CN107055918A - A kind of preparation technology of selenium-rich mountain spring water - Google Patents
A kind of preparation technology of selenium-rich mountain spring water Download PDFInfo
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- CN107055918A CN107055918A CN201710054256.4A CN201710054256A CN107055918A CN 107055918 A CN107055918 A CN 107055918A CN 201710054256 A CN201710054256 A CN 201710054256A CN 107055918 A CN107055918 A CN 107055918A
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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
- C02F9/00—Multistage 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
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
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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
- C02F1/34—Treatment of water, waste water, or sewage with mechanical oscillations
- C02F1/36—Treatment of water, waste water, or sewage with mechanical oscillations ultrasonic vibrations
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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
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
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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
- C02F1/48—Treatment of water, waste water, or sewage with magnetic or electric fields
- C02F1/487—Treatment of water, waste water, or sewage with magnetic or electric fields using high frequency electromagnetic fields, e.g. pulsed electromagnetic fields
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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
- C02F1/52—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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- 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
- C02F1/68—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water
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- 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
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/206—Manganese or manganese compounds
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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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/02—Non-contaminated water, e.g. for industrial water supply
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2209/02—Temperature
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/10—Solids, e.g. total solids [TS], total suspended solids [TSS] or volatile solids [VS]
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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
- C02F2303/00—Specific treatment goals
- C02F2303/04—Disinfection
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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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
Abstract
The invention discloses a kind of preparation technology of selenium-rich mountain spring water, comprise the following steps：(1) precipitation process；(2) microorganism is removed；(3) selenium-rich is handled：Modification of chitosan absorption plasma selenium is added in the mountain spring water after removing microorganism, stirred with 50 100r/min speed after 30 40min, take out the modification of chitosan after absorption plasma selenium, then the 20min of mountain spring water 10 is handled by the condition electromagnetic pulse that 20 100J, frequency are 65 120KHz of single pulse energy, the modification of chitosan rejoined after absorption plasma selenium, with the ultrasonically treated 150min of mountain spring water 120 of the condition of 1500 2000W power, after ultrafiltration membrance filter, filtrate is selenium-rich mountain spring water.The preparation technology simple possible of the present invention, process control, selenium-rich mountain spring water Se content height, the quality better of preparation, with wide market popularization value.
Description
【Technical field】
The present invention relates to the preparation field of mountain spring water, more particularly to a kind of preparation technology of selenium-rich mountain spring water.
【Background technology】
Selenium is one of 14 kinds of trace elements needed by human, and selenium deficiency can induce hepatopathy, nephrosis, Kaschin-Beck disease, cardiovascular and cerebrovascular
40 kinds of diseases such as disease, diabetes, various cancers, stomach tract disease, myopia, amblyopia and senile cataract, tracheitis and pulmonary emphysema
Disease, so as to bring heavy burden to personal, family and society.It is internationally recognized selenium deficiency area that, which there is 70% territory in China, because
This is in order to improve the general level of the health and resistance against diseases of our people, and people have carried out numerous studies work, successively pickle and develop
The product such as selenium-enriched food and selenium-rich water, but be due to the shortage of natural selenium-rich water, therefore plasma selenium is enriched with by research one kind
It is following development trend to be then produced into selenium-rich water afterwards.
Mountain spring water is to be gushed out naturally using massif, seepage flow formation or gather in massif, do not got dirty in certain area through drilling well
Contaminate and take preventive measures and avoid the water of pollution, and the water source of non-rivers, lake (on mountain except lake) and public water facilities,
Only through the PROCESS FOR TREATMENT such as appropriate filtering and sterilization, retain in water source a certain amount of original mineral matter and trace element and without
Any chemicals, are sealed in the water for being available for directly drinking in packing container.Mountain spring water contains abundant trace element, is suitable for disappearing
The long-term of expense person is drunk, in the present invention, study it is a kind of plasma selenium is enriched with after the selenium-rich mountain spring water that generates have it is vast
Market popularization value.
【The content of the invention】
It is an object of the invention to provide a kind of preparation technology of selenium-rich mountain spring water, the present invention is first to the particle in mountain spring water
Precipitation process is carried out with suspension, the microorganism in mountain spring water is then removed, plasma selenium selenium-rich processing then is carried out to mountain spring water,
Make after plasma selenium enrichment, plasma selenium is discharged again after excessive heavy metal ion to be removed, selenium-rich mountain spring water, the preparation work is made
Skill simple possible, process control, selenium-rich mountain spring water Se content height, the quality better of preparation, with wide market popularization value.
To solve the above problems, the technical solution adopted in the present invention is：A kind of preparation technology of selenium-rich mountain spring water, including
Following steps：
(1) precipitation process：Mountain spring water is introduced after tube settler, added according to the 0.01-0.05% of mountain spring water weight
Flocculant, precipitation takes supernatant liquor, the mountain spring water after being precipitated after 2-4 days；
(2) microorganism is removed：Mountain spring water after precipitation is warming up to 35-40 DEG C, by 0.2-0.5m3/ min flow velocity is flowed through
Filter containing biofiltration layer, obtains removing the mountain spring water after microorganism；
(3) selenium-rich is handled：Count by weight, 3-5 parts of modified shells are added in the mountain spring water after 100 parts of removal microorganisms
Glycan adsorbs plasma selenium, after 50-100r/min speed stirring 30-40min, takes out the modification shell after absorption plasma selenium and gathers
Sugar, then by 20-100J of single pulse energy, frequency for 65-120KHz condition electromagnetic pulse processing mountain spring water 10-
20min, the modification of chitosan rejoined after absorption plasma selenium, with the ultrasonically treated mountain spring water of the condition of 1500-2000W power
120-150min, after ultrafiltration membrance filter, filtrate is selenium-rich mountain spring water.
In the present invention, as further illustrating, the modification of chitosan described in step (3) is prepared by following methods：By weight
Number meter is measured, 3-5 parts of chitosans are dissolved in the formic acid solution that 60-100 parts of mass fractions are 10-20%, with 200-300r/
Min speed stirring 30-45min, obtains chitosan colloidal sol, 20-30 parts of hydroxyapatites is then added in chitosan colloidal sol,
Mixed gel is obtained, mixed gel 2-4h is stirred with 1000-2000r/min speed when accelerator is added dropwise, washed with distillation
Wash 3 times, freezed at -17 DEG C after 48-70h, be then dried in vacuo 30-48h at 50-60 DEG C, after crushing, obtain being modified shell and gather
Sugar.
In the present invention, as further illustrating, the flocculant described in step (1) is carboxymethyl cellulose grafted propylene acid
Copolymer.
In the present invention, as further illustrating, the filtrate of the biofiltration layer described in step (2) is that particle diameter is 4-6mm
Haydites of book structure.
In the present invention, as further illustrating, described accelerator is by weight 10-20：8-15：30-50 phosphorus
Sour potassium, butanediol and pure water are mixed.
In the present invention, as further illustrating, described carboxymethyl cellulose grafted propylene acid copolymer is by following sides
It is prepared by method：Count by weight, by 15-20 parts of sodium carboxymethylcelluloses, 20-32 parts of acrylic acid and 1 part of ammonium nitrate in Ring
In border, temperature be 130-150 DEG C, mixing speed be to react 5-8h under conditions of 200-400r/min, filter, dry, obtain
Carboxymethyl cellulose grafted propylene acid copolymer.
In the present invention, as further illustrating, described gas is nitrogen or helium.
The function introduction of part material is as follows in the present invention：
Chitosan, also known as chitosan, are that the chitin being widely present by nature is obtained by deacetylation
, chemical name is Chitosan (1-4) -2- amino-B-D glucose.Biological functionality and compatibility, the blood of chitosan
The premium properties such as compatibility, security, microbic resolvability are by all trades and professions extensive concern, in medicine, food, chemical industry, cosmetic
The application study of the numerous areas such as product, water process, METAL EXTRACTION and recovery, biochemical and biomedical engineering achieve it is great enter
Exhibition.In the present invention, chitosan is used for the matrix material for preparing modification of chitosan.
Formic acid, also referred to as formic acid, chemical formula are HCOOH.Formic acid fusing point is 8.4 DEG C, and boiling point is 100.8 DEG C, colourless and have
Penetrating odor, and be corrosive, can bubble redness after human skin contact.In the present invention, formic acid is used to dissolve chitosan.
Hydroxyapatite, is a kind of natural apatite mineral, and its molecular formula is Ca10(PO4)6(OH)2, by two molecules
The crystal structure of composition.Hydroxyapatite is to contain pure end member hydroxy in apatite.In the present invention, hydroxyapatite is used for
Chitosan is modified.
Haydites of book structure, uses natural rock -- and shale is refined and formed through high temperature, roasting for raw material.Its is nontoxic, tasteless, anti-
Pressure is wear-resisting and corrosion-resistant, and with good absorption property and intensity, it is adaptable to the purified treatment of all kinds of water quality.In the present invention
In, haydites of book structure is used as the material for core of filter, for filtering algae and microorganism in mountain spring water.
Potassium phosphate, colourless or white orthorhombic system crystallization.There are anhydride, heptahydrate and nonahydrate.Common person is nothing
Water thing, there is hygroscopy.It is soluble in water, insoluble in ethanol.In the present invention, potassium phosphate is used for the main material for preparing accelerator.
Butanediol, appearance colorless is transparent, 193 DEG C of boiling point, 394 DEG C of burning-point, energy adsorbed water molecule, with superpower moisturizing energy
Power, and moisturizing security is fabulous, is usually used in skin care item.In the present invention, butanediol is used for the main material for preparing accelerator.
Sodium carboxymethylcellulose, outward appearance is white or slightly yellow fibrous powder or white powder, odorless, tasteless, nontoxic；
Cold water or hot water are soluble in, forms gluey, solution is neutral or alkalescence, is had insoluble in ethanol, ether, isopropanol, acetone etc.
Machine solvent.In the present invention, sodium carboxymethylcellulose is used for the matrix material for preparing carboxymethyl cellulose grafted propylene acid copolymer
Material.
Acrylic acid, also known as acryl acid, are simplest unsaturated carboxylic acids, are made up of a vinyl and a carboxyl.
Pure acrylic acid is colorless clear liquid, the penetrating odor with feature, is corrosive.It can be mutual with water, alcohol, ether and chloroform
It is molten, it is to be prepared by the propylene obtained from oil plant.The characteristic reaction of carboxylic acid can occur for acrylic acid, and phase is also can obtain with alcohol reaction
The esters answered.In the present invention, acrylic acid is used for the main material for preparing carboxymethyl cellulose grafted propylene acid copolymer.
Ammonium nitrate, the clear crystals of no color or smell or white crystallization, soluble in water, easy moisture absorption caking.Ammonium salt by
It is hot easily to decompose, meet caustic digestion.It is oxidant, for chemical fertilizer and industrial chemicals.In the present invention, ammonium nitrate is used to prepare carboxymethyl
The material of cellulose graft acrylic copolymer.
Nitrogen, helium are used as protective gas in reaction in the present invention.
The invention has the advantages that：
1. modification of chitosan prepared by the present invention can oriented attachment plasma selenium, first plasma selenium is enriched with, Ran Hou
Plasma selenium is removed under strong external force effect, and then the plasma selenium content in mountain spring water can be subjected to free management, reaches and carries
The effect of high Se content.Main with selenate and selenite in the form of presence of the plasma selenium in water, the present invention is by first adopting
Chitosan is dissolved with strong solvent formic acid, chitosan is dissolved into colloid, is then mixed in accelerator potassium phosphate and butanediol
Under the facilitation of liquid, hydroxyapatite cuttage is entered in chitosan gum body, outer layer is formed for chitosan, internal layer is hydroxy-apatite
The capsule material of stone, solves the problem of hydroxyapatite is easily reunited.And the capsule material is from inside to outside containing substantial amounts of
Hydroxyl, under the strong acidic condition of formic acid, hydroxyl can enter line replacement reaction with the selenate radical in mountain spring water, selenite radical, enter
And the orientation reaction to plasma selenium is realized, play a part of being enriched with plasma selenium；And selenate radical, the selenite radical after displacement can
In the presence of strong external force, the chemical bond of connection is destroyed, and then realizes the disengaging of selenate radical, selenite radical, further real
Freely managing for plasma selenium is showed.The technology used in the present invention means cooperate, mutually promoted, all linked with one another, common rush
Enter and plasma selenium in mountain spring water is freely managed, and then reach the purpose for the content for improving the plasma selenium in mountain spring water.
2. the present invention uses carboxymethyl cellulose grafted propylene acid copolymer as flocculant, can be efficiently to mountain spring water
In particle and suspension flocculated, purify water.The present invention by by sodium carboxymethylcellulose acrylic acid in ammonium nitrate
, can be by acrylic acid-grafted on sodium carboxymethylcellulose, with the semi-rigid chain of sodium carboxymethylcellulose under high-temperature catalysis
For skeleton, grafted propylene acid monomers make carboxymethyl cellulose have carbonyl and carbon-carbon double bond, are more prone to and solid particle and outstanding
Float goes hydration and adsorption bridging to act on and remove solid particle and suspension, and it produces total sedimentation effect much
Higher than the summation of the effect produced by single component.
3. present invention employs the skill that the technological means of electromagnetic pulse removing heavy metals ion, modification of chitosan adsorb plasma selenium
Art means and the technological means of ultrasound removing plasma selenium are combined processing mountain spring water, make after the plasma selenium in mountain spring water is collected,
Further remove the heavy metal ion such as lead, manganese excessive in mountain spring water, then under ultrasonically treated, the chemical bond quilt on adsorbent
Destruction, plasma selenium is discharged the technique effect of processing again, this three cooperate, mutually promote, realize jointly for
Plasma selenium is freely managed in mountain spring water, improves the quality of mountain spring water jointly.
【Embodiment】
Embodiment 1：
1. early-stage preparations：
The preparation of accelerator：Count by weight, 10 parts of potassium phosphates, 8 parts of butanediols and 30 pure water are mixed, promoted
Enter agent.
The preparation of modification of chitosan：Count by weight, 3 parts of chitosans are dissolved in the formic acid that 60 parts of mass fractions are 10%
In solution, 30min is stirred with 200r/min speed, chitosan colloidal sol is obtained, 20 parts of hydroxyls are then added in chitosan colloidal sol
Base apatite, obtains mixed gel, stirs mixed gel 2h with 1000r/min speed when accelerator is added dropwise, uses distilled water
Washing 3 times, freezes after 48h at -17 DEG C, is then dried in vacuo 30h at 50 DEG C, after crushing, obtains modification of chitosan.
The preparation of carboxymethyl cellulose grafted propylene acid copolymer：Count by weight, by 15 parts of sodium carboxymethylcelluloses,
20 parts of acrylic acid and 1 part of ammonium nitrate in nitrogen environment, temperature be 130 DEG C, mixing speed be under conditions of 200r/min it is anti-
5h is answered, is filtered, dries, obtains carboxymethyl cellulose grafted propylene acid copolymer.
The material of above-mentioned preparation is used for the preparation technology of following described selenium-rich mountain spring waters.
2. a kind of preparation technology of selenium-rich mountain spring water, comprises the following steps：
(1) precipitation process：Mountain spring water is introduced after tube settler, carboxymethyl is added according to the 0.01% of mountain spring water weight
Cellulose graft acrylic copolymer, precipitation takes supernatant liquor, the mountain spring water after being precipitated after 2 days；
(2) microorganism is removed：Mountain spring water after precipitation is warming up to 35 DEG C, by 0.2m3/ min flow velocity is flowed through containing life
The filter of thing filter layer, the filtrate of biofiltration layer is the haydites of book structure that particle diameter is 4mm, obtains removing the mountain spring after microorganism
Water；
(3) selenium-rich is handled：Count by weight, adding 3 parts of modified shells in the mountain spring water after 100 parts of removal microorganisms gathers
Sugar absorption plasma selenium, after 50r/min speed stirring 30min, takes out the modification of chitosan after absorption plasma selenium, then with list
Subpulse energy is the condition electromagnetic pulse processing mountain spring water 10min that 20J, frequency are 65KHz, is rejoined after absorption plasma selenium
Modification of chitosan, with the ultrasonically treated mountain spring water 120min of the condition of 1500W power, after ultrafiltration membrance filter, filtrate is
Selenium-rich mountain spring water.
Embodiment 2：
1. early-stage preparations：
The preparation of accelerator：Count by weight, 14 parts of potassium phosphates, 11 parts of butanediols and 37 pure water are mixed, obtained
Accelerator.
The preparation of modification of chitosan：Count by weight, 3.5 parts of chitosans are dissolved in the first that 80 parts of mass fractions are 13%
In acid solution, 38min is stirred with 250r/min speed, chitosan colloidal sol is obtained, 26 parts are then added in chitosan colloidal sol
Hydroxyapatite, obtains mixed gel, mixed gel 2.5h is stirred when accelerator is added dropwise with 1400r/min speed, with steaming
Distilled water is washed 3 times, is freezed at -17 DEG C after 50h, is then dried in vacuo 40h at 57 DEG C, after crushing, obtains modification of chitosan.
The preparation of carboxymethyl cellulose grafted propylene acid copolymer：Count by weight, by 18 parts of sodium carboxymethylcelluloses,
29 parts of acrylic acid and 1 part of ammonium nitrate in helium environment, temperature be 135 DEG C, mixing speed be under conditions of 275r/min it is anti-
6h is answered, is filtered, dries, obtains carboxymethyl cellulose grafted propylene acid copolymer.
The material of above-mentioned preparation is used for the preparation technology of following described selenium-rich mountain spring waters.
2. a kind of preparation technology of selenium-rich mountain spring water, comprises the following steps：
(1) precipitation process：Mountain spring water is introduced after tube settler, carboxymethyl is added according to the 0.04% of mountain spring water weight
Cellulose graft acrylic copolymer, precipitation takes supernatant liquor, the mountain spring water after being precipitated after 3 days；
(2) microorganism is removed：Mountain spring water after precipitation is warming up to 36 DEG C, by 0.4m3/ min flow velocity is flowed through containing life
The filter of thing filter layer, the filtrate of biofiltration layer is the haydites of book structure that particle diameter is 4.5mm, obtains removing the mountain after microorganism
Spring；
(3) selenium-rich is handled：Count by weight, adding 4 parts of modified shells in the mountain spring water after 100 parts of removal microorganisms gathers
Sugar absorption plasma selenium, after 65r/min speed stirring 37min, takes out the modification of chitosan after absorption plasma selenium, then with list
Subpulse energy is the condition electromagnetic pulse processing mountain spring water 13min that 50J, frequency are 75KHz, is rejoined after absorption plasma selenium
Modification of chitosan, with the ultrasonically treated mountain spring water 145min of the condition of 1700W power, after ultrafiltration membrance filter, filtrate is
Selenium-rich mountain spring water.
Embodiment 3：
1. early-stage preparations：
The preparation of accelerator：Count by weight, 14 parts of potassium phosphates, 12 parts of butanediols and 40 pure water are mixed, obtained
Accelerator.
The preparation of modification of chitosan：Count by weight, 4 parts of chitosans are dissolved in the formic acid that 90 parts of mass fractions are 12%
In solution, 40min is stirred with 240r/min speed, chitosan colloidal sol is obtained, 26 parts of hydroxyls are then added in chitosan colloidal sol
Base apatite, obtains mixed gel, mixed gel 3.5h is stirred when accelerator is added dropwise with 1600r/min speed, with distillation
Water washing 3 times, freezes after 60h at -17 DEG C, is then dried in vacuo 39h at 53 DEG C, after crushing, obtains modification of chitosan.
The preparation of carboxymethyl cellulose grafted propylene acid copolymer：Count by weight, by 17 parts of sodium carboxymethylcelluloses,
30 parts of acrylic acid and 1 part of ammonium nitrate are in nitrogen or helium environment, in the bar that temperature is 140 DEG C, mixing speed is 320r/min
6h is reacted under part, is filtered, dries, obtains carboxymethyl cellulose grafted propylene acid copolymer.
The material of above-mentioned preparation is used for the preparation technology of following described selenium-rich mountain spring waters.
2. a kind of preparation technology of selenium-rich mountain spring water, comprises the following steps：
(1) precipitation process：Mountain spring water is introduced after tube settler, carboxymethyl is added according to the 0.02% of mountain spring water weight
Cellulose graft acrylic copolymer, precipitation takes supernatant liquor, the mountain spring water after being precipitated after 2.5 days；
(2) microorganism is removed：Mountain spring water after precipitation is warming up to 39 DEG C, by 0.4m3/ min flow velocity is flowed through containing life
The filter of thing filter layer, the filtrate of biofiltration layer is the haydites of book structure that particle diameter is 5mm, obtains removing the mountain spring after microorganism
Water；
(3) selenium-rich is handled：Count by weight, 4.5 parts of modified shells are added in the mountain spring water after 100 parts of removal microorganisms
Glycan adsorbs plasma selenium, after 65r/min speed stirring 38min, takes out the modification of chitosan after absorption plasma selenium, then with
Single pulse energy is the condition electromagnetic pulse processing mountain spring water 15min that 60J, frequency are 100KHz, rejoin absorption selenium from
Modification of chitosan after son, with the ultrasonically treated mountain spring water 130min of the condition of 1700W power, after ultrafiltration membrance filter, filtrate
As selenium-rich mountain spring water.
Embodiment 4：
1. early-stage preparations：
The preparation of accelerator：Count by weight, 13 parts of potassium phosphates, 12 parts of butanediols and 40 pure water are mixed, obtained
Accelerator.
The preparation of modification of chitosan：Count by weight, 3.5 parts of chitosans are dissolved in the first that 75 parts of mass fractions are 16%
In acid solution, 42min is stirred with 260r/min speed, chitosan colloidal sol is obtained, 24 parts are then added in chitosan colloidal sol
Hydroxyapatite, obtains mixed gel, mixed gel 3.5h is stirred when accelerator is added dropwise with 1400r/min speed, with steaming
Distilled water is washed 3 times, is freezed at -17 DEG C after 55h, is then dried in vacuo 44h at 53 DEG C, after crushing, obtains modification of chitosan.
The preparation of carboxymethyl cellulose grafted propylene acid copolymer：Count by weight, by 16 parts of sodium carboxymethylcelluloses,
30 parts of acrylic acid and 1 part of ammonium nitrate in nitrogen environment, temperature be 136 DEG C, mixing speed be under conditions of 360r/min it is anti-
7h is answered, is filtered, dries, obtains carboxymethyl cellulose grafted propylene acid copolymer.
The material of above-mentioned preparation is used for the preparation technology of following described selenium-rich mountain spring waters.
2. a kind of preparation technology of selenium-rich mountain spring water, comprises the following steps：
(1) precipitation process：Mountain spring water is introduced after tube settler, carboxymethyl is added according to the 0.04% of mountain spring water weight
Cellulose graft acrylic copolymer, precipitation takes supernatant liquor, the mountain spring water after being precipitated after 3.5 days；
(2) microorganism is removed：Mountain spring water after precipitation is warming up to 37 DEG C, by 0.4m3/ min flow velocity is flowed through containing life
The filter of thing filter layer, the filtrate of biofiltration layer is the haydites of book structure that particle diameter is 5.5mm, obtains removing the mountain after microorganism
Spring；
(3) selenium-rich is handled：Count by weight, adding 4 parts of modified shells in the mountain spring water after 100 parts of removal microorganisms gathers
Sugar absorption plasma selenium, after 85r/min speed stirring 35min, takes out the modification of chitosan after absorption plasma selenium, then with list
Subpulse energy is the condition electromagnetic pulse processing mountain spring water 12min that 60J, frequency are 90KHz, is rejoined after absorption plasma selenium
Modification of chitosan, with the ultrasonically treated mountain spring water 135min of the condition of 1800W power, after ultrafiltration membrance filter, filtrate is
Selenium-rich mountain spring water.
Embodiment 5：
1. early-stage preparations：
The preparation of accelerator：Count by weight, 15 parts of potassium phosphates, 13 parts of butanediols and 45 pure water are mixed, obtained
Accelerator.
The preparation of modification of chitosan：Count by weight, 4.5 parts of chitosans are dissolved in the first that 73 parts of mass fractions are 14%
In acid solution, 41min is stirred with 270r/min speed, chitosan colloidal sol is obtained, 24 parts are then added in chitosan colloidal sol
Hydroxyapatite, obtains mixed gel, mixed gel 3h is stirred when accelerator is added dropwise with 1300r/min speed, with distillation
Water washing 3 times, freezes after 65h at -17 DEG C, is then dried in vacuo 45h at 52 DEG C, after crushing, obtains modification of chitosan.
The preparation of carboxymethyl cellulose grafted propylene acid copolymer：Count by weight, by 18 parts of sodium carboxymethylcelluloses,
27 parts of acrylic acid and 1 part of ammonium nitrate in helium environment, temperature be 138 DEG C, mixing speed be under conditions of 280r/min it is anti-
6h is answered, is filtered, dries, obtains carboxymethyl cellulose grafted propylene acid copolymer.
The material of above-mentioned preparation is used for the preparation technology of following described selenium-rich mountain spring waters.
2. a kind of preparation technology of selenium-rich mountain spring water, comprises the following steps：
(1) precipitation process：Mountain spring water is introduced after tube settler, carboxymethyl is added according to the 0.03% of mountain spring water weight
Cellulose graft acrylic copolymer, precipitation takes supernatant liquor, the mountain spring water after being precipitated after 3.5 days；
(2) microorganism is removed：Mountain spring water after precipitation is warming up to 37 DEG C, by 0.4m3/ min flow velocity is flowed through containing life
The filter of thing filter layer, the filtrate of biofiltration layer is the haydites of book structure that particle diameter is 5mm, obtains removing the mountain spring after microorganism
Water；
(3) selenium-rich is handled：Count by weight, 4.5 parts of modified shells are added in the mountain spring water after 100 parts of removal microorganisms
Glycan adsorbs plasma selenium, after 75r/min speed stirring 38min, takes out the modification of chitosan after absorption plasma selenium, then with
Single pulse energy is the condition electromagnetic pulse processing mountain spring water 11min that 40J, frequency are 110KHz, rejoin absorption selenium from
Modification of chitosan after son, with the ultrasonically treated mountain spring water 135min of the condition of 1600W power, after ultrafiltration membrance filter, filtrate
As selenium-rich mountain spring water.
Embodiment 6：
1. early-stage preparations：
The preparation of accelerator：Count by weight, 20 parts of potassium phosphates, 15 parts of butanediols and 50 pure water are mixed, obtained
Accelerator.
The preparation of modification of chitosan：Count by weight, 5 parts of chitosans are dissolved in the first that 100 parts of mass fractions are 20%
In acid solution, 45min is stirred with 300r/min speed, chitosan colloidal sol is obtained, 30 parts are then added in chitosan colloidal sol
Hydroxyapatite, obtains mixed gel, mixed gel 4h is stirred when accelerator is added dropwise with 2000r/min speed, with distillation
Water washing 3 times, freezes after 70h at -17 DEG C, is then dried in vacuo 48h at 60 DEG C, after crushing, obtains modification of chitosan.
The preparation of carboxymethyl cellulose grafted propylene acid copolymer：Count by weight, by 20 parts of sodium carboxymethylcelluloses,
32 parts of acrylic acid and 1 part of ammonium nitrate in helium environment, temperature be 150 DEG C, mixing speed be under conditions of 400r/min it is anti-
8h is answered, is filtered, dries, obtains carboxymethyl cellulose grafted propylene acid copolymer.
The material of above-mentioned preparation is used for the preparation technology of following described selenium-rich mountain spring waters.
2. a kind of preparation technology of selenium-rich mountain spring water, comprises the following steps：
(1) precipitation process：Mountain spring water is introduced after tube settler, carboxymethyl is added according to the 0.05% of mountain spring water weight
Cellulose graft acrylic copolymer, precipitation takes supernatant liquor, the mountain spring water after being precipitated after 4 days；
(2) microorganism is removed：Mountain spring water after precipitation is warming up to 40 DEG C, by 0.5m3/ min flow velocity is flowed through containing life
The filter of thing filter layer, the filtrate of biofiltration layer is the haydites of book structure that particle diameter is 6mm, obtains removing the mountain spring after microorganism
Water；
(3) selenium-rich is handled：Count by weight, adding 5 parts of modified shells in the mountain spring water after 100 parts of removal microorganisms gathers
Sugar absorption plasma selenium, after 100r/min speed stirring 40min, takes out the modification of chitosan after absorption plasma selenium, then with
Single pulse energy is the condition electromagnetic pulse processing mountain spring water 20min that 100J, frequency are 120KHz, rejoin absorption selenium from
Modification of chitosan after son, with the ultrasonically treated mountain spring water 150min of the condition of 2000W power, after ultrafiltration membrance filter, filtrate
As selenium-rich mountain spring water.
Comparative example 1：The specific steps of the preparation technology of selenium-rich mountain spring water, raw material are substantially the same manner as Example 1, and difference exists
In：The core for the filter that step (2) is used is activated carbon.
Comparative example 2：The specific steps of the preparation technology of selenium-rich mountain spring water, raw material are substantially the same manner as Example 1, and difference exists
In：Step (3) uses chitosan to adsorb plasma selenium.
Comparative example 3：The specific steps of the preparation technology of selenium-rich mountain spring water, raw material are substantially the same manner as Example 1, and difference exists
In：Without addition accelerator in the preparation process of modification of chitosan.
Comparative example 4：The specific steps of the preparation technology of selenium-rich mountain spring water, raw material are substantially the same manner as Example 1, and difference exists
In：The flocculant used is polyacrylamide.
Contrast test 1：The selenium-rich mountain spring water 500g respectively prepared according to comparative example 1-4 and embodiment 1-6, detects selenium-rich mountain spring
The composition of water, examination criteria is performed by DBS44/001-2011, and whole testing results are shown in Table 1.
Table 1：
The result of table 1 shows：Se content is higher, illustrates that the plasma selenium content of mountain spring water is higher, selenium-rich effect is better.Contrast
Se content in example 2 is minimum, illustrates that the adsorption effect to plasma selenium of chitosan is not obvious, passes through the method for the embodiment of the present invention
The selenium-rich mountain spring water of preparation, reaches the effect for the Se content that can be greatly improved in mountain spring water；
The content of lead ion and manganese ion is lower, illustrates that the content of beary metal in mountain spring water is lower, is more good for one's health, right
The content of lead ion and manganese ion in ratio 2 is all highest, illustrates chitosan to the adsorption effect of lead ion and manganese ion not
Substantially, the selenium-rich mountain spring water prepared by the method for the embodiment of the present invention, reach the lead content that can be greatly reduced in mountain spring water and
The effect of manganese content；
The quantity of bacterium colony group's number is fewer, illustrates that the bacterium in mountain spring water is fewer, is more beneficial to health.In comparative example 1
Bacterium colony group number numerical value highest, illustrate that activated carbon is weaker for the adsorption capacity of microorganism and algae, pass through the present invention implement
Selenium-rich mountain spring water prepared by the method for example, reaches the effect for the bacterium colony group's number that can be greatly reduced in mountain spring water.
Described above is the detailed description for the present invention preferably possible embodiments, but embodiment is not limited to this hair
The equal change or modification change completed under bright patent claim, the technical spirit suggested by all present invention, all should belong to
Cover the scope of the claims in the present invention.
Claims (7)
1. a kind of preparation technology of selenium-rich mountain spring water, it is characterised in that：Comprise the following steps：
(1) precipitation process：Mountain spring water is introduced after tube settler, adds and flocculates according to the 0.01-0.05% of mountain spring water weight
Agent, precipitation takes supernatant liquor, the mountain spring water after being precipitated after 2-4 days；
(2) microorganism is removed：Mountain spring water after precipitation is warming up to 35-40 DEG C, by 0.2-0.5m3/ min flow velocity flow through containing
The filter of biofiltration layer, obtains removing the mountain spring water after microorganism；
(3) selenium-rich is handled：Count by weight, 3-5 parts of modification of chitosan are added in the mountain spring water after 100 parts of removal microorganisms
Plasma selenium is adsorbed, after 50-100r/min speed stirring 30-40min, the modification of chitosan after absorption plasma selenium is taken out, so
Afterwards by 20-100J of single pulse energy, frequency be 65-120KHz condition electromagnetic pulse processing mountain spring water 10-20min, weight
The new modification of chitosan added after absorption plasma selenium, with the ultrasonically treated mountain spring water 120- of the condition of 1500-2000W power
150min, after ultrafiltration membrance filter, filtrate is selenium-rich mountain spring water.
2. a kind of preparation technology of selenium-rich mountain spring water according to claim 1, it is characterised in that：Changing described in step (3)
Property chitosan is prepared by following methods：Count by weight, 3-5 parts of chitosans are dissolved in 60-100 parts of mass fractions for 10-
In 20% formic acid solution, 30-45min is stirred with 200-300r/min speed, chitosan colloidal sol is obtained, then in chitosan
20-30 parts of hydroxyapatites are added in colloidal sol, mixed gel is obtained, when accelerator is added dropwise with 1000-2000r/min speed
Mixed gel 2-4h is stirred, with water washing is distilled 3 times, is freezed at -17 DEG C after 48-70h, then vacuum is done at 50-60 DEG C
Dry 30-48h, after crushing, obtains modification of chitosan.
3. a kind of preparation technology of selenium-rich mountain spring water according to claim 1, it is characterised in that：Wadding described in step (1)
Solidifying agent is carboxymethyl cellulose grafted propylene acid copolymer.
4. a kind of preparation technology of selenium-rich mountain spring water according to claim 1, it is characterised in that：Life described in step (2)
The filtrate of thing filter layer is the haydites of book structure that particle diameter is 4-6mm.
5. a kind of preparation technology of selenium-rich mountain spring water according to claim 2, it is characterised in that：Described accelerator be by
Weight compares 10-20：8-15：30-50 potassium phosphate, butanediol and pure water is mixed.
6. a kind of preparation technology of selenium-rich mountain spring water according to claim 3, it is characterised in that：Described carboxymethyl cellulose
Plain grafted propylene acid copolymer is prepared by following methods：Count by weight, by 15-20 parts of sodium carboxymethylcelluloses, 20-32 parts
Acrylic acid and 1 part of ammonium nitrate are in gaseous environment, in the condition that temperature is 130-150 DEG C, mixing speed is 200-400r/min
Lower reaction 5-8h, is filtered, and is dried, is obtained carboxymethyl cellulose grafted propylene acid copolymer.
7. a kind of preparation technology of selenium-rich mountain spring water according to claim 6, it is characterised in that：Described gas is nitrogen
Or helium.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110720576A (en) * | 2019-10-29 | 2020-01-24 | 柳士贤 | Preparation method of selenium-rich fleece-flower root mineral water |
| CN110759517A (en) * | 2019-09-29 | 2020-02-07 | 临沂大学 | A enrichment concentrator for preparing natural mineral water that contains selenium |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105712570A (en) * | 2014-12-05 | 2016-06-29 | 中国石油化工股份有限公司 | Processing method of high concentration selenium-containing wastewater |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105712570A (en) * | 2014-12-05 | 2016-06-29 | 中国石油化工股份有限公司 | Processing method of high concentration selenium-containing wastewater |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110759517A (en) * | 2019-09-29 | 2020-02-07 | 临沂大学 | A enrichment concentrator for preparing natural mineral water that contains selenium |
| CN110720576A (en) * | 2019-10-29 | 2020-01-24 | 柳士贤 | Preparation method of selenium-rich fleece-flower root mineral water |
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