CN114195235A - Flocculating agent, raw material composition thereof, and preparation method and application thereof - Google Patents
Flocculating agent, raw material composition thereof, and preparation method and application thereof Download PDFInfo
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- CN114195235A CN114195235A CN202010909838.8A CN202010909838A CN114195235A CN 114195235 A CN114195235 A CN 114195235A CN 202010909838 A CN202010909838 A CN 202010909838A CN 114195235 A CN114195235 A CN 114195235A
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- 239000000203 mixture Substances 0.000 title claims abstract description 37
- 239000002994 raw material Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000008394 flocculating agent Substances 0.000 title abstract description 19
- 239000002699 waste material Substances 0.000 claims abstract description 66
- 238000004537 pulping Methods 0.000 claims abstract description 64
- 239000003999 initiator Substances 0.000 claims abstract description 61
- 239000007788 liquid Substances 0.000 claims abstract description 59
- 229920002401 polyacrylamide Polymers 0.000 claims abstract description 56
- 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 22
- 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- 239000002351 wastewater Substances 0.000 claims abstract description 13
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 10
- 230000008569 process Effects 0.000 claims abstract description 10
- 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 8
- 229920001131 Pulp (paper) Polymers 0.000 claims abstract description 8
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims abstract description 8
- 239000012028 Fenton's reagent Substances 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims description 48
- 238000002156 mixing Methods 0.000 claims description 31
- 239000007864 aqueous solution Substances 0.000 claims description 26
- 239000000706 filtrate Substances 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 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
- 230000000977 initiatory effect Effects 0.000 claims description 12
- 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 10
- 239000007787 solid Substances 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- 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
- 229920005610 lignin Polymers 0.000 claims description 6
- -1 salt compound Chemical class 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
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 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
- UMHJEEQLYBKSAN-UHFFFAOYSA-N Adipaldehyde Chemical compound O=CCCCCC=O UMHJEEQLYBKSAN-UHFFFAOYSA-N 0.000 claims description 2
- 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
- 229940015043 glyoxal 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
- 238000005189 flocculation Methods 0.000 abstract description 12
- 230000016615 flocculation Effects 0.000 abstract description 12
- 238000003756 stirring Methods 0.000 description 27
- 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
- 238000007873 sieving Methods 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 5
- 238000004062 sedimentation Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 2
- 125000003172 aldehyde group Chemical group 0.000 description 2
- 231100000086 high toxicity 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
- 150000003839 salts Chemical class 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 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
- 238000001816 cooling 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
- 230000003311 flocculating effect Effects 0.000 description 1
- 239000007863 gel particle Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002772 monosaccharides Chemical group 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000006228 supernatant Substances 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 flocculating agent, 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, 0.1-0.2 part of polyacrylamide, 0.05-0.1 part of initiator and 0.1-0.2 part of cross-linking agent; the initiator comprises an initiator A and an initiator B, wherein the initiator A and the initiator B are respectively and independently one or more of sodium persulfate, potassium persulfate, ammonium persulfate, Fenton reagent and azo initiators, and the initiator A and the initiator B are different substances; the pulping waste liquor is the waste liquor produced in the process of preparing high-yield paper 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 flocculating agent, a raw material composition thereof, a preparation method and application thereof.
Background
Currently, chemical flocculants are generally classified into two categories, one is an inorganic flocculant represented by iron salt and aluminum salt, and the other is a polymeric flocculant represented by polyacrylamide. Although the use of chemical flocculants has long been known, there are some drawbacks, for example, the flocculation effect of inorganic flocculants is not ideal, and polymeric flocculants typified by polyacrylamide have high toxicity and are prone to secondary pollution.
The high-yield pulping technology shows good development prospect due to the characteristics of high pulp yield and environmental friendliness. The utilization rate of the high-yield paper pulp prepared by the high-yield pulping technology to natural fibers is almost twice that of chemical pulp, the pollution discharge amount is only 1/3-1/6 of the chemical pulp, the production investment is saved by half compared with that of a chemical pulp factory, and based on the advantages, the high-yield paper pulp is vigorously developed and produced. However, the post-treatment of the waste liquid generated by the high-yield pulping technology also becomes a main factor restricting the development of the high-yield pulping technology, most of organic matters in the waste liquid are cellulose, hemicellulose and lignin, and if the waste liquid can be recycled, the pressure of the post-treatment of the waste liquid can be reduced, and the high-efficiency utilization of resources can be realized.
Therefore, the development of a flocculant which has the advantages of wide raw material source, low cost, high-efficiency utilization of resources, high flocculation efficiency, complete flocculation, no toxicity and no secondary pollution is urgently needed in the field.
Disclosure of Invention
The invention aims to solve the technical problems that the chemical flocculant in the prior art has high toxicity and is easy to cause secondary pollution; and the high-yield pulping technology is adopted to overcome the defects of low utilization rate of waste liquid generated in the pulping process, high post-treatment difficulty and the like, and the flocculant, the raw material composition thereof, the preparation method and the application thereof are provided. 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, 0.1-0.2 part of polyacrylamide, 0.05-0.1 part of initiator and 0.1-0.2 part of cross-linking agent;
the initiator comprises an initiator A and an initiator B, wherein the initiator A and the initiator B are respectively and independently one or more of sodium persulfate, potassium persulfate, ammonium persulfate, Fenton reagent and azo initiators, 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 paper pulp.
In the present invention, the method for preparing the high-yield pulp may be a PRC-APMP method or an APMP method, preferably a PRC-APMP method, which is conventionally used by those skilled in the art.
In the 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 the mass percentage of the residual materials after the pulping waste liquid is subjected to solvent removal and drying in 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 compound.
Wherein, the reducing sugar can be monosaccharide or disaccharide with free aldehyde group in molecule, which is conventionally considered by those skilled in the art to contain free aldehyde group or ketone group, and is generally one or more of xylose, arabinose and galactose, preferably xylose.
Wherein the salt compound is a salt product which is conventionally generated in the pulping process or an added salt raw material, for example, one or more of sodium acetate, sodium carbonate and potassium carbonate, and preferably sodium acetate.
Wherein the cellulose is preferably 50 to 53 parts by weight.
Wherein the weight portion of the lignin is preferably 13 to 15 portions.
Wherein, the weight portion of the reducing sugar is preferably 0.15 to 0.18 portion.
Wherein, the weight portion of the salt compound is preferably 32 to 35 portions.
In the present invention, the polyacrylamide may be cationic polyacrylamide, preferably cationic polyacrylamide, which is conventionally used in the field of flocculants.
In the present invention, the polyacrylamide may have a number average molecular weight of 7 × 106～9×106Preferably 9 × 106。
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 percentage of the initiator in the aqueous initiator solution can be conventional in the art, and is preferably 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, malonaldehyde, succinaldehyde, glutaraldehyde and adipaldehyde, more preferably glutaraldehyde and/or formaldehyde.
In the present invention, the raw material composition may further include water.
Wherein, the weight portion of the water is 3 to 6.5 portions, preferably 4 to 6.5 portions.
In the present invention, the weight portion of the polyacrylamide is preferably 0.1 to 0.15.
In the invention, the weight part of the initiator is preferably 0.05-0.08.
In the invention, the weight ratio of the initiator A to the initiator B can be (0.6-1): 1, preferably (0.67-0.8): 1.
in the present invention, the weight portion of the crosslinking agent is preferably 0.14 to 0.2 portion.
The invention also provides a preparation method of the flocculant, wherein the raw material of the flocculant comprises the raw material composition; the preparation method of the flocculant comprises the following steps:
(1) carrying out initiation reaction on the mixture of the pulping waste liquid and the polyacrylamide and the initiator A to prepare a material A;
(2) carrying out initiation reaction on the material A and the initiator B to prepare a material B;
(3) and reacting the material B with the cross-linking agent to obtain the material B.
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 batch mode conventionally used in the field.
Wherein the batch addition is generally based on the criterion that the system does not form gel particles per addition of polyacrylamide. The number of the addition in portions is generally 3 or more.
Wherein, the mixing time can be the time of the operation routine in the field, and is preferably 10-15 min.
In the step (1), the pulping waste liquid can further comprise the operations of diluting, filtering and collecting filtrate before use.
Wherein, the solid content of the diluted system can be 7-15%, preferably 7.6-10%.
Wherein the mesh number of the filtering screen can be 80-100 meshes.
In the step (1), the initiator a may be added dropwise in a manner conventionally used in the art.
The dropping time of the initiator A can be the time of the operation routine in the field, and is generally 10-30 min, preferably 10-20 min.
In the step (1), the temperature of the initiation reaction may be a temperature conventional in the art, preferably 40 to 60 ℃, and more preferably 50 to 60 ℃.
In the step (1), the time for initiating the reaction may be a time conventionally used in the reaction of this kind in the art, and is preferably 25 to 70min, and more preferably 30 to 70 min.
In the step (2), the initiator B may be added dropwise in a manner conventionally used in the art.
The dropping time of the initiator B can be the time of the operation routine in the field, and is generally 10-30 min, preferably 15-30 min.
In the step (2), the temperature of the initiation reaction may be a temperature conventional in the art, preferably 40 to 60 ℃, and more preferably 50 to 60 ℃.
In the step (2), the time for initiating the reaction may be a time conventionally used in the reaction of this kind in the art, and is preferably 25 to 60min, and more preferably 30 to 60 min.
In the step (3), the reaction process is accompanied by cooling operation, and the temperature of the system is reduced to room temperature.
Wherein the room temperature can be 10-30 ℃ which is conventionally considered by the person skilled in the art.
The invention also provides a flocculant prepared by the preparation method of the flocculant.
The invention also provides application of the flocculant in sewage treatment.
On the basis of the common knowledge in the field, the above preferred conditions can be combined randomly to obtain the preferred embodiments of the invention.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows: the flocculant prepared by the invention takes pulping waste liquid as a main raw material, can realize high-efficiency utilization of resources, and changes waste into valuable; the pulping waste liquid is cheap and easy to obtain, and is sufficient in supply and nontoxic; the flocculant prepared by combining pulping waste liquid with other raw materials has the advantages of relatively simple raw material formula, simple preparation steps, easy operation, small using amount during wastewater treatment, high flocculation efficiency, capability of improving settleability of various substances in water, great reduction of COD value in wastewater, complete flocculation, low cost, no secondary pollution and the like.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
In the following examples and comparative examples; the preparation method of the pulping waste liquid comprises the following steps: the method is characterized in that poplar is used as a raw material, pulp is made through a PRC-APMP pulping method, the residual material after the pulp is removed 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.
The polyacrylamides in the following examples are cationic polyacrylamides with a number average molecular weight of 9X 106Left and right.
Example 1
(1) Adding 50g of pulping waste liquid and 325g of deionized water into a 500mL beaker, stirring for 5min, sieving by using a 80-mesh sieve, and collecting filtrate;
adding the filtrate into a four-neck flask with a condensing tube 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;
under the condition that the temperature is 50 ℃, 10g of ammonium persulfate aqueous solution with the mass percentage of 10% is dripped into the mixture of the pulping waste liquid and the polyacrylamide, and the dripping time is 10 min; after the dripping is finished, continuously mixing and reacting 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 15 min; after the dripping is finished, continuously mixing and reacting 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 reduce the temperature of the system to room temperature to obtain the flocculant.
Example 2
(1) Adding 50g of pulping waste liquid and 325g of deionized water into a 500mL beaker, stirring for 5min, sieving by using a 80-mesh sieve, and collecting filtrate;
adding the filtrate into a four-neck flask with a condensing tube and a stirring rotor, adding 5g of polyacrylamide into the four-neck flask at room temperature for six times, and mixing for 10min to obtain a mixture of pulping waste liquid and polyacrylamide;
under the condition that the temperature is 50 ℃, 10g of ammonium persulfate aqueous solution with the mass percentage of 10% is dripped into the mixture of the pulping waste liquid and the polyacrylamide, and the dripping time is 10 min; after the dripping is finished, continuously mixing and reacting 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 15 min; after the dripping is finished, continuously mixing and reacting 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 reduce the temperature of the system to room temperature to obtain the flocculant.
Example 3
(1) Adding 50g of pulping waste liquid and 325g of deionized water into a 500mL beaker, stirring for 5min, sieving by using a 80-mesh sieve, and collecting filtrate;
adding the filtrate into a four-neck flask with a condensing tube and a stirring rotor, adding 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;
dripping 10g of 10 mass percent ammonium persulfate aqueous solution into the mixture of the pulping waste liquid and the polyacrylamide at the temperature of 60 ℃, wherein the dripping time is 10 min; after the dripping is finished, continuously mixing and reacting 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 15 min; after the dripping is finished, continuously mixing and reacting 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 reduce the temperature of the system to room temperature to obtain the flocculant.
Example 4
(1) Adding 50g of pulping waste liquid and 200g of deionized water into a 500mL beaker, stirring for 5min, sieving by using a 80-mesh sieve, and collecting filtrate;
adding the filtrate into a four-neck flask with a condensing tube and a stirring rotor, adding 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;
under the condition that the temperature is 50 ℃, 10g of ammonium persulfate aqueous solution with the mass percentage of 10% is dripped into the mixture of the pulping waste liquid and the polyacrylamide, and the dripping time is 10 min; after the dripping is finished, continuously mixing and reacting 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 15 min; after the dripping is finished, continuously mixing and reacting 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 reduce the temperature of the system to room temperature to obtain the flocculant.
Example 5
(1) Adding 50g of pulping waste liquid and 325g of deionized water into a 500mL beaker, stirring for 5min, sieving by using a 80-mesh sieve, and collecting filtrate;
adding the filtrate into a four-neck flask with a condensing tube and a stirring rotor, adding 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;
under the condition that the temperature is 50 ℃, 20g of 10 percent aqueous solution of ammonium persulfate is dripped into the mixture of the pulping waste liquid and the polyacrylamide for 20 min; after the dripping is finished, continuously mixing and reacting for 30min to obtain a material A;
(2) dripping 30g of 10 mass percent potassium persulfate aqueous solution into the material A prepared in the step (1) at the temperature of 50 ℃ for 30 min; after the dripping is finished, continuously mixing and reacting 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 reduce the temperature of the system to room temperature to obtain the flocculant.
Example 6
(1) Adding 50g of pulping waste liquid and 325g of deionized water into a 500mL beaker, stirring for 5min, sieving by using a 80-mesh sieve, and collecting filtrate;
adding the filtrate into a four-neck flask with a condensing tube and a stirring rotor, adding 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;
dripping 10g of 10 mass percent aqueous solution of sodium persulfate into the mixture of the pulping waste liquor and the polyacrylamide at the temperature of 50 ℃ for 10 min; after the dripping is finished, continuously mixing and reacting 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 15 min; after the dripping is finished, continuously mixing and reacting 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 reduce the temperature of the system to room temperature to obtain the flocculant.
Example 7
(1) Adding 50g of pulping waste liquid and 325g of deionized water into a 500mL beaker, stirring for 5min, sieving by using a 80-mesh sieve, and collecting filtrate;
adding the filtrate into a four-neck flask with a condensing tube and a stirring rotor, adding 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;
under the condition that the temperature is 50 ℃, 10g of ammonium persulfate aqueous solution with the mass percentage of 10% is dripped into the mixture of the pulping waste liquid and the polyacrylamide, and the dripping time is 10 min; after the dripping is finished, continuously mixing and reacting 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 15 min; after the dripping is finished, continuously mixing and reacting 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 reduce the temperature of the system to room temperature to obtain the flocculant.
Example 8
(1) Adding 50g of pulping waste liquid and 325g of deionized water into a 500mL beaker, stirring for 5min, sieving by using a 80-mesh sieve, and collecting filtrate;
adding the filtrate into a four-neck flask with a condensing tube and a stirring rotor, adding 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;
under the condition that the temperature is 50 ℃, 10g of ammonium persulfate aqueous solution with the mass percentage of 10% is dripped into the mixture of the pulping waste liquid and the polyacrylamide, and the dripping time is 10 min; continuously mixing and reacting for 60min after the dripping is finished to prepare 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 15 min; 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 reduce the temperature of the system to room temperature to obtain the flocculant.
Example 9
(1) Adding 50g of pulp waste liquid and 325g of deionized water into a 500mL beaker, stirring for 5min, sieving by using a 80-mesh sieve, and collecting filtrate;
adding the filtrate into a four-neck flask with a condensing tube and a stirring rotor, adding 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;
under the condition that the temperature is 50 ℃, 10g of ammonium persulfate aqueous solution with the mass percentage of 10% is dripped into the mixture of the pulping waste liquid and the polyacrylamide, and the dripping time is 10 min; after the dripping is finished, continuously mixing and reacting 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 15 min; after the dripping is finished, continuously mixing and reacting 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 reduce the temperature of the system to room temperature to obtain the flocculant.
Comparative example 1
Compared with the example 1, the method has the difference that no pulping waste liquid is added in the step (1), and other condition parameters are the same as those of the example 1.
Comparative example 2
Compared with the example 1, the difference is that no polyacrylamide is added in the step (1), and other condition parameters are the same as the example 1.
Comparative example 3
Compared with the example 1, the difference is that in the step (1), the adding amount of the ammonium persulfate aqueous solution is adjusted to 5g from 10g, and the dropping time is adjusted to 5 min; in the step (2), the amount of the potassium persulfate aqueous solution added was adjusted from 15g to 10g, the dropping time was adjusted to 10min, and the other condition parameters were the same as those in example 1.
Comparative example 4
Compared with the example 1, the difference is that in the step (1), the adding amount of the ammonium persulfate aqueous solution is adjusted to 30g from 10g, and the dropping time is adjusted to 30 min; in the step (2), the amount of the potassium persulfate aqueous solution added was adjusted from 15g to 30g, the dropping time was adjusted to 30min, and the other condition parameters were the same as those in example 1.
Comparative example 5
Compared with the example 1, the difference is that no glutaraldehyde is added in the step (3), and other condition parameters are the same as the example 1.
Comparative example 6
Compared with the example 1, the difference is only that in the step (2), the potassium persulfate aqueous solution is replaced by the ammonium persulfate aqueous solution with equal mass, and other condition parameters are the same as those in the example 1.
Comparative example 7
Compared with the example 1, the difference is only that in the step (1), the pulping waste liquid is replaced by the same mass of the cellulose aqueous solution with the solid content of 57%, and other condition parameters are the same as the example 1.
Effects of the embodiment
Preparing a flocculant solution: the flocculants prepared in the above examples 1 to 9 and comparative examples 1 to 7 and the polyacrylamide flocculant (PAM) purchased were mixed with deionized water, respectively, to prepare 17 parts of a 0.2% flocculant solution by mass for use.
Different batches of wastewater of a chemical plant are treated by the prepared flocculant solution, and the sedimentation rate of flocs (the result is shown in table 1), the removal rate of COD (the result is shown in table 2) and the removal rate of turbidity (the result is shown in table 3) are calculated. The dosage is calculated according to the weight of the flocculating agent in the flocculating agent solution, namely 20mg flocculating agent is added into each liter of wastewater. And a blank set was set, i.e., no flocculant was added.
Pouring a wastewater sample obtained from a sewage treatment center of a chemical plant into a measuring cylinder with a plug and an inner diameter of 3cm and a volume of 100mL, adding a certain amount of prepared flocculant solution, turning the measuring cylinder filled with a water sample upside down for a plurality of times, standing the measuring cylinder on a horizontal desktop, starting timing at the same time, standing for 1min, and calculating the sedimentation rate; taking supernatant to measure COD and turbidity, wherein the COD is measured by adopting a potassium dichromate method according to the national standard HJ-T399-2007, and the measuring equipment is a 6B-24 type double-temperature-zone intelligent digestion instrument and a 6B-2000 type water quality rapid measuring instrument; the turbidity of the wastewater was measured using an EFZ-200P turbidity meter.
The sedimentation rate is the distance of floc descending per unit time and is given in cm/min.
Turbidity removal rate (turbidity)Waste water original shapeTurbidity toAfter treatment) TurbidityWaste water original shape×100％。
COD removal rate (COD)Waste water original shape-CODAfter treatment)/CODWaste water original shape×100％。
TABLE 1
TABLE 2
TABLE 3
When the flocculant prepared in the embodiment is used for flocculation treatment, the addition amount of the flocculant is 1/3-1/2 of the currently commercially available flocculant.
As can be seen from the data in tables 1 to 3, the flocculating agents prepared in examples 1 to 9 can effectively improve the sedimentation rate, turbidity removal rate and COD removal rate of the flocculating body compared with the flocculating agents prepared in comparative examples 1 to 6; the settling 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 flocculating agent prepared in the comparative example 7 is used for flocculation treatment, the floc stability is poor, and the floc is easy to disperse in the filter pressing process, so that harmful substances in the wastewater rise, and the flocculating agent is not beneficial to industrial large-scale use; when the flocculating agent prepared in the embodiment 1-9 is used for flocculation treatment, the floc stability is good, and the floc is not scattered in the filter pressing process.
The foregoing is only a preferred embodiment of the present invention, and those skilled in the art will understand that the present invention is not limited by these embodiments, and the above embodiments and the description are only for illustrating the principle of the present invention, and any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The raw material composition is characterized by comprising 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;
the initiator comprises an initiator A and an initiator B, wherein the initiator A and the initiator B are respectively and independently one or more of sodium persulfate, potassium persulfate, ammonium persulfate, Fenton reagent and azo initiators, 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 paper pulp.
2. The raw material composition of claim 1, wherein the high yield pulp is produced by a PRC-APMP process or an APMP process, preferably a PRC-APMP process;
and/or the solid content of the pulping waste liquid is 50-60%, preferably 57-60%;
and/or the pulping waste liquid 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 compound;
and/or the polyacrylamide is cationic polyacrylamide;
and/or the polyacrylamide has a number average molecular weight of 7 x 106～9×106Preferably 9 × 106；
And/or the initiator A is ammonium persulfate and/or sodium persulfate;
and/or the initiator B is potassium persulfate; preferably, when the initiator B is potassium persulfate, the initiator A is ammonium persulfate or sodium 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, malonaldehyde, succinaldehyde, glutaraldehyde and adipaldehyde, preferably glutaraldehyde and/or formaldehyde;
and/or, the raw material composition further comprises water.
3. A feedstock composition according to claim 2, wherein said reducing sugar is one or more of xylose, arabinose and galactose, preferably xylose;
and/or, the salt compound is one or more of sodium acetate, sodium carbonate and potassium carbonate, preferably sodium acetate;
and/or the cellulose accounts for 50-53 parts by weight;
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 the salt compound is 32-35 parts by weight;
and/or the mass percentage of the initiator in the initiator aqueous solution is 8-15%, preferably 10%;
and/or the water accounts for 3-6.5 parts by weight, preferably 4-6.5 parts by weight.
4. The raw material composition according to any one of claims 1 to 3, wherein the polyacrylamide is present in an amount of 0.1 to 0.15 parts by weight;
and/or the initiator accounts for 0.05-0.08 part by weight;
and/or the weight ratio of the initiator A to the initiator B is (0.6-1): 1, preferably (0.67-0.8): 1;
and/or the weight part of the cross-linking agent is 0.14-0.2 part.
5. A method for preparing a flocculant, wherein a raw material of the flocculant comprises the raw material composition according to any one of claims 1 to 4;
the preparation method comprises the following steps:
(1) carrying out initiation reaction on the mixture of the pulping waste liquid and the polyacrylamide and the initiator A to prepare a material A;
(2) carrying out initiation reaction on the material A and the initiator B to prepare a material B;
(3) and reacting the material B with the cross-linking agent to obtain the material B.
6. The method for preparing the flocculant according to claim 5, wherein in the step (1), the mixture of the pulping waste liquor and the polyacrylamide is obtained by mixing the pulping waste liquor and the polyacrylamide;
the polyacrylamide is preferably added in batches; the number of times of the batch addition is preferably 3 or more;
the mixing time is preferably 10 to 15 min.
7. The method for preparing the flocculant according to claim 5, wherein in the step (1), the pulping waste liquor further comprises the operations of diluting, filtering and collecting filtrate before use;
the solid content of the diluted system is preferably 7-15%, more preferably 7.6-10%;
the mesh number of the filtering screen is preferably 80-100 meshes.
8. The method for preparing the flocculant according to any one of claims 5 to 7, wherein the initiator A is added dropwise; the dropping time of the initiator A is preferably 10-30 min, more preferably 10-20 min;
and/or in the step (1), the temperature of the initiation reaction is 40-60 ℃, preferably 50-60 ℃;
and/or in the step (1), the time for initiating the reaction is 25-70 min, preferably 30-70 min;
and/or, in the step (2), the addition mode of the initiator B is dropwise addition; the dripping time of the initiator B is preferably 10-30 min, more preferably 15-30 min;
and/or in the step (2), the temperature of the initiation reaction is 40-60 ℃, preferably 50-60 ℃;
and/or, in the step (2), the time for initiating the reaction is 25-60 min, preferably 30-60 min;
and/or, in the step (3), the reaction process is accompanied with the operation of temperature reduction, and the temperature of the system is reduced to room temperature.
9. A flocculant produced by the method for producing a flocculant according to any one of claims 5 to 8.
10. Use of a flocculant according to claim 9 in the treatment of wastewater.
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