CN106824119A - A kind of xanthogenation shitosan and preparation method thereof - Google Patents
A kind of xanthogenation shitosan and preparation method thereof Download PDFInfo
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- CN106824119A CN106824119A CN201710213138.3A CN201710213138A CN106824119A CN 106824119 A CN106824119 A CN 106824119A CN 201710213138 A CN201710213138 A CN 201710213138A CN 106824119 A CN106824119 A CN 106824119A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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Abstract
The present invention provides a kind of xanthogenation shitosan and preparation method thereof, is related to field of polymer technology.The preparation method of xanthogenation shitosan, including：With shitosan as substrate, the amino to shitosan carries out protecting prepared Chitosan Schiff Base, is obtained in the shitosan parent grafting dithiocarboxyl of Chitosan Schiff Base.Xanthogenation shitosan obtained in preparation method according to above-mentioned xanthogenation shitosan.The preparation method of this xanthogenation shitosan is protected by the way that shitosan is synthesized into Chitosan Schiff Base to the amino of shitosan parent, afterwards, xanthogenation shitosan is obtained by being grafted to Chitosan Schiff Base.With simple to operate, easily controllable and lower-cost feature.Obtained xanthogenation shitosan is the high-molecule chelated flocculating agent that heavy metal ion has chelating precipitation and flocculation sediment double action.
Description
Technical field
The present invention relates to field of polymer technology, and more particularly to a kind of xanthogenation shitosan and preparation method thereof.
Background technology
Heavy metal wastewater thereby essentially from industry such as mining, non-ferrous metal, plating, electrolysis, agricultural chemicals, medicine, paint, pigment,
The heavy metals such as cadmium, chromium, mercury, zinc, copper are mainly contained, its species, content and existing forms are different with Production conditions.Copper-containing wastewater is
A kind of common heavy metal wastewater thereby, unprocessed discharge can cause environmental pollution and be detrimental to health.In terms of environment, copper from
Son is gathered in crop root part, hinders absorption of the crops to nutrient so that crops occur related defect phenomenon.Therefore, it is right
Copper-containing wastewater is processed to be discharged again, both can effectively be reduced to environment and harm, it is also possible to realize that copper is reclaimed, from
And reach the purpose of resource circulation utilization.
Chemical precipitation method is a kind of wide variety of except the method for heavy metal in waste water.Shitosan can effectively remove low dense
Degree or micro heavy the ion ,-NH that its structure contains2There is stronger combination to metal ion with-OH groups, be one
Plant very good heavy metal absorbent.But, during shitosan is easily soluble in acidic materials, absorption when easily influenceed by water body pH
Etc. weakness.
The content of the invention
The first object of the present invention is to provide a kind of preparation method of xanthogenation shitosan, is carried out by shitosan
It is modified, improve the disposal ability of the materials such as shitosan heavy metal.
The second object of the present invention is to provide a kind of xanthogenation shitosan, is obtained with by the above method, is a kind of
Heavy metal ion has the high-molecule chelated-flocculant of chelating precipitation and flocculation sediment double action.
The third object of the present invention is the application for providing a kind of xanthogenation shitosan in except Cu in waste water ion,
Copper ion is efficiently removed in purification of waste water.
The present invention is solved its technical problem and is realized using following technical scheme.
The present invention proposes a kind of preparation method of xanthogenation shitosan, including：With shitosan as substrate, to shitosan
Amino is carried out protecting prepared Chitosan Schiff Base, and dithiocarboxyl system is grafted in the shitosan parent of Chitosan Schiff Base
.
A kind of xanthogenation shitosan, the preparation method according to above-mentioned xanthogenation shitosan is obtained.
The beneficial effect of the embodiment of the present invention is：
The preparation method of this xanthogenation shitosan synthesizes Chitosan Schiff Base to shitosan parent by by shitosan
Amino protected, afterwards, xanthogenation shitosan is obtained by being grafted dithiocarboxyl to Chitosan Schiff Base.Have
Simple to operate, easily controllable and lower-cost feature.
Xanthogenation shitosan obtained in the preparation method of this xanthogenation shitosan, both ensure that chitosan structure contained
Amino to metal ion combination, dithiocarboxyl is introduced again, the sulphur atom in dithiocarboxyl and metal ion have
There is chelation to form the chelating precipitation thing of stabilization.It is appreciated that obtained xanthogenation shitosan is heavy metal ion tool
There is the high-molecule chelated-flocculant of chelating precipitation and flocculation sediment double action.
Brief description of the drawings
Technical scheme in order to illustrate more clearly the embodiments of the present invention, below will be attached to what is used needed for embodiment
Figure is briefly described, it will be appreciated that the following drawings illustrate only certain embodiments of the present invention, thus be not construed as it is right
The restriction of scope, for those of ordinary skill in the art, on the premise of not paying creative work, can also be according to this
A little accompanying drawings obtain other related accompanying drawings.
Fig. 1 a are the infrared spectrogram of shitosan；
Fig. 1 b are the infrared spectrogram of Chitosan Schiff Base prepared by the present invention；
Fig. 1 c are the infrared spectrogram of xanthogenation shitosan prepared by the present invention；
Fig. 2 is that the carbon disulfide consumption that the embodiment of the present invention 1 is provided removes Cu to XCTS2+The result figure of effect；
Fig. 3 is that the naoh concentration that the embodiment of the present invention 2 is provided removes Cu to XCTS2+The result figure of effect；
Fig. 4 is the pre-reaction temperature T that the embodiment of the present invention 3 is provided1Cu is removed to XCTS2+The result figure of effect；
Fig. 5 is the pre-reaction time t that the embodiment of the present invention 4 is provided1Cu is removed to XCTS2+The result figure of effect；
Fig. 6 is the main reaction temperature T that the embodiment of the present invention 5 is provided2Cu is removed to XCTS2+The result figure of effect；
Fig. 7 is the main reaction time t that the embodiment of the present invention 6 is provided2Cu is removed to XCTS2+The result figure of effect；
Fig. 8 is that the pH value that application examples of the present invention 1 is provided removes Cu to XCTS2+The result figure of effect；
Fig. 9 is the Cu that application examples of the present invention 2 is provided2+Concentration removes Cu to XCTS2+The result figure of effect.
Specific embodiment
To make the purpose, technical scheme and advantage of the embodiment of the present invention clearer, below will be in the embodiment of the present invention
Technical scheme be clearly and completely described.Unreceipted actual conditions person, builds according to normal condition or manufacturer in embodiment
The condition of view is carried out.Agents useful for same or the unreceipted production firm person of instrument, are the conventional product that can be obtained by commercially available purchase
Product.
Xanthogenation shitosan of the embodiment of the present invention and preparation method thereof is specifically described below.
A kind of preparation method of xanthogenation shitosan, including：
The structural formula of shitosan (CTS) is as follows：
To the C of shitosan2Bit amino (- NH2) carry out protection generation Chitosan Schiff Base.Wherein, amino is that have coordination
The active group of effect.
From deacetylation >=95% shitosan as modified substrate.Given birth to using benzaldehyde and shitosan synthetic reaction
Realized to C into Chitosan Schiff Base2The protection of bit amino.
It is 1 according to the amount ratio of material by shitosan and aldehyde compound：After 5~10 mixing, at a temperature of 60~80 DEG C
3~6h of reaction, is obtained Chitosan Schiff Base.
Aldehyde compound is selected from fatty aldehyde and aromatic aldehyde.Preferably, fatty aldehyde be selected from acetaldehyde, propionic aldehyde, glutaraldehyde, hexanal,
Octanal, certain herbaceous plants with big flowers aldehyde and lauric aldehyde.Preferably, aromatic aldehyde be selected from salicylide, furfural, benzaldehyde, nitrobenzaldehyde, to Dimethylaminobenzene
Formaldehyde and hydroxy benzaldehyde.It is highly preferred that aldehyde compound is selected from salicylide, furfural and benzaldehyde, most preferably, aldehydes chemical combination
Thing is selected from benzaldehyde.
By taking benzaldehyde as an example, in order to ensure the extent of reaction of shitosan and benzaldehyde, shitosan is preferentially carried out before the reaction
It is swelling.For example, the shitosan per 1g is after swelling 20~40min in the glacial acetic acid of the 3~5vol% of 15~25mL, add thereto
The absolute ethyl alcohol for entering 15~25mL is diluted.By swelling operation, it is ensured that shitosan it is abundant with the reaction of subsequent reactions thing.
In order to be further ensured that the extent of reaction of shitosan and benzaldehyde, benzaldehyde is preferentially diluted before the reaction.Example
Such as, the benzaldehyde of every 3.8~7.6g adds the absolute ethyl alcohol of 15~20mL to be diluted.
Obtained Chitosan Schiff Base is washed before grafting with ethanol.For example, the shitosan per 1g with every 3.8~
The benzaldehyde reaction of 7.6g is washed using the ethanol of 15~20mL.By ethanol by reactant unnecessary in Chitosan Schiff Base
With the washes clean such as sweller, it is to avoid it produces influence to follow-up preparation process.
Dithiocarboxyl is grafted to the C of shitosan parent in Chitosan Schiff Base6Position hydroxyl, is obtained xanthogenation shell
Glycan (XCTS).Wherein, dithiocarboxyl is the active group with chelation, and shell is grafted to as sulphur atom coordinating group
Glycan parent so that xanthogenation shitosan has chelating ability.
Specifically, by Chitosan Schiff Base, alkali and carbon disulfide (CS2) after mixing, first, in 20~35 DEG C of temperature
0~45min of lower reaction；Secondly, 120~300min is reacted at a temperature of 40~70 DEG C.It is appreciated that in shitosan Schiff
The process that alkali prepares xanthogenation shitosan is divided into two processes, and the first process is defined as into pre-reaction process, pre-reaction temperature
T1It is 20~35 DEG C, pre-reaction time t1It is 0~45min.In this process, carbon disulfide generates xanthan in the environment of alkali presence
Sour sodium (containing dithiocarboxyl group), i.e., mainly realize the conversion of carbon disulfide.Second process is defined as main reaction process,
Main reaction temperature T2It it is 40~70 DEG C, the main reaction time is t2It is 120~300min.In this process, dithiocarboxyl exists in alkali
In the environment of be grafted to Chitosan Schiff Base.
It is appreciated that pre-reaction process realizes carbon disulfide and NaOH reaction generation sodium xanthogenate, and in master
Reactive grafting is to Chitosan Schiff Base.
It is 46.3 DEG C because the boiling point of carbon disulfide is relatively low, possesses extremely strong volatility.Divide by by above-mentioned course of reaction
It is pre-reaction process and main reaction process, in pre-reaction process, temperature is controlled all the time less than the boiling point of carbon disulfide, it is to avoid two sulphur
Change the volatilization of carbon and cause that most carbon disulfide both participates in reaction, in main reaction process, realized by improving reaction temperature
Accelerate reaction speed, it is ensured that xanthogenation shitosan is quickly and efficiently obtained.
In process of grafting, the consumption of carbon disulfide and alkali is calculated all in accordance with the consumption of shitosan substrate.
Shitosan is 1 with the mol ratio of carbon disulfide：2~8.Preferably, shitosan and the mol ratio of carbon disulfide are 1：2
~7.It is highly preferred that shitosan is 1 with the mol ratio of carbon disulfide：2.5~6.5.
Alkali is inorganic base.Preferably, alkali is inorganic strong alkali.More preferably, alkali elects alkali metal hydroxide, such as hydroxide as
Sodium (NaOH), potassium hydroxide (KOH) and lithium hydroxide (LiOH).
Shitosan is 1 with the mol ratio of alkali：4~24.Preferably, shitosan and the mol ratio of alkali are 1：5~22.More preferably
Ground, shitosan is 1 with the mol ratio of alkali：5~20.
In xanthogenation shitosan preparation process, the effect of alkali includes：One is the hydrophobic that alkali can be low with respond
Property material carbon disulfide react reaction of formation activity water-soluble substances sodium xanthogenate high；Two is that alkali can make shitosan C6
It is hydroxy activated on position.These effects of alkali can strengthen the carrying out that Chitosan Schiff Base reacts with carbon disulfide.Meanwhile,
The concentration of alkali is unsuitable too high, and excessively high-alkali concentration can make the alkalescence increase of reactant system viscosity and product system, and then lead
Cause Chitosan Schiff Base that side reaction occurs with carbon disulfide, cause the yield of sodium xanthogenate shitosan relatively low.So as to also reduce
Removal effect of the xanthogenation shitosan to copper ion.
Hold above-mentioned, the preparation method of this xanthogenation shitosan is gathered by the way that shitosan is synthesized into Chitosan Schiff Base to shell
The amino of sugared parent is protected, and afterwards, is gathered by being grafted the prepared xanthogenation shell of dithiocarboxyl to Chitosan Schiff Base
Sugar.With simple to operate, easily controllable and lower-cost feature.
Shitosan is vacuum dried.It is vacuum dried after being washed to Chitosan Schiff Base using absolute ethyl alcohol.
After washing precipitating and filtration washing are carried out to xanthogenation shitosan using absolute methanol, it is vacuum dried.Using KBr
(KBr) pressed disc method carries out infrared spectrum analysis to shitosan, Chitosan Schiff Base and xanthogenation shitosan respectively.Shitosan
Result see Fig. 1 a, the result of Chitosan Schiff Base is shown in Fig. 1 b, and the result of xanthogenation shitosan is shown in Fig. 1 c.
Shitosan and benzaldehyde reaction generation Chitosan Schiff Base, the design feature with carbon-to-nitrogen double bon and phenyl ring.Figure
1b understands that Chitosan Schiff Base is in 1644cm compared with the infrared spectrum of Fig. 1 a-1And 1581cm-1There is new absworption peak in place,
For C=N is symmetrical in conjugated system and asymmetric stretching vibration peak；Chitosan Schiff Base is in 693cm-1And 757cm-1The peak at place
It is a pair single-substituted sharp peaks of Chitosan Schiff Base；Chitosan Schiff Base is in 2878cm-1、1452cm-1And 859cm-1
The peak at place is the flexible and flexural vibrations peak of the C-H groups of Chitosan Schiff Base；Chitosan Schiff Base is in 1152cm-1、
1068cm-1And 1028cm-1The peak at place is the C-O stretching vibration peaks of Chitosan Schiff Base.Shitosan parent is in 1609cm-1Place
- NH2The peak of group disappears, and illustrates that benzaldehyde generates Chitosan Schiff Base with shitosan.
The scope of C=S key stretching vibration peaks is 1501~1200cm-1；The scope of C-S key stretching vibration peaks is 600~
700cm-1.Fig. 1 c understand that shitosan parent is in 1499cm compared with the infrared spectrum of Fig. 1 b-1There is new absworption peak in place, is C
The stretching vibration peak of=S；Xanthogenation shitosan is in 689cm-1The peak at place, is the stretching vibration peak of C-S；Xanthogenation shitosan
In 880cm-1The peak at place, is the deformation vibration peak of C-S keys, illustrates that dithiocarboxyl has been grafted to the-CH of shitosan parent2OH
Group.
By xanthogenation shitosan obtained in the preparation method of above-mentioned xanthogenation shitosan, shitosan knot had both been ensure that
The amino that structure contains introduces dithiocarboxyl again to metal ion combination, sulphur atom and metal in dithiocarboxyl
There is ion chelation to form the chelating precipitation thing of stabilization.It is appreciated that obtained xanthogenation shitosan is heavy metal
Ion has the high-molecule chelated-flocculant of chelating precipitation and flocculation sediment double action.
Application of the above-mentioned xanthogenation shitosan in copper removal.By the amino in shitosan parent and copper ion (Cu2 +) coordination and dithiocarboxyl in sulphur atom and copper atom chelation, stabilization can be formed with copper ion
Sediment is so as to remove the copper ion in waste water.
Feature of the invention and performance are described in further detail with reference to embodiments.
A) instrument：JB-2 type constant temperature blender with magnetic force, Lei Cixin rivers rising in Ningxia and flowing into central Shaanxi, Shanghai Instrument Ltd.；FA2004N types electronics day
It is flat, Shanghai Precision Scientific Apparatus Co., Ltd；KH5200DB type numerical control ultrasonic cleaners, the Kunshan standing grain wound limited public affairs of ultrasonic instrument
Department；The program control coagulation experiment stirring instrument of TS6 series, Wuhan Hengling Technology Co., Ltd.；SpectrAA 220FS types Atomic absorption point
Light photometer, U.S. Wa Lian；ORION828 type pH testers, Ao Lilong Chinese companies of the U.S.；IR Prestige-21 types are red
Outer spectrophotometer, Japanese Shimadzu Corporation.
B) reagent：Shitosan (CTS, it is deacetylation >=95%), benzaldehyde, NaOH, carbon disulfide, hydrochloric acid, anhydrous
Ethanol, absolute methanol and copper chloride (CuCl2·2H2O) it is analysis pure；
Copper water sample：Running water and CuCl are used under laboratory condition2·2H2O is made into copper water sample.Wherein, Cu2+For
25mg/L, pH value is 6.0.
Embodiment 1
Influence of the carbon disulfide consumption to preparation xanthogenation shitosan.
Embodiment 1a
Weigh the shitosan of 1g and add in the glacial acetic acid of the 3vol% of 20mL after swelling 30min, plus 20mL absolute ethyl alcohols
Dilution.Above sample is transferred to the there-necked flask of 250mL, and there-necked flask is placed in ultrasonic field is stirred and is adjusted pH value and be
5.After the benzaldehyde of 7 times of amounts of chitosan material is dissolved in into the absolute ethyl alcohol of 20mL, benzaldehyde is slowly dripped using separatory funnel
Enter shitosan, 4h is reacted at a temperature of 70 DEG C.Washed using ethanol wash obtaining shitosan to obtaining product
Schiff.
It is 10% sodium hydrate aqueous solution and the carbon disulfide of 1.0mL to mass fraction is added in Chitosan Schiff Base
Afterwards, it is placed in constant temperature blender with magnetic force.Successively in 20 DEG C of (T1) at a temperature of react 30min (t1) and in 60 DEG C of (T2) at a temperature of
Reaction 240min (t2), xanthogenation shitosan is obtained.
Embodiment 1b
The consumption for changing carbon disulfide is 1.5mL, and remaining is with embodiment 1a.
Embodiment 1c
The consumption for changing carbon disulfide is 2.0mL, and remaining is with embodiment 1a.
Embodiment 1d
The consumption for changing carbon disulfide is 2.5mL, and remaining is with embodiment 1a.
Six groups of copper water samples are taken, every group includes four parts.By embodiment 1a, embodiment 1b, embodiment 1c and embodiment 1d
Obtained xanthogenation shitosan is added to 45mg/L, 60mg/L, 75mg/L, 90mg/L, 105mg/L and 120mg/L respectively
Six groups of copper water samples are placed in stirring in program control coagulation experiment stirring instrument.In 50r/ after 2min being stirred under the rotating speed of 140r/min
10min is stirred under the rotating speed of min, 10min is staticly settled.Determine six groups of copper water samples respectively using atomic absorption spectrophotometer
Residual copper ion concentration.Result is as shown in Figure 2.
Figure it is seen that increasing with the consumption of carbon disulfide, xanthogenation shitosan increases to the clearance of copper ion
Plus.Because in reaction system carbon disulfide content increase, be conducive to the generation of xanthan acidification response so that the Huang of preparation
The content of dithiocarboxyl increases in ortho acid shitosan macromolecule chain, improves its clearance to Determined Copper in Aqueous Solution.When two
When nitric sulfid is not excessive, Chitosan Schiff Base can completely react with sodium xanthogenate；When carbon disulfide is excessive, exist in alkali
Orange red accessory substance can be generated under environment.When carbon disulfide consumption is respectively 2.0mL and 2.5mL, the xanthogenation shell of generation gathers
Sugar is respectively 89.8% and 87.2% to copper ion clearance.Therefore, carbon disulfide consumption is 2.0mL, xanthogenation shitosan
Dosage is optimal to copper ion removal effect when being 105mg/L.
Embodiment 2
Influence of the naoh concentration to preparation xanthogenation shitosan.
Embodiment 2a
Weigh 1g shitosans and add in the glacial acetic acid of the 3vol% of 20mL after swelling 30min, plus 20mL absolute ethyl alcohols are dilute
Release.Above sample is transferred to the there-necked flask of 250mL, and there-necked flask is placed in ultrasonic field is stirred and is adjusted pH value for 5.
After the benzaldehyde of 7 times of amounts of chitosan material is dissolved in into the absolute ethyl alcohol of 20mL, benzaldehyde is slowly dropped into using separatory funnel
Shitosan, 4h is reacted at a temperature of 70 DEG C.Washed using ethanol wash obtaining shitosan to obtaining product
Schiff.
To the curing of the sodium hydrate aqueous solution and 2.0mL that addition mass fraction in Chitosan Schiff Base is 2.5%
After carbon, constant temperature blender with magnetic force is placed in.Successively in 20 DEG C of (T1) at a temperature of react 30min (t1) and in 60 DEG C of (T2) temperature
Lower reaction 240min (t2), xanthogenation shitosan is obtained.
Embodiment 2b
The mass fraction for changing NaOH is 5%, and remaining is with embodiment 2a.
Embodiment 2c
The mass fraction for changing NaOH is 7.5%, and remaining is with embodiment 2a.
Embodiment 2d
The mass fraction for changing NaOH is 10%, and remaining is with embodiment 2a.
Embodiment 2e
The mass fraction for changing NaOH is 15%, and remaining is with embodiment 2a.
Six groups of copper water samples are taken, every group includes five parts.By embodiment 2a, embodiment 2b, embodiment 2c and embodiment 2d
Obtained xanthogenation shitosan is added to 45mg/L, 60mg/L, 75mg/L, 90mg/L, 105mg/L and 120mg/L respectively
Six groups of copper water samples are placed in stirring in program control coagulation experiment stirring instrument.In 50r/ after 2min being stirred under the rotating speed of 140r/min
10min is stirred under the rotating speed of min, 10min is staticly settled.Determine six groups of copper water samples respectively using atomic absorption spectrophotometer
Residual copper ion concentration.Result is as shown in Figure 3.
From figure 3, it can be seen that xanthogenation shitosan to the clearance of copper ion with the increase elder generation of naoh concentration
Reduced after rising.And, when naoh concentration is 5%, xanthogenation shitosan is optimal to copper ion removal effect, and highest is gone
Except rate is 93.5%.
Embodiment 3
Pre-reaction temperature (T1) to prepare xanthogenation shitosan influence.
Embodiment 3a
Weigh 1g shitosans and add in the glacial acetic acid of the 3vol% of 20mL after swelling 30min, plus 20mL absolute ethyl alcohols are dilute
Release.Above sample is transferred to the there-necked flask of 250mL, and there-necked flask is placed in ultrasonic field is stirred and is adjusted pH value for 5.
After the benzaldehyde of 7 times of amounts of chitosan material is dissolved in into the absolute ethyl alcohol of 20mL, benzaldehyde is slowly dropped into using separatory funnel
Shitosan, 4h is reacted at a temperature of 70 DEG C.Washed using ethanol wash obtaining shitosan to obtaining product
Schiff.
It is 5% sodium hydrate aqueous solution and the carbon disulfide of 2.0mL to mass fraction is added in Chitosan Schiff Base
Afterwards, it is placed in constant temperature blender with magnetic force.Successively in 20 DEG C of (T1) at a temperature of react 30min (t1) and in 60 DEG C of (T2) at a temperature of
Reaction 240min (t2), xanthogenation shitosan is obtained.
Embodiment 3b
Change the temperature T of pre-reaction1It it is 25 DEG C, remaining is with embodiment 3a.
Embodiment 3c
Change the temperature T of pre-reaction1It it is 30 DEG C, remaining is with embodiment 3a.
Embodiment 3d
Change the temperature T of pre-reaction1It it is 35 DEG C, remaining is with embodiment 3a.
Six groups of copper water samples are taken, every group includes four parts.By embodiment 3a, embodiment 3b, embodiment 3c and embodiment 3d
Obtained xanthogenation shitosan is added to 45mg/L, 60mg/L, 75mg/L, 90mg/L, 105mg/L and 120mg/L respectively
Six groups of copper water samples are placed in stirring in program control coagulation experiment stirring instrument.In 50r/ after 2min being stirred under the rotating speed of 140r/min
10min is stirred under the rotating speed of min, 10min is staticly settled.Determine six groups of copper water samples respectively using atomic absorption spectrophotometer
Residual copper ion concentration.Result is as shown in Figure 4.
From fig. 4, it can be seen that with pre-reaction temperature T1Rising, removal of the xanthogenation shitosan to copper ion take the lead in
Reduce after increase.And, pre-reaction temperature T1For 30 DEG C when obtained xanthogenation shitosan removal effect it is best.Pre-reaction
Temperature T1When relatively low, carbon disulfide is incomplete with NaOH reaction；Pre-reaction temperature T1During rising, reaction rate is improved.But by
There is stronger volatility in carbon disulfide, pre-reaction temperature is controlled under the boiling point of carbon disulfide all the time, to ensure sodium xanthogenate
Yield.
Embodiment 4
Pre-reaction time t1Influence to preparing xanthogenation shitosan.
Embodiment 4a
Weigh 1g shitosans and add in the glacial acetic acid of the 3vol% of 20mL after swelling 30min, plus 20mL absolute ethyl alcohols are dilute
Release.Above sample is transferred to the there-necked flask of 250mL, and there-necked flask is placed in ultrasonic field is stirred and is adjusted pH value for 5.
After the benzaldehyde of 7 times of amounts of chitosan material is dissolved in into the absolute ethyl alcohol of 20mL, benzaldehyde is slowly dropped into using separatory funnel
Shitosan, 4h is reacted at a temperature of 70 DEG C.Washed using ethanol wash obtaining shitosan to obtaining product
Schiff.
After adding mass fraction to be 5% sodium hydroxide solution and the carbon disulfide of 2.0mL in Chitosan Schiff Base,
It is placed in constant temperature blender with magnetic force.Successively in 20 DEG C of (T1) at a temperature of react 0min (t1) and in 60 DEG C of (T2) at a temperature of react
240min(t2), xanthogenation shitosan is obtained.It is appreciated that without pre-reaction process.
Embodiment 4b
Change pre-reaction time t1It is 15min, remaining is with embodiment 4a.
Embodiment 4c
Change pre-reaction time t1It is 30min, remaining is with embodiment 4a.
Embodiment 4d
Change pre-reaction time t1It is 45min, remaining is with embodiment 4a.
Six groups of copper water samples are taken, every group includes four parts.By embodiment 4a, embodiment 4b, embodiment 4c and embodiment 4d
Obtained xanthogenation shitosan is added to 45mg/L, 60mg/L, 75mg/L, 90mg/L, 105mg/L and 120mg/L respectively
Six groups of copper water samples are placed in stirring in program control coagulation experiment stirring instrument.In 50r/ after 2min being stirred under the rotating speed of 140r/min
10min is stirred under the rotating speed of min, 10min is staticly settled.Determine six groups of copper water samples respectively using atomic absorption spectrophotometer
Residual copper ion concentration.Result is as shown in Figure 5.
From fig. 5, it can be seen that with pre-reaction time t1Increase, removal of the xanthogenation shitosan to copper ion take the lead in
Reduce after increase.As pre-reaction time t1During for 30min, xanthogenation shitosan is to the clearance highest of copper ion, clearance
Reach 97.7%.Pre-reaction time t1It is shorter, react insufficient；But pre-reaction time t1More long, it may occur that side reaction, influence is yellow
The yield of former acidified chitosan.
Embodiment 5
Main reaction temperature T2Influence to preparing xanthogenation shitosan.
Embodiment 5a
Weigh 1g shitosans and add in the glacial acetic acid of the 3vol% of 20mL after swelling 30min, plus 20mL absolute ethyl alcohols are dilute
Release.Above sample is transferred to the there-necked flask of 250mL, and there-necked flask is placed in ultrasonic field is stirred and is adjusted pH value for 5.
After the benzaldehyde of 7 times of amounts of chitosan material is dissolved in into the absolute ethyl alcohol of 20mL, benzaldehyde is slowly dropped into using separatory funnel
Shitosan, 4h is reacted at a temperature of 70 DEG C.Washed using ethanol wash obtaining shitosan to obtaining product
Schiff.
After adding mass fraction to be 5% sodium hydroxide solution and the carbon disulfide of 2.0mL in Chitosan Schiff Base,
It is placed in constant temperature blender with magnetic force.Successively in 20 DEG C of (T1) at a temperature of react 30min (t1) and in 40 DEG C of (T2) at a temperature of react
240min(t2), xanthogenation shitosan is obtained.
Embodiment 5b
Change main reaction temperature T2It it is 50 DEG C, remaining is with embodiment 5a.
Embodiment 5c
Change main reaction temperature T2It it is 60 DEG C, remaining is with embodiment 5a.
Embodiment 5d
Change main reaction temperature T2It it is 70 DEG C, remaining is with embodiment 5a.
Six groups of copper water samples are taken, every group includes four parts.By embodiment 5a, embodiment 5b, embodiment 5c and embodiment 5d
Obtained xanthogenation shitosan is added to 45mg/L, 60mg/L, 75mg/L, 90mg/L, 105mg/L and 120mg/L respectively
Six groups of copper water samples are placed in stirring in program control coagulation experiment stirring instrument.In 50r/ after 2min being stirred under the rotating speed of 140r/min
10min is stirred under the rotating speed of min, 10min is staticly settled.Determine six groups of copper water samples respectively using atomic absorption spectrophotometer
Residual copper ion concentration.Result is as shown in Figure 6.
From fig. 6, it can be seen that xanthogenation shitosan to the clearance of copper ion with main reaction temperature T2Increase and
First increases and then decreases.And, main reaction temperature T2For 60 DEG C when, xanthogenation shitosan goes to the clearance highest of copper ion
Except rate reaches 97.7%.
Embodiment 6
Main reaction time t2Influence to preparing xanthogenation shitosan.
Embodiment 6a
Weigh 1g shitosans and add in the glacial acetic acid of the 3vol% of 20mL after swelling 30min, plus 20mL absolute ethyl alcohols are dilute
Release.Above sample is transferred to the there-necked flask of 250mL, and there-necked flask is placed in ultrasonic field is stirred and is adjusted pH value for 5.
After the benzaldehyde of 7 times of amounts of chitosan material is dissolved in into the absolute ethyl alcohol of 20mL, benzaldehyde is slowly dropped into using separatory funnel
Shitosan, 4h is reacted at a temperature of 70 DEG C.Washed using ethanol wash obtaining shitosan to obtaining product
Schiff.
After adding mass fraction to be 5% sodium hydroxide solution and the carbon disulfide of 2.0mL in Chitosan Schiff Base,
It is placed in constant temperature blender with magnetic force.Successively in 20 DEG C of (T1) at a temperature of react 30min (t1) and in 60 DEG C of (T2) at a temperature of react
120min(t2), xanthogenation shitosan is obtained.It is appreciated that without pre-reaction process.
Embodiment 6b
Change main reaction time t2It is 180min, remaining is with embodiment 6a.
Embodiment 6c
Change main reaction time t2It is 240min, remaining is with embodiment 6a.
Embodiment 6d
Change main reaction time t2It is 300min, remaining is with embodiment 6a.
Six groups of copper water samples are taken, every group includes four parts.By embodiment 6a, embodiment 6b, embodiment 6c and embodiment 6d
Obtained xanthogenation shitosan is added to 45mg/L, 60mg/L, 75mg/L, 90mg/L, 105mg/L and 120mg/L respectively
Six groups of copper water samples are placed in stirring in program control coagulation experiment stirring instrument.In 50r/ after 2min being stirred under the rotating speed of 140r/min
10min is stirred under the rotating speed of min, 10min is staticly settled.Determine six groups of copper water samples respectively using atomic absorption spectrophotometer
Residual copper ion concentration.Result is as shown in Figure 7.
From figure 7 it can be seen that with pre-master it is seasonable between t2Increase, removal of the xanthogenation shitosan to copper ion take the lead in
Reduce after increase.As main reaction time t2During for 240min, xanthogenation shitosan is to the clearance highest of copper ion, clearance
Reach 97.7%.Main reaction time t2It is shorter, react insufficient；But main reaction time t2More long, it may occur that side reaction, influence is yellow
The yield of former acidified chitosan.
Application examples 1
Weigh 1g shitosans and add in the glacial acetic acid of the 3vol% of 20mL after swelling 30min, plus 20mL absolute ethyl alcohols are dilute
Release.Above sample is transferred to the there-necked flask of 250mL, and there-necked flask is placed in ultrasonic field is stirred and is adjusted pH value for 5.
After the benzaldehyde of 7 times of amounts of chitosan material is dissolved in into the absolute ethyl alcohol of 20mL, benzaldehyde is slowly dropped into using separatory funnel
Shitosan, 4h is reacted at a temperature of 70 DEG C.Washed using ethanol wash obtaining shitosan to obtaining product
Schiff.
After adding mass fraction to be 5% sodium hydroxide solution and the carbon disulfide of 2.0mL in Chitosan Schiff Base,
It is placed in constant temperature blender with magnetic force.Successively in 30 DEG C of (T1) at a temperature of react 30min (t1) and in 60 DEG C of (T2) at a temperature of react
240min(t2), xanthogenation shitosan is obtained.
The copper water sample that six parts of initial copper ion concentrations are 25mg/L is taken, is adjusted successively and is connect its pH value and be：3.0、4.0、5.0、
6.0th, 7.0 and 8.0, obtained xanthogenation shitosan is added thereto carries out flocculating experiment, and its result is shown in Fig. 8.
From figure 8, it is seen that when the pH value of copper water sample is 6.0, when the dosage of xanthogenation shitosan is 90mg/L,
The clearance highest of copper ion, clearance is up to 97.7%.It is appreciated that with the rising of pH value in waste water, xanthogenation shell
The xanthogen that glycan participates in reaction increases, and the sequestering power with copper ion strengthens；When pH value can influence chelating flco to give birth to more than 6
Into the reduction of copper ion clearance.In use, the pH value of waste water is adjusted into 6 being advisable.
Application examples 2
Xanthogenation shitosan is prepared with the method for application examples 1.
It is 6.0 and the cupric of copper ion initial mass concentration respectively 5mg/L, 15mg/L, 25mg/L, 50mg/L to take pH value
Water sample, being separately added into xanthogenation shitosan carries out flocculating experiment, as a result as shown in Figure 9.
From fig. 9, it can be seen that there is optimal dispensing point in the xanthogenation shitosan copper water sample different to initial concentration
(i.e. dosage).When xanthogenation shitosan input amount increases, the group for participating in reaction increases, and flco is collided and chelating ligands
Probability increases, and settling property enhancing causes the clearance of copper ion to raise；When reaching optimal dispensing point, copper ion clearance is most
It is high.After xanthogenation shitosan exceedes optimal dispensing point, there is excessive electronegative xanthogenation shitosan in system,
The reduction of flco collision probability is difficult coagulation, therefore the clearance of copper ion is reduced.
Embodiments described above is a part of embodiment of the invention, rather than whole embodiments.Reality of the invention
The detailed description for applying example is not intended to limit the scope of claimed invention, but is merely representative of selected implementation of the invention
Example.Based on the embodiment in the present invention, what those of ordinary skill in the art were obtained under the premise of creative work is not made
Every other embodiment, belongs to the scope of protection of the invention.
Claims (10)
1. a kind of preparation method of xanthogenation shitosan, it is characterised in that including：It is poly- to the shell with shitosan as substrate
The amino of sugar carries out protecting prepared Chitosan Schiff Base, thio in the shitosan parent grafting two of the Chitosan Schiff Base
Carboxyl is obtained.
2. the preparation method of xanthogenation shitosan according to claim 1, it is characterised in that the dithiocarboxyl connects
Branch is in the C of the shitosan parent6Position.
3. the preparation method of xanthogenation shitosan according to claim 1, it is characterised in that the shitosan Schiff
Alkali is obtained by following steps：It is 1 according to the ratio of the amount of material by shitosan and aldehyde compound：After 5~10 mixing, 60~80
3~6h is reacted at a temperature of DEG C.
4. the preparation method of xanthogenation shitosan according to claim 3, it is characterised in that the shitosan with institute
Before stating aldehyde compound mixing, it is swelling in glacial acetic acid after diluted with absolute ethyl alcohol.
5. the preparation method of xanthogenation shitosan according to claim 4, it is characterised in that the aldehyde compound choosing
At least one from fatty aldehyde and aromatic aldehyde, preferably described fatty aldehyde is selected from acetaldehyde, propionic aldehyde, glutaraldehyde, hexanal, octanal, certain herbaceous plants with big flowers
At least one in aldehyde and lauric aldehyde, preferably described aromatic aldehyde be selected from salicylide, furfural, benzaldehyde, nitrobenzaldehyde, to diformazan
At least one in amido benzaldehyde and hydroxy benzaldehyde, more preferably selects at least one in salicylide, furfural and benzaldehyde,
It is most preferably selected from benzaldehyde.
6. the preparation method of xanthogenation shitosan according to claim 1, it is characterised in that the grafting two thio carboxylic
The step of base, includes：The Chitosan Schiff Base, alkali and carbon disulfide mixing after, at a temperature of 20~35 DEG C react 0~
After 45min, 120~300min is reacted at a temperature of 40~70 DEG C prepared.
7. the preparation method of xanthogenation shitosan according to claim 6, it is characterised in that the shitosan with it is described
The mol ratio of carbon disulfide is 1：2~8, preferably 1：2~7, more preferably 1：2.5~6.5.
8. the preparation method of xanthogenation shitosan according to claim 6, it is characterised in that the alkali is inorganic base,
Preferably inorganic strong alkali, more preferably alkali metal hydroxide, such as NaOH, potassium hydroxide and lithium hydroxide.
9. the preparation method of the xanthogenation shitosan according to claim 6 or 8, it is characterised in that the shitosan with
The mol ratio of the alkali is 1：4~24, preferably 1：5~22, more preferably 1：5~20.
10. a kind of xanthogenation shitosan, it is characterised in that the xanthogenation shell according to any one of claim 1~9 gathers
The preparation method of sugar is obtained.
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