CN101955551B - Method for preparing adsorbent by coupling chitosan with bamboo charcoal by using monoaldehyde - Google Patents
Method for preparing adsorbent by coupling chitosan with bamboo charcoal by using monoaldehyde Download PDFInfo
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- CN101955551B CN101955551B CN2010102955131A CN201010295513A CN101955551B CN 101955551 B CN101955551 B CN 101955551B CN 2010102955131 A CN2010102955131 A CN 2010102955131A CN 201010295513 A CN201010295513 A CN 201010295513A CN 101955551 B CN101955551 B CN 101955551B
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- bamboo charcoal
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- 235000017166 Bambusa arundinacea Nutrition 0.000 title claims abstract description 53
- 235000017491 Bambusa tulda Nutrition 0.000 title claims abstract description 53
- 241001330002 Bambuseae Species 0.000 title claims abstract description 53
- 235000015334 Phyllostachys viridis Nutrition 0.000 title claims abstract description 53
- 239000011425 bamboo Substances 0.000 title claims abstract description 53
- 239000003610 charcoal Substances 0.000 title claims abstract description 53
- 229920001661 Chitosan Polymers 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 15
- 230000008878 coupling Effects 0.000 title claims abstract description 7
- 238000010168 coupling process Methods 0.000 title claims abstract description 7
- 238000005859 coupling reaction Methods 0.000 title claims abstract description 7
- 239000003463 adsorbent Substances 0.000 title abstract 5
- 239000011259 mixed solution Substances 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims abstract description 5
- 239000002594 sorbent Substances 0.000 claims description 23
- 239000000843 powder Substances 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 7
- 239000003929 acidic solution Substances 0.000 claims description 5
- 239000007822 coupling agent Substances 0.000 claims description 5
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 3
- 239000012065 filter cake Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 238000002203 pretreatment Methods 0.000 claims description 2
- 239000000047 product Substances 0.000 claims description 2
- 235000019260 propionic acid Nutrition 0.000 claims description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 2
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 239000010865 sewage Substances 0.000 abstract description 21
- 239000010802 sludge Substances 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 7
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000000376 reactant Substances 0.000 abstract description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000010355 oscillation Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000000274 adsorptive effect Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000001458 anti-acid effect Effects 0.000 description 1
- 210000000576 arachnoid Anatomy 0.000 description 1
- 150000003934 aromatic aldehydes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006196 deacetylation Effects 0.000 description 1
- 238000003381 deacetylation reaction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 235000019830 sodium polyphosphate Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Landscapes
- Water Treatment By Sorption (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention relates to a method for preparing an adsorbent by coupling chitosan with bamboo charcoal by using monoaldehyde. The method comprises the following steps of: preparing acid solution of the chitosan; pre-treating the bamboo charcoal; preparing acid mixed solution of the bamboo charcoal and the chitosan; preparing a coupling reactant of the chitosan and the bamboo charcoal; and preparing a bamboo charcoal adsorbent coupled with the chitosan. The invention relates to a production method of the adsorbent for treating domestic sewage. The adsorbent produced by the method has better effect of reducing CODcr, turbidity and ammonia nitrogen of the domestic sewage than the bamboo charcoal or activated sludge.
Description
Technical field
The present invention relates to technical field of sewage, specifically is a kind of preparation method of domestic sewage treating compound.
Background technology
Chitosan and link coupled chitosan are vesicular structure because of microcosmic, so good sewage purification ability is all arranged.But chitosan exists loss and the big shortcoming of consumption easily.Bamboo charcoal has flourishing hole, big specific surface area, and strong adsorptive power, and price is more cheap, more is used in the processing of sewage.But bamboo charcoal be adsorbed with a saturation ratio.
The present invention utilizes the advantage of the two simultaneously, adopts new method that the two is combined and obtains the more excellent sewage-treating agent of performance.Utilize the high absorption capacity of bamboo charcoal; The adding coupling agent makes the polymer of chitosan and bamboo charcoal coupling Cheng Gengda; Chitosan antiacid dissolved and water-soluble all apparently higher than link coupled chitosan not after the coupling, behind the bamboo charcoal coupled chitosan, further improves the effect of disposing of sewage.
Through retrieval and market survey, do not find in sanitary sewage disposal, make the report of sorbent material with monoaldehyde coupled chitosan and bamboo charcoal, more do not have to appear on the market about the report and the related prods of this type sorbent material working method.
Summary of the invention
The technical problem that the present invention will solve provides a kind of sodium polyphosphate coupled chitosan and the sorbent material of bamboo charcoal powder and working method of this agent that is used for sanitary sewage disposal.
The technical scheme that solves the problems of the technologies described above is: with the working method of the sorbent material of monoaldehyde coupled chitosan and bamboo charcoal powder through the following step:
(1) preparation of chitosan acidic solution: the concentration that the chitosan of 5-10 weight part is joined the 1250-2500 weight part is in 5% the acetate; Or the concentration of 2000-4000 weight part is in 1% the formic acid; Or 3500-5500 weight part concentration is in 2% the propionic acid, to be stirred well to chitosan and all to dissolve;
(2) pre-treatment of bamboo charcoal: commercially available bamboo charcoal is used deionized water wash, and vacuum-drying is ground into 150-2000 purpose bamboo charcoal powder again to constant weight;
(3) preparation of bamboo charcoal powder and chitosan acidic mixed solution: 50-90 weight part bamboo charcoal powder is added in any acidic solution of step (1), fully stirred 5-6 hour, left standstill 6-8 hour:
(4) preparation of the linked reaction thing of chitosan and bamboo charcoal: use 225-675 weight part concentration is 0.2% formalin; Or with the acetaldehyde solution of 800-1600 weight part concentration 0.2%; Or use 1850-5550 weight part concentration is 0.2% the salicylic aldehyde aqueous solution; Dropwise be added to as coupling agent in bamboo charcoal powder and the chitosan acid mixed solution of step (3) and carry out linked reaction, stirred 7-8 hour, slowly add sodium hydroxide then or Pottasium Hydroxide is adjusted to pH=10-11; Stirred 2-3 hour, and stopped linked reaction;
(5) coupling has the producing of bamboo charcoal sorbent material of chitosan: the coupled product of step (4) is carried out solid-liquid separation, get solids, solids is added in the entry; Stirred 1 hour; Solid-liquid separation once more, again solids being joined the 125-250 weight part concentration that is used for washing is 95% ethanol, stirs 1 hour; Filter, with filter cake 40 ℃ of dry 24h under vacuum
Said monoaldehyde is monobasic alkanoic or monobasic aromatic aldehyde, and by the chemical property decision, other monoaldehyde all can be used as coupling agent of the present invention basically.
Beneficial effect of the present invention: the sorbent material with present method is produced than with bamboo charcoal or active sludge, has the COD of better reduction sewage in handling sewage
Cr, turbidity, ammonia nitrogen ability.And it is reusable.
Embodiment
The present invention makes further detailed description below in conjunction with embodiment: each raw material and weight part thereof are listed in table 1 by 10 embodiment at present.
Table 1
Embodiment 1 (raw material and the weight part thereof of embodiment 1 correspondence in the synopsis 1):
Get 5 parts of weight of chitosan and add in the acetic acid soln of 1250 parts of weight 5%, fully stirring is dissolved chitosan fully.Add 50 parts of weight of bamboo charcoal then, fully stirred 5-6 hour, placed 6-8 hour.Get 1.5 part of 30% formaldehyde and add water and be made into 225 part of 0.2% solution, formaldehyde solution is dropwise added in above-mentioned bamboo charcoal and the chitosan acidic mixed solution, stirred 7-8 hour; Slowly add sodium hydroxide solution to pH=10-11, continue to stir 2-3 hour, stop linked reaction; Again reactant is carried out solid-liquid separation, get solids, solids is added in 150 weight parts waters wash; Stirred 1 hour, solid-liquid separation joins solids in 125 part of 95% ethanol more once more; Stirred 1 hour, and filtered, filter cake dry 24h under vacuum.Promptly make this sorbent material.Above-mentioned solid-liquid separation can adopt filtration, method such as centrifugal.
The used acid oxalic acid of available pH=3.95-4.88 also in the preparation chitosan acidic solution, phosphoric acid, in the boric acid any.Chitosan is wanted to buy to Zhejiang Province's Yuhuan county marine biochemistry Ltd, and deacetylation is 90%.
Corresponding embodiment raw material and parts by weight thereof in the equal synopsis of all the other embodiment 2-10 are processed with embodiment 1 same procedure, and are wherein preferred with embodiment 2.
The sorbent material of producing with the working method of the sorbent material of monoaldehyde coupled chitosan and bamboo charcoal; The link coupled chitosan can form the coupled chitosan film of arachnoid or film like in the space of bamboo charcoal; And because linked reaction is also carried out in the hole of bamboo charcoal; The aperture of bamboo charcoal and the shape in hole all change to some extent, and the specific surface area of sorbent material is 2997m
2/ g, mean pore size is 2.63nm, total pore volume is 1.94cm
3/ g.
Through utilizing bamboo charcoal flourishing gap structure and good adsorption performance, the link coupled chitosan adds coupling agent again linked reaction is occurred in the space of bamboo charcoal to saturated to make bamboo charcoal adsorb not earlier.Following several benefits is arranged like this: 1, since not the link coupled chitosan to compare the link coupled chitosan molecule less, bamboo charcoal adsorbs that the link coupled chitosan is uneasier than absorption link coupled chitosan; 2, chitosan specific surface absorption in the bamboo charcoal cavity more helps being used for WWT.
The experimental example of the sorbent treatment sewage of present method production is introduced by bottom:
Under the normal temperature situation, relatively this sorbent material, bamboo charcoal and active sludge are to the processing power of sewage.Add each 4g of this sorbent material, bamboo charcoal and active sludge, handle the 150mL sewage, sewage is added in the 250mL Erlenmeyer flask; Again Erlenmeyer flask is put in the vibrator of 130r/min speed; Continuous oscillation 24h leaves standstill 2h, gets supernatant and measures turbidity, pH, COD
Cr, the ammonia nitrogen index, concrete experimental data is seen table 2.
This sorbent material of table 2, bamboo charcoal and active sludge are to the contrast table as a result of sewage
At continuous oscillation 24h, turbidity is 21NTU, COD
CrFor 151.7mg/L, ammonia nitrogen concentration are under the condition of 56.2mg/L, this sorbent material is to the COD of sewage
CrClearance is 41%, than bamboo charcoal to sewage COD
CrRemoval effect 18% and active sludge are to sewage COD
CrRemoval effect 31% obviously will be got well; The denitrogenation ability to, the ammonia nitrogen removal frank of this sorbent material, bamboo charcoal and active sludge is respectively 36%, 13%, 22%, and this sorbent material is all better than the denitrification effect of bamboo charcoal and active sludge; The turbidity removal effect also is that this sorbent material is best, and the turbidity removal rate of this sorbent material, bamboo charcoal and active sludge is respectively 38%, 4.7%, 14%.Than bamboo charcoal or active sludge treatment sewage, this sorbent material has the COD of better reduction sewage
Cr, turbidity, ammonia nitrogen effect.
Claims (1)
1. working method with the sorbent material of monoaldehyde coupled chitosan and bamboo charcoal is characterized in that through the following step:
(1) preparation of chitosan acidic solution: the concentration that the chitosan of 5-10 weight part is joined the 1250-2500 weight part is in 5% the acetate; Or the concentration of 2000-4000 weight part is in 1% the formic acid; Or 3500-5500 weight part concentration is in 2% the propionic acid, to be stirred well to chitosan and all to dissolve;
(2) pre-treatment of bamboo charcoal: commercially available bamboo charcoal is used deionized water wash, and vacuum-drying is ground into 150-2000 purpose bamboo charcoal powder again to constant weight;
(3) preparation of bamboo charcoal powder and chitosan acidic mixed solution: 50-90 weight part bamboo charcoal powder is added in any acidic solution of step (1), fully stirred 5-6 hour, left standstill 6-8 hour;
(4) preparation of the linked reaction thing of chitosan and bamboo charcoal: use 225-675 weight part concentration is 0.2% formalin; Or with the acetaldehyde solution of 800-1600 weight part concentration 0.2%; Or use 1850-5550 weight part concentration is 0.2% the salicylic aldehyde aqueous solution; Dropwise be added to as coupling agent in bamboo charcoal powder and the chitosan acid mixed solution of step (3) and carry out linked reaction, stirred 7-8 hour, slowly add sodium hydroxide then or Pottasium Hydroxide is adjusted to pH=10-11; Stirred 2-3 hour, and stopped linked reaction;
(5) coupling has the producing of bamboo charcoal sorbent material of chitosan: the coupled product of step (4) is carried out solid-liquid separation, get solids, solids is added in the entry; Stirred 1 hour; Solid-liquid separation once more, again solids being joined 125-250 weight part concentration is in 95% the ethanol, stirs 1 hour; Filter, with filter cake 40 ℃ of dry 24h under vacuum.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102955131A CN101955551B (en) | 2010-09-27 | 2010-09-27 | Method for preparing adsorbent by coupling chitosan with bamboo charcoal by using monoaldehyde |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102955131A CN101955551B (en) | 2010-09-27 | 2010-09-27 | Method for preparing adsorbent by coupling chitosan with bamboo charcoal by using monoaldehyde |
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| CN101955551B true CN101955551B (en) | 2012-06-06 |
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| KR100393267B1 (en) * | 2001-02-15 | 2003-07-31 | 에코그린텍 (주) | Staircase type waste water disposal system and adsorbent for purification of livestock waste water |
| CN1724142A (en) * | 2005-06-07 | 2006-01-25 | 武汉大学 | Process for preparing shell glycan composite adsorbent |
| CN101215384A (en) * | 2008-01-11 | 2008-07-09 | 大连理工大学 | Method for preparing adsorbent recombination chitosan micro-sphere crosslinked resin |
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