CN107055918B - Preparation process of selenium-rich spring water - Google Patents

Preparation process of selenium-rich spring water Download PDF

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CN107055918B
CN107055918B CN201710054256.4A CN201710054256A CN107055918B CN 107055918 B CN107055918 B CN 107055918B CN 201710054256 A CN201710054256 A CN 201710054256A CN 107055918 B CN107055918 B CN 107055918B
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spring water
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preparation process
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CN107055918A (en
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覃克明
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Lu Chuan County Meters Town Hemei Breeding Cooperatives Association
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Lu Chuan County Meters Town Hemei Breeding Cooperatives Association
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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
    • 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
    • C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • 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
    • 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
    • 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
    • C02F1/48—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
    • 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
    • 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
    • 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
    • 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
    • C02F2101/206—Manganese or manganese compounds
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/02—Temperature
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/10—Solids, e.g. total solids [TS], total suspended solids [TSS] or volatile solids [VS]
    • 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
    • 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

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  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
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  • Separation Of Suspended Particles By Flocculating Agents (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
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Abstract

The invention discloses a preparation process of selenium-rich spring water, which comprises the following steps: (1) carrying out precipitation treatment; (2) removing microorganisms; (3) selenium enrichment treatment: adding modified chitosan into the mountain spring water after microorganisms are removed to adsorb selenium ions, stirring for 30-40min at the speed of 50-100r/min, taking out the modified chitosan after selenium ions are adsorbed, then treating the mountain spring water for 10-20min by using electromagnetic pulse with single pulse energy of 20-100J and frequency of 65-120KHz, adding the modified chitosan after selenium ions are adsorbed again, treating the mountain spring water for 120-fold and 150min by using ultrasonic with the power of 1500-fold and 2000W, and filtering by using an ultrafiltration membrane to obtain filtrate which is the selenium-rich mountain spring water. The preparation process is simple and feasible, the process is controllable, and the prepared selenium-rich spring water has high selenium content, good quality and wide market popularization value.

Description

Preparation process of selenium-rich spring water
[ technical field ] A method for producing a semiconductor device
The invention relates to the field of preparation of spring water, in particular to a preparation process of selenium-rich spring water.
[ background of the invention ]
Selenium is one of 14 trace elements essential to human body, and selenium deficiency can induce 40 diseases such as liver disease, nephropathy, Kaschin-Beck disease, cardiovascular and cerebrovascular diseases, diabetes, various cancers, gastrointestinal tract diseases, myopia, amblyopia, senile cataract, tracheitis, emphysema and the like, thereby bringing heavy burden to individuals, families and society. 70% of China's land is internationally recognized selenium-deficient areas, so in order to improve the health level and disease resistance of Chinese people, people carry out a great deal of research work, and sequentially pickle and develop products such as selenium-enriched food, selenium-enriched water and the like, but due to the lack of natural selenium-enriched water, the research of enriching selenium ions and then producing the selenium-enriched water is a future development trend.
The spring water is water which is naturally emitted from a mountain, is formed by seepage or is collected from the mountain through drilling, is not polluted in a certain area and is prevented from being polluted by taking preventive measures, and is not a water source of rivers, lakes (except lakes on the mountain) and public water supply systems, a certain amount of original mineral substances and trace elements in the water source are reserved only through proper processes such as filtering, disinfection and sterilization, and no chemical is added, and the spring water is sealed in a packaging container and can be directly drunk. The spring water contains rich trace elements and is suitable for long-term drinking of consumers, and the research on the selenium-rich spring water generated by enriching selenium ions has wide market popularization value.
[ summary of the invention ]
The invention aims to provide a preparation process of selenium-rich spring water, which comprises the steps of firstly carrying out precipitation treatment on particles and suspended matters in the spring water, then removing microorganisms in the spring water, then carrying out selenium ion selenium enrichment treatment on the spring water, and releasing selenium ions again after excessive heavy metal ions are removed after the selenium ions are enriched to prepare the selenium-rich spring water.
In order to solve the problems, the technical scheme adopted by the invention is as follows: a preparation process of selenium-rich spring water comprises the following steps:
(1) and (3) precipitation treatment: introducing the spring water into an inclined tube sedimentation tank, adding a flocculating agent according to 0.01-0.05% of the weight of the spring water, precipitating for 2-4 days, and taking supernatant to obtain the precipitated spring water;
(2) removing microorganisms: heating the precipitated spring water to 35-40 deg.C at a temperature of 0.2-0.5m3Flowing through a filter containing a biological filter layer at a flow rate of/min to obtain mountain spring water with microorganisms removed;
(3) selenium enrichment treatment: adding 3-5 parts of modified chitosan into 100 parts of mountain spring water from which microorganisms are removed to adsorb selenium ions, stirring at the speed of 50-100r/min for 30-40min, taking out the modified chitosan after adsorbing the selenium ions, treating the mountain spring water for 10-20min by using an electromagnetic pulse with the single pulse energy of 20-100J and the frequency of 65-120KHz, adding the modified chitosan after adsorbing the selenium ions again, treating the mountain spring water for 120-150min by using ultrasonic waves with the power of 1500-2000W, and filtering by using an ultrafiltration membrane to obtain filtrate which is the selenium-rich mountain spring water.
In the present invention, as a further illustration, the modified chitosan of step (3) is prepared by the following method: dissolving 3-5 parts by weight of chitosan in 60-100 parts by weight of 10-20% formic acid solution, stirring at the speed of 200 plus materials and 300r/min for 30-45min to obtain chitosan sol, then adding 20-30 parts by weight of hydroxyapatite into the chitosan sol to obtain mixed gel, stirring the mixed gel at the speed of 1000 plus materials and 2000r/min while dropwise adding an accelerant for 2-4h, washing with distilled water for 3 times, freezing at-17 ℃ for 48-70h, then vacuum drying at 50-60 ℃ for 30-48h, and crushing to obtain the modified chitosan.
In the present invention, as a further illustration, the flocculant described in step (1) is carboxymethyl cellulose grafted acrylic acid copolymer.
In the invention, as a further explanation, the filter material of the biological filter layer in the step (2) is shale ceramsite with the particle size of 4-6 mm.
In the invention, as further illustration, the accelerator is a mixture of 10-20 by weight: 8-15: 30-50 parts of potassium phosphate, butanediol and purified water.
In the present invention, as a further illustration, the carboxymethyl cellulose grafted acrylic acid copolymer is prepared by the following method: according to the weight portion, 15-20 portions of sodium carboxymethylcellulose, 20-32 portions of acrylic acid and 1 portion of ammonium nitrate are reacted for 5-8 hours in a gas environment at the temperature of 130-.
In the present invention, the gas is nitrogen or helium as a further illustration.
The functions of part of raw materials in the invention are introduced as follows:
chitosan, also known as chitosan, is obtained by deacetylation of chitin, which is widely present in nature, and is chemically named polyglucosamine (1-4) -2-amino-B-D glucose. Excellent performances of chitosan such as biological functionality and compatibility, blood compatibility, safety, microbial degradability and the like are widely concerned by various industries, and application research in various fields such as medicine, food, chemical industry, cosmetics, water treatment, metal extraction and recovery, biochemistry, biomedical engineering and the like is greatly advanced. In the present invention, chitosan is used to prepare a matrix material of modified chitosan.
Formic acid, also known as formic acid, has the chemical formula HCOOH. Formic acid has a melting point of 8.4 ℃ and a boiling point of 100.8 ℃, is colorless, has pungent odor and corrosive properties, and foams and swells when being contacted with human skin. In the present invention, formic acid is used to dissolve chitosan.
Hydroxyapatite is a natural apatite mineral with the molecular formula of Ca10(PO4)6(OH)2A crystal structure consisting of two molecules. Hydroxyapatite is a pure end-member of hydroxyl radicals in apatite. In the present invention, hydroxyapatite is used to modify chitosan.
Shale ceramisite is made up of shale as raw material through high-temp roasting and refining. It is non-toxic, tasteless, compression-resistant, wear-resistant and corrosion-resistant, and has good adsorption property and strength, and is suitable for purification treatment of various water qualities. In the invention, the shale ceramisite is used as a filter element material of a filter and is used for filtering algae and microorganisms in the mountain spring water.
Potassium phosphate, colorless or white orthorhombic crystals. There are anhydrate, heptahydrate and nonahydrate. Usually, it is anhydrous and deliquescent. Is easily soluble in water and insoluble in ethanol. In the present invention, potassium phosphate is used as a main material for preparing the accelerator.
Butanediol is colorless and transparent in appearance, has a boiling point of 193 ℃ and a burning point of 394 ℃, can adsorb water molecules, has super-strong moisturizing capability and excellent moisturizing safety, and is commonly used in skin care products. In the present invention, butanediol is used as a main material for producing the accelerator.
The sodium carboxymethylcellulose is white or yellowish fibrous powder or white powder in appearance, is odorless, tasteless and nontoxic; it is easily dissolved in cold water or hot water to form gel, and the solution is neutral or slightly alkaline and insoluble in organic solvent such as ethanol, diethyl ether, isopropanol, and acetone. In the present invention, sodium carboxymethylcellulose is used to prepare the matrix material of the carboxymethyl cellulose grafted acrylic copolymer.
Acrylic acid, also known as acrylic acid, is the simplest unsaturated carboxylic acid, consisting of one vinyl group and one carboxyl group. Pure acrylic acid is a colorless clear liquid with a characteristic pungent odor and is corrosive. It is miscible with water, alcohols, ethers and chloroform and is prepared from propylene obtained from an oil refinery. Acrylic acid can react with carboxylic acid to obtain corresponding ester. In the present invention, acrylic acid is used as a main material for preparing the carboxymethyl cellulose-grafted acrylic copolymer.
Ammonium nitrate, colorless and odorless transparent crystal or white crystal, is easily dissolved in water and is easy to absorb moisture and agglomerate. Ammonium salt is easily decomposed by heating and is decomposed by alkali. Is an oxidant used for chemical fertilizers and chemical raw materials. In the present invention, ammonium nitrate is used for the material for preparing the carboxymethyl cellulose-grafted acrylic copolymer.
Nitrogen, helium are used as protective gases in the reaction in the present invention.
The invention has the following beneficial effects:
1. the modified chitosan prepared by the invention can directionally adsorb selenium ions, firstly enrich the selenium ions, and then remove the selenium ions under the action of strong external force, so that the selenium ion content in mountain spring water can be freely managed, and the effect of improving the selenium content is achieved. The invention adopts strong solvent formic acid to dissolve chitosan, so that the chitosan can be dissolved into colloid, then inserts hydroxyapatite in the chitosan colloid under the promoting action of accelerator potassium phosphate and butanediol mixed liquor to form a capsule material with an outer layer of chitosan and an inner layer of hydroxyapatite, thus solving the problem that the hydroxyapatite is easy to agglomerate. The capsule material contains a large number of hydroxyl groups from inside to outside, and under the strong acid condition of formic acid, the hydroxyl groups can perform a displacement reaction with selenate and selenite in spring water, so that a directional reaction on selenium ions is realized, and a function of enriching the selenium ions is achieved; and the replaced selenate and selenite can break the chemical bond under the action of strong external force, so that the selenate and selenite are separated, and the free management of selenium ions is further realized. The technical means adopted by the invention are mutually matched, mutually promoted and linked in a circular way, so that the free management of the selenium ions in the mountain spring water is promoted together, and the aim of improving the content of the selenium ions in the mountain spring water is further achieved.
2. The invention adopts carboxymethyl cellulose grafted acrylic acid copolymer as flocculant, which can efficiently flocculate particles and suspended matters in the mountain spring water and purify the water quality. According to the invention, the acrylic acid can be grafted to the sodium carboxymethyl cellulose under the high-temperature catalysis of ammonium nitrate, the semi-rigid chain of the sodium carboxymethyl cellulose is taken as a framework, and the acrylic acid monomer is grafted, so that the carboxymethyl cellulose has carbonyl and carbon-carbon double bonds, and is easier to perform dehydration and adsorption bridging with solid particles and suspended matters to remove the solid particles and the suspended matters, and the total precipitation effect is far higher than the sum of the effects generated by single components.
3. The invention adopts the technical means of electromagnetic pulse heavy metal ion removal, the technical means of selenium ion adsorption by modified chitosan and the technical means of selenium ion ultrasonic removal to process the spring water in a combined manner, so that the selenium ions in the spring water are collected and then the excessive heavy metal ions such as lead, manganese and the like in the spring water are further removed, then under the ultrasonic treatment, the chemical bond on the adsorbent is destroyed, the selenium ions are released again, the three technical effects are mutually matched and mutually promoted, the free management of the selenium ions in the spring water is jointly realized, and the quality of the spring water is jointly improved.
[ detailed description ] embodiments
Example 1:
1. early preparation:
preparation of the accelerator: mixing 10 parts of potassium phosphate, 8 parts of butanediol and 30 parts of purified water according to parts by weight to obtain the promoter.
Preparing modified chitosan: dissolving 3 parts by weight of chitosan in 60 parts by weight of 10% formic acid solution, stirring at the speed of 200r/min for 30min to obtain chitosan sol, then adding 20 parts by weight of hydroxyapatite into the chitosan sol to obtain mixed gel, stirring the mixed gel at the speed of 1000r/min for 2h while dropwise adding an accelerant, washing with distilled water for 3 times, freezing at-17 ℃ for 48h, then drying at 50 ℃ in vacuum for 30h, and crushing to obtain the modified chitosan.
Preparation of carboxymethyl cellulose grafted acrylic acid copolymer: according to the weight portion, 15 portions of sodium carboxymethyl cellulose, 20 portions of acrylic acid and 1 portion of ammonium nitrate react for 5 hours under the conditions of temperature of 130 ℃ and stirring speed of 200r/min, and then are filtered and dried to obtain the carboxymethyl cellulose grafted acrylic acid copolymer.
The prepared substances are used for the preparation process of the selenium-rich spring water.
2. A preparation process of selenium-rich spring water comprises the following steps:
(1) and (3) precipitation treatment: introducing the spring water into an inclined tube sedimentation tank, adding carboxymethyl cellulose grafted acrylic acid copolymer according to 0.01% of the weight of the spring water, precipitating for 2 days, and taking supernatant to obtain precipitated spring water;
(2) removing microorganisms: heating the precipitated spring water to 35 deg.C at a pressure of 0.2m3Flowing at a flow rate of/min through a filter containing a biological filter layer, wherein a filter material of the biological filter layer is shale ceramsite with the particle size of 4mm, so as to obtain mountain spring water with microorganisms removed;
(3) selenium enrichment treatment: adding 3 parts of modified chitosan into 100 parts of mountain spring water from which microorganisms are removed to adsorb selenium ions, stirring at the speed of 50r/min for 30min, taking out the modified chitosan after adsorbing the selenium ions, treating the mountain spring water for 10min by using an electromagnetic pulse with the single pulse energy of 20J and the frequency of 65KHz, adding the modified chitosan after adsorbing the selenium ions again, treating the mountain spring water for 120min by using ultrasonic waves with the power of 1500W, and filtering by using an ultrafiltration membrane to obtain filtrate, namely the selenium-enriched mountain spring water.
Example 2:
1. early preparation:
preparation of the accelerator: and mixing 14 parts of potassium phosphate, 11 parts of butanediol and 37 parts of purified water according to parts by weight to obtain the promoter.
Preparing modified chitosan: according to the weight portion, 3.5 portions of chitosan is dissolved in 80 portions of formic acid solution with the mass fraction of 13 percent, the mixture is stirred for 38min at the speed of 250r/min to obtain chitosan sol, 26 portions of hydroxyapatite are added into the chitosan sol to obtain mixed gel, the mixed gel is stirred for 2.5h at the speed of 1400r/min while the accelerant is dropwise added, the mixed gel is washed for 3 times by distilled water, after being frozen for 50h at minus 17 ℃, the mixed gel is dried for 40h under the vacuum of 57 ℃, and the modified chitosan is obtained after being crushed.
Preparation of carboxymethyl cellulose grafted acrylic acid copolymer: according to the weight portion, 18 portions of sodium carboxymethyl cellulose, 29 portions of acrylic acid and 1 portion of ammonium nitrate react for 6 hours in a helium environment under the conditions that the temperature is 135 ℃ and the stirring speed is 275r/min, and the carboxymethyl cellulose grafted acrylic acid copolymer is obtained after filtration and drying.
The prepared substances are used for the preparation process of the selenium-rich spring water.
2. A preparation process of selenium-rich spring water comprises the following steps:
(1) and (3) precipitation treatment: introducing the spring water into an inclined tube sedimentation tank, adding carboxymethyl cellulose grafted acrylic acid copolymer according to 0.04% of the weight of the spring water, precipitating for 3 days, and taking supernatant to obtain precipitated spring water;
(2) removing microorganisms: heating the precipitated spring water to 36 deg.C at a pressure of 0.4m3Flowing through a filter containing a biological filter layer at a flow rate of/min, wherein a filter material of the biological filter layer is shale ceramsite with the particle size of 4.5mm, so as to obtain mountain spring water with microorganisms removed;
(3) selenium enrichment treatment: adding 4 parts of modified chitosan into 100 parts of mountain spring water from which microorganisms are removed to adsorb selenium ions, stirring for 37min at a speed of 65r/min, taking out the modified chitosan after adsorbing the selenium ions, treating the mountain spring water for 13min by using an electromagnetic pulse with single pulse energy of 50J and frequency of 75KHz, adding the modified chitosan after adsorbing the selenium ions again, treating the mountain spring water for 145min by using ultrasonic waves with power of 1700W, and filtering by using an ultrafiltration membrane to obtain filtrate, namely the selenium-enriched mountain spring water.
Example 3:
1. early preparation:
preparation of the accelerator: and mixing 14 parts of potassium phosphate, 12 parts of butanediol and 40 parts of purified water according to parts by weight to obtain the promoter.
Preparing modified chitosan: dissolving 4 parts by weight of chitosan in 90 parts by weight of 12% formic acid solution, stirring at the speed of 240r/min for 40min to obtain chitosan sol, then adding 26 parts by weight of hydroxyapatite into the chitosan sol to obtain mixed gel, stirring the mixed gel at the speed of 1600r/min while dropwise adding an accelerator for 3.5h, washing with distilled water for 3 times, freezing at-17 ℃ for 60h, then vacuum drying at 53 ℃ for 39h, and crushing to obtain the modified chitosan.
Preparation of carboxymethyl cellulose grafted acrylic acid copolymer: according to the weight portion, 17 portions of sodium carboxymethyl cellulose, 30 portions of acrylic acid and 1 portion of ammonium nitrate react for 6 hours in a nitrogen or helium environment under the conditions that the temperature is 140 ℃ and the stirring speed is 320r/min, and the carboxymethyl cellulose grafted acrylic acid copolymer is obtained after filtration and drying.
The prepared substances are used for the preparation process of the selenium-rich spring water.
2. A preparation process of selenium-rich spring water comprises the following steps:
(1) and (3) precipitation treatment: introducing the spring water into an inclined tube sedimentation tank, adding carboxymethyl cellulose grafted acrylic acid copolymer according to 0.02% of the weight of the spring water, precipitating for 2.5 days, and taking supernatant to obtain precipitated spring water;
(2) removing microorganisms: heating the precipitated spring water to 39 deg.C, and keeping the temperature at 0.4m3Flowing at a flow rate of/min through a filter containing a biological filter layer, wherein a filter material of the biological filter layer is shale ceramsite with the particle size of 5mm, so as to obtain mountain spring water with microorganisms removed;
(3) selenium enrichment treatment: adding 4.5 parts of modified chitosan into 100 parts of mountain spring water from which microorganisms are removed to adsorb selenium ions, stirring at the speed of 65r/min for 38min, taking out the modified chitosan from which the selenium ions are adsorbed, treating the mountain spring water with electromagnetic pulse with single pulse energy of 60J and frequency of 100KHz for 15min, adding the modified chitosan from which the selenium ions are adsorbed again, treating the mountain spring water with ultrasonic waves with power of 1700W for 130min, and filtering with an ultrafiltration membrane to obtain filtrate, namely the selenium-enriched mountain spring water.
Example 4:
1. early preparation:
preparation of the accelerator: and mixing 13 parts of potassium phosphate, 12 parts of butanediol and 40 parts of purified water according to parts by weight to obtain the promoter.
Preparing modified chitosan: according to parts by weight, 3.5 parts of chitosan is dissolved in 75 parts of 16 mass percent formic acid solution and stirred for 42min at the speed of 260r/min to obtain chitosan sol, then 24 parts of hydroxyapatite is added into the chitosan sol to obtain mixed gel, the mixed gel is stirred for 3.5h at the speed of 1400r/min while an accelerator is dropwise added, the mixed gel is washed for 3 times by distilled water and frozen for 55h at minus 17 ℃, then vacuum drying is carried out for 44h at 53 ℃, and the modified chitosan is obtained after crushing.
Preparation of carboxymethyl cellulose grafted acrylic acid copolymer: according to the weight portion, 16 portions of sodium carboxymethyl cellulose, 30 portions of acrylic acid and 1 portion of ammonium nitrate react for 7 hours under the conditions that the temperature is 136 ℃ and the stirring speed is 360r/min, and then the carboxymethyl cellulose grafted acrylic acid copolymer is obtained after filtration and drying.
The prepared substances are used for the preparation process of the selenium-rich spring water.
2. A preparation process of selenium-rich spring water comprises the following steps:
(1) and (3) precipitation treatment: introducing the spring water into an inclined tube sedimentation tank, adding carboxymethyl cellulose grafted acrylic acid copolymer according to 0.04% of the weight of the spring water, precipitating for 3.5 days, and taking supernatant to obtain precipitated spring water;
(2) removing microorganisms: heating the precipitated spring water to 37 deg.C, and keeping the temperature at 0.4m3Flowing through a filter containing a biological filter layer at a flow rate of/min, wherein a filter material of the biological filter layer is shale ceramsite with the particle size of 5.5mm, and obtaining mountain spring water after microorganisms are removed;
(3) selenium enrichment treatment: adding 4 parts of modified chitosan into 100 parts of mountain spring water from which microorganisms are removed to adsorb selenium ions, stirring at the speed of 85r/min for 35min, taking out the modified chitosan after adsorbing the selenium ions, treating the mountain spring water with electromagnetic pulse with single pulse energy of 60J and frequency of 90KHz for 12min, adding the modified chitosan after adsorbing the selenium ions again, treating the mountain spring water with ultrasonic waves with power of 1800W for 135min, and filtering with an ultrafiltration membrane to obtain filtrate, namely the selenium-enriched mountain spring water.
Example 5:
1. early preparation:
preparation of the accelerator: mixing 15 parts of potassium phosphate, 13 parts of butanediol and 45 parts of purified water according to parts by weight to obtain the accelerant.
Preparing modified chitosan: dissolving 4.5 parts by weight of chitosan in 73 parts by weight of a formic acid solution with the mass fraction of 14%, stirring for 41min at the speed of 270r/min to obtain chitosan sol, then adding 24 parts by weight of hydroxyapatite into the chitosan sol to obtain mixed gel, stirring the mixed gel at the speed of 1300r/min for 3h while dropwise adding an accelerator, washing the mixed gel for 3 times with distilled water, freezing for 65h at the temperature of-17 ℃, then drying for 45h at the temperature of 52 ℃ in vacuum, and crushing to obtain the modified chitosan.
Preparation of carboxymethyl cellulose grafted acrylic acid copolymer: according to the weight portion, 18 portions of sodium carboxymethyl cellulose, 27 portions of acrylic acid and 1 portion of ammonium nitrate react for 6 hours in a helium environment under the conditions that the temperature is 138 ℃ and the stirring speed is 280r/min, and the carboxymethyl cellulose grafted acrylic acid copolymer is obtained after filtration and drying.
The prepared substances are used for the preparation process of the selenium-rich spring water.
2. A preparation process of selenium-rich spring water comprises the following steps:
(1) and (3) precipitation treatment: introducing the spring water into an inclined tube sedimentation tank, adding carboxymethyl cellulose grafted acrylic acid copolymer according to 0.03 percent of the weight of the spring water, precipitating for 3.5 days, and taking supernatant to obtain the precipitated spring water;
(2) removing microorganisms: heating the precipitated spring water to 37 deg.C, and keeping the temperature at 0.4m3Flowing at a flow rate of/min through a filter containing a biological filter layer, wherein a filter material of the biological filter layer is shale ceramsite with the particle size of 5mm, so as to obtain mountain spring water with microorganisms removed;
(3) selenium enrichment treatment: adding 4.5 parts of modified chitosan into 100 parts of mountain spring water from which microorganisms are removed to adsorb selenium ions, stirring at the speed of 75r/min for 38min, taking out the modified chitosan from which the selenium ions are adsorbed, treating the mountain spring water with electromagnetic pulse with single pulse energy of 40J and frequency of 110KHz for 11min, adding the modified chitosan from which the selenium ions are adsorbed again, treating the mountain spring water with ultrasonic waves with power of 1600W for 135min, and filtering with an ultrafiltration membrane to obtain filtrate, namely the selenium-enriched mountain spring water.
Example 6:
1. early preparation:
preparation of the accelerator: and mixing 20 parts of potassium phosphate, 15 parts of butanediol and 50 parts of purified water according to parts by weight to obtain the promoter.
Preparing modified chitosan: dissolving 5 parts by weight of chitosan in 100 parts by weight of 20% formic acid solution, stirring for 45min at the speed of 300r/min to obtain chitosan sol, then adding 30 parts by weight of hydroxyapatite into the chitosan sol to obtain mixed gel, stirring the mixed gel at the speed of 2000r/min for 4h while dropwise adding an accelerator, washing the mixed gel for 3 times by using distilled water, freezing for 70h at the temperature of-17 ℃, then drying for 48h at the temperature of 60 ℃ in vacuum, and crushing to obtain the modified chitosan.
Preparation of carboxymethyl cellulose grafted acrylic acid copolymer: according to the weight portion, 20 portions of sodium carboxymethyl cellulose, 32 portions of acrylic acid and 1 portion of ammonium nitrate react for 8 hours in a helium environment under the conditions that the temperature is 150 ℃ and the stirring speed is 400r/min, and the carboxymethyl cellulose grafted acrylic acid copolymer is obtained after filtration and drying.
The prepared substances are used for the preparation process of the selenium-rich spring water.
2. A preparation process of selenium-rich spring water comprises the following steps:
(1) and (3) precipitation treatment: introducing the spring water into an inclined tube sedimentation tank, adding carboxymethyl cellulose grafted acrylic acid copolymer according to 0.05 percent of the weight of the spring water, precipitating for 4 days, and taking supernatant to obtain the precipitated spring water;
(2) removing microorganisms: heating the precipitated spring water to 40 deg.C, and keeping the temperature at 0.5m3Flowing at a flow rate of/min through a filter containing a biological filter layer, wherein a filter material of the biological filter layer is shale ceramsite with the particle size of 6mm, so as to obtain mountain spring water with microorganisms removed;
(3) selenium enrichment treatment: adding 5 parts of modified chitosan into 100 parts of mountain spring water from which microorganisms are removed to adsorb selenium ions, stirring at the speed of 100r/min for 40min, taking out the modified chitosan after adsorbing the selenium ions, treating the mountain spring water with electromagnetic pulse with single pulse energy of 100J and frequency of 120KHz for 20min, adding the modified chitosan after adsorbing the selenium ions again, treating the mountain spring water with ultrasonic waves with power of 2000W for 150min, and filtering with an ultrafiltration membrane to obtain filtrate, namely the selenium-enriched mountain spring water.
Comparative example 1: the specific steps and raw materials of the preparation process of the selenium-rich spring water are basically the same as those of the embodiment 1, and the difference is that: the core material of the filter adopted in the step (2) is activated carbon.
Comparative example 2: the specific steps and raw materials of the preparation process of the selenium-rich spring water are basically the same as those of the embodiment 1, and the difference is that: and (4) adsorbing selenium ions by adopting chitosan in the step (3).
Comparative example 3: the specific steps and raw materials of the preparation process of the selenium-rich spring water are basically the same as those of the embodiment 1, and the difference is that: no promoter is added in the preparation process of the modified chitosan.
Comparative example 4: the specific steps and raw materials of the preparation process of the selenium-rich spring water are basically the same as those of the embodiment 1, and the difference is that: the flocculant is polyacrylamide.
Comparative experiment 1: the components of the selenium-rich spring water were measured according to 500g of the selenium-rich spring water prepared in each of comparative examples 1 to 4 and examples 1 to 6, the measurement standards were performed according to DBS44/001-2011, and all the measurement results are shown in Table 1.
Table 1:
Figure GDA0002243029140000091
Figure GDA0002243029140000101
the results in table 1 show that: the higher the selenium content is, the higher the selenium ion content of the mineral water is, and the better the selenium-rich effect is. The content of selenium in the comparative example 2 is the lowest, which shows that the adsorption effect of chitosan on selenium ions is not obvious, and the selenium-enriched spring water prepared by the method provided by the embodiment of the invention can greatly improve the selenium content in the spring water;
the lower the content of the lead ions and the manganese ions is, the lower the content of the heavy metals in the mountain spring water is, the more beneficial the health is, the highest the content of the lead ions and the manganese ions in the comparative example 2 is, the adsorption effect of chitosan on the lead ions and the manganese ions is not obvious, and the selenium-rich mountain spring water prepared by the method disclosed by the embodiment of the invention can greatly reduce the content of the lead ions and the content of the manganese ions in the mountain spring water;
the smaller the number of colony groups, the less bacteria in the mountain spring water, and the more beneficial the human health. The number of colony groups in the comparative example 1 is the highest, which shows that the adsorption capacity of the activated carbon on microorganisms and algae is weaker, and the selenium-enriched spring water prepared by the method provided by the embodiment of the invention can greatly reduce the number of colony groups in the spring water.
The above description is intended to describe in detail the preferred embodiments of the present invention, but the embodiments are not intended to limit the scope of the claims of the present invention, and all equivalent changes and modifications made within the technical spirit of the present invention should fall within the scope of the claims of the present invention.

Claims (6)

1. A preparation process of selenium-rich spring water is characterized by comprising the following steps: the method comprises the following steps:
(1) and (3) precipitation treatment: introducing the spring water into an inclined tube sedimentation tank, adding a flocculating agent according to 0.01-0.05% of the weight of the spring water, precipitating for 2-4 days, and taking supernatant to obtain the precipitated spring water;
(2) removing microorganisms: heating the precipitated spring water to 35-40 deg.C at a temperature of 0.2-0.5m3Flowing through a filter containing a biological filter layer at a flow rate of/min to obtain mountain spring water with microorganisms removed;
(3) selenium enrichment treatment: adding 3-5 parts of modified chitosan into 100 parts of mountain spring water from which microorganisms are removed to adsorb selenium ions, stirring at the speed of 50-100r/min for 30-40min, taking out the modified chitosan after adsorbing the selenium ions, treating the mountain spring water for 10-20min by using an electromagnetic pulse with the single pulse energy of 20-100J and the frequency of 65-120KHz, adding the modified chitosan after adsorbing the selenium ions again, treating the mountain spring water for 120-150min by using ultrasonic waves with the power of 1500-2000W, and filtering by using an ultrafiltration membrane to obtain filtrate which is the selenium-rich mountain spring water;
the modified chitosan is prepared by the following method: dissolving 3-5 parts by weight of chitosan in 60-100 parts by weight of 10-20% formic acid solution, stirring at the speed of 200 plus materials and 300r/min for 30-45min to obtain chitosan sol, then adding 20-30 parts by weight of hydroxyapatite into the chitosan sol to obtain mixed gel, stirring the mixed gel at the speed of 1000 plus materials and 2000r/min while dropwise adding an accelerant for 2-4h, washing with distilled water for 3 times, freezing at-17 ℃ for 48-70h, then vacuum drying at 50-60 ℃ for 30-48h, and crushing to obtain the modified chitosan.
2. The preparation process of the selenium-rich spring water according to claim 1, which is characterized by comprising the following steps of: the flocculating agent in the step (1) is carboxymethyl cellulose grafted acrylic acid copolymer.
3. The preparation process of the selenium-rich spring water according to claim 1, which is characterized by comprising the following steps of: the filtering material of the biological filtering layer in the step (2) is shale ceramsite with the particle size of 4-6 mm.
4. The preparation process of the selenium-rich spring water according to claim 1, which is characterized by comprising the following steps of: the accelerant is prepared from the following components in a weight ratio of 10-20: 8-15: 30-50 parts of potassium phosphate, butanediol and purified water.
5. The preparation process of the selenium-rich spring water according to claim 2, which is characterized by comprising the following steps of: the carboxymethyl cellulose grafted acrylic copolymer is prepared by the following method: according to the weight portion, 15-20 portions of sodium carboxymethylcellulose, 20-32 portions of acrylic acid and 1 portion of ammonium nitrate are reacted for 5-8 hours in a gas environment at the temperature of 130-.
6. The preparation process of the selenium-rich spring water according to claim 5, wherein the preparation process comprises the following steps: the gas is nitrogen or helium.
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