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CN112642405B - Recyclable adsorbent and preparation method and application thereof - Google Patents

Recyclable adsorbent and preparation method and application thereof Download PDF

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Publication number
CN112642405B
CN112642405B CN202011384067.1A CN202011384067A CN112642405B CN 112642405 B CN112642405 B CN 112642405B CN 202011384067 A CN202011384067 A CN 202011384067A CN 112642405 B CN112642405 B CN 112642405B
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sodium alginate
quaternary ammonium
ammonium salt
modified sodium
adsorbent
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CN112642405A (en
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周大钊
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Anhui Hongchang Sugar Industry Technology Co ltd
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Anhui Hongchang Sugar Industry Technology Co ltd
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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
    • 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
    • B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
    • B01J20/046—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium containing halogens, e.g. halides
    • 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
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • 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
    • B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
    • 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
    • B01J20/28002—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 physical properties
    • B01J20/28009—Magnetic properties
    • 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
    • B01J20/28016—Particle form
    • B01J20/28021—Hollow particles, e.g. hollow spheres, microspheres or cenospheres
    • C—CHEMISTRY; METALLURGY
    • C13—SUGAR INDUSTRY
    • C13B—PRODUCTION OF SUCROSE; APPARATUS SPECIALLY ADAPTED THEREFOR
    • C13B20/00—Purification of sugar juices
    • C13B20/12—Purification of sugar juices using adsorption agents, e.g. active carbon
    • C—CHEMISTRY; METALLURGY
    • C13—SUGAR INDUSTRY
    • C13B—PRODUCTION OF SUCROSE; APPARATUS SPECIALLY ADAPTED THEREFOR
    • C13B20/00—Purification of sugar juices
    • C13B20/12—Purification of sugar juices using adsorption agents, e.g. active carbon
    • C13B20/123—Inorganic agents, e.g. active carbon
    • C—CHEMISTRY; METALLURGY
    • C13—SUGAR INDUSTRY
    • C13B—PRODUCTION OF SUCROSE; APPARATUS SPECIALLY ADAPTED THEREFOR
    • C13B20/00—Purification of sugar juices
    • C13B20/12—Purification of sugar juices using adsorption agents, e.g. active carbon
    • C13B20/126—Organic agents, e.g. polyelectrolytes
    • 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
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/46—Materials comprising a mixture of inorganic and organic materials
    • 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
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
    • 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
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
    • 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
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
    • B01J2220/4825—Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • Electrochemistry (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

The invention discloses a preparation method of a recyclable adsorbent, which comprises the following steps: uniformly mixing a quaternary ammonium salt modified sodium alginate aqueous solution, a nano magnetic material, an ethanol solution of tetraethoxysilane and a surfactant, then adjusting pH=9.5-10, reacting, and defoaming to obtain a material A; extruding the material A, adding the extruded material A into a calcium chloride aqueous solution, performing crosslinking, performing solid-liquid separation, washing, and performing vacuum freeze drying to obtain the recyclable adsorbent. The invention also discloses a recyclable adsorbent, which is prepared according to the preparation method of the recyclable adsorbent. The invention also discloses application of the recyclable adsorbent in removing impurities and decoloring the cane sugar liquid. The invention has good adsorption, desalination and decoloration effects, and can be recycled.

Description

Recyclable adsorbent and preparation method and application thereof
Technical Field
The invention relates to the technical field of adsorbents, in particular to a recyclable adsorbent, and a preparation method and application thereof.
Background
White granulated sugar is an important sweetener and is widely used in the industries of foods, medicines and the like. The existing production process of sucrose mainly comprises the processes of juice extraction, cleaning, evaporation, crystallization, honey separation, drying and the like. Cleaning is the key to control the quality of white granulated sugar. At present, a cane sugar factory adopts a sulfurous acid method clarification production process, uses calcium sulfite generated by the reaction of sulfur dioxide and lime milk as a main clarifier and a decoloring agent, has the advantages of short flow, simple process and the like, but white sugar produced by the method has the problem of residual sulfur, can not meet the requirements of partial special enterprises such as medicines, foods and the like, and is easy to yellow along with the extension of storage time.
Disclosure of Invention
Based on the technical problems in the background technology, the invention provides a recyclable adsorbent, a preparation method and application thereof, and the recyclable adsorbent has good adsorption, desalination and decoloration effects and can be recycled.
The invention provides a preparation method of a recyclable adsorbent, which comprises the following steps: uniformly mixing a quaternary ammonium salt modified sodium alginate aqueous solution, a nano magnetic material, an ethanol solution of tetraethoxysilane and a surfactant, then adjusting pH=9.5-10, reacting, and defoaming to obtain a material A; extruding the material A, adding the extruded material A into a calcium chloride aqueous solution, performing crosslinking, performing solid-liquid separation, washing, and performing vacuum freeze drying to obtain the recyclable adsorbent.
Preferably, the quaternary ammonium salt modified sodium alginate is 3-chloro-2-hydroxypropyl trimethyl ammonium chloride grafted modified sodium alginate.
The quaternary ammonium salt modified sodium alginate can be prepared by modification according to a conventional method in the field.
Preferably, the reaction temperature is 40-50 ℃ and the reaction time is 3.5-4.5h.
Preferably, crosslinking is carried out at room temperature for 20-40min.
Preferably, the temperature of the vacuum freeze-drying is from-20 to-15 ℃.
Preferably, the weight ratio of the quaternary ammonium salt modified sodium alginate to the nano magnetic material to the tetraethoxysilane is 1:0.1-0.15:2-2.5.
Preferably, the weight ratio of the quaternary ammonium salt modified sodium alginate to the surfactant is 1:0.01-0.02.
Preferably, the mass fraction of the quaternary ammonium salt modified sodium alginate aqueous solution is 2.5-3wt%.
Preferably, the mass fraction of the ethyl orthosilicate in the ethanol solution is 1-1.5wt%.
Preferably, the pH is adjusted with ammonia.
Preferably, the nanomagnetic material is nano ferroferric oxide.
The surfactant can be span, tween, etc.
The water is deionized water.
The invention also provides a recyclable adsorbent, which is prepared according to the preparation method of the recyclable adsorbent.
The invention also provides application of the recyclable adsorbent in removing impurities and decoloring the cane sugar liquid.
The beneficial effects are that:
according to the invention, quaternary ammonium salt modified sodium alginate and ethyl orthosilicate are uniformly mixed, hydrolysis reaction of the ethyl orthosilicate is carried out firstly, and then calcium chloride is used for crosslinking, so that silicon dioxide is uniformly distributed in sodium alginate microspheres, the microspheres have a three-dimensional reticular structure by the silicon dioxide, reticular cavities are formed, the adsorption performance of the microspheres is improved, the adsorption performance of the microspheres can be further improved by-OH on the surface of the silicon dioxide, and in addition, the microspheres can simultaneously play the roles of adsorption, bridging and electric neutralization by matching with the quaternary ammonium salt, so that the adsorption and flocculation effects of the invention are improved, impurities and pigments in cane sugar liquid can be well removed, and desalination and decolorization are carried out; in addition, the nano magnetic material and the surfactant are added into the raw materials, so that the magnetic material is uniformly coated in the porous microspheres, and the ferroferric oxide is matched with the porous microspheres, thereby improving the adsorption performance of the invention on heavy metal ions, improving the safety of sugarcane juice, and enabling the invention to be easily recovered and recycled.
Drawings
FIG. 1 is a graph showing the change in the decoloring rate 5 times according to the present invention.
FIG. 2 is a graph showing the change of the purity difference of 5 times according to the present invention.
Detailed Description
The technical scheme of the invention is described in detail through specific embodiments.
Example 1
A method for preparing a recyclable adsorbent, comprising the steps of:
adding 1g of sodium alginate and 5g of sodium hydroxide into 95ml of water, heating in a water bath at 40 ℃ and stirring to dissolve, then dropwise adding an aqueous solution of 3-chloro-2-hydroxypropyl trimethyl ammonium chloride (0.05 g), reacting for 6h under heat preservation and stirring, and adjusting the pH to be neutral by using an aqueous solution of hydrochloric acid; adding ethanol, stirring to obtain precipitate, filtering, washing the precipitate with water, and drying to obtain quaternary ammonium salt modified sodium alginate;
dissolving 1g of quaternary ammonium salt modified sodium alginate in 33ml of water, adding 0.15g of nano ferroferric oxide and 0.01g of span 80, uniformly mixing, adding 167ml of ethanol solution of 1.5wt% of tetraethoxysilane, uniformly mixing, transferring into a water bath at 40 ℃, regulating pH to be 10 by ammonia water, stirring for 3.5h, standing for 10min, and defoaming to obtain a material A; extruding the material A and adding the material A into a 3wt% calcium chloride aqueous solution at a speed of 300r/minStirring and crosslinking for 40min, performing solid-liquid separation by magnet adsorption, and washing the solid with water until no Ca exists in the water 2+ And then vacuum freeze-drying at-20 ℃ to obtain the recyclable adsorbent.
Example 2
A method for preparing a recyclable adsorbent, comprising the steps of:
preparation of quaternary ammonium salt modified sodium alginate is the same as in example 1;
dissolving 1g of quaternary ammonium salt modified sodium alginate in 40ml of water, adding 0.1g of nano ferroferric oxide and 0.02g of span 80, uniformly mixing, adding 200ml of ethanol solution of which the mass fraction is 1wt% of ethyl orthosilicate, uniformly mixing, transferring into a water bath at 50 ℃, regulating pH to be 9.5 by ammonia water, stirring and reacting for 4.5 hours, standing for 10 minutes, and defoaming to obtain a material A; extruding the material A, adding the material A into 3wt% calcium chloride water solution, stirring and crosslinking for 20min at the speed of 300r/min, performing solid-liquid separation by using magnet adsorption, and washing the solid with water until no Ca exists in the water 2+ And then vacuum freeze-drying at-15 ℃ to obtain the recyclable adsorbent.
Example 3
A method for preparing a recyclable adsorbent, comprising the steps of:
preparation of quaternary ammonium salt modified sodium alginate is the same as in example 1;
dissolving 1g of quaternary ammonium salt modified sodium alginate in 40ml of water, adding 0.12g of nano ferroferric oxide and 0.015g of span 80, uniformly mixing, adding 200ml of ethanol solution of which the mass fraction is 1.2wt% of ethyl orthosilicate, uniformly mixing, transferring into a water bath at 45 ℃, regulating pH=9.7 by using ammonia water, stirring for reacting for 4 hours, standing for 10 minutes, and defoaming to obtain a material A; extruding the material A, adding the material A into 3wt% calcium chloride water solution, stirring and crosslinking for 30min at the speed of 300r/min, performing solid-liquid separation by using magnet adsorption, and washing the solid with water until no Ca exists in the water 2+ And then vacuum freeze-drying at-17 ℃ to obtain the recyclable adsorbent.
Comparative example 1
Preparation of silica: 200ml of ethanol solution of 1.2wt% ethyl orthosilicate is taken and transferred into a water bath with the temperature of 45 ℃, the pH value of the ethanol solution is regulated to be 9.7 by ammonia water, the ethanol solution is stirred and reacts for 4 hours, the mixture is stood for 10 minutes, and then the material A is obtained by defoaming; then vacuum freeze drying at-17 deg.C.
Comparative example 2
Preparation of quaternary ammonium salt modified sodium alginate microspheres: 1g of quaternary ammonium salt modified sodium alginate (prepared as in example 1) was dissolved in 40ml of water, then added to a 3wt% aqueous solution of calcium chloride, crosslinked for 30min with stirring at a rate of 300r/min, filtered, and the filter cake was washed with water until no Ca was present in the water 2+ Then vacuum freeze drying at-17 deg.C.
Experiment 1
The sugar cane mixed juice is taken to pass through a 200-mesh filter screen, then phosphoric acid (the concentration of which is 300 mg/L) is added, lime milk is used for adjusting the pH value to be 6.6, then 6 parts are equally divided, each part is 100ml,
taking 5 parts of the mixture, heating to 50 ℃, then adding the mixture into the mixture in examples 1-3 and comparative examples 1-2 (the mass fractions of the examples 1-3 and the comparative examples 1-2 are 2 wt%) respectively recorded as an experimental group 1-3 and a control group 1-2, then adjusting pH=7.0 by lime milk, heating to 90 ℃, then adding polyacrylamide (the concentration of each group is 2 mg/L), preserving heat, settling, and carrying out solid-liquid separation to obtain clear juice;
part 6 is introduced with 20ml SO 2 (marked as a control group 3), heating to 90 ℃, adding polyacrylamide (with the concentration of 2 mg/L), preserving heat, settling, and carrying out solid-liquid separation to obtain clear juice.
The difference in purity Delta G.P between the mixed juice and the clear juice, the decoloring rate and the sedimentation rate of 100ml of the mixed juice of the sugarcane after the above treatment were measured according to the method for analysis of sugar cane sugar manufacturing chemistry management, and the results are shown in Table 1.
Δ G.P = gravity purity of juice-gravity purity of juice mix.
Decoloring Rate= (IU) Clear juice -IU Mixed juice ) 100% of the IU mixed juice, wherein the color value IU is detected at 420 nm.
TABLE 1 detection results
Grouping Purity is poor% Decoloring rate% Sedimentation rate cm/min
Experiment group 1 3.1 79 56
Experiment group 2 3.2 78 53
Experiment group 3 3.2 80 55
Control group 1 0.9 47 26
Control group 2 0.5 31 15
Control group 3 1.2 51 12
As can be seen from Table 1, the adsorbent of the invention has the advantages of poor purity, decoloration rate and sedimentation rate superior to those of pure silicon dioxide, pure quaternary ammonium salt modified sodium alginate microspheres and a sulfurous acid method, and no residual sulfur problem; and the magnetism of the invention makes the invention easy to recycle.
Experiment 2
The adsorbent prepared in example 3 was treated in the manner of experiment 1 to obtain a clear juice; and the purity difference and the decolorization rate of the clear juice obtained each time are examined through 5 adsorption-desorption cycles, the result is shown in figure 1, figure 1 is a change chart of the decolorization rate for 5 times in the invention, and figure 2 is a change chart of the purity difference for 5 times in the invention.
As can be seen from FIGS. 1-2, the present invention has no obvious change in the purity of the clear juice and the decolorization rate after 5 adsorption-desorption cycles, and can be reused.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.

Claims (4)

1. A method for preparing a recyclable adsorbent, comprising the steps of: uniformly mixing a quaternary ammonium salt modified sodium alginate aqueous solution, a nano magnetic material, an ethanol solution of tetraethoxysilane and a surfactant, then adjusting pH=9.5-10, reacting, and defoaming to obtain a material A; extruding the material A, adding the material A into a calcium chloride aqueous solution, crosslinking, carrying out solid-liquid separation, washing, and carrying out vacuum freeze drying to obtain a recyclable adsorbent;
the quaternary ammonium salt modified sodium alginate is 3-chloro-2-hydroxypropyl trimethyl ammonium chloride grafted modified sodium alginate;
the reaction temperature is 40-50 ℃ and the reaction time is 3.5-4.5h; crosslinking for 20-40min at room temperature;
vacuum freeze drying at-20 to-15 ℃;
the weight ratio of the quaternary ammonium salt modified sodium alginate to the nano magnetic material to the tetraethoxysilane is 1:0.1-0.15:2-2.5;
the weight ratio of the quaternary ammonium salt modified sodium alginate to the surfactant is 1:0.01-0.02;
the mass fraction of the quaternary ammonium salt modified sodium alginate aqueous solution is 2.5-3wt%; the mass fraction of the ethyl orthosilicate in the ethanol solution is 1-1.5wt%;
the nano magnetic material is nano ferroferric oxide; the surfactant is span 80.
2. The method for producing a recyclable adsorbent according to claim 1, wherein the pH is adjusted with aqueous ammonia.
3. A recyclable adsorbent, characterized by being produced according to the method for producing a recyclable adsorbent as described in claim 1 or 2.
4. Use of a recoverable adsorbent according to claim 3 in the removal of impurities from sugar cane juice.
CN202011384067.1A 2020-12-01 2020-12-01 Recyclable adsorbent and preparation method and application thereof Active CN112642405B (en)

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CN106732451A (en) * 2016-12-05 2017-05-31 浙江海洋大学 A kind of novel saccharification liquid decolouring reagent
CN107362779A (en) * 2017-06-12 2017-11-21 安徽省颍上县正泰电器有限责任公司 A kind of preparation method of nano-cellulose composite mesopore silica temperature sensitive type water suction microballoon
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