CN106986396A - A kind of modification of chitosan and preparation method thereof - Google Patents
A kind of modification of chitosan and preparation method thereof Download PDFInfo
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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
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- 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
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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- 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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- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
- C02F1/5245—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
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- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/105—Phosphorus compounds
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
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- 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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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/14—NH3-N
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2209/16—Total nitrogen (tkN-N)
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/02—Odour removal or prevention of malodour
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Abstract
The invention discloses a kind of modification of chitosan, the weight proportion of wherein each component is：10 15 parts of chitosan, 10 15 parts of aluminium polychloride, 35 parts of ethylenediamine, 35 parts of silane coupler, 15 parts of sodium hydroxide, 15 parts of polyacrylamide, 15 parts of aluminum sulfate, 15 parts of modification infusorial earth, the wherein ratio of polyacrylamide and modification infusorial earth are 1:1.A kind of modification of chitosan that the present invention is obtained, can effectively reduce the content of COD in water, total nitrogen, total phosphorus and ammonia nitrogen, effect is notable in terms of denitrogenation dephosphorizing.
Description
Technical field
The present invention relates to a kind of water treatment agent, particularly a kind of modification of chitosan and preparation method thereof.
Background technology
The bait added during fish culture all can not utilize effectively by cultivation object, have 70% ~ 80% to feed
Material is to dissolve or particulate form is discharged into water body, wherein there are about 51% nitrogen and 64% phosphorus is discharged into ring in the form of pollutant
In border.The eutrophication process of water proximate will be further exacerbated by, and wherein the higher of phosphorus concentration is to cause algae bio crazy
Long principal element, therefore the concentration of reduction water body nitrogen phosphorus especially phosphorus is the primary approach for solving the problems, such as body eutrophication.With
Industrial wastewater is compared with sanitary sewage, and aquiculture waste water has that pollutant load is low, the big and pollutant that need to handle water
The characteristics of main component, structure are different from common Lu Yuan sewage.Main processing method has physics, chemistry and biological treatment,
Wherein, the engineering measure investment of physical method is huge, often cures the symptoms, not the disease；Chemical method easily causes secondary pollution；Biology side
The method cycle of operation is long, and single treatment does not reach discharge standard.In view of the defect of above-mentioned conventional method, adsorption treatment method can yet be regarded as one
Important physico-chemical process is planted, is played an important role all the time in cultivating wastewater purification.
Chitosan (CTS) is the deacetylated products of chitin N-, is the nitrogen-containing basic polysaccharide that nature is uniquely largely present.From
Since 1970s, chitosan, chitin are utilized and studied with its unique physicochemical properties and bioactivity, are enjoyed
The favor of researcher, it is considered to be " green water treatment agent ", currently turns into the study hotspot in environment-friendly material field.Cause
Contain substantial amounts of hydroxyl and amino in chitosan and its modifier molecule, there is very strong chelation to metal ion, can be with
For reclaiming the industrial wastewater of heavy metal and processing containing heavy metal ion.But currently without modified chitosan in sewage disposal
The effect of middle denitrogenation dephosphorizing is also less desirable.
The content of the invention
A kind of one kind of high-efficient denitrification and dephosphorization is provided the invention aims to solve above-mentioned the deficiencies in the prior art
Modification of chitosan and preparation method thereof.
To achieve these goals, a kind of modification of chitosan designed by the present invention, the weight proportion of wherein each component is：
It is 10-15 parts of chitosan, 10-15 parts of aluminium polychloride, 3-5 parts of ethylenediamine, 3-5 parts of silane coupler, 1-5 parts of sodium hydroxide, poly-
1-5 parts of acrylamide, 1-5 parts of aluminum sulfate, 1-5 parts of modification infusorial earth, the ratio of wherein polyacrylamide and modification infusorial earth is
1:1。
Each component weight proportion in the modification infusorial earth is 60 parts of diatomite, 15 parts of pomelo peel, 5 parts of activated carbon, stone
Black 10 parts of alkene, 2 parts of poly-ferric chloride, 3 parts of cerous nitrate, 5 parts of oxalic acid.
The polyacrylamide is PAMC, and its molecular weight is 10,000,000.
The chitosan is water soluble chitosan.
A kind of preparation method of modification of chitosan, comprises the following steps：
Step 1, pomelo peel is cleaned with distilled water, dries 2h after chopping at 105 DEG C, ground after taking-up, taken after crossing 100 mesh sieves
15 parts are put into beaker, add 5 parts of activated carbon, it is well mixed after be put into the 2- well prepared in advance being made up of 5 parts of oxalic acid
In 3mol/L oxalic acid solution, 60 parts of diatomite, 10 parts of graphene, 2 parts of poly-ferric chloride, 3 parts of cerous nitrate are then sequentially placed into,
By stirring mixing, after the normal-temperature reaction of 24 hours, deliver in baking oven, take out cooling after being dried in 105 DEG C, be ground to
100 mesh, it is standby to make to obtain modification infusorial earth；
Step 2, it is 10-15 parts of 10-15 parts of chitosan and aluminium polychloride is soluble in water, it is then slow while stirring at 80 DEG C
1-5 parts of sodium hydroxide is added, 3-5 parts of ethylenediamine, 3-5 parts of silane coupler is subsequently added into, after being uniformly mixed, stood
24 hours, then air-dry at normal temperatures, obtain mixture A standby to make；
Step 3, it is 1-5 parts of aluminum sulfate, 1-5 parts of polyacrylamide is soluble in water, mixed by mixing apparatus, at normal temperatures and pressures
By 100 turns per minute, through 10 ~ 20 minutes be thoroughly mixed, mixture B is obtained standby to make；
Step 4, it is soluble in water after mixture A is mixed with mixture B, then 1-5 parts of modification infusorial earth is put into, in normal temperature and pressure
Under, after the mixing that 30 ~ 60 minutes are carried out by 100 turns per minute of speed, natural air drying is the modification shell for obtaining the present invention
Glycan.
Wherein chitosan (CTS) is white plates or pulverulent solids with pearly luster, with biodegradability,
Various bacteria, the growth of fungi can also be suppressed.Chitosan causes the concern of people as material for water treatment, living on its strand
Property amino and hydroxyl have very strong suction-operated to pollutant, its absorption to pollutant mainly has physical absorption, chemistry to inhale
Echo ion exchange absorption.Chitosan contains substantial amounts of hydroxyl and amino, can generate chelate with metal formation coordinate bond.Change
It is monolayer adsorption to learn absorption, selective.Physical absorption is the suction by electrostatic attraction, hydrophobic reciprocation, Van der Waals force etc.
It is attached, it is multilayer absorption.Many hydroxyls, amino and some N- acetylaminos are dispersed with the macromolecular chain of chitosan, can be in acidity
The cationic polyelectrolyte of high charge density is formed in solution, similar network structure can be also formed by hydrogen bond or ionic bond
Cage molecule, is settled so as to condense the suspension in water.
There is aluminium polychloride (PAC) color to be in yellow, there is the performances such as absorption, cohesion, precipitation, aluminium polychloride stability
Difference.Toxicity and protection are corrosive, and with powder is thin, particle is uniform, soluble in water, flocculating effect is good, purification efficient stable, throw
Dosage is few, the low feature of cost.It is suitable in terms of drink water purifying, city water purification and industrial water supply purification；It is applied to
The source water of various turbidity, pH is applied widely, and it is fast that alumen ustum forms big, fast, sinking speed.Due to spray dried products stability
Good, adaptation waters is wide, and hydrolysis rate is fast, high adsorption capacity, forms alumen ustum greatly, and soon, delivery turbidity is low, dewatering for the close precipitation of matter
Good the advantages of, in the case of same water quality, spray drying aluminium polychloride throwing amount is reduced.
By the way that chitosan and aluminium polychloride are mixed, then cause on chitosan on hydroxyl radical free radical with the aluminium in aluminium chloride
Ion coordination, aluminium ion covers chitosan surface increase surface area and space, increases adsorbance.Increase ethylenediamine simultaneously, draw
More NH are entered2, obtained compound adsorbent is increased than the adsorption activity point of chitosan, so as to improve adsorbance.
Increase silane coupler, then introduce SiO2The density of chitosan is increased, makes made compound adsorbent more heavy than chitosan
Reduction of speed rate is accelerated.
Simultaneously polyacrylamide also have good flocculability, the frictional resistance between liquid can be reduced, with aluminium from
During son mixing, its flocculation ability can be strengthened, increase the cohesiveness of adsorbed material to a certain extent.Chitosan-aluminium-polypropylene
Acid amides three can promote mutually, improve flocculation ability.
Other diatomite is a kind of siliceous organism sedimentary rock, and main chemical is SiO2, and contain a small amount of Al2O3,
P2O5, CaO, MgO etc., it is made up of the wall shell of diatom, has multistage, a large amount of, micropore of ordered arrangement on wall shell, surface has largely
Carboxyl is covered, thus aobvious faintly acid, is referred to as solid acid in catalytic field.Diatomite light weight, porous, relative density are small, aperture
Distribution is big, and porosity is high, and high adsorption capacity can adsorb 1.5~4 times of impurity of own wt.Therefore, by diatomite
Unique microcellular structure, waste water is handled using its absorption property can not only reduce cost, but also can more effective land productivity
With the mineral resources of China's abundant.And in this patent, diatomite is modified using graphene and poly-ferric chloride so that change
Diatomite after property is greatly improved for the clearance of organic matter.When graphene and poly-ferric chloride are distributed in diatomaceous surface
When, there is stronger cohesiveness to the organic matter in sewage so that more organic matters are attracted in microcellular structure.While nitre
The addition of sour cerium then improves facilitation, improves the activity of graphene and poly-ferric chloride.The shaddock peel powder that it is possible to additionally incorporate
End, is also the material with stronger adsorption capacity, and both diatomite and pomelo peel powder cooperate, had to organic removal rate
Bigger enhancement effect, and the toxic heavy metal ion that pomelo peel powder can be in absorption effluent.Wherein activated carbon has
There are certain deodorizing capability and adsorption capacity, to having certain improvement result on sanitary sewage smell.
A kind of modification of chitosan that the present invention is obtained, organic matter that can effectively in absorption effluent, so as to reduce in water
COD, total nitrogen, the content of total phosphorus and ammonia nitrogen, effect is notable in terms of denitrogenation dephosphorizing.
Embodiment
With reference to embodiment, the present invention is further described.
Embodiment 1：
A kind of modification of chitosan that the present embodiment is provided, the weight proportion of each component is：10 parts of chitosan, aluminium polychloride 10
Part, 3 parts of ethylenediamine, 3 parts of silane coupler, 2 parts of sodium hydroxide, 3 parts of polyacrylamide, 3 parts of aluminum sulfate, 3 parts of modification infusorial earth.
Each component weight proportion in the modification infusorial earth is 60 parts of diatomite, 15 parts of pomelo peel, 5 parts of activated carbon, stone
Black 10 parts of alkene, 2 parts of poly-ferric chloride, 3 parts of cerous nitrate, 5 parts of oxalic acid.
A kind of preparation method of modification of chitosan, comprises the following steps：
Step 1, pomelo peel is cleaned with distilled water, dries 2h after chopping at 105 DEG C, ground after taking-up, taken after crossing 100 mesh sieves
15 parts are put into beaker, add 5 parts of activated carbon, it is well mixed after be put into the 2- well prepared in advance being made up of 5 parts of oxalic acid
In 3mol/L oxalic acid solution, 60 parts of diatomite, 10 parts of graphene, 2 parts of poly-ferric chloride, 3 parts of cerous nitrate are then sequentially placed into,
By stirring mixing, after the normal-temperature reaction of 24 hours, deliver in baking oven, take out cooling after being dried in 105 DEG C, be ground to
100 mesh, it is standby to make to obtain modification infusorial earth；
Step 2, it is 10 parts of 10 parts of chitosan and aluminium polychloride is soluble in water, then hydrogen is slowly added to while stirring at 80 DEG C
2 parts of sodium oxide molybdena, is subsequently added into 32 parts of ethylenediamine, 32 parts of silane coupler, after being uniformly mixed, and stands 24 hours, so
Air-dry at normal temperatures afterwards, obtain mixture A standby to make；
Step 3, it is 3 parts of aluminum sulfate, 3 parts of polyacrylamide is soluble in water, mixed by mixing apparatus, at normal temperatures and pressures by every
100 turns of minute, through 10 ~ 20 minutes be thoroughly mixed, obtain mixture B standby to make；
Step 4, it is soluble in water after mixture A is mixed with mixture B, then 1-5 parts of modification infusorial earth is put into, in normal temperature and pressure
Under, after the mixing that 30 ~ 60 minutes are carried out by 100 turns per minute of speed, natural air drying is the modification shell for obtaining the present invention
Glycan.
Modification of chitosan made from the present embodiment is used to handle breeding wastewater, its result is as follows：COD, total nitrogen, total phosphorus and
The clearance of ammonia nitrogen is respectively：93.4%、87.1%、87.3%、92.5%.
Embodiment 2：
A kind of modification of chitosan that the present embodiment is provided and preparation method thereof is substantially same as Example 1, and its main distinction point exists
In the weight proportion of each component is in the present embodiment：It is 15 parts of chitosan, 15 parts of aluminium polychloride, 3 parts of ethylenediamine, silane coupled
33 parts of agent, 2 parts of sodium hydroxide, 5 parts of polyacrylamide, 5 parts of aluminum sulfate, 5 parts of modification infusorial earth.
Modification of chitosan made from the present embodiment is used to handle breeding wastewater, its result is as follows：COD, total nitrogen, total phosphorus and
The clearance of ammonia nitrogen is respectively：92.5%、88.3%、86.9%、93.1%.
Embodiment 3：
A kind of modification of chitosan that the present embodiment is provided and preparation method thereof is substantially same as Example 1, and its main distinction point exists
In the weight proportion of each component is in the present embodiment：It is 12 parts of chitosan, 12 parts of aluminium polychloride, 5 parts of ethylenediamine, silane coupled
5 parts of agent, 5 parts of sodium hydroxide, 4 parts of polyacrylamide, 4 parts of aluminum sulfate, 4 parts of modification infusorial earth.
Modification of chitosan made from the present embodiment is used to handle breeding wastewater, its result is as follows：COD, total nitrogen, total phosphorus and
The clearance of ammonia nitrogen is respectively：93.6%、88.3%、87.9%、92.8%.
Claims (5)
1. a kind of modification of chitosan, it is characterized in that the weight proportion of each component is：10-15 parts of chitosan, aluminium polychloride 10-15
Part, 3-5 parts of ethylenediamine, 3-5 parts of silane coupler, 1-5 parts of sodium hydroxide, 1-5 parts of polyacrylamide, 1-5 parts of aluminum sulfate, modification
1-5 parts of diatomite, the wherein ratio of polyacrylamide and modification infusorial earth are 1:1.
2. a kind of modification of chitosan according to claim 1, it is characterized in that each component weight in the modification infusorial earth
Match as 60 parts of diatomite, 15 parts of pomelo peel, 5 parts of activated carbon, 10 parts of graphene, 2 parts of poly-ferric chloride, 3 parts of cerous nitrate, oxalic acid
5 parts.
3. a kind of modification of chitosan according to claim 1, it is characterized in that the polyacrylamide is cation polypropylene
Acid amides, its molecular weight is 10,000,000.
4. a kind of modification of chitosan according to claim 1, it is characterized in that the chitosan is water soluble chitosan.
5. a kind of preparation method of modification of chitosan as claimed in claim 1, it is characterized in that comprising the following steps：
Step 1, pomelo peel is cleaned with distilled water, dries 2h after chopping at 105 DEG C, ground after taking-up, taken after crossing 100 mesh sieves
15 parts are put into beaker, add 5 parts of activated carbon, it is well mixed after be put into the 2- well prepared in advance being made up of 5 parts of oxalic acid
In 3mol/L oxalic acid solution, 60 parts of diatomite, 10 parts of graphene, 2 parts of poly-ferric chloride, 3 parts of cerous nitrate are then sequentially placed into,
By stirring mixing, after the normal-temperature reaction of 24 hours, deliver in baking oven, take out cooling after being dried in 105 DEG C, be ground to
100 mesh, it is standby to make to obtain modification infusorial earth；
Step 2, it is 10-15 parts of 10-15 parts of chitosan and aluminium polychloride is soluble in water, it is then slow while stirring at 80 DEG C
1-5 parts of sodium hydroxide is added, 3-5 parts of ethylenediamine, 3-5 parts of silane coupler is subsequently added into, after being uniformly mixed, stood
24 hours, then air-dry at normal temperatures, obtain mixture A standby to make；
Step 3, it is 1-5 parts of aluminum sulfate, 1-5 parts of polyacrylamide is soluble in water, mixed by mixing apparatus, at normal temperatures and pressures
By 100 turns per minute, through 10 ~ 20 minutes be thoroughly mixed, mixture B is obtained standby to make；
Step 4, it is soluble in water after mixture A is mixed with mixture B, then 1-5 parts of modification infusorial earth is put into, in normal temperature and pressure
Under, after the mixing that 30 ~ 60 minutes are carried out by 100 turns per minute of speed, natural air drying is the modification shell for obtaining the present invention
Glycan.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109319895A (en) * | 2018-10-23 | 2019-02-12 | 四川意德康环保科技有限公司 | A kind of aluminium polychloride and preparation method thereof that Nano chitosan is modified |
| CN112127049A (en) * | 2020-09-30 | 2020-12-25 | 安徽灵春医用耗材有限公司 | Preparation method of polypropylene melt-blown non-woven fabric material for mask |
| CN112320914A (en) * | 2020-10-13 | 2021-02-05 | 神美科技有限公司 | Phosphorus removal agent with composite function and phosphorus removal method |
| CN114105245A (en) * | 2021-12-09 | 2022-03-01 | 宝钢湛江钢铁有限公司 | Treatment process for removing soluble organic matters in reverse osmosis concentrated water |
| CN114275832A (en) * | 2021-12-22 | 2022-04-05 | 江苏宿迁润泰环保科技有限公司 | Biological polysaccharide-based sewage treatment agent and application thereof in sewage treatment process |
| CN116789331A (en) * | 2023-08-22 | 2023-09-22 | 青岛中润设备仪表有限公司 | Sea water desalination process |
| CN117142548A (en) * | 2023-10-30 | 2023-12-01 | 中国科学院东北地理与农业生态研究所 | Wastewater treatment material based on graphene composite modification and preparation method thereof |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109319895A (en) * | 2018-10-23 | 2019-02-12 | 四川意德康环保科技有限公司 | A kind of aluminium polychloride and preparation method thereof that Nano chitosan is modified |
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| CN112127049A (en) * | 2020-09-30 | 2020-12-25 | 安徽灵春医用耗材有限公司 | Preparation method of polypropylene melt-blown non-woven fabric material for mask |
| CN112320914A (en) * | 2020-10-13 | 2021-02-05 | 神美科技有限公司 | Phosphorus removal agent with composite function and phosphorus removal method |
| CN112320914B (en) * | 2020-10-13 | 2022-09-27 | 神美科技有限公司 | Phosphorus removal agent with composite function and phosphorus removal method |
| CN114105245A (en) * | 2021-12-09 | 2022-03-01 | 宝钢湛江钢铁有限公司 | Treatment process for removing soluble organic matters in reverse osmosis concentrated water |
| CN114275832A (en) * | 2021-12-22 | 2022-04-05 | 江苏宿迁润泰环保科技有限公司 | Biological polysaccharide-based sewage treatment agent and application thereof in sewage treatment process |
| CN114275832B (en) * | 2021-12-22 | 2022-10-18 | 江苏宿迁润泰环保科技有限公司 | Biological polysaccharide-based sewage treatment agent and application thereof in sewage treatment process |
| CN116789331A (en) * | 2023-08-22 | 2023-09-22 | 青岛中润设备仪表有限公司 | Sea water desalination process |
| CN116789331B (en) * | 2023-08-22 | 2023-11-10 | 青岛中润设备仪表有限公司 | Sea water desalination process |
| CN117142548A (en) * | 2023-10-30 | 2023-12-01 | 中国科学院东北地理与农业生态研究所 | Wastewater treatment material based on graphene composite modification and preparation method thereof |
| CN117142548B (en) * | 2023-10-30 | 2024-01-09 | 中国科学院东北地理与农业生态研究所 | Wastewater treatment material based on graphene composite modification and preparation method thereof |
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Application publication date: 20170728 |