CN1284903C - Use of N-(2-hydroxy-3-trimethyl) propyl ammonium chloride chitosan and nano silicon dioxide - Google Patents
Use of N-(2-hydroxy-3-trimethyl) propyl ammonium chloride chitosan and nano silicon dioxide Download PDFInfo
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- CN1284903C CN1284903C CN 200410061200 CN200410061200A CN1284903C CN 1284903 C CN1284903 C CN 1284903C CN 200410061200 CN200410061200 CN 200410061200 CN 200410061200 A CN200410061200 A CN 200410061200A CN 1284903 C CN1284903 C CN 1284903C
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- ammonium
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- propyl group
- shitosan
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Abstract
The present invention discloses a purpose which utilizes N-(2-hydroxy-3-trimethyl) propyl ammonium chloride chitosan and nano silicon dioxide to serve as a papermaking retention and filter aid. When the pH valve of slurry is from 7 to 8, the water filtration performance on straw slurry with the beating degree of 38 degrees to 50 degreesSR is enhanced by 15% to 26% through the aid, the retention rate on fine and small fiber and hemicellulose is enhanced by 30% to 50%, and the retention rate on CaCO3 achieves from 80% to 89%. In the premise of the similar flocculation effect on CaCO3 suspension, the dosage of the chitosan quaternary ammonium salt accounts for 4% to 8% of that of the cationic starch.
Description
Technical field
The invention belongs to chemical technology field, relate to a kind of novel papermaking retention auxiliary agent filtering system----N-(2-hydroxyl-3-chlorination front three ammonium) propyl group shitosan-nano silicon.This auxiliary agent is suitable for face width, can be used for acid system, and especially centering, alkaline paper-making system more have practical value.Fiber fines in the non-wood pulp material such as reed pulp, straw pulp and dissolubility, colloid shape carbohydrate and inorganic filler particle had well keep.
Background technology
Domestic papermaking straw pulp retention and drainage aid agent commonly used at present mainly contains cationic polyacrylamide, cationic starch etc.Shortcomings such as the former is a synthetic high polymer, although price is lower, performance is good, exists degraded difficult, and carrying capacity of environment is big.Native starch is used for the history of the existing more than one thousand years of paper industry, and its cation-modified thing is widely used in retention agent now, but also has some defectives, and is big as consumption, deciding property of paper is poor, easily produce machine dirt etc.; Chitosan quaternary ammonium salt has high positive electricity, can produce electrostatic interaction with the carboxyl negative charge on the cellulose, further strengthen the active force between itself and fiber, filler, improve the retention of fiber fines, filler grain, but this unit system also has its deficiency, evenness as page is not satisfactory, and retention aid and filtering aid obviously is subjected to the influence of shearing force.
Summary of the invention
Problem to be solved by this invention provides the application as paper retention and filter aid of N-(2-hydroxyl-3-chlorination front three ammonium) propyl group shitosan and nano silicon, this retention and drainage aid agent use amount is little, performance is excellent, easy to use, paper machine operation speed in effectively improving, in the alkaline paper-making, reduce white water consistency, alleviate sewage pollution.
Technical scheme provided by the invention is: N-(2-hydroxyl-3-chlorination front three ammonium) propyl group shitosan and nano silicon are as the application of paper retention and filter aid.
The molecular weight of described N-(2-hydroxyl-3-chlorination front three ammonium) propyl group shitosan is 30,000-300,000, and substitution value is 40%--95%.The specific area of described nano silicon is 350-450m
2/ g, average grain diameter 13-27nm.
The weight ratio of the consumption of N-(2-hydroxyl-3-chlorination front three ammonium) propyl group shitosan and nano silicon is 1: 0.125 to 1: 0.75.
N-(2-hydroxyl-3-chlorination front three ammonium) propyl group shitosan is made by laxative remedy: (1) cationic substituent: under pH=8.5-9.5 with trimethylamine hydrochloride and epoxychloropropane by 1: 1 to 1.3: 1 molar ratio hybrid reaction 1-3 hour, obtain cationic intermediates behind the reduction vaporization; (2) preparation of chitosan quaternary ammonium salt: by cationic intermediates and 4: 1 to 10: 1 molar ratio of shitosan, above-mentioned cationic intermediates is joined in the aqueous suspension of shitosan of 1-1.5wt%, in 60--85 ℃, reaction is 4-8 hour under the pH=9-10 condition, take out the crude product ultrafiltration, concentrate the back and after 80-120 ℃ of vacuumize, promptly obtain N-(2-hydroxyl-3-chlorination front three ammonium) propyl group shitosan.
The synthetic route of N-(2-hydroxyl-3-chlorination front three ammonium) propyl group shitosan:
The present invention also provides above-mentioned N-(2-hydroxyl-3-chlorination front three ammonium) propyl group shitosan-nano silicon to be used for the embodiment of paper making wet part additive: attach order and be slurry---filler grain---auxiliary agent.Be that 7-9, beating degree are that to add concentration in the wheat slurry of 30-55 ° of SR or the reed pulp slurry be N-(2-hydroxyl-3-chlorination front three ammonium) the propyl group chitosan aqueous solution of 0.02-0.2wt% at PH promptly, the addition of N-(2-hydroxyl-3-chlorination front three ammonium) propyl group chitosan aqueous solution is counted the 2.5-6mg/g oven dry stock with N-(2-hydroxyl-3-chlorination front three ammonium) propyl group shitosan; Adding concentration after stirring is 0.01-0.5wt% nano silicon solution, and the addition of nano silicon solution is counted the 0.05--1mg/g oven dry stock with silica; The molecular weight of used N-(2-hydroxyl-3-chlorination front three ammonium) propyl group shitosan is 30,000-300,000, and substitution value is 40-95%; The specific area of silica is 350--450m
2/ g, average grain diameter 13-27nm.Be that 7-9, beating degree are to add CaCO in the wheat slurry of 30-55 ° of SR or the reed pulp slurry perhaps at PH
3Solid content is the 1-6wt%CaCO of the 10-20wt% of oven dry stock
3Turbid liquid obtains mixed liquor, adding concentration in mixed liquor is N-(2-hydroxyl-3-chlorination front three ammonium) the propyl group chitosan aqueous solution of 0.02-0.2wt%, and the addition of N-(2-hydroxyl-3-chlorination front three ammonium) propyl group chitosan aqueous solution is counted the 2.4-10.6mg/g oven dry stock with N-(2-hydroxyl-3-chlorination front three ammonium) propyl group shitosan; Add the nano silicon solution that concentration is 0.01-0.5wt% after stirring, the addition of nano silicon solution is counted the 0.05--1mg/g oven dry stock with silica; The molecular weight of used N-(2-hydroxyl-3-chlorination front three ammonium) propyl group shitosan is 30,000-300,000, and substitution value is 40-95%; The specific area of silica is 350--450m
2/ g, average grain diameter 13-27nm.
When the present invention is 7-8 at the PH of slurries, be the water filtering performance raising 15%-26% of the straw pulp material of 38-50 ° of SR to beating degree, to the retention raising 30%-50% of fiber fines and hemicellulose, to CaCO
3Retention reach 80%-89%.To CaCO
3Under the close prerequisite of the flocculating effect of turbid liquid, the consumption of chitosan quaternary ammonium salt is about the 4%-8% of cationic starch.
The present invention will introduce cation radical in the chitosan molecule, as trimethyl hydroxypropyl ammonium, can make shitosan in, water-soluble under the alkali condition, satisfy demand transition of paper industry.Simultaneously, chitosan quaternary ammonium salt has high positive electricity, can produce electrostatic interaction with the carboxyl negative charge on the cellulose, has further strengthened the active force of the two.As in the paper pulp that adds chitosan quaternary ammonium salt, introducing nano silicon, because the synergy of chitosan quaternary ammonium salt and nano silicon, can cause the particulate flocculation in the slurry system to increase substantially, and it is poly-to allow broken wadding polymers wad a quilt with cotton again, has the function of stronger anti-shearing force.Therefore the present invention is as paper retention and filter aid, and its use amount is little, and performance is excellent, in effectively improving, alkaline paper-making paper machine operation speed, reduces white water consistency, alleviates sewage pollution.
The specific embodiment
Embodiment 1: in beating degree is that 38 ° of SR, concentration are the CaCO that adds relative dry pulp 20% in the reed pulp material of 0.1wt%
3(average grain diameter: 2.69 μ m, specific area: 41684cm
2/ g) pressed powder, adding molecular weight after stirring is 19 * 10
4, substitution value is 93%, N-(2-hydroxyl-3-chlorination front three ammonium) the propyl group chitosan aqueous solution of concentration 0.1wt%, the addition of N-(2-hydroxyl-3-chlorination front three ammonium) propyl group chitosan aqueous solution is counted with respect to oven dry stock 0.32wt% with N-(2-hydroxyl-3-chlorination front three ammonium) propyl group shitosan; Stirred for 10 seconds, (specific area is 350--450m to add concentration 0.04wt% silica again
2/ g, average grain diameter 14nm) colloidal solution (addition is 0.07 milligram of silica/every gram oven dry stock), CaCO
3Retention is 85%.The retention of the carbon water thing of fiber fines and dissolubility colloid shape is 37%.
Embodiment 2: molecular weight is 7 * 10
4Substitution value is 53%, concentration is N-(2-hydroxyl-3-chlorination front three ammonium) the propyl group chitosan aqueous solution of 0.02wt%, join beating degree 38-42 ° SR, concentration is in the reed pulp liquid of 0.5wt%, in 10 seconds of stir about, adding concentration again is that (specific area is 350--450m to 0.01wt% silica
2/ g, average grain diameter 25nm) colloidal solution, be the 2.5mg/g oven dry stock in N-(2-hydroxyl-3-chlorination front three ammonium) propyl group chitosan dosage, when silica is the 0.14mg/g oven dry stock, its water filtering performance improves 20-26%.
Embodiment 3: with molecular weight is 10 * 10
4Substitution value is that 60% N-(2-hydroxyl-3-chlorination front three ammonium) propyl group shitosan is mixed with 0.2wt% solution, joining beating degree is that 38-42 ° of SR, pH are that 7-8, concentration are in the reed pulp material of 0.3wt%, in 10 seconds of stir about, adding concentration again is that (specific area is 350--450m to 0.4wt% silica
2/ g, average grain diameter 13-27nm) colloidal solution, when N-(2-hydroxyl-3-chlorination front three ammonium) propyl group chitosan dosage be the 3.2mg/g oven dry stock, when the silica consumption is the 0.14mg/g oven dry stock, the water filtering performance of slurry improves 22-25%.
Embodiment 4: at pH is that 7-8, beating degree are that 43 ° of SR, concentration are the heavy CaCO that adds relative oven dry stock 20% in the straw slurry of 0.2wt%
3(average grain diameter: 2.69 μ m, specific area: 41684cm
2/ g), after stirring, add molecular weight 17.5 * 10
4, substitution value is 69%, concentration is N-(2-hydroxyl-3-chlorination front three ammonium) the propyl group chitosan solution of 0.08wt%, in 10 seconds of stir about, adding concentration again is that (specific area is 350--450m to 0.2wt% silica
2/ g, average grain diameter 13-27nm) colloidal solution, copy sheet then.As N-(2-hydroxyl-3-chlorination front three ammonium) when the propyl group chitosan dosage is the 3.2mg/g dry pulp, when the silica consumption was 0.14mg/g, the retention of calcium carbonate improved 89.4%, and the retention of the carbon water thing of fiber fines and dissolubility colloid shape improves 43%.
Claims (7)
1.N-(2-hydroxyl-3-chlorination front three ammonium) propyl group shitosan and nano silicon are as the purposes of paper retention and filter aid.
2. purposes according to claim 1 is characterized in that: the molecular weight of described N-(2-hydroxyl-3-chlorination front three ammonium) propyl group shitosan is 30,000-300,000, and substitution value is 40%-95%.
3. purposes according to claim 1 is characterized in that: the specific area of described nano silicon is 350-450m
2/ g,
4. according to claim 1 or 2 or 3 described purposes, it is characterized in that: the weight ratio of the consumption of N-(2-hydroxyl-3-chlorination front three ammonium) propyl group shitosan and nano silicon is 1: 0.125 to 1: 0.75.
5. according to claim 1 or 2 or 3 described purposes, it is characterized in that: N-(2-hydroxyl-3-chlorination front three ammonium) propyl group shitosan is made by laxative remedy: (1) cationic substituent: under pH=8.5-9.5 with trimethylamine hydrochloride and epoxychloropropane by 1: 1 to 1.3: 1 molar ratio hybrid reaction 1-3 hour, obtain cationic intermediates behind the reduction vaporization; (2) preparation of chitosan quaternary ammonium salt: by cationic intermediates and 4: 1 to 10: 1 molar ratio of shitosan, above-mentioned cationic intermediates is joined in the aqueous suspension of shitosan of 1-1.5wt%, in 60--85 ℃, reaction is 4-8 hour under the pH=9-10 condition, take out the crude product ultrafiltration, concentrate the back and after 80-120 ℃ of vacuumize, promptly obtain N-(2-hydroxyl-3-chlorination front three ammonium) propyl group shitosan.
6. according to claim 1 or 2 or 3 described purposes, it is characterized in that: at PH is that 7-9, beating degree are that to add concentration in the wheat slurry of 30-55 ° of SR or the reed pulp slurry be N-(2-hydroxyl-3-chlorination front three ammonium) the propyl group chitosan aqueous solution of 0.02-0.2wt%, and the addition of N-(2-hydroxyl-3-chlorination front three ammonium) propyl group chitosan aqueous solution is counted the 2.5-6mg/g oven dry stock with N-(2-hydroxyl-3-chlorination front three ammonium) propyl group shitosan; Adding concentration after stirring is 0.01-0.5wt% nano silicon solution, and the addition of nano silicon solution is counted the 0.05--1mg/g oven dry stock with silica; The molecular weight of used N-(2-hydroxyl-3-chlorination front three ammonium) propyl group shitosan is 30,000-300,000, and substitution value is 40-95%; The specific area of silica is 350-450m
2/ g, average grain diameter 13-27nm.
7. according to claim 1 or 2 or 3 described purposes, it is characterized in that: at PH is that 7-9, beating degree are to add CaCO in the wheat slurry of 30-55 ° of SR or the reed pulp slurry
3Solid content is the 1-6wt%CaCO of the 10-20wt% of oven dry stock
3Turbid liquid obtains mixed liquor, adding concentration in mixed liquor is N-(2-hydroxyl-3-chlorination front three ammonium) the propyl group chitosan aqueous solution of 0.02-0.2wt%, and the addition of N-(2-hydroxyl-3-chlorination front three ammonium) propyl group chitosan aqueous solution is counted the 2.4-10.6mg/g oven dry stock with N-(2-hydroxyl-3-chlorination front three ammonium) propyl group shitosan; Add the nano silicon solution that concentration is 0.01-0.5wt% after stirring, the addition of nano silicon solution is counted the 0.05--1mg/g oven dry stock with silica; The molecular weight of used N-(2-hydroxyl-3-chlorination front three ammonium) propyl group shitosan is 30,000-300,000, and substitution value is 40-95%; The specific area of silica is 350--450m
2/ g, average grain diameter 13-27nm.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410061200 CN1284903C (en) | 2004-11-29 | 2004-11-29 | Use of N-(2-hydroxy-3-trimethyl) propyl ammonium chloride chitosan and nano silicon dioxide |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410061200 CN1284903C (en) | 2004-11-29 | 2004-11-29 | Use of N-(2-hydroxy-3-trimethyl) propyl ammonium chloride chitosan and nano silicon dioxide |
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| CN1616765A CN1616765A (en) | 2005-05-18 |
| CN1284903C true CN1284903C (en) | 2006-11-15 |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101020725B (en) * | 2007-03-23 | 2010-09-15 | 天津大学 | Amphiphilic chitosan quatermary ammonium salt with long alkane radical and its preparation |
| CN104163876B (en) * | 2014-08-25 | 2016-05-25 | 吉林君同行生物科技有限公司 | Chitosan quaternary ammonium product salt and preparation method thereof |
| CN105753125B (en) * | 2016-05-04 | 2018-06-01 | 山西澳科特环境工程有限公司 | A kind of excellent flocculant of flco sediment dehydration property |
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