CN108795392A - 一种用于食品保鲜的不冻液 - Google Patents
一种用于食品保鲜的不冻液 Download PDFInfo
- Publication number
- CN108795392A CN108795392A CN201810664876.4A CN201810664876A CN108795392A CN 108795392 A CN108795392 A CN 108795392A CN 201810664876 A CN201810664876 A CN 201810664876A CN 108795392 A CN108795392 A CN 108795392A
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- CN
- China
- Prior art keywords
- freezing solution
- freezing
- krill
- protolysate
- mass percentage
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/08—Materials not undergoing a change of physical state when used
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P60/80—Food processing, e.g. use of renewable energies or variable speed drives in handling, conveying or stacking
- Y02P60/85—Food storage or conservation, e.g. cooling or drying
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Abstract
本发明公开了一种用于食品保鲜的不冻液,其包含食用酒精、丙二醇、丙三醇、氯化钙、氯化钠、氨基酸、平均分子量为50~100KDa的南极磷虾蛋白水解物、表面活性剂和水,其中表面活性剂为磷脂、吐温‑20、吐温‑60、吐温‑80中的一种或几种;各组分均为食品级,质量百分比含量表示如下:食用酒精15‑30%,丙二醇10‑30%,丙三醇2‑15%,氯化钙1‑10%,氯化钠3‑10%,氨基酸0.1‑0.15%,南极磷虾蛋白水解物0.01‑0.3%,表面活性剂0.005‑0.5%,余量为水。本发明提供的不冻液,可以降低不冻液的冻结点,提高传热效率,抑制不冻液在低温搅拌过程中出现的结晶现象产生以及提高不冻液的稳定性。
Description
(一)技术领域
本发明属于食品保鲜冷冻加工领域,涉及一种用于快速冻结生鲜食品的抗冷冻结晶不冻液。
(二)背景技术
不冻液冻结又称浸渍冻结,是将水产品直接或间接与载冷剂接触,与载冷剂换热后迅速降温及冻结,是一种高效的水产品快速冻结方式。相比于传统的冻结方式,如:鼓风冻结、平板冻结等,它具有冻结时间短、冻结速率快、降低能耗等优点。不冻液的选择直接决定着冻品品质。因此,选择一种性能良好的冷冻液是不冻液冻结加工技术的关键。用于水产品冻结的不冻液必须具有冻结点低、传热系数大、粘度小的特点;其次是要求性质稳定、绿色安全、对人体无任何危害。
目前常用的不冻液多为氯化钠水溶液、氯化钙水溶液、乙二醇水溶液或糖类水溶液等。早期使用的不冻液多为冷盐水,常用于冷却和冻结虾、金枪鱼等水产品,高浓度的盐水不仅会渗透到水产品中且对设备有严重腐蚀。糖类、氯化钠的混合溶液多用于一些水果蔬菜的冷却和冻结,具有粘度大、冻结点较高等缺点。乙二醇溶液在工业生产中使用较多,但其具有一定的毒性,不能高浓度使用,经济性较差。
当不冻液处于过饱和状态时,低温下溶液中的溶质会形成细小的晶体,这样的过程为晶体成核过程(初级成核)。初级成核多为非均相成核。在一定杂质存在的情况下,成核所需的能量会大大降低。非均相成核一般发生在相对较低的过饱和度下,此情况下的自由能减少依赖于固相的接触角。
晶体成核后会发生二次成核。在高速搅拌下,晶体的微观侵蚀或碰撞或摩擦会导致小颗粒晶体的形成。这些形成晶核的机理叫接触成核,此时晶体会成长、变大。接触成核主要包括三种方式:晶体-晶体,晶体-搅拌器,晶体-器壁。
南极磷虾(Euphausia superba)是一种生活在南极海域的小型浮游类海洋动物,生物资源量巨大,目前处于尚未充分开发利用的状态。由于南极磷虾生活于寒凉的南极海域(水温约为-1.9℃),为了适应南极海域严苛的低温环境,南极磷虾适应性地产生了抗冻活性物质,能够破坏晶体微观结构,抑制晶核繁殖,降低成核数量,具有良好的抗结晶性。
近年来一些研究发明公开了用于食品冻结的不冻液新配方,如:
1、中国专利201210558113.4公开了一种用于食品浸渍冷冻的三元载冷剂,其由乙醇、丙二醇与水构成。其低温工作温度为-30℃~-40℃。所述载冷剂按质量百分比计含10~30%乙醇,18~43%丙二醇,47%水。
2、中国专利201210196843.4公开了一种用于食品直接浸渍冻结用的冻结液,主要包括以下质量百分含量的各组分:甜菜碱18~25%;浓度95%以上的食用酒精15~20%;氯化钠2~8%;水47~65%。采用甜菜碱作为冻结液的主要组成部分。
3、中国专利201110174042.3公开了一种用于食品浸渍冷冻的四元载冷剂,由乙醇、氯化钠、水与水溶性蛋白构成。当浸渍冻结工作温度在-20℃以上时,载冷剂组分为:乙醇5%~8%,氯化钠20%,水溶性蛋白0.5%,余量为水;当浸渍冻结工作温度在-30℃以上时,载冷剂组分为:乙醇23%~25%,氯化钠14%~20%,水溶性蛋白0.5%,余量为水;当浸渍冻结工作温度在-40℃~-44℃时,载冷剂组分为:乙醇43%~55%,氯化钠5~14%,水溶性蛋白0.3~0.5%,余量为水。
目前已有的二元、三元、四元及以上载冷剂组成的不冻液中都存在一些不足:
(1)含有高浓度的氯化钠,对设备有腐蚀作用,设备维护难;
(2)乙醇浓度较高且容易挥发,不冻液长期贮藏时蒸发量较高,造成冻结点上升;
(3)糖醇类物质含量高造成不冻液粘度较高,影响传热;
(4)不冻液在低温下搅拌时,会出现冷冻结晶现象,传热性能明显下降。
(5)不冻液在低温下长期使用,会有溶质如盐类等物质析出,造成冻结点上升,性质不稳定,经济效益变差。
针对这些问题,本发明提供了一种用于食品保鲜冻结的抗冷冻结晶不冻液制备方法。
(三)发明内容
本发明的目的是为了克服现有技术中的不足之处,提供一种可用于食品快速冻结的不冻液,以降低不冻液的冻结点,提高传热效率,抑制不冻液在低温搅拌过程中出现的结晶现象产生以及提高不冻液的稳定性。
本发明解决其技术问题所采用的技术方案是:
一种用于食品保鲜的不冻液,包含食用酒精、丙二醇、丙三醇、氯化钙、氯化钠、氨基酸、平均分子量为50~100KDa的南极磷虾蛋白水解物、表面活性剂和水,其中表面活性剂为磷脂、吐温-20、吐温-60、吐温-80中的一种或几种;各组分均为食品级,质量百分比含量表示如下:
进一步,丙二醇的质量百分比含量优选为10-20%。
进一步,丙三醇的质量百分比含量优选为2-5%。
进一步,氯化钙的质量百分比含量优选为1-5%。
进一步,所述的南极磷虾蛋白水解物,是以南极磷虾为原料,首先采用木瓜蛋白酶酶解得到南极磷虾粗酶液;然后依次通过膜孔分子量100KDa和膜孔分子量50KDa的超滤膜,获得平均分子量为50~100KDa的蛋白质水解物。50~100KDa的磷虾蛋白质水解物在低温下具有抗结晶的作用,抑制不冻液在低温下冷冻晶核的产生。
进一步,木瓜蛋白酶进行酶解,加酶量为1000U/g蛋白质,酶解条件为:在40℃、pH6.5条件下酶解3h。
进一步,所述的氨基酸选自下列一种或任意几种的组合:甘氨酸、丙氨酸、精氨酸中的一种或者几种。
进一步,所述的水可以是自来水、蒸馏水、纯净水等。
进一步,所述的不冻液由食用酒精、丙二醇、丙三醇、氯化钙、氯化钠、氨基酸、平均分子量为50~100KDa的南极磷虾蛋白水解物、表面活性剂和水组成。
本发明所述的用于食品保鲜的不冻液,其制备方法为首先将盐类、氨基酸类物质和表面活性剂用水溶解后,加入食用酒精、丙二醇、丙三醇和南极磷虾蛋白水解物搅拌均匀后使用。
与现有技术相比,本发明具有以下的特色:
(1)本发明所使用的不冻液配方,其组分完全采用对人体健康无任何危害的物质,满足食品安全性的要求。
(2)本发明所述的不冻液降低了氯化钠或氯化钙的含量,减少对仪器的腐蚀,并且用丙二醇部分代替工业上使用的乙二醇,更加绿色环保。
(3)添加少量的50~100KDa的南极磷虾蛋白水解物,不仅降低了溶液的冻结点,提高了传热效率,并且抑制了不冻液在搅拌过程中出现的结晶现象产生。
(4)添加少量表面活性剂,通过表面活性剂与醇类物质间的范德华力及氢键作用,可有效降低不冻液组分中醇类物质的挥发性,使各组分组成的不冻液体系更加稳定。
(5)本发明所述不冻液,最低冻结点可达-45℃以下,粘度适中,挥发较少,性能稳定,可根据需要温度进行不同配比选择。
(四)附图说明
图1是加南极磷虾蛋白水解物的不冻液A的图片;
图2是不加南极磷虾蛋白水解物的不冻液B的图片;
图3是不同温度冻结下鱼块的冻结曲线。
(五)具体实施方式
以下结合实施例对本发明的具体实施作进一步说明。
采用食用酒精(95%)、食品级丙二醇、食品级丙三醇、食品级氯化钙、食用氯化钠、食品级氨基酸、南极磷虾蛋白水解物、食品级表面活性剂和自来水为原料配置不冻液。
实施例1:南极磷虾蛋白水解物的制备
是以100kg南极磷虾为原料,首先采用木瓜蛋白酶(南宁庞博生物工程有限公司,酶活100万U/g)进行酶解,加酶量为1000U/g蛋白质,在40℃、pH6.5条件下酶解3h得到南极磷虾粗酶液;然后使南极磷虾粗酶液依次通过膜孔分子量100KDa和膜孔分子量50KDa的超滤膜,获得平均分子量为50~100KDa的蛋白质水解物。
实施例2
一种用于食品保鲜不冻液,各组分按质量百分比如下:95%食用酒精15%,丙二醇10%,丙三醇2%,氯化钠3%,氯化钙1%,甘氨酸0.1%,南极磷虾蛋白水解物0.014%,磷脂0.1%,余量为水。制备方法为首先将300g氯化钠、100g氯化钙、10g甘氨酸和10g磷脂用6878.6g水溶解后,加入1500g食用酒精、1000g丙二醇、200g丙三醇和1.4g南极磷虾蛋白水解物搅拌均匀后得到不冻液。所得不冻液的冻结点为-25℃,有良好的流动性,粘度为46.8mPa·S,比朱志伟等人发明的三元载冷剂[中国专利201210558113.4]粘度低,挥发少。在低温下快速搅拌时不冻液不会产生冷冻结晶现象。
将4×4×4(长×宽×高)大小鱼块冻至中心温度-18℃,本发明的不冻液冻结只需12.5min,而传统平板空气冻结需要180min以上。冻结曲线如图3所示。
同样,将2×2×2(长×宽×高)大小牛肉冻至中心温度-15℃,本发明的不冻液冻结只需6min,而传统平板空气冻结需要100min以上。
将温度计探头插入杨梅中心(直径2cm),将杨梅中心温度冻至-10℃,本发明的不冻液冻结只需4.5min,而传统平板空气冻结需要60min以上。
实施例3
一种用于食品保鲜不冻液,各组分按质量百分比如下:95%食用酒精20%,丙二醇15%,丙三醇4%,氯化钠4%,氯化钙2%,丙氨酸0.12%,南极磷虾蛋白水解物0.30%,吐温(20)0.15%,余量为水。制备方法为首先将400g氯化钠、200g氯化钙、12g丙氨酸和15g吐温(20)用5443g水溶解后,加入2000g食用酒精、1500g丙二醇、400g丙三醇和30g南极磷虾蛋白水解物搅拌均匀后得到不冻液。所得不冻液的冻结点为-35℃,在低温下有良好的流动性,粘度为185mPa·S。比秦海杰[中国专利201110174042.3]发明的四元载冷剂不冻液,挥发少且盐类含量低,对设备腐蚀小。在低温下快速搅拌时不冻液不会产生冷冻结晶现象。
将4×4×4(长×宽×高)大小鱼块冻至中心温度-18℃,本发明的不冻液冻结只需7.2min,而传统平板空气冻结需要180min以上。冻结曲线如图3所示。
将2×2×2(长×宽×高)大小牛肉冻至中心温度-15℃,本发明的不冻液冻结只需3min,而传统平板空气冻结需要100min以上。
将温度计探头插入杨梅中心(直径2cm),将杨梅中心温度冻至-10℃,本发明的不冻液冻结只需2min,而传统平板空气冻结需要60min以上。
实施例4
一种用于食品保鲜不冻液,各组分按质量百分比如下:95%食用酒精25%,丙二醇20%,丙三醇5%,氯化钠6%,氯化钙4%,精氨酸0.15%,南极磷虾蛋白水解物0.18%,磷脂0.12%,吐温(60)0.15%,余量为水,配方以占不冻液总重量百分比计。制备方法为首先将600g氯化钠、400g氯化钙、15g精氨酸、12g磷脂和15g吐温(20)用3940g水溶解后,加入2500g食用酒精、2000g丙二醇、500g丙三醇和18g南极磷虾蛋白水解物搅拌均匀后得到不冻液。所得不冻液的冻结点为-45℃,在低温下有良好的流动性,粘度为224.8mPa·S。比张临新[中国专利201310653196.X]发明的冷冻保鲜液,相同温度下粘度更小,盐类含量低,对设备腐蚀小。不冻液在低温下快速搅拌时不会产生冷冻结晶现象。
将切成4×4×4(长×宽×高)大小鱼块冻至中心温度-18℃,本发明的不冻液冻结只需6min,而传统平板空气冻结需要180min左右,冻结曲线如图3所示。
将2×2×2(长×宽×高)大小牛肉冻至中心温度-15℃,本发明的不冻液冻结只需1.8min,而传统平板空气冻结需要60min以上。
将温度计探头插入杨梅中心(直径2cm),将杨梅中心温度冻至-10℃,本发明的不冻液冻结只需1.2min,而传统平板空气冻结需要60min以上。
以上实施例仅用于阐述本发明,而本发明的保护范围并非仅仅局限与以上实施例。所述技术领域的普通技术人员依据以上本发明公开的内容和各参数范围,均可实现本发明的目的。
对比实验1:
加南极磷虾蛋白水解物的不冻液A:各组分按质量百分比如下:95%食用酒精26%,丙二醇20%,丙三醇5%,氯化钠7%,氯化钙3%,甘氨酸0.15%,南极磷虾蛋白水解物0.2%,余量为水,配方以占不冻液总重量百分比计。制备方法为首先将70g氯化钠、30g氯化钙、1.5g甘氨酸用386.5g水溶解后,加入260g食用酒精、200g丙二醇、50g丙三醇和2g南极磷虾蛋白水解物搅拌均匀后得到不冻液A。
未加南极磷虾蛋白水解物的不冻液B:各组分按质量百分比如下:95%食用酒精26%,丙二醇20%,丙三醇5%,氯化钠7%,氯化钙3%,甘氨酸0.15%,余量为水,配方以占不冻液总重量百分比计。制备方法为首先将70g氯化钠、30g氯化钙、1.5g甘氨酸用388.5g水溶解后,加入260g食用酒精、200g丙二醇、50g丙三醇搅拌均匀后得到不冻液B。
不冻液A和B都放置在-80℃环境中降温。未加南极磷虾蛋白水解物的不冻液B其最低冻结点为-45.6℃,溶液出现结晶现象(如图1),加入0.2%南极磷虾蛋白水解物的不冻液A,不仅溶液结晶现象消失,而且最低冻结点降为-47℃±1.2℃(如图2)。
对比例2
加表面活性剂的不冻液C:各组分按质量百分比如下:95%食用酒精25%,丙二醇20%,丙三醇5%,氯化钠6%,氯化钙2%,甘氨酸0.15%,吐温(20)0.2%,余量为水,配方以占不冻液总重量百分比计。制备方法为首先将60g氯化钠、20g氯化钙、1.5g甘氨酸和2g表面活性剂用416.5g水溶解后,加入250g食用酒精、200g丙二醇、50g丙三醇搅拌均匀后得到不冻液C。
未加表面活性剂的不冻液D:各组分按质量百分比如下:95%食用酒精25%,丙二醇20%,丙三醇5%,氯化钠6%,氯化钙2%,甘氨酸0.15%,余量为水,配方以占不冻液总重量百分比计。制备方法为首先将60g氯化钠、20g氯化钙、1.5g甘氨酸用418.5g水溶解后,加入250g食用酒精、200g丙二醇、50g丙三醇搅拌均匀后得到不冻液D。
将不冻液C和D两组敞口放置在4℃环境中一个月,测定两组不冻液的质量。在一个月后未加表面活性剂的不冻液D挥发为16%,加入表面活性剂的不冻液C挥发为12%。
实验:配置两组等质量不冻液,一组加0.2%的表面活性剂,一组未加表面活性剂;其余成分一致:醇类45%;盐类8%;氨基酸0.15%;两组敞口放置在4℃环境中一个月,测定两组不冻液的质量。在一个月后未加表面活性剂的不冻液挥发为16%,加入表面活性剂后不冻液挥发为12%。
Claims (10)
1.一种用于食品保鲜的不冻液,包含食用酒精、丙二醇、丙三醇、氯化钙、氯化钠、氨基酸、平均分子量为50~100KDa的南极磷虾蛋白水解物、表面活性剂和水,其中表面活性剂为磷脂、吐温-20、吐温-60、吐温-80中的一种或几种;各组分均为食品级,质量百分比含量表示如下:
。
2.如权利要求1所述的不冻液,其特征在于:所述的南极磷虾蛋白水解物,是以南极磷虾为原料,首先采用木瓜蛋白酶酶解得到南极磷虾粗酶液;然后依次通过膜孔分子量100KDa和膜孔分子量50KDa的超滤膜,获得平均分子量为50~100KDa的蛋白水解物。
3.如权利要求2所述的不冻液,其特征在于:酶解条件为:加酶量为1000U/g蛋白质,在40℃、pH6.5条件下酶解3h。
4.如权利要求1所述的不冻液,其特征在于:所述的氨基酸选自下列一种或任意几种的组合:甘氨酸、丙氨酸、精氨酸中的一种或者几种。
5.如权利要求1~4之一所述的不冻液,其特征在于:丙二醇的质量百分比含量为10-20%。
6.如权利要求1~4之一所述的不冻液,其特征在于:丙三醇的质量百分比含量为2-5%。
7.如权利要求1~4之一所述的不冻液,其特征在于:氯化钙的质量百分比含量为1-5%。
8.如权利要求1~4之一所述的不冻液,其特征在于:丙二醇的质量百分比含量为10-20%,丙三醇的质量百分比含量为2-5%,氯化钙的质量百分比含量为1-5%。
9.如权利要求1~4之一所述的不冻液,其特征在于:所述的不冻液由食用酒精、丙二醇、丙三醇、氯化钙、氯化钠、氨基酸、平均分子量为50~100KDa的南极磷虾蛋白水解物、表面活性剂和水组成。
10.如权利要求8所述的不冻液,其特征在于:所述的不冻液由食用酒精、丙二醇、丙三醇、氯化钙、氯化钠、氨基酸、平均分子量为50~100KDa的南极磷虾蛋白水解物、表面活性剂和水组成。
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