STARCH-BASED ADSORBENT WITH NANOPORES AND PREPARATION METHOD THEREOF

Abstract

A preparation method for a nanopore starch-based adsorbent. The method mainly comprises: constructing a large number of lamellar crystals on surfaces of starch granules, and inducing the formation of a nano-scale pore channel structure by means of the lamellar crystals. A large number of control tests have proved that the flaky crystals have direct influence on the formation of the nano-scale pore channel structure. The construction of a pore channel structure in a starch matrix material greatly increases the specific surface area, and improves the adsorption properties. In addition, the method is beneficial to the introduction of functional particles (magnetic particles), and avoids the problem of pore channel blockage due to first forming pores and then introducing functional particles.

Claims

1. A preparation method of a starch-based adsorbent with nanopores, at least comprising the following steps: (1) adding zero-valent metal particles I into a starch aqueous solution subjected to a hydroxyl ionization treatment to induce a surface mineralization of the starch, thereby forming flake-like mineralized crystals on surfaces of the starch particles; and (2) mixing the mineralized starch with an amylase preparation, and then forming the starch-based adsorbent with nanopores by an enzymatic screw extrusion.

2. The method according to claim 1, wherein the surface mineralization of step (1) at least comprises the following steps: (1.1) carrying out the hydroxyl ionization treatment on the starch, the hydroxyl ionization treatment comprising: mixing divalent or higher-valent metal salt with the starch in a water bath having a pH value of 5 to 9 and a temperature of 10° C. to 50° C. for 30 min to 360 min, and then sieving and cleaning to obtain a modified starch with oxygen atoms of hydroxyls thereof combined with metal ions, wherein the divalent or higher-valent metal salt is one or more selected from the group consisting of magnesium, calcium, strontium, barium, titanium, zirconium, chromium, molybdenum, manganese, cobalt, nickel, copper, zinc and aluminum; and (1.2) mixing the starch with ionized hydroxyls with the zero-valent metal particles I, wherein the zero-valent metal particles I lose electrons and become metal ions, and the metal ions compound with the ionized hydroxyls of the starch in situ to induce the surface mineralization of the starch.

3. The method according to claim 1, further comprising adding functional zero-valent iron particles Fe.sup.0 Ps during the extrusion process in step (2), wherein the mass ratio of the starch to the zero-valent metal particles II ranges from 100:2 to 100:50.

4. The method according to claim 3, comprising the following steps: (A1) ionizing hydroxyls of the starch: mixing divalent or higher-valent metal salt with the starch in a water bath having a pH value of 5 to 9 and a temperature of 10° C. to 50° C. for 30 min to 360 min, wherein the mass ratio of the divalent or higher-valent metal salt to the starch ranges from 0.05 g/g to 0.6 g/g, and the concentration of the starch ranges from 50 g/L to 200 g/L, and sieving and cleaning to obtain a modified starch with oxygen atoms of hydroxyls thereof combined with metal ions; (A2) mineralizing the modified starch: placing the modified starch with ionized hydroxyls in step (A1) into an aqueous solution with a temperature of 20° C. to 45° C., adding zero-valent iron particles Fe.sup.0 Ps, and stirring and mixing for 5 min to 15 min until the color of the modified starch turns yellow brown, wherein the volume fraction of the starch in the aqueous solution ranges from 100 g/L to 800 g/L; (A3) sieving and drying at a low temperature of 30° C. to 45° C.; and (A4) forming the starch with nanopores by k enzymatic screw extrusion: adding the amylase preparation into the dried product in step (A3) for pre-conditioning and obtaining a mixture, and feeding the mixture into a cavity of an extruding machine for reaction, and discharging to obtain the starch-based adsorbent with nanopores.

5. The method according to claim 3, comprising the following steps: (B1) ionizing hydroxyls of the starch: mixing divalent or higher-valent metal salt with the starch in a water bath having a pH value of 5 to 9 and a temperature of 10° C. to 50° C. for 30 min to 360 min, wherein the mass ratio of the divalent or higher-valent metal salt to the starch ranges from 0.05 g/g to 0.6 g/g, and the concentration of the starch ranges from 50 g/L to 200 g/L, and sieving and cleaning to obtain a modified starch with oxygen atoms of hydroxyls thereof combined with metal ions; (B2) mineralizing the modified starch: placing the modified starch with ionized hydroxyls in step (B1) into an aqueous solution with a temperature of 20° C. to 45° C., adding zero-valent iron particles Fe.sup.0 Ps, and stirring and mixing for 5 min to 15 min until the color of the modified starch turns yellow brown; (B3) sucking out the remaining Fe.sup.0 Ps by a magnet, and sieving and drying at a low temperature of 30° C. to 45° C.; and (B4) forming the starch with nanopores by the enzymatic screw extrusion: adding the amylase preparation into the dried product in step (B3) for pre-conditioning and acquiring a mixture, feeding the mixture into a cavity of an extruding machine for a pre-extrusion reaction, adding Fe.sup.0 Ps for a continuous extrusion reaction after the pre-extrusion reaction, and discharging after the continuous extrusion reaction to obtain the starch-based adsorbent with nanopores.

6. The method according to claim 4, wherein the average particle size of the zero-valent iron particles Fe.sup.0 Ps ranges from 50 nm to 100 μm.

7. The method according to claim 4, wherein the amylase preparation is one or more selected from the group consisting of thermostable α-amylase, mesophilic α-amylase, β-amylase, pullulanase and isoamylase.

8. The method according to claim 4, wherein the mixture preconditioned by the amylase preparation has a humidity ranging from 26 wt % to 52 wt %, an enzyme content ranging from 0.01% to 1.5%, and a pH value ranging from 4.5 to 9.5.

9. The method according to claim 4, wherein operating parameters of the enzymatic screw extrusion comprise an extrusion temperature ranging from 50° C. to 120° C., a screw speed ranging from 30 rpm to 400 rpm, and an extrusion treatment time ranging from 2 min to 15 min.

10. The method according to claim 5, wherein operating parameters of the enzymatic screw extrusion comprise an extrusion temperature ranging from 50° C. to 120° C., a screw speed of 30 rpm to 400 rpm, an extrusion treatment time of materials in a pre-extrusion stage which is controlled within 1 min to 6 min, and another extrusion treatment time of materials in a continuous extrusion stage which is controlled within 1 min to 9 min.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0041] FIG. 1 is a schematic diagram of the formation of modified (zincified) starch-iron particle extrudates, i.e., extruded mineralized starch biomaterial ((Zn-St).sub.10Fe.sup.0n Es);

[0042] FIGS. 2(b˜c) are SEM images of raw starch (St) and zinced starch (Zn-St Ps); FIGS. 2(d-e) are SEM images of mineralized modified starch before the enzymatic reactive extrusion (eREX) process at different magnifications;

[0043] FIGS. 3(a˜c) are SEM images of zinced starch-iron particle extrudates ((Zn-St).sub.10Fe.sup.0.sub.2 Es) with 20% iron (Zn-St, db) at different magnifications;

[0044] FIG. 4 is a digital image comparing non-mineralized starch (St@Fe.sup.0 Ps) (left) and mineralized starch (Zn-St@Fe.sup.0 Ps) (right);

[0045] FIGS. 5(a˜c) are SEM images of Zn-St Es obtained without mineralization at different magnifications;

[0046] FIG. 6(a) is an SEM image of Zn-ST@Fe.sup.0 Ps; FIG. 6(b) shows an EDS result of Zn-ST@Fe.sup.0 Ps. FIGS. 6(c-f) are element mappings of C, O, Fe and Zn of Zn-St@Fe.sup.0 Ps;

[0047] FIG. 7(d) shows an EDS result of (Zn-St).sub.10Fe.sup.0.sub.2 Es; FIG. 7(e) is an element mapping of C, O, Fe and Zn of (Zn-St).sub.10Fe.sup.0.sub.2 Es;

[0048] FIGS. 8(a-b), (c) and (d-e) show N.sub.2 adsorption, Hg adsorption, FT-IR, XPS Fe2p and Zn2p spectra of extruded mineralized starch, respectively; and

[0049] FIG. 9(a) shows a variation curve which shows the magnetization of extruded mineralized starch material as a function of the content of Fe.sup.0 Ps during extrusion; FIG. 9(b) shows variation curves which shows the adsorption capacity of (Zn-St).sub.10Fe.sup.0n Es as a function of the content of Fe.sup.0 Ps under different concentrations of methylene blue (MB); FIG. 9(c) is an SEM image of (Zn-St).sub.10Fe.sup.02 Es which have adsorbed MB; FIG. 9(d) is a comparison chart of the adsorption capacity of (Zn-St).sub.10Fe.sup.02 Es with St, Zn-St Es and Fe.sup.0 Ps under different reuse cycles.

DETAILED DESCRIPTION OF THE EMBODIMENTS

[0050] As shown in FIG. 1, in the modified starch with ionized hydroxyl of the present disclosure, oxygen atoms of hydroxyls are combined with positive metal ions M.sup.n+, which causes unsaturated metal ions in aqueous solution to repel H.sup.+ and attract OH.sup.− through an electrostatic interaction, thereby modifying physical and chemical properties and electrical properties of the starch. After adding zero-valent metal particles, for example, zero-valent iron Fe.sup.0 particles, Fe.sup.0 particles and the modified starch particles contact with each other to form multiple groups of “micro-primary cells”. Iron as a negative electrode loses electrons and becomes Fe.sup.2+, and the modified starch as a positive electrode makes H.sup.+ get electrons e to release H.sub.2, resulting in enrichment of OH.sup.− around O-M.sup.n+ on the surfaces of the modified starch, which, based on ionic electrification, attracts Fe.sup.2+ to move and deposit on the surfaces of starch to form crossed flake-like iron oxide compounds or prismatic iron oxide compounds, thereby mineralizing the surfaces of starch. Then, in the micro-mixing reaction process of enzymatic extrusion, the starch matrix is sheared, dispersed, mixed, and reorganized, and nanopores are formed based on the mineralization effect and locally selective starch enzymolysis. Some of the intact Fe.sup.0 particles presenting in the extrusion process are embedded in the frameworks of the porous starch-based material and function as magnets, and the other which are exposed outside can provide chemical adsorption for pollutant removal.

[0051] The following describes the present disclosure in detail with reference to examples.

Example 1

[0052] The present disclosure provides a starch-based adsorbent with nanopores, and the preparation method of the starch-based adsorbent with nanopores includes the following steps:

[0053] (1) mixing zinc metal salt and corn starch (as shown in FIG. 2b which is obtained by scanning electron microscope (SEM)) in a water bath (the volume fraction of the starch is 250 g/L) with a pH value of 6.5 at 35° C. for 360 min, wherein the mass ratio of the zinc metal salt to the corn starch is 0.2 g/g; and then sieving and cleaning to obtain the modified starch with oxygen atoms of hydroxyls thereof combined with zinc ions (as shown in FIG. 2c which is obtained by SEM).

[0054] The aqueous solution which is enriched with aluminium metal salt can be retained and be recycled to prepare the modified starch by adding corn starch until the mass ratio of the zinc metal salt to the corn starch is 0.2 gig.

[0055] (2) placing the modified starch with ionized hydroxyl by zinc obtained in step (1) into an aqueous solution with a room temperature of 25° C. (the volume fraction of the starch is 600 g/L); adding zero-valent iron particles Fe.sup.0 Ps with an average particle size of 26 μm (the mass ratio of Fe.sup.0 to the modified starch is 0.2 g/g) and stirring and mixing for 10 min; after the color of the modified starch turns yellow-brown, sucking out the remaining Fe.sup.0 Ps by a magnet; and sieving and drying at a low temperature of 40° C. to obtain the mineralized modified starch with Fe ions on the surfaces thereof (as shown in FIGS. 2b to 2e which are obtained by SEM). FIG. 6 shows an EDS spectrum of the mineralized modified starch, wherein the content of the iron element on the surfaces of the mineralized modified starch is up to about 7%, which indicates that there are iron mineralized crystals on the surfaces.

[0056] (3) pre-conditioning the mixture of the mineralized modified starch obtained in step (2) and thermostable α-amylase (0.1%) (the humidity of the mixture is pre-conditioned to be 36 wt %); placing the mixture into a cavity of an extruding machine for reaction (the extrusion temperature is 90° C., the screw speed is 150 rpm, and the extrusion time is 15 min, which is calculated in the case where a certain material is continuously fed), and then discharging the material so as to obtain the starch-based adsorbent with nanopores, as shown in FIG. 3. FIG. 7 shows an EDS spectrum of the extruded mineralized starch material, wherein the content of the iron element in the resulted nanopores is about 0.8%, which indicates that the iron mineralized crystals on the surfaces of the raw starch are sheared and mixed in the extrusion process, so that the iron mineralized crystals are uniformly dispersed in the starch matrix, thereby inducing the formation of the nanopores.

[0057] FIG. 8 shows N.sub.2 adsorption, Hg adsorption, FT-KR XPS Fe2p and Zn2p spectra of the extruded mineralized starch material, from which it can be concluded that: (1) the extruded material has a porous structure, and the specific surface area and pore volume of the porous structure of the extruded material are greater than those of the raw starch, wherein the pore size generally ranges from 2 nm to 4 nm, from 50 nm to 300 nm and from 5 μm to 100 μm, and the probability of pore formation is 46.5%; (2) The resulted structure is a compound of starch chain, Fe element and Zn element.

[0058] FIG. 9 shows the magnetization characteristics and methylene blue adsorption of the extruded mineralized starch material, indicating that the material not only has good magnetic separation ability, but also has the feasibility of cyclically adsorbing methylene blue, and the adsorption rate of methylene blue (as an example of pollutant) reaches 61.0 mg/g.

Comparative Example 1

[0059] placing starch which is not modified by ionizing hydroxyl with zinc into an aqueous solution with a room temperature of 25° C. (the volume fraction of the starch is 600 g/L), adding zero-valent iron particles Fe.sup.0Ps with an average particle size of 26 μm (the mass ratio of Fe.sup.0 to the modified starch is 0.2 g/g), and stirring and mixing for 10 min. The color of the starch does not change.

[0060] As shown in FIG. 4, compared with the mineralized modified starch obtained in step 2 of Example 1, the color of the starch of Comparative example 1 is white, which is the same as that of the raw starch, indicating that the surfaces of the starch are not mineralized to generate iron mineralized crystals.

Comparative Example 2

[0061] (1) mixing zinc metal salt and corn starch in a water bath (the volume fraction of the starch is 250 g/L) with a pH value of 6.5 at 35° C./L, wherein the mass ratio of the zinc metal salt to the corn starch is 0.2 g/g for 360 min; and then sieving and cleaning to obtain the modified starch with oxygen atoms of hydroxyls thereof combined with metal zinc ions; and

[0062] (2) pre-conditioning the mixture of the modified starch obtained in step (1) and thermostable α-amylase (0.1%) (the humidity of the mixture is pre-conditioned to be 36 wt %); placing the mixture into a cavity of an extruding machine for reaction (the extrusion temperature is 90° C., the screw speed is 150 rpm, and the extrusion time is 15 min which is calculated in the case where a certain material is continuously fed), and then discharging the material so as to obtain the starch-based adsorbent with nanopores, as shown in FIG. 5. It shows that the starch, which is only modified by ionizing hydroxyls but not mineralized, cannot form nanopores after the enzymatic screw extrusion.

Example 2

[0063] The present disclosure provides a starch-based magnetic adsorbent with nanopores, and the preparation method of the starch-based magnetic adsorbent with nanopores includes the following steps:

[0064] (1) mixing aluminium metal salt and potato starch in a water bath (the volume fraction of the starch is 200 g/L) with a pH value of 9 at 50° C. for 30 min, wherein the mass ratio of the aluminium metal salt to the potato starch is 0.05 g/g; and then sieving and cleaning to obtain the modified starch with oxygen atoms of hydroxyls thereof combined with aluminium ions. Through SEM observation, the surfaces of the modified starch particles are the same as those of unmodified starch particles.

[0065] The aqueous solution which is enriched with aluminium metal salt can be retained and be recycled to prepare the modified starch by adding potato starch until the mass ratio of the aluminium metal salt to the potato starch is 0.05 g/g;

[0066] (2) placing the modified starch with ionized hydroxyl by aluminium obtained in step (1) into an aqueous solution with a temperature of 20° C. (the volume fraction of the starch is 800 g/L); adding zero-valent iron particles Fe.sup.0 Ps with an average particle size of 100 μm (the mass ratio of Fe.sup.0 to the modified starch is 1 g/g) and stirring and mixing for 15 min; after the color of the modified starch turns yellow-brown, sieving and drying at a low temperature of 45° C. to obtain the mineralized modified starch with Fe ions loaded on the surfaces thereof. Through SEM observation, there are a large number of flake-like crystals on the surfaces of the mineralized modified starch; EDS spectrum shows that the content of the iron element on the surfaces of the mineralized modified starch is up to about 7%, which indicates that there are iron mineralized crystals covered on the surfaces.

[0067] (3) pre-conditioning the mixture of the mineralized modified starch obtained in the step (2), mesophilic α-amylase (1.5%) and isoamylase (0.01%) (the humidity of the mixture is pre-conditioned to be 52 wt %); placing the mixture into a cavity of an extruding machine for reaction (the extrusion temperature is 50° C., the screw speed is 30 rpm, and the extrusion time is 2 min which is calculated in the case where a certain material is continuously fed), and then discharging the material so as to obtain the starch-based magnetic adsorbent with nanopores, the structure of which is similar to the structure as shown in FIG. 3.

[0068] The starch-based magnetic adsorbent with nanopores obtained in this example has nanopore sizes ranging from 20 nm to 80 nm, a probability of pore formation of 31.2%, a saturation magnetization value of 106.24 emu/g, and an adsorption rate of methylene blue (as an example of pollutant) of 28.3 mg/g.

Example 3

[0069] The present disclosure provides a starch-based magnetic adsorbent with nanopores, and the preparation method of starch-based magnetic adsorbent with nanopores includes the following steps:

[0070] (1) mixing zinc metal salt and cassava starch in a water bath (the volume fraction of the starch is 125 g/L) with a pH value of 7 at 35° C. for 180 min, wherein the mass ratio of the zinc metal salt to the cassava starch is 0.2 g/g; and then sieving and cleaning to obtain the modified starch with oxygen atoms of hydroxyls thereof combined with metal zinc ions. The surfaces of the modified starch are the same as those of unmodified starch particles under SEM observation.

[0071] (2) placing the modified starch with ionized hydroxyl by zinc obtained in step (1) into an aqueous solution with a temperature of 30° C. (the volume fraction of the starch is 300 g/L); adding zero-valent iron particles Fe.sup.0 Ps (the mass ratio of Fe.sup.0 to the modified starch is 0.3 g/g) with an average particle size of 30 μm and stirring and mixing for 8 min; after the color of the modified starch turns yellow-brown, sucking out the Fe.sup.0Ps by magnet; sieving and drying at a low temperature of 40° C. to obtain the mineralized modified starch with Fe ions loaded on the surfaces thereof. Through SEM observation, there are a large number of flake-like crystals on the surfaces of the mineralized modified starch; EDS spectrum shows that the content of the iron element on the surfaces of the mineralized modified starch is up to about 7%, which indicates that there are iron mineralized crystals on the surface.

[0072] (3) pre-conditioning the mixture of the mineralized modified starch obtained in step (2) and thermostable α-amylase (1%)(the humidity of the mixture is pre-conditioned to be 42 wt %); placing the mixture into a cavity of an extruding machine for reaction, wherein the extrusion time is 6 min which is calculated in the case where a certain material is continuously fed, and adding Fe.sup.0 particles into the mixture for reaction, wherein the mass ratio of Fe.sup.0 particles to the starch is 0.3 g/g, the extrusion temperature is 90° C., the screw speed is 200 rpm, and the extrusion time is 9 min which is calculated in the case where a certain material is continuously fed, and then discharging the material so as to obtain the starch-based magnetic adsorbent with nanopores.

[0073] The starch-based magnetic adsorbent with nanopores obtained in this example has nanopore sizes ranging from 50 nm to 200 nm, a probability of pore formation of 63.7%, a saturation magnetization value of 40.72 emu/g, and an adsorption rate of methylene blue (as an example of pollutant) of 76.13 mg/g.

Example 4

[0074] The present disclosure relates to a starch-based magnetic adsorbent with nanopores, and the preparation method of starch-based magnetic adsorbent with nanopores includes the following steps:

[0075] (1) mixing manganese metal salt and corn starch in a water bath (the volume fraction of the starch is 50 g/L) with a pH value of 5 at 10° C. for 360 min, wherein the mass ratio of the manganese metal salt to the corn starch is 0.6 g/g; and then sieving and cleaning to obtain the modified starch with oxygen atoms of hydroxyls thereof combined with metal manganese ions. The surfaces of the modified starch are the same as those of unmodified starch particles under SEM observation.

[0076] (2) placing the modified starch with ionized hydroxyl by manganese obtained step (1) into an aqueous solution with a temperature of 45° C. (the volume fraction of the starch is 100 g/L); adding zero-valent iron particles Fe.sup.0 Ps with an average particle size of 50 nm (the mass ratio of Fe.sup.0 to the modified starch is 0.02 g/g) and stirring and mixing for 5 minutes; after the color of the modified starch turns yellow-brown, sucking out the Fe.sup.0 Ps by magnet; sieving and drying at a low temperature of 30° C. to obtain the mineralized modified starch with Fe ions loaded on the surfaces thereof. Through SEM observation, there are a large number of flake-like crystals on the surface of the mineralized modified starch; EDS spectrum shows that the content of the iron element on the surface the mineralized modified is up to about 7%, which indicates that there are iron mineralized crystals on the surface.

[0077] (3) pre-conditioning the mixture of the mineralized modified starch obtained in step (2), thermostable α-amylase (0.1%), and pullulanase (1.5%) (the humidity of the mixture is pre-conditioned to be 26 wt %); placing the mixture into a cavity of an extruding machine for reaction, wherein the extrusion time is 1 min which is calculated in the case where a certain material is continuously fed, and adding Fe.sup.0 particles into the mixture for reaction, wherein the mass ratio of Fe.sup.0 particles to the starch is 0.02 g/g, the extrusion temperature is 120° C., the screw speed is 30 rpm, and the extrusion time is 1 min which is calculated in the case where a certain material is continuously fed, and then discharging the material so as to obtain the starch-based magnetic adsorbent with nanopores.

[0078] The starch-based magnetic adsorbent with nanopores obtained in this example has nanopore sizes ranging from 100 nm to 500 nm, a probability of pore formation of 47.82%, a saturation magnetization value of 5.23 emu/g, and an adsorption rate of methylene blue (as an example of pollutant) of 35.73 mg/g.