CN106035371B - A kind of drinking water bactericidal ball based on shell microcellular structure - Google Patents
A kind of drinking water bactericidal ball based on shell microcellular structure Download PDFInfo
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- CN106035371B CN106035371B CN201610358507.3A CN201610358507A CN106035371B CN 106035371 B CN106035371 B CN 106035371B CN 201610358507 A CN201610358507 A CN 201610358507A CN 106035371 B CN106035371 B CN 106035371B
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/06—Aluminium; Calcium; Magnesium; Compounds thereof
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
- A01N25/10—Macromolecular compounds
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/34—Shaped forms, e.g. sheets, not provided for in any other sub-group of this main group
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
- B01J20/043—Carbonates or bicarbonates, e.g. limestone, dolomite, aragonite
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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
- C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/08—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing carbon dioxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/10—Water or water-releasing compounds
Abstract
The present invention relates to water sterilization agent fields, disclose a kind of drinking water bactericidal ball based on shell microcellular structure, substance including following parts by weight is prepared: 400-600 parts of conch meal, 4-6 parts of silica solution, 80-100 parts of neutral polyether polyalcohol, 100-160 parts of isocyanates, 0.1-0.2 parts of catalyst, 4-6 parts of phenoxy resin, 0.1-0.2 parts of Tea Saponin, 1-3 parts of polyethylene glycol, 3-5 parts of water.Drinking water bactericidal ball of the invention can be launched directly and carry out Adsorption and Sterilization in drinking water, and duration is long, easy to use, at low cost；The drinking water bactericidal ball is harmless to water quality safety using conch meal as primary raw material；And the conch meal large specific surface area, pore size distribution uniformity is good, and connectivity is good between duct, high to the absorption fastness of bacterium.
Description
Technical field
The present invention relates to water sterilization agent field more particularly to a kind of drinking water bactericidal balls based on shell microcellular structure.
Background technique
With the raising of people's life life, the requirement for drinking water is also higher and higher.Current drinking water is generally all
It is tap water or bottled water, although tap water and bottled water pass through disinfection treatment, in prolonged transport, pouring process
In, if early period, disinfection was not thorough, it can still grow bacterium, the health of harmful to human.Sterilization for drinking water is general at present
It is the installation ultraviolet light sterilization device on water dispenser, but the water dispenser higher cost containing ultraviolet light sterilization device, and sterilize
Effect is general, not ideal enough, sterilizes in the time that can only be opened in a short time, cannot play long term sterilizing.
Also have by adding fungicide in drinking water come what is sterilized, such as application No. is in 201410644645.9
State's invention patent discloses a kind of preparation method of nano combined filtrate, using following technical scheme: A, by algae clay, E33 and
Zeolite powder mixing, mills；B, mixture obtained by step A is stirred and evenly mixed with active carbon, water is added；C, high temperature is fired, and D, will be walked
The rapid made product of C is mixed with nano-titanium dioxide, obtains a kind of nano combined filtrate.The nano combined filtrate of the invention has preferable
Adsorption capacity, the heavy metal in water and bacterium can be removed；And it is safe and non-toxic, it is without secondary pollution, it can be used for drinking water or sewage
Purification.
But above-mentioned nano combined filtrate mainly using algae clay, zeolite and active carbon etc. as main component, exist with
Lower disadvantage: 1, since its specific surface area is still not big enough, the contact area of Yu Shuiti is smaller, and germicidal efficiency is low；Although 2, these
Material internal has duct, has certain adsorption capacity to bacterium, but its internal gutter size distributed pole is uneven, big
Very big, small very little, can only adsorb the lesser bacterium of some certain sizes, and the bacterium big for some sizes can not be adsorbed,
And these ducts be all it is single existing, the connectivity between duct is poor, thus bacterium be adsorbed after still be able to " escape " out
It goes, absorption fastness is not ideal enough.3, above-mentioned material (especially conch meal) can generate after (1000 DEG C or more) of high temperature calcinings
Some alkaline metal oxides (for example generating calcium oxide after conch meal high-temperature calcination), will affect the pH value of drinking water.4, above-mentioned
Nano combined filtrate could use after can only being mounted on filter core as filtrate, cannot be dispersed directly into water and be sterilized, therefore
Ancillary filter device is needed to use, it is at high cost.
Summary of the invention
In order to solve the above-mentioned technical problems, the present invention provides a kind of drinking water bactericidal balls based on shell microcellular structure.
Drinking water bactericidal ball of the invention can be launched directly and carry out Adsorption and Sterilization in drinking water, and duration is long, easy to use, cost
It is low；The drinking water bactericidal ball is harmless to water quality safety using conch meal as primary raw material；And the conch meal large specific surface area, duct
Size distribution uniformity is good, and connectivity is good between duct, high to the absorption fastness of bacterium.
The specific technical proposal of the invention is: a kind of drinking water bactericidal ball based on shell microcellular structure, including it is following heavy
The substance of amount part is prepared:
400-600 parts of conch meal,
4-6 parts of silica solution,
80-100 parts of neutral polyether polyalcohol,
100-160 parts of isocyanates,
0.1-0.2 parts of catalyst,
4-6 parts of phenoxy resin,
0.1-0.2 parts of Tea Saponin,
1-3 parts of polyethylene glycol,
3-5 parts of water.
The present invention selects conch meal as the main component of drinking water bactericidal ball, and the present invention selects conch meal by specific work
The calcining of skill, the duct with 0.1-1.5 micron-scale, and pore size is evenly distributed, the connectivity between duct is preferable, phase
The separately distributed disconnected structure in the ducts such as specific activity charcoal, specific surface area is up to 20-30 times of active carbon specific surface area, to thin
More preferably, the length of bacillus is about 0.2-1 microns wide generally at 0.5-10 microns in bacterium, and coccus diameter is about for the adsorption effect of bacterium
0.3-1.2 microns, the pore size of conch meal can just accommodate bacterial adsorption, and in absorption, due to the connection between duct
Property is good, and bacterium " will not run out of " again, make bacterium only import but no export.
Drinking water bactericidal ball of the invention can direct plunge into drinking water, can carry out Adsorption and Sterilization for a long time, be not necessarily to mating mistake
Filter, it is at low cost, it is easy to use.
Preferably, drinking water bactericidal ball partial size is in 0.5-4em.
Preferably, polyethylene glycol is Macrogol 4000.
Preferably, the preparation method of the drinking water bactericidal ball based on shell microcellular structure the following steps are included:
A, clean shell is calcined at 300-450 DEG C 40-80min, then naturally cools to room temperature.
In step, it needs to the stringent control of calcine technology, under above-mentioned calcine technology, organic matter is decomposed in shell,
Shell forms the skeleton of countless microcellular structures, to have outstanding adsorptivity, and pore size rational, size distribution is equal
One property is good, and connectivity is good.If calcining is insufficient, it is not ideal enough to will lead to absorption property.And if calcining excessively, can generate greatly
Calcium oxide is measured, water pH value is influenced.It is more purposive compared in the prior art at 1000 DEG C or more to conch meal calcining.
B, calcined shell is crushed be for granularity 50-800 mesh conch meal.
C, by the conch meal and silica solution, phenoxy resin, neutral polyether polyalcohol, isocyanates, catalyst, tea soap
Element, polyethylene glycol and water are uniformly mixed, and foaming is stirred at 50-60 DEG C, and after placing 5-15min, it is compound that shell base is made
Material.
The other materials such as conch meal and silica solution, phenoxy resin, neutral polyether polyalcohol, isocyanates are composite foamed,
Neutral polyether polyalcohol and isocyanates can form composite foam material, and conch meal is sufficiently handed over other materials in foaming process
Connection, obtains lightweight, porous shell based composites, compared with other adhesives directly bond, it can be ensured that adhesion-molded
The duct of conch meal is not covered by adhesive afterwards, to substantially reduce specific surface area.Silica solution and phenoxy resin play bonding
The effect of agent, dosage is less to influence too much conch meal specific surface area.And shell based composites soak for a long time
It ducks in drink, very high to the requirement of its water resistance, phenoxy resin can not only bond material, and can greatly improve material
Water resistance disintegrates it not.Water and polyethylene glycol are capable of forming various sizes of duct as two kinds of foaming agents, further increase
Add the specific surface area of drinking water bactericidal ball, Tea Saponin is added as emulsifier and stabilizer.
D, the shell based composites are prepared into spheroiding by molding equipment；Under room temperature after aging 3-5h, in 160-
It is dried in vacuo at 200 DEG C, the drinking water bactericidal ball based on shell microcellular structure is made.
After the shell based composites aging of ball-type, internal structure is stablized, and is being dried, and on the one hand removes material
In volatile substances, on the other hand can phenoxy resin carry out heat cure, reinforcing material structural stability.In addition, silica solution
After the drying of higher temperature, the silica aerogel with three-dimensional net structure, increasing specific surface area can be also generated.
Preferably, the shell is selected from least one of mussel, scallop, pearl shell, clam.
Preferably, the granularity of the conch meal is 100-300 mesh.
Preferably, catalyst described in step C is selected from triethylene diamine, stannous octoate or dibutyl tin dilaurate.
Preferably, neutral polyether polyalcohol described in step C the preparation method is as follows: by 10 parts of wood powders and 20-30 parts
Be added in 200-300 parts of phenol after lignin mixing and be stirred to react 60-80min at 155-165 DEG C, during the reaction by
Gradually add the sodium hydroxide solution that 200-300 parts of concentration are 15wt%, after reaction solution is then adjusted to neutrality with sodium citrate, drop
Temperature continues to be stirred to react 1-2h to 65-75 DEG C after 400-600 parts of furfurals, 60-80 parts of natural polyols are added, and day is made
Right polyether polyol, above-mentioned number are parts by weight.
Neutral polyether polyalcohol of the invention is natural material, environmentally protective, minimizes the secondary pollution to drinking water
Preferably, the natural polyols are at least one of maltitol, xylitol, sorbierite.
Preferably, the phenoxy resin the preparation method is as follows: by being obtained after bisphenol A type epoxy resin, bisphenol-A mixing
Mixture then adds the propylene glycol monomethyl ether of mixture quality 20-30%, is heated to 60-100 DEG C；In bisphenol A type epoxy resin
Epoxy group, the molar ratio of phenolic hydroxyl group is 1: 1.1-1.2 in bisphenol-A；Then the triphenyl of mixture quality 0.1-0.3% is added
Butyl bromide phosphine reacts 2-4h at 120-140 DEG C；During reaction, the propylene glycol first of mixture quality 30-40% is at the uniform velocity added
Ether；Continue the propylene glycol monomethyl ether of addition mixture quality 5-15% after reaction, phenoxy resin is made after final drying.This hair
The phenoxy resin of bright preparation has more phenolic hydroxyl group, and good to the adhesiveness of inorganic material, water-tolerant, resistance to shrinkage is good, energy
The dimensional stability for enough reinforcing drinking water bactericidal ball, prevents its adsorption swelling from disintegrating.
It is compared with the prior art, the beneficial effects of the present invention are: drinking water bactericidal ball of the invention can directly be launched into drink
With Adsorption and Sterilization is carried out in water, duration is long, easy to use, at low cost；The drinking water bactericidal ball using conch meal as primary raw material,
It is harmless to water quality safety；And the conch meal large specific surface area, pore size distribution uniformity is good, and connectivity is good between duct, right
The absorption fastness of bacterium is high.
Specific embodiment
The present invention will be further described with reference to the examples below.
Embodiment 1
A kind of drinking water bactericidal ball based on shell microcellular structure, partial size are 2.5cm or so, the object including following parts by weight
Matter is prepared:
500 parts of conch meal, 5 parts of silica solution, 90 parts of neutral polyether polyalcohol, 130 parts of isocyanates, triethylene diamine 0.15
Part, 5 parts of phenoxy resin, 0.15 part of Tea Saponin, 2 parts of Macrogol 4000,4 parts of water.
The pre-prepared preparation of raw material:
The preparation of neutral polyether polyalcohol: it is added in 250 parts of phenol after 10 parts of wood powders and 25 parts of lignin are mixed
It is stirred to react 70min at 160 DEG C, gradually adds the sodium hydroxide solution that 250 parts of concentration are 15wt% during the reaction, then
After reaction solution is adjusted to neutrality with sodium citrate, 70 DEG C are cooled to, is continued after 500 parts of furfurals, 70 parts of maltitols are added
It is stirred to react 1.5h, neutral polyether polyalcohol is made, above-mentioned number is parts by weight.
The preparation of phenoxy resin: mixture will be obtained after bisphenol A type epoxy resin, bisphenol-A mixing, then adds mixture
The propylene glycol monomethyl ether of quality 25% is heated to 80 DEG C；Mole of phenolic hydroxyl group in epoxy group, bisphenol-A in bisphenol A type epoxy resin
Than being 1: 1.15；Then the triphenylbut base bromide phosphine for adding mixture quality 0.2%, reacts 3h at 130 DEG C；The reaction phase
Between, at the uniform velocity add the propylene glycol monomethyl ether of mixture quality 35%；Continue to add the third the two of mixture quality 10% after reaction
Phenoxy resin is made after final drying in alcohol methyl ether.
Drinking water bactericidal ball the preparation method comprises the following steps:
A, clean mussel, scallop, pearl shell, clam are calcined at 375 DEG C 60min, then naturally cools to room temperature.
B, calcined shell is crushed be for granularity 350-450 mesh conch meal.
C, by the conch meal and silica solution, phenoxy resin, neutral polyether polyalcohol, isocyanates, triethylene diamine, tea
Saponin, polyethylene glycol and water are uniformly mixed, and foaming is stirred at 55 DEG C, and after placing 10min, shell base composite wood is made
Material.
D, the shell based composites are prepared into spheroiding by molding equipment；Under room temperature after aging 4h, at 180 DEG C
The drinking water bactericidal ball based on shell microcellular structure is made in lower vacuum drying.
Embodiment 2
A kind of drinking water bactericidal ball based on shell microcellular structure, partial size are 0.5em or so, the object including following parts by weight
Matter is prepared:
400 parts of conch meal, 4 parts of silica solution, 80 parts of neutral polyether polyalcohol, 100 parts of isocyanates, 0.1 part of stannous octoate,
4 parts of phenoxy resin, 0.1 part of Tea Saponin, 1 part of Macrogol 4000,3 parts of water.
The pre-prepared preparation of raw material:
The preparation of neutral polyether polyalcohol: it is added in 200 parts of phenol after 10 parts of wood powders and 20 parts of lignin are mixed
It is stirred to react 80min at 155 DEG C, gradually adds the sodium hydroxide solution that 200 parts of concentration are 15wt% during the reaction, then
After reaction solution is adjusted to neutrality with sodium citrate, 65 DEG C are cooled to, continues to stir after 400 parts of furfurals, 60 parts of xylitols are added
Reaction 2h is mixed, neutral polyether polyalcohol is made, above-mentioned number is parts by weight.
The preparation of phenoxy resin: mixture will be obtained after bisphenol A type epoxy resin, bisphenol-A mixing, then adds mixture
The propylene glycol monomethyl ether of quality 20% is heated to 60 DEG C；Mole of phenolic hydroxyl group in epoxy group, bisphenol-A in bisphenol A type epoxy resin
Than being 1: 1.1；Then the triphenylbut base bromide phosphine for adding mixture quality 0.1%, reacts 4h at 120 DEG C；During reaction,
At the uniform velocity add the propylene glycol monomethyl ether of mixture quality 40%；Continue the propylene glycol first of addition mixture quality 5% after reaction
Phenoxy resin is made after final drying in ether.
Drinking water bactericidal ball the preparation method comprises the following steps:
A, clean mussel, scallop, pearl shell, clam are calcined at 300 DEG C 80min, then naturally cools to room temperature.
B, calcined shell is crushed be for granularity 50-100 mesh conch meal.
C, by the conch meal and silica solution, phenoxy resin, neutral polyether polyalcohol, isocyanates, stannous octoate, tea soap
Element, polyethylene glycol and water are uniformly mixed, and foaming is stirred at 50 DEG C, and after placing 15min, shell based composites are made.
D, the shell based composites are prepared into spheroiding by molding equipment；Under room temperature after aging 3h, at 160 DEG C
The drinking water bactericidal ball based on shell microcellular structure is made in lower vacuum drying.
Embodiment 3
A kind of drinking water bactericidal ball based on shell microcellular structure, partial size are 4cm or so, the substance including following parts by weight
It is prepared:
600 parts of conch meal, 6 parts of silica solution, 100 parts of neutral polyether polyalcohol, 160 parts of isocyanates, two fourth of tin dilaurate
0.2 part of base tin, 6 parts of phenoxy resin, 0.2 part of Tea Saponin, 3 parts of Macrogol 4000,5 parts of water.
The pre-prepared preparation of raw material:
The preparation of neutral polyether polyalcohol: it is added in 300 parts of phenol after 10 parts of wood powders and 30 parts of lignin are mixed
It is stirred to react 60min at 165 DEG C, gradually adds the sodium hydroxide solution that 300 parts of concentration are 15wt% during the reaction, then
After reaction solution is adjusted to neutrality with sodium citrate, 75 DEG C are cooled to, continues to stir after 600 parts of furfurals, 80 parts of sorbierites are added
Reaction 2h is mixed, neutral polyether polyalcohol is made, above-mentioned number is parts by weight.
The preparation of phenoxy resin: mixture will be obtained after bisphenol A type epoxy resin, bisphenol-A mixing, then adds mixture
The propylene glycol monomethyl ether of quality 30% is heated to 100 DEG C；Phenolic hydroxyl group rubs in epoxy group, bisphenol-A in bisphenol A type epoxy resin
You are than being 1: 1.2；Then the triphenylbut base bromide phosphine for adding mixture quality 0.3%, reacts 2h at 140 DEG C；The reaction phase
Between, at the uniform velocity add the propylene glycol monomethyl ether of mixture quality 30%；Continue to add the third the two of mixture quality 15% after reaction
Phenoxy resin is made after final drying in alcohol methyl ether.
Drinking water bactericidal ball the preparation method comprises the following steps:
A, clean mussel, scallop, pearl shell, clam are calcined at 450 DEG C 40min, then naturally cools to room temperature.
B, calcined shell is crushed be for granularity 600-800 mesh conch meal.
C, by the conch meal and silica solution, phenoxy resin, neutral polyether polyalcohol, isocyanates, two fourth of tin dilaurate
Ji Xi, Tea Saponin, polyethylene glycol and water are uniformly mixed, and foaming is stirred at 60 DEG C, and after placing 5min, it is multiple that shell base is made
Condensation material.
D, the shell based composites are prepared into spheroiding by molding equipment；Under room temperature after aging 5h, at 200 DEG C
The drinking water bactericidal ball based on shell microcellular structure is made in lower vacuum drying.
Embodiment 4
A kind of drinking water bactericidal ball based on shell microcellular structure, partial size are 2cm or so, the substance including following parts by weight
It is prepared:
450 parts of conch meal, 4 parts of silica solution, 85 parts of neutral polyether polyalcohol, 120 parts of isocyanates, di lauric dibutyl
0.1 part of tin, 4.5 parts of phenoxy resin, 0.1 part of Tea Saponin, 1.5 parts of Macrogol 4000,3.5 parts of water.
The pre-prepared preparation of raw material:
The preparation of neutral polyether polyalcohol: it is added in 240 parts of phenol after 10 parts of wood powders and 24 parts of lignin are mixed
It is stirred to react 75min at 160 DEG C, gradually adds the sodium hydroxide solution that 260 parts of concentration are 15wt% during the reaction, then
After reaction solution is adjusted to neutrality with sodium citrate, 68 DEG C are cooled to, 450 parts of furfurals, 30 parts of maltitols, 35 parts of xylitols are added
After continue to be stirred to react 1.5h, be made neutral polyether polyalcohol, above-mentioned number is parts by weight.
The preparation of phenoxy resin: mixture will be obtained after bisphenol A type epoxy resin, bisphenol-A mixing, then adds mixture
The propylene glycol monomethyl ether of quality 22% is heated to 70 DEG C；Mole of phenolic hydroxyl group in epoxy group, bisphenol-A in bisphenol A type epoxy resin
Than being 1: 1.1；Then the triphenylbut base bromide phosphine for adding mixture quality 0.15%, reacts 2.5h at 125 DEG C；The reaction phase
Between, at the uniform velocity add the propylene glycol monomethyl ether of mixture quality 35%；Continue to add the third the two of mixture quality 10% after reaction
Phenoxy resin is made after final drying in alcohol methyl ether.
Drinking water bactericidal ball the preparation method comprises the following steps:
A, clean mussel, scallop, pearl shell, clam are calcined at 360 DEG C 50min, then naturally cools to room temperature.
B, calcined shell is crushed be for granularity 100-300 mesh conch meal.
C, by the conch meal and silica solution, phenoxy resin, neutral polyether polyalcohol, isocyanates, two fourth of tin dilaurate
Ji Xi, Tea Saponin, polyethylene glycol and water are uniformly mixed, and foaming is stirred at 55 DEG C, and after placing 9min, it is multiple that shell base is made
Condensation material.
D, the shell based composites are prepared into spheroiding by molding equipment；Under room temperature after aging 3.5h, 170
It is dried in vacuo at DEG C, the drinking water bactericidal ball based on shell microcellular structure is made.
For the specific surface area for the conch meal that the present invention selects up to 20-30 times of active carbon, average pore size is active carbon
4-6 times, the adsorption effect of bacterium is obviously improved.
Raw materials used in the present invention, equipment is unless otherwise noted the common raw material, equipment of this field；In the present invention
Method therefor is unless otherwise noted the conventional method of this field.
The above is only presently preferred embodiments of the present invention, is not intended to limit the invention in any way, it is all according to the present invention
Technical spirit any simple modification, change and equivalent transformation to the above embodiments, still fall within the technology of the present invention side
The protection scope of case.
Claims (8)
1. a kind of drinking water bactericidal ball based on shell microcellular structure, it is characterised in that: the substance preparation including following parts by weight
It forms:
400-600 parts of conch meal,
4-6 parts of silica solution,
80-100 parts of neutral polyether polyalcohol,
100-160 parts of isocyanates,
0.1-0.2 parts of catalyst,
4-6 parts of phenoxy resin,
0.1-0.2 parts of Tea Saponin,
1-3 parts of polyethylene glycol,
3-5 parts of water；
The preparation method of the drinking water bactericidal ball based on shell microcellular structure the following steps are included:
A, clean shell is calcined at 300-450 DEG C 40-80min, then naturally cools to room temperature；
B, calcined shell is crushed be for granularity 50-800 mesh conch meal；
C, by the conch meal and silica solution, phenoxy resin, neutral polyether polyalcohol, isocyanates, catalyst, Tea Saponin, poly-
Ethylene glycol and water are uniformly mixed, and foaming is stirred at 50-60 DEG C, and after placing 5-15min, shell based composites are made；
D, the shell based composites are prepared into spheroiding by molding equipment；Under room temperature after aging 3-5h, in 160-200
It is dried in vacuo at DEG C, the drinking water bactericidal ball based on shell microcellular structure is made；
The neutral polyether polyalcohol the preparation method is as follows: 10 parts of wood powders and 20-30 parts of lignin are mixed after be added to
60-80min is stirred to react at 155-165 DEG C in 200-300 parts of phenol, gradually add during the reaction 200-300 parts it is dense
Degree is the sodium hydroxide solution of 15wt%, after reaction solution is then adjusted to neutrality with sodium citrate, is cooled to 65-75 DEG C, is added
Continue to be stirred to react 1-2h after 400-600 parts of furfurals, 60-80 parts of natural polyols, neutral polyether polyalcohol is made, it is above-mentioned
Number is parts by weight.
2. a kind of drinking water bactericidal ball based on shell microcellular structure as described in claim 1, which is characterized in that partial size exists
0.5-4cm。
3. a kind of drinking water bactericidal ball based on shell microcellular structure as claimed in claim 1 or 2, which is characterized in that poly- second
Glycol is Macrogol 4000.
4. a kind of drinking water bactericidal ball based on shell microcellular structure as described in claim 1, which is characterized in that the shell
Selected from least one of mussel, scallop, pearl shell, clam.
5. a kind of drinking water bactericidal ball based on shell microcellular structure as claimed in claim 1 or 2, which is characterized in that described
The granularity of conch meal is 100-300 mesh.
6. a kind of drinking water bactericidal ball based on shell microcellular structure as described in claim 1, which is characterized in that in step C
The catalyst is selected from triethylene diamine, stannous octoate or dibutyl tin dilaurate.
7. a kind of drinking water bactericidal ball based on shell microcellular structure as described in claim 1, which is characterized in that described natural
Polyalcohol is at least one of maltitol, xylitol, sorbierite.
8. a kind of drinking water bactericidal ball based on shell microcellular structure as described in claims 1 or 2 or 4 or 6, feature exist
In, the phenoxy resin the preparation method is as follows: by mixture is obtained after bisphenol A type epoxy resin, bisphenol-A mixing, then add
The propylene glycol monomethyl ether for adding mixture quality 20-30%, is heated to 60-100 DEG C；Epoxy group, bisphenol-A in bisphenol A type epoxy resin
The molar ratio of middle phenolic hydroxyl group is 1:1.1-1.2；Then the butyltriphenylphosphonium bromide phosphine for adding mixture quality 0.1-0.3%,
2-4h is reacted at 120-140 DEG C；During reaction, the propylene glycol monomethyl ether of mixture quality 30-40% is at the uniform velocity added；After reaction
Continue the propylene glycol monomethyl ether of addition mixture quality 5-15%, phenoxy resin is made after final drying.
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| CN109350548A (en) * | 2018-11-30 | 2019-02-19 | 奚正华 | A kind of spontaneous heating ferment collagen fabric dry state facial mask |
| CN109364107A (en) * | 2018-11-30 | 2019-02-22 | 奚正华 | A kind of absorbefacient emplastrum of releiving of aching of spontaneous heating |
| CN110256893B (en) * | 2019-06-18 | 2021-10-12 | 山东交通学院 | Coating additive for guardrail capable of assisting in purifying automobile exhaust and preparation method thereof |
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| CN1046924C (en) * | 1994-11-28 | 1999-12-01 | 李少勇 | Composition for purifying and mineralizing drinking water |
| WO2001067866A1 (en) * | 2000-03-13 | 2001-09-20 | Surfcera Co., Ltd. | Antibacterial agent comprising shell, method for purifying water by using the antibacterial agent and method for washing farm product by using the antibacterial agent |
| CN101116449A (en) * | 2006-08-01 | 2008-02-06 | 赵松江 | Antimicrobials and surface peeling agent formed by burning kinds of mixed shells and uses thereof |
| CN101481168B (en) * | 2008-07-30 | 2012-01-25 | 张金松 | Drinking water purification treatment material, and manufacturing method and use thereof |
| CN103125484B (en) * | 2013-03-19 | 2014-03-26 | 浙江海洋学院 | Ballast water bactericide and preparation method thereof |
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| CN101269318A (en) * | 2008-04-28 | 2008-09-24 | 江汉大学 | Metallic ion adsorption material and preparation method thereof |
| CN101690882A (en) * | 2009-10-14 | 2010-04-07 | 南开大学 | Natural adsorbent for removing heavy metal ions in water and preparation method and application thereof |
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