CN109569530A - A kind of compound adsorbent adsorbing heavy metal in waste water lead - Google Patents
A kind of compound adsorbent adsorbing heavy metal in waste water lead Download PDFInfo
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- CN109569530A CN109569530A CN201910052788.3A CN201910052788A CN109569530A CN 109569530 A CN109569530 A CN 109569530A CN 201910052788 A CN201910052788 A CN 201910052788A CN 109569530 A CN109569530 A CN 109569530A
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- alginate
- sodium alginate
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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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/14—Diatomaceous earth
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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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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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
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
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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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- 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
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
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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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- Engineering & Computer Science (AREA)
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
This application involves a kind of compound adsorbents for adsorbing heavy metal in waste water lead, belong to technical field of environmental pollution treatment.The compound adsorbent includes the component of following portions by weight: calcium alginate 5-8 parts modified, 3-4 parts of active carbon, 1-2 parts of diatomite, 0.5-1 parts of beer yeast slurry and 2-3 parts of chitosan；The modified calcium alginate is that sodium alginate is made by modified react again with soluble calcium salt of cysteine and ethylenediamine.The compound adsorbent of the application is high to the adsorbance of heavy metal in waste water lead, selectivity is good and the good cycle of compound adsorbent.
Description
Technical field
This application involves a kind of compound adsorbents for adsorbing heavy metal in waste water lead, belong to environmental pollution treatment technology neck
Domain.
Background technique
Contain a large amount of heavy metal ion, such as copper, lead, chromium, arsenic in industrial wastewater.Inorganic lead and its chemical combination in environment
Object is sufficiently stable, is not easy to be metabolized and degrade.Lead is accumulation property to the murder by poisoning of human body, and the lead 25% of human body sucking is deposited on lung
In, blood is partially entered by the dissolution of water.
Chinese patent application CN201611238989.5 discloses a kind of bentonite adsorption material that Quaternary Ammonium Salt of Chitosan is modified
Material, is first to be modified to sodium bentonite with chitosan, and the chitosan molecule of macromolecular and bentonite is compound；Use again (2,
3- glycidyl) trimethyl ammonium chloride as modifying agent to chitosan sodium bentonite carry out intercalation modifying, obtain with stratiform
The modified bentonite adsorption material of the Quaternary Ammonium Salt of Chitosan of hole configurations, the bentonite adsorption material have biggish specific surface area,
There is good absorption property to the lead ion in waste water, adsorbance maximum can achieve 91.81mg/g, meet Langmuir etc.
Warm Adsorption Model and pseudo-second order kinetic model, belong to mono layer adsorption, are chemisorptions.
In the prior art to there are many processing methods of heavy metal lead, wherein absorption method is that have high ratio using adsorbent material
Surface area, the method that more porous counterweight metal ion is handled.The more active charcoal of adsorbent, zeolite are applied now
Deng.This method have the characteristics that absorption it is high-efficient, rate is fast, easy to operate.But adsorbent, which has absorption to lead element, to be held
The problems such as measuring low, selectivity and poor circulation.
Summary of the invention
The technical problem to be solved by the application is to provide a kind of compound adsorbents for adsorbing heavy metal in waste water lead, this is multiple
It closes the adsorption capacity height of adsorbent, be selected from the advantages of high property and good cycle.
To achieve the above object, the application technical solution to be solved are as follows:
This application provides a kind of compound adsorbents for adsorbing heavy metal in waste water lead, and the compound adsorbent includes following
The component of parts by weight: modified calcium alginate 5-8 parts, 3-4 parts of active carbon, 1-2 parts of diatomite, 0.5-1 parts of beer yeast slurry and
2-3 parts of chitosan；
The modified calcium alginate is that sodium alginate is modified anti-with soluble calcium salt again by cysteine and ethylenediamine
It should be made.
Optionally, the compound adsorbent includes the component of following portions by weight: modified 6.5 parts of calcium alginate, active carbon
Part 3.7,1.4 parts of diatomite, 0.8 part of beer yeast slurry and 2.6 parts of chitosan.
Optionally, the mass ratio of the ethylenediamine and cysteine is 1:0.5-1.2.
Optionally, the mass ratio of the ethylenediamine and cysteine is 1:0.8.
Optionally, the preparation method of the modified calcium alginate includes the following steps:
1) sodium alginate, EDCHCl and NHS are mixed with the buffer solution that pH value is 4.0-6.0, mixed solution is made
A；
2) will after at least 4h is mixed in mixed solution A and ethylenediamine, be added under the conditions of being protected from light cysteine stir to
Few 1h, is added ethanol solution, filtering precipitating, and modified sodium alginate is made in washing；
3) by modified sodium alginate aqueous solution and soluble calcium salt aqueous solution hybrid filtering, the modification is made in freeze-drying
Calcium alginate.
Optionally, the mass ratio of the sodium alginate, EDCHCl and NHS are 1:1-2:1-1.5.
Optionally, the mass ratio of the sodium alginate and ethylenediamine is 1:0.3-0.8.
Optionally, the buffer solution is phosphate buffer solution.
Optionally, the compound adsorbent preparation method the following steps are included:
Chitosan, diatomite, beer yeast slurry are mixed in glacial acetic acid, remove solvent seasoning after be granulated, and with mix
It is granulated in modified calcium alginate, active carbon mixing, obtains the compound adsorbent.
According to the another aspect of the application, a kind of compound adsorbent is provided in the application of absorption Pb In Exhausted Water, it is described multiple
It closes adsorbent and is selected from above-mentioned compound adsorbent.
EDCHCl in the application is 1- ethyl-(3- dimethylaminopropyl) phosphinylidyne diimmonium salt hydrochlorate；NHS is N-
HOSu NHS.
The beneficial effect of the application includes but is not limited to:
The compound adsorbent of the application preparation has high adsorption capacity, absorption selected from property the heavy metal lead element in water
Good and high cyclic utilization rate advantage.
Specific embodiment
The application is described in detail below with reference to embodiment, but the application is not limited to these embodiments.
Unless otherwise instructed, raw material being related in embodiments herein etc. is bought by commercial sources.
Embodiment 1
The preparation of modified calcium alginate 1#
1) 1.0g sodium alginate is mixed with the pH dibastic sodium phosphate buffer solution for being 4.8, after stirring and dissolving, is added
1.3gEDCHCl and 1.3gNHS stirs 2h, and mixed solution A is made；
2) after 5h being mixed in mixed solution A and 0.5mL ethylenediamine solution, half Guang ammonia of 0.4g is added under the conditions of being protected from light
Acid stirring 2h, is added ethanol solution and generates completely until precipitating, filtering ethanol washing, under the conditions of 80 DEG C after drying, is made and changes
Property sodium alginate；
3) modified sodium alginate made from step 2) is dissolved in 100mL water, instills 0.3mol/L under stirring conditions
Calcium chloride solution generate hydrogel, by hydrogel vacuum freeze drying obtained, modified calcium alginate 1# is made.
The preparation of compound adsorbent 1#:
1) 2h is mixed in chitosan 2.6g, diatomite 1.4g, beer yeast slurry 0.8g in glacial acetic acid, evaporation removes
Solvent, drying, ground 200 mesh；
2) particle is made in step 1) to mix with the modified calcium alginate 1# of 6.5g, active carbon 3.7g, obtains composite adsorption
Agent 1#.
Embodiment 2
Compound adsorbent 2# is prepared, the compound adsorbent 1# difference prepared with embodiment 1 are as follows:
Modified calcium alginate 5g, active carbon 3g, diatomite 1g, beer yeast slurry 0.5g and chitosan 2g.
Embodiment 3
Compound adsorbent 3# is prepared, the compound adsorbent 1# difference prepared with embodiment 1 are as follows:
Modified calcium alginate 8g, active carbon 4g, diatomite 2g, beer yeast slurry 1g and chitosan 3g.
Embodiment 4
The preparation of modified calcium alginate 2#:
1) 1.0g sodium alginate is mixed with the pH dibastic sodium phosphate buffer solution for being 5.1, after stirring and dissolving, 1.8g is added
EDCHCl and 1.5g NHS stirs 2h, and mixed solution A is made；
2) after 6h being mixed in mixed solution A and 0.8mL ethylenediamine solution, half Guang ammonia of 0.9g is added under the conditions of being protected from light
Acid stirring 2h, is added ethanol solution and generates completely until precipitating, filtering ethanol washing, under the conditions of 80 DEG C after drying, is made and changes
Property sodium alginate；
3) modified sodium alginate made from step 2) is dissolved in 100mL water, instills 0.6mol/L under stirring conditions
Calcium chloride solution generate hydrogel, by hydrogel vacuum freeze drying obtained, modified calcium alginate 2# is made.
The preparation of compound adsorbent 4#:
1) 2h is mixed in chitosan 2.6g, diatomite 1.4g, beer yeast slurry 0.8g in glacial acetic acid, evaporation removes
Solvent, drying, ground 200 mesh；
2) particle is made in step 1) to mix with the modified calcium alginate 2# of 6.5g, active carbon 3.7g, obtains composite adsorption
Agent 4#.
Comparative example 1
Preparation comparison compound adsorbent D1#, the compound adsorbent 1# difference prepared with embodiment 1 are as follows: comparison is multiple
Closing adsorbent D1# only includes modified calcium alginate 1#.
Comparative example 2
Preparation comparison compound adsorbent D2#, the compound adsorbent 1# difference prepared with embodiment 1 are as follows:
1) by chitosan 2.6g, diatomite 1.4g, beer yeast slurry 0.8g, 6.5g modified calcium alginate, active carbon 3.7g
Directly it is mixed to prepare comparison compound adsorbent D2#.
Comparative example 3
Preparation comparison compound adsorbent D3#, the compound adsorbent 1# difference prepared with embodiment 1 are as follows:
Compare the preparation of modified calcium alginate D1#
1) 1.0g sodium alginate is mixed with the pH dibastic sodium phosphate buffer solution for being 4.8, after stirring and dissolving, is added
1.3gEDCHCl and 1.3gNHS stirs 2h, and mixed solution A is made；
2) after 5h being mixed in mixed solution A and 1.2mL ethylenediamine solution, half Guang ammonia of 1.7g is added under the conditions of being protected from light
Acid stirring 2h, is added ethanol solution and generates completely until precipitating, filtering ethanol washing, under the conditions of 80 DEG C after drying, is made and changes
Property sodium alginate；
3) modified sodium alginate made from step 2) is dissolved in 100mL water, instills 0.3mol/L under stirring conditions
Calcium chloride solution generate hydrogel, by hydrogel vacuum freeze drying obtained, modified calcium alginate D1# is made.
Embodiment 5
Respectively with the pH of leaded 300mg/L be 6.5 waste water and, the waste water that the pH of cupric 70mg/L is 6.5 be processing pair
As.
Each 7 parts of above-mentioned waste water to be processed, every part of 1L are taken respectively, use compound adsorbent 1#-4#, and the compound suction of comparison respectively
Attached dose of each 1g of D1#-D3# handles above-mentioned waste water, to be constantly stirred in treatment process, handle at normal temperature
2.5h。
By the compound adsorbent 1#-4# of the testing example 1-4 respectively and comparison compound adsorbent D1#- of comparative example 1-3
The removal rate of lead element, copper in D3# treated waste water, the results are shown in Table 1:
Table 1
As known from Table 1, in 270mg/g, the application's answers the large amount of adsorption of the lead in compound adsorbent 1#-4# processing waste water
It is high to the adsorbance of heavy metal lead to close adsorbent, and the adsorption time of compound adsorbent is short；Adsorbent D1#-D3# is compared to waste water
In copper content adsorbance it is poor.Compound adsorbent 1#-4#, comparison adsorbent D1#-D3# have certain suction to copper
Attached rate, but adsorbent 1#-4# is approximate relative to processing result of the comparison adsorbent D1#-D3# to copper.
Embodiment 6
Illustrate the regeneration of compound adsorbent by taking compound adsorbent 1# prepared by embodiment 1 as an example and recycles effect.It will
Compound adsorbent 1# using 0.2mol/L hydrochloric acid solution desorption after, processing lead 300mg/L pH be 6.5 waste water, recycle into
It is 270mg/g to the adsorbance of lead after row 10 times, adsorbance is not substantially reduced.
The above-mentioned specific embodiment to the application is described, but the limitation not to the application protection scope, institute
The field technical staff of stating should be understood that on the basis of the technical solution of the application, those skilled in the art do not need to pay wound
Any modification or deformation that the property made labour can be made are still within the protection scope of the application.
Claims (10)
1. a kind of compound adsorbent for adsorbing heavy metal in waste water lead, which is characterized in that the compound adsorbent includes following heavy
Measure the component of number: calcium alginate 5-8 parts modified, 3-4 parts of active carbon, 1-2 parts of diatomite, 0.5-1 parts of beer yeast slurry and shell
2-3 parts of glycan；
The modified calcium alginate is by sodium alginate by cysteine and the modified system of reacting with soluble calcium salt again of ethylenediamine
?.
2. compound adsorbent according to claim 1, which is characterized in that the compound adsorbent includes following portions by weight
Component: modified 6.5 parts of calcium alginate, 3.7 parts of active carbon, 1.4 parts of diatomite, 0.8 part of beer yeast slurry and chitosan 2.6
Part.
3. compound adsorbent according to claim 1, which is characterized in that the mass ratio of the ethylenediamine and cysteine
For 1:0.5-1.2.
4. compound adsorbent according to claim 1, which is characterized in that the mass ratio of the ethylenediamine and cysteine
For 1:0.8.
5. compound adsorbent according to claim 1, which is characterized in that the preparation method of the modified calcium alginate includes
Following step:
1) sodium alginate, EDCHCl and NHS are mixed with the buffer solution that pH value is 4.0-6.0, mixed solution A is made；
2) after at least 4h being mixed in mixed solution A and ethylenediamine, cysteine is added under the conditions of being protected from light and stirs at least 1h,
Ethanol solution, filtering precipitating is added, modified sodium alginate is made in washing；
3) by modified sodium alginate aqueous solution and soluble calcium salt aqueous solution hybrid filtering, the modified seaweed is made in freeze-drying
Sour calcium.
6. compound adsorbent according to claim 5, which is characterized in that the matter of the sodium alginate, EDCHCl and NHS
Amount is than being 1:1-2:1-1.5.
7. compound adsorbent according to claim 5, which is characterized in that the mass ratio of the sodium alginate and ethylenediamine is
1:0.3-0.8。
8. compound adsorbent according to claim 5, which is characterized in that the buffer solution is phosphate buffer solution.
9. compound adsorbent according to any one of claims 1 to 8, which is characterized in that the preparation of the compound adsorbent
Method the following steps are included:
Chitosan, diatomite, beer yeast slurry are mixed in glacial acetic acid, are granulated after removing solvent seasoning, and and mixing granulation
In modified calcium alginate, active carbon mixing, the compound adsorbent is obtained.
10. a kind of compound adsorbent is in the application of absorption Pb In Exhausted Water, which is characterized in that the compound adsorbent is selected from right
It is required that compound adsorbent described in 1-9 any one.
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Cited By (3)
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| CN110449120A (en) * | 2019-09-05 | 2019-11-15 | 苏州科技大学 | A kind of dephosphorization adsorbent and preparation method 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 |
| CN113332960A (en) * | 2021-03-23 | 2021-09-03 | 中南大学 | Supported apatite composite adsorption material and preparation method and application thereof |
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Cited By (4)
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| 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 |
| CN113332960A (en) * | 2021-03-23 | 2021-09-03 | 中南大学 | Supported apatite composite adsorption material and preparation method and application thereof |
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Application publication date: 20190405 |