CN109985605A - A kind of native starch adsorbing material of water soluble organic dye and preparation method thereof - Google Patents
A kind of native starch adsorbing material of water soluble organic dye and preparation method thereof Download PDFInfo
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- CN109985605A CN109985605A CN201910158364.5A CN201910158364A CN109985605A CN 109985605 A CN109985605 A CN 109985605A CN 201910158364 A CN201910158364 A CN 201910158364A CN 109985605 A CN109985605 A CN 109985605A
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- native starch
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- water soluble
- soluble organic
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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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- 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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28047—Gels
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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
-
- 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
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
Abstract
The invention discloses a kind of for quickly removing the preparation method of the native starch adsorbing material of water soluble organic dye, belongs to environment-friendly materials technical field.The specific steps are that: a certain amount of native starch is completely dissolved to uniform solution in dimethyl sulfoxide at a temperature of 60 DEG C-80 DEG C, a certain amount of highly basic is added, it stirs evenly to form cornstarch highly basic mixed liquor, the dimethyl sulphoxide solution of a certain amount of 0.01-0.5mol/L BADGE is slowly added to said mixture, at a certain temperature, it is reacted 1-12 hours with 300-500 revs/min of stirring condition, washing is multiple and is centrifuged, and isolated milk white gel product is drying to obtain adsorbent.Technical solution of the present invention has excellent absorption property and adsorption rate for the starch base gel adsorber of water soluble organic dye preparation, has bright prospects in the development of environmental protection industry (epi) technology.
Description
Technical field: the invention discloses a kind of native starch adsorbing material of water soluble organic dye and its preparation sides
Method belongs to environment-friendly materials technical field.
Background technique: with the development of the industries such as weaving, leather, biology, there is genotoxic potential and carcinogenicity waste water from dyestuff
Discharge increasingly sharpen.Water soluble organic dye wherein with hydrophilic radicals such as hydroxyl, carboxyl, amino and sulfonic groups
(WSODs) the more difficult removal because having certain solubility in water, causes to seriously threaten to human health and water ecological environment.
Therefore water soluble organic dye adsorbent material efficiently, environmentally friendly is studied, the method that water soluble organic dye quickly removes is established, it is right
Water prevention and cure of pollution and the development of human health are of great significance.
Currently, Coagulation Method, chemical oxidization method, membrane filter method, electrochemical process, biochemical process and absorption method etc. are common
Remove water soluble organic dye method, wherein absorption method because its have many advantages, such as it is easy to operate, reuse, economically feasible by
To extensive concern.And starch and its derivative due to chemical stability is good, reactivity is high, rich reserves, it is cheap,
The features such as pollution-free, renewable and the raw material for being more and more used to prepare adsorbent material.But native starch itself does not have
The standby specific function group that can be interacted with contaminant molecule, so generally need to chemical method using crosslinking agent by being crosslinked
Starch is modified, to prepare high performance effect adsorbent material.
Present invention research for crosslinking agent, is prepared for a kind of novel, efficient absorption with bisphenol A diglycidyl ether (BADGE)
The modified starch adsorbing material of performance, improves the absorption property to water soluble organic dye.
Summary of the invention:
For the shortcomings in the field, the purpose of the present invention is to provide one kind quickly, efficiently removal is water-soluble organic
The native starch adsorbing material of dyestuff.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is that:
A kind of native starch adsorbing material quickly, efficiently removing water soluble organic dye, which is characterized in that including such as
Lower step:
1) certain mass native starch is added in dimethyl sulfoxide solvent, is heated to 60 DEG C -80 DEG C, keep temperature constant
10-50min；
2) alkaline drug is added in the 1 of above-mentioned preparation) solution, 60 DEG C of -80 DEG C of temperature of constant temperature are kept, be vortexed concussion 3-
30min, it is spare；
3) dimethyl sulphoxide solution for preparing 0.01-0.5mol/L BADGE, be vortexed concussion 1-5min, stands, spare；
4) by above-mentioned steps 3) above-mentioned steps 2 are added in solution) in solution, temperature is held constant at 60 DEG C -80 DEG C, 50-
800rpm stirring is lower to react 1-12h；
5) organic solvent and deionized water washing reaction product, centrifugation after completion of the reaction, are used respectively, and it is solidifying to obtain white
Gum-like product, freeze-drying, obtains adsorbent material, spare.
Further, the step 1) native starch include tapioca, sweet potato starch, starch from sweet potato, potato starch,
Cornstarch it is one or more.
Further, the additional amount of the step 1) native starch is the 0.02-0.5 wt% of dimethyl sulfoxide quality.
Further, step 2) the alkaline drug is sodium hydroxide, Anhydrous potassium carbonate, one of potassium hydroxide or more
Kind, preferably drug is sodium hydroxide.
Further, the step 2) addition amount of sodium hydroxide is the 0.005-0.01 wt% of cornstarch quality.
Further, step 4) the BADGE additional amount is 0.01-1wt% of step 1) the cornstarch quality.
Further, step 4) reaction system mixing speed is preferably 300-500rpm.
Further, the step 5) organic solvent be one or more of methylene chloride, ethyl alcohol, acetone, acetonitrile, it is excellent
Selecting organic solvent is methylene chloride, ethyl alcohol.
The embodiment of the invention also provides the native starch adsorbing materials being prepared by preceding method.
Detailed description of the invention:
Fig. 1 is that SEM shape appearance figure is lyophilized in 1 starch adsorbing material of the embodiment of the present invention.
Fig. 2 is that SEM shape appearance figure is lyophilized in 2 starch adsorbing material of the embodiment of the present invention.
Fig. 3 is that shape appearance figure is not lyophilized for 3 starch adsorbing material of the embodiment of the present invention.
The beneficial effects of the present invention are:
It is proposed by the present invention a kind of for quickly removing the native starch adsorbing material of water soluble organic dye, have at
The advantages that this is low, preparation is simple, good water solubility, environmental protection, high, quick removal efficiency.The adsorbent material is using native starch as former material
Material, using BADGE as crosslinking agent, is introduced greatly by crosslinked action on the starch material surface with great amount of hydroxy group hydrophilic radical
Hydrophobic grouping is measured, is prepared for that there is the hydrophobic native starch adsorbing material of hydrophilic, hydrophobic grouping parent-simultaneously.The native starch
Adsorbing material not only water solubility with higher, but also there is enough hydrophobicitys, it is significant to water soluble organic dye absorption property
It improves.The native starch adsorbing material provides a kind of new absorption quickly to remove water soluble organic dye in environmental system
Material, this is of great significance and preferable application value in terms of improving existing water soluble organic dye adsorbent material.
Specific embodiment:
The following examples are used to illustrate the present invention, but are not intended to limit the scope of the present invention..
Unless otherwise specified, the conventional means that technological means used in embodiment is well known to those skilled in the art.
With reference to the accompanying drawing and specific embodiment the invention will be further described.
Embodiment 1
Weigh 10g cornstarch to be added in three-neck flask, 50g dimethyl sulfoxide be added thereto, when being heated to 70 DEG C to
0.07g NaOH is wherein added to mix, it is spare.1.498g BADGE is dissolved in the dimethyl sulfoxide of 5g, is mixed, then in 2h
It is slowly dropped in above-mentioned three-neck flask.Holding revolving speed is 450rmp, and temperature of reaction system is 70 DEG C, is reacted 10 hours.Centrifugation
Then precipitated product is obtained milk white gel, is lyophilized with methylene chloride, ethyl alcohol, distillation water washing respectively.
Embodiment 2
Weigh 10g cornstarch to be added in three-neck flask, 50g dimethyl sulfoxide be added thereto, when being heated to 70 DEG C to
0.07g NaOH is wherein added to mix, it is spare.8.99g BADGE is dissolved in the dimethyl sulfoxide of 5g, is mixed, is then delayed in 2h
Slowly it is added drop-wise in above-mentioned three-neck flask.Holding revolving speed is 450rmp, and temperature of reaction system is 70 DEG C, is reacted 10 hours.Centrifugation is heavy
Shallow lake product, and obtained milk white gel with methylene chloride, ethyl alcohol, distillation water washing respectively, be lyophilized.
Embodiment 3
Weigh 10g cornstarch to be added in three-neck flask, 50g dimethyl sulfoxide be added thereto, when being heated to 70 DEG C to
0.07g NaOH is wherein added to mix, it is spare.1.498g BADGE is dissolved in the dimethyl sulfoxide of 5g, is mixed, then in 2h
It is slowly dropped in above-mentioned three-neck flask.Holding revolving speed is 450rmp, and temperature of reaction system is 70 DEG C, is reacted 10 hours.Centrifugation
Precipitated product is obtained such as following figure light yellow gel.
Embodiment 4
The step of according to embodiment 1, changes native starch type, the additional amount of BADGE, dimethyl sulfoxide, NaOH, changes
Become the experiment conditions such as reaction time, mixing speed, temperature, synthesizes ten kinds of different native starch adsorbing materials, it is spare.Tool
Experiment condition in body embodiment is as shown in table 1.
The selected basic fuchsin belonged in WSODs utilizes starch base adsorption material made from above-mentioned steps as research object
Material carries out Adsorption thermodynamics experimental study: compound concentration is in the Basic Fuchsin in Aqueous Solution of 50-800mg/L as target stains first
Object takes 20ml Basic Fuchsin in Aqueous Solution in colorimetric bottle under each concentration gradient, and the absorption of starch base made from 50mg is added
Agent.Under the conditions of 25 DEG C of temperature, sample is placed in shake in the shaking table that speed is 180rpm and reacts 2h.Then sample taking-up is made
With 0.45 μm of polypropylene syringe filter separating adsorbent from solution.The concentration for adsorbing the Basic Fuchsin in Aqueous Solution of front and back is purple
Outside-Visible Spectroscopy measures.This experiment is averaged so three parts of sample.
Adsorption capacity calculation formula is as follows:
Wherein qe and qm (mg/g) is the equilibrium adsorption capacities and maximum adsorption capacity of Langmuir monolayer adsorption. Ce
(mg/L) be dyestuff equilibrium concentration.KLIt (L/mg) is Lang Gemiaoer constant.The maximum of different native starch adsorbing materials is inhaled
Attached capacity Qm is as shown in table 1.
The selected basic fuchsin belonged in WSODs as research object, prepared by the method starch-based absorbent into
Row the adsorption kinetic data research: compound concentration is the Basic Fuchsin in Aqueous Solution of 100mg/L as target contaminant first, takes 20ml
Starch-based absorbent made from 50mg is added in colorimetric bottle in Basic Fuchsin in Aqueous Solution.Under the conditions of the temperature of 298K, by sample
It is placed in shake in the shaking table that speed is 180rpm and react, sampled in the time gradient of 0-60min respectively.Then sample taking-up is made
With 0.45 μm of polypropylene syringe filter separating adsorbent from solution.The concentration for adsorbing the Basic Fuchsin in Aqueous Solution of front and back is purple
Outside-Visible Spectroscopy measures.This experiment is averaged so three parts of sample.The following institute of adsorption capacity calculation formula
Show:
Wherein qe and qm (mg/g) is the equilibrium adsorption capacities and maximum adsorption capacity of pseudo- first order kinetics fitting.k1
(min-1) it is pseudo- First order kinetic constant.
From table 1 it follows that equilibrium adsorption capacities are distributed between 4.6-359.4mg/g, maximum adsorption capacity can
Reach 359.4mg/g, much higher than similar other adsorbent materials to the adsorption capacity of basic fuchsin.It should be the result shows that this research synthesizes
Native starch adsorbing material to WSODs have good adsorption capacity.
In addition, starch-based absorbent can reach the absorption of basic fuchsin substantially from table 1 it can also be seen that in 2-5min
To saturation state, compared with similar other adsorbent materials of existing registration, the present invention is exceedingly fast to basic fuchsin adsorption rate.The knot
Fruit shows that the native starch adsorbing material of this research synthesis has faster adsorption rate to WSODs.
Claims (9)
1. a kind of native starch adsorbing material preparation method of water soluble organic dye, which comprises the steps of:
1) certain mass native starch is added in dimethyl sulfoxide solvent, is heated to 60 DEG C -80 DEG C, keep the constant 10- of temperature
50min；
2) alkaline drug is added in the 1 of above-mentioned preparation) solution, 60 DEG C of -80 DEG C of temperature of constant temperature are kept, be vortexed concussion 3-30min, standby
With；
3) dimethyl sulphoxide solution for preparing 0.01-0.5mol/L bisphenol A diglycidyl ether, be vortexed concussion 1-5min, stands,
It is spare；
4) by above-mentioned steps 3) above-mentioned steps 2 are added in solution) in solution, temperature is held constant at 60 DEG C -80 DEG C, 50-800rpm
Stirring is lower to react 1-12h；
5) after completion of the reaction, white gels shape is obtained with organic solvent and deionized water washing reaction product, centrifugation respectively
Product, freeze-drying, obtains adsorbent material.
2. the method according to claim 1, wherein the native starch include tapioca, it is sweet potato starch, red
Sweet potato starch, potato starch, cornstarch it is one or more.
3. the method according to claim 1, wherein the additional amount of the native starch is dimethyl sulfoxide quality
0.02-0.5wt%.
4. the method according to claim 1, wherein the alkalinity drug is sodium hydroxide, Anhydrous potassium carbonate, hydrogen
One of potassium oxide is a variety of, and preferably drug is sodium hydroxide.
5. the method according to claim 1, wherein the alkalinity adding amount of medicines is native starch quality
0.005-0.01wt%.
6. the method according to claim 1, wherein the bisphenol A diglycidyl ether additional amount is natural forms sediment
0.01-1wt% of silty amount.
7. the method according to claim 1, wherein reaction system mixing speed is preferably 300-500rpm.
8. the method according to claim 1, wherein the organic solvent is methylene chloride, ethyl alcohol, acetone, second
One or more of nitrile, preferable organic solvent are methylene chloride, ethyl alcohol.
9. the native starch adsorbing material being prepared by method of any of claims 1-8.
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| CN201910158364.5A CN109985605A (en) | 2019-03-01 | 2019-03-01 | A kind of native starch adsorbing material of water soluble organic dye and preparation method thereof |
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| CN201910158364.5A CN109985605A (en) | 2019-03-01 | 2019-03-01 | A kind of native starch adsorbing material of water soluble organic dye and preparation method thereof |
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