CN107694543A - A kind of method for preparing adsorbent for heavy metal using mao bamboon paper cellulose modification - Google Patents
A kind of method for preparing adsorbent for heavy metal using mao bamboon paper cellulose modification Download PDFInfo
- Publication number
- CN107694543A CN107694543A CN201710926981.6A CN201710926981A CN107694543A CN 107694543 A CN107694543 A CN 107694543A CN 201710926981 A CN201710926981 A CN 201710926981A CN 107694543 A CN107694543 A CN 107694543A
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- cellulose
- mao bamboon
- heavy metal
- solution
- adsorbent
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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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- 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
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
Abstract
The invention discloses a kind of method for preparing adsorbent for heavy metal using mao bamboon paper cellulose modification.Main points using method are dissolved in mao bamboon paper cellulose in the mixed solution of sodium hydroxide and thiocarbamide, and cryogenic freezing handles the mao bamboon paper cellulose solution being uniformly dissolved, then reacts to obtain adsorbent product with the thiocarbamide in system after oxidation processes.The present invention introduces subsequent reactions raw material in cellulose solvent system, reactions steps are advantageously reduced, reduces and prepares cost, while propose higher value application bamboo resource one opens one's minds, the income of bamboo area of China peasant can be improved conscientiously, had important practical significance.
Description
Technical field
It is more particularly to a kind of to utilize mao bamboon paper pulp fiber the present invention relates to a kind of method for preparing adsorbent for heavy metal
The modified method for preparing adsorbent for heavy metal of element, belongs to high-molecular organic material field.
Background technology
With the development of recent decades process of industrialization, the discharge capacity of waste water is increasingly sharpened, so as to cause the serious of environment
Destroy.Various harmful materials are enriched in biological chain by water body in waste water, eventually enter into human body, are brought to the mankind serious
Deleterious effects.The heavy metal ion wherein contained is environmental pollution most serious and the harmful substance to human health risk maximum
One of.Therefore, the most attention that heavy metal wastewater thereby has been subjected to all circles how is administered.
The technique that efficiently separates for being presently used for removing heavy metal ions in sewage has：Precipitation, ion exchange, at electrochemistry
Reason, membrane technology, evaporation coagulation, counter-infiltration and electrodialysis etc., but the application of these technologies is limited by technique and economy sometimes, its
Middle absorption method receives very big concern.
Cellulose is the natural polymer that content is most abundant on the earth, by single D-Glucose unit by β-
1,4- glycosidic bond chains are formed by connecting.Contain many hydrophilic oh groups in cellulosic molecule, with porous and compare surface
The characteristics of product is big, itself just has certain adsorptivity, turns into the good material of adsorbent.Due to cellulose have it is a variety of not
Isostructural reactive group, chemical reactivity is big, so being modified available for efficient cellulose chemistry, turns into good chemistry
Reaction raw materials.But because cellulose is insoluble in the property of water, so being extremely difficult to during chemical modification is carried out to it
Homogeneous reaction, cause reaction not abundant enough.
Some researchs of adsorbent are being prepared using cellulose modified at present, most of is directly changed cellulose
Property, few see fully dissolves cellulose carry out homogeneous reaction.In metal ion adsorbent preparation field, Chinese patent
(CN 102476044A) " the cellulose base sorbing material and its preparation method that are used to remove heavy metal cation in water removal " is with a diameter of
The matrix material of 10nm-100 μm of native cellulose or the fiber of cellulose derivative as sorbing material, in described fiber
Plain substrate material surface is grafted the polyolefin containing carboxylic group, so that cellulosic matrix material surface carries carboxylic group,
With heavy metal cation electrostatic attraction effect occurs for the carboxylic group of institute's band, so as to by the Cd in water2+、Cr2+、Cu2+、Hg2+、Ni2 +、Pb2+And/or Zn2+Removed Deng deleterious cations, compared with heavy metal cation sorbent material of the prior art, this invention
Using native cellulose or cellulose derivative as absorption carrier, cost performance is higher, can contain the heavy metal cation in water
Amount is significantly less than state-set standard；" a kind of heavy metal ion has adsorption capacity to Chinese patent (CN 101274268A)
The ability of the boiomacromolecules such as microcrystalline cellulose, chitin is dissolved in biological adsorption agent and its preparation method and application " using ion liquid energy,
The hydridization intermingling material with absorption heavy metal ion ability is prepared, and describes its appearance structure and absorption property is carried out
Primary Study；Chinese patent (CN 104437410A) " is used to adsorb heavy metal ion, the modified cellulosic of organic pollution
Material and preparation method " activates to obtain alkalinized celluloses using cellulose as raw material, through alkali, then is made with ammonium ceric nitrate and azodiisobutyronitrile
Composite initiator, monomer 2- cyano group -3- ethoxy ethyl acrylates are grafted on alkalinized celluloses, using hydroxylamine solution to it
Amidoximeization is modified, and a kind of modified cellulosic materials not only rolled into a ball containing amidoxime group but also comprising azanol oximido, this invention is prepared
Raw material is cheap and easy to get, and preparation technology is simple, easy controlled operation, is easy to produce in batches, available for absorption heavy metal ions in wastewater, has
Organic pollutants；United States Patent (USP) (US20110008543A1) " Biodegradable biopolymers, method for their
Preparation and functional materials constituted by these biopolymers " use silk
Fibroin and it is at least one reacted selected from cellulose, Chitosan-phospholipid complex, the material can be by by silk element egg
White water solution is cast on the surface of base material, then the solution applied is dried to form membranaceous biodegradable life
Thing polymeric material, the biodegradable bio-polymer material effectively serve as metal ion adsorption material；United States Patent (USP)
(US 2016263554A1) " Nanofibrous materials for heavy metal adsorption " have to be modified
The nano-cellulose for having thiol group prepares water filtration film, and this film includes the material for effectively combining heavy metal ion, can applied
It is suitable for removing heavy metal ion from water in support.So far, yet there are no using mao bamboon paper cellulose in hydroxide
The related process technologies that dissolving prepares adsorbent for heavy metal in sodium/Thiourea occur.
The content of the invention
In order to overcome the fibrous raw material supply for preparing sorbent material at present insufficient, expensive, the problems such as complicated is reacted,
Pollution and destruction of the heavy metal ion to environment are reduced simultaneously, prepare the biodegradable adsorption of metal ions green wood of high added value
Material, it is an object of the invention to provide a kind of method for preparing adsorbent for heavy metal using mao bamboon paper cellulose modification.
To achieve the above object, the technical scheme is that using following steps：
1) mao bamboon pulpboard is shredded, dried, crushed using plant pulverizer, through 100 mesh sieve net filtrations, obtain particle diameter and be less than
Mao bamboon paper cellulose powder equal to 0.15mm；
2) the mao bamboon paper cellulose powder that step 1) obtains is added to 1~2h of precooling sodium hydroxide and thiocarbamide and mixed
Close in solution, be positioned in -10~-14 DEG C of environment and fully dissolve, obtain mao bamboon paper cellulose solution；
3) 0.6~1.0g sodium metaperiodate is added in the mao bamboon paper cellulose solution that step 2) obtains, 40~60
2~6h of mechanic whirl-nett reaction under the conditions of DEG C, reaction add ethylene glycol solution after terminating and terminate oxidation reaction, the fibre after being aoxidized
Tie up plain solution；
4) cellulose solution after the oxidation for obtaining step 3) is placed at room temperature, reacts 1~3h with the thiocarbamide in system,
Obtain modified cellulose suspension；
5) the modified cellulose suspension for obtaining step 4) is dialysed 2~3 days in bag filter, removes complete small of unreacted
Molecular raw material, product is freeze-dried, finally gives adsorbent for heavy metal.
Described sodium hydroxide and thiocarbamide mixed solution, the mass fraction of wherein sodium hydroxide and thiocarbamide is respectively 10~
The solid-to-liquid ratio of 11wt% and 8~9wt%, cellulose and mixed solution is 1:50~100；Ethylene glycol dosage is 1~3mL.
Described bag filter molecular cut off is 7000~9000D.
Compared with background technology, the invention has the advantages that：
The present invention introduces cellulose during sorbent reactions are prepared, and improves product biodegradability, carries simultaneously
Gone out to introduce subsequent reactions raw material in the dicyandiamide solution of dissolving cellulose one opens one's minds, and reduces experimental procedure, section
About experimental cost, meet national development circular economy policy.
Brief description of the drawings
Fig. 1 is the field emission scanning electron microscope photo of adsorbent for heavy metal prepared by embodiment 1.Wherein, (a1) is weight
Metal ion adsorbent amplifies 500 times of photos, and (a2) is that adsorbent for heavy metal amplifies 1000 times of photos.
Embodiment
With reference to specific embodiment, the invention will be further described.
Embodiment 1:
1) mao bamboon pulpboard is shredded, dried, crushed using plant pulverizer, through 100 mesh sieve net filtrations, obtain particle diameter and be less than
Mao bamboon paper cellulose powder equal to 0.15mm；
2) the mao bamboon paper cellulose powder for obtaining step 1) is by cellulose and mixed solution 1:75 solid-to-liquid ratio adds
The mass fraction of sodium hydroxide and thiocarbamide to precooling 1.5h is respectively in 10.5wt% and 8.5wt% mixed solution, is put
It is placed in -12 DEG C of environment and fully dissolves, obtains mao bamboon paper cellulose solution；
3) 0.8g sodium metaperiodate, the machine under the conditions of 50 DEG C are added in the mao bamboon paper cellulose solution that step 2) obtains
Tool stirring reaction 4h, reaction add 1mL ethylene glycol solutions after terminating and terminate oxidation reaction, the cellulose solution after being aoxidized；
4) cellulose solution after the oxidation for obtaining step 3) is placed at room temperature, is reacted 2h with the thiocarbamide in system, is obtained
To modified cellulose suspension；
5) the modified cellulose suspension that step 4) obtains is dialysed 2 days in the bag filter that molecular cut off is 8000D,
The complete small-molecule starting material of unreacted is removed, product is freeze-dried, finally gives adsorbent for heavy metal (a).
Embodiment 2:
1) mao bamboon pulpboard is shredded, dried, crushed using plant pulverizer, through 100 mesh sieve net filtrations, obtain particle diameter and be less than
Mao bamboon paper cellulose powder equal to 0.15mm；
2) the mao bamboon paper cellulose powder for obtaining step 1) is by cellulose and mixed solution 1:100 solid-to-liquid ratio adds
The mass fraction of sodium hydroxide and thiocarbamide to precooling 1h is respectively in 11wt% and 8wt% mixed solution, is positioned over -10
DEG C environment in fully dissolve, obtain mao bamboon paper cellulose solution；
3) 1.0g sodium metaperiodate, the machine under the conditions of 60 DEG C are added in the mao bamboon paper cellulose solution that step 2) obtains
Tool stirring reaction 6h, reaction add 2mL ethylene glycol solutions after terminating and terminate oxidation reaction, the cellulose solution after being aoxidized；
4) cellulose solution after the oxidation for obtaining step 3) is placed at room temperature, is reacted 1h with the thiocarbamide in system, is obtained
To modified cellulose suspension；
5) the modified cellulose suspension that step 4) obtains is dialysed 3 days in the bag filter that molecular cut off is 9000D,
The complete small-molecule starting material of unreacted is removed, product is freeze-dried, finally gives adsorbent for heavy metal (b).
Embodiment 3:
1) mao bamboon pulpboard is shredded, dried, crushed using plant pulverizer, through 100 mesh sieve net filtrations, obtain particle diameter and be less than
Mao bamboon paper cellulose powder equal to 0.15mm；
2) the mao bamboon paper cellulose powder for obtaining step 1) is by cellulose and mixed solution 1:50 solid-to-liquid ratio adds
The mass fraction of sodium hydroxide and thiocarbamide to precooling 2h is respectively in 10wt% and 9wt% mixed solution, is positioned over -14
DEG C environment in fully dissolve, obtain mao bamboon paper cellulose solution；
3) 0.6g sodium metaperiodate, the machine under the conditions of 40 DEG C are added in the mao bamboon paper cellulose solution that step 2) obtains
Tool stirring reaction 2h, reaction add 3mL ethylene glycol solutions after terminating and terminate oxidation reaction, the cellulose solution after being aoxidized；
4) cellulose solution after the oxidation for obtaining step 3) is placed at room temperature, is reacted 3h with the thiocarbamide in system, is obtained
To modified cellulose suspension；
5) the modified cellulose suspension that step 4) obtains is dialysed 2 days in the bag filter that molecular cut off is 7000D,
The complete small-molecule starting material of unreacted is removed, product is freeze-dried, finally gives adsorbent for heavy metal (c).
The constituent content for the three heavy metal species ion adsorbents that measure embodiment 1,2,3 is prepared.Table 1 is by embodiment
1st, the EDS constituent content characterization results of 2,3 adsorbent for heavy metal prepared.From data in table 1, using institute of the present invention
Adsorbent for heavy metal (a), adsorbent for heavy metal (b), the adsorbent for heavy metal (c) for the preparation method acquisition stated
In have the appearance of N element and S elements compared with cellulose, this shows that thiocarbamide has successfully been grafted on cellulose.
Such as Fig. 1, the field emission scanning electron microscope photo of the adsorbent for heavy metal prepared from embodiment 1 can be seen that, its shape
Looks are generally proximate to cellulose pattern, and in club shaped structure, many fine particle shape materials are adhered on fiber, it is added and compares surface
Product, be advantageous to be lifted the adsorption effect of heavy metal ion.
Table 1
Listed above is only the specific embodiment of the present invention.The invention is not restricted to above example, can also there is many
Deformation.All deformations that one of ordinary skill in the art directly can export or associate from present disclosure, all should
It is considered protection scope of the present invention.
Claims (3)
- A kind of 1. method for preparing adsorbent for heavy metal using mao bamboon paper cellulose modification, it is characterised in that including with Lower step：1) mao bamboon pulpboard is shredded, dried, crushed using plant pulverizer, through 100 mesh sieve net filtrations, obtain particle diameter and be less than or equal to 0.15mm mao bamboon paper cellulose powder；2) the mao bamboon paper cellulose powder that step 1) obtains is added molten to 1~2h of precooling sodium hydroxide and thiocarbamide mixing In liquid, it is positioned in -10~-14 DEG C of environment and fully dissolves, obtains mao bamboon paper cellulose solution；3) 0.6~1.0g sodium metaperiodate is added in the mao bamboon paper cellulose solution that step 2) obtains, in 40~60 DEG C of bars 2~6h of mechanic whirl-nett reaction under part, reaction add ethylene glycol solution after terminating and terminate oxidation reaction, the cellulose after being aoxidized Solution；4) cellulose solution after the oxidation for obtaining step 3) is placed at room temperature, is reacted 1~3h with the thiocarbamide in system, is obtained Modified cellulose suspension；5) the modified cellulose suspension for obtaining step 4) is dialysed 2~3 days in bag filter, removes the complete small molecule of unreacted Raw material, product is freeze-dried, finally gives adsorbent for heavy metal.
- A kind of 2. side that adsorbent for heavy metal is prepared using mao bamboon paper cellulose modification according to claim 1 Method, it is characterised in that：Described sodium hydroxide and thiocarbamide mixed solution, the mass fraction of wherein sodium hydroxide and thiocarbamide are respectively The solid-to-liquid ratio of 10~11wt% and 8~9wt%, cellulose and mixed solution is 1:50~100；Ethylene glycol dosage is 1~3mL.
- A kind of 3. side that adsorbent for heavy metal is prepared using mao bamboon paper cellulose modification according to claim 1 Method, it is characterised in that：Described bag filter molecular cut off is 7000~9000D.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109012638A (en) * | 2018-07-20 | 2018-12-18 | 浙江理工大学 | A kind of preparation method of carboxylated multi-stage porous cellulose adsorbing sphere |
| CN109777439A (en) * | 2019-03-07 | 2019-05-21 | 安徽省农业科学院土壤肥料研究所 | Soil heavy metal passivant and its application in reduction tomato Accumulation of heavy metals amount |
| CN113318570A (en) * | 2021-06-11 | 2021-08-31 | 浙江红狮环保股份有限公司 | Method for removing mercury in flue gas |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109012638A (en) * | 2018-07-20 | 2018-12-18 | 浙江理工大学 | A kind of preparation method of carboxylated multi-stage porous cellulose adsorbing sphere |
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| CN109777439A (en) * | 2019-03-07 | 2019-05-21 | 安徽省农业科学院土壤肥料研究所 | Soil heavy metal passivant and its application in reduction tomato Accumulation of heavy metals amount |
| CN113318570A (en) * | 2021-06-11 | 2021-08-31 | 浙江红狮环保股份有限公司 | Method for removing mercury in flue gas |
| CN113318570B (en) * | 2021-06-11 | 2022-04-19 | 浙江红狮环保股份有限公司 | Method for removing mercury in flue gas |
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