CN104959107A - Preparing method and application of bio-adsorbent - Google Patents
Preparing method and application of bio-adsorbent Download PDFInfo
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- CN104959107A CN104959107A CN201510347274.2A CN201510347274A CN104959107A CN 104959107 A CN104959107 A CN 104959107A CN 201510347274 A CN201510347274 A CN 201510347274A CN 104959107 A CN104959107 A CN 104959107A
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- diatom
- lead ion
- bio
- adsorbent
- heavy metal
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Abstract
The invention relates to the field of treatment of heavy metal pollution, in particular to a preparing method of bio-adsorbent. The preparing method includes the steps of A, introducing a diatom source to a seawater culture medium, and performing aeration cultivation at the ambient temperature until a stable growth phase so as to acquire diatom liquid; B, centrifuging the diatom liquid to obtain diatom concentrate; C, drying the diatom concentrate to obtain dried diatom powder; and D, pickling, drying and roasting the dried diatom powder to obtain diatom shells. The invention further discloses application, of the bio-adsorbent prepared by the preparing method, in treating lead ion containing solution. The bio-adsorbent is especially effective in selectively adsorbing heavy metal ions Pb2+; besides adsorption, the bio-adsorbent further has the advantages such that adsorption capacity is high, adsorption efficiency is high, the cost is low, and cyclic utilization is available; the adsorbing performance of the bio-adsorbent is far better than that of common bio-adsorbents; the bio-adsorbent has promising applicable prospect.
Description
Technical field
The invention belongs to Heavy Metal Pollution Control method field, specifically, relate to a kind of preparation method of biological adsorption agent, and use this biological adsorption agent process containing the method for lead solution.
Background technology
China's heavy metal pollution problem is serious, needs the heavy metal ion (Pb of high-performance, low cost badly
2+, Cu
2+, Cd
2+, Ni
2+, Ag
+deng) sorbing material; But the adsorption capacity of some common inorganic adsorbing materials is all lower at present, as shown in table 1.
The common inorganic adsorbing material of table 1 is to Pb
2+absorption property contrast
Marine diatom frustule extracts from marine diatom, and frustule surface has the microcellular structure of a large amount of nano-micro levels, and specific area is large, is extremely beneficial to the absorption of heavy metal ion; Meanwhile, marine diatom has that fast growth, growth cycle are short, biomass content high, also wider to the tolerance range of condition of culture.People wish to utilize marine resources to obtain a kind of biological adsorption agent of excellent performance, the pollution problem of process heavy metal ion.
Summary of the invention
For solving above-mentioned prior art Problems existing, the invention provides a kind of preparation method of biological adsorption agent, and utilize this biological adsorption agent process containing the method for lead ion in lead solution, can be realized it at hybrid piles (Pb
2+, Cu
2+, Cd
2+, Ni
2+, Ag
+deng) efficient selective of lead ion is adsorbed in waste water.
In order to reach foregoing invention object, present invention employs following technical scheme:
A preparation method for biological adsorption agent, comprises step: A, in sea water medium, introduce diatom source, and under environment temperature, aeration is cultured to the stable growth phase, obtains diatom liquid; B, centrifugal treating is carried out to described diatom liquid, obtain diatom concentrate; C, dry described diatom concentrate, obtain diatom dry powder; D, described diatom dry powder obtain diatom frustule through pickling, drying, roasting.
Further, in described step D, the reagent of described pickling is hydrochloric acid solution, and the mass concentration of described hydrochloric acid solution is not less than 2%, and pickling time is at least 0.5h; The temperature of described roasting is not less than 600 DEG C, and roasting time is at least 0.5h.
Further, described sea water medium for add artificial seawater nutritional agents in natural sea-water.
Further, described diatom source is isolated Bacillariophyceae algae kind; Or in sea water medium under environment temperature aeration be cultured to the stable growth phase obtain mixed diatom algae kind.
Further, described diatom is selected from any one in Chaetoceros muelleri, Nitzschia closterium minutissima, hailian seaweed, cocoon shape algae.
Another object of the present invention is also to provide a kind of method utilizing above-mentioned biological adsorption agent process lead ion, comprise step: be added to by diatom frustule in leaded solion, vibrate under room temperature more than 4h, makes described diatom frustule adsorpting lead ion reach balance, obtains lead ion-diatom frustule; Wherein, the pH of described leaded solion is 3 ~ 6.
Further, in described leaded solion, the concentration of lead ion is 40ppm ~ 350ppm.
Further, the solid-to-liquid ratio of described diatom frustule and described leaded solion is 1g/L ~ 10g/L.
Further, also comprise desorption step: by dry after described lead ion-diatom frustule centrifugation, obtain lead ion-diatom frustule dry powder; Be added in 0.1mol/L hydrochloric acid solution by described lead ion-diatom frustule dry powder, vibrate under room temperature 0.5h ~ 24h; Wherein, the solid-to-liquid ratio of described lead ion-diatom frustule dry powder and hydrochloric acid is 1g/L ~ 5g/L.
Diatom used in the present invention is as the main primary productivity in ocean, and having aboundresources, widely distributed feature, is the dominant groups in coastal waters; This diatom has that fast growth, growth cycle are short, biomass content high, also wider to the tolerance range of condition of culture.Using diatom through dry powder preparation, the diatom frustule that obtains after pickling as a kind of biological adsorption agent, it has the characteristic such as a large amount of microcellular structures and larger specific area, and importantly diatom frustule achieves heavy metal ion Pb
2+selective absorption, this adsorption process also has that adsorption capacity is large, clearance is high, absorption property is far superior to common other biological adsorbent simultaneously; In addition, the method for the treatment of in accordance with the present invention lead ion also can avoid follow-up heavy metal ion Pb
2+because of the problem that other heavy metal ion coexist recycling complex procedures caused in recycling process, thus realize directly recycling efficiently.
Detailed description of the invention
Below, embodiments of the invention will be described in detail.But, the present invention can be implemented in many different forms, and the present invention should not be interpreted as being limited to the specific embodiment of setting forth here.On the contrary, provide these embodiments to be to explain principle of the present invention and practical application thereof, thus enable others skilled in the art understand various embodiment of the present invention and be suitable for the various amendments of certain expected application.
Embodiment 1
According to the preparation method of a kind of biological adsorption agent of the present invention, comprise the steps:
Step one: introduce diatom source in sea water medium, under environment temperature, aeration is cultured to stable growth phase acquisition diatom liquid.
Below the preparation of sea water medium is described in detail.The present embodiment gathers seawater from Bay in Shenzhen coastal waters, first using the natural sea-water through sand filtration as cultivation solvent, each nutritive salt is added in natural sea-water makes sea water medium according to artificial seawater nutritional agents (be also called f/2 culture medium, concrete component is see table 2-table 4).
Table 2 f/2 culture medium prescription
Table 3 Trace Metal solution (Trace Metal Solution) component
Table 4 vitamin solution (Vitamin Solution) component
Then the acquisition in diatom source is described in detail.The present embodiment is with f/2 nutrient solution, and (20 DEG C ~ 30 DEG C) are cultured to the advantage diatom hybrid of stable growth phase acquisition is at ambient temperature algae kind source; Be introduced in sea water medium by the diatom source of acquisition again, under indoor illumination shaking flask or outdoor environment temperature, aeration is cultured to stable growth after date and obtains diatom liquid.Wherein, those skilled in the art know, and the stable growth phase is the division of phalangeal cell and decline arrival one metastable time, characterizes by cell density curve; Namely monitor the cell density of diatom every day, and with number of days, cell densities is mapped, be tending towards constant with cultivated days when observing cell density or change not obvious, can be judged as that the grown cultures of diatom carries out the stable growth phase.
Step 2: carry out centrifugal treating to the diatom liquid that step one obtains, obtains diatom concentrate.
Step 3: the diatom concentrate that step 2 obtains is dried and obtained diatom dry powder at 60 DEG C.Diatom dry powder is crossed 200 mesh sieve, obtains even diatom dry powder.Source due to this diatom is diatom hybrid, and therefore this diatom dry powder is the bulk variety dry powder of diatom.After testing, the BET specific surface area of this diatom dry powder reaches 5.18m
2/ g, pore volume is 0.034cm
3/ g.
What deserves to be explained is, the method for diatom concentrate process to diatom dry powder being not limited to dry, can also be freeze drying.
Step 4: vibrate after diatom dry powder step 3 obtained and 2% (wt%) mixed in hydrochloric acid pickling 0.5h, and dry at 60 DEG C, roasting 0.5h at 600 DEG C, obtain the diatom frustule of white powder.After testing, the BET specific surface area of this diatom frustule reaches 143m
2/ g, pore volume is 0.224cm
3/ g, compared with diatom dry powder before, BET specific surface area and pore volume significantly improve, and absorption property also strengthens greatly.
What deserves to be explained is, in above-mentioned steps four, the temperature and time of pickling time and roasting is not limited to described in the present embodiment; Usually, pickling time controls to be no less than 0.5h, sintering temperature is not less than 600 DEG C and roasting time is no less than 0.5h.
Below, the diatom frustule of said method acquisition is introduced at process heavy metal ion Pb
2+the application of aspect.
With containing heavy metal ion Pb in the present embodiment
2+, Cu
2+, Cd
2+, Ni
2+, Ag
+solution be absorption object, show the absorption property of biological adsorption agent of the present embodiment.
First, the solution containing heavy metal ion of the present embodiment is respectively:
Experimental group 1: initial ion concentration be 200ppm respectively containing heavy metal ion Pb
2+, Cu
2+, Cd
2+, Ni
2+, Ag
+single solion;
Experimental group 2: initial ion concentration is the heavy metal ion Pb of 200ppm
2+, Cu
2+, Cd
2+, Ni
2+, Ag
+the mixed ion solutions coexisted.
The pH scope of above-mentioned each single solion and mixed ion solutions is regulated to be 4 ~ 6.
Then, be that the diatom frustule obtained by said method is joined in each solution of experimental group 1 and experimental group 2 by the ratio of 1g/L respectively according to solid-to-liquid ratio, be placed in constant-temperature table to vibrate at 25 DEG C more than 4h, 24h is preferably in the present embodiment, controlling constant-temperature table frequency of oscillation is 100rpm, until make described diatom frustule Adsorption of Heavy Metal Ions reach capacity (i.e. adsorption equilibrium).
After adsorption reaction terminates, the solution that takes a morsel in above-mentioned each single solion and mixed ion solutions respectively crosses 0.45 μm of filter membrane, then uses inductively coupled plasma instrument (ICP) to detect Pb in filtrate respectively
2+, Cu
2+, Cd
2+, Ni
2+, Ag
+etc. the concentration of heavy metal ion, testing result is as shown in table 5.
Table 5 diatom frustule is to the absorption result of each heavy metal ion in each single solion and mixed ion solutions
As known from Table 5, the diatom frustule of the present embodiment acquisition is to Pb
2+, Cu
2+, Cd
2+, Ni
2+, Ag
+five heavy metal species ions all have certain absorption property; But organize in 1 and experimental group 2 by experiment and see on the adsorption effect of different heavy metal ion, this diatom frustule is especially for heavy metal ion Pb
2+adsorption effect best, adsorption capacity reaches 100.7mg/g; Meanwhile, the adsorption effect in experimental group 2 indicates when there is the competitive Adsorption between contents of many kinds of heavy metal ion, and this diatom frustule still can heavy metal ion Pb
2+realize the selective absorption of advantage, illustrate that this diatom frustule is to the heavy metal ion Pb of this concentration range
2+there is good selective absorption effect.
Embodiment 2
The present embodiment be the diatom frustule obtained in embodiment 1 basis on after adsorpting lead ion reaches capacity, analyze the performance of its desorption.
Initial pH scope be 4 ~ 6, initial concentration be 200ppm containing heavy metal ion Pb
2+the aqueous solution (the initial ion concentration namely in above-mentioned experimental group 1 be 200ppm containing Pb
2+single solion) in, the ratio being 1g/L according to solid-to-liquid ratio adds diatom frustule wherein, be placed in constant-temperature table vibrate under room temperature (25 DEG C) absorption 24h.Other steps are see shown in embodiment 1.
Control sorption reaction time is 24h, treats diatom frustule Adsorption of Heavy Metal Ions Pb
2+reach adsorption equilibrium, then under room temperature (25 DEG C), centrifugal treating (temperature 25 DEG C, time 10min, rotating speed 4000rpm) is carried out to the aqueous solution containing lead ion-diatom frustule.Collect the lead ion-diatom frustule after adsorption equilibrium, dry acquisition lead ion-diatom frustule dry powder at 60 DEG C, room temperature (25 DEG C) saves backup.
Carry out desorption process to described lead ion-diatom frustule dry powder, desorption agent is hydrochloric acid solution.By described lead ion-diatom frustule dry powder is fed in the hydrochloric acid solution of 0.1mol/L by certain solid-to-liquid ratio, vibrate under room temperature 0.5h ~ 24h, and in the present embodiment, duration of oscillation is 24h, and controlling constant-temperature table frequency of oscillation is 100rpm.The solution that takes a morsel after reaction crosses 0.45 μm of filter membrane, uses inductively coupled plasma instrument (ICP) to detect heavy metal ion Pb in filtrate respectively
2+concentration.Testing result is as shown in table 6.
Table 6 different solid is than the desorption result of lower hydrochloric acid solution to lead ion-diatom frustule dry powder
As can be seen from Table 6, hydrochloric acid solution is to the Pb in lead ion-diatom frustule dry powder
2+a desorption rate along with the increase of solid-to-liquid ratio in reduction trend, but hydrochloric acid solution all presents good desorption effect to lead ion-diatom frustule dry powder.
Embodiment 3
In the description of embodiment 3, do not repeat them here with the something in common of embodiment 1, only describe the difference with embodiment 1.Embodiment 3 is with the difference of embodiment 1:
In the present embodiment, the solution containing heavy metal ion is respectively:
Experimental group 3: initial ion concentration be 100ppm respectively containing heavy metal ion Pb
2+, Cu
2+, Cd
2+, Ni
2+, Ag
+single solion;
Experimental group 4: initial ion concentration is the heavy metal ion Pb of 100ppm
2+, Cu
2+, Cd
2+, Ni
2+, Ag
+the mixed ion solutions coexisted.
The pH scope of above-mentioned each single solion and mixed ion solutions is regulated to be 4 ~ 6.
Other steps are see (reaction time is 24h) shown in embodiment 1.Testing result is as shown in table 7.
Table 7 diatom frustule is to the absorption result of each heavy metal ion in each single solion and mixed ion solutions
As known from Table 7, the diatom frustule of the present embodiment acquisition is to Pb
2+, Cu
2+, Cd
2+, Ni
2+, Ag
+five heavy metal species ions all have certain absorption property; But organize in 3 and experimental group 4 by experiment and see on the adsorption effect of different heavy metal ion, when there is the competitive Adsorption between contents of many kinds of heavy metal ion, this diatom frustule heavy metal ion Pb
2+adsorption rate still can reach 50.67%, be non-competing absorption time adsorption rate (71.03%) 71.34%; That is, when there is the competitive Adsorption between contents of many kinds of heavy metal ion, this diatom frustule is especially for heavy metal ion Pb
2+adsorption effect best, adsorption rate reaches 50.67%; Meanwhile, the experimental group 3 in contrast the present embodiment and the testing result of experimental group 1 in embodiment 1, experimental group 3 is this diatom frustule heavy metal ion Pb in experimental group 1 comparatively
2+adsorption rate higher, illustrate that this diatom frustule is to this concentration range (heavy metal ion Pb
2+initial concentration be no more than 100ppm) heavy metal ion Pb
2+there is better selective absorption effect.
Embodiment 4
In the description of embodiment 4, do not repeat them here with the something in common of embodiment 1, only describe the difference with embodiment 1.Embodiment 4 is with the difference of embodiment 1, and employing diatom source is four kinds of isolated Bacillariophyceae algae kinds, is respectively Chaetoceros muelleri, Nitzschia closterium minutissima, hailian seaweed, cocoon shape algae; Then Chaetoceros muelleri, Nitzschia closterium minutissima, hailian seaweed, cocoon shape algae frustule is obtained respectively according to the preparation method in embodiment 1.
Be that above-mentioned four kinds of diatom frustules add containing heavy metal ion Pb by the ratio of 1g/L respectively according to solid-to-liquid ratio
2+initial concentration be (should containing heavy metal ion Pb in the aqueous solution of 350ppm
2+the pH of the aqueous solution be 4 ~ 6), be placed in constant-temperature table and vibrate at 25 DEG C 24h, controlling constant-temperature table frequency of oscillation is 100rpm; Reaction time upon adsorption is after 24h, and the solution that takes a morsel crosses 0.45 μm of filter membrane, and detects heavy metal ion Pb in filtrate with inductively coupled plasma instrument (ICP)
2+concentration.Testing result is as shown in table 8.
The diatom frustule heavy metal ion Pb of the different isolated kind of table 8
2+adsorption effect
As can be seen from Table 8, the diatom frustule heavy metal ion Pb of different isolated kind
2+still have good adsorption effect, wherein, cocoon shape algae frustule is to Pb
2+adsorption effect best, its adsorption capacity is up to 168.13mg/g.
What deserves to be explained is, above-mentioned diatom frustule is to Pb in leaded solion
2+absorption, general keep the pH of this leaded solion to be 3 ~ 6, wherein the concentration of lead ion is 40ppm ~ 350ppm; And in adsorption process, the solid-to-liquid ratio of diatom frustule and leaded solion controls, for 1g/L ~ 10g/L, can reach object of the present invention.
The absorption property of the biological adsorption agent heavy metal ion prepared according to the preparation method of biological adsorption agent of the present invention is not only far superior to the absorption property of other common adsorbents in prior art, simultaneously its especially heavy metal ion Pb
2+there is good adsorption effect; Further, when contents of many kinds of heavy metal ion coexist, there is competitive Adsorption time, according to biological adsorption agent heavy metal ion Pb of the present invention
2+adsorption effect more embody the selective absorption effect of advantage.
Although illustrate and describe the present invention with reference to specific embodiment, but it should be appreciated by those skilled in the art that: when not departing from the spirit and scope of the present invention by claim and equivalents thereof, the various changes in form and details can be carried out at this.
Claims (9)
1. a preparation method for biological adsorption agent, is characterized in that, comprises step:
A, in sea water medium, introduce diatom source, under environment temperature, aeration is cultured to the stable growth phase, obtains diatom liquid;
B, centrifugal treating is carried out to described diatom liquid, obtain diatom concentrate;
C, dry described diatom concentrate, obtain diatom dry powder;
D, described diatom dry powder obtain diatom frustule through pickling, drying, roasting.
2. preparation method according to claim 1, is characterized in that, in described step D, the reagent of described pickling is hydrochloric acid solution, and the mass concentration of described hydrochloric acid solution is not less than 2%, and pickling time is at least 0.5h; The temperature of described roasting is not less than 600 DEG C, and roasting time is at least 0.5h.
3. preparation method according to claim 1, is characterized in that, described sea water medium for add artificial seawater nutritional agents in natural sea-water.
4. preparation method according to claim 1, is characterized in that, described diatom source is isolated Bacillariophyceae algae kind; Or in sea water medium under environment temperature aeration be cultured to the stable growth phase obtain mixed diatom algae kind.
5. preparation method according to claim 1, is characterized in that, described diatom be selected from Chaetoceros muelleri, Nitzschia closterium minutissima, hailian seaweed, cocoon shape algae any one.
6. one kind utilizes the method for the arbitrary described biological adsorption agent process lead ion of claim 1-5, it is characterized in that, comprise step: be added to by diatom frustule in leaded solion, vibrate under room temperature more than 4h, make described diatom frustule adsorpting lead ion reach balance, obtain lead ion-diatom frustule; Wherein, the pH of described leaded solion is 3 ~ 6.
7. the method for process lead ion according to claim 6, is characterized in that, in described leaded solion, the concentration of lead ion is 40ppm ~ 350ppm.
8. the method for process lead ion according to claim 6, is characterized in that, the solid-to-liquid ratio of described diatom frustule and described leaded solion is 1g/L ~ 10g/L.
9. the method for process lead ion according to claim 6, is characterized in that, also comprise desorption step: by dry after described lead ion-diatom frustule centrifugation, obtain lead ion-diatom frustule dry powder; Be added in 0.1mol/L hydrochloric acid solution by described lead ion-diatom frustule dry powder, vibrate under room temperature 0.5h ~ 24h; Wherein, the solid-to-liquid ratio of described lead ion-diatom frustule dry powder and hydrochloric acid is 1g/L ~ 5g/L.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050207955A1 (en) * | 2004-03-17 | 2005-09-22 | Bo Wang | Mercury adsorbent composition, process of making same and method of separating mercury from fluids |
| CN103831081A (en) * | 2014-02-28 | 2014-06-04 | 深圳市兆凯生物工程研发中心有限公司 | Adsorbent for processing heavy metal wastewater and heavy metal wastewater processing method |
| CN104587975A (en) * | 2015-01-23 | 2015-05-06 | 北京大学深圳研究生院 | Preparation method and application of bio-adsorbent |
-
2015
- 2015-06-19 CN CN201510347274.2A patent/CN104959107B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050207955A1 (en) * | 2004-03-17 | 2005-09-22 | Bo Wang | Mercury adsorbent composition, process of making same and method of separating mercury from fluids |
| CN103831081A (en) * | 2014-02-28 | 2014-06-04 | 深圳市兆凯生物工程研发中心有限公司 | Adsorbent for processing heavy metal wastewater and heavy metal wastewater processing method |
| CN104587975A (en) * | 2015-01-23 | 2015-05-06 | 北京大学深圳研究生院 | Preparation method and application of bio-adsorbent |
Non-Patent Citations (2)
| Title |
|---|
| 秦捷等: "硅藻壳对重金属Cu2+吸附性能的研究", 《广东化工》 * |
| 蒋文凯等: "升温速率对活体硅藻壳提纯的影响", 《光学精密工程》 * |
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