CN110124624A - A kind of preparation method of the dithiocar-bamate adsorbent based on corn stalk fiber element - Google Patents
A kind of preparation method of the dithiocar-bamate adsorbent based on corn stalk fiber element Download PDFInfo
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- CN110124624A CN110124624A CN201910444341.0A CN201910444341A CN110124624A CN 110124624 A CN110124624 A CN 110124624A CN 201910444341 A CN201910444341 A CN 201910444341A CN 110124624 A CN110124624 A CN 110124624A
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- 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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Abstract
The present invention discloses a kind of preparation method based on corn stalk fiber element dithiocar-bamate adsorbent, belongs to effluent containing heavy metal ions processing and field of environment protection.The corn stalk fiber element that purification obtains successively is reacted to obtain dithiocar-bamate adsorbent with epoxychloropropane, polyethyleneimine, carbon disulfide, product is lurid fiber dust.Adsorbent material in the present invention can effectively handle heavy metal ion-containing waste water, all have good adsorption effect to the various heavy metal ion such as copper, lead, cadmium.The present invention has many advantages, such as that preparation method is simple, raw material are cheap and easy to get, adsorption efficiency is good, can recycled for multiple times, degradable.
Description
Technical field
The present invention relates to a kind of preparation method based on corn stalk fiber element dithiocar-bamate adsorbent and answer
With technology, belong to Industrial Waste Water Treatments range, is to handle the Industry Waste containing heavy metal ion using the adsorbent specifically
Water all has effective removal effect in pH > 3 to heavy metal ion such as copper, lead, chromium, and treated, and waste water can reach state
The discharge standard that family requires.
Background technique
With the rapid development of China's modern industry, effluent containing heavy metal ions are environmentally safe and biological health causes sternly
The threat of weight.Since to have the characteristics that toxicity big, difficult to degrade for heavy metal ion, thus how to carry out appropriate recycling to it is mesh
Preceding people's urgent problem to be solved.
A kind of Chinese patent " preparation method and application of corn stalk fiber element xanthic acid magnesium salts " (application number
201510475001.6) a kind of method that adsorbent is prepared as raw material using corn stover and carbon disulfide is disclosed.Chinese patent
One kind is disclosed in " a kind of modified peanut shell cationic adsorbent preparation method and application " (publication No. CN102553538A)
A kind of method for preparing cation adsorbent as raw material using peanut shell, triethylene tetramine.But the absorption prepared by these methods
Agent all has the shortcomings that adsorption capacity is small, the rate of adsorption is slow.
Surface area, surface topography, the surface functional group of adsorbent all have significant impact to absorption property.Corn stalk
Stalk fiber element has many advantages, such as renewable, cheap, large specific surface area, is easily modified, and is a kind of good biomass carrier.It is logical
The method of purification in the present invention is crossed, finely dispersed tubular fiber element has been obtained, has been a kind of with the outstanding of bigger serface
Adsorbing agent carrier.Polyethyleneimine is a kind of high molecular polymer of height collateralization, containing a large amount of amino group, with two sulphur
Changing the dithiocarbamate-based group formed after carbon esterification has more excellent sequestering power to heavy metal ion.For these spies
Point, the present invention in will be amine-modified in cellulose surface with three-dimensional netted polyethyleneimine, generation is then reacted with carbon disulfide
Dithiocarbamate-based group is prepared for a kind of adsorbent with Large ratio surface again with outstanding adsorption capacity.Carry out
When adsorption operations, the functional group of adsorbent surface realizes the efficient trapping to heavy metal ion just as fine and close fishing net.
Summary of the invention
There is outstanding heavy metal ion trapping ability but soluble easily in water and corn stalk fiber for polyethyleneimine
The feature that plain utilization rate is low, adsorption effect is poor, the purpose of the present invention is to provide a kind of two sulphur based on corn stalk fiber element
For the preparation method of carbaminate adsorbent, method is simple, raw material is easy to get.
It is another object of the present invention to provide a kind of corn stalk fiber element dithiocar-bamate adsorbents
Using.The adsorbent of the method for the invention preparation can be used for the processing of heavy metal ion-containing waste water, can be to copper, lead, cadmium
Ion is efficiently removed.
To achieve the above object, technical scheme is as follows:
A kind of preparation method of the dithiocar-bamate based on corn stalk fiber element of the present invention, the method are as follows:
(1) corn stover is cleaned, crushed, be sieved after dry, obtain maize straw powder to be processed；
(2) maize straw powder after weighing screening is added in sodium chlorite aqueous solution, using the p hour of second acid-conditioning solution,
Using secondary water washing filtering after reaction, the white stalk powder of removal lignin is obtained.
(3) obtained stalk powder in step (2) is soaked in lye, to remove hemicellulose and destroy cellulose
Intermolecular hydrogen bonding is activated, and is successively filtered using secondary water and ethanol washing, and the cellulose powder of white is obtained after dry.
(4) immersion of cellulose powder obtained in step (3) is swollen in a solvent, then carries out ether with epoxychloropropane
Change reaction, obtains etherified cellulose after filtering.
(5) by etherified cellulose obtained in step (4) and polyethyleneimine solution reaction, then successively using secondary water and
Ethyl alcohol carries out washing filtering, obtains aminocellulose powder.
(6) obtained aminocellulose will be immersed in lye in step (5), under room temperature using constant pressure titration funnel by
Carbon disulfide is added dropwise in drop, and rear temperature reaction is added dropwise.Washing filtering successively is carried out using secondary water and ethyl alcohol after completion of the reaction,
Vacuum drying, grinding, finally obtain lurid corn stalk fiber element dithiocar-bamate adsorbent.
After corn stover in the step (1) is cleaned, in thermostatic drying chamber 80-110 DEG C it is 12-24 hours dry；It crosses
50 meshes are used when sieve.
Reaction temperature is 70-80 DEG C in the step (2), reaction time 2-3 hour, mechanical stirring；It is adjusted using acetic acid
The pH of sodium chlorite aqueous solution is 4-5, and the half an hour before reaction terminates, adding quality is stalk powder quality 1/10th
Sodium chlorite.
Lye used in the step (3) is sodium hydroxide, the potassium hydroxide solution of 8-15%；In a vacuum drying oven
It is dried in vacuo 10-15 hours at 60 DEG C.
Solvent is one kind of dimethylformamide, dimethyl acetamide in the step (4)；It first will treated stalk
Powder is adequately swollen in a solvent, and temperature is 50 DEG C, and the time is 1-2 hours；Wherein cellulose powder and solvent, epoxy
The dose ratio of chloropropane is 2 g:20 mL:5 mL.
The molecular weight of polyethyleneimine is 5000-10000 in the step (5).
Lye is sodium hydroxide, the potassium hydroxide solution of 10-20% in the step (6)；Wherein carbon disulfide will be dissolved in
In ethanol solution so as to fibrin reaction；Wherein the dose ratio of cellulose powder and aqueous slkali, carbon disulfide, ethyl alcohol is 2 g:
20 mL:5 mL:5 mL。
Beneficial effect
1. the present invention has the characteristics that efficient removal ability to heavy metal ion for polyethyleneimine, being loaded to has greatly
On the corn stalk fiber element of specific surface, then by being reacted with carbon disulfide, to make the adsorbent that there is very outstanding suction
Attached ability.The preparation method both can provide an approach for the utilization of agriculture and forestry organic waste material, also have to the improvement of environment positive
Meaning, and sorbent material is also biodegradable.
2. corn stalk fiber element dithiocar-bamate adsorbent of the invention, is experimentally confirmed: invention behaviour
Make the adsorbent epigranular that step is simple, obtains, property is stablized, and has very high absorption appearance to copper, lead, the cadmium ion in water
Amount and the cracking rate of adsorption.Biological adsorption agent of the invention can be realized by desorption and is recycled, and be made by 5 circulations
It remains to be maintained at 95% or so with rear adsorption efficiency.
Detailed description of the invention
Fig. 1 is that the process of the invention for preparing cellulose base dithiocar-bamate adsorbent using corn stover is illustrated
Figure.
Fig. 2 is according to embodiments of the present invention 1, the SEM figure of obtained Studies On Preparation And Properties of Cellulose-based Adsorbents.
Fig. 3 is according to embodiments of the present invention 4, obtained Studies On Preparation And Properties of Cellulose-based Adsorbents circular regeneration effect picture.
Specific embodiment
The contents of the present invention are described further combined with specific embodiments below, but the present invention be not limited solely to it is following
Embodiment, specific steps are referring to each embodiment.
Embodiment 1
(1) corn stover is cleaned, is crushed, sieved with 100 mesh sieve after dry, obtains maize straw powder to be processed；
(2) it takes 20 g maize straw powders that the sodium chlorite aqueous solution that 500 mL mass fractions are 2 % is added, 5 mL is then added dropwise
Acetic acid, 75 DEG C at a temperature of reaction 2 hours after, add 2 g sodium chlorites and 1 mL acetic acid, the reaction was continued 30 min.Make
Filtering is washed with secondary water, obtains the stalk powder of removal lignin.
(3) obtained stalk powder in step (2) is soaked in the sodium hydroxide solution of 500 mL, 10 %, 35
It is reacted 8 hours at a temperature of DEG C, is activated to remove hemicellulose and destroy intermolecular hydrogen bonding, successively use secondary water
It is filtered with ethanol washing, gained powder is dried in a vacuum drying oven, the cellulose powder after finally obtaining purification.
(4) 5 g cellulose powders are weighed to be immersed in 100 mL DMF solvents, are swollen 2 hours at 50 DEG C, then with
10 mL epoxychloropropane are etherified at 100 DEG C, and reaction continues 1 hour, and etherified cellulose is obtained by filtration.
(5) 5 g etherified celluloses are then weighed to react with the polyethylenimine solution that 5 mL molecular weight are 7500, is used
DMF makees solvent, reacts 2 hours at 100 DEG C, then carries out washing filtering using secondary water, obtain milky amino fibre
Plain powder.
(6) 5 g aminocelluloses are weighed to be placed in there-necked flask, the sodium hydroxide solution of 100 mL, 20 % is then added,
The CS that 25mL volume fraction is 20% is added dropwise dropwise using constant pressure titration funnel at room temperature2Ethanol solution, heat up after being added dropwise
It is reacted 2 hours to 45 DEG C.Washing filtering successively is carried out using secondary water and ethyl alcohol after completion of the reaction, at 70 DEG C of vacuum oven
Drying crushes, and finally obtains lurid corn stover dithiocar-bamate.
Embodiment 2
Corn stalk fiber element is made according to preceding 3 steps in embodiment 1, the corn stalk fiber after then taking 5 g to activate
Element is placed in 100 mL DMA, is swollen 2 hours at room temperature, and 15 mL epoxychloropropane are then added and carry out etherification reaction, filtering
Obtain etherified cellulose.Then the polyethylenimine solution for being 10000 with 5 mL molecular weight reacts 1 hour at 100 DEG C again, according to
It is secondary to be filtered using secondary water and ethanol washing, obtain aminocellulose.Obtained aminocellulose is placed in there-necked flask, then
10% sodium hydroxide solution of 100 mL is added, 25 mL volume fractions are added dropwise dropwise using constant pressure titration funnel at room temperature is
20% CS2Ethanol solution, be warming up to after being added dropwise 45 DEG C react 2 hours.Then successively using secondary water and ethyl alcohol into
Row washing filters, and 70 DEG C of drying, crushing, obtain lurid cellulose base aminodithioformic acid in a vacuum drying oven
Salt.
Embodiment 3
The adsorbent is tested to the removal ability of different heavy metal ion: respectively using copper nitrate, plumbi nitras, cadmium nitrate as raw material,
The solion for the use of secondary water configuration concentration being 100 mg/L, the pH value of solution are natural value.Take 5 mL copper (II), lead
(II), cadmium (II) solution is respectively placed in the concussion pipe of 10 mL, and 0.01g cellulose base aminodithioformic acid is then respectively added
Salt adsorbent shakes 30 minutes at 25 DEG C, filtering, takes supernatant using the residue of flame atomic absorption method detection metal ion
Amount, experiments have shown that the adsorbent reaches 99.9% to the removal rate of copper (II), lead (II), cadmium (II).
Embodiment 4
Test the renewable ability of the adsorbent: the adsorbent after collecting absorption, using the nitric acid solution of 0.5 M come to absorption
Agent is recycled.Then its absorption property is tested according still further to the method in embodiment 3, experimental result is as shown in figure 3, the suction
Attached dose has stilled remain in 95% or more to removal rate after 5 sorption cycles, to copper, lead, cadmium, it was demonstrated that the adsorbent
With good circular regeneration performance.
Claims (7)
1. the method for preparing dithiocar-bamate adsorbent using corn stalk fiber element, it is characterised in that: specific preparation
Steps are as follows:
(1) it after being cleaned and dried corn stover, is crushed using pulverizer, it is spare then to filter out the powder with certain partial size；
(2) stalk powder obtained in step (1) is reacted with sodium chlorite to remove lignin, wherein being adjusted using acetic acid
The pH of sodium chlorite aqueous solution obtains white powder using secondary water washing filtering after reaction；
(3) obtained white powder in step (2) is reacted with caustic lye of soda to remove hemicellulose, is successively made after reaction
It is filtered with secondary water and ethanol washing, the white fiber element powder after being purified；
(4) cellulose powder obtained in step (3) is impregnated after being swollen a period of time in a solvent, epoxy chloropropionate is then added
Alkane is etherified, and etherified cellulose is obtained by filtration after reaction；
(5) it reacts etherified cellulose obtained in step (4) to obtain aminocellulose with polyethyleneimine, two is used after reaction
Secondary water washing filtering, obtains aminocellulose；
(6) aminocellulose obtained in step (5) is immersed in sodium hydroxide solution, is then esterified with carbon disulfide, instead
It is successively filtered using secondary water and ethanol washing after answering, obtains target affinity agent after dry.
2. method of the preparation based on corn stalk fiber element dithiocar-bamate adsorbent according to claim 1,
It is characterized by: after the corn stover defoliation in the step (1) is cleaned, the 80-110 DEG C of dry 10-24 in thermostatic drying chamber
Hour, it is screened after crushing using 50-200 mesh.
3. the preparation method according to claim 1 based on corn stalk fiber element dithiocar-bamate adsorbent,
It is characterized by: the mass ratio of stalk powder and sodium chlorite in the step (2) is 5:1, reaction temperature is 70-80 DEG C,
Reaction time 2-3 hour, mechanical stirring；PH value of solution is adjusted between 4-5 using acetic acid；The half an hour before reaction terminates, then
The sodium chlorite of stalk powder quality 1/10th is added.
4. the method that the method according to claim 11 prepares corn stalk fiber element dithiocar-bamate adsorbent,
It is characterized by: lye used in the step (3) is sodium hydroxide, the potassium hydroxide solution of 8-15%；In vacuum oven
In be dried in vacuo 10-15 hours at 60 DEG C.
5. method of the preparation based on corn stalk fiber element dithiocar-bamate adsorbent according to claim 1,
It is characterized by: solvent is one kind of dimethylformamide, dimethyl acetamide in the step (4)；First by cellulose powder
End is adequately swollen in a solvent, and temperature is 50 DEG C, and the time is 1-2 hours；Wherein cellulose powder and solvent, epoxy
The dose ratio of chloropropane is 2 g:20 mL:5 mL.
6. method of the preparation based on corn stalk fiber element dithiocar-bamate adsorbent according to claim 1,
It is characterized by: polyethyleneimine molecular weight used in the step (5) is between 5000-10000.
7. method of the preparation based on corn stalk fiber element dithiocar-bamate adsorbent according to claim 1,
It is characterized by: lye is sodium hydroxide, the potassium hydroxide solution of 10-20% in the step (6)；Wherein cellulose powder with
Lye, carbon disulfide, ethyl alcohol dose ratio be 2 g:20 mL:5 mL:5 mL.
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Cited By (3)
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| CN113019335A (en) * | 2021-03-30 | 2021-06-25 | 南昌大学 | Bifunctional modified corn straw cellulose adsorbent, control synthesis method and application |
| CN115814766A (en) * | 2022-12-06 | 2023-03-21 | 武汉市强龙化工新材料有限责任公司 | Polyethyleneimine composite material and preparation method thereof |
| CN117801126A (en) * | 2024-03-01 | 2024-04-02 | 山东百川集大环境工程有限公司 | Cellulose-based multiple binding site heavy metal sewage treatment agent and preparation method and application thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113019335A (en) * | 2021-03-30 | 2021-06-25 | 南昌大学 | Bifunctional modified corn straw cellulose adsorbent, control synthesis method and application |
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| CN117801126A (en) * | 2024-03-01 | 2024-04-02 | 山东百川集大环境工程有限公司 | Cellulose-based multiple binding site heavy metal sewage treatment agent and preparation method and application thereof |
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