WO2018095220A1 - 一种利用非晶颗粒态淀粉吸附乙烯气体的方法 - Google Patents

一种利用非晶颗粒态淀粉吸附乙烯气体的方法 Download PDF

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WO2018095220A1
WO2018095220A1 PCT/CN2017/110101 CN2017110101W WO2018095220A1 WO 2018095220 A1 WO2018095220 A1 WO 2018095220A1 CN 2017110101 W CN2017110101 W CN 2017110101W WO 2018095220 A1 WO2018095220 A1 WO 2018095220A1
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starch
ethylene
amorphous
ethylene gas
ethanol
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黄强
石林凡
张斌
扶雄
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South China University of Technology SCUT
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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
    • C08J3/12—Powdering or granulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/81—Solid phase processes
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23B—PRESERVATION OF FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES; CHEMICAL RIPENING OF FRUIT OR VEGETABLES
    • A23B7/00—Preservation of fruit or vegetables; Chemical ripening of fruit or vegetables
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23B—PRESERVATION OF FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES; CHEMICAL RIPENING OF FRUIT OR VEGETABLES
    • A23B7/00—Preservation of fruit or vegetables; Chemical ripening of fruit or vegetables
    • A23B7/14—Preserving or ripening with chemicals not covered by group A23B7/08 or A23B7/10
    • A23B7/144—Preserving or ripening with chemicals not covered by group A23B7/08 or A23B7/10 in the form of gases, e.g. fumigation; Compositions or apparatus therefor
    • A23B7/152—Preserving or ripening with chemicals not covered by group A23B7/08 or A23B7/10 in the form of gases, e.g. fumigation; Compositions or apparatus therefor in a controlled atmosphere comprising other gases in addition to CO2, N2, O2 or H2O ; Elimination of such other gases
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/72—Organic compounds not provided for in groups B01D53/48 - B01D53/70, e.g. hydrocarbons
    • 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
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
    • 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
    • C08B30/06—Drying; Forming
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B31/00—Preparation of derivatives of starch
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23V—INDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
    • A23V2002/00—Food compositions, function of food ingredients or processes for food or foodstuffs
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/20—Organic adsorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B01D2257/702—Hydrocarbons
    • B01D2257/7022—Aliphatic hydrocarbons
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/45—Gas separation or purification devices adapted for specific applications
    • B01D2259/4525—Gas separation or purification devices adapted for specific applications for storage and dispensing systems
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/45—Gas separation or purification devices adapted for specific applications
    • B01D2259/455—Gas separation or purification devices adapted for specific applications for transportable use
    • 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
    • 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
    • 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
    • C08J2303/04—Starch derivatives

Definitions

  • the invention relates to a method for adsorbing ethylene gas, in particular to a method for adsorbing ethylene gas by using amorphous granular starch, which relates to embedding ethylene gas, and belongs to the fields of food and chemical industry.
  • Atmospheric storage is to place fruits and vegetables in a relatively closed environment, and to effectively control the respiration of the fruits by adjusting the concentration of gas around the fruits and vegetables, thereby delaying the deterioration of fruits and vegetables or regulating the ripening of fruits.
  • the annual rate of decay of fruits and vegetables due to improper storage in China is 20% to 30%, ranking first in the world, resulting in economic losses of up to 75 billion yuan.
  • the post-harvest storage of fruits and vegetables in China only accounts for 20% of the total output, and the fruits and vegetables stored in the atmosphere are less than 1% of the total output, which is far from the average post-harvest storage of 80% in developed countries.
  • Gases are typically stored and transported in high pressure resistant cylinders, but there is a risk of leakage and explosion during use.
  • the adsorption of gas into a solid medium can effectively avoid such defects, and the physical capture of the gas in the solid medium has the characteristics of slow release, and has an important application when the demand is small and needs to be continuously possessed.
  • the solid powder medium adsorbed with ethylene gas can be placed in a warehouse or transport vehicle, and the slowly released ethylene gas can ripen the fruit for a period of time to achieve the regulation of fruits. The purpose of maturity time.
  • Ethylene is an important gas regulating plant maturation. It is known as “plant hormone” and can accelerate fruit ripening or promote seed germination (such as mung bean). In the field of vegetable and fruit preservation, ethephon is widely used to induce the release of ethylene from plants or fruits, but it has certain toxicity, and its safety has attracted much attention.
  • the preparation method is mainly a liquid phase method.
  • the cyclodextrin powder was formulated into a saturated solution, placed in an autoclave, ethylene was introduced, and reacted at 25 ° C for 120 h, and washed and dried to obtain a sample of ethylene cyclodextrin adsorbed.
  • the recovery rate of the sample is 15% to 40%
  • the adsorption rate of ethylene is 2.3% to 2.8% (Ho, BT, Joyce, DC, Bhandari, BR (2011).
  • the object of the present invention is to provide a low cost, simple operation, sample recovery rate and adsorption rate for ethylene gas.
  • the starch granules are processed into an amorphous granular starch by an ethanol-alkali process, and the double helix structure in the starch is developed by using NaOH, and at the same time, the ethanol solution can inhibit the swelling of the particles, thereby maintaining the integrity of the particles.
  • the starch molecule forms a V-shaped single spiral complex with ethanol, and the starch volatilizes during the drying process, and a single spiral cavity of starch is formed in the particle.
  • the hydrophobic cavity of the amorphous granular starch facilitates the entry of non-polar gases to achieve the purpose of adsorbing ethylene.
  • the invention adopts the amorphous granular starch as the embedding wall material to adsorb ethylene, and has the characteristics of simple process and low cost, in particular, the recovery rate of the product and the adsorption amount of ethylene are significantly improved compared with the prior art.
  • the amorphous particulate starch used in the invention adsorbs ethylene, the preparation process is simple and quick, the cost is low, the sample recovery rate and the ethylene adsorption rate are high, which provides a new choice and possibility for the novel food preservation technology.
  • gas adsorption and embedding technologies There are developments in gas adsorption and embedding technologies.
  • a method for adsorbing ethylene gas by using amorphous granular starch comprising the following steps and process conditions:
  • step b) reaction: the starch slurry in step a) is heated to 25 ⁇ 40 ° C in a water bath, adding NaOH solution, stirring reaction for 20 ⁇ 60min;
  • step b) neutralization: the starch slurry obtained in step b) is centrifuged, washed with an ethanol solution, neutralized with an ethanolic hydrochloric acid solution, centrifuged, and washed with ethanol;
  • step d) drying: drying the starch obtained in step c), sieving; obtaining amorphous granular starch;
  • Amorphous granular starch adsorption of ethylene The amorphous granular starch is placed in a high pressure reactor, the amount of which is 20% to 30% of the volume of the reactor, the reaction kettle is evacuated, and ethylene gas is introduced at 0.8. ⁇ 1.5Mpa, the reaction is carried out for 15 to 25 hours under the condition of 20 to 30 ° C. After the reaction is completed, the gas outlet valve is opened to absorb the unadsorbed ethylene to obtain a starch powder product adsorbed with ethylene.
  • the starch raw material of the starch slurry is corn starch, tapioca starch or potato starch.
  • the corn starch is ordinary corn starch or high chain corn starch (Hylon-5 and Hylon-7).
  • the concentration of the NaOH solution is 1-5 mol/L, and the mass ratio of the dry starch to the NaOH solution is 1:1 to 1:10.
  • the NaOH solution has a dropping rate of 2 to 6 g/min.
  • the concentration of the aqueous ethanol solution is 30% to 50% by mass; the mass concentration of the ethanol solution washed with the ethanol solution is 70% to 90%; and the ethanol solution is washed with ethanol solution and anhydrous
  • the starch is washed with ethanol; the number of times the ethanol solution is washed with absolute ethanol is 1-4 times.
  • the concentration of the ethanolic hydrochloric acid solution is 1 to 5 mol/L.
  • the stirring reaction has a stirring speed of 80 to 120 rpm/min and a centrifugal force of 1811 ⁇ g.
  • the drying is performed by drying the starch obtained in the step c) in an oven at 40 to 60 ° C for 1 to 3 hours; and the sieving is passing through a sieve of 120 to 200 mesh.
  • the absorption of unadsorbed ethylene is absorbed by bromine water; the vacuum of the reaction vessel is -0.01 to -0.10 MPa.
  • the invention has the advantages of:
  • the method can significantly increase the adsorption rate of ethylene.
  • the adsorption of ethylene by cyclodextrin has an adsorption rate of 2.0 to 2.9% (w/w), and the adsorption rate of ethylene of the invention reaches ⁇ 30% (w/w), and the product has the characteristics of being soluble in cold water.
  • the invention adopts the solid embedding method, and has the advantages of fast, time saving, high efficiency and large quantity compared with the traditional liquid phase embedding method.
  • the liquid phase embedding method is usually carried out in an aqueous medium, the reaction time is greater than 72 h, and the sample recovery rate is less than 45%.
  • the reaction time of the solid embedding method is generally 15 to 25 h, and the sample recovery rate is 100%.
  • the method of the invention has the characteristics that the adsorption material is cheap and easy to obtain, the source is wide, the required equipment and the preparation process are simple.
  • Figure 1 is a scanning electron micrograph of the adsorption of ethylene amorphous starch granules in Example 1.
  • the method for determining the ethylene content of the product is as follows: accurately weigh 20 mg of the product into a 20 mL headspace vial, add 1 mL of distilled water, and quickly tighten the cap. After magnetic stirring at 600 rpm for 5 min, the content of ethylene was determined by headspace-gas chromatography. The conversion of the peak area of ethylene to the ethylene concentration was calculated based on the ethylene standard. Since ethylene is slightly soluble in water, the total ethylene content consists of two parts: ethylene for the headspace phase test and ethylene dissolved in water. Ethylene dissolved in water is calculated using Henry's law:
  • Y is the ethylene content of the sample
  • Cw and Ch are the ethylene content in the water and headspace sampler at 25 ° C, respectively.
  • the prior art uses cyclodextrin to adsorb ethylene: the cyclodextrin powder is formulated into a saturated solution at 25 ° C, placed in a reaction kettle, and the reaction kettle is vacuum-treated, then ethylene gas is introduced and reacted at 1.5 MPa. 120h. After the reaction is completed, the sample is subjected to vacuum filtration to obtain a cyclodextrin to which ethylene is adsorbed, and dried to a constant weight at room temperature, and sealed in a sealed bag, and stored in a dry, low-temperature, dark-proof environment.
  • a method for adsorbing ethylene gas by using amorphous granular starch comprising the following steps and process conditions:
  • step b) Reaction: The starch slurry in step a) was thermostated to 35 ° C in a water bath, and a 3 mol/L NaOH solution was added dropwise at a rate of 5 g/min, and the reaction was stirred for 20 min. The mass ratio of starch to NaOH solution was 1:4.
  • the amorphous granular starch was placed in an autoclave, the sample amount was 20% of the volume of the reactor, and the reaction kettle was evacuated to a vacuum of -0.10 MPa.
  • the ethylene gas is introduced and reacted at 1.0 Mpa at 25 ° C for 24 hours.
  • the gas outlet valve is opened, and the unadsorbed ethylene is absorbed by bromine water to obtain a starch powder product adsorbed with ethylene, and the product is packaged in a sealed bag. Store under dry, low temperature and dark conditions.
  • FIG. 1 is a scanning electron micrograph of amorphous starch granules adsorbed with ethylene in Example 1.
  • the sample was fixed on the sample stage with conductive paste, placed in an ion sputtering apparatus for gold spraying, and photographed by a QUANTA 200 scanning electron microscope.
  • the particle morphology has changed greatly.
  • the starch granules have increased in size under alkaline conditions, but still maintain the state of the granule powder, which is beneficial to product dispersion and packaging.
  • the complexation between ethylene and cyclodextrin occurs on the surface of the solution, depending on the ethylene and cyclodextrin molecules. Natural convection on the interface. The reaction between these reactions is weak, the process takes a long time, and the sample recovery rate and ethylene adsorption rate are low. Compared with Comparative Example 1, the sample recovery rate and the ethylene adsorption rate of the method of Example 1 were greatly improved. After the starch granules are treated with alkali, the double helix unwinds, and the cavity inside the single helix is hydrophobic, and can adsorb non-polar gas ethylene to form a V-type composite.
  • the sample obtained in this embodiment has the characteristics of slowly releasing the embedded ethylene gas under certain temperature and humidity conditions, and can be used for ripening fruits (such as bananas, apples, and mangoes), thereby achieving the purpose of regulating fruit ripening time.
  • a method for adsorbing ethylene gas by using amorphous granular starch comprising the following steps and process conditions:
  • Potato starch was adjusted to a starch slurry with a dry mass fraction of 12% using an aqueous ethanol solution (40%, w/w).
  • step b) Reaction: The starch slurry in step a) was thermostated to 35 ° C in a water bath, and a 3 mol/L NaOH solution was added dropwise at a rate of 5 g/min, and the reaction was stirred for 20 min. The mass ratio of starch to NaOH solution was 1:3.5.
  • the amorphous granular starch was placed in an autoclave, the sample amount was 20% of the volume of the reactor, and the reaction kettle was evacuated to a vacuum of -0.10 MPa.
  • the ethylene gas was introduced and reacted at 1.1 MPa at 25 ° C for 24 h.
  • the gas outlet valve was opened, and the unadsorbed ethylene was absorbed by bromine water to obtain a starch powder product adsorbed with ethylene.
  • the product was packaged in a sealed bag and placed. Store under dry, low temperature and dark conditions.
  • a method for adsorbing ethylene gas by using amorphous granular starch comprising the following steps and process conditions:
  • High amylose corn starch (Hylon-5) was adjusted to a starch slurry with a dry mass fraction of 12% with an aqueous ethanol solution (40%, w/w).
  • step b) Reaction: The starch slurry in step a) was thermostated to 35 ° C in a water bath, and a 3 mol/L NaOH solution was added dropwise at a rate of 5 g/min, and the reaction was stirred for 30 min.
  • the mass ratio of starch to NaOH solution is 1:5.
  • the amorphous granular starch was placed in an autoclave, the sample amount was 20% of the volume of the reactor, and the reaction kettle was evacuated to a vacuum of -0.10 MPa.
  • the ethylene gas is introduced and reacted at 1.2 MPa for 24 hours at 25 ° C.
  • the gas outlet valve is opened, and the unadsorbed ethylene is absorbed by bromine water to obtain a starch powder product adsorbed with ethylene, and the product is packaged in a sealed bag. Store under dry, low temperature and dark conditions.
  • a method for adsorbing ethylene gas by using amorphous granular starch comprising the following steps and process conditions:
  • High amylose corn starch (Hylon-7) was adjusted to a starch slurry with a dry mass fraction of 12% with an aqueous ethanol solution (40%, w/w).
  • step b) Reaction: The starch slurry in step a) was thermostated to 35 ° C in a water bath, and a 3 mol/L NaOH solution was added dropwise at a rate of 5 g/min, and the reaction was stirred for 30 min. The mass ratio of starch to NaOH solution was 1:8.
  • the amorphous granular starch was placed in an autoclave, the sample amount was 20% of the volume of the reactor, and the reaction kettle was evacuated to a vacuum of -0.10 MPa.
  • the ethylene gas is introduced and reacted at 1.2 MPa for 24 hours at 25 ° C.
  • the gas outlet valve is opened, and the unadsorbed ethylene is absorbed by bromine water to obtain a starch powder product adsorbed with ethylene, and the product is packaged in a sealed bag. Store under dry, low temperature and dark conditions.
  • Starch is a large-scale industrial raw material, and the raw material price is about one tenth of that of cyclodextrin. Therefore, the present invention has the original In addition, the invention adopts the solid embedding method, and has the advantages of fast, time-saving, high-efficiency and large embedding amount compared with the liquid phase embedding method of the traditional cyclodextrin.
  • the liquid phase embedding method is usually carried out in an aqueous medium, the reaction time is more than 72 h, and the product recovery rate is less than 45%.
  • the reaction time of the solid embedding method is generally 15 to 25 hours, and the product recovery rate is 100%.

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Abstract

一种利用非晶颗粒态淀粉吸附乙烯气体的方法。该方法首先制备非晶颗粒态淀粉：将淀粉用乙醇水溶液调成淀粉浆液，滴加NaOH溶液，于30～35℃条件下反应20～50min，离心，用乙醇盐酸溶液进行中和，洗涤，干燥，制得非晶颗粒态淀粉。将非晶颗粒态淀粉置于高压反应釜中，抽真空后通入乙烯气体，于0.8～1.5Mpa，20～30℃下反应15～25h，得到吸附有乙烯的淀粉粉末产品。经测试，所得产品中乙烯的含量可达30％以上，该方法对于乙烯的吸附工艺简单、高效、成本低，产品在果蔬气调保鲜领域具有广泛的应用前景。

Description

一种利用非晶颗粒态淀粉吸附乙烯气体的方法 技术领域
本发明涉及一种乙烯气体的吸附方法，特别是涉及一种利用非晶颗粒态淀粉吸附乙烯气体的方法，该方法涉及乙烯气体的包埋，属于食品、化工领域。
背景技术
气调贮藏是将果蔬置于相对密闭的环境中，通过调节果蔬周围的气体浓度来有效控制其呼吸作用，从而达到延缓果蔬变质或调节水果成熟的目的。据统计,我国每年果蔬因贮藏不当造成的腐烂率达到20％～30％，居全球首位，造成的经济损失高达750亿元。我国果蔬采后贮藏量仅占总产量的20％，气调贮藏的果蔬不到总产量的1％，与发达国家平均80％的采后贮藏量有很大差距。
气体通常以耐高压的钢瓶进行贮存和运输，但在使用过程中存在泄露和爆炸等风险。而将气体吸附于固体介质中能有效避免这种缺陷，以物理形式捕获在固体介质中的气体具有缓慢释放等特点，在需求量少且需持续拥有时具有重要的应用。如在香蕉或苹果采收后的储运过程中，可将吸附有乙烯气体的固体粉末介质置于仓库或运输车中，缓慢释放的乙烯气体能在一段时间内催熟水果，从而达到调控水果成熟时间的目的。
乙烯是调控植物成熟的重要气体，被誉为“植物激素”，能加速水果熟化过程或促进种子的发芽(如绿豆)。在蔬果保鲜领域，目前广泛使用乙烯利可诱导植物或水果释放乙烯，但具有一定毒性，其安全性备受关注。
目前，用环糊精吸附乙烯气体已有报道，制备方法主要是液相法。将环糊精粉末配制成饱和溶液，置于高压反应釜中，通入乙烯，于25℃的条件下反应120h，洗涤干燥后得到吸附乙烯的环糊精样品。其中，样品的回收率为15％～40％，乙烯的吸附率为2.3％～2.8％(Ho,B.T.,Joyce,D.C.,Bhandari,B.R.(2011).Encapsulation of ethylene gas into α-cyclodextrin and characterisation of the inclusion complexes,Food Chemistry,127,572-580)。但该方法所用的环糊精价格高，所采用吸附工艺复杂，样品回收率及乙烯的吸附率较低，不适用于大规模的食品工业生产。
发明内容
本发明目的在于提供一种成本低廉，操作简便，样品回收率和对乙烯气体的吸附率有 明显提高的利用非晶颗粒态淀粉吸附乙烯气体的方法。
本发明将淀粉颗粒通过乙醇‐碱法处理后制备成非晶颗粒态淀粉，利用NaOH使淀粉中双螺旋结构展开，同时，乙醇溶液能抑制颗粒溶胀，从而保持颗粒的完整性。处理过程中，淀粉分子与乙醇形成了V型单螺旋复合物，淀粉在干燥过程中乙醇挥发，颗粒内形成淀粉的单螺旋空腔。非晶颗粒态淀粉的疏水性空腔有利于非极性气体的进入，从而达到吸附乙烯的目的。本发明以非晶颗粒态淀粉为包埋壁材吸附乙烯，具有工艺简单，成本较低的特点，尤其是产品的回收率和乙烯的吸附量相比现有技术有显著提高。总体而言，本发明使用的非晶颗粒态淀粉吸附乙烯，制备工艺简单快捷，成本低，样品回收率及乙烯的吸附率高，为新型食品保鲜技术提供了新的选择和可能，是对现有气体吸附和包埋技术的发展。
本发明目的通过如下技术方案实现：
一种利用非晶颗粒态淀粉吸附乙烯气体的方法，包括如下步骤和工艺条件：
(1)非晶颗粒态淀粉的制备
a)调浆：用乙醇水溶液调成干基质量分数为10％～15％的淀粉浆液；
b)反应：将步骤a)中淀粉浆液在水浴中恒温至25～40℃，滴加NaOH溶液，搅拌反应20～60min；
c)中和：将步骤b)中得到的淀粉浆液离心，用乙醇溶液洗涤后，用乙醇盐酸溶液中和，离心，乙醇洗涤；
d)干燥：将步骤c)得到的淀粉干燥，过筛；得到非晶颗粒态淀粉；
(2)非晶颗粒态淀粉吸附乙烯：将非晶颗粒态淀粉置于高压反应釜中，加入量为反应釜体积的20％～30％，将反应釜抽真空，通入乙烯气体，于0.8～1.5Mpa，20～30℃的条件下反应15～25h，反应结束后打开出气阀，吸收未吸附的乙烯，得到吸附有乙烯的淀粉粉末产品。
为进一步实现本发明目的，优选地，所述淀粉浆液的淀粉原料为玉米淀粉、木薯淀粉或马铃薯淀粉。进一步优选，所述玉米淀粉为普通玉米淀粉或高链玉米淀粉(Hylon-5和Hylon-7)。
优选地，所述NaOH溶液的浓度为1～5mol/L，干基淀粉与NaOH溶液的质量比为1:1～1:10。
优选地，所述NaOH溶液滴加速度为2～6g/min。
优选地，所述乙醇水溶液的浓度为质量分数30％～50％；所述用乙醇溶液洗涤的乙醇溶液的质量浓度为70％～90％；所述乙醇溶液洗涤是分别用乙醇溶液和无水乙醇将淀粉洗涤；所述乙醇溶液与无水乙醇洗涤的次数为1-4次。
优选地，所述乙醇盐酸溶液的浓度为1～5mol/L。
优选地，所述搅拌反应的搅拌速度为80～120rpm/min，离心力为1811×g。
优选地，所述干燥是将步骤c)得到的淀粉置于40～60℃的烘箱中干燥1～3h；所述过筛为过120～200目筛。
优选地，所述吸收未吸附的乙烯是用溴水吸收；所述反应釜抽真空的真空度为-0.01～-0.10Mpa。
本发明与现有技术相比，其优点在于：
1)本方法可明显提高乙烯的吸附率。采用环糊精对乙烯进行吸附，吸附率为2.0～2.9％(w/w)，本发明乙烯的吸附率达到≥30％(w/w)，且产品具有冷水可溶的特点。
2)本发明采用固体包埋法，相对于传统的液相包埋法，具有快速、省时、高效、量多的优点。液相包埋法通常在水介质中进行，反应时间大于72h，样品回收率小于45％。固体包埋法的反应时间一般为15～25h，样品回收率为100％。
3)与现有乙烯吸附方法相比，本发明方法具有吸附材料便宜易得，来源广泛，所需设备和制备工艺简单等特点。
附图说明
图1为实施例1吸附乙烯非晶淀粉颗粒的扫描电镜照片。
具体实施方式
为了更好的理解本发明，下面结合实施例对本发明做进一步说明，但本发明要求保护的范围并不仅仅局限于实例表述的范围。
实施例中，产物中吸附乙烯含量的测定方法：准确称量20mg的产物于20mL顶空瓶中，加入1mL的蒸馏水，快速拧紧瓶帽。600rpm磁力搅拌5min后，用顶空-气相色谱测定乙烯的含量。将乙烯的峰面积换算为乙烯浓度是根据乙烯标准品来进行计算的。由于乙烯微溶于水，所以乙烯总含量由两部分组成：用于进行顶空气相测试的乙烯和溶于水的乙烯。溶于水的乙烯用亨利定律进行计算：
Cw＝0.119×Ch      (1)
Y＝Cw+Ch        (2)
其中，Y为样品中乙烯的含量，Cw和Ch分别是在25℃下，水中与顶空进样器中的乙烯含量。
对比实施例1
现有技术使用环糊精吸附乙烯：在25℃下，将环糊精粉末配制成饱和溶液，将其置于反应釜中，反应釜抽真空处理后，通入乙烯气体，于1.5MPa下反应120h。反应结束后，将样品进行真空抽滤，得到吸附有乙烯的环糊精，室温下干燥至恒重，用密封袋封装，置于干燥、低温、避光的环境中保存。
经测试，样品的回收率为40％，乙烯的吸附率为2.5％(w/w)。
实施例1
一种利用非晶颗粒态淀粉吸附乙烯气体的方法，包括如下步骤和工艺条件：
(1)非晶颗粒态淀粉的制备
a)调浆：将普通玉米淀粉用乙醇水溶液(40％，w/w)调成干基质量分数为12％的淀粉浆液。
b)反应：将步骤a)中淀粉浆液在水浴恒温至35℃，以5g/min的速度滴加3mol/L的NaOH溶液，搅拌反应20min。淀粉与NaOH溶液的质量比为1:4。
c)中和：将步骤b)中得到的淀粉浆液在1811×g下离心，用乙醇溶液(40％，w/w)洗涤两次后，用3mol/L的乙醇盐酸溶液中和，离心，乙醇溶液(95％，w/w)洗涤一次后再用无水乙醇洗涤一次。
d)干燥：将得到的淀粉置于60℃的烘箱中干燥5h，过150目筛得到非晶颗粒态淀粉。
(2)非晶颗粒态淀粉吸附乙烯
将非晶颗粒态淀粉置于高压反应釜中，样品量为反应釜体积的20％，将反应釜抽真空处理，真空度为-0.10Mpa。通入乙烯气体，于1.0Mpa，25℃的条件下反应24h，反应结束后打开出气阀，用溴水吸收未吸附的乙烯，得到吸附有乙烯的淀粉粉末产品，产品用密封袋包装，置于干燥、低温、避光条件下保存。
经测试，样品的回收率为100％，乙烯的吸附率为13.8％(w/w)。
图1为实施例1吸附乙烯的非晶淀粉颗粒的扫描电镜照片。将样品用导电胶将样品固定在样品台上，置于离子溅射仪中进行喷金，采用QUANTA200型扫描电子显微镜进行观察拍照。相对于原淀粉来说，颗粒形貌发生了很大变化，淀粉颗粒在碱性条件膨胀尺寸有所增加，但仍保持颗粒粉末状态，有利于产品分散和包装。
对比实施例中，乙烯和环糊精之间的络合发生在溶液表面，取决于乙烯与环糊精分子 在界面上的自然对流。这种反应相互间的作用力较弱，过程耗时长，且样品回收率和乙烯吸附率较低。与对比实施例1相比，本实施例1方法的样品回收率和乙烯吸附率都有很大的提升。淀粉颗粒经过碱处理后，双螺旋解旋，单螺旋内部的空腔具有疏水性，可吸附非极性气体乙烯，形成V型复合物。在一定的压力下，乙烯分子与非晶颗粒态淀粉内部的空腔间的界面相互作用力促使乙烯分子进入，从而包埋乙烯气体。由于反应过程没有水分的参与，样品的回收率为100％。本实施例所得样品在一定的温湿度条件下具有缓慢释放被包埋的乙烯气体的特点，可用于水果(如香蕉、苹果和芒果等)的催熟，从而达到调控水果成熟时间的目的。
实施例2
一种利用非晶颗粒态淀粉吸附乙烯气体的方法，包括如下步骤和工艺条件：
(1)非晶颗粒态淀粉的制备
a)调浆：将马铃薯淀粉用乙醇水溶液(40％，w/w)调成干基质量分数为12％的淀粉浆液。
b)反应：将步骤a)中淀粉浆液在水浴恒温至35℃，以5g/min的速度滴加3mol/L的NaOH溶液，搅拌反应20min。淀粉与NaOH溶液的质量比为1:3.5。
c)中和：将b)中得到的淀粉浆液在1811×g下离心，用乙醇溶液(40％，w/w)洗涤两次后，用3mol/L的乙醇盐酸溶液中和，离心，乙醇溶液(95％，w/w)洗涤一次后再用无水乙醇洗涤一次。
d)干燥：将得到的淀粉置于60℃的烘箱中干燥5h，过150目筛得到非晶颗粒态淀粉。
(2)非晶颗粒态淀粉吸附乙烯
将非晶颗粒态淀粉置于高压反应釜中，样品量为反应釜体积的20％，将反应釜抽真空处理，真空度为-0.10Mpa。通入乙烯气体，于1.1Mpa，25℃的条件下反应24h，反应结束后打开出气阀，用溴水吸收未吸附的乙烯，得到吸附有乙烯的淀粉粉末产品，产品用密封袋包装，置于干燥、低温、避光条件下保存。
经测试，样品的回收率为100％，乙烯的吸附率为12.8％(w/w)。
实施例3
一种利用非晶颗粒态淀粉吸附乙烯气体的方法，包括如下步骤和工艺条件：
(1)非晶颗粒态淀粉的制备
a)调浆：将高直链玉米淀粉(Hylon-5)用乙醇水溶液(40％，w/w)调成干基质量分数为12％的淀粉浆液。
b)反应：将步骤a)中淀粉浆液在水浴恒温至35℃，以5g/min的速度滴加3mol/L的NaOH溶液，搅拌反应30min。淀粉与NaOH溶液的质量比为1:5。
c)中和：将b)中得到的淀粉浆液在1811×g下离心，用乙醇溶液(40％，w/w)洗涤两次后，用3mol/L的乙醇盐酸溶液中和，离心，乙醇溶液(95％，w/w)洗涤一次后再用无水乙醇洗涤一次。
d)干燥：将得到的淀粉置于60℃的烘箱中干燥6h，过150目筛得到非晶颗粒态淀粉。
(2)非晶颗粒态淀粉吸附乙烯
将非晶颗粒态淀粉置于高压反应釜中，样品量为反应釜体积的20％，将反应釜抽真空处理，真空度为-0.10Mpa。通入乙烯气体，于1.2Mpa，25℃的条件下反应24h，反应结束后打开出气阀，用溴水吸收未吸附的乙烯，得到吸附有乙烯的淀粉粉末产品，产品用密封袋包装，置于干燥、低温、避光条件下保存。
经测试，样品的回收率为100％，乙烯的吸附率为23.8％(w/w)。
实施例4
一种利用非晶颗粒态淀粉吸附乙烯气体的方法，包括如下步骤和工艺条件：
(1)非晶颗粒态淀粉的制备
a)调浆：将高直链玉米淀粉(Hylon-7)用乙醇水溶液(40％，w/w)调成干基质量分数为12％的淀粉浆液。
b)反应：将步骤a)中淀粉浆液在水浴恒温至35℃，以5g/min的速度滴加3mol/L的NaOH溶液，搅拌反应30min。淀粉与NaOH溶液的质量比为1:8。
c)中和：将b)中得到的淀粉浆液在1811×g下离心，用乙醇溶液(40％，w/w)洗涤两次后，用3mol/L的乙醇盐酸溶液中和，离心，乙醇溶液(95％，w/w)洗涤一次后再用无水乙醇洗涤一次。
d)干燥：将得到的淀粉置于60℃的烘箱中干燥6h，过150目筛得到非晶颗粒态淀粉。
(2)非晶颗粒态淀粉吸附乙烯
将非晶颗粒态淀粉置于高压反应釜中，样品量为反应釜体积的20％，将反应釜抽真空处理，真空度为-0.10Mpa。通入乙烯气体，于1.2Mpa，25℃的条件下反应24h，反应结束后打开出气阀，用溴水吸收未吸附的乙烯，得到吸附有乙烯的淀粉粉末产品，产品用密封袋包装，置于干燥、低温、避光条件下保存。
经测试，样品的回收率为100％，乙烯的吸附率为31.8％(w/w)。
淀粉是一种大宗的工业原料，原料价格约为环糊精的十分之一，因此，本发明具有原 料成本优势；此外，本发明采用固体包埋法，相对于传统环糊精的液相包埋法，具有快速、省时、高效、包埋量大等优点。液相包埋法通常在水介质中进行，反应时间大于72h，产品回收率小于45％。固体包埋法的反应时间一般为15～25h，产品回收率为100％。

Claims (10)

  1. 一种利用非晶颗粒态淀粉吸附乙烯气体的方法，其特征在于包括如下步骤和工艺条件：
    (1)非晶颗粒态淀粉的制备
    a)调浆：用乙醇水溶液调成干基质量分数为10％～15％的淀粉浆液；
    b)反应：将步骤a)中淀粉浆液在水浴中恒温至25～40℃，滴加NaOH溶液，搅拌反应20～60min；
    c)中和：将步骤b)中得到的淀粉浆液离心，用乙醇溶液洗涤后，用乙醇盐酸溶液中和，离心，乙醇洗涤；
    d)干燥：将步骤c)得到的淀粉干燥，过筛；得到非晶颗粒态淀粉；
    (2)非晶颗粒态淀粉吸附乙烯：将非晶颗粒态淀粉置于高压反应釜中，加入量为反应釜体积的20％～30％，将反应釜抽真空，通入乙烯气体，于0.8～1.5Mpa，20～30℃的条件下反应15～25h，反应结束后打开出气阀，吸收未吸附的乙烯，得到吸附有乙烯的淀粉粉末产品。
  2. 根据权利要求1所述的利用非晶颗粒态淀粉吸附乙烯气体的方法，其特征在于，所述淀粉浆液的淀粉原料为玉米淀粉、木薯淀粉或马铃薯淀粉。
  3. 根据权利要求2所述的利用非晶颗粒态淀粉吸附乙烯气体的方法，其特征在于，所述玉米淀粉为普通玉米淀粉或高链玉米淀粉(Hylon-5和Hylon-7)。
  4. 根据权利要求1所述的利用非晶颗粒态淀粉吸附乙烯气体的方法，其特征在于，所述NaOH溶液的浓度为1～5mol/L，干基淀粉与NaOH溶液的质量比为1:1～1:10。
  5. 根据权利要求1或4所述的利用非晶颗粒态淀粉吸附乙烯气体的方法，其特征在于，所述NaOH溶液滴加速度为2～6g/min。
  6. 根据权利要求1所述的利用非晶颗粒态淀粉吸附乙烯气体的方法，其特征在于，所述乙醇水溶液的浓度为质量分数30％～50％；所述用乙醇溶液洗涤的乙醇溶液的质量浓度为70％～90％；所述乙醇溶液洗涤是分别用乙醇溶液和无水乙醇将淀粉洗涤；所述乙醇溶液与无水乙醇洗涤的次数为1-4次。
  7. 根据权利要求1所述的利用非晶颗粒态淀粉吸附乙烯气体的方法，其特征在于，所述乙醇盐酸溶液的浓度为1～5mol/L。
  8. 根据权利要求1所述的利用非晶颗粒态淀粉吸附乙烯气体的方法，其特征在于，所述搅拌反应的搅拌速度为80～120rpm/min，离心力为1811×g。
  9. 根据权利要求1所述的利用非晶颗粒态淀粉吸附乙烯气体的方法，其特征在于，所述干燥是将步骤c)得到的淀粉置于40～60℃的烘箱中干燥1～3h；所述过筛为过120～200目筛。
  10. 根据权利要求1所述的利用非晶颗粒态淀粉吸附乙烯气体的方法，其特征在于，所述吸收未吸附的乙烯是用溴水吸收；所述反应釜抽真空的真空度为-0.01～-0.10Mpa。
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