CN108017799B - A kind of preparation method of starch base oil absorption material - Google Patents
A kind of preparation method of starch base oil absorption material Download PDFInfo
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- CN108017799B CN108017799B CN201711081988.9A CN201711081988A CN108017799B CN 108017799 B CN108017799 B CN 108017799B CN 201711081988 A CN201711081988 A CN 201711081988A CN 108017799 B CN108017799 B CN 108017799B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
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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
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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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
- B01J20/28054—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 surface properties or porosity
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B30/00—Preparation of starch, degraded or non-chemically modified starch, amylose, or amylopectin
- C08B30/12—Degraded, destructured or non-chemically modified starch, e.g. mechanically, enzymatically or by irradiation; Bleaching of starch
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B30/00—Preparation of starch, degraded or non-chemically modified starch, amylose, or amylopectin
- C08B30/12—Degraded, destructured or non-chemically modified starch, e.g. mechanically, enzymatically or by irradiation; Bleaching of starch
- C08B30/18—Dextrin, e.g. yellow canari, white dextrin, amylodextrin or maltodextrin; Methods of depolymerisation, e.g. by irradiation or mechanically
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2303/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
- C08J2303/02—Starch; Degradation products thereof, e.g. dextrin
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Abstract
The invention discloses a kind of preparation methods of starch base oil absorption material, belong to starch development technique field.Starch carries out restricted degradation, and then high temperature enzyme deactivation to starch molecule using frequency sweep ultrasonic auxiliary alpha-amylase after being sufficiently gelatinized.Under stirring conditions, it is added dropwise with the hexadecyl trimethoxy silane mixed liquor of methanol-water solution prehydrolysis, the starch molecule of gelatinization occurs three-dimensional cross-linked to form network structure by Hyarogen-bonding and silane；Meanwhile the crosslinking of hydrolysising silane itself also promotes the formation of starch molecule three-dimensional net structure, to complete the sol-gel process of starch.Above-mentioned gel is poured into after mold molding quick-frozen in liquid nitrogen, and then being freeze-dried makes starch molecule and hydrolysising silane dehydrating condensation form covalent bond and a kind of starch base porous oil-absorbing material is made.
Description
Technical field
A kind of preparation method of starch base oil absorption material is related to the restricted degradable starch of ultrasonic wave added starch enzyme process point
Son, silane prehydrolysis and silane non-adsorbed starch molecule cross-link form the theory and technology of three-dimensional net structure, belong to starch exploitation
Technical field.
Background technique
Currently, oily pollution and organic solvent pollution in water environment oneself become influence human health several big problems it
One, how effectively to remove such pollution sources and has become current urgent problem to be solved.Traditional adsorbent material such as active carbon, silica gel
Etc. can solve subproblem, but the problem of it is there are oil suction difference of magnification, and oily matter easily oozes out after oil suction.For this drawback, one
The nano thin-film of a little cross-linked copolymers, organic or inorganic, such as polyurethane foam, styroflex, silicone sponge material
It comes into being, has the advantages that high oil absorption rate, highly selective and high-selenium corn amount, obtained extensive research at present.
However, the shortcomings that this analog copolymer also brings non-degradable while application.In addition, it is directed to after absorbing organic pollutant
The processing of itself also becomes problem of environmental pollution to be solved simultaneously.
Starch polymer itself has degradable characteristic, is the bio-based materials of a kind of " green ".However, its polyhydroxy
Chemical property limit its application in organic field.Siloxanes can be sent out due to forming multiple activity hydroxies after its hydrolysis
Raw self-condensation adsorbs after-condensation with polyol, to form three-dimensional net structure.If to the size of starch molecule,
The main bodys parameter such as conformation and branch rate is controlled, and then by reasonably matching, inhales silane and starch molecule by hydrogen bond
Attached, dehydrating condensation and the three-dimensional net structure for being crosslinked and being formed densification, make this three-dimensional network knot finally by freeze-drying process
A kind of degradable biological base oil absorption material can be prepared in structure porous.
In view of the deficiencies of the prior art, the present invention is glutinous by frequency sweep ultrasonic pretreated starch cream drop, after adding alpha-amylase
Frequency sweep ultrasonic processing adjusts materialization and the conformation parameter of enzyme activity control starch molecule, adjusts the proportion and dried strip of silane and starch
The factors such as part realize the purpose adjusted to starch base oil absorption material porosity, on the basis of guaranteeing oil absorption, retain it certainly
The degradable characteristic of body.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation methods of starch base oil absorption material, improve starch added value, expand
Its big application range.
The technical solution of the present invention is as follows: a kind of preparation method of starch base oil absorption material, is original with common corn starch
Material assists alpha-amylase to its restricted degradation after gelatinization by frequency sweep ultrasonic, and the cetyl three of prehydrolysis is added dropwise after enzyme deactivation
Methoxy silane promotes absorption of the hydrolysising silane to starch molecule, and then selectivity is crosslinked with starch molecule and forms three dimensional network
A kind of porous-starch base oil absorption material is made in freeze-drying after its pre-freeze by network structure.
A kind of preparation method of starch base oil absorption material carries out as steps described below:
(1) the restricted degradation of starch:
The common corn starch cream that 15%~35% (w/v) is prepared with the phosphate buffer of pH=5~7, in 95 DEG C of conditions
1~2h is stirred with the speed of 50~200rpm to be gelatinized, is cooled to 40 degree or so, is placed in frequency sweep ultrasonic wave operation system
In system (single-frequency frequency sweep mode: (22 ± 2), (28 ± 2), (33 ± 2), (40 ± 2), (68 ± 2) kHz), setting temperature is 40 DEG C,
Unit volume ultrasonic power 60W/L~180W/L, the working time 10s of impulse ultrasound, intermittent time 3s, ultrasonic frequency sweep cycle
The alpha-amylase of 100~400u/g starch is added after 500ms, 15~30min of processing, frequency sweep ultrasonic continues with 30~60min
High temperature enzyme deactivation is spare afterwards；
(2) silane prehydrolysis:
The methanol-water solution of 60%~80% (v/v) is prepared, the benzoyl peroxide first of 0.01%~0.04% (w/v) is added
Acyl, it is to be dissolved after with the pH of acetic acid regulation system be 4~5, add hexadecyl trimethoxy silane (0.1%~0.5%, v/
V) 1~5h of stirring hydrolysis is spare under conditions of 100~300rpm；
(3) formation of three-dimensional net structure:
Prehydrolized silane obtained in step (2) is added dropwise to step by constant flow pump with the flow velocity of 10~30mL/min
(1) in the restricted degradable starch cream of resulting alpha-amylase, 100~300rpm of mixing speed.After being added dropwise to complete, in centrifugation removal
Layer solution three times with the methanol-water solution washing of 40%~60% (v/v) takes lower sediment；
(4) formation of porous structure:
Gained sample in step (3) is placed in die for molding, it is quick-frozen in liquid nitrogen, and then be freeze-dried, obtain one kind
The porous High oil-absorbing resin of starch base.
The density of material obtained in the step (4) is 0.08~0.3g/cm3, porosity is 85%~95%, to petroleum
The absorptivity with higher such as ether, normal octane and chloroform, can reach 10~15 times of its own weight, and repeatable make
With.
The volume fraction of prehydrolized silane and restricted degradable starch cream is 10%~20% in the step (3).
Beneficial effects of the present invention:
(1) the present invention provides a kind of preparation methods of starch base oil absorption material, compared with traditional cross-linked copolymer,
Under the premise of ensure that identical oil absorption, there is biodegradable characteristic, and infiltration rate is fast, can be recycled.
Specific embodiment
Embodiment 1
(1) the common corn starch cream that 15% (w/v) is prepared with the phosphate buffer of pH=5, under the conditions of 95 DEG C with
The speed of 100rpm is stirred 1h and is gelatinized, and is cooled to 40 degree or so, is placed in (single-frequency in frequency sweep ultrasonic wave operating system
Frequency sweep mode: (22 ± 2), (28 ± 2), (33 ± 2), (40 ± 2), (68 ± 2) kHz), setting temperature is 40 DEG C, unit volume
After ultrasonic power 60W/L, the working time 10s of impulse ultrasound, intermittent time 3s, ultrasonic frequency sweep cycle 500ms, processing 15min
The alpha-amylase of 400u/g starch is added, high temperature enzyme deactivation is spare after frequency sweep ultrasonic continues with 60min；
(2) methanol-water solution for preparing 80% (v/v), adds the benzoyl peroxide of 0.01% (w/v), after to be dissolved
With the pH=5 of acetic acid regulation system, adds hexadecyl trimethoxy silane (0.5%, v/v) and stirred under conditions of 300rpm
Hydrolyze 5h；
(3) that prehydrolized silane is added dropwise to ultrasonic wave added alpha-amylase by constant flow pump with the flow velocity of 10mL/min is restricted
In the starch milk of degradation, mixing speed 300rpm.After the completion of addition, centrifugation removal upper solution, with the methanol-of 40% (v/v)
Aqueous solution washs three times, and lower sediment thing is taken to be placed in die for molding, quick-frozen in liquid nitrogen, and then is freeze-dried, and obtains finished product.
Density of material is 0.15g/cm3, porosity 90%；
(4) this starch base oil absorption material is totally submerged into organic solvent, keep 1min after take out, stand 2min with
The organic solvent for keeping surface layer unadsorbed drips naturally, so weigh and compared with its original weight, find its to petroleum ether,
Normal octane and chloroform uptake with higher, about the 14 of its own weight times.
Embodiment 2
(1) the common corn starch cream that 35% (w/v) is prepared with the phosphate buffer of pH=7, in 95 DEG C of conditions with
The speed stirring 2h of 200rpm is gelatinized, and is cooled to 40 degree or so, is placed in (single-frequency frequency sweep in frequency sweep ultrasonic wave operating system
Mode: (22 ± 2), (28 ± 2), (33 ± 2), (40 ± 2), (68 ± 2) kHz), setting temperature is 40 DEG C, unit volume ultrasound
It is added after power 180W/L, the working time 10s of impulse ultrasound, intermittent time 3s, ultrasonic frequency sweep cycle 500ms, processing 30min
The alpha-amylase of 400u/g starch, high temperature enzyme deactivation is spare after frequency sweep ultrasonic continues with 30min；
(2) methanol-water solution for preparing 80% (v/v), adds the benzoyl peroxide of 0.04% (w/v), after to be dissolved
With the pH=4 of acetic acid regulation system, adds hexadecyl trimethoxy silane (0.5%, v/v) and stirred under conditions of 300rpm
Hydrolyze 3h；
(3) that prehydrolized silane is added dropwise to ultrasonic wave added alpha-amylase by constant flow pump with the flow velocity of 30mL/min is restricted
In the starch milk of hydrolysis, mixing speed 300rpm.After being added dropwise to complete, it is centrifuged off upper solution, with the methanol-of 60% (v/v)
Aqueous solution washs three times, and lower sediment thing is taken to be placed in die for molding, quick-frozen in liquid nitrogen, and then is freeze-dried, and obtains finished product.
Density of material is 0.2g/cm3, porosity 85%；
(4) this starch base oil absorption material is totally submerged into organic solvent, keep 1min after take out, stand 2min with
The organic solvent for keeping surface layer unadsorbed drips naturally, so weigh and compared with its original weight, find its to petroleum ether,
Normal octane and chloroform uptake with higher, about the 12 of its own weight times.
Claims (4)
1. a kind of preparation method of starch base oil absorption material, it is characterised in that carry out as steps described below
(1) the restricted degradation of starch:
The common corn starch cream that 15%~35%w/v is prepared with the phosphate buffer that pH is 5~7, in 95 DEG C of conditions with 50~
The speed of 200rpm is stirred 1~2h and is gelatinized, and is cooled to 40 DEG C, is placed in frequency sweep ultrasonic wave operating system, setting
Temperature is 40 DEG C, unit volume ultrasonic power 60W/L~180W/L, the working time 10s of impulse ultrasound, intermittent time 3s, is surpassed
The alpha-amylase of 100~400u/g starch is added after sound frequency sweep cycle 500ms, 15~30min of processing, frequency sweep ultrasonic continues with
High temperature enzyme deactivation is spare after 30~60min；
(2) silane prehydrolysis:
The methanol-water solution of 60%~80%v/v is prepared, the benzoyl peroxide of 0.01%~0.04%w/v is added, it is to be dissolved
Afterwards with the pH of acetic acid regulation system for 4~5, add the hexadecyl trimethoxy silane of 0.1%~0.5%v/v 100~
1~5h of stirring hydrolysis under conditions of 300rpm；
(3) formation of three-dimensional net structure:
Prehydrolized silane obtained in step (2) is added dropwise to step (1) institute by constant flow pump with the flow velocity of 10~30mL/min
In the restricted degradable starch cream obtained, 100~300rpm of mixing speed；After the completion of addition, centrifugation removal upper solution, with 40%
The methanol-water solution washing of~60%v/v three times, takes lower sediment thing；
(4) formation of porous structure:
Gained sample in step (3) is placed in die for molding, it is quick-frozen in liquid nitrogen, and then be freeze-dried, obtain a kind of starch
Quito hole High oil-absorbing resin.
2. a kind of preparation method of starch base oil absorption material according to claim 1, which is characterized in that frequency sweep ultrasonic wave
It is single-frequency frequency sweep mode: 22 ± 2,28 ± 2,33 ± 2,40 ± 2,68 ± 2kHz in operating system.
3. a kind of preparation method of starch base oil absorption material according to claim 1, which is characterized in that the step
(3) volume fraction of prehydrolized silane and restricted degradable starch cream is 10%~20% in.
4. a kind of preparation method of starch base oil absorption material according to claim 1, which is characterized in that the step
(4) density of material obtained in is 0.08~0.3g/cm3, porosity is 85%~95%, to petroleum ether, normal octane and trichlorine
Methane absorptivity with higher can reach 10~15 times of its own weight, and reusable.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103710409A (en) * | 2013-12-18 | 2014-04-09 | 西北大学 | Microporous starch with controllable degradation rate and preparation method thereof |
| CN104945656A (en) * | 2015-06-25 | 2015-09-30 | 华南理工大学 | High-performance cellulose base oil absorption material and preparing method thereof |
| CN105924686A (en) * | 2016-04-13 | 2016-09-07 | 四川大学 | Biology base polymer aerogel oil absorption material and preparation method thereof |
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| JP3378256B2 (en) * | 1996-09-11 | 2003-02-17 | ザ、プロクター、エンド、ギャンブル、カンパニー | Modified porous starch |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103710409A (en) * | 2013-12-18 | 2014-04-09 | 西北大学 | Microporous starch with controllable degradation rate and preparation method thereof |
| CN104945656A (en) * | 2015-06-25 | 2015-09-30 | 华南理工大学 | High-performance cellulose base oil absorption material and preparing method thereof |
| CN105924686A (en) * | 2016-04-13 | 2016-09-07 | 四川大学 | Biology base polymer aerogel oil absorption material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 2种前处理方法对多孔淀粉吸油率的影响;张洪微等;《中国粮油学报》;20160825(第08期);摘要 * |
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