CN115287944A - Tea-flavored disposable paper cup paper and preparation method thereof - Google Patents
Tea-flavored disposable paper cup paper and preparation method thereof Download PDFInfo
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- CN115287944A CN115287944A CN202211002284.9A CN202211002284A CN115287944A CN 115287944 A CN115287944 A CN 115287944A CN 202211002284 A CN202211002284 A CN 202211002284A CN 115287944 A CN115287944 A CN 115287944A
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
- D21H27/10—Packing paper
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0009—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid alpha-D-Glucans, e.g. polydextrose, alternan, glycogen; (alpha-1,4)(alpha-1,6)-D-Glucans; (alpha-1,3)(alpha-1,4)-D-Glucans, e.g. isolichenan or nigeran; (alpha-1,4)-D-Glucans; (alpha-1,3)-D-Glucans, e.g. pseudonigeran; Derivatives thereof
- C08B37/0012—Cyclodextrin [CD], e.g. cycle with 6 units (alpha), with 7 units (beta) and with 8 units (gamma), large-ring cyclodextrin or cycloamylose with 9 units or more; Derivatives thereof
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
- D21H11/12—Pulp from non-woody plants or crops, e.g. cotton, flax, straw, bagasse
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/02—Material of vegetable origin
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/03—Non-macromolecular organic compounds
- D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
- D21H17/14—Carboxylic acids; Derivatives thereof
- D21H17/15—Polycarboxylic acids, e.g. maleic acid
- D21H17/16—Addition products thereof with hydrocarbons
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/03—Non-macromolecular organic compounds
- D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
- D21H17/17—Ketenes, e.g. ketene dimers
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
- D21H17/24—Polysaccharides
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/63—Inorganic compounds
- D21H17/64—Alkaline compounds
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/71—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes
- D21H17/72—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes of organic material
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/10—Coatings without pigments
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/06—Paper forming aids
- D21H21/10—Retention agents or drainage improvers
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/16—Sizing or water-repelling agents
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- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
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- D21H21/18—Reinforcing agents
- D21H21/20—Wet strength agents
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Abstract
The invention belongs to the technical field of papermaking, and provides a preparation method of tea-flavored disposable paper cup paper, which comprises the following steps: preparing chemical pulp paper making cup paper by using tea leaves; (2) Preparing an AKD sizing agent by taking a cyclodextrin organic framework synthesized by ODSA modified cyclodextrin and potassium hydroxide in the presence of methanol and CTAB as a stabilizer; (3) And (3) coating and sizing the surface of the tea residue paper cup paper by using an AKD sizing agent to obtain the disposable paper cup paper. The invention recycles the tea leaf waste such as tea tree stems and the like generated in the picking and processing processes of the tea from the aspect of paper making, increases the economic benefit of the tea processing industry, improves the limitation of the previous tea leaf treatment mode, and reduces the damage of the tea leaves to the natural environment.
Description
Technical Field
The invention belongs to the technical field of papermaking, and particularly relates to disposable paper cup paper which is made from tea leaves and tea leaves as main raw materials and has good hydrophobicity and a preparation method thereof.
Background
The main fiber raw materials of paper making enterprises in China are imported, wherein one fiber raw material is from imported paper pulp (such as wood pulp, waste paper pulp and the like) and imported waste paper, and the other fiber raw material is from domestic products, such as domestic wood pulp, non-wood pulp, domestic waste paper and the like. As China is a China with deficient forest resources, the wood is mainly used for producing furniture after being grown, the mature wood which can be used for papermaking is less and is suitable for the shortage of total forest resources for pulping and papermaking, the fiber quality is poorer, and the raw materials of only several conventional model pulping enterprises in China mostly depend on import (mainly southeast Asia wood chips). Beginning in 2017, the state tightens import policies of foreign wastes, and the foreign waste quotas of paper-making enterprises are getting smaller and smaller. In 2018, the wood pulp in the raw materials for papermaking in China accounts for 30 percent. The waste paper pulp (pulp produced by using waste paper as a raw material) accounts for 58%, the non-wood pulp accounts for 7%, and the wood pulp and non-wood pulp accounts for an increasing amount in 2019 and 2020 along with the sharp decrease of the amount of imported waste paper. In 2021, after the import and the external waste are completely prohibited in China, the raw materials of the Chinese paper industry are once deficient, the cost of paper factories is increased, the direct reaction is on the paper price, namely the price of packaging paper rises rapidly, and the frequent fluctuation of the paper price brings influence on the paper industry and the downstream printing and packaging industry. The sudden reduction of external waste forces paper making enterprises to make great adjustments in the aspects of raw material purchase, production process, product structure and the like, and at present, the raw materials used in the paper making industry mainly comprise three types of wood pulp, non-wood pulp (such as wheat straw pulp, bamboo pulp, reed pulp, bagasse pulp and the like) and waste paper pulp. Enterprises using fibers such as wood, reed, bamboo, bagasse and the like as raw materials for papermaking are less than 200, unreasonable raw material structures influence product grade and competitiveness, and the paper is serious in pollution and high in environmental protection cost. The non-wood fiber has the advantage of low cost, so that the construction of large-scale production lines is encouraged, and with the increase of shortage pressure of Chinese fiber raw material resources and the continuous improvement and improvement of non-wood fiber pulping technology, the paper pulp taking the non-wood fiber as the raw material becomes an indispensable important component.
China is a big country for tea planting. According to statistics, the yield of the Chinese tea leaves in 2020 is 297 ten thousand tons. China is not only a large country for tea production, but also a large country for tea consumption. According to the statistics of the international tea committee, the tea yield and the sales volume of China are in the top place. Now that people are more aware of the important role played by tea in health care, the tea industry is undergoing a process of transition from the traditional tea industry to the deep processing tea industry. China only needs 7.4 percent of the total amount of deeply processed tea leaves, and the world average level is 22 percent, which means that huge market space still exists. A large amount of tea residues are generated due to deep processing of tea drinks and tea leaves every year, and the tea residues can reach over 7 ten thousand tons roughly estimated. With the vigorous development of tea food, how to solve the problem of a large amount of tea residues caused by the deep processing of tea is an important component for developing the tea deep processing industry. At present, the tea leaves are mainly treated by composting, burning and burying. However, large quantities of tea grounds are difficult to degrade in all of these ways. The renewable biomass resources not only cause great pressure on the environment, but also arouse great interest in the development and utilization of the biomass resources. The tea tree stems left after tea picking and processing are the main components of the tea leaves at present, and in order to solve the problem of tea leaf recycling, relieve the resource shortage dilemma of raw materials in the papermaking field of China and reduce the damage of the papermaking field to the nature, the tea leaves are used as the raw materials, clean and high-yield pulping processes are explored, the key technology of making special tea leaf paper products is broken through, the waste tea leaves are recycled and reprocessed, and the tea leaf paper products using the tea leaves as the main raw materials are prepared.
Disclosure of Invention
Aiming at the problem that the tea leaves are difficult to clean and recycle thoroughly to cause environmental pollution at present, the invention provides a preparation method of food-grade disposable paper cup paper which takes the tea leaves as a main raw material and has good hydrophobicity, and the prepared paper cup paper has high strength, safety and no toxicity.
In order to achieve the purpose, the invention adopts the following technical scheme.
A preparation method of tea-flavored disposable paper cup paper comprises the following steps:
(1) Preparing tea residue paper cup paper:
(a) Adding the dried tea leaves into caustic soda-anthraquinone cooking liquor for pre-soaking, and then cooking to obtain tea leaf chemical pulp;
(b) Washing the chemical pulp of the tea leaves to remove alkali, and pulping to obtain tea leaf pulp;
(c) Selectively adding bamboo pulp into the tea residue pulp to obtain paper pulp, adding a retention and filtration aid and a wet strength agent into the paper pulp to manufacture low-basis-weight paper, and then carrying out hot pressing on the paper to obtain tea residue paper cup paper;
(2) Preparing a food-grade AKD sizing agent emulsion:
(i) Dispersing Cyclodextrin (CD) in deionized water, heating and stirring uniformly, adjusting the pH of the suspension to 8.5, then dropwise adding 1-octadecenyl succinic anhydride (ODSA) for reaction, adjusting the pH to 6.5, and washing and drying the obtained product after freeze-drying by using a cleaning agent to obtain modified CD;
(ii) Dissolving modified CD and KOH in water, adding methanol and Cetyl Trimethyl Ammonium Bromide (CTAB), reacting at room temperature, carrying out solid-liquid separation on a reaction system, washing solids, and drying to obtain modified CD-MOFs;
(iii) Taking Alkyl Ketene Dimer (AKD) in a molten state as an oil phase; soaking tea in water of 100 deg.C, filtering, concentrating to obtain tea juice, and uniformly dispersing modified CD-MOFs in the tea juice as water phase; shearing and emulsifying the water phase and the oil phase under the condition of heat preservation, and then carrying out ice-water bath to obtain a food-grade AKD sizing agent;
(3) Preparing disposable paper cup paper: and (3) coating and sizing the surface of the tea residue paper cup paper by using a food-grade AKD sizing agent to obtain the disposable paper cup paper.
In the step (a), the material-liquid ratio of the tea residue to the cooking liquor is 1 (8-14) g/mL.
In the step (a), the using amount of caustic soda is 13-18% of the weight of the tea leaves; the amount of anthraquinone is 0.03-0.08% of the tea residue.
In the step (b), the beating degree is SR40-SR55.
In the step (c), the adding amount of the bamboo pulp is 0-20% of the weight of the tea residue pulp.
In the step (c), the retention and drainage aid is cationic starch and cationic polyacrylamide mixed according to the mass ratio of 1:1, and the dosage of the retention and drainage aid is 0.5-1.0 percent of the mass of dry matter of the paper pulp. The wet strength agent is polyamide polyepichlorohydrin resin, and the dosage of the wet strength agent is 0.3 to 0.8 percent of the mass of dry matter of the paper pulp.
In the step (c), the basis weight of the low basis weight paper is 90g/m 2 -110g/m 2 。
In step (i), the cyclodextrin can be beta-cyclodextrin or gamma-cyclodextrin; preferred is gamma-cyclodextrin. The concentration of cyclodextrin is 0.09-0.13wt%.
In the step (i), the mass ratio of octadecenyl succinic anhydride to cyclodextrin is 1.
In step (i), the heating temperature was 50 ℃.
In step (i), the cleaning agent is a mixed solution of equal volumes of hexane and isopropanol.
In step (ii), the mass ratio of the modified CD to the KOH is 2.5; the mass ratio of the modified CD to the CTAB is 1:1-1.5; the concentration of the modified CD in water is 3% -3.5% by weight.
In step (ii), the volume ratio of methanol to water is 1.5.
In step (ii), the solvent for washing is isopropanol.
In step (iii), the molten alkyl ketene dimer is alkyl ketene dimer at 65-80 ℃.
In the step (iii), the mass ratio of the tea leaves to the deionized water is 1.
In step (iii), the concentration of the modified CD-MOFs in the aqueous phase is 0.1% -4% wt.
In step (iii), the volume ratio of the oil phase to the aqueous phase is 1:3-1.
In step (iii), the temperature for heat preservation is 65-80 ℃.
In step (iii), the soaking time is 5-20min.
In the step (3), the coating sizing amount of the food-grade AKD sizing agent is 2-20g/m 2 More preferably 8 to 12g/m 2 。
A tea-fragrance disposable paper cup obtained by the preparation method.
The tea-fragrance disposable paper cup can be used for preparing disposable paper cups and food packages.
The invention has the following advantages:
the disposable paper cup paperboard which takes the tea dregs as the main papermaking raw material and takes the bamboo pulp as the auxiliary raw material is prepared by the preparation method, and the disposable paper cup paperboard has good hydrophobicity after being sized by the food-grade AKD papermaking sizing agent. In the papermaking process, the paper can have stronger paper performance without adding too much papermaking chemicals.
The food-grade AKD sizing agent takes the modified CD-MOFs as an emulsifier, and the tea juice is a water phase, so that the food-grade AKD sizing agent has light tea fragrance. Modifying the raw material CD by octadecenyl succinic anhydride (ODSA), so that the water stability of CD-MOFs is enhanced, and the amphipathy of the CD-MOFs is increased; the modified CD-MOFs particles and tea polyphenol in tea juice form a network cross-linked compact particle film, so that the AKD emulsion has a strong promotion effect on the emulsion stability of AKD, and has the characteristics of bacteriostasis, tea fragrance and the like; in addition, the tea juice provides weak acidity for the AKD emulsification environment, so that the emulsion has stronger hydrolytic stability. Because the sizing agent uses food-grade raw materials, the sizing agent has good biocompatibility, simple production process, no environmental pollution and low production cost.
The invention recycles the tea residue wastes such as tea tree stems and the like generated in the picking and processing processes of the tea from the aspect of paper making, increases the economic benefit of the tea processing industry, improves the limitation of the traditional tea residue treatment mode, reduces the damage of the tea residue to the natural environment, and has important significance for improving the added value of the tea, prolonging the processing chain of the tea industry and ensuring the healthy development of the tea industry.
Drawings
FIG. 1 is an appearance and photomicrograph of a tea residue slurry;
FIG. 2 is an appearance and micrograph of an AKD sizing agent emulsion;
FIG. 3 is a graph of the hydrophobic effect of AKD sizing agents before and after sizing;
FIG. 4 is an appearance and micrograph of tea grounds cupped paper;
FIG. 5 shows the appearance (left) of the disposable paper cup and the state (right) after filling water with different amounts of bamboo pulp.
Detailed Description
The present invention will be further described with reference to the following examples and the accompanying drawings, but the present invention is not limited by the following examples.
Example 1 preparation of tea scented Disposable paper cup paper
S1, preparation of tea residue paper cup paper
(1) Dissolving 15 parts by weight of NaOH and 0.05 part by weight of anthraquinone in 1000 parts by weight of water to obtain a cooking liquor, and adding 100 parts by weight of oven-dried tea leaves into the cooking liquor for soaking for 2 hours; placing the soaked tea residue and the cooking liquid into a rotary cooking pot, setting the highest cooking temperature to be 150 ℃, the heating rate to be 1 ℃/min, and preserving the heat for 30min at the highest cooking temperature of 150 ℃ to obtain tea residue chemical pulp;
(2) Repeatedly cleaning the tea residue chemical pulp to remove alkali, pulping by a PFI pulping machine, wherein the pulping degree SR is 45, and obtaining tea residue pulp; the appearance and microscope image are shown in fig. 1: the tea residue is steamed and boiled, the fiber bundle is basically removed, the fiber length is 1mm-1.5mm, the fiber width is 10 μm-20 μm, and the tea residue is suitable for being screened and made into paper;
(3) Adding 10% of bamboo pulp into the tea residue pulp according to the mass of dry matters to obtain paper pulp, adding a mixture of cationic starch and cationic polyacrylamide which are 0.7% of the mass of the dry matters of the paper pulp and 0.7% of the mass of the dry matters of the paper pulp into the paper pulp as a retention and drainage aid, and adding polyamide polyepichlorohydrin which is 0.5% of the mass of the dry matters of the paper pulpResin is used as wet strength agent for making paper with 100g/m 2 Then two sheets of paper of 100g/m are put 2 The tea residue paper cup is obtained after the paper is hot-pressed.
S2, preparation of food-grade AKD sizing agent
(1) Modification of gamma-CD: dissolving 100 parts by weight of gamma-CD in deionized water to enable the mass fraction of the gamma-CD to be 1.11%, magnetically stirring the mixture for 1 hour at 50 ℃, and adjusting the pH value of the suspension to 8.5 by using NaOH solution; then 5 parts by weight of 1-octadecenylsuccinic anhydride (ODSA) was slowly added, neutralized to pH 6.5 with hydrochloric acid when pH reached a constant value, and then freeze-dried; using a hexane/isopropanol isometric mixed solution as a cleaning agent, shaking and washing on a shaking table at 160rpm for 15min, centrifuging at 8000rpm for 20min, collecting the precipitate, washing for 2 times under the same condition, and drying the precipitate to obtain modified gamma-CD;
(2) Preparation of modified gamma-CD-MOFs particles: dissolving 29 parts by weight of modified gamma-CD and 10 parts by weight of KOH in deionized water to ensure that the mass fraction of the gamma-CD is 3.25%, adding 1.5 times of methanol and 22 parts by weight of CTAB according to the water amount, standing at room temperature for 24h for reaction after the CTAB is completely dissolved, washing with isopropanol, centrifuging at 8000rpm for 20min to collect precipitates, washing for 2 times under the same condition, and vacuum-drying the precipitates at 60 ℃ for 12h to obtain modified gamma-CD-MOFs; the appearance of the modified gamma-CD-MOFs particles is a regular hexahedron, and about 90 percent of the particle size is distributed between 400 and 500nm; the contact angle with water is 77 degrees, and the three-phase contact angle (water-solid-oil) is 98 degrees;
(3) Preparation of food-grade AKD sizing agent: taking Alkyl Ketene Dimer (AKD) in a molten state at 70 ℃ as an oil phase; soaking 2 parts by weight of Pu' er tea pieces in 20 parts by weight of deionized water at 100 ℃ for 10min to obtain tea water, and dispersing the modified gamma-CD-MOFs in the tea water as a water phase to ensure that the mass fraction of the modified gamma-CD-MOFs is 1.0%; mixing the oil phase and the water phase according to a volume ratio of 1. The appearance and emulsion micrographs of the food grade AKD sizing agent obtained are shown in figure 2: the emulsion takes tea water as water phase, has a grey brown appearance, is uniform, and has tea fragrance. The average particle size of emulsion droplets is 2.2 μm, and the emulsion droplets are uniformly distributed.
S3, preparation of disposable paper cup paper
Diluting the food-grade AKD sizing agent emulsion by 10 times, and then coating and sizing the surface of the tea residue paper cup: placing paper to be glued on a nano-cellulose film/coating machine (CUF 5-200 type, sumet, germany), adding diluted AKD glue emulsion into a coating material box, adjusting the coating speed to be 1.5cm/s, the coating pressure to be 10N/m, the coating drying temperature to be 105 ℃, the drying time to be 30min, and the coating weight to be 6g/m 2 . The water contact angle of the sizing paper reaches 133 degrees, the sizing degree is 2640s, and the sizing effect is excellent. The effect before and after sizing is shown in figure 3: the paper cup paper before gluing can be obviously soaked by water, and the paper cup paper after gluing has obvious hydrophobic effect. The paper cup paper tear rate is 1520mN (GB/T455-2002), the ring crush strength is 160N (GB/T2679.8-2016), and the dry tensile index is 73 N.m/g (GB/T12914-2018). The appearance and micrograph of the obtained disposable paper cup paper are shown in fig. 4: the paperboard is complete and free from breakage, has good strength, and meets the processing requirements of disposable paper cups.
Example 2 preparation of tea scented Disposable paper cup paper
S1, preparation of tea residue paper cup paper
(1) Dissolving 13 parts by weight of NaOH and 0.03 part by weight of anthraquinone in 800 parts by weight of water to obtain a cooking liquor, and adding 100 parts by weight of oven-dried tea leaves into the cooking liquor for soaking for 2 hours; placing the soaked tea leaves and the cooking liquor into a rotary cooking pot, setting the highest cooking temperature to be 120 ℃, the heating rate to be 1 ℃/min, and preserving the heat for 60min at the highest cooking temperature of 120 ℃ to obtain tea leaf chemical pulp;
(2) Repeatedly cleaning the tea residue chemical pulp to remove alkali, pulping by a PFI pulping machine, wherein the pulping degree SR is 40, and obtaining tea residue pulp;
(3) Pure tea residue pulp is taken as paper pulp for papermaking, cationic starch accounting for 0.5 percent of the dry matter mass of the paper pulp and cationic polyacrylamide accounting for 0.5 percent of the dry matter mass of the paper pulp are added into the paper pulp to be taken as retention and drainage aids, polyamide polyepichlorohydrin resin accounting for 0.3 percent of the dry matter mass of the paper pulp is taken as a wet strength agent, and 90g/m of pure tea residue pulp is made 2 Then two sheets of paper of 100g/m are put 2 The tea residue paper cup is obtained after the paper is hot-pressed.
S2, preparation of food-grade AKD sizing agent
(1) Modification of γ -D: dissolving 100 parts by weight of gamma-CD in deionized water to enable the mass fraction of the gamma-CD to be 1.11%, magnetically stirring the gamma-CD for 1 hour at 50 ℃, and adjusting the pH value of the suspension to 8.5 by using a NaOH solution; then 5 parts by weight of 1-octadecenylsuccinic anhydride (ODSA) was slowly added, neutralized to pH 6.5 with hydrochloric acid when pH reached a constant value, and then freeze-dried; using a hexane/isopropanol isometric mixed solution as a cleaning agent, oscillating and washing on a 160rpm shaker for 15min, centrifuging at 8000rpm for 20min, collecting precipitates, washing for 2 times under the same condition, and drying the precipitates to obtain modified gamma-CD;
(2) Preparation of modified gamma-CD-MOFs particles: dissolving 25 parts by weight of modified gamma-CD and 10 parts by weight of KOH in deionized water to ensure that the mass fraction of the gamma-CD is 3.25%, adding 2 times of methanol and 25 parts by weight of CTAB according to the water amount, standing at room temperature for 24h for reaction after the CTAB is completely dissolved, washing with isopropanol, centrifuging at 8000rpm for 20min, collecting precipitate, washing for 2 times under the same condition, and vacuum-drying the precipitate at 60 ℃ for 12h to obtain modified gamma-CD-MOFs; the particle size of the modified gamma-CD-MOFs particles is distributed between 60 and 300nm; the contact angle with water is 67 degrees, and the three-phase contact angle (water-solid-oil) is 91 degrees;
(3) Preparation of a food-grade AKD sizing agent: taking Alkyl Ketene Dimer (AKD) in a molten state at 65 ℃ as an oil phase; soaking 2 parts by weight of Pu' er tea pieces in 20 parts by weight of deionized water at 100 ℃ for 10min to obtain tea water, and dispersing the modified gamma-CD-MOFs in the tea water as a water phase to ensure that the mass fraction of the modified gamma-CD-MOFs is 1.0%; mixing the oil phase and the water phase according to a volume ratio of 1:3, shearing and stirring at 12000rpm under the heating condition of 65 ℃ for 5min, and rapidly cooling in ice bath to obtain an oil-in-water Pickering emulsion, namely a food-grade AKD sizing agent, wherein the average particle size of droplets of the emulsion is 3.7 mu m.
S3, preparation of disposable paper cup paper
Diluting the food-grade AKD sizing agent emulsion by 10 times, and then coating and sizing the surface of the tea residue paper cup paper, wherein the coating weight is 4g/m 2 The sizing degree is 1215s, the water contact angle of the sized paper reaches 109 degrees, the hydrophobic effect of the sized disposable paper cup paper is obvious, and the disposable paper cup paper has obvious tea fragrance. The paper cup paper tear strength is 700mN, and the ring crush strength is 65N, dry tensile index 42N m/g.
EXAMPLE 3 preparation of tea scented Disposable paper cup paper
S1, preparation of tea residue paper cup paper
(1) Dissolving 18 parts by weight of NaOH and 0.08 part by weight of anthraquinone in 1400 parts by weight of water to obtain cooking liquor, and adding 100 parts by weight of oven-dried tea leaves into the cooking liquor for soaking for 2 hours; placing the soaked tea leaves and the cooking liquor into a rotary cooking pot, setting the highest cooking temperature to be 180 ℃, the heating rate to be 1 ℃/min, and keeping the temperature at the highest cooking temperature of 180 ℃ for 260min to obtain tea leaf chemical pulp;
(2) Repeatedly cleaning the tea residue chemical pulp to remove alkali, pulping by a PFI pulping machine, wherein the pulping degree SR is 55 to obtain tea residue pulp;
(3) Adding 5% of bamboo pulp into the tea residue pulp according to the dry matter mass to obtain paper pulp, adding a mixture of cationic starch and cationic polyacrylamide which are 0.5% of the dry matter mass of the paper pulp and 0.5% of the dry matter mass of the paper pulp into the paper pulp as a retention and drainage aid, using polyamide-polyepichlorohydrin resin which is 0.3% of the dry matter mass of the paper pulp as a wet strength agent, and making 90g/m 2 Then two sheets of paper of 100g/m are put 2 The tea residue paper cup is obtained after the paper is hot-pressed.
S2, preparation of food-grade AKD sizing agent
(1) Modification of beta-CD: dissolving 100 parts by weight of beta-CD in deionized water to enable the mass fraction of the beta-CD to be 1.11%, magnetically stirring the beta-CD for 1 hour at 50 ℃, and adjusting the pH value of the suspension to 8.5 by using NaOH solution; then 11 parts by weight of 1-octadecenylsuccinic anhydride (ODSA) was slowly added, neutralized to pH 6.5 with hydrochloric acid when pH reached a constant value, and then freeze-dried; using a hexane/isopropanol isometric mixed solution as a cleaning agent, shaking and washing on a shaking table at 160rpm for 15min, centrifuging at 8000rpm for 20min, collecting precipitates, washing for 2 times under the same condition, and drying the precipitates to obtain modified beta-CD;
(2) Preparation of modified beta-CD-MOFs particles: dissolving 35 parts by weight of modified beta-CD and 10 parts by weight of KOH in deionized water to ensure that the mass fraction of the beta-CD is 3.25%, adding 2.5 times of methanol and 23 parts by weight of CTAB according to the water amount, standing at room temperature for 24h for reaction after the CTAB is completely dissolved, washing with isopropanol, centrifuging at 8000rpm for 20min to collect precipitates, washing for 2 times under the same condition, and vacuum-drying the precipitates at 60 ℃ for 12h to obtain modified alpha-CD-MOFs; the appearance of the modified beta-CD-MOFs particles is cubic, and the particle size is distributed between 80 and 250nm; the contact angle with water is 55 degrees, and the three-phase contact angle (water-solid-oil) is 83 degrees;
(3) Preparation of food-grade AKD sizing agent: taking Alkyl Ketene Dimer (AKD) in a molten state at 85 ℃ as an oil phase; soaking 3 parts by weight of broken tea in 20 parts by weight of deionized water at 100 ℃ for 10min to obtain tea water, and dispersing modified beta-CD-MOFs in the tea water to be used as a water phase, so that the mass fraction of the modified beta-CD-MOFs is 4.0%; mixing the oil phase and the water phase according to a volume ratio of 1.
S3, preparation of disposable paper cup paper
Diluting the food-grade AKD sizing agent emulsion by 10 times, and then coating and sizing the surface of the tea residue paper cup paper, wherein the coating weight is 10g/m 2 The water contact angle of the sizing paper reaches 125 degrees, the sizing degree is 3730s, and the paper board has extremely strong hydrophobic property after sizing and has obvious tea fragrance. The paper cup paper tear is 2100mN, the ring pressure strength is 210N, and the dry tensile index is 96N m/g.
Application example 1 preparation of Disposable paper cup
Tea-flavored disposable paper cups were prepared as in example 1, except that: adding 1%, 2%, 5%, 10%, 12%, 15% or 20% bamboo pulp into the tea residue pulp according to dry matter mass to obtain paper pulp, wherein the amount of the sizing agent is 10g/m 2 . And die-cutting the prepared paper, putting the paper into a material port of a paper cup forming machine, sealing by the machine, and flushing the bottom to obtain the disposable paper cup paper.
Table 1 sizing agent sizing degree of paper cup paper at different bamboo pulp dosage at 10% coating weight
The sizing degree of the different patterns was determined as shown in table 1: along with the increase of the using amount of the bamboo pulp, under the condition that the AKD coating amount of the paper cup paper is fixed and unchanged, the sizing degree (hydrophobic property) of the paper cup paper is higher and reaches the highest value at 10 percent, and the sizing degree is only slightly increased when the using amount of the bamboo pulp is continuously increased, probably because the AKD reacts with hydroxyl groups in the bamboo pulp fiber and the tea residue fiber to be saturated, the additional hydrophobic property cannot be generated when the using amount of the bamboo pulp is increased, the cost is increased, and the using amount of the bamboo pulp is preferably 10 percent under the condition of ensuring the basic using property of the paper cup paper.
The appearance of the disposable paper cup with different bamboo pulp addition amounts and the state after water filling are shown in figure 5, the appearance has no great difference when the bamboo pulp is used by 10 percent, 15 percent and 20 percent, and the appearance has no difference in a period of time after water filling, which indicates that the use requirement of the disposable paper cup can be met by 10 percent of the bamboo pulp.
Claims (9)
1. A preparation method of tea-flavored disposable paper cup paper is characterized by comprising the following steps:
(1) Preparing tea residue paper cup paper:
(a) Adding the dried tea leaves into caustic soda-anthraquinone cooking liquor for pre-soaking, and then cooking to obtain tea leaf chemical pulp;
(b) Washing the chemical pulp of the tea leaves to remove alkali, and pulping to obtain tea leaf pulp;
(c) Selectively adding bamboo pulp into the tea residue pulp to obtain paper pulp, adding a retention and filtration aid and a wet strength agent into the paper pulp to manufacture low-basis-weight paper, and then carrying out hot pressing on the paper to obtain tea residue paper cup paper;
(2) Preparing a food-grade AKD sizing agent emulsion:
(i) Dispersing cyclodextrin in deionized water, heating and stirring uniformly, adjusting the pH of the suspension to 8.5, then dropwise adding 1-octadecenyl succinic anhydride for reaction, adjusting the pH to 6.5, and washing and drying the obtained product after freeze-drying by using a cleaning agent to obtain modified CD;
(ii) Dissolving modified CD and KOH in water, adding methanol and hexadecyl trimethyl ammonium bromide, reacting at room temperature, carrying out solid-liquid separation on a reaction system, washing solids, and drying to obtain modified CD-MOFs;
(iii) Taking molten alkyl ketene dimer as an oil phase; soaking tea in water of 100 deg.C, filtering, concentrating to obtain tea juice, and uniformly dispersing modified CD-MOFs in the tea juice as water phase; shearing and emulsifying the water phase and the oil phase under the heat preservation condition, and then carrying out ice-water bath to obtain a food-grade AKD sizing agent;
(3) Preparing disposable paper cup paper: and (3) coating and sizing the surface of the tea residue paper cup paper by using a food-grade AKD sizing agent to obtain the disposable paper cup paper.
2. The preparation method according to claim 1, wherein in the step (a), the material-liquid ratio of the tea residue to the cooking liquor is 1 (8-14) g/mL; the usage amount of the caustic soda is 13 to 18 percent of the weight of the tea residue; the usage amount of anthraquinone is 0.03-0.08% of the weight of the tea residue.
3. The method according to claim 1, wherein in step (b), the freeness is SR40-SR55.
4. The preparation method according to claim 1, wherein in the step (c), the bamboo pulp is added in an amount of 0-20% by mass of the tea residue pulp;
the retention and drainage aid is cationic starch and cationic polyacrylamide mixed by 1:1 in mass ratio, and the dosage of the retention and drainage aid is 0.5 to 1.0 percent of the mass of dry matter of the paper pulp; the wet strength agent is polyamide polyepichlorohydrin resin, and the dosage of the wet strength agent is 0.3 to 0.8 percent of the mass of dry matter of the paper pulp;
the basis weight of the low basis weight paper was 90g/m 2 -110g/m 2 。
5. The method according to claim 1, wherein in step (i), the cyclodextrin is selected from the group consisting of β -cyclodextrin, γ -cyclodextrin; the concentration of cyclodextrin is 0.09-0.13wt%; the mass ratio of the octadecenyl succinic anhydride to the cyclodextrin is 1;
in step (ii), the mass ratio of the modified CD to the KOH is (2.5); the mass ratio of the modified CD to the hexadecyl trimethyl ammonium bromide is 1:1-1.5; a concentration of the modified CD in water of 3% to 3.5% by weight;
(iv) in step (iii), the concentration of the modified CD-MOFs in the aqueous phase is 0.1% -4% by weight; the volume ratio of the oil phase to the water phase is 1:3-1.
6. The method according to claim 1, wherein in the step (i), the temperature of heating is 50 ℃; the cleaning agent is a mixed solution of hexane and isopropanol with equal volume;
in step (ii), the volume ratio of methanol to water is 1.5; the solvent for washing is isopropanol;
in step (iii), the molten alkyl ketene dimer is alkyl ketene dimer at 65-80 ℃; the temperature of heat preservation is 65-80 ℃;
in the step (iii), the mass ratio of the tea leaves to the deionized water is 1; the soaking time is 5-20min.
7. The method of claim 1, wherein the food grade AKD sizing agent is applied at a size of 2-20g/m in step (3) 2 。
8. A tea-flavored disposable paper cup obtained by the process according to any one of claims 1 to 7.
9. Use of the tea scented disposable paper cup of claim 8 in the manufacture of disposable paper cups, food packaging.
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