CN110002702B - Preparation method of papermaking sludge recycling agent - Google Patents
Preparation method of papermaking sludge recycling agent Download PDFInfo
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- CN110002702B CN110002702B CN201910315045.0A CN201910315045A CN110002702B CN 110002702 B CN110002702 B CN 110002702B CN 201910315045 A CN201910315045 A CN 201910315045A CN 110002702 B CN110002702 B CN 110002702B
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- mixture
- recycling agent
- methacrylic acid
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- polyvinyl alcohol
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
- C08F290/12—Polymers provided for in subclasses C08C or C08F
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/26—Nature of the water, waste water, sewage or sludge to be treated from the processing of plants or parts thereof
- C02F2103/28—Nature of the water, waste water, sewage or sludge to be treated from the processing of plants or parts thereof from the paper or cellulose industry
Abstract
The invention discloses a preparation method of a paper sludge recycling agent, which comprises the steps of carrying out esterification reaction on polyvinyl alcohol and methacrylic acid to generate polyester, polymerizing the polyester with cationic monomer DMC and acrylamide to form high-molecular polymer under the action of initiator ammonium persulfate, and grafting chitosan on the surface to obtain the recycling agent.
Description
Technical Field
The invention relates to the technical field of clean production and waste treatment, in particular to a preparation method of a papermaking sludge recycling agent.
Background
In the papermaking production process, along with the flowing of sewage circulating water, a large amount of fine fibers, calcium carbonate, talcum powder, starch, sizing agents and the like are lost along with water, lost substances are polluted by anaerobic bacteria in a water body for a long time to become sludge, solid waste is formed, a large amount of raw materials are wasted, and the formed solid waste also seriously pollutes the environment.
Aiming at the treatment of the existing papermaking sludge, filter-pressing landfill incineration or the preparation of other sludge plates with low interest rate by using the papermaking sludge is mostly adopted, the treatment method of the filter-pressing landfill cannot essentially eliminate pollution, the incineration can generate a large amount of smoke to cause new pollution, the interest rate of the prepared sludge plates is low, the sludge cannot be efficiently utilized, the economic benefit is influenced, and the method is not suitable for industrial production, and the important is that the treatment method cannot fully utilize the raw materials for papermaking, save the cost and improve the paper quality.
Therefore, how to prepare a medicament capable of recycling the raw materials lost in the paper sludge is an urgent problem to be solved by the technical personnel in the field.
Disclosure of Invention
In view of the above, the invention provides a preparation method of a paper sludge recycling agent, which is used for preparing a medicament capable of recycling paper making raw materials such as fine fibers lost in paper sludge, so that the retention rate and the utilization rate of the raw materials are improved, the quality of paper products is improved, the output of solid wastes is reduced, and the subsequent sludge treatment cost is saved.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a papermaking sludge recycling agent comprises the following steps:
(1) mixing polyvinyl alcohol and methacrylic acid, stirring uniformly, placing in a closed container for reaction for 2-3h, and cooling to room temperature to obtain a mixture of polyvinyl alcohol methacrylate and polyvinyl alcohol dimethacrylate;
(2) adding excessive deionized water and a certain amount of cationic monomer DMC into the mixture of the polyvinyl alcohol methacrylate and the polyvinyl alcohol dimethacrylate obtained in the step (1), then adding acrylamide, and stirring the mixture uniformly;
(3) adding ammonium persulfate into the mixture obtained in the step (2), uniformly stirring, and then heating to react for 2.5-3.5h to obtain a hydrophilic high molecular polymer;
(4) and (4) cooling the hydrophilic high molecular polymer prepared in the step (3), adding the carboxylated chitosan, stirring for reacting for 10-15min, and discharging to obtain the papermaking sludge recycling agent.
Preferably, the catalyst in the step (1) is p-toluenesulfonic acid, and the molar ratio of the p-toluenesulfonic acid to the mixture of the polyacrylic alcohol and the methacrylic acid is (0.005-0.015): 1.
preferably, the reaction temperature in the step (1) is 130-165 ℃.
The beneficial effects of the preferred technical scheme are as follows: the esterification reaction is very slow or even impossible at low temperature, and methacrylic acid self-polymerization reaction can occur at too high temperature to cause reaction failure and prevent the product from being prepared, so the temperature is limited to 130-165 ℃ in the invention, and the reaction has the highest reaction efficiency on the premise of smooth reaction.
Preferably, the molar ratio of the polyvinyl alcohol to the methacrylic acid in the step (1) is 1: (1.1-1.3).
The beneficial effects of the preferred technical scheme are as follows: the ratio of the polyvinyl alcohol methacrylic monoester and the polyvinyl alcohol methacrylic diester reacted at this ratio can be optimized.
Preferably, the reaction in step (1) is carried out in a nitrogen atmosphere.
The beneficial effects of the preferred technical scheme are as follows: nitrogen is used as a water-carrying agent and a reaction protective agent, so that other impurities can not be brought in, and the reaction can be isolated from the influence of air.
Preferably, the molar ratio of the cationic monomer DMC added in the step (2) to the mixture of the polypropylene alcohol and the methacrylic acid is (0.03-0.05): 1, the molar ratio of the added acrylamide to the mixture of the polypropylene alcohol and the methacrylic acid is (0.02-0.03:) 1.
The beneficial effects of the preferred technical scheme are as follows: cationic monomer DMC has brought the cationicity for the product, makes it carry positive charge, can be fine with the tiny fiber of negative charge in mud, calcium carbonate filler, gluing thing etc. combine, better with it recycle in the paper, the rate of recycling can't be guaranteed to the quantity low excessively, the quantity is too high then can make mud mutual exclusion, unable retrieval and utilization.
Preferably, the molar ratio of the ammonium persulfate to the mixture of the polypropylene alcohol and the methacrylic acid added in the step (3) is (0.017-0.026): 1.
the beneficial effects of the preferred technical scheme are as follows: the low dosage of the initiator can cause the molecular weight of the product to be too high, the reaction is insufficient, and the product performance can not reach the standard; the use amount of the initiator is too high, so that the molecular weight of the product is too low, and residues appear in the product, thereby influencing the use effect.
Preferably, the reaction temperature in the step (3) is 72-82 ℃.
The beneficial effects of the preferred technical scheme are as follows: the temperature is low, the reaction rate is low, monomers can be accumulated in the reaction kettle, the monomer reaction can not be carried out according to the fine polymerization rate of the normal proportion, the effective amount of a target product can not be effectively controlled, and the molecular weight of the product is too high; the reaction rate is too fast due to high temperature, the polymerization heat can not be effectively dissipated, the reaction can be suddenly aggregated, the particle size of the product is large, and the performance of the product is influenced.
Preferably, the molar ratio of the carboxylated chitosan added in the step (4) to the mixture of the polyacrylic alcohol and the methacrylic acid is (0.1-0.16): 1.
The beneficial effects of the preferred technical scheme are as follows: within this range, the effect of carboxylation of chitosan is most strongly bound to the hydrogen bond of the upper product, and the performance of the product is the best.
Preferably, the temperature reduction in the step (4) is to be reduced to 50 ℃.
The beneficial effects of the preferred technical scheme are as follows: the temperature is too high, the danger in the reaction process is large, the potential safety hazard is caused, and the hydrogen bond combination of the carboxylated chitosan and the product is not facilitated due to too low temperature.
According to the technical scheme, compared with the prior art, the preparation method of the papermaking sludge recycling agent is characterized in that a plurality of raw materials are subjected to esterification, polymerization initiation, chitosan grafting and other reactions to prepare the papermaking sludge recycling agent, the recycling agent has cationic charges, so that a product can be well combined with negative charge fine fibers, calcium carbonate fillers, stickies and the like in sludge and can be combined with pulp fibers, the high molecular weight of the product can increase the combination probability of the product and the pulp fibers, the sludge can be better recycled into paper, the raw material retention rate can be effectively improved, papermaking raw materials such as fine fibers, calcium carbonate, talcum powder, starch, sizing agents and the like lost along with circulating water in the papermaking sludge are recycled, papermaking slurry can be saved, the raw material utilization rate is improved, the quality of the prepared paper is improved, and the generation amount of the sludge is reduced, thereby saving the energy consumption and the cost of sludge treatment and being beneficial to industrial production.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is a graph showing a comparison of pulp retention tests for a recycling agent made in accordance with an embodiment of the present invention;
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The invention provides a preparation method of a papermaking sludge recycling agent, which specifically comprises the following steps:
(1) mixing polyvinyl alcohol and methacrylic acid according to a molar ratio of 1: (1.1-1.3) and the mixture of polyvinyl alcohol and methacrylic acid in the molar ratio of (0.005-0.015): 1, uniformly mixing and stirring the p-toluenesulfonic acid, placing the mixture in a closed container to react for 2 to 3 hours in the environment of 130-165 ℃ in the nitrogen atmosphere, and cooling to room temperature to obtain a mixture of polyvinyl alcohol methacrylate and polyvinyl alcohol dimethacrylate;
(2) adding excessive deionized water into the mixture of the polyvinyl alcohol methacrylate and the polyvinyl alcohol dimethacrylate obtained in the step (1) and ensuring that the molar ratio of the deionized water to the mixture of the polyvinyl alcohol and the methacrylic acid is (0.03-0.05): 1, adding acrylamide with the molar ratio of the mixture of the polypropylene glycol and the methacrylic acid being (0.02-0.03:)1, and stirring the mixture evenly;
(3) adding a mixture of polypropylene glycol and methacrylic acid into the mixture obtained in the step (2) in a molar ratio of (0.017-0.026): 1, uniformly stirring, heating to 72-82 ℃, and reacting for 2.5-3.5h to obtain a hydrophilic high molecular polymer;
(4) and (3) cooling the hydrophilic high molecular polymer prepared in the step (4) to 50 ℃, adding carboxylated chitosan with the molar ratio of the mixture of the polypropylene glycol and the methacrylic acid being (0.1-0.16):1, stirring for reaction for 10-15min, and discharging to obtain the papermaking sludge recycling agent.
The technical effects of the present invention will be further explained below by using the specific values of examples 2 to 9 and the papermaking sludge recycling agent prepared by the method of example 1:
the recycling performance of the recycling agent prepared in the above examples 1-3 was tested by using the same batch of paper sludge, and the results were as follows:
the specific comparison of the retention rate of the paper making sludge produced by the technical scheme of the invention with that of the pulp without the addition of the recycling agent is shown in the attached drawing 1, and the attached drawing 1 shows that the paper making sludge recycling agent produced by the technical scheme of the invention can effectively improve the retention rate of the pulp, reduce the loss amount of effective components of raw materials, improve the utilization rate of the raw materials, further improve the product quality, reduce the generation of sludge, and has higher economic utility value and production application value.
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other. The device disclosed by the embodiment corresponds to the method disclosed by the embodiment, so that the description is simple, and the relevant points can be referred to the method part for description.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. The preparation method of the papermaking sludge recycling agent is characterized by comprising the following steps:
(1) mixing and uniformly stirring polyvinyl alcohol, methacrylic acid and a catalyst, placing the mixture in a closed container for reaction for 2 to 3 hours, and cooling to room temperature to obtain a mixture of polyvinyl alcohol methacrylate and polyvinyl alcohol dimethacrylate;
(2) adding excessive deionized water and a certain amount of cationic monomer DMC into the mixture of the polyvinyl alcohol methacrylate and the polyvinyl alcohol dimethacrylate obtained in the step (1), then adding acrylamide, and stirring the mixture uniformly;
(3) adding ammonium persulfate into the mixture obtained in the step (2), uniformly stirring, and then heating to react for 2.5-3.5h to obtain a hydrophilic high molecular polymer;
(4) and (4) cooling the hydrophilic high molecular polymer prepared in the step (3), adding the carboxylated chitosan, stirring for reacting for 10-15min, and discharging to obtain the papermaking sludge recycling agent.
2. The preparation method of the paper-making sludge recycling agent according to claim 1, wherein the catalyst in the step (1) is p-toluenesulfonic acid, and the molar ratio of the p-toluenesulfonic acid to the mixture of the polyacrylic alcohol and the methacrylic acid is (0.005-0.015): 1.
3. the method as claimed in claim 1, wherein the reaction temperature in step (1) is 130-165 ℃.
4. The preparation method of the recycling agent for paper mill sludge according to claim 1, wherein the molar ratio of the polyvinyl alcohol to the methacrylic acid in the step (1) is 1: (1.1-1.3).
5. The method for preparing the recycling agent of paper sludge according to claim 1, wherein the reaction in the step (1) is performed in a nitrogen atmosphere.
6. The preparation method of the paper-making sludge recycling agent according to claim 1, wherein the molar ratio of the cationic monomer DMC added in the step (2) to the mixture of the polypropylene alcohol and the methacrylic acid is (0.03-0.05): 1, the molar ratio of the added acrylamide to the mixture of the polypropylene alcohol and the methacrylic acid is (0.02-0.03:) 1.
7. The preparation method of the recycling agent for paper mill sludge according to claim 1, wherein the molar ratio of the ammonium persulfate to the mixture of the polypropylene alcohol and the methacrylic acid added in the step (3) is (0.017-0.026): 1.
8. the method for preparing the recycling agent of paper mill sludge according to claim 1, wherein the reaction temperature in the step (3) is 72-82 ℃.
9. The preparation method of the paper mill sludge recycling agent according to claim 1, wherein the molar ratio of the amount of the carboxylated chitosan added in the step (4) to the mixture of the polyacrylic alcohol and the methacrylic acid is (0.1-0.16): 1.
10. The method for preparing the recycling agent of paper mill sludge according to claim 1, wherein the temperature reduction in the step (4) is to be 50 ℃.
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| CN105601818A (en) * | 2016-01-29 | 2016-05-25 | 青岛祥泽化工有限公司 | Modified guar gum thickener for papermaking paints and preparation method thereof |
| WO2017072694A2 (en) * | 2015-10-30 | 2017-05-04 | Università Degli Studi Di Milano - Bicocca | A process for coating polymeric substrates and paper |
| CN108371728A (en) * | 2018-03-09 | 2018-08-07 | 西南交通大学 | A kind of imitative mussel for tissue repair contacts the preparation method of anti-bacterial hydrogel |
| CN109069876A (en) * | 2015-12-31 | 2018-12-21 | 欧莱雅 | The composition containing polycarbodiimide and latex polymer for treatment of keratinous substrates |
| EP3443950A1 (en) * | 2014-07-30 | 2019-02-20 | Symrise AG | A fragrance composition |
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2019
- 2019-04-18 CN CN201910315045.0A patent/CN110002702B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1424012A (en) * | 2001-11-08 | 2003-06-18 | 莱雅公司 | Cosmetic composition containing aminosiloxanes and thickening agent and its use |
| CN102115998A (en) * | 2010-12-31 | 2011-07-06 | 永港伟方（北京）科技股份有限公司 | Dry strengthening agent used for making papers and preparation method and application thereof |
| EP3443950A1 (en) * | 2014-07-30 | 2019-02-20 | Symrise AG | A fragrance composition |
| WO2017072694A2 (en) * | 2015-10-30 | 2017-05-04 | Università Degli Studi Di Milano - Bicocca | A process for coating polymeric substrates and paper |
| CN109069876A (en) * | 2015-12-31 | 2018-12-21 | 欧莱雅 | The composition containing polycarbodiimide and latex polymer for treatment of keratinous substrates |
| CN105601818A (en) * | 2016-01-29 | 2016-05-25 | 青岛祥泽化工有限公司 | Modified guar gum thickener for papermaking paints and preparation method thereof |
| CN108371728A (en) * | 2018-03-09 | 2018-08-07 | 西南交通大学 | A kind of imitative mussel for tissue repair contacts the preparation method of anti-bacterial hydrogel |
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