide reacts with an initiator A in an initiation way to prepare a material A;
(2) The material A and the initiator B are subjected to an initiation reaction to prepare a material B;
(3) The material B reacts with a cross-linking agent to obtain the material;
the raw materials of the flocculant comprise the following raw material compositions; the raw material composition comprises the following components in parts by weight: 1 part of pulping waste liquid, 0.1-0.2 part of polyacrylamide, 0.05-0.1 part of initiator and 0.1-0.2 part of cross-linking agent;
wherein the initiator comprises an initiator A and an initiator B, the initiator A and the initiator B are respectively and independently potassium persulfate or ammonium persulfate, and the initiator A and the initiator B are different substances; the pulping waste liquid is waste liquid generated in the process of preparing high-yield pulp;
wherein, the pulping waste liquid consists of the following components in parts by weight: 45-55 parts of cellulose, 10-15 parts of lignin, 0.1-0.2 part of reducing sugar and 30-35 parts of salt compound;
wherein the number average molecular weight of the polyacrylamide is。
2. The method for preparing a flocculant according to claim 1, wherein the method for preparing high-yield pulp is PRC-APMP method or APMP method;
and/or the solid content of the pulping waste liquid is 50% -60%;
and/or, the polyacrylamide is cationic polyacrylamide;
and/or the number average molecular weight of the polyacrylamide is；
And/or the initiator A is ammonium persulfate and/or sodium persulfate;
and/or, the initiator B is potassium persulfate;
and/or, the initiator is added in the form of an aqueous initiator solution;
and/or the cross-linking agent is one or more of formaldehyde, glyoxal, malondialdehyde, succinaldehyde, glutaraldehyde and glyoxal;
and/or, the raw material composition further comprises water.
3. The method of preparing a flocculant according to claim 2, wherein the method of preparing high-yield pulp is a PRC-APMP method;
and/or the solid content of the pulping waste liquid is 57% -60%;
and/or, when the initiator B is potassium persulfate, the initiator A is ammonium persulfate or sodium persulfate;
and/or the cross-linking agent is glutaraldehyde and/or formaldehyde.
4. The method of preparing a flocculant according to claim 2, wherein the reducing sugar is one or more of xylose, arabinose, and galactose;
and/or the salt compound is one or more of sodium acetate, sodium carbonate and potassium carbonate;
and/or 50-53 parts by weight of cellulose;
and/or 13-15 parts of lignin by weight;
and/or the weight part of the reducing sugar is 0.15-0.18 part;
and/or 32-35 parts by weight of the salt compound;
and/or the mass percentage of the initiator in the initiator aqueous solution is 8% -15%;
and/or 3-6.5 parts by weight of water.
5. The method of producing a flocculant according to claim 4, wherein the reducing sugar is xylose;
and/or the salt compound is sodium acetate;
and/or, the mass percentage of the initiator in the initiator aqueous solution is 10 percent;
and/or 4-6.5 parts by weight of water.
6. The method for preparing a flocculant according to any one of claims 1 to 5, wherein the polyacrylamide is 0.1 to 0.15 parts by weight;
and/or 0.05-0.08 parts by weight of an initiator;
and/or the weight ratio of the initiator A to the initiator B is (0.6-1): 1, a step of;
and/or the weight part of the cross-linking agent is 0.14-0.2 part.
7. The method for preparing a flocculant according to claim 6, wherein the weight ratio of the initiator a to the initiator B is (0.67 to 0.8): 1.
8. the method according to claim 1, wherein in the step (1), the mixture of the pulping waste liquid and the polyacrylamide is obtained by mixing the pulping waste liquid and the polyacrylamide.
9. The method for preparing a flocculant according to claim 8, wherein the polyacrylamide is added in batches.
10. The method for producing a flocculant according to claim 9, wherein the number of times of addition in batches is 3 or more.
11. The method for preparing a flocculant according to claim 8, wherein the mixing time is 10 to 15min.
12. The method for preparing a flocculant according to claim 1, wherein in the step (1), the pulping waste liquid further comprises operations of diluting, filtering, and collecting filtrate before use.
13. The method for preparing a flocculant according to claim 12, wherein the solid content of the diluted system is 7% -15%.
14. The method for preparing a flocculant according to claim 13, wherein the solid content of the diluted system is 7.6% -10%.
15. The method of preparing a flocculant according to claim 12, wherein the number of screen meshes of the filtration is 80 to 100 mesh.
16. The method for preparing the flocculant according to claim 1, wherein the initiator A is added dropwise;
and/or, in the step (1), the temperature for initiating the reaction is 40-60 ℃;
and/or, in the step (1), the time for initiating the reaction is 25-70 min;
and/or, in the step (2), the initiator B is added dropwise;
and/or, in the step (2), the temperature for initiating the reaction is 40-60 ℃;
and/or, in the step (2), the time for initiating the reaction is 25-60 min;
and/or in the step (3), the temperature of the system is reduced to the room temperature along with the temperature reduction operation in the reaction process.
17. The method for preparing a flocculant according to claim 16, wherein the dropping time of the initiator a is 10 to 30min;
and/or, in the step (1), the temperature for initiating the reaction is 50-60 ℃;
and/or, in the step (1), the time for initiating the reaction is 30-70 min;
and/or in the step (2), the dropwise adding time of the initiator B is 10-30 min;
and/or, in the step (2), the temperature for initiating the reaction is 50-60 ℃;
and/or, in the step (2), the time for initiating the reaction is 30-60 min.
18. The method for preparing a flocculant according to claim 17, wherein the dripping time of the initiator a is 10 to 20min;
and/or in the step (2), the dropwise adding time of the initiator B is 15-30 min.
19. Flocculant, characterized in that it is produced by a process for the preparation of a flocculant according to any one of claims 1 to 18.
20. Use of the flocculant of claim 19 in sewage treatment.
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