CN106368050B - A kind of wastewaters with modified calcium sulfate whiskers paper making raw material and application - Google Patents

A kind of wastewaters with modified calcium sulfate whiskers paper making raw material and application Download PDF

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Publication number
CN106368050B
CN106368050B CN201610935886.8A CN201610935886A CN106368050B CN 106368050 B CN106368050 B CN 106368050B CN 201610935886 A CN201610935886 A CN 201610935886A CN 106368050 B CN106368050 B CN 106368050B
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calcium sulfate
paper
wastewaters
raw material
dosage
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CN106368050A (en
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桂明生
赵小兵
王鹏飞
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Leshan Fox Technology Co Ltd
Sichuan University of Science and Engineering
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Leshan Fox Technology Co Ltd
Sichuan University of Science and Engineering
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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
    • D21H15/00—Pulp or paper, comprising fibres or web-forming material characterised by features other than their chemical constitution
    • D21H15/02—Pulp or paper, comprising fibres or web-forming material characterised by features other than their chemical constitution characterised by configuration
    • D21H15/10—Composite fibres
    • D21H15/12—Composite fibres partly organic, partly inorganic
    • 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
    • D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
    • D21H13/36—Inorganic fibres or flakes
    • 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
    • D21H17/07—Nitrogen-containing compounds
    • 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
    • D21H17/28—Starch
    • D21H17/29—Starch cationic
    • 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
    • D21H17/31—Gums
    • D21H17/32—Guar or other polygalactomannan gum
    • 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
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/53—Polyethers; Polyesters
    • 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
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/54—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen
    • D21H17/55—Polyamides; Polyaminoamides; Polyester-amides
    • 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
    • D21H17/74—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes of organic and inorganic material

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Paper (AREA)

Abstract

The present invention relates to a kind of wastewaters with modified calcium sulfate whiskers paper making raw material, belong to pulp technology for making paper.The raw material replaces the dosage of 20~35% wooden (bamboo) slurries using wastewaters with modified calcium sulfate whiskers.The wastewaters with modified calcium sulfate whiskers filters after being sufficiently stirred at a certain temperature for raw material sulphuric acid calcium pyroborate is scattered in the water added with modifying agent and produces wastewaters with modified calcium sulfate whiskers.The invention further relates to application of the wastewaters with modified calcium sulfate whiskers in papermaking.The present invention is modified to calcium sulfate crystal whiskers, can be significantly improved the retention of whisker, be strengthened the intensity of paper；The present invention substitutes part wooden (bamboo) slurry using wastewaters with modified calcium sulfate whiskers, reduces the usage amount of paper making raw material wooden (bamboo) slurry, reaches the purpose for reducing production cost and environmental protection.Paper making raw material technique of the present invention and supplementary product consumption, the dissolving of modified calcium sulfate and the interaction of whisker and plant fibre surface chemical bond are taken into full account, has made the retention of paper and intensity all secure.

Description

A kind of wastewaters with modified calcium sulfate whiskers paper making raw material and application
Technical field
The invention belongs to pulp technology for making paper, more particularly to paper making raw material and technique, specially a kind of modified calcium sulfate is brilliant Must paper making raw material and application.
Background technology
Calcium sulfate crystal whiskers, alias：Crystal whisker of gypsum, gypsum fiber.Using gypsum as raw material, by manual control, with monocrystalline Form growth, there is uniform cross section, complete profile, the threadiness of perfect internal structure (palpus shape) monocrystal.Have Certain draw ratio, the tensile strength and modulus having had, heap density is small, and calcium sulfate crystal whiskers have two water (CaSO4·2H2O), half Water (CaSO4·0.5H2O), without water soluble and anhydrous dead roasting (CaSO4) point.Preparation method currently mainly has hydro-thermal method and normal pressure Acidization.
Calcium sulfate crystal whiskers are slightly soluble in water, and whisker draw ratio is up to 10~300, are compared than conventional paper-making fibre and belong to short and small fibre Dimension, replaces string use in papermaking to produce very big economic effect with wastewaters with modified calcium sulfate whiskers.
The scientific paper on wastewaters with modified calcium sulfate whiskers papermaking rests on theory study stage, or even some mostly at this stage Research conclusion applies contradictory part with actual papermaking.The subject matter that wastewaters with modified calcium sulfate whiskers is applied in papermaking：(1) theory On mistake：Many researchers think wastewaters with modified calcium sulfate whiskers be in filler, and traditional papermaking plus talcum powder, calcium powder do not have it is assorted Difference.Because whisker price is far above calcium powder and talcum powder, so whisker papermaking loses the market advantage, it is unreal by production Apply on border.(2) application technical research can not meet the needs of production.Wastewaters with modified calcium sulfate whiskers answering in papermaking in the prior art By the use of being to imitate as filler to add, its amount added, processing mode and paper technology are defective, do not take into full account sulfuric acid Calcium pyroborate dissolves and the influence of whisker fibre surface chemistries confrontation papermaking.Finally, cause that retention is low, tensile strength of paper refers to The low problem of number.
The content of the invention
It is an object of the invention to provide a kind of whisker retention is high, paper tensile strength is good, it is economical and practical, available for reality The wastewaters with modified calcium sulfate whiskers paper making raw material of border production and application, the present invention replace part wooden (bamboo) slurry using wastewaters with modified calcium sulfate whiskers As paper making raw material, compared to being the paper technology of major ingredient with simple wooden (bamboo) slurry, it has more preferable economic effect, and is made The paper obtained can reach simple wooden (bamboo) slurry and can achieve the effect that, be a kind of new paper making raw material.The object of the invention is led to Following technical proposals are crossed to realize：
A kind of wastewaters with modified calcium sulfate whiskers paper making raw material, the raw material replace 20~35% wood using wastewaters with modified calcium sulfate whiskers The dosage of (bamboo) slurry；
Raw material sulphuric acid calcium pyroborate is is scattered in the water added with modifying agent by the wastewaters with modified calcium sulfate whiskers, in certain temperature Under be sufficiently stirred after filter and produce wastewaters with modified calcium sulfate whiskers；
The mass ratio of the water and calcium sulfate crystal whiskers is 8:1~12:1, the temperature is 80~90 DEG C, the mixing time For 30~50min.
A kind of wastewaters with modified calcium sulfate whiskers paper making raw material, the raw material replace 22~28% wood using wastewaters with modified calcium sulfate whiskers The dosage of (bamboo) slurry.
A kind of wastewaters with modified calcium sulfate whiskers paper making raw material, the raw material replace 25% wooden (bamboo) slurry using wastewaters with modified calcium sulfate whiskers Dosage.
Preferably, the modifying agent is one kind as a kind of wastewaters with modified calcium sulfate whiskers paper making raw material specific embodiment of the present invention Two or more in ten water sodium phosphates, sodium tripolyphosphate, calgon, sodium carboxymethylcellulose, cationic starch；It is described The addition of ten water sodium phosphates is the 0.2~5% of the dry whisker quality of calcium sulfate；The addition of the sodium tripolyphosphate is calcium sulfate The 0.5~3% of dry whisker quality；The addition of the calgon is the 0~3% of the dry whisker quality of calcium sulfate；The carboxylic The addition of sodium carboxymethylcellulose pyce is the 0~2% of the dry whisker quality of calcium sulfate；The addition of the cationic starch is calcium sulfate The 0~3% of dry whisker quality.
One kind as a kind of wastewaters with modified calcium sulfate whiskers paper making raw material specific embodiment of the present invention is preferred, the ten water phosphoric acid The addition of sodium is the 0.5% of the dry whisker quality of calcium sulfate；The addition of the sodium tripolyphosphate is the dry whisker quality of calcium sulfate 1%；The addition of the calgon is the 1% of the dry whisker quality of calcium sulfate；The addition of the sodium carboxymethylcellulose Measure as the 2% of the dry whisker quality of calcium sulfate, the addition of the cationic starch is the 0.1% of the dry whisker quality of calcium sulfate.
Each modifying agent can substantially be divided into three classes by its function in the present invention.The first kind is ten water sodium phosphates, main to play resistance Only calcium sulfate dissolves；Second class is sodium tripolyphosphate and calgon, is mainly served excessively bonded；3rd class is carboxymethyl Sodium cellulosate and cationic starch, it is main to play a part of to be bonded string.This three classes reagent function is each different but mutual Association, first, in order to prevent the dissolving of calcium sulfate, the fact that be much smaller than calcium sulfate using calcium phosphate solubility product, first kind modification The water sodium phosphate of agent ten can form one layer of more insoluble calcium phosphate on calcium sulfate crystal whiskers surface, prevent the dissolving of internal layer calcium sulfate；The Two class reagent trimerizations and hexametaphosphate the polymer phosphate root in water exist in the form of middle long-chain, and this chain one end is easily with Chemical key connection occurs for the calcium phosphate of a kind of modifying agent effect, forms a kind of middle long-chain organic layer for being rich in hydroxyl.In addition, in temperature The lower trimerization of degree effect and hexametaphosphate hydrolyzable go out a small amount of phosphate radical, and phosphate radical caused by hydrolysis is with first kind modifying agent function Equally, form calcium phosphate to seal calcium sulfate crystal whiskers surface, further reduce the solubility of calcium sulfate.3rd class is modified Agent, sodium carboxymethylcellulose and cationic starch are belonged to backbone.After being dissolved in water, the functional group on its chain is very Easily combined with the polymer phosphate chain in the second class modifying agent in the form of hydrogen bond, complete grafting.By sodium carboxymethylcellulose and After cationic starch grafting, the surface chemistry attribute and plant fibre surface of calcium sulfate crystal whiskers are basically identical.Therefore modified sulphur Sour calcium pyroborate can increase the tensile strength of oneself retention and paper in papermaking as paper making raw material.
In summary, in dosage, the second class modifying agent is can to supplement the first kind to change for the first kind and the second class modifying agent Property agent, but in the case where considering modified cost, the dissolving of calcium sulfate is first prevented with small, the cheap phosphate of molecular weight It is more to one's profit.3rd class modifying agent and second of modifying agent are the relations of mutual bonding, so their dosage needs conjunction Suitable proportionate relationship, this is that the 3rd class modifying agent sufficiently ensures in calcium sulfate crystal whiskers surface graft.The class modifying agent phase of the above three Mutually influence, dosage is crossed at most production cost and increased, causes to waste；It is too low, retention of the whisker in paper can be caused low and paper Open the phenomenon that tensile strength declines.
The present invention is calcium sulfate whisker modified to be mainly divided into three steps：It is that phosphate, part tripolyphosphate and six are inclined first Phosphate, phosphate radical and the calcium sulfate on whisker surface after being ionized in water react, generate calcium phosphate precipitation, it is molten to form resistance Layer, prevent calcium sulfate crystal whiskers from dissolving, reduce solubility of the calcium sulfate crystal whiskers in water；This is to ensure calcium sulfate crystal whiskers high retention rate The most important condition.Second step is that one end that tripolyphosphate and hexametaphosphate have backbone is easily formed with whisker surface Calcium phosphate bond together to form the polymer phosphate root transition zone with middle backbone；Finally, when cellulose and cationic starch lean on When near, polymer phosphate root layer is connected to form graft layer with starch and cellulose in the form of hydrogen bond, and graft layer has fine with plant Chemical bond as dimension table noodles, preferably it can be combined with string；In addition, starch surface Fuyang ion, when cloudy with band During the string contact of ion, the two can be combined together by the way that electrostatic interaction is stronger.The present invention is carried out to calcium sulfate It is modified, the conjugation of calcium sulfate crystal whiskers and string can be significantly improved, so as to reach enhancing paper strength, whisker is improved and stays The purpose of rate.
The present invention also provides application of the wastewaters with modified calcium sulfate whiskers paper making raw material in papermaking, and the modified calcium sulfate is brilliant Palpus paper making raw material is applied to paper industry, comprises the following steps：
1) cationic starch is gelatinized at 70~90 DEG C after 20~40min and cationic guar solution mixing for standby use；
2) it is standby after mixing auxiliary agent and PAMC solution；
3) by wastewaters with modified calcium sulfate whiskers, gelatinization after cationic starch and cation guar gum mixed liquor, auxiliary agent and sun from The mixed liquor of sub- polyacrylamide is added sequentially in the back flow water pump equipped with wooden (bamboo) slurry, and is sufficiently stirred, and adds dispersant；
4) slurries blended in back flow water pump are squeezed into net groove by fan pump, and obtained by squeezing, drying process Product paper.
Preferably, the dispersant is one kind as wastewaters with modified calcium sulfate whiskers paper making raw material application specific embodiment of the present invention Polyethylene glycol oxide (PEO).
Preferably, the cation forms sediment one kind as wastewaters with modified calcium sulfate whiskers paper making raw material application specific embodiment of the present invention The dosage of powder is the 5~1.2wt% that wooden (bamboo) starches that gives money as a gift；The dosage of the cation guar gum is to give money as a gift the 0.01 of wooden (bamboo) slurry ~0.1wt%, 0.05~0.1wt% that the PAMC dosage is starched for wood (bamboo) of giving money as a gift, the auxiliary dosage For 0.5~1wt% of wooden (bamboo) slurry of giving money as a gift, the dosage of the dispersant is the 0.01~0.08wt% that wooden (bamboo) starches that gives money as a gift.
Preferably, the cation forms sediment one kind as wastewaters with modified calcium sulfate whiskers paper making raw material application specific embodiment of the present invention The dosage of powder is the 0.7~1wt% that wooden (bamboo) starches that gives money as a gift；The dosage of the cation guar gum is to give money as a gift the 0.04 of wooden (bamboo) slurry ~0.07wt%, the PAMC dosage are the 0.05~0.08wt% that wooden (bamboo) starches that gives money as a gift, and the auxiliary agent is used Measure as 0.7~0.9wt% of wooden (bamboo) slurry of giving money as a gift, the dosage of the dispersant be give money as a gift wooden (bamboo) slurry 0.03~ 0.06wt%.
Preferably, the cation forms sediment one kind as wastewaters with modified calcium sulfate whiskers paper making raw material application specific embodiment of the present invention The dosage of powder is the 0.8wt% that wooden (bamboo) starches that gives money as a gift；The dosage of the cation guar gum is wooden (bamboo) slurry of giving money as a gift 0.05wt%, the PAMC dosage are the 0.07wt% that wooden (bamboo) starches that gives money as a gift, and the auxiliary dosage is to give money as a gift The 0.75wt% of wooden (bamboo) slurry, the dosage of the dispersant is the 0.04wt% that wooden (bamboo) starches that gives money as a gift.
In paper plane, it is connected with each other between cellulose molecular chain by Hydrogenbond, fiber is made by mashing effect Beam separation, sub-wire, chopped fiber is even shut off into, increase the binding site between fiber and fiber, it is certain so as to assign page Intensity.But because cellulose fibre is actually to be formed by the very strong cellulose aggregation of molecule chain rigidity, molecule interchain and The physical entanglement effect very little of molecule interfascicular, makes the adhesion of page between layers smaller, therefore assign page using mashing Intensity be limited, it is necessary to add reinforcing agent to improve the intensity of page.Reinforcing agent surface polarity is larger, can be with fiber shape Into stronger Van der Waals force and chemical bond, improve paper strength, to meet that industry is neutralized in life to different paper The requirement of energy.The reinforcing agent of the present invention selects cation guar gum, cationic starch and PAMC.
There is no non-polar group on guar gum straight chain, most of primary hydroxyl and secondary hydroxyl are at outside, and galactolipin Side chain does not have the alcoholic extract hydroxyl group for covering activity.Thus, guar gum has maximum Hydrogenbond area, when being combined with fiber, For the Hydrogenbond of formation apart from short, adhesion is big.To assign the more preferable performance of guar gum, generally Guar collagen powder is carried out Chemical modification.Cation guar gum is to introduce cation group on former guar gum strand, so as to obtain certain electropositive, As with quaternary ammonium salt 3- chlorine 2- hydroxypropyl ammonium chlorides.The modified guar of this positively charged can with electronegative fiber, fill out Particle interaction is expected so as to improve original retention, drainage and enhancing effect.
Cationic starch is a kind of modified starch that the U.S. develops and is developed in the sixties, and its preparation method is to form sediment Powder under base catalyst effect, with nitrogenous etherifying agent react, and it is introduced quaternary ammonium and tertiary amine groups in the structure by heating, so that Starch has cationic.Cationic starch carries positive electricity, directly can be combined to form with the fibre compact with negative charge Stronger fiber bonding strength, so that the intensity of paper improves.Cationic starch has extremely strong absorption affinity, quaternary ammonium salt to fiber Type starch can almost go all to adsorb with fiber.Cationic starch is in slurry between fiber, auxiliary material and other additives Play a part of ionic bridge, the retention of fiber fines and filler can be improved, and pass through long fine on Preferential adsorption and fiber fines Dimension surrounds fiber fines, forms cohesive network, improves the intensity of paper, improves printing performance.
The preparation of PAMC can be generated by acrylamide monomer and cationic monomer copolymerization.Cation gathers The molecular weight and carboxyl-content of acrylamide have a great influence to enhancing effect, and the molecular weight of general PAMC exists 50~700,000, when carboxyl-content is 10%, tensile strength, rupture strength, the folding strength highest of paper, effect is best.Sun from Sub- polyacrylamide with improving due to positive charge, so can directly adsorb on fiber, being kept.
The use of auxiliary agent is a kind of quaternary ammonium salt high-molecular Papermaking Retention, filter aid in the present invention, there is water-soluble branched structure, Good fluidity, dissolution velocity are fast.Effect is retention when increasing paper pulp online, strengthens drainability, so as to increase paper yield, subtracts Few energy consumption, beneficial to copy paper.There is the effect for strengthening dry paper intensity simultaneously, reduce fiber fines and amount of filler in water outlet, mitigate useless The load of water process.The adjuvant used present invention is pulp technology for making paper conven-tional adjuvants, as long as the purpose of retention can be realized.Property Can feature：There is excellent Retention to fiber fines and filler, section slurry is substantially.Reduce white water consistency, improve raw material yield and White water recycle efficiency.Wet end chemistry conditional stability can be kept, improves paper-forming evenness and paper physical property.Strengthen drainage, reduce The dehydration energy of shaping, squeezing and drying process.
For paper-making process, fiber, filler and some auxiliary agents etc. are all water-insolubles, and they have in aqueous The trend of self-assemble, and often as far as possible remote because of incompatibility between different material, thus it is difficult to obtain performance equal Even, the preferable paper of intensity.Adding dispersant can then make solid particle surfaces form bilayer structure, outer layer dispersant pole Property end and water have compared with strong affinity, add the degree that solids are spontaneously wet out by water.It is because of electrostatic repulsion and remote between solid particle From reaching fine dispersion effect.Polyethylene glycol oxide (PEO) has the characteristics that the viscosity, good water solubility, lubricity of height are good.It is poly- Ethylene oxide (PEO), also with retention, humidification, adapts to pH value model in addition to having good peptizaiton to long and short fiber Enclose width.In addition, it can also improve paper pliability and smoothness.It is typically used as the average molecular matter of polyethylene glycol oxide during dispersant Amount is 3,000,000.When relative molecular mass is less than this value, dosage can be very big；When relative molecular mass is below 500,000, it can lose completely Just fiber is gone to prevent the effect of cohesion.
The plant fibre surface of paper making raw material is rich in various chemical bonds, easily forms hydrogen bond with other hydrophilic radicals, this Invention strengthens the knot of wastewaters with modified calcium sulfate whiskers and string by adding reinforcing agent, auxiliary agent and dispersant in papermaking process Right, the higher wastewaters with modified calcium sulfate whiskers of its conjugation replaces wooden (bamboo) to starch the retention of string and tensile strength index also can It is higher.Raw material, reinforcing agent and the auxiliary agent proportioning that the present invention uses can cooperate, and carry the retention of wastewaters with modified calcium sulfate whiskers Height, the paper produced meet tensile strength and the requirement of other performances.
Beneficial effects of the present invention：
1st, the present invention is modified by adding modifying agent to calcium sulfate crystal whiskers, and modified calcium sulfate crystal whiskers are used for papermaking In can significantly improve the retention of whisker, strengthen the intensity of paper.
2nd, the dosage that the present invention substitutes 20~35% wood (bamboo) slurry using wastewaters with modified calcium sulfate whiskers changes as paper making raw material Property calcium sulfate crystal whiskers price be less than wooden (bamboo) and starch, cost of material can be reduced while paper quality is ensured；And modified sulphur Sour calcium pyroborate whiteness is higher without bleaching, easily scattered, can save paper pulp because of expense caused by bleaching and being beaten, reach reduction The purpose of production cost.
2nd, wastewaters with modified calcium sulfate whiskers is a kind of nontoxic mineral fibres, it is possible to reduce because what is brought using wooden (bamboo) slurry Environmental pollution, reach the purpose of environmental protection.
3rd, paper making raw material of the present invention and auxiliary material is added in paper-making process usage amount from paper cost and quality, lead to Cross raw material, reinforcing agent, auxiliary agent and dispersant to cooperate, take into full account wastewaters with modified calcium sulfate whiskers dissolving and its surface and plant The INTERACTION PROBLEMS of fiber surface chemical bond, the retention and intensity of paper are secure.
Brief description of the drawings
Fig. 1 is the process chart that wastewaters with modified calcium sulfate whiskers of the present invention is applied in paper industry；
Fig. 2 is the outward appearance comparison diagram that the paper of embodiment 1 prepares paper with pure wooden (bamboo) slurry, wherein：A is the paper of embodiment 1 Outside drawing, B starch texture of paper figure for tradition pure wooden (bamboo)；
Fig. 3 is that the paper of embodiment 1 prepares the ash content comparison diagram after paper calcining with pure wooden (bamboo) slurry of tradition, wherein：A is real The grey component after the calcining of the paper of example 1 is applied, B is that tradition pure wooden (bamboo) starches the grey component after paper calcining；
Fig. 4 is the microscope comparison diagram that the paper of embodiment 1 prepares paper with pure wooden (bamboo) slurry of tradition, wherein：A is embodiment The microscope enlarged drawing of 1 paper, B are the microscope enlarged drawing that tradition pure wooden (bamboo) starches paper, and C is that embodiment 1 adds preceding modification Dihydrate gypsum whiskers microscope figure, D are the microscope enlarged drawing of ash content after the calcining of the paper of embodiment 1.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, it is right below in conjunction with drawings and Examples The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and It is not used in the restriction present invention.
The preparation of wastewaters with modified calcium sulfate whiskers：
Calcium sulfate crystal whiskers raw material is modified by method of modifying of the present invention, specific modifying process is：By raw material sulphuric acid calcium Whisker is scattered in the water added with modifying agent, and calcium sulfate crystal whiskers are separated from water by filtering after being sufficiently stirred at a certain temperature produces Wastewaters with modified calcium sulfate whiskers；Wherein, the mass ratio of water and calcium sulfate crystal whiskers is 10:1, temperature is 85 DEG C, and the mixing time is 40min。
Wherein, modifier component and dosage are as shown in table 1 below：
The modifier component of table 1 and dosage
Wastewaters with modified calcium sulfate whiskers is making 13g/m2Application in toilet paper industry
Embodiment 1
The present embodiment paper technology is as follows：
1) cationic starch is gelatinized at 85 DEG C after 30min and cationic guar solution mixing for standby use；
2) it is standby after mixing auxiliary agent and PAMC solution；
3) cationic starch and cation guar gum after the wastewaters with modified calcium sulfate whiskers for preparing above-mentioned formula 1, gelatinization mix The mixed liquor for closing liquid, quaternary ammonium salt assitant and PAMC is added sequentially in the back flow water pump equipped with wooden (bamboo) slurry, and It is sufficiently stirred, adds polyethylene glycol oxide；
4) slurries blended in back flow water pump are squeezed into net groove by fan pump, and obtained by squeezing, drying process Product paper；
5) plain boiled water in net groove flows back into back flow water pump and reused.
The dosage of raw material and each auxiliary material is as shown in table 2 below.Wherein, the use that wastewaters with modified calcium sulfate whiskers is measured for replacement wooden (bamboo) Amount, cationic starch, cation guar gum, PAMC, quaternary ammonium salt assitant, the dosage of dispersant are relatively wooden The amount that (bamboo) slurry is given money as a gift.
The dosage of the paper making raw material of 2 embodiment of table 1 and auxiliary material
The present embodiment wastewaters with modified calcium sulfate whiskers substitutes the paper that 25% wooden (bamboo) slurry dosage produce as paper making raw material and now There is the paper performance contrast of pure wooden (bamboo) slurry production as shown in table 1 below：
The paper performance of table 3 contrasts
Tensile strength index ratio：Add the tensile strength index of institute's papermaking and pure wooden (bamboo) slurry paper tensile strength index after whisker Ratio, intensity index ratio is bigger, then illustrates that the Strength Mass of whisker paper is higher.
Index ash content accumulates：The product of tensile strength index and paper calcining (670 DEG C, 3h) ash content afterwards.Index ash integration can be used Come verify wastewaters with modified calcium sulfate whiskers in papermaking using whether feasible, typically, the performance of the bigger explanation paper of its value is better.
From table 3 it can be seen that paper its tensile index, tensile strength index when index ash content that the present embodiment is prepared Paper prepared by product wooden (bamboo) slurry all pure higher than tradition, and paper whisker retention manufactured in the present embodiment is up to 92%, explanation The present embodiment prepares the functional of paper.
Paper manufactured in the present embodiment prepares texture of paper contrast as shown in Figure 2 with pure wooden (bamboo) slurry.Can from Fig. 2 Go out, the paper that the present embodiment is prepared can reach the whiteness that pure wooden (bamboo) slurry of tradition prepares paper, and outward appearance is wooden (bamboo) with tradition Paper prepared by slurry is no different, and can reach the outward appearance demand of paper.
Fig. 3 is that paper manufactured in the present embodiment prepares the ash content comparison diagram after paper calcining with pure wooden (bamboo) slurry of tradition.From Fig. 3 can be seen that paper that the present embodiment is prepared after high-temperature calcination, with the presence of a large amount of ash contents, and ash content shape and paper The shape for opening folding before being burnt is the same.It is brilliant that this shows that the present embodiment paper making raw material and technique are not only successfully realized modified calcium sulfate Wooden (bamboo) must be replaced to starch for papermaking, and calcium sulfate crystal whiskers are uniformly dispersed in prepared paper, illustrate modified in paper Calcium sulfate crystal whiskers retention is high and is uniformly dispersed.The paper prepared using pure wooden (bamboo) slurry of tradition is not almost had after being calcined Ash content is present.
Fig. 4 is the microscope enlarged drawing that paper manufactured in the present embodiment prepares paper with pure wooden (bamboo) slurry of tradition.From Fig. 4 A And 4B can be clearly seen that, the paper that paper manufactured in the present embodiment is prepared with pure wooden (bamboo) slurry of tradition does not have on fibre structure There is the difference of essence, what is seen under microscope is string.Without discovery modified sulphur in paper manufactured in the present embodiment Sour calcium pyroborate, this is probably the shorter and smaller (modification single Fig. 4 C of its fiber because wastewaters with modified calcium sulfate whiskers is compared with string Dihydrate gypsum whiskers) and be uniformly attached to caused by string.However, ash content progress after being calcined to paper is micro- During amplifying observation, it can be found that gained ash content is almost clear and legible wastewaters with modified calcium sulfate whiskers (Fig. 4 D) entirely.
Embodiment 2
The present embodiment paper technology is as follows：
1) cationic starch is gelatinized at 75 DEG C after 35min and cationic guar solution mixing for standby use；
2) it is standby after mixing auxiliary agent and PAMC solution；
3) cationic starch and cation guar gum after the wastewaters with modified calcium sulfate whiskers for preparing above-mentioned formula 1, gelatinization mix The mixed liquor for closing liquid, quaternary ammonium salt assitant and PAMC is added sequentially in the back flow water pump equipped with wooden (bamboo) slurry, and It is sufficiently stirred, adds polyethylene glycol oxide；
4) slurries blended in back flow water pump are squeezed into net groove by fan pump, and obtained by squeezing, drying process Product paper；
5) plain boiled water in net groove flows back into back flow water pump and reused.
The dosage of raw material and each auxiliary material is as shown in table 4 below.Wherein, the use that wastewaters with modified calcium sulfate whiskers is measured for replacement wooden (bamboo) Amount, cationic starch, cation guar gum, PAMC, quaternary ammonium salt assitant, the dosage of dispersant are relatively wooden The amount that (bamboo) slurry is given money as a gift.
The dosage of the paper making raw material of 4 embodiment of table 1 and auxiliary material
The present embodiment wastewaters with modified calcium sulfate whiskers substitutes the paper that 35% wooden (bamboo) slurry dosage produce as paper making raw material and now There is the paper performance contrast of pure bamboo pulp production as shown in table 5 below：
The paper performance of table 5 contrasts
As can be seen from Table 5, the present embodiment is prepared paper its tensile index, tensile strength index when index ash content The paper that product is all prepared higher than the pure bamboo pulp of tradition, and paper whisker retention 90% manufactured in the present embodiment, illustrate the present embodiment Prepare the functional of paper.
The paper that the present embodiment is prepared is prepared in outward appearance, calcining ash content and microscope amplification fiber distribution with embodiment 1 Paper there is identical performance, herein without enumerating.
Embodiment 3
The present embodiment paper technology is as follows：
1) cationic starch is gelatinized at 90 DEG C after 25min and cationic guar solution mixing for standby use；
2) it is standby after mixing auxiliary agent and PAMC solution；
3) cationic starch and cation guar gum after the wastewaters with modified calcium sulfate whiskers for preparing above-mentioned formula 2, gelatinization mix The mixed liquor for closing liquid, quaternary ammonium salt assitant and PAMC is added sequentially in the back flow water pump equipped with wooden (bamboo) slurry, and It is sufficiently stirred, adds polyethylene glycol oxide；
4) slurries blended in back flow water pump are squeezed into net groove by fan pump, and obtained by squeezing, drying process Product paper；
5) plain boiled water in net groove flows back into back flow water pump and reused.
The dosage of raw material and each auxiliary material is as shown in table 6 below.Wherein, the use that wastewaters with modified calcium sulfate whiskers is starched for replacement wooden (bamboo) Amount, cationic starch, cation guar gum, PAMC, quaternary ammonium salt assitant, the dosage of dispersant are relatively wooden The amount that (bamboo) slurry is given money as a gift.
The dosage of the paper making raw material of 6 embodiment of table 1 and auxiliary material
The present embodiment wastewaters with modified calcium sulfate whiskers substitute 20% wooden (bamboo) slurry dosage as paper making raw material production paper with now There is the paper performance contrast of pure wooden (bamboo) slurry production as shown in table 7 below：
The paper performance of table 7 contrasts
As can be seen from Table 7, the present embodiment is prepared paper its tensile index, tensile strength index when index ash content Paper prepared by product wooden (bamboo) slurry all pure higher than tradition, and paper whisker retention manufactured in the present embodiment is up to 94%, explanation The present embodiment prepares the functional of paper.
The paper that the present embodiment is prepared is prepared in outward appearance, calcining ash content and microscope amplification fiber distribution with embodiment 1 Paper there is identical performance, herein without enumerating.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention All any modification, equivalent and improvement made within refreshing and principle etc., should be included in the scope of the protection.

Claims (10)

1. a kind of wastewaters with modified calcium sulfate whiskers paper making raw material, it is characterised in that the raw material replaces 20 using wastewaters with modified calcium sulfate whiskers The dosage of~35% paper pulp, the paper pulp are wood pulp or bamboo pulp；
The wastewaters with modified calcium sulfate whiskers is filled at a certain temperature for raw material sulphuric acid calcium pyroborate is scattered in the water added with modifying agent Divide after stirring to filter and produce wastewaters with modified calcium sulfate whiskers；
The mass ratio of the water and calcium sulfate crystal whiskers is 8:1~12:1, the temperature is 80~90 DEG C, and the mixing time is 30 ~50min；
The modifying agent is ten water sodium phosphates, sodium tripolyphosphate, calgon, sodium carboxymethylcellulose and cationic starch group Into mixture；Modifying agent is divided into three classes by function, and the first kind is ten water sodium phosphates, and main rise prevents calcium sulfate from dissolving；Second Class is sodium tripolyphosphate and calgon, is mainly served excessively bonded；3rd class is sodium carboxymethylcellulose and cation Starch, it is main to play a part of to be bonded string.
2. a kind of wastewaters with modified calcium sulfate whiskers paper making raw material as claimed in claim 1, it is characterised in that the raw material uses modified sulphur Sour calcium pyroborate replaces the dosage of 22~28% paper pulp.
3. a kind of wastewaters with modified calcium sulfate whiskers paper making raw material as claimed in claim 2, it is characterised in that the raw material uses modified sulphur Sour calcium pyroborate replaces the dosage of 25% paper pulp.
4. a kind of wastewaters with modified calcium sulfate whiskers paper making raw material as claimed in claim 1, it is characterised in that the ten water sodium phosphate adds Enter 0.2~5% that amount is the dry whisker quality of calcium sulfate；The addition of the sodium tripolyphosphate is the 0.5 of the dry whisker quality of calcium sulfate ~3%；The addition of the calgon is the 1~3% of the dry whisker quality of calcium sulfate；The addition of the sodium carboxymethylcellulose Measure as the 0.5~2% of the dry whisker quality of calcium sulfate；The addition of the cationic starch for the dry whisker quality of calcium sulfate 0.1~ 3%。
5. a kind of wastewaters with modified calcium sulfate whiskers paper making raw material as claimed in claim 4, it is characterised in that the ten water sodium phosphate adds Enter 0.5% that amount is the dry whisker quality of calcium sulfate；The addition of the sodium tripolyphosphate is the 1% of the dry whisker quality of calcium sulfate；Institute The addition for stating calgon is the 1% of the dry whisker quality of calcium sulfate；The addition of the sodium carboxymethylcellulose is calcium sulfate The 2% of dry whisker quality, the addition of the cationic starch are the 0.1% of the dry whisker quality of calcium sulfate.
A kind of 6. application of wastewaters with modified calcium sulfate whiskers paper making raw material as described in any one of claim 1 to 5, it is characterised in that institute State wastewaters with modified calcium sulfate whiskers paper making raw material and be applied to paper industry, comprise the following steps：
1）Cationic starch is gelatinized at 70~90 DEG C after 20~40min and cationic guar solution mixing for standby use；
2）It is standby after auxiliary agent and PAMC solution are mixed；
3）Cationic starch and cation guar gum mixed liquor after wastewaters with modified calcium sulfate whiskers, gelatinization, auxiliary agent and cation are gathered The mixed liquor of acrylamide is added sequentially in the back flow water pump equipped with paper pulp, and is sufficiently stirred, and adds dispersant；
4）Slurries blended in back flow water pump are squeezed into net groove by fan pump, and product is obtained by squeezing, drying process Paper.
7. a kind of application of wastewaters with modified calcium sulfate whiskers paper making raw material as claimed in claim 6, it is characterised in that the dispersant is Polyethylene glycol oxide.
8. a kind of application of wastewaters with modified calcium sulfate whiskers paper making raw material as claimed in claim 6, it is characterised in that the cation forms sediment The dosage of powder is the 0.5~1.2wt% of paper pulp of giving money as a gift；The dosage of the cation guar gum be give money as a gift paper pulp 0.01~ 0.1wt%, the PAMC dosage are the 0.05~0.1wt% of paper pulp of giving money as a gift, and the auxiliary dosage is paper of giving money as a gift 0.5~1wt% of slurry, the dosage of the dispersant are the 0.01~0.08wt% of paper pulp of giving money as a gift.
9. a kind of application of wastewaters with modified calcium sulfate whiskers paper making raw material as claimed in claim 8, it is characterised in that the cation forms sediment The dosage of powder is the 0.7~1wt% of paper pulp of giving money as a gift；The dosage of the cation guar gum be give money as a gift paper pulp 0.04~ 0.07wt%, the PAMC dosage are the 0.05~0.08wt% of paper pulp of giving money as a gift, and the auxiliary dosage is gives money as a gift 0.7~0.9wt% of paper pulp, the dosage of the dispersant are the 0.03~0.06wt% of paper pulp of giving money as a gift.
A kind of 10. application of wastewaters with modified calcium sulfate whiskers paper making raw material as claimed in claim 9, it is characterised in that the cation The dosage of starch is the 0.8wt% of paper pulp of giving money as a gift；The dosage of the cation guar gum is the 0.05wt% of paper pulp of giving money as a gift, the sun Cationic polyacrylamide dosage is the 0.07wt% of paper pulp of giving money as a gift, and the auxiliary dosage is the 0.75wt% of paper pulp of giving money as a gift, described point The dosage of powder is the 0.04wt% of paper pulp of giving money as a gift.
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CN108103839B (en) * 2017-12-08 2020-03-20 四川理工学院 Preparation method of modified calcium sulfate whisker papermaking filler
CN110924220B (en) * 2019-12-02 2022-07-08 上海大学 Preparation method of bagasse fiber paper enhanced by high-strength calcium sulfate whiskers
CN110934323A (en) * 2020-01-07 2020-03-31 湖北中烟工业有限责任公司 Method for preparing tobacco sheets by compounding gypsum whiskers
CN112482080A (en) * 2020-11-27 2021-03-12 陕西科技大学 Resource utilization method of bamboo residues
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CN102852031B (en) * 2012-09-07 2014-11-05 长沙理工大学 Modified calcium sulfate crystal whisker papermaking filler, preparation method and applications thereof
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