Background technology
From SARS (2003, the whole world has 2781 routine non-iodine pneumonia cases, wherein 111 example death), " bird flu " and " Influenza A H1N1 " is (by January 2nd, 2009, in China, 31 provinces, ground report confirmed cases 120940 examples altogether) occur since, people more focus on the safety of surrounding enviroment, particularly with the live anti-microbial property of closely-related various material and goods thereof of people.Paper products be people produce and live in indispensable product, be widely used in daily life, toilet paper, face tissue, paper for kitchen, food wrapper, children's book paper using, decoration paper, health and medicinal paper, bank-note paper etc. occupy an important position in people's life
Therefore, development has the paper that itself has antibacterial functions, the microorganism of paper surface is had to the antibacterial functions of inhibit feature, can bring more safety factor for life, has important practical significance.
In slurry, the additive process antiseptic that anti-bacteria paper uses of manufacturing paper with pulp mainly forms with inorganic matter supported metal ions such as zeolite, diatomite, and the antiseptic of the immobilized metal of these inorganic matters exists the shortcomings such as retention is low, stability is not strong,
Because the large multicomponent in oil-tea camellia husks (lignin, cellulose, hemicellulose etc.) is close with paper stock, when copy paper, it is easily kept in paper, and the Tea Saponin in oil-tea camellia husks itself also has anti-microbial property in addition.
Oil tea and oil palm, olive and coconut are also called the large woody edible oil tannin plant in the world four.Oil tea is the distinctive woody oleiferous plants of China, and according to statistics, more than 347 ten thousand hectares of national existing oil tea areas, produce tea seed 56,600,000,000 kg per year, approximately 30,000,000,000 kg of oil-tea camellia husks.But a large amount of oil-tea camellia husks is taken as fuel or is used as fertilizer, caused the great wasting of resources and environmental pollution, if be prepared into the agent of papermaking antiseptic, will be a kind of important material, the benefit that can improve oil tea plantation simultaneously, has good economy and Significance for Environment.
Summary of the invention
The shortcomings such as, poor stability low for current inorganic matter supported metal ion type antiseptic retention in papermaking, a kind of product stability is good, retention is high oil-tea camellia husks paper grade (stock) antiseptic and preparation technology thereof are provided, metal is attached in the surface and micropore of oil-tea camellia husks by effects such as static, ion chelatings, dispersiveness and the stability with height, to realize efficient and lasting antibacterial effect.
To achieve these goals, the present invention has adopted following technical scheme:
By 10 parts by weight of crushed, to particle size range, the oil-tea camellia husks particle between 500~1000um joins in the glutaraldehyde water solution that 25~30 weight portions are 3% containing mass concentration, stirs and adds 350~400 weight portion concentrated hydrochloric acids, stirring reaction 4 h at 60~75 ℃; Add 0.5~5 weight portion silver, zinc or copper metallization compound solid, stir and make it dissolve rear continuation stirring 4~12 hours completely; Filter, with distilled water, wash filter residue, to filtrate, be neutral, filter residue is added in the alkali lye or reductant that 5 weight portions are 3% containing mass concentration to stirring reaction 0.5~3 h at 40~80 ℃; Filter, with distilled water, wash filter residue, to filtrate, be neutral, filter residue is dried to constant weight at 40~80 ℃, obtains oil-tea camellia husks base papermaking antiseptic.
Described metallic compound solid is the mixture of one or more than two composition in silver nitrate, copper chloride, cupric sulfate pentahydrate, zinc chloride or zinc sulfate.
Described alkali lye is a kind of or two kinds of mixtures that arbitrary proportion forms in NaOH or barium hydroxide.
Described reductant is a kind of in sodium thiosulfate or sodium borohydride or two kinds of mixtures that arbitrary proportion forms wherein.
Adsorbent of the present invention compared with prior art, has advantages of as follows:
(1) the present invention utilizes discarded object oil-tea camellia husks for raw materials, and wide material sources are cheap; Be conducive to the comprehensive utilization of oil-tea camellia husks, reduce the discharge of refuse.
(2) preparation technology of the present invention is simple, and cost is lower, in slurry, in additive process papermaking, has high retention rate.
(3) reaction condition gentleness of the present invention is easy to control, and modification procedure is simple, and process equipment is few, easy operating.
The specific embodiment
Below by embodiment, technical scheme of the present invention is done more specifically bright.
Embodiment 1
By 10 kilograms, be crushed to particle size range and join in the glutaraldehyde water solution that 30 kilograms is 3% containing mass concentration at the oil-tea camellia husks particle of 800um, stir and add 40 kilograms of concentrated hydrochloric acids, stirring reaction 4 h at 60 ℃; Add 1 kilogram of silver nitrate solid, stir and make it dissolve rear continuation stirring 6 hours completely; Filter, with distilled water, wash filter residue, to filtrate, be neutral, filter residue is added in the sodium borohydride that is 3% containing mass concentration in 5 kilograms to stirring reaction 2 h at 60 ℃; Filter, with distilled water, wash filter residue, to filtrate, be neutral, filter residue is dried to constant weight at 60 ℃, obtains oil-tea camellia husks base papermaking antiseptic.
Oil-tea camellia husks base papermaking antiseptic prepared by the present embodiment, respectively different strain carried out to the comparative test of antibacterial circle diameter size, result shows: Escherichia coli antibacterial circle diameter 16.5 mm, staphylococcus aureus antibacterial circle diameter 12.3 mm, intestines class salmonella antibacterial circle diameter 13.4mm.Result shows that fungistatic effect is obvious.
Embodiment 2
By 10 kilograms, be crushed to particle size range and join in the glutaraldehyde water solution that 25 kilograms is 3% containing mass concentration at the oil-tea camellia husks particle of 500um, stir and add 350 kilograms of concentrated hydrochloric acids, stirring reaction 4 h at 60 ℃; Add 1.5 kilograms of cupric sulfate pentahydrates, stir and make it dissolve rear continuation stirring 8 hours completely; Filter, with distilled water, wash filter residue, to filtrate, be neutral, filter residue is added in the sodium hydrate aqueous solution that is 3% containing mass concentration in 5 kilograms to stirring reaction 1.5 h at 70 ℃; Filter, with distilled water, wash filter residue, to filtrate, be neutral, filter residue is dried to constant weight at 70 ℃, obtains oil-tea camellia husks base papermaking antiseptic.
Oil-tea camellia husks base papermaking antiseptic prepared by the present embodiment, respectively different strain carried out to the comparative test of antibacterial circle diameter size, result shows: Escherichia coli antibacterial circle diameter 15.5 mm, staphylococcus aureus antibacterial circle diameter 12.5 mm, intestines class salmonella antibacterial circle diameter 12.4mm.Result shows that fungistatic effect is obvious.
Embodiment 3
By 10 kilograms, be crushed to the oil-tea camellia husks particle of particle size range between 1000um and join in the glutaraldehyde water solution that 28 kilograms is 3% containing mass concentration, stir and add 400 kilograms of concentrated hydrochloric acids, stirring reaction 4 h at 60 ℃; Add 3.5 kilograms of zinc chloride solids, stir and make it dissolve rear continuation stirring 6 hours completely; Filter, with distilled water, wash filter residue, to filtrate, be neutral, filter residue is added to the NaOH that is 3% containing mass concentration in 5 kilograms, stirring reaction 2.5h at 65 ℃; Filter, with distilled water, wash filter residue, to filtrate, be neutral, filter residue is dried to constant weight at 70 ℃, obtains oil-tea camellia husks base papermaking antiseptic.
Oil-tea camellia husks base papermaking antiseptic prepared by the present embodiment, respectively different strain carried out to the comparative test of antibacterial circle diameter size, result shows: Escherichia coli antibacterial circle diameter 18.3 mm, staphylococcus aureus antibacterial circle diameter 14.8 mm, intestines class salmonella antibacterial circle diameter 12.6mm.Result shows that fungistatic effect is obvious.
Embodiment 4
By 10 kilograms, be crushed to particle size range and join in the glutaraldehyde water solution that 25 kilograms is 3% containing mass concentration at the oil-tea camellia husks particle of 700um, stir and add 350 kilograms of concentrated hydrochloric acids, stirring reaction 4h at 60 ℃; Add 0.5 kilogram of copper chloride solid, stir and make it dissolve rear continuation stirring 12 hours completely; Filter, with distilled water, wash filter residue, to filtrate, be neutral, filter residue is added in the baryta water that is 3% containing mass concentration in 5 kilograms to stirring reaction 1 h at 70 ℃; Filter, with distilled water, wash filter residue, to filtrate, be neutral, filter residue is dried to constant weight at 70 ℃, obtains oil-tea camellia husks base papermaking antiseptic.
Embodiment 5
By 10 kilograms, be crushed to particle size range and join in the glutaraldehyde water solution that 30 kilograms is 3% containing mass concentration at the oil-tea camellia husks particle of 600um, stir and add 400 kilograms of concentrated hydrochloric acids, stirring reaction 4h at 60 ℃; Add 0.75 kilogram of zinc chloride, 2 kilograms of copper chloride solids, stir and make it dissolve rear continuation stirring 10 hours completely; Filter, with distilled water, wash filter residue, to filtrate, be neutral, filter residue is added in the baryta water that is 3% containing mass concentration in 5 kilograms to stirring reaction 2h at 55 ℃; Filter, with distilled water, wash filter residue, to filtrate, be neutral, filter residue is dried to constant weight at 70 ℃, obtains oil-tea camellia husks base papermaking antiseptic.
Embodiment 6
By 10 kilograms, be crushed to particle size range and join in the glutaraldehyde water solution that 25 kilograms is 3% containing mass concentration at the oil-tea camellia husks particle of 800um, stir and add 350 milliliters of concentrated hydrochloric acids, stirring reaction 4 h at 60 ℃; Add 1.2 kilograms of silver nitrate solids, stir and make it dissolve rear continuation stirring 6 hours completely; Filter, with distilled water, wash filter residue, to filtrate, be neutral, by the aqueous solution of 2 kilograms of filter residue 3 kilograms, the sodium thiosulfate that to add containing mass concentration be 3% and sodium borohydrides, stirring reaction 0.75 h at 75 ℃; Filter, with distilled water, wash filter residue, to filtrate, be neutral, filter residue is dried to constant weight at 75 ℃, obtains oil-tea camellia husks base papermaking antiseptic.
Embodiment 7
By 10 kilograms, be crushed to particle size range and join in the glutaraldehyde water solution that 28 kilograms is 3% containing mass concentration at the oil-tea camellia husks particle of 500um, stir and add 400 kilograms of concentrated hydrochloric acids, stirring reaction 4h at 60 ℃; Add 0.5 kilogram of copper chloride, 1 kilogram of cupric sulfate pentahydrate solid, stir and make it dissolve rear continuation stirring 5 hours completely; Filter, with distilled water, wash filter residue, to filtrate, be neutral, by the aqueous solution of 1 kilogram of filter residue 4 kilograms, the sodium thiosulfate that to add containing mass concentration be 3% and sodium borohydride, stirring reaction 2 h at 70 ℃; Filter, with distilled water, wash filter residue, to filtrate, be neutral, filter residue is dried to constant weight at 70 ℃, obtains oil-tea camellia husks base papermaking antiseptic.
Embodiment 8
By 10 kilograms, be crushed to particle size range and join in the glutaraldehyde water solution that 27 kilograms is 3% containing mass concentration at the oil-tea camellia husks particle of 1000um, stir and add 400 kilograms of concentrated hydrochloric acids, stirring reaction 4h at 60 ℃; Add 0.65 kilogram of silver nitrate solid, stir and make it dissolve rear continuation stirring 6 hours completely; Filter, with distilled water, wash filter residue, to filtrate, be neutral, filter residue is added in the sodium borohydride aqueous solution that is 3% containing mass concentration in 5 kilograms to stirring reaction 1h at 65 ℃; Filter, with distilled water, wash filter residue, to filtrate, be neutral, filter residue is dried to constant weight at 65 ℃, obtains oil-tea camellia husks base papermaking antiseptic.
In addition to the implementation, the present invention can also have other embodiments.All employings are equal to the technical scheme of replacement or equivalent transformation formation, all drop on the protection domain of requirement of the present invention.