CN106589416A - 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 PDFInfo
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Abstract
本发明公开了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
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 intoα-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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CN108371180A (zh) * | 2018-03-19 | 2018-08-07 | 华南理工大学 | 一种具有缓释性能的乙烯气体的包埋物以及包埋方法 |
CN110064375A (zh) * | 2019-04-11 | 2019-07-30 | 华南理工大学 | 一种具有高效吸附和控释乙烯的改性淀粉制备方法 |
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