CN110215848A - A kind of preparation method of high intensity sewage treatment composite membrane - Google Patents
A kind of preparation method of high intensity sewage treatment composite membrane Download PDFInfo
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- CN110215848A CN110215848A CN201910416527.5A CN201910416527A CN110215848A CN 110215848 A CN110215848 A CN 110215848A CN 201910416527 A CN201910416527 A CN 201910416527A CN 110215848 A CN110215848 A CN 110215848A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
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- 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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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3021—Milling, crushing or grinding
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
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- 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
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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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
- B01J2220/4825—Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton
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- B01J2220/00—Aspects relating to sorbent materials
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- B01J2220/4875—Sorbents characterised by the starting material used for their preparation the starting material being a waste, residue or of undefined composition
- B01J2220/4881—Residues from shells, e.g. eggshells, mollusk shells
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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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Abstract
The present invention relates to a kind of preparation methods of high-intensitive sewage treatment composite membrane, belong to technical field of sewage.Bamboo plate is placed in steam blasting tank by the present invention carry out in steam blasting the obtained steam explosion product of steam blasting, steam explosion product is mixed with egg shell then, sodium chlorite and lye mixing are added simultaneously, add 2, 3- epoxypropyltrimethylchloride chloride mixes pyroreaction and reaction product is made, then reaction product is freeze-dried and is mixed into copper sulphate, citric acid solution reaction, calcined product is made in high-temperature calcination after reaction, finally by calcined product and collagen solution, chitosan is uniformly mixed and is laid on mold, film is taken off after drying, and high-intensitive sewage treatment composite membrane is made, the present invention is mixed with bamboo plate using egg shell and therefrom extracts organic principle, make to introduce each organic substance in bamboo fibre, enhance crosslink density, improve the mechanical strength of composite membrane, being mixed into chitosan simultaneously makes composite membrane have bactericidal effect, have Wide application prospect.
Description
Technical field
The present invention relates to a kind of preparation methods of high-intensitive sewage treatment composite membrane, belong to technical field of sewage.
Background technique
With the development of industry, heavy metal pollution is increasingly severe, the propagation that the contaminated wastewater of heavy metal passes through food chain
Far-reaching influence will be generated for environment, the contaminated wastewater of heavy metal is increasingly becoming global research topic.Currently, water
Weight metallic pollution repairing and treating uses following two Basic Ways: first is that reducing the bioavailability of heavy metal and in water body
In transfer ability；Second is that heavy metal is thoroughly removed from polluted water body, mainly there are a following three classes: chemical method, physico
Method and bioanalysis.
In heavy metal-polluted water process, the absorption method in physical method is most common technical method, mainly using porous
Property solid matter absorption water pollutant handle waste water.The active charcoal of traditional adsorbent, zeolite, vermiculite, sepiolite, diatom
Scholar, haydite etc., wherein haydite is a kind of product of relatively inexpensive carry out wastewater treatment, and existing research haydite is usually adopted
It is prepared with sintering process and unburned method, but the requirement of high-efficiency environment friendly development, the especially surface of ardealite product can not have been adapted to
Since the internal soluble impurity content of ardealite itself is higher, overall performance is poor, therefore for absorption heavy metal ion
Attention of the research of ardealite product by researcher.
In the prior art for the surface of the ardealite product of heavy metal containing sewage adsorption treatment since ardealite itself is internal
Soluble impurity content it is higher, especially sodium content is higher, leads to surface dusting, thereby reduces ardealite composite membrane product
Intensity and toughness, and then lead to the second-rate of ardealite product, the weatherability and corrosion resistance of product are poor, use the longevity
Order the problems such as more of short duration.
There are at high cost, low efficiencys, secondary pollution problems for traditional sewage water treatment method.Studies have shown that being urged with light
The semiconductor nano grade oxide for the property changed can utilize ultraviolet degradation multiple pollutant, can by hydro carbons in water, surfactant,
The oxygenolysis such as organic dyestuff, itrogenous organic substance, organophosphorus insecticide, timber preservative, can be used for sewage treatment.Using powder
When composite membrane made from photocatalytic oxide carries out sewage treatment, there are the recycling of powder difficulty, suspension powders to influence light penetration
The problems such as；Therefore titanium deoxid film is mostly used to carry out photocatalysis in recent years, but there are contacts area smaller, catalytic efficiency
Low, the problems such as service life is not high.
Summary of the invention
The technical problems to be solved by the invention: current sewage treatment composite membrane mechanical strength difference easy fracture, chemistry are directed to
The bad defect of stability, strainability provides a kind of preparation method of high-intensitive sewage treatment composite membrane.
In order to solve the above technical problems, the technical solution adopted by the present invention is that:
The specific preparation step of high-intensitive sewage treatment composite membrane are as follows:
Weigh sieving product, the vinegar that collagen solution, chitosan and the mass fraction that mass fraction is 5~8% are 4~6%
Acid solution is put into reaction kettle, 80~100min is mixed with the revolving speed of 800~900r/min with blender, prefabricated production is made
Object uniformly spreads in pre product in mold, and liquid level thickness is about 2~3mm, is 55 in temperature by mold as in baking oven
16~18h of freeze-day with constant temperature under conditions of~65 DEG C, cooling conjunctiva is up to high-intensitive sewage treatment composite membrane；
The specific preparation step of sieving product are as follows:
(1) reaction product is put into vacuum freezing drying oven, is -40~-36 DEG C in temperature, vacuum degree is 120~140Pa's
Under the conditions of freeze-drying 24~26h be made desciccate, by desciccate, copper sulphate, citric acid and mass fraction be 13~15%
Acetic acid solution investment beaker in be uniformly mixed obtain modified product；
(2) modified product is put into beaker, the sodium hydroxide solution that mass fraction is 15~19% is added dropwise into beaker and adjusts pH
Filter residue is obtained by filtration after standing 2~3h under room temperature, filter residue is placed in horse by filter residue 3~5 times wash with distilled water to 10~11 in value
Not in furnace, under argon atmosphere, in-furnace temperature is increased, 50~60min of high-temperature calcination is made calcined product, calcined product is put into
Ground 150 mesh obtains sieving product in grinder；
The specific preparation step of reaction product are as follows:
(1) 600~800g bamboo plate is placed in steam blasting tank, into steam blasting tank, delivery temperature is 230~250 DEG C
Vapor seals cavity charge containers until air pressure is increased to 1.5~1.7MPa in tank, and constant temperature and pressure stands 45~55min, and vapour is made
Quick-fried product, by steam explosion product and egg shell investment planetary ball mill in, with the revolving speed mixed grinding 80 of 400~420r/min~
Mixture is made in 100min；
(2) mixture is placed in baking oven, desciccate is made in dry 10~12h under conditions of temperature is 65~75 DEG C, will
The pure and mild mass fraction of desciccate, sodium chlorite, benzene be 15~17% sodium hydroxide solution put into beaker in, with blender with
40~50min is mixed in the revolving speed of 500~520r/min, stands 4~5h under room temperature after stirring and solidliquid mixture is made；
(3) by solidliquid mixture and 2,3- epoxypropyltrimethylchloride chloride puts into reaction kettle, reactor temperature is increased
To 62~66 DEG C, 35~45min of isothermal reaction, 65~75min is mixed with the revolving speed of 230~250r/min with blender,
It increases reactor temperature again, is mixed 50 under conditions of revolving speed is 500~520r/min with blender under constant temperature
Reaction product is made in~60min.
Preferably according to parts by weight, sieving product is 8~10 parts, the collagen solution that mass fraction is 5~8% is 5
~7 parts, the acetum that chitosan is 1.5~1.9 parts, mass fraction is 4~6% be 18~20 parts.
In the specific preparation step (1) of sieving product preferably according to parts by weight, desciccate is 8~10 parts, sulfuric acid
The acetic acid solution that copper is 5~7 parts, citric acid is 1.6~1.8 parts, mass fraction is 13~15% is 15~17 parts.
The Muffle in-furnace temperature in the specific preparation step (2) of product that is sieved is increased to 350~370 DEG C.
The mass ratio of steam explosion product and egg shell is 3:1 in the specific preparation step (1) of reaction product.
In the specific preparation step (2) of reaction product preferably according to parts by weight, desciccate is 7~9 parts, chlorous acid
The sodium hydroxide solution that sodium is 1.3~1.5 parts, benzene alcohol is 3~5 parts, mass fraction is 15~17% is 16~18 parts.
Solidliquid mixture and 2 in the specific preparation step (3) of reaction product, the quality of 3- epoxypropyltrimethylchloride chloride
Than for 8:1.
Reactor temperature is increased to 73~75 DEG C in the specific preparation step (3) of reaction product.
The method have the benefit that:
(1) bamboo plate is placed in steam blasting tank carries out the obtained steam explosion product of steam blasting first by the present invention, then by steam explosion
Product is mixed with egg shell is added sodium chlorite and the obtained solidliquid mixture of lye mixing immersion simultaneously, adds 2,3- epoxy
Hydroxypropyltrimonium chloride mix pyroreaction be made reaction product, then reaction product is freeze-dried and is mixed into copper sulphate,
Citric acid solution reaction, calcined product is made in high-temperature calcination after reaction, finally by calcined product and collagen solution, chitosan
It is uniformly mixed and is laid on mold, film is taken off after drying, high-intensitive sewage treatment composite membrane is made, the present invention utilizes steam blasting
Mode separates the bamboo fibre ingredient in bamboo chip, anti-using 2,3- epoxypropyltrimethylchloride chloride after bamboo fibre is mixed with eggshell
It answers, bonds bamboo fibre in conjunction with the protein, inorganic salts and other organic principles that decompose in egg shell, and in bamboo fibre
A large amount of organo-functional group is introduced on the strand of dimension, is conducive to form Hydrogen Binding Adsorption and covalent bond between each ingredient of composite membrane
Absorption, thus reinforce the intensity of microstructure in composite film material, it is comprehensive in conjunction with the mechanical property and toughness of bamboo fibre itself
The mechanical strength of composite membrane is improved, while bonding adsorbing metal ions using ionic bond, chelation, passes through covalent bond, hydrogen bond
And suction-operated of the charge adsorption enhancing composite membrane to pollutant, improve the filter capacity of composite membrane；
(2) present invention is reacted using copper sulphate by modified bamboo fibre, makes bamboo fibre surface that activity be precipitated very strong
Calcium ion forms ion cavities on bamboo fibre surface after calcium ion precipitation, to have negative electrical charge, reinforces a huge sum of money in absorption effluent
The ability for belonging to ion, improves the strainability of composite membrane, present invention introduces the ingredients such as collagen, chitosan not only have and kill
Antibacterial effect of bacterium, moreover it is possible to reinforce the cross-link intensity inside composite membrane between each component, improve the crosslinking of each molecule in composite membrane
Density makes composite membrane be difficult to be broken, decompose to reinforce the mechanical strength and chemical stability of composite membrane, and service life is more
Long, detersive efficiency is higher, has broad application prospects.
Specific embodiment
600~800g bamboo plate is placed in steam blasting tank, into steam blasting tank, delivery temperature is 230~250 DEG C
Vapor seal cavity charge containers until air pressure is increased to 1.5~1.7MPa in tank, constant temperature and pressure stands 45~55min, is made
Steam explosion product puts into steam explosion product and egg shell 3:1 in mass ratio in planetary ball mill, with the revolving speed of 400~420r/min
Mixture is made in 80~100min of mixed grinding；Said mixture is placed in baking oven, under conditions of temperature is 65~75 DEG C
Desciccate is made in dry 10~12h, according to parts by weight, by 7~9 parts of desciccates, 1.3~1.5 parts of sodium chlorites, 3~5
The sodium hydroxide solution that part pure and mild 16~18 parts of mass fractions of benzene are 15~17% is put into beaker, with blender with 500~
40~50min is mixed in the revolving speed of 520r/min, stands 4~5h under room temperature after stirring and solidliquid mixture is made；It will be above-mentioned solid
Liquid mixture and 2,3- epoxypropyltrimethylchloride chloride 8:1 in mass ratio put into reaction kettle, reactor temperature are increased
To 62~66 DEG C, 35~45min of isothermal reaction, 65~75min is mixed with the revolving speed of 230~250r/min with blender,
Reactor temperature is increased again to 73~75 DEG C, under constant temperature with blender under conditions of revolving speed is 500~520r/min
50~60min is mixed, reaction product is made；Above-mentioned reaction product is put into vacuum freezing drying oven, is -40 in temperature
~-36 DEG C, desciccate is made in 24~26h of freeze-drying under conditions of vacuum degree is 120~140Pa, according to parts by weight, will
The second that 8~10 parts of desciccates, 5~7 parts of copper sulphate, 1.6~1.8 parts of citric acids and 15~17 parts of mass fractions are 13~15%
It is uniformly mixed in acid solution investment beaker and obtains modified product；Above-mentioned modified product is put into beaker, matter is added dropwise into beaker
It measures the sodium hydroxide solution that score is 15~19% and adjusts pH value to 10~11, filter residue is obtained by filtration after standing 2~3h under room temperature,
Filter residue 3~5 times wash with distilled water, filter residue is placed in Muffle furnace, under argon atmosphere, increases in-furnace temperature to 350~370
DEG C, calcined product is made in 50~60min of high-temperature calcination, and calcined product is put into ground 150 mesh in grinder and is sieved
Product；According to parts by weight, it is molten for 5~8% collagen that 8~10 parts of above-mentioned sieving products, 5~7 parts of mass fractions are weighed
The acetum that liquid, 1.5~1.9 parts of chitosans and 18~20 parts of mass fractions are 4~6% is put into reaction kettle, uses blender
80~100min is mixed with the revolving speed of 800~900r/min, pre product is made, pre product is uniformly spread in into mold
In, liquid level thickness is about 2~3mm, by mold as in baking oven, under conditions of temperature is 55~65 DEG C freeze-day with constant temperature 16~
18h, cooling conjunctiva is up to high-intensitive sewage treatment composite membrane.
Example 1
The preparation of mixture:
600g bamboo plate is placed in steam blasting tank, the vapor that delivery temperature is 230 DEG C into steam blasting tank, until tank
Interior air pressure is increased to 1.5MPa, seals cavity charge containers, and constant temperature and pressure stands 45min, steam explosion product is made, by steam explosion product and egg
Shell 3:1 in mass ratio is put into planetary ball mill, and mixture is made with the revolving speed mixed grinding 80min of 400r/min.
The preparation of solidliquid mixture:
Said mixture is placed in baking oven, desciccate is made in dry 10h under conditions of temperature is 65 DEG C, in parts by weight
7 parts of desciccates, 1.3 parts of sodium chlorites, the sodium hydroxide solution that the pure and mild 16 parts of mass fractions of 3 parts of benzene are 15% are put into and are burnt by meter
In cup, 40min is mixed with the revolving speed of 500r/min with blender, 4h is stood under room temperature after stirring and solidliquid mixture is made.
The preparation of reaction product:
By above-mentioned solidliquid mixture and 2,3- epoxypropyltrimethylchloride chloride 8:1 in mass ratio puts into reaction kettle, will react
Temperature in the kettle is increased to 62 DEG C, isothermal reaction 35min, 65min is mixed with the revolving speed of 230r/min with blender, then increase
50min system is mixed to 73 DEG C in reactor temperature with blender under conditions of revolving speed is 500r/min under constant temperature
Obtain reaction product.
The preparation of modified product:
Above-mentioned reaction product is put into vacuum freezing drying oven, is -40 DEG C in temperature, vacuum degree is cold under conditions of being 120Pa
Dry desciccate obtained for 24 hours is lyophilized, according to parts by weight, by 8 parts of desciccates, 5 parts of copper sulphate, 1.6 parts of citric acids and 15 parts
The acetic acid solution that mass fraction is 13%, which puts into be uniformly mixed in beaker, obtains modified product.
The preparation of sieving product:
Above-mentioned modified product is put into beaker, the sodium hydroxide solution that mass fraction is 15% is added dropwise into beaker and adjusts pH value
To 10, filter residue is obtained by filtration after standing 2h under room temperature, filter residue 3 times, filter residue is placed in Muffle furnace wash with distilled water, in argon gas
Under atmosphere, in-furnace temperature is increased to 350 DEG C, and calcined product is made in high-temperature calcination 50min, and calcined product is put into grinder and is ground
Honed 150 mesh obtains sieving product.
The preparation of high-intensitive sewage treatment composite membrane:
According to parts by weight, it is poly- that 8 parts of above-mentioned sieving products, the collagen solution that 5 parts of mass fractions are 5%, 1.5 parts of shells are weighed
The acetum that sugar and 18 parts of mass fractions are 4% is put into reaction kettle, is mixed with blender with the revolving speed of 800r/min
Pre product is made in 80min, pre product is uniformly sprawled with mold, liquid level thickness is about 2mm, by mold as baking oven
In, freeze-day with constant temperature 16h under conditions of temperature is 55 DEG C, cooling conjunctiva is up to high-intensitive sewage treatment composite membrane.
Example 2
The preparation of mixture:
700g bamboo plate is placed in steam blasting tank, the vapor that delivery temperature is 240 DEG C into steam blasting tank, until tank
Interior air pressure is increased to 1.6MPa, seals cavity charge containers, and constant temperature and pressure stands 50min, steam explosion product is made, by steam explosion product and egg
Shell 3:1 in mass ratio is put into planetary ball mill, and mixture is made with the revolving speed mixed grinding 90min of 410r/min.
The preparation of solidliquid mixture:
Said mixture is placed in baking oven, desciccate is made in dry 11h under conditions of temperature is 70 DEG C, in parts by weight
8 parts of desciccates, 1.4 parts of sodium chlorites, the sodium hydroxide solution that the pure and mild 17 parts of mass fractions of 4 parts of benzene are 16% are put into and are burnt by meter
In cup, 45min is mixed with the revolving speed of 510r/min with blender, 4h is stood under room temperature after stirring and solidliquid mixture is made.
The preparation of reaction product:
By above-mentioned solidliquid mixture and 2,3- epoxypropyltrimethylchloride chloride 8:1 in mass ratio puts into reaction kettle, will react
Temperature in the kettle is increased to 64 DEG C, isothermal reaction 40min, 70min is mixed with the revolving speed of 240r/min with blender, then increase
55min system is mixed to 74 DEG C in reactor temperature with blender under conditions of revolving speed is 510r/min under constant temperature
Obtain reaction product.
The preparation of modified product:
Above-mentioned reaction product is put into vacuum freezing drying oven, is -38 DEG C in temperature, vacuum degree is cold under conditions of being 130Pa
Dry 25h is lyophilized, desciccate is made, according to parts by weight, by 9 parts of desciccates, 6 parts of copper sulphate, 1.7 parts of citric acids and 16 parts
The acetic acid solution that mass fraction is 14%, which puts into be uniformly mixed in beaker, obtains modified product.
The preparation of sieving product:
Above-mentioned modified product is put into beaker, the sodium hydroxide solution that mass fraction is 17% is added dropwise into beaker and adjusts pH value
To 10, filter residue is obtained by filtration after standing 2h under room temperature, filter residue 4 times, filter residue is placed in Muffle furnace wash with distilled water, in argon gas
Under atmosphere, in-furnace temperature is increased to 360 DEG C, and calcined product is made in high-temperature calcination 55min, and calcined product is put into grinder and is ground
Honed 150 mesh obtains sieving product.
The preparation of high-intensitive sewage treatment composite membrane:
According to parts by weight, it is poly- that 9 parts of above-mentioned sieving products, the collagen solution that 6 parts of mass fractions are 7%, 1.7 parts of shells are weighed
The acetum that sugar and 19 parts of mass fractions are 5% is put into reaction kettle, is mixed with blender with the revolving speed of 850r/min
Pre product is made in 90min, pre product is uniformly sprawled with mold, liquid level thickness is about 2mm, by mold as baking oven
In, freeze-day with constant temperature 17h under conditions of temperature is 60 DEG C, cooling conjunctiva is up to high-intensitive sewage treatment composite membrane.
Example 3
The preparation of mixture:
600~800g bamboo plate is placed in steam blasting tank, the vapor that delivery temperature is 250 DEG C into steam blasting tank,
Until air pressure is increased to 1.7MPa in tank, cavity charge containers are sealed, constant temperature and pressure stands 55min, steam explosion product is made, by steam explosion product
In egg shell 3:1 in mass ratio investment planetary ball mill, mixture is made with the revolving speed mixed grinding 100min of 420r/min.
The preparation of solidliquid mixture:
Said mixture is placed in baking oven, desciccate is made in dry 12h under conditions of temperature is 75 DEG C, in parts by weight
9 parts of desciccates, 1.5 parts of sodium chlorites, the sodium hydroxide solution that the pure and mild 18 parts of mass fractions of 5 parts of benzene are 17% are put into and are burnt by meter
In cup, 50min is mixed with the revolving speed of 520r/min with blender, 5h is stood under room temperature after stirring and solidliquid mixture is made.
The preparation of reaction product:
By above-mentioned solidliquid mixture and 2,3- epoxypropyltrimethylchloride chloride 8:1 in mass ratio puts into reaction kettle, will react
Temperature in the kettle is increased to 66 DEG C, isothermal reaction 45min, 75min is mixed with the revolving speed of 250r/min with blender, then increase
60min system is mixed to 75 DEG C in reactor temperature with blender under conditions of revolving speed is 520r/min under constant temperature
Obtain reaction product.
The preparation of modified product:
Above-mentioned reaction product is put into vacuum freezing drying oven, is -36 DEG C in temperature, vacuum degree is cold under conditions of being 140Pa
Dry 26h is lyophilized, desciccate is made, according to parts by weight, by 10 parts of desciccates, 7 parts of copper sulphate, 1.8 parts of citric acids and 17 parts
The acetic acid solution that mass fraction is 15%, which puts into be uniformly mixed in beaker, obtains modified product.
The preparation of sieving product:
Above-mentioned modified product is put into beaker, the sodium hydroxide solution that mass fraction is 19% is added dropwise into beaker and adjusts pH value
To 11, filter residue is obtained by filtration after standing 3h under room temperature, filter residue 5 times, filter residue is placed in Muffle furnace wash with distilled water, in argon gas
Under atmosphere, in-furnace temperature is increased to 370 DEG C, and calcined product is made in high-temperature calcination 60min, and calcined product is put into grinder and is ground
Honed 150 mesh obtains sieving product.
The preparation of high-intensitive sewage treatment composite membrane:
According to parts by weight, it is poly- that 10 parts of above-mentioned sieving products, the collagen solution that 7 parts of mass fractions are 8%, 1.9 parts of shells are weighed
The acetum that sugar and 20 parts of mass fractions are 6% is put into reaction kettle, is mixed with blender with the revolving speed of 900r/min
Pre product is made in 100min, pre product is uniformly sprawled with mold, liquid level thickness is about 3mm, by mold as baking oven
In, freeze-day with constant temperature 18h under conditions of temperature is 65 DEG C, cooling conjunctiva is up to high-intensitive sewage treatment composite membrane.
Comparative example 1: it is essentially identical with the preparation method of embodiment 1, it has only the difference is that solidliquid mixture is not added.
Comparative example 2: it is essentially identical with the preparation method of embodiment 2, it has only the difference is that modified product is not added.
Comparative example 3: the composite membrane of company, Zhejiang Province production.To high-intensitive sewage treatment composite membrane produced by the present invention
Performance detection is carried out with the composite membrane in comparative example, testing result is as shown in table 1:
Test method:
Toughness test
Each group composite membrane is placed in electronic tensile machine, the length of composite membrane when measuring fracture is stretched, is obtained divided by original length
Elongation at break.
Chemical stability test
The potassium hydroxide for being successively 5~7% with mass fraction in the sulfuric acid solution that mass fraction is 5~7% by each group composite membrane
2~3h is impregnated in solution, is put into after 3~5 times wash with distilled water in baking oven after immersion under conditions of temperature is 45~55 DEG C
Drying weighs quality, obtains mass ratio divided by original quality, measures chemical stability, the bigger stabilization of ratio than size according to quality
Property is better.
1 performance measurement result of table
| Test item | Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Elongation at break (%) | 115.3 | 116.8 | 118.5 | 95.7 | 90.6 | 84.2 |
| Reaction front and back mass ratio (%) | 96.9 | 97.4 | 98.6 | 93.6 | 91.4 | 90.5 |
It is difficult to be broken well according to above-mentioned detection data high-intensitive sewage treatment composite membrane mechanical strength produced by the present invention, change
It learns property stabilization to be difficult to by soda acid, strainability is good, has broad application prospects.
Claims (8)
1. a kind of preparation method of high intensity sewage treatment composite membrane, it is characterised in that specific preparation step are as follows:
Weigh sieving product, the vinegar that collagen solution, chitosan and the mass fraction that mass fraction is 5~8% are 4~6%
Acid solution is put into reaction kettle, 80~100min is mixed with the revolving speed of 800~900r/min with blender, prefabricated production is made
Object uniformly spreads in pre product in mold, and liquid level thickness is about 2~3mm, is 55 in temperature by mold as in baking oven
16~18h of freeze-day with constant temperature under conditions of~65 DEG C, cooling conjunctiva is up to high-intensitive sewage treatment composite membrane；
The specific preparation step of the sieving product are as follows:
(1) reaction product is put into vacuum freezing drying oven, is -40~-36 DEG C in temperature, vacuum degree is 120~140Pa's
Under the conditions of freeze-drying 24~26h be made desciccate, by desciccate, copper sulphate, citric acid and mass fraction be 13~15%
Acetic acid solution investment beaker in be uniformly mixed obtain modified product；
(2) modified product is put into beaker, the sodium hydroxide solution that mass fraction is 15~19% is added dropwise into beaker and adjusts pH
Filter residue is obtained by filtration after standing 2~3h under room temperature, filter residue is placed in horse by filter residue 3~5 times wash with distilled water to 10~11 in value
Not in furnace, under argon atmosphere, in-furnace temperature is increased, 50~60min of high-temperature calcination is made calcined product, calcined product is put into
Ground 150 mesh obtains sieving product in grinder；
The specific preparation step of the reaction product are as follows:
(1) 600~800g bamboo plate is placed in steam blasting tank, into steam blasting tank, delivery temperature is 230~250 DEG C
Vapor seals cavity charge containers until air pressure is increased to 1.5~1.7MPa in tank, and constant temperature and pressure stands 45~55min, and vapour is made
Quick-fried product, by steam explosion product and egg shell investment planetary ball mill in, with the revolving speed mixed grinding 80 of 400~420r/min~
Mixture is made in 100min；
(2) mixture is placed in baking oven, desciccate is made in dry 10~12h under conditions of temperature is 65~75 DEG C, will
The pure and mild mass fraction of desciccate, sodium chlorite, benzene be 15~17% sodium hydroxide solution put into beaker in, with blender with
40~50min is mixed in the revolving speed of 500~520r/min, stands 4~5h under room temperature after stirring and solidliquid mixture is made；
(3) by solidliquid mixture and 2,3- epoxypropyltrimethylchloride chloride puts into reaction kettle, reactor temperature is increased
To 62~66 DEG C, 35~45min of isothermal reaction, 65~75min is mixed with the revolving speed of 230~250r/min with blender,
It increases reactor temperature again, is mixed 50 under conditions of revolving speed is 500~520r/min with blender under constant temperature
Reaction product is made in~60min.
2. a kind of preparation method of high-intensitive sewage treatment composite membrane according to claim 1, it is characterised in that: preferred
According to parts by weight, the sieving product is 8~10 parts, the collagen solution that mass fraction is 5~8% is 5~7 parts, shell
The acetum that glycan is 1.5~1.9 parts, mass fraction is 4~6% is 18~20 parts.
3. a kind of preparation method of high-intensitive sewage treatment composite membrane according to claim 1, it is characterised in that: sieving produces
In the specific preparation step (1) of object preferably according to parts by weight, the desciccate is 8~10 parts, copper sulphate is 5~7
Part, the acetic acid solution that citric acid is 1.6~1.8 parts, mass fraction is 13~15% are 15~17 parts.
4. a kind of preparation method of high-intensitive sewage treatment composite membrane according to claim 1, it is characterised in that: sieving produces
Muffle in-furnace temperature described in the specific preparation step (2) of object is increased to 350~370 DEG C.
5. a kind of preparation method of high-intensitive sewage treatment composite membrane according to claim 1, it is characterised in that: reaction produces
The mass ratio of steam explosion product described in the specific preparation step (1) of object and egg shell is 3:1.
6. a kind of preparation method of high-intensitive sewage treatment composite membrane according to claim 1, it is characterised in that: reaction produces
In the specific preparation step (2) of object it is preferred according to parts by weight, the desciccate is 7~9 parts, sodium chlorite 1.3
~1.5 parts, the sodium hydroxide solution that benzene alcohol is 3~5 parts, mass fraction is 15~17% be 16~18 parts.
7. a kind of preparation method of high-intensitive sewage treatment composite membrane according to claim 1, it is characterised in that: reaction produces
Solidliquid mixture and 2 described in the specific preparation step (3) of object, the mass ratio of 3- epoxypropyltrimethylchloride chloride are 8:1.
8. a kind of preparation method of high-intensitive sewage treatment composite membrane according to claim 1, it is characterised in that: reaction produces
Reactor temperature described in the specific preparation step (3) of object is increased to 73~75 DEG C.
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