CN107226507A - A kind of preparation method of the cysteine-modifying celluloses of L for removal of heavy metal ions - Google Patents
A kind of preparation method of the cysteine-modifying celluloses of L for removal of heavy metal ions Download PDFInfo
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- CN107226507A CN107226507A CN201710492534.4A CN201710492534A CN107226507A CN 107226507 A CN107226507 A CN 107226507A CN 201710492534 A CN201710492534 A CN 201710492534A CN 107226507 A CN107226507 A CN 107226507A
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- modified cellulose
- cellulose
- heavy metal
- removal
- metal ions
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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
-
- 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
-
- 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
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The present invention discloses a kind of preparation method available for the cysteine-modifying celluloses of L of heavy-metal ion removal in water, and modifying process mechanism is as follows：Substitution reaction occurs for the chlorine atom on the hydroxyl and epoxychloropropane on No. 6 carbon atoms on cellulose, form epocel element, hereafter the epoxy that the amino on cysteine is attacked above epocel element, promote epoxy addition so as in epocel element grafting cysteine, the cysteine-modifying celluloses of L are ultimately formed, so as to be grafted Shang Liangzhong functional group's sulfydryls and carboxyl simultaneously on cellulose.It is an advantage of the invention that：Adsorption of Heavy Metals ion efficiency is high, adsorption capacity is big, treatment effect is stable, water insoluble（It can be easily separated after absorption）.
Description
Technical field
The invention belongs to modified cellulose absorbing heavy metal ions in water processing technology field, more particularly to a kind of Guangs of L- half
The preparation method of propylhomoserin modified cellulose.
Background technology
With the development of modern industry so that problem of environmental pollution is increasingly serious, the sewage that wherein industrial enterprise are discharged
Present in plurality of heavy metal ion, such as Hg2+, Pb2+, Cd2+, Cr3+, Ni2+, to the threat caused by health of people,
It is the serious problems that world industry city faces.Changed based on the etherificate of hydroxyl, esterification, crosslinking, substitution etc. on cellulosic molecule
Reaction is learned, can synthesize heavy metal ion by modification has the derivative of good adsorption properties.Especially some nitrogenous, sulphur,
The heteroatomic derivative such as phosphorus, shows the enrichment good to noble metal, and most of cellulose derivative is insoluble in addition
It is easy to separate from system after Yu Shui, absorption, is conducive to sewage disposal.
Cys have a sulfydryl, three kinds of functional groups of carboxyl and amino, and these three functional groups are in Adsorption of Heavy Metals
All there is preferable adsorption effect.The Guang amino acid of L- half of one molecular weight connects cellulose will be while connect two kinds of forms
Functional group.The cellulose being modified through Cys is greatly improved on adsorption effect compared to cellulosic material tool.
The content of the invention
It is modified the technical problem to be solved in the present invention is to provide a kind of Cys for removal of heavy metal ions fine
The preparation method of element is tieed up, modified cellulose effect in Adsorption of Heavy Metals is obvious.
In order to solve the above-mentioned technical problem, the technical scheme is that a kind of L- for removal of heavy metal ions
The preparation method of cysteine-modifying cellulose, the preparation method of the modified cellulose：The plain preparation of alkali process, epocel,
It is cysteine-modifying.
Preferably, the preparation method of the Cys modified cellulose for removal of heavy metal ions：At alkali
During reason, weigh a certain amount of cellulose and be added in the NaOH solution that mass fraction is 14%, soak 24h, suction filtration is washed with distillation
To neutral, 60 DEG C of forced air dryings.
Preferably, the preparation method of the Cys modified cellulose for removal of heavy metal ions：Weigh
The cellulose of a certain amount of process alkali process adds 10mL ~ 30mL epoxychloropropane, 30mL ~ 50mL N, N- bis- into four-hole boiling flask
NMF（DMF), 90 DEG C ~ 120 DEG C stirring reaction 1h.Room temperature is cooled to, reacted mixture is first gone with absolute ethyl alcohol
Except organic solvent, then plumbi nitras is added to be produced without white precipitate into filtrate with a large amount of distilled water flushing suction filtrations.60 DEG C of air blast are done
It is dry.
Preferably, the preparation method of the Cys modified cellulose for removal of heavy metal ions：Will
The potassium carbonate that 0.5g is dried is dissolved in 60mL acetone solns, then the cellulose 2g weighed in previous step is added in above-mentioned solution,
1h is heated to reflux at 80 DEG C ~ 95 DEG C, then addition 0.2g ~ 0.8g cysteines, heating stirring backflow 2h ~ 8h, by product suction filtration,
Washed again with deionized water and ethanol, 60 DEG C of forced air dryings.
The present invention is with less expensive cellulose material（Paper pulp, wood chip, stalk etc.）For raw material, by alkali process, ring
Oxygen chloropropane is modified and Cys are modified, and finally synthesizes the adsorbent of Cys modified cellulose, this adsorbent
With Adsorption of Heavy Metals ion efficiency is high, adsorption capacity is big, treatment effect is stable, water insoluble（It can be easily separated after absorption）Etc. excellent
Point.
Brief description of the drawings
Fig. 1 is a kind of changing for the preparation method of Cys modified cellulose for removal of heavy metal ions of the invention
Property process mechanism figure.
Embodiment
The embodiment to the present invention is described further below.Herein it should be noted that for these implementations
The explanation of mode is used to help understand the present invention, but does not constitute limitation of the invention.In addition, invention described below
As long as involved technical characteristic does not constitute conflict and can be just mutually combined each other in each embodiment.
Embodiment 1
Experimental rig platform is built, a certain amount of paper pulp is weighed and is added in the NaOH solution that mass fraction is 14%, immersion
24h, suction filtration is washed to neutrality, forced air drying with distillation.
Paper pulp of the 2.5g after alkali process is weighed into four-hole boiling flask, 20mL epoxychloropropane, 40mL N, N- diformazans is added
Base formamide（DMF), 120 DEG C of stirring reaction 1h.Room temperature is cooled to, reacted mixture is first removed organic molten with absolute ethyl alcohol
Agent, then adds plumbi nitras to be produced without white precipitate with a large amount of distilled water flushing suction filtrations into filtrate.60 DEG C of forced air dryings.
The 0.5g potassium carbonate dried is dissolved in 60mL acetone solns, then the paper pulp 2g weighed in previous step be added to it is above-mentioned
In solution, 1h is heated to reflux at 80 DEG C, 0.4g cysteines are then added, heating stirring backflow 6h by product suction filtration, then is spent
Ionized water and ethanol washing, 60 DEG C of forced air dryings.
Embodiment 2
Experimental rig platform is built, a certain amount of paper pulp is weighed and is added in the NaOH solution that mass fraction is 14%, immersion
24h, suction filtration is washed to neutrality, forced air drying with distillation.
Paper pulp of the 2.5g after alkali process is weighed into four-hole boiling flask, 20mL epoxychloropropane, 40mL N, N- diformazans is added
Base formamide（DMF), 120 DEG C of stirring reaction 1h.Room temperature is cooled to, reacted mixture is first removed organic molten with absolute ethyl alcohol
Agent, then adds plumbi nitras to be produced without white precipitate with a large amount of distilled water flushing suction filtrations into filtrate.60 DEG C of forced air dryings.
The 0.5g potassium carbonate dried is dissolved in 60mL acetone solns, then the paper pulp 2g weighed in previous step be added to it is above-mentioned
In solution, 1h is heated to reflux at 90 DEG C, 0.4g cysteines are then added, heating stirring backflow 6h by product suction filtration, then is spent
Ionized water and ethanol washing, 60 DEG C of forced air dryings.
Embodiment 3
Experimental rig platform is built, a certain amount of paper pulp is weighed and is added in the NaOH solution that mass fraction is 14%, immersion
24h, suction filtration is washed to neutrality, forced air drying with distillation.
Paper pulp of the 2.5g after alkali process is weighed into four-hole boiling flask, 20mL epoxychloropropane, 40mL N, N- diformazans is added
Base formamide（DMF), 110 DEG C of stirring reaction 1h.Room temperature is cooled to, reacted mixture is first removed organic molten with absolute ethyl alcohol
Agent, then adds plumbi nitras to be produced without white precipitate with a large amount of distilled water flushing suction filtrations into filtrate.60 DEG C of forced air dryings.
The 0.5g potassium carbonate dried is dissolved in 60mL acetone solns, then the paper pulp 2g weighed in previous step be added to it is above-mentioned
In solution, 1h is heated to reflux at 90 DEG C, 0.4g cysteines are then added, heating stirring backflow 6h by product suction filtration, then is spent
Ionized water and ethanol washing, 60 DEG C of forced air dryings.
Embodiment 4
Experimental rig platform is built, a certain amount of paper pulp is weighed and is added in the NaOH solution that mass fraction is 14%, immersion
24h, suction filtration is washed to neutrality, forced air drying with distillation.
Paper pulp of the 2.5g after alkali process is weighed respectively into four-hole boiling flask, adds 20mL epoxychloropropane, 40mL N, N-
Dimethylformamide（DMF), 110 DEG C of stirring reaction 1h.Room temperature is cooled to, reacted mixture is first removed with absolute ethyl alcohol to be had
Machine solvent, then adds plumbi nitras to be produced without white precipitate with a large amount of distilled water flushing suction filtrations into filtrate.60 DEG C of forced air dryings.
The 0.5g potassium carbonate dried is dissolved in 60mL DMF solutions, then the paper pulp 2g weighed respectively in previous step is added to
In above-mentioned solution, 1h is heated to reflux at 85 DEG C, then addition 0.4g cysteines, heating stirring backflow 6h, by product suction filtration, then
Washed with deionized water and ethanol, 60 DEG C of forced air dryings.The same operating condition of Chinese hemlock spruce wood chip does one group.
Application example 1
This example is that obtained adsorbent is used for mercury-containing waste water evaluating absorbing：
The adsorption effect of the adsorbent heavy metal ion is detected with mercury-containing waste water.It is 50ppm mercurous anti-to prepare mercury content
Liquid is answered, 25mL is measured and is put into hard straight plastic tube, add the above-mentioned adsorbents of 0.05g.2h is shaken on oscillator.Examined with atomic fluorescence
Survey its mercurous final mercury content of reaction solution.Removal efficiency of mercury see the table below.
| Adsorbent | Example 1 | Example 2 | Example 3 |
| Adsorption efficiency（%） | 92.10 | 98.72 | 93.15 |
| Adsorption capacity（mg/g） | 23.02 | 24.68 | 23.29 |
Application example 2
The adsorption effect of the adsorbent heavy metal ion is surveyed with the mercury-containing waste water under condition of different pH.Preparation pH is 1-6
Mercury content is 50ppm mercurous reaction solution, measure 25m be put into hard straight plastic tube add it is modified in 0.025g embodiments 4
Paper pulp and wood chip.2h is shaken on oscillator.Its mercurous final mercury content of reaction solution is detected with atomic fluorescence.Removal efficiency of mercury is seen below
Table.Find that acid condition has little to no effect to the adsorption effect of this adsorbent from adsorption effect.Illustrate answering for this adsorbent
It is wider with scope.The adsorption effect of Modified Iron cedar sawdust and paper pulp is about the same, illustrates that this method of modifying has to cellulose general
Adaptive.
Application example 3
The adsorption effect of the adsorbent heavy metal ion is surveyed under the conditions of change adsorbent dosage to mercury-containing waste water.Prepare
PH is the mercurous reaction solution that 4 mercury contents are 50ppm, measures 25ML and is put into addition 0.0125g-0.4g implementations in hard straight plastic tube
Modified paper pulp and wood chip adsorbent in example 4.2h is shaken on oscillator.Detect that its mercurous reaction solution finally contains with atomic fluorescence
Mercury quantity.Find that adsorption efficiency and adsorption capacity intersections of complex curve, when dosage is 1g/L, illustrate industrial optimal throwing in experiment
Dosage is 1g/L.And the adsorbent optimum dosage for preparing before is mostly all in 2g/L, relatively before adsorbent, this adsorbent energy
It is preferably cost-effective in commercial Application.
Application example 4
The adsorption effect of the adsorbent heavy metal ion is surveyed under the conditions of different mercury stoste to mercury-containing waste water.Preparing pH is
4 mercury contents are 1ppm-150ppm mercurous reaction solution, measure 25m and are put into hard straight plastic tube in addition 0.025g embodiments 4
Modified paper pulp and wood chip adsorbent.2h is shaken on oscillator.Its mercurous final mercury content of reaction solution is detected with atomic fluorescence.
This application example is adsorption isotherm experiment, and experimental data is fitted.It was found that adsorbent thermoisopleth prepared by this method of modifying
Meet Langmuir equations.The method Modified Iron cedar sawdust can be calculated by Langmuir equations and adsorb mercury solution maximum adsorption
Capacity can reach 104mg/g, and this method of modifying modified pulp absorption mercury solution maximum adsorption capacity can reach 78mg/g.Can
See that Cellulose-based Adsorbents maximum adsorption capacity prepared by this method of modifying is higher.
Embodiments of the present invention are explained in detail above, but the invention is not restricted to described embodiment.It is right
For those skilled in the art, in the case where not departing from the principle of the invention and spirit, these embodiments are carried out many
Change, modification, replacement and modification are planted, are still fallen within protection scope of the present invention.
Claims (7)
1. a kind of preparation method of Cys modified cellulose for removal of heavy metal ions, it is characterised in that：It is described
The raw material of modified cellulose is less expensive cellulose material（Paper pulp, wood chip, stalk etc.）.
2. a kind of preparation side of Cys modified cellulose for removal of heavy metal ions according to claim 1
Method, it is characterised in that：The preparation method of the modified cellulose includes alkali process, epocel element is prepared and cysteine changes
Property.
3. a kind of preparation side of Cys modified cellulose for removal of heavy metal ions according to claim 2
Method, it is characterised in that：During the alkali process, weigh a certain amount of cellulose and be added in the NaOH solution that mass fraction is 14%,
24h is soaked, suction filtration is washed to neutrality, 60 DEG C of forced air dryings with distillation.
4. a kind of preparation side of Cys modified cellulose for removal of heavy metal ions according to claim 2
Method, it is characterised in that：The preparation process of epocel element, weighs the cellulose of a certain amount of process alkali process to four-hole boiling flask
In, add 10mL ~ 30mL epoxychloropropane, 30mL ~ 50mL DMFs（DMF), 90 DEG C ~ 120 DEG C stirring reactions
1h, is cooled to room temperature, reacted mixture first removes organic solvent with absolute ethyl alcohol, then with a large amount of distilled water flushing suction filtrations
Plumbi nitras is added to be produced without white precipitate into filtrate, 60 DEG C of forced air dryings.
5. a kind of preparation side of Cys modified cellulose for removal of heavy metal ions according to claim 2
Method, it is characterised in that：The cysteine-modifying process, the potassium carbonate that 0.5g is dried is dissolved in 60mL acetone solns, then claims
Take the cellulose 2g in previous step to be added in above-mentioned solution, 1h is heated to reflux at 80 DEG C ~ 95 DEG C, then add 0.2g ~ 0.8g
Cysteine, heating stirring backflow 2h ~ 8h, is washed, 60 DEG C of forced air dryings by product suction filtration, then with deionized water and ethanol.
6. a kind of preparation side of Cys modified cellulose for removal of heavy metal ions according to claim 2
Method, it is characterised in that：The adsorption effect of the Cys modified cellulose in acid condition is barely affected.
7. a kind of preparation side of Cys modified cellulose for removal of heavy metal ions according to claim 2
Method, it is characterised in that：The Cys modified cellulose adsorbent thermoisopleth meets Langmuir equations.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107497407A (en) * | 2017-10-16 | 2017-12-22 | 云南圣清环保科技有限公司 | A kind of preparation method of biomass new material targeting adsorbent for mercury-containing waste water processing and application |
| CN107694527A (en) * | 2017-10-16 | 2018-02-16 | 云南圣清环保科技有限公司 | A kind of preparation method of the 2 amino terephthalic acid (TPA) modified celluloses for heavy metals removal |
| CN109126738A (en) * | 2018-08-09 | 2019-01-04 | 张剑 | A kind of preparation method of metal ion adsorbent |
| CN109289811A (en) * | 2018-11-06 | 2019-02-01 | 大连理工大学 | Cellulose nanocrystal body adsorbent and preparation method thereof containing sulfydryl and amino |
| CN110381969A (en) * | 2017-03-03 | 2019-10-25 | 共生国际大学 | The method for removing from effluent by nonactive-active biological process and recycling Cr VI |
| CN111229170A (en) * | 2020-01-10 | 2020-06-05 | 辽宁大学 | Amino acid modified cellulose composite ferric oxide adsorbent and preparation method and application thereof |
| CN111545174A (en) * | 2020-04-15 | 2020-08-18 | 济南大学 | Preparation method of modified fiber balls for adsorbing and separating trifluoro-benzene pyrimidine |
| EP4264638A4 (en) * | 2020-12-18 | 2024-04-10 | The Catholic University Of America | Methods for removing iodate from aqueous solutions |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103447009A (en) * | 2013-09-26 | 2013-12-18 | 济南大学 | Preparation and application of cysteine modified loofah adsorbent |
| CN103464119A (en) * | 2013-09-28 | 2013-12-25 | 济南大学 | Preparation method and application of modified cysteine palm bark adsorbent |
-
2017
- 2017-06-26 CN CN201710492534.4A patent/CN107226507A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103447009A (en) * | 2013-09-26 | 2013-12-18 | 济南大学 | Preparation and application of cysteine modified loofah adsorbent |
| CN103464119A (en) * | 2013-09-28 | 2013-12-25 | 济南大学 | Preparation method and application of modified cysteine palm bark adsorbent |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110381969A (en) * | 2017-03-03 | 2019-10-25 | 共生国际大学 | The method for removing from effluent by nonactive-active biological process and recycling Cr VI |
| CN107497407A (en) * | 2017-10-16 | 2017-12-22 | 云南圣清环保科技有限公司 | A kind of preparation method of biomass new material targeting adsorbent for mercury-containing waste water processing and application |
| CN107694527A (en) * | 2017-10-16 | 2018-02-16 | 云南圣清环保科技有限公司 | A kind of preparation method of the 2 amino terephthalic acid (TPA) modified celluloses for heavy metals removal |
| CN107694527B (en) * | 2017-10-16 | 2020-06-19 | 云南圣清环保科技有限公司 | Preparation method of 2-amino terephthalic acid modified cellulose for removing heavy metals |
| CN109126738A (en) * | 2018-08-09 | 2019-01-04 | 张剑 | A kind of preparation method of metal ion adsorbent |
| CN109289811A (en) * | 2018-11-06 | 2019-02-01 | 大连理工大学 | Cellulose nanocrystal body adsorbent and preparation method thereof containing sulfydryl and amino |
| CN111229170A (en) * | 2020-01-10 | 2020-06-05 | 辽宁大学 | Amino acid modified cellulose composite ferric oxide adsorbent and preparation method and application thereof |
| CN111229170B (en) * | 2020-01-10 | 2022-04-05 | 辽宁大学 | Amino acid modified cellulose composite ferric oxide adsorbent and preparation method and application thereof |
| CN111545174A (en) * | 2020-04-15 | 2020-08-18 | 济南大学 | Preparation method of modified fiber balls for adsorbing and separating trifluoro-benzene pyrimidine |
| EP4264638A4 (en) * | 2020-12-18 | 2024-04-10 | The Catholic University Of America | Methods for removing iodate from aqueous solutions |
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Application publication date: 20171003 |