CN110512451A - One kind having high bacteriostatic activity viscose fiber and preparation method thereof - Google Patents

Abstract

The present invention discloses a kind of with high bacteriostatic activity viscose fiber and preparation method thereof, belong to technical field of fiber preparation, it is described to have high bacteriostatic activity viscose fiber beating degree for 16~25 ° of SR, a length of 4~the 6km of brisement, folding number is 65~80 times, whiteness is 22~25%ISO, and permanganate number is 80~100, bacteriostasis rate >=90%.The preparation method with high bacteriostatic activity viscose fiber includes stock, boiling, antimicrobial treatment, and cooking liquor used in the boiling method is few, not sulfur compound, and the time of boiling and heat preservation is short, is a kind of both economically and environmentally beneficial boiling method.

Description

One kind having high bacteriostatic activity viscose fiber and preparation method thereof

Technical field

The invention belongs to technical field of fiber preparation, and in particular to one kind has high bacteriostatic activity viscose fiber and its preparation Method.

Background technique

It is raw in the case where not destroying forest and environment since the shortage of current worldwide timber resources increasingly aggravates Producing paper pulp and papermaking becomes the target that each papermaking enterprise is pursued.Make scheme to solve this problem, utilizes 1 year or biennial Plant is such as: sugarcane stem, the rice and kernel grass discarded after farm waste, bamboo, sugaring are fine by non-wood plant as main material The technology of dimension manufacture paper pulp is constantly subjected to pay close attention to.

Amenities is mainly used for women, children, old man, patient and disposable medical amenities, therefore, to health It is more demanding.But it is had the following problems in existing amenities preparation process:

(1) raw material for preparing of existing amenities uses bleached pulp more, and part material also added brightening agent and color developing agent, but It is, since bleaching process will generate environmentally harmful chemical substance, during chlorine drift other than generating chloroform, waste liquid In also contain more than 40 kinds of organic chlorides, wherein with various chlorinated phenols be it is most, such as dichloro- phenol, three chlorinated phenols, also generation two English and furans product are disliked, more than 10 kinds are hypertoxic.Therefore, be bleached on fiber all can residual contamination carcinogen, harm life State and human health；

(2) prior art mostly uses chemical pulping method in pulping process, as Chinese patent 2007101296351 discloses one The high-hardness pulp and preparation method thereof that kind is prepared using dogstail plant as raw material, using dogstail plant as raw material, using sulfurous acid ammonia Method, anthraquinone-soda processes, sulfate and potassium sulphite process prepare high-hardness pulp；Chinese patent 200510108294.0 discloses one Kind prepares bamboo fibre paper pulp using anthraquinone-soda processes, subtracts using the method and its paper pulp of bamboo production cellulose pulp Lack the consumption of drug and the energy, reduces the nuisances such as generated dioxin as far as possible in bleaching process；In pre-hydrolysis process Hemicellulose produced can produce xylose.Due to having used sulfide in boiling, the remaining sulfide of meeting, also unfavorable in product With the health of consumer.

Therefore, it is badly in need of developing original of the plant fiber of a kind of draw materials easy, antibiotic property height, health environment-friendly as amenities Material.

Summary of the invention

The purpose of the present invention is to overcome the shortcomings of the existing technology, and providing one kind has high bacteriostatic activity viscose fiber, should Fiber has a longer fibre length, high-flexibility, preferable water imbibition, water-retaining property, and soft, fluffy, antibiotic property it is strong, The natural gray for maintaining bamboo fibre 100% significantly improves the quality of downstream product.

Another object of the present invention is to provide the preparation method of the viscose fiber, this method has easy to operate, production Convenient, at low cost, environmentally protective characteristic.

The purpose of the present invention is achieved through the following technical solutions:

A kind of viscose fiber with high bacteriostatic activity, beating degree are 16~25 ° of SR, a length of 4~6km of brisement, folding number It is 65~80 times, whiteness is 22~25%ISO, and permanganate number is 80~100, bacteriostasis rate >=90%.

Further, described to have high biocidal property viscose fiber to bacteriostasis rate >=92% of Escherichia coli, to golden yellow grape Bacteriostasis rate >=99% of coccus.

The above-mentioned preparation method with high bacteriostatic activity viscose fiber, it the following steps are included:

S1. it stocks up: by bamboo plant raw material wet feed preparation at bamboo chip；

S2. boiling: the potassium hydroxide solution to over dry material quantity 8~12% is added in bamboo chip, solid-liquid ratio is 1:3~4；It is logical Enter steam to be heated, be heated to temperature be 110~125 DEG C when keep the temperature 50~60 minutes, obtain bamboo fiber material with it is black Liquid；

S3. antimicrobial treatment: carrying out defibrination process for the bamboo fiber material obtained through boiling, and it is poly- that polymer shell is added into slurry Sugar, additional amount are the 0.01~0.015% of over dry amount of slurry.

Further, the polymer chitosan lotion the preparation method comprises the following steps: chitosan powder is made in pure natural chitin End, wherein the relative molecular weight of chitosan is 200~3,000,000, and Chitosan powder forms chitosan lotion after hydration process.

Further, the preparation method of the polymer chitosan lotion specifically: press Chitosan powder and distilled water It is mixed according to the ratio of 1:500,45-55 DEG C is heated up to after mixing, stirring and emulsifying, mixing speed 150-280r/min will Particle diameter after dispersion is dissolved to 0.8-1.8 μm.

Further, the bamboo plant raw material is one of moso bamboo, bambusa textile, cizu, fishscale bamboo, white folder bamboo, west wind bamboo Or a variety of combination.

It further, further include that impregnation is carried out to the bamboo chip of wet feed preparation before the boiling step, impregnation is adopted Mode are as follows: maceration extract is impregnated into bamboo plant raw material, makes solid-liquid ratio reach 1:3~4, under normal pressure in 85 DEG C or more in spiral shell It revolves and keeps the temperature and mix 50 minutes in infuser or more；The maceration extract is the mixed liquor of aqueous slkali or aqueous slkali and black liquor.

Further, the aqueous slkali is the potassium hydroxide solution to over dry material quantity 8~12%, the concentration of the black liquor For 8~10 ° of B é.

Further, the relative molecular weight of the polymer chitosan is 200~3,000,000.

It is described that there is high bacteriostatic activity viscose fiber to be used to prepare packaging material, paper for daily use, tobacco added material, women and infants Articles.

The chemical composition of common bamboo plant raw material is analyzed, finds total fiber element weight percentage are as follows: 74.52%, total lignin weight percentage is 25.08%, and poly-pentose weight percentage is 20.67%, stupid -ol extract weight Percentage composition is 27.25%.Digestion process is the committed step of slurrying, due to the institutional framework of timber and bamboo material, microcosmic knot Structure, chemical composition and lignin molecular structure etc. are variant, and therefore, delignification reaction course also has very big during the cooking process Difference.For bamboo class raw material soda cooking delignification reaction course, including heat up and keep the temperature two sections.

The process of boiling generally comprises three processes: 1, process of the cooking liquor to raw material internal penetration.2, lye and raw material The process of chemically reactive；3, the process that reactant is dissolved out from raw material.This three process not only stage by stage, but also almost intersect simultaneously into Row, according to the needs of different materials, the lignin and impurity appropriate removed in raw material declines the binding force between fiber, promotees Frotation is slurried.Therefore, the purpose of boiling is the effect using cooking liquor, suitably removes the lignin in raw material, to the greatest extent Cellulose and hemicellulose may be retained in favor of papermaking.During the cooking process, due to thermophilic digestion and chemical steaming medical fluid Effect, certain chemical change can occur for lignin, cellulose and hemicellulose and other compositions in raw material, by not With the degradation and damage of degree.

For this special pulping raw material of bamboo plant fiber, in method of the invention, chemical steaming medical fluid is carried out Stringent control, its concentration is reduced, reduce to ingredient required for slurrying for example cellulose, hemicellulose, lignin degradation and Damage.Meanwhile during low temperature boiling, the method for reducing boiling temperature in method of the invention as far as possible, so that bamboo class The time that plant is in high temperature shortens, thus reduces the degradation of each component in bamboo plant raw material.Therefore, method of the invention In protect ingredient needed for slurrying in bamboo plant raw material to greatest extent, while substantially reducing soaking time, drop significantly Low energy consumption.

The potassium method technique that the present invention uses is exactly the effect using lye, the lignin appropriate removed in raw material, as far as possible Retain cellulose and hemicellulose in favor of papermaking.Actually during the cooking process due to the effect of high temperature highly basic, in raw material Certain chemical change can occur for lignin, cellulose, hemicellulose and other compositions, by different degrees of degradation and damage Wound, it is therefore necessary to study raw material in the changing rule of digestion process bamboo, formulate suitable conditions of cooking.Potassium method technique of the invention In, system is carried out by the height of the length of selection, dosage and concentration, boiling and soaking time to cooking liquor, boiling temperature Research, reducing cellulose and hemicellulose damage as far as possible and retain lignin appropriate as far as possible under the conditions of is steamed It boils, both reduces production cost to reach, it is energy saving, and the purpose of pulping yield can be improved.

The invention has the following advantages that

1. the method for the present invention utilizes low alkali, without sulphur production technology in boiling step, in process of production will be without sulfur dioxide, two The generation for disliking the harmful substances such as English, produces the high-performance biomass bamboo fibre without harmful substances such as sulfur dioxide, dioxin New material can prevent the generation of foul smell in production process and reduce COD discharge amount up to 70% or more.Anthraquinone in the prior art Addition can reduce digestion time, protect cellulose and hemicellulose, but can deepen delignification, and the present invention claims protect as far as possible A certain amount of lignin is stayed, therefore the addition of anthraquinone is not suitable for present invention technical effect to be achieved.Used in the boiling method Cooking liquor it is few, it is a kind of both economically and environmentally beneficial boiling method that the time of not sulfur compound, boiling and heat preservation is short.

2. the method for the present invention in process of production bamboo pulp without bleaching, therefore have raw materials consumption is low, yield is high, Advantage at low cost, pollution is small avoids bamboo pulp and causes to damage fiber bring in bleaching process, therefore has longer fibre Length, high-flexibility, preferable water imbibition, water-retaining property are tieed up, and soft, fluffy, significantly improves the quality of downstream product； And pollution of the exhaust gas, waste liquid for having prevented to generate by bleaching to environment, therefore, inventive method has the characteristic of ecological, environmental protective

3. bamboo pulp avoids chemicals pair used in bleaching process without bleaching to the method for the present invention in process of production Without containing two uh English and adsorbable in the possible injury of human body and the prepared true qualities bamboo pulp product with high bacteriostatic activity The carcinogens such as organohalogen compounds keep the natural gray of bamboo fibre 100%.

4. the method for the present invention is added to polymer chitosan as bacteriostatic agent, therefore, using the present invention in process of production The amenities of the true qualities bamboo pulp manufacture of method is much cleaner, more environmentally friendly, and the physiological hygiene and physical and mental health to human body have more preferable Protectiveness, test proves that bamboo pulp of the invention is to bacteriostasis rate >=99% of Staphylococcus aureus, to the bacteriostasis rate of Escherichia coli ≥92%；

5. the raw material that the present invention uses is bamboo plants, sufficiently effective to be utilized significantly instead of perennial woody plant Natural resources has saved perennial woody plant resource, protects ecological environment.Raw materials are cheap and easy to get, can be country A large amount of timber and foreign exchange are saved, there are significant economic results in society.

6. in step S2 of the present invention, before potassium hydroxide solution is added into bamboo plant raw material, further including To the process that bamboo plant raw material is impregnated, impregnation is by the way of are as follows: maceration extract is impregnated bamboo plant raw material, is made Solid-liquid ratio reaches 1:3~4, keep the temperature and mix 50 minutes in spiral infuser in 85 DEG C or more under normal pressure or more, wherein Heat preservation mixing 50~80 minutes between 85~95 DEG C, preferably 60 minutes preferably.It comes into full contact with maceration extract with raw material in this way, makes original The dipping of material is uniformly complete.The maceration extract is certain density aqueous slkali, the hydroxide for being such as 8~12% to over dry material quantity Potassium solution, preferably 10% potassium hydroxide solution are also possible to the mixed liquor of alkali and black liquor, and the concentration of black liquor used is 8~ 10 ° of Be ' (20 DEG C).Pretreatment has been carried out to raw material, the black liquor as waste material is utilized, black liquor is made to have obtained circulation benefit With reducing the pressure that environment handles black liquor, due to raw material pretreatment, so that being deviate from heat treatment miscellaneous Cell, hemicellulose, the black liquid separation based on lignin exclude, and prepare for the digestion process of next step.

Specific embodiment

The present invention will be further described with reference to the examples below, and described embodiment is only present invention a part Embodiment is not whole embodiment.Based on the embodiments of the present invention, those skilled in the art are not making Other all embodiments obtained, belong to protection scope of the present invention under the premise of creative work.

Prepare polymer chitosan lotion:

(1) by pure natural chitin be made the step of forming Chitosan powder, preparing chitosan can be used existing chemical degradation, The methods of microculture, microwave technology, the relative molecular weight of obtained chitosan are 200~3,000,000, preferably 2,000,000,240 Ten thousand, 2,600,000,2,800,000,3,000,000；

(2) Chitosan powder and distilled water are mixed according to the ratio of 1:500,45-55 DEG C is heated up to after mixing, stirring cream Change, the particle diameter after dispersion is dissolved to 0.8-1.8 μm by mixing speed 150-280r/min.

Embodiment 1:

S1. the pressure of subsequent technique can be mitigated, and improve to remove the impurity such as sand, stone using conventional wet feed preparation in this way The quality of bamboo fiber material；Wet feed preparation can use existing conventional equipment, such as bamboo cutter, screening machine, dust removal machine；By standby For the length of bamboo plant raw material after material in 20~30mm, the bamboo for removing moisture removal after stock is fine fodder, is deducted The moisture of bamboo is over dry raw material.Bamboo chip after wet feed preparation is by dipping spiral organ, in dipping spiral organ and to exhausted The potassium hydroxide solution that dry bamboo chip amount is 8% is mixed with dipping, and solid-liquid ratio 1:4 is protected in spiral infuser at normal pressure, 85 DEG C Mild mixing 60 minutes；

S2. it is then fed into continuously cooking pipe, the potassium hydroxide solution to over dry material quantity 8% is added in bamboo plant raw material, Solid-liquid ratio is 1:4；It is logical to be steam heated to 120 DEG C, keep this temperature condition；The speed of service for adjusting continuously cooking pipe, makes bamboo chip Residence time in continuously cooking pipe is 60 minutes, obtains bamboo fiber material；

S3. bamboo fiber material enters highly concentrated mill progress defibrination process by discharge valve, and it is 2,000,000 that molecular weight is added into slurry Polymer chitosan lotion, additional amount are the 0.01~0.015% of over dry amount of slurry, and the black liquor of generation is recycled.

The beating degree of the true qualities bamboo fibre is 16 ° of SR, and a length of 4km of brisement, folding number is 65 times, whiteness 22%ISO, Permanganate number is 80, bacteriostasis rate >=90%, and the bacteriostasis rate to Escherichia coli is 92%, and the bacteriostasis rate to staphylococcus aureus is 99%。

Embodiment 2:

S1. the bamboo chip after wet feed preparation is 10% in dipping spiral organ and to over dry bamboo chip amount by dipping spiral organ Potassium hydroxide solution is mixed with dipping, solid-liquid ratio 1:4, is kept the temperature and is mixed 80 minutes in spiral infuser at normal pressure, 90 DEG C；

S2. it is then fed into continuously cooking pipe, the potassium hydroxide solution to over dry material quantity 10% is added in bamboo plant raw material, Its solid-liquid ratio is 1:4, logical to be steam heated to 110 DEG C, keeps this temperature condition；The speed of service for adjusting continuously cooking pipe, makes bamboo Residence time of the piece in continuously cooking pipe is 55 minutes, obtains bamboo fiber material；

S3. bamboo fiber material enters highly concentrated mill progress defibrination process by discharge valve, and it is 3,000,000 that molecular weight is added into slurry Polymer chitosan lotion, additional amount be over dry amount of slurry 0.011%, the black liquor of generation is recycled.

The beating degree of the true qualities bamboo fibre is 25 ° of SR, and a length of 6km of brisement, folding number is 80 times, whiteness 25%ISO, Permanganate number is 100, bacteriostasis rate >=90%, and the bacteriostasis rate to Escherichia coli is 95%, to the bacteriostasis rate of staphylococcus aureus It is 99.52%.

Embodiment 3:

S1. the bamboo chip after wet feed preparation is 12% in dipping spiral organ and to over dry bamboo chip amount by dipping spiral organ, Potassium solution is mixed with dipping, solid-liquid ratio 1:3, is kept the temperature and is mixed 80 minutes in spiral infuser at normal pressure, 95 DEG C；

S2. it is then fed into continuously cooking pipe, the potassium hydroxide solution to over dry material quantity 9% is added in bamboo plant raw material, Solid-liquid ratio is 1:3, logical to be steam heated to 125 DEG C, keeps this temperature condition；The speed of service for adjusting continuously cooking pipe, makes bamboo chip Residence time in continuously cooking pipe is 50 minutes, obtains bamboo fiber material；

S3. bamboo fiber material enters highly concentrated mill progress defibrination process by discharge valve, and it is 2,400,000 that molecular weight is added into slurry Polymer chitosan lotion, additional amount be over dry amount of slurry 0.012%, the black liquor of generation is recycled.

The beating degree of the true qualities bamboo fibre is 18 ° of SR, and a length of 5km of brisement, folding number is 70 times, whiteness 23%ISO, Permanganate number is 85, bacteriostasis rate >=90%, and the bacteriostasis rate to Escherichia coli is 96%, and the bacteriostasis rate to staphylococcus aureus is 99.82%。

Embodiment 4:

S1. the bamboo chip after wet feed preparation is mixed with dipping in dipping spiral organ with maceration extract by dipping spiral organ, described Maceration extract is the black liquor mixed liquor of the potassium hydroxide solution and 8 ° of B é that are 10% to over dry bamboo chip amount, solid-liquid ratio 1:4, normal pressure, It keeps the temperature and mixes 50 minutes in spiral infuser at 95 DEG C；

S2. it is then fed into continuously cooking pipe, the potassium hydroxide solution to over dry material quantity 9% is added in bamboo plant raw material, Solid-liquid ratio is 1:4, logical to be steam heated to 125 DEG C, keeps this temperature condition；The speed of service for adjusting continuously cooking pipe, makes bamboo chip Residence time in continuously cooking pipe is 60 minutes, obtains bamboo fiber material；

S3. bamboo fiber material enters highly concentrated mill progress defibrination process by discharge valve, and it is 2,600,000 that molecular weight is added into slurry Polymer chitosan lotion, additional amount be over dry amount of slurry 0.013%, the black liquor of generation is recycled.

The beating degree of the true qualities bamboo fibre is 20 ° of SR, and a length of 6m of brisement, folding number is 73 times, whiteness 24%ISO, high Potassium manganate value is 92, bacteriostasis rate >=90%, and the bacteriostasis rate to Escherichia coli is 96%, and the bacteriostasis rate to staphylococcus aureus is 99.86%。

Embodiment 5:

S1. the bamboo chip after wet feed preparation is mixed with dipping in dipping spiral organ with maceration extract by dipping spiral organ, described Maceration extract is the black liquor mixed liquor of the potassium hydroxide solution and 10 ° of B é that are 10% to over dry bamboo chip amount, solid-liquid ratio 1:3.5, normal It presses, keep the temperature and mix 70 minutes in spiral infuser at 95 DEG C；

S2. it is then fed into continuously cooking pipe, the potassium hydroxide solution to over dry material quantity 12% is added in bamboo plant raw material, Its solid-liquid ratio is 1:4, logical to be steam heated to 115 DEG C, keeps this temperature condition；The speed of service for adjusting continuously cooking pipe, makes bamboo Residence time of the piece in continuously cooking pipe is 60 minutes；

S3. bamboo fiber material enters highly concentrated mill progress defibrination process by discharge valve, and it is 2,800,000 that molecular weight is added into slurry Polymer chitosan lotion, additional amount be over dry amount of slurry 0.015%, the black liquor of generation is recycled.

The beating degree of the true qualities bamboo fibre is 23 ° of SR, and a length of 5km of brisement, folding number is 76 times, whiteness 25%ISO, Permanganate number is 95, bacteriostasis rate >=90%, and the bacteriostasis rate to Escherichia coli is 93%, and the bacteriostasis rate to staphylococcus aureus is 99.78%。

Disclosed above is only presently preferred embodiments of the present invention, cannot limit the right model of the present invention with this certainly It encloses, therefore makees ground equivalent variations according to the claims in the present invention, be still within the scope of the present invention.

Claims (9)

1. one kind have high biocidal property viscose fiber, which is characterized in that its beating degree be 16~25 ° of SR, a length of 4~6km of brisement, Folding number is 65~80 times, and whiteness is 22~25%ISO, and permanganate number is 80~100, bacteriostasis rate >=90%.

2. a kind of viscose fiber with high bacteriostatic activity as described in claim 1, which is characterized in that described to have height antibacterial Property viscose fiber is to bacteriostasis rate >=92% of Escherichia coli, to bacteriostasis rate >=99% of staphylococcus aureus.

3. as claimed in claim 1 or 2 with the preparation method of high biocidal property viscose fiber, which is characterized in that including following Step:

S1. it stocks up: by bamboo plant raw material wet feed preparation at bamboo chip；

S2. boiling: the potassium hydroxide solution to over dry material quantity 8~12% is added in bamboo chip, solid-liquid ratio is 1:3~4；It is passed through Steam is heated, and is heated to when temperature is 110~125 DEG C and is kept the temperature 50~60 minutes, obtains bamboo fiber material and black liquor；

S3. antimicrobial treatment: carrying out defibrination process for the bamboo fiber material through boiling, and polymer chitosan cream is added into slurry Liquid, additional amount are the 0.01~0.015% of over dry amount of slurry.

4. as claimed in claim 3 with the preparation method of high bacteriostatic activity viscose fiber, which is characterized in that the macromolecule Chitosan lotion the preparation method comprises the following steps: Chitosan powder is made in pure natural chitin, wherein the relative molecular weight of chitosan is 200~3,000,000, Chitosan powder forms chitosan lotion after hydration process.

5. as claimed in claim 4 with the preparation method of high bacteriostatic activity viscose fiber, which is characterized in that the macromolecule The preparation method of chitosan lotion specifically: mix Chitosan powder and distilled water according to the ratio of 1:500, after mixing It is heated up to 45-55 DEG C, the particle diameter after dispersion is dissolved to 0.8-1.8 by stirring and emulsifying, mixing speed 150-280r/min μm。

6. as claimed in claim 3 with the preparation method of high bacteriostatic activity viscose fiber, which is characterized in that the bamboo class is planted Raw material is one of moso bamboo, bambusa textile, cizu, fishscale bamboo, white folder bamboo, west wind bamboo or a variety of combinations.

7. a kind of preparation method with high bacteriostatic activity viscose fiber as claimed in claim 3, which is characterized in that the steaming Boiling further includes carrying out impregnation to the bamboo chip of wet feed preparation before step, and impregnation is by the way of are as follows: impregnates maceration extract Bamboo plant raw material makes solid-liquid ratio reach 1:3~4, keeps the temperature and mix under normal pressure 50 in spiral infuser in 85 DEG C or more Minute or more；The maceration extract is the mixed liquor of aqueous slkali or aqueous slkali and black liquor.

8. a kind of preparation method with high bacteriostatic activity viscose fiber as claimed in claim 7, which is characterized in that the alkali Solution is the potassium hydroxide solution to over dry material quantity 8~12%, and the concentration of the black liquor is 8~10 ° of B é.

9. a kind of preparation method with high bacteriostatic activity viscose fiber as claimed in claim 7, which is characterized in that in normal pressure Under kept the temperature in spiral infuser between 85~95 DEG C and mixing 50~80 minutes.