CN1077451C - Modified cellulose adsorbent and its preparation and regeneration - Google Patents
Modified cellulose adsorbent and its preparation and regeneration Download PDFInfo
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- CN1077451C CN1077451C CN98112002A CN98112002A CN1077451C CN 1077451 C CN1077451 C CN 1077451C CN 98112002 A CN98112002 A CN 98112002A CN 98112002 A CN98112002 A CN 98112002A CN 1077451 C CN1077451 C CN 1077451C
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Abstract
The present invention relates to a modified cellulose adsorbing agent, the molecular formulas of cellulose derivatives generated on carriers are shown as following, and a preparation method for the adsorbing agent comprises the steps of soaking twice and rolling twice, drying, baking, water washing, acid boiling and water washing in sequence, and finally, finished products can be obtained. The adsorbing agent can be used in the manner that the adsorbing agent can be put into printing and dyeing waste water containing anionic dyes for 30 to 60 minutes; then, the adsorbing agent can be desorbed by being put into a sodium carbonate solution and boiled for 5 to 10 minutes, and the desorbed adsorbing agent can be soaked into a water solution of which the pH value is 2 to 4 for about 10 minutes.
Description
The present invention is relevant with the use renovation process with modified cellulose adsorbent and preparation method thereof.
Existing modified cellulose adsorbent is quaternized cellulose as " quaternized cellulose is used for the purification of hydrolysed reactive dye waste liquid " (TexT.Chem.col.1955,27 (4), 25) literary composition report, and its structural formula is: cellulose-O-CH
2CH (OH) CH
2N
+(CH
3)
3, it handles object is hydrolysed reactive dye, its regeneration condition is for handling carrier in the NaOH of 1M solution, get off being adsorbed in the dyestuff desorb that tree refers to.Under this highly basic condition, may reduce the adsorption capacity and the service life of resin.
The purpose of this invention is to provide a kind of recessive quaternized cellulose adsorbent that utilizes the tertiary amine cellulose to change into.This adsorbents adsorb ability is strong, long service life.
Another object of the present invention provides above-mentioned preparation of adsorbent method.
Another purpose of the present invention provides a kind of the use and the method for the above-mentioned adsorbent of regenerating.
The present invention is achieved in that
Modified cellulose adsorbent of the present invention is a carrier with the cellulosic fabric, it is characterized in that the molecular formula of the cellulose derivative that generates on the carrier is:
Cellulose-O-CH
2CH (OH) CH
2N
+H (CH
2CH
3)
2,
The preparation method of modified cellulose adsorbent, its technological process is as follows:
(1) following prescription is mixed with liquid weight %
1,1-two ethyls-3 hydroxyl chlorination azetidine 2-4
Be called for short azetidine derivatives
NaOH 1.5-3
Penetrating agent JFC-aliphatic alcohol polyethenoxy base ether 0.1
Water all the other,
(2) with carrier (cellulose fibre kind fabric, yarn etc.) impregnated in the liquid of preparation 3-5 minutes, taking out carrier then extracts, again carrier is immersed and flooded in the liquid 3-5 minutes, taking out carrier again extracts, make liquid carrying rate reach 80-100% (weight), liquid carrying rate=(wet carrier-dried carrier)/dried carrier.
(3) carrier of extracting is placed oven dry in 70-80 ℃ the drying room, temperature is risen to about 150 ℃ baked 3-5 minutes again,
(4) carrier with oven dry goes unreacted 1,1-two ethyls-3 hydroxyl nitrogenize azetidines (azetidine derivatives) and residual NaOH with eccysis in the running water,
(5) add in the entry carrier boiled with the glacial acetic acid of the concentration 98% of 1% (weight) and boil 5-10 minutes, with residual NaOH in fully and on the carrier,
Dry after (6) washing carrier totally.
The using method of modified cellulose adsorbent, its processing step is as follows:
Adsorbent is put into the dyeing and printing sewage that contains anionic dye, and its consumption is to contain 1.5 weight portion dyestuffs in the sewage, and the adsorbent of adding is 100 weight portions, and adsorption temp is 50-60 ℃, and adsorbent is 1: 20 with the ratio of sewage, and adsorption time is 30-60 minutes.
The renovation process of modified cellulose adsorbent, its processing step is as follows:
(1) adsorbent that will be adsorbed with dyestuff boils with the sodium carbonate that contains 2-5g/L and boils 5-10 minutes, can with micromolecular anionic dye from the adsorbent fully desorb get off,
(2) adsorbent after the desorb is soaked in the aqueous solution of pH=2-4 and soaked 10 minutes, make its absorption property regeneration, the sorbent circulation after the regeneration is used repeatedly and absorption property descends small.
To be adsorbed with the modified cellulose adsorbent regeneration of macromolecular anionic dye, its processing step is as follows:
With the modified cellulose adsorbent that is adsorbed with macromolecular anionic dye earlier with the sodium carbonate of 2-5g/l boil boil 5-10 minutes after, use N again, N-dimethyl formamide extraction will lean on the big molecular dye desorb of hydrogen bond and Van der Waals force combination to get off, N after the extraction, N-dimethyl formamide reclaims system by distillation with it and uses, adsorbent after the desorb is soaked in the aqueous solution of pH=2-4 and soaked 10 minutes, make the regeneration of its absorption property, the sorbent circulation after the regeneration is used repeatedly and absorption property descends small.
Fig. 1 is the attached desorption performance table of telling of the present invention.
The present invention has following advantage and effect
1, adsorbent is to the high adsorption capacity of various anionic dyes.
From Fig. 1 table as can be seen, this adsorbent all has very strong adsorption capacity to various types of anionic dyes, similarly to the azoic coupling component of azoic dyes, the leuco compound of reducing dye, sulfur dye leuco compound and have the dyestuff of strong polar group such as coating particle etc. all has very strong adsorption capacity, this is because this adsorbent is actually cellulosic tertiary amines derived thing, has formed cellulosic quaternary ammonium derivative after boiling by acid.Thereby this adsorbent that has positive charge has very strong electrostatic attraction to containing anionic dyestuff, thereby very strong to the adsorption capacity of anionic dye.
2, the regenerability of adsorbent is good.
As can be seen from Figure 1, this adsorbent by absorption-→ desorb-→ regeneration-→ again absorption, so recycle 10 times after, its adsorption rate to various types of anionic dyes all descends seldom, (the reactive violet K-3R), the rate of descent of adsorption capacity is all below 3% except that indivedual dyestuffs.The decline of adsorption rate mainly is owing to form the part covalent bond between reactive dye and the adsorbent, thereby is detained on adsorbent and has occupied absorption and dye seat.And in fact most of (almost whole) reactive dye exist with the form of hydrolysed reactive dye in actual dyeing and printing sewage, and interact with sat linkage, hydrogen bond, Van der Waals force between the adsorbent, thereby its adsorption capacity all can remain unchanged substantially after being repeatedly used.Quaternary ammonium compound has the antimildew and antibacterial performance, and contains recessive quaternary ammonium group on the adsorbent, thereby has the antimildew and antibacterial performance, thereby makes adsorbent use and unlikely going mouldy hydrolysis in the sewage midium or long term.It is very important that this point is used for sewage decoloring to this resinoid.Therefore this both absorption properties are strong, desorb easily again, and system is saturating convenient, and cost is low, is difficult for again going mouldy, and the adsorbent of hydrolysis is for dyeing sewage decoloration has been opened up a brand-new approach.
Following is embodiments of the invention:
One, preparation of adsorbent
Carrier: cellulose fibre kind fabric, yarn, chip etc.
Technology preparation: weight %
1,1-two ethyls-3 hydroxyl chlorination azetidine 2-4%
NaOH 1.5-3%
Penetrating agent JFC 0.1%
(aliphatic alcohol polyethenoxy base ether)
Add water and be supplemented to 100%
Concrete technology preparation sees the following form:
Wherein NaOH plays the derivative of catalytic chlorination azetidine and cellulose, fiber-reactive, and penetrating agent JFC plays a part to help above-mentioned institute dispense liquid to infiltrate through in the fiber.
Technological operation: carrier (cellulose fibre kind fabric, yarn etc.) be impregnated in the above-mentioned liquid of preparing can the submergence carrier get final product) flooded 3-5 minutes, taking out carrier then extracts, again carrier is immersed and flooded in the liquid 3-5 minutes, take out carrier again and extract, make liquid carrying rate reach 80-100% (liquid carrying rate
Be placed on 70-80 ° the interior oven dry of drying room then, again temperature is risen to about 150 ℃ and baked 3-5 minutes, and then this carrier is washed about 5 minutes to remove unreacted 1 with running water, 1-two ethyls-3 hydroxyl chlorination azetidine and residual NaOH, use 1% glacial acetic acid (98%) to boil at last and boil 5-10 minutes, with residual NaOH in fully and on the carrier, after washing is clean this carrier oven dry is promptly obtained adsorbent.Its molecular formula is:
Cellulose-O-CH
2CH (OH) CH
2N
+H (CH
2CH
3)
2
Two, adsorbent is to the adsorption capacity test of anionic dye.
In the experiment, we place the dye liquor that contains a certain amount of anionic dye with prepared adsorbent, measure the adsorption rate of its absorbing dye and weigh the adsorption capacity of this adsorbent to anionic dye.
Adsorbent: cellulose-O-CH
2CH (OH) CH
2N
+H (CH
2CH
3)
2
Anionic dye: reactive brilliant red X-3B, active gorgeous purple K-3R, the gorgeous purple K-3R of hydrolysing activity, the reactive brilliant yellow X-4G of inactivation, reactive brilliant blue K-GR, direct fast scarlet 4 BS, anionic dyes such as acid orange R, tracid light yellow 2G.
Adsorption conditions: dye liquor concentration 1.5% (heavy to adsorbent, i.e. 100g absorption.Add the 1.5g dyestuff), 50-60 ℃ of adsorption temps; The bath raio ratio of dye liquor (adsorbent with)=1: 20; Adsorbed 30-60 minutes.
Test and operation: accurately take by weighing each 0.500g of various dyestuffs, put into small beaker, the adding distil water dissolving moves in the 100ml volumetric flask then, and it is stand-by that adding distil water is diluted to scale.
Install and inhale the look device, various two covers respectively that dye.Join each 30ml of dye liquor with the above-mentioned institute of the accurate absorption of pipette and go in each dyeing apparatus, add 170ml water to 200 then.Then dyeing apparatus is put into thermostat water bath, when treating that temperature rises to 50-60 ℃, in one of them dyeing apparatus, add adsorbent 10g rapidly, take out adsorbent after 60 minutes, keep raffinate.
Above-mentioned raffinate and blank dye bath (not adding the dye bath of adsorbent) are used its absorbance A of spectrophotometric determination (blank dye bath is too dense, can suitably water down) respectively.
A wherein
1Behind various dyestuffs usefulness adsorbents adsorb certain hours, the absorbance of raffinate, A
0Absorbance for the blank dyestuff of correspondence.
Three, be adsorbed in the desorb of the dyestuff on the adsorbent
With the adsorbent that is adsorbed with dyestuff with the sodium carbonate of 2-5g/l boil boil 5-10 minutes can be with reactive dye, micromolecular anionic dye such as hydrolysed reactive dye from the adsorbent fully desorb get off.If be adsorbed with macromolecular anionic dye on the desorb incomplete specification adsorbent, this moment can be formerly with 2-5g/l sodium carbonate as stated above after the desorb, use N again, N-dimethyl formamide extraction gets off with the dyestuff desorb of hydrogen bond and the gravitation combination of model DS China on a small quantity with remaining.N after the extraction, N-dimethyl formamide still can be by distillation with its recyclings.
Four, the regeneration of adsorbent
Last adsorbent behind the said method desorb dyestuff is soaked in the aqueous solution (regulating) of pH=2-4 and soaked about 10 minutes, can make its absorption property regeneration with the hydrochloric acid of 98% acetic acid or 37%.
Adsorbent after the regeneration-→ the adsorpting anion dyestuff, and measure adsorption rate ,-→ desorb-→ regeneration-→ the adsorpting anion dyestuff-→ recycle.
Sorbent circulation uses the rate of descent of N back adsorption capacity to calculate by following formula:
The regenerability of adsorbent sees the following form:
Annotate: N time is 10 times or 5 times.
Claims (5)
1, a kind of modified cellulose adsorbent is a carrier with the cellulosic fabric, it is characterized in that the molecular formula of the cellulose derivative that generates on the carrier is:
Cellulose-O-CH
2CH (OH) CH
2N
+H (CH
2CH
3)
2,
2, the preparation method of modified cellulose adsorbent as claimed in claim 1, its technological process is as follows:
(1) following prescription is mixed with liquid weight %
1,1-two ethyls-3 hydroxyl chlorination azetidine 2-4
NaOH 1.5-3
Penetrating agent JFC-aliphatic alcohol polyethenoxy base ether 0.1
Water all the other,
(2) with carrier impregnation in the preparation liquid in 3-5 minutes, take out carrier then and extract, carrier is immersed flooded in the liquid 3-5 minutes again, take out carrier again and extract, make liquid carrying rate reach 80-100% (weight),
(3) carrier of extracting is placed oven dry in 70-80 ℃ the drying room, temperature is risen to about 150 ℃ baked 3-5 minutes again,
(4) carrier of oven dry is removed unreacted 1,1-two ethyls-3 hydroxyl nitrogenize azetidine and residual NaOH with the running water flushing,
(5) add in the entry carrier boiled with the glacial acetic acid of the concentration 98% of 1% (weight) and boil 5-10 minutes, with residual NaOH in fully and on the carrier,
Dry after (6) washing carrier totally.
3, the using method of modified cellulose adsorbent as claimed in claim 1, its processing step is as follows:
Adsorbent is put into the dyeing and printing sewage that contains anionic dye, its consumption is to contain 1.5 weight portion dyestuffs in the sewage, and the adsorbent of adding is 100 weight portions, and adsorption temp is 50-60 ℃, adsorbent is 1: 20 (weight) with the ratio of sewage, and adsorption time is 30-60 minutes.
4, the renovation process of modified cellulose adsorbent as claimed in claim 1, its processing step is as follows:
(1) adsorbent that will be adsorbed with dyestuff boils with the sodium carbonate that contains 2-5g/l and boils 5-10 minutes, can with micromolecular the moon from give dyestuff from the adsorbent fully desorb get off,
(2) adsorbent after the desorb is soaked in the aqueous solution of pH=2-4 and soaked 10 minutes, make its absorption property regeneration, the sorbent circulation after the regeneration is used repeatedly and absorption property descends small.
5, the renovation process of modified cellulose adsorbent as claimed in claim 1 will be adsorbed with the modified cellulose adsorbent regeneration of macromolecular anionic dye, and its processing step is as follows:
With the modified cellulose adsorbent that is adsorbed with macromolecular anionic dye earlier with the sodium carbonate of 2-5g/l boil boil 5-10 minutes after, use N again, N-dimethyl formamide extraction will lean on the big molecular dye desorb of hydrogen bond and Van der Waals force combination to get off, N after the extraction, N-dimethyl formamide is by distilling its recycling, adsorbent after the desorb is soaked in the aqueous solution of pH=2-4 and soaked 10 minutes, make the regeneration of its absorption property, the sorbent circulation after the regeneration is used repeatedly and absorption property descends small.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98112002A CN1077451C (en) | 1998-05-14 | 1998-05-14 | Modified cellulose adsorbent and its preparation and regeneration |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98112002A CN1077451C (en) | 1998-05-14 | 1998-05-14 | Modified cellulose adsorbent and its preparation and regeneration |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1201713A CN1201713A (en) | 1998-12-16 |
| CN1077451C true CN1077451C (en) | 2002-01-09 |
Family
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|---|---|---|---|
| CN98112002A Expired - Fee Related CN1077451C (en) | 1998-05-14 | 1998-05-14 | Modified cellulose adsorbent and its preparation and regeneration |
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|---|---|
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1120044C (en) * | 1999-12-31 | 2003-09-03 | 西安交通大学 | Cellulose fibre ion-exchange adsorbent for decolouring and its compounding technology |
| BR112017008995B1 (en) * | 2014-11-11 | 2022-06-28 | Rohm And Haas Company | DETERGENT COMPOSITION FOR CLOTHING |
| CN104984742B (en) * | 2015-07-15 | 2017-08-15 | 江南大学 | A kind of preparation method and applications of Studies On Preparation And Properties of Cellulose-based Adsorbents |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4577013A (en) * | 1983-12-22 | 1986-03-18 | Ciba-Geigy Corporation | Ionically modified cellulose material, its preparation and its use |
| JPH01130726A (en) * | 1987-11-16 | 1989-05-23 | Daicel Chem Ind Ltd | Gelatinous substance |
| JPH02253813A (en) * | 1989-03-29 | 1990-10-12 | Mitsubishi Nuclear Fuel Co Ltd | Adsorptive filter membrane |
| EP0616845A1 (en) * | 1993-03-25 | 1994-09-28 | Angel Research Institute Co. | Adsorptive materials and process for producing them |
| JPH07100372A (en) * | 1993-10-05 | 1995-04-18 | Daiso Co Ltd | Adsorbent for dye contained in waste water and its production |
| JPH07149830A (en) * | 1993-10-05 | 1995-06-13 | Daiso Co Ltd | Allylic (co)polymer and its intermedate and new cationic material obtained from the same (co)polymer and its production |
-
1998
- 1998-05-14 CN CN98112002A patent/CN1077451C/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4577013A (en) * | 1983-12-22 | 1986-03-18 | Ciba-Geigy Corporation | Ionically modified cellulose material, its preparation and its use |
| JPH01130726A (en) * | 1987-11-16 | 1989-05-23 | Daicel Chem Ind Ltd | Gelatinous substance |
| JPH02253813A (en) * | 1989-03-29 | 1990-10-12 | Mitsubishi Nuclear Fuel Co Ltd | Adsorptive filter membrane |
| EP0616845A1 (en) * | 1993-03-25 | 1994-09-28 | Angel Research Institute Co. | Adsorptive materials and process for producing them |
| JPH07100372A (en) * | 1993-10-05 | 1995-04-18 | Daiso Co Ltd | Adsorbent for dye contained in waste water and its production |
| JPH07149830A (en) * | 1993-10-05 | 1995-06-13 | Daiso Co Ltd | Allylic (co)polymer and its intermedate and new cationic material obtained from the same (co)polymer and its production |
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| Publication number | Publication date |
|---|---|
| CN1201713A (en) | 1998-12-16 |
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