CN108311120A - A kind of inorganic composite materials and preparation method thereof of aquaculture wastewater processing - Google Patents
A kind of inorganic composite materials and preparation method thereof of aquaculture wastewater processing Download PDFInfo
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- CN108311120A CN108311120A CN201810033382.6A CN201810033382A CN108311120A CN 108311120 A CN108311120 A CN 108311120A CN 201810033382 A CN201810033382 A CN 201810033382A CN 108311120 A CN108311120 A CN 108311120A
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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
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
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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
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/12—Naturally occurring clays or bleaching earth
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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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28047—Gels
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
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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
- C02F2103/20—Nature of the water, waste water, sewage or sludge to be treated from animal husbandry
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- Environmental & Geological Engineering (AREA)
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- Geochemistry & Mineralogy (AREA)
- Inorganic Chemistry (AREA)
- Biological Treatment Of Waste Water (AREA)
- Farming Of Fish And Shellfish (AREA)
Abstract
The invention belongs to sea-farming sewage treatment fields, and in particular to a kind of inorganic composite materials and preparation method thereof of aquaculture wastewater processing.The present invention utilizes natural inorganic material, by polyvinyl alcohol and triethylene tetramine graft copolymerization, is made using squeezing out；Raw material key component includes：Inorganic particle, polyvinyl alcohol, crosslinking agent, surface conditioning agent, triethylene tetramine, compatilizer, resorcinol, ethylenediamine, natural fiber.The present invention utilizes the characteristic of graft copolymerization, makes polyvinyl alcohol and triethylene tetramine graft copolymerization, effectively can have high suction-operated to impurity in aquaculture wastewater；The inorganic composite materials, stabilized structure, the permanently effective processing breeding wastewater of energy；Natural inorganic material technology used in preparation process is simple, at low cost, has broad mass market application prospect.
Description
Technical field
The invention belongs to sea-farming sewage treatment fields, and in particular to a kind of inorganic composite materials of aquaculture wastewater processing
And preparation method thereof.
Background technology
China is mariculture big country.With the fast development of Chinese mariculture industry, coastal nursery and cultivation
Field wastewater discharge is growing day by day, offshore waters environment severe exacerbation, the unbalance, red tide so as to cause safeguard of coast and marine ecological system
It takes place frequently, disease is grown.May include particulate form solid waste, the solubilised state generation from excrement and feed in marine culture wastewater
Waste, solubilised state nutritive salt, anti-microbial agents and medicament residue etc. are thanked, thus after it is largely discharged, can cause to cultivate
Water and vicinity waters eutrophication or water quality deterioration.Breeding wastewater is unprocessed to be discharged into offshore sea waters, will pollute neighbouring marine site,
So that ecological environment bears ever-increasing pressure.
It is very urgent to solve the pollution problem that sea-farming is brought.Due to the extensive and large scale feature of sea-farming,
So far still lack ideal technical method.The method of organic matter is mainly in removing aquaculture wastewater at present：(1) Physical：It is main
To include precipitation, sand coarse aggregate ratio etc.；(2) chemical method：Chemical reagent is added, makes harmful substance flocculation etc.；(3) bioanalysis：Utilize micro- life
Object decomposing harmful substances.
Seawater hydraulics water emission problem can be effectively solved using natural inorganic composite material.It is one that this, which meets material,
Kind is by polyvinyl alcohol and triethylene tetramine graft copolymerization, using crowded using composite inorganic materials such as natural inorganic powders
Go out, hot pressing obtains a kind of sea-farming sewage disposal composite material.
Invention content
To solve the above problems, the present invention provides a kind of inorganic composite materials of aquaculture wastewater processing and its preparation sides
Method solves the technical barrier of marine culture wastewater processing.
The present invention the technical solution adopted is that：
A kind of inorganic composite materials of aquaculture wastewater processing pass through polyvinyl alcohol and triethylene using natural inorganic material
Tetramine graft copolymerization is made using squeezing out；Feed components are according to the mass fraction：30~60 parts of inorganic particle, polyvinyl alcohol
10~30 parts, 0.5~5 part of crosslinking agent, 0.1~0.2 part of surface conditioning agent, 60~80 parts of triethylene tetramine, compatilizer 0.01~
0.2 part, 1~10 part of resorcinol, 0.4~1 part of ethylenediamine, 10~20 parts of natural fiber.
The inorganic particle be zeolite, montmorillonite, vermiculite, bentonite, pyrophyllite, alunite, hydrotalcite, sepiolite,
The one or more mixing of serpentine compound different inorganic particles according to the requirement in discharge waters, to reach protection ecology of water ring
The requirement in border.
The compatilizer is maleic anhydride graft phenylethene, maleic anhydride grafted propylene nitrile-butadiene styrene copolymerization
One or more mixing in object.
The surface conditioning agent is one or more mixing in stearate, ethylenediamine phosphate, phosphoric acid propane diamine.
The crosslinking agent is the one or both mixing in ammonium ceric nitrate, succinic anhydride.
A kind of preparation method of the inorganic composite materials of aquaculture wastewater processing, includes the following steps：
(1) in terms of mass fraction, 30~60 parts of inorganic particles are crushed to grain size≤1 μm, then be placed in high-speed mixer,
0.1~0.2 part of surface conditioning agent is added, for control temperature at 90~100 DEG C, rotating speed is 1000~1400r/min, stirring 15~
20min is cooled to room temperature, and obtains product A；
(2) it by 10~30 parts of polyvinyl alcohol, is made it completely dissolved in 90~120 DEG C of 5~10min of stirred in water bath；It is added
0.5~5 part of crosslinking agent is slowly added to 60~80 parts of triethylene tetramines in whipping process, carries out chain initiated polymerization, control
60~80 DEG C, 2~4h of polymerization time of polymerization temperature, obtains polyvinyl alcohol/triethylene tetramine copolymer；
(3) the product A that obtains the polyvinyl alcohol obtained by step (2)/triethylene tetramine copolymer and step (1) and
0.01~0.2 part of compatilizer, 1~10 part of resorcinol, 0.4~1 part of ethylenediamine, 10~20 parts of natural fibers are added to reaction kettle
In, 2~3h is reacted under 30~60 DEG C of temperature, 6~7 stirring condition of pH value, obtains plural gel；
(4) step (3) obtained plural gel is obtained into a breeding by extruder by melting, mixing, pelletizing
Grow the inorganic composite materials of sewage disposal.
Present invention natural inorganic powder body material, via polyvinyl alcohol/triethylene tetramine graft copolymerization, using squeeze out,
Hot pressing obtains a kind of sea-farming sewage disposal composite material.The material use inorganic particle makees the high absorption of aquaculture wastewater
With stable structure, simple process and low cost is environmentally friendly, is easily recycled, and can be mass-produced.
Beneficial effects of the present invention：
1, a kind of inorganic composite materials of aquaculture wastewater processing of the present invention make polyvinyl alcohol using the characteristic of graft copolymerization
With triethylene tetramine graft copolymerization, effectively there can be high suction-operated to impurity in aquaculture wastewater.
2, a kind of inorganic composite materials of aquaculture wastewater processing of the present invention, stabilized structure, processing that can be permanently effective cultivate
Waste water.
3, the inorganic composite materials of a kind of aquaculture wastewater of present invention processing, the natural inorganic material used in preparation process
Simple process and low cost has broad mass market application prospect.
Specific implementation mode
Specific embodiments of the present invention are described in detail below in conjunction with technical solution.
Embodiment 1：
(1) in terms of mass fraction, 40 parts of inorganic particle zeolites are crushed to grain size≤1 μm, then be placed in high-speed mixer,
0.11 part of surface conditioning agent is added, control temperature under the conditions of rotating speed is 1200r/min, stirs 18min, finally cool down at 100 DEG C
To room temperature；
(2) it by 20 parts of polyvinyl alcohol, is made it completely dissolved in 100 DEG C of stirred in water bath 8min, 3 parts of crosslinking agents is added,
It is slowly added to 65 parts of triethylene tetramines in whipping process, carries out chain initiated polymerization, control polymerization temperature is at 80 DEG C, polymerization
Between be 2h, obtain polyvinyl alcohol/triethylene tetramine copolymer；
(3) by the product of copolymer and step (1) obtained by step (2) and 0.15 part of compatilizer, 5 parts of resorcinols,
0.5 part of ethylenediamine, 10 parts of natural fibers are added in reaction kettle, temperature is 60 DEG C, pH value is to react under 6.5 stirring conditions
2h obtains plural gel；
(4) step (3) obtained plural gel is obtained into a breeding by extruder by melting, mixing, pelletizing
Grow the inorganic composite materials of sewage disposal.
Example 2：
(1) in terms of mass fraction, 50 parts of inorganic particle hydrotalcites are crushed to grain size≤1 μm, then be placed in high-speed mixer
In, 0.15 part of surface conditioning agent is added, control temperature under the conditions of rotating speed is 1200r/min, stirs 20min, finally at 100 DEG C
It is cooled to room temperature；
(2) it by 25 parts of polyvinyl alcohol, is made it completely dissolved in 100 DEG C of stirred in water bath 10min, 3.5 parts of crosslinking agents is added,
It is slowly added to 70 parts of triethylene tetramines in whipping process, carries out chain initiated polymerization, control polymerization temperature is at 80 DEG C, polymerization
Time is 3h, obtains polyvinyl alcohol/triethylene tetramine copolymer；
(3) by the product of copolymer and step (1) obtained by step (2) and 0.18 part of compatilizer, 8 parts of resorcinols,
0.8 part of ethylenediamine, 15 parts of natural fibers are added in reaction kettle, temperature is 60 DEG C, pH value is to react 3h under 7 stirring conditions,
Obtain plural gel；
(4) step (3) obtained plural gel is obtained into a breeding by extruder by melting, mixing, pelletizing
Grow the inorganic composite materials of sewage disposal.
Example 3：
(1) in terms of mass fraction, 60 parts of inorganic particle zeolites and hydrotalcite is mixed and are crushed to grain size≤1 μm, then are placed in
In high-speed mixer, 0.2 part of surface conditioning agent is added, control temperature is at 95 DEG C, under the conditions of rotating speed is 1400r/min, stirring
20min is finally cooled to room temperature；
(2) it by 30 parts of polyvinyl alcohol, is made it completely dissolved in 120 DEG C of stirred in water bath 10min, 5 parts of crosslinking agents is added,
It is slowly added to 80 parts of triethylene tetramines in whipping process, carries out chain initiated polymerization, control polymerization temperature is at 70 DEG C, polymerization
Between be 4h, obtain polyvinyl alcohol/triethylene tetramine copolymer；
(3) product and 0.2 part of compatilizer, 10 parts of resorcinols, 1 by the copolymer obtained by step (2) with step (1)
Part ethylenediamine, 20 parts of natural fibers are added in reaction kettle, temperature is 50 DEG C, pH value is to react 3h under 7 stirring conditions, are obtained
Plural gel；
(4) step (3) obtained plural gel is obtained into a breeding by extruder by melting, mixing, pelletizing
Grow the inorganic composite materials of sewage disposal.
Claims (9)
1. a kind of inorganic composite materials of aquaculture wastewater processing, which is characterized in that utilize natural inorganic material, pass through polyvinyl alcohol
With triethylene tetramine graft copolymerization, it is made using squeezing out；Feed components are according to the mass fraction：30~60 parts of inorganic particle,
It is 10~30 parts of polyvinyl alcohol, 0.5~5 part of crosslinking agent, 0.1~0.2 part of surface conditioning agent, 60~80 parts of triethylene tetramine, compatible
0.01~0.2 part of agent, 1~10 part of resorcinol, 0.4~1 part of ethylenediamine, 10~20 parts of natural fiber.
2. a kind of preparation method of the inorganic composite materials of aquaculture wastewater processing described in claim 1, which is characterized in that including
Following steps：
(1) in terms of mass fraction, 30~60 parts of inorganic particles are crushed to grain size≤1 μm, then be placed in high-speed mixer, be added
0.1~0.2 part of surface conditioning agent, for control temperature at 90~100 DEG C, rotating speed is 1000~1400r/min, stirs 15~20min,
It is cooled to room temperature, obtains product A；
(2) it by 10~30 parts of polyvinyl alcohol, is made it completely dissolved in 90~120 DEG C of 5~10min of stirred in water bath；Addition 0.5~
5 parts of crosslinking agents are slowly added to 60~80 parts of triethylene tetramines in whipping process, carry out chain initiated polymerization, control polymerization
60~80 DEG C, 2~4h of polymerization time of temperature, obtains polyvinyl alcohol/triethylene tetramine copolymer；
(3) the product A and 0.01 for obtaining the polyvinyl alcohol obtained by step (2)/triethylene tetramine copolymer and step (1)~
0.2 part of compatilizer, 1~10 part of resorcinol, 0.4~1 part of ethylenediamine, 10~20 parts of natural fibers are added in reaction kettle,
2~3h is reacted under 30~60 DEG C of temperature, 6~7 stirring condition of pH value, obtains plural gel；
(4) step (3) obtained plural gel is passed through into extruder, by melting, mixing, pelletizing, it is dirty obtains a kind of cultivation
The inorganic composite materials of water process.
3. preparation method according to claim 2, which is characterized in that the inorganic particle is zeolite, montmorillonite, leech
The one or more mixing of stone, bentonite, pyrophyllite, alunite, hydrotalcite, sepiolite, serpentine.
4. preparation method according to claim 2 or 3, which is characterized in that the compatilizer is that maleic anhydride is grafted benzene
One or more mixing in ethylene, maleic anhydride grafted propylene nitrile-butadienestyrene copolymer.
5. preparation method according to claim 2 or 3, which is characterized in that the surface conditioning agent is stearate, phosphorus
One or more mixing in sour ethylenediamine, phosphoric acid propane diamine.
6. preparation method according to claim 4, which is characterized in that the surface conditioning agent is stearate, phosphoric acid
One or more mixing in ethylenediamine, phosphoric acid propane diamine.
7. according to the preparation method described in claim 2,3 or 6, which is characterized in that the crosslinking agent is ammonium ceric nitrate, fourth two
One or both mixing in acid anhydrides.
8. preparation method according to claim 4, which is characterized in that the crosslinking agent is ammonium ceric nitrate, succinic anhydride
In one or both mixing.
9. preparation method according to claim 5, which is characterized in that the crosslinking agent is ammonium ceric nitrate, succinic anhydride
In one or both mixing.
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| CN201810033382.6A CN108311120A (en) | 2018-01-15 | 2018-01-15 | A kind of inorganic composite materials and preparation method thereof of aquaculture wastewater processing |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109487358A (en) * | 2018-11-16 | 2019-03-19 | 安徽碧深高纤有限公司 | A kind of high strength fibre and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5120349A (en) * | 1990-12-07 | 1992-06-09 | Landec Labs, Inc. | Microcapsule having temperature-dependent permeability profile |
| US20020161132A1 (en) * | 1992-06-10 | 2002-10-31 | Yoshio Irie | Method for production of hydrophilic resin |
| CN103008024A (en) * | 2012-11-27 | 2013-04-03 | 安徽皖东化工有限公司 | Preparation method of macroporous slightly-alkaline acrylonitrile anion exchange resin |
| CN105582903A (en) * | 2015-12-25 | 2016-05-18 | 成都新柯力化工科技有限公司 | Flaky plural gel material for sewage treatment and preparation method thereof |
-
2018
- 2018-01-15 CN CN201810033382.6A patent/CN108311120A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5120349A (en) * | 1990-12-07 | 1992-06-09 | Landec Labs, Inc. | Microcapsule having temperature-dependent permeability profile |
| US20020161132A1 (en) * | 1992-06-10 | 2002-10-31 | Yoshio Irie | Method for production of hydrophilic resin |
| CN103008024A (en) * | 2012-11-27 | 2013-04-03 | 安徽皖东化工有限公司 | Preparation method of macroporous slightly-alkaline acrylonitrile anion exchange resin |
| CN105582903A (en) * | 2015-12-25 | 2016-05-18 | 成都新柯力化工科技有限公司 | Flaky plural gel material for sewage treatment and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109487358A (en) * | 2018-11-16 | 2019-03-19 | 安徽碧深高纤有限公司 | A kind of high strength fibre and preparation method thereof |
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Application publication date: 20180724 |