WO2017071313A1 - 一种工业化生产臭氧冰的方法 - Google Patents

一种工业化生产臭氧冰的方法 Download PDF

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WO2017071313A1
WO2017071313A1 PCT/CN2016/090605 CN2016090605W WO2017071313A1 WO 2017071313 A1 WO2017071313 A1 WO 2017071313A1 CN 2016090605 W CN2016090605 W CN 2016090605W WO 2017071313 A1 WO2017071313 A1 WO 2017071313A1
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ozone
water
ice
concentration
temperature
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PCT/CN2016/090605
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English (en)
French (fr)
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张旭
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张旭
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25C—PRODUCING, WORKING OR HANDLING ICE
    • F25C1/00—Producing ice

Definitions

  • the invention relates to the field of ozone application, in particular to a method for industrially producing ozone ice.
  • Ozone is a strong oxidant with an oxidation-reduction potential of 2.07 eV in water and an oxidation capacity higher than chlorine (1.36 eV) and chlorine dioxide (1.5 eV), second only to fluorine (2.5 eV).
  • Ozone can destroy the cell wall that breaks down bacteria, so it can quickly diffuse into bacterial cells, and break down and destroy macromolecular polymers such as DNA, RNA, protein, lipids and polysaccharides, destroying the normal metabolism and reproduction of bacteria, and achieving bactericidal effect. .
  • Ozone maintains a relatively stable molecular structure at different pH values, and is self-reduced to oxygen after disinfection without any disinfection by-products.
  • hypochlorite disinfectants are unstable in an acidic environment and produce disinfection by-products such as chloramines, trihalomethanes, and chlorine, which require further subsequent treatment.
  • ozone sterilization ability and efficiency are much stronger than traditional hypochlorous acid disinfectants.
  • ozone can quickly and completely eliminate various odors in the air and water, and has high utilization value in a wide range of fields.
  • the effect of ozone sterilization is closely related to its concentration, and the ozone threshold concentration and the optimum ozone concentration are not the same for different disinfection purposes.
  • the ozone threshold concentration refers to the lowest concentration when ozone has a certain bactericidal ability; the optimum ozone concentration refers to the ozone concentration when the comprehensive bactericidal effect is the best.
  • the higher the ozone concentration the higher the sterilization rate, but the excessive ozone concentration does not necessarily lead to the optimal combined sterilization effect.
  • the sterilization rate is three times that when the ozone concentration is 5ppm; but the meat treated with 10ppm ozone loses the original meat.
  • the taste of the class, the quality is greatly reduced, and this problem does not occur when using 5ppm ozone sterilization.
  • Ozone has poor stability at normal temperature and pressure, and is easily decomposed into oxygen by itself, making it difficult to store.
  • the method for manufacturing ozone ice in the prior art generally comprises: converting oxygen into ozone by using an ozone manufacturing machine, then dissolving the ozone in water by using a gas-water mixing device, and finally passing it through a rapid freezing system to make it contain Ice cubes of ozone.
  • this process is relatively simple, and there is no parameter optimization for the specific requirements of industrial production, and it is difficult to apply to mass production.
  • this process does not control the concentration of ozone in ice cubes and cannot meet the needs of different disinfection purposes. This allows ozone ice to be used sporadically only in narrower areas.
  • a method for industrially producing ozone ice comprising the steps of:
  • the low-temperature water obtained in the step (1) and the ozone produced by the ozone generating device are pressure-mixed into ozone water in a pressure vessel; and the ozone concentration in the ozone water is monitored online by the sensor using the ozone concentration Monitoring is performed to maintain the ozone concentration in the ozone water in the ozone concentration setting value of the ozone concentration online monitoring sensor;
  • the ozone water is initially formed in a freezing device with a temperature of ⁇ -10 ° C, so that the surface rapidly forms an ozone ice film and freezes into primary ozone ice; the volume of the ozone ice film accounts for 2 to 30% of the total volume of ozone water;
  • the primary ozone ice obtained in the step (3) is transferred to another freezing apparatus, and at least one freeze setting is performed at a temperature of ⁇ 0 ° C to form a finished ozone ice.
  • ozone has a low solubility in water. Therefore, before the ozone is mixed with water, it is necessary to previously cool the water and mix under pressure.
  • the ozone generating device used in the step (2) can be selected from a commercially available ozone generator capable of converting oxygen into ozone.
  • the ozone concentration on-line monitoring sensor in step (2) can adjust the amount of ozone generated by adjusting the driving current and driving frequency of the ozone generator. Therefore, as long as the parameters of the ozone concentration on-line monitoring sensor are set, ozone water of different ozone concentrations can be obtained according to specific production needs, thereby obtaining ozone ice with different ozone concentrations.
  • Ozone water ozone concentration and use of the ozone The concentration of ozone in the condensed ozone ice is proportional.
  • the specific ratio between the two varies according to the specific equipment used and the ozone concentration in the ozone water. Pre-experiment can be carried out before mass production. The ratio was measured. In the embodiment of the present invention, the ratio of the ozone concentration in the ozone water to the ozone concentration of the ozone ice produced using the ozone water is 8 to 15..1.
  • the pressure applied by the pressure vessel in the step (1) is in the range of 0.1 to 0.45 MPa; the ozone concentration in the step (2) is set to 0.1 ° in the ozone concentration monitoring sensor. Within the range of 150ppm.
  • the present invention uses at least two molding processes to freeze the ozone water into ozone ice, whereas the prior art simply reduces the ozone water into ozone ice at a time.
  • one-time cooling molding requires large-scale refrigeration equipment to achieve.
  • Large-scale refrigeration equipment requires large production sites, high energy consumption, high production costs, and adverse effects on the environment.
  • the method of the invention preferably performs preliminary forming and freezing setting in different equipments, and under the premise of satisfying the mass production quantity, the investment cost and the land area of the ozone ice production line can be greatly reduced, and the environment is green.
  • the preliminary molding described in the step (3) of the present invention has the characteristics of faster freezing speed, and preferably uses a low-temperature line equipment: after the ozone water is placed in the container, it is initially formed on the low-temperature line conveyor belt. In addition, it can also be frozen using a common freezer. Once the ozone water reaches the initial molding requirements, the primary ozone ice can be transferred to the freezing equipment of the setting step for shaping, and the freezing equipment used in the molding step can be vacant for the next batch to be formed, and the turnover is flexible.
  • the freezing setting in the step (4) of the present invention may be one time or more than one time, and is adjusted according to whether or not the ozone ice is further processed in actual production: if there are further steps such as demoulding or packaging, it is required Perform the remodeling after these steps.
  • the tempered temperature can be specifically configured according to the required production rate. If you want to get the finished product in a short period of time, you can lower the setting temperature.
  • the freezing device used in the step (4) is preferably a freezer.
  • the water used in step (1) is water that meets drinking water standards.
  • the stability of ozone water is greatly affected by impurities contained in water. If the water contains organic matter, it will consume ozone dissolved in water; if some metal ions are present in the water, ozone will quickly decompose into oxygen. Therefore, preferably for use
  • the water is pretreated by filtration to achieve the water quality as required by the national GB5749-2006 "Sanitary Standard for Drinking Water".
  • step (1) the temperature of the water is monitored using a temperature online monitoring sensor, and the mixing of the water and ozone is controlled according to the feedback signal of the online monitoring sensor.
  • the ozone concentration of ozone water can be stabilized by precise control of the temperature of the low temperature water mixed with ozone.
  • the water in step (1) is cooled in a freezer which is directly connected to the gas-liquid mixing device of step (2).
  • the inlet valve of the gas-liquid mixing device When the water of the freezing device reaches the temperature preset by the temperature monitoring sensor, the inlet valve of the gas-liquid mixing device is opened, the low-temperature water enters the gas-liquid mixing device from the freezing device, and is mixed with ozone; when the water temperature in the freezing device The inlet valve closes above or below the sensor's preset temperature.
  • the ozone water may be first introduced into a mold having a different size and shape, and then preliminary frozen.
  • the ozone concentration of the finished ozone ice described in the step (4) is 0.05 to 14 ppm.
  • the daily output of each production line can reach more than 40 tons, and the annual output can reach more than 14,400 tons.
  • the specification conversion can be realized by replacing the ice tank mold, and the conversion efficiency is 2h/time.
  • the specification conversion can be realized by replacing the freezing device, and the conversion efficiency is 8 h/time.
  • the method of secondary cooling is used to freeze the ozone water, which increases the flexibility of production and reduces the production cost and energy consumption.
  • the tap water filter used is preferably an activated carbon filter produced by Tianyu Water Treatment Equipment (Zhangzhou) Co., Ltd.; the tap water cooling equipment used is preferably a model produced by Guangzhou Aoxue Refrigeration Equipment Co., Ltd.
  • the PSA industrial oxygen generator used is preferably a PSA industrial oxygen generator produced by Guangzhou Chuanghuan Ozone Electric Equipment Co., Ltd.
  • the ozone generator used is preferably Guangzhou Huanhuan Ozone
  • the small vertical ozone generator (CH-WZQ) produced by Electrical Equipment Co., Ltd.
  • the gas-liquid mixing device used is preferably CH-QY-B2 ozone water pressure mixer produced by Guangzhou Chuanghuan Ozone Electric Equipment Co., Ltd.
  • the ozone concentration online monitoring sensor used is preferably an ATI Q45H/64 dissolved ozone analyzer purchased from Zibo Aidier Measurement and Control Technology Co., Ltd.; the freezing equipment used in the preliminary molding step is preferably produced by Guangzhou Chuanghuan Ozone Electric Equipment Co., Ltd. CH-SD-B1 line-type quick freezing device or CH-SD-B2 low temperature freezer; excellent freezing equipment used in the freezing setting step
  • the low-temperature freezer model BKDB-100L-135 or BKDW-318L-65 produced by Shenzhen Fidelity Refrigeration Equipment Co., Ltd.;
  • the temperature monitoring sensor used is preferably the wireless temperature sensor produced by Shenzhen Taishite Technology Co., Ltd. .
  • those skilled in the art can achieve the object of the present invention by selecting other products having similar properties to those of the above-listed products according to the conventional selection.
  • the low temperature water obtained in the step (1) is introduced into the gas-liquid mixing device at a rate of 2 t/h; the ozone obtained in the step (2) is fed into the gas-liquid mixing device at a rate of 20 g/h, and is in a low-temperature water Ozone water was thoroughly mixed under a pressure of 0.3 MPa.
  • the ozone concentration online monitoring sensor monitors the ozone concentration in the ozone water, and feeds back the signal to the ozone generator, thereby performing the driving current and the driving frequency of the ozone generator. Adjusting to adjust the concentration of ozone in the mixed gas generated by the ozone generator to maintain the ozone concentration in the ozone water between 8 ppm and 9 ppm;
  • the ozone water was subjected to preliminary molding at a temperature of -35 °C.
  • the surface of ozone ice forms an ozone ice film within 30s and freezes into primary ozone ice; the volume of the ozone ice film accounts for 5% of the total volume of ozone water;
  • the primary ozone ice obtained in the step (3) is conveyed into a freezing device through a conveyor belt, and is subjected to one-time freezing setting at a temperature of -12 ° C, and the finished ozone ice is formed after 8 hours.
  • the ozone concentration in the ozone ice is from 0.6 ppm to 0.7 ppm.
  • the low temperature water obtained in the step (1) is introduced into the gas-liquid mixing device at a rate of 2 t/h; the ozone obtained in the step (2) is fed into the gas-liquid mixing device at a rate of 20 g/h, and is in a low-temperature water
  • the mixture was thoroughly mixed into ozone water under a pressure of 0.2 MPa.
  • the ozone concentration online monitoring sensor monitors the ozone concentration in the ozone water, and feeds back a signal to the ozone generator, thereby adjusting the driving current and the driving frequency of the ozone generator to adjust the ozone in the mixed gas generated by the ozone generator.
  • the concentration is such that the ozone concentration in the ozone water is maintained between 12 ppm and 13 ppm;
  • the ozone water was initially formed at a temperature of -30 °C.
  • the surface of ozone ice forms an ozone ice film within 30s and freezes into primary ozone ice; the volume of the ozone ice film accounts for 2% of the total volume of ozone water;
  • the primary ozone ice obtained in the step (3) is conveyed into a freezing device through a conveyor belt, and is subjected to a freezing setting at a temperature of -20 ° C, and a finished ozone ice is formed after 6 hours.
  • the ozone concentration in the ozone ice is from 0.9 ppm to 1 ppm.
  • the low temperature water of 4 ° C obtained in the step (1) is input into the gas-liquid mixing device at a rate of 2 t / h; the ozone obtained in the step (2) is input into the gas-liquid mixing device at a rate of 20 g / h, and The low temperature water is thoroughly mixed into ozone water under a pressure of 0.1 MPa.
  • the ozone concentration online monitoring sensor monitors the ozone concentration in the ozone water, and feeds back a signal to the ozone generator, thereby adjusting the driving current and the driving frequency of the ozone generator to adjust the ozone in the mixed gas generated by the ozone generator.
  • the concentration is such that the ozone concentration in the ozone water is maintained between 0.1 ppm and 1 ppm;
  • the obtained ozone water was introduced into a square mold, and preliminary molding was carried out at a temperature of -60 °C.
  • the surface of the ozone ice forms an ozone ice film within 120s and freezes into primary ozone ice; the volume of the ozone ice film accounts for 30% of the total volume of the ozone water;
  • the primary ozone ice obtained in the step (3) is passed through a conveyor belt, conveyed into a freezing device, and frozen at a temperature of -5 ° C for 5 hours, and then demolded after preliminary setting; then, frozen at -10 ° C. After 10 hours, a cube of ozone ice was obtained.
  • the ozone concentration in the ozone ice is 0.05 to 0.2 ppm.
  • the low temperature water obtained in the step (1) is introduced into the gas-liquid mixing device at a rate of 2 t/h; the ozone obtained in the step (2) is fed into the gas-liquid mixing device at a rate of 40 g/h, and is in a low-temperature water It is thoroughly mixed into ozone water under a pressure of 0.45 MPa.
  • the ozone concentration online monitoring sensor monitors the ozone concentration in the ozone water, and feeds back the signal to the ozone generator, thereby performing the driving current and the driving frequency of the ozone generator. Adjusting to adjust the concentration of ozone in the mixed gas generated by the ozone generator to maintain the ozone concentration in the ozone water between 149 ppm and 150 ppm;
  • the obtained ozone water was introduced into a rectangular parallelepiped mold, and preliminary molding was carried out at a temperature of -10 °C.
  • the surface of the ozone ice forms an ozone ice film within 120s and freezes into primary ozone ice; the volume of the ozone ice film accounts for 3% of the total volume of the ozone water;
  • the primary ozone ice obtained in the step (3) is conveyed into a freezing device through a conveyor belt, frozen at -20 ° C for 2 hours, and demolded after preliminary setting; then frozen at -25 ° C for 1 hour to be packaged. Finally, cuboid ozone ice was formed after freezing at -30 ° C for 5 hours.
  • the ozone concentration in the ozone ice is 13 ppm to 14 ppm.
  • the low temperature water obtained in the step (1) is introduced into the gas-liquid mixing device at a rate of 2 t/h; the ozone obtained in the step (2) is introduced into the gas-liquid mixing device at a rate of 30 g/h, and is in a low-temperature water Ozone water was thoroughly mixed under a pressure of 0.35 MPa.
  • the ozone concentration online monitoring sensor monitors the ozone concentration in the ozone water, and feeds back a signal to the ozone generator, thereby adjusting the driving current and the driving frequency of the ozone generator to adjust the ozone in the mixed gas generated by the ozone generator.
  • the concentration is such that the ozone concentration in the ozone water is maintained between 99 ppm and 100 ppm;
  • the ozone water is initially formed at a temperature of -40 °C.
  • the surface of ozone ice forms an ozone ice film within 120s and freezes into primary ozone ice; the volume of the ozone ice film accounts for 23% of the total volume of ozone water;
  • the primary ozone ice obtained in the step (3) is conveyed into a freezing device through a conveyor belt, and is subjected to one-time freezing setting at a temperature of -120 ° C, and a finished ozone ice is formed 0.5 hours later.
  • the ozone concentration in the ozone ice is 7 ppm to 8 ppm.

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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Mechanical Engineering (AREA)
  • Thermal Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Production, Working, Storing, Or Distribution Of Ice (AREA)
  • Treatment Of Water By Oxidation Or Reduction (AREA)
  • Oxygen, Ozone, And Oxides In General (AREA)

Abstract

一种工业化生产臭氧冰的方法，包括以下步骤：（1）制备低温水；（2）将步骤（1）所得的低温水和由臭氧发生装置生产的臭氧在压力容器中加压混合为臭氧水；使用臭氧浓度监控传感器对臭氧水中的臭氧浓度进行监控，以使臭氧水中的臭氧浓度保持在设定值；（3）将臭氧水在温度≤-10℃的冷冻设备中进行初步成型；（4）将步骤（3）所得的初级臭氧冰输送至另一冷冻设备中，进行至少一次冷冻定型。

Description

一种工业化生产臭氧冰的方法 技术领域
本发明涉及臭氧应用领域，尤其涉及一种工业化生产臭氧冰的方法。
背景技术
臭氧(O3)是一种强氧化剂，它在水中的氧化还原电位为2.07eV，氧化能力高于氯(1.36eV)和二氧化氯(1.5eV)，仅次于氟(2.5eV)。臭氧能破坏分解细菌的细胞壁，从而能够很快地扩散入细菌细胞内，并分解和破坏DNA、RNA、蛋白质、脂质和多糖等大分子聚合物，破坏细菌正常的代谢和繁殖，达到杀菌效果。臭氧在不同的pH值下均保持较为稳定的分子结构，在消毒后会自行还原成氧气，不产生任何消毒副产物。与此相对，传统的次氯酸类消毒剂在酸性环境下不稳定，且会产生氯胺类、三卤甲烷类、氯等消毒副产物，需要进一步的后续处理。此外，臭氧的杀菌能力和效率都大大强于传统的次氯酸类消毒剂。除了杀菌之外，臭氧还可迅速而彻底的消除空气中和水中的各种异味，在广泛的领域中均有较高的利用价值。
臭氧杀菌的效果与其浓度密切相关，而对于不同的消毒目的而言，臭氧阀值浓度和最适臭氧浓度并不相同。臭氧阈值浓度是指当臭氧具有一定杀菌能力时的最低浓度；最适臭氧浓度是指综合杀菌效果最好时的臭氧浓度。尽管一般而言，臭氧浓度越高时杀菌速率越高，但过高的臭氧浓度并不一定会带来最理想的综合杀菌效果。例如：尽管当臭氧浓度为10ppm时，肉类表面99％的细菌能够在10秒内被消灭，杀菌速率是当臭氧浓度为5ppm时的三倍；但经10ppm臭氧处理的肉类失去了原本肉类的味道，品质大幅下降，而使用5ppm臭氧杀菌时则不会出现这样的问题。
臭氧在常温常压下稳定性较差，容易自行分解为氧气，难以保存。研究发现臭氧在接近0℃的冰水中比较稳定，在冰块中尤其稳定，半衰期可达2000年。现有技术中的制造臭氧冰的方法一般为：利用臭氧制造机将氧气转变为臭氧，接着利用气水混合装置将臭氧溶于水中，最后再经过快速冰冻系统，将其制成含 臭氧的冰块。然而，这种工艺较为简略，并没有针对工业生产的具体要求进行参数的优化，难以应用到批量化生产中。此外，这种工艺并不能控制冰块内的臭氧浓度，无法满足不同消毒目的的需要。这使得臭氧冰仅在较窄的领域中得到零星的应用。
发明内容
本发明的目的在于提供一种工业化生产臭氧冰的方法，可实现大规模批量化生产，且能够根据生产的具体需要，制造具有不同臭氧浓度的臭氧冰。
为了达到上述发明目的，本发明采用以下技术方案：
一种工业化生产臭氧冰的方法，其特征在于包括以下步骤：
(1)制备低温水：将水降温至3～5℃；
(2)制备臭氧水：将步骤(1)所得的低温水和由臭氧发生装置生产的臭氧在压力容器中加压混合为臭氧水；使用臭氧浓度在线监控传感器对所述的臭氧水中的臭氧浓度进行监控，以使所述的臭氧水中的臭氧浓度保持在臭氧浓度在线监控传感器的臭氧浓度设定值上；
(3)初步冷冻：将所述的臭氧水在温度≤-10℃的冷冻设备中进行初步成型，使其表面快速形成臭氧冰膜，冻结成初级臭氧冰；所述的臭氧冰膜的体积占臭氧水总体积的2～30％；
(4)冷冻定型：将步骤(3)所得的初级臭氧冰输送至另一冷冻设备中，在＜0℃的温度下进行至少一次冷冻定型，形成成品臭氧冰。
在常温和常压下，臭氧在水中的溶解度较低。因此在将臭氧与水混合之前，需要预先对水进行降温，并在加压的条件下进行混合。步骤(2)所使用的臭氧发生装置可选用市面上常见的臭氧发生器，其能够将氧气转化为臭氧。在一个优选的实施方案中，步骤(2)中的臭氧浓度在线监控传感器可以通过调整臭氧发生器的驱动电流和驱动频率，调整所产生的臭氧量。因此，只要对臭氧浓度在线监控传感器的参数进行设定，便可以根据具体的生产需要，得到不同臭氧浓度的臭氧水，从而得到不同臭氧浓度的臭氧冰。臭氧水的臭氧浓度与使用该臭氧 水凝结成的臭氧冰中的臭氧浓度呈正比，二者之间的具体比值根据所使用的具体设备以及臭氧水中的臭氧浓度等因素的不同而不同，在进行大规模生产前可通过进行预实验，对该比值进行测定。在本发明的实施例中，臭氧水中的臭氧浓度与使用该臭氧水制成的臭氧冰的臭氧浓度的比值为8～15︰1。
在本发明推荐的实施方式中，步骤(1)中的压力容器所施加的压力在0.1～0.45Mpa的范围内；步骤(2)中的臭氧浓度在线监控传感器的臭氧浓度设定值在0.1～150ppm的范围内。
本发明采用至少两次成型工序，将臭氧水冻结为臭氧冰，而现有技术仅简单地将臭氧水一次降温成型为臭氧冰。在工业化大批量的生产中，一次降温成型需要大型的冷冻设备才能实现。大型冷冻设备需要的生产场地较大、耗能高、生产成本高，对环境也有不利的影响。本发明的方法优选在不同的设备中进行初步成型和冷冻定型，在满足大批量生产量的前提下，可大大降低臭氧冰生产线的投资成本和用地面积，同时绿色环保。
本发明的步骤(3)所述的初步成型具有冷冻速度较快的特点，优选地采用低温流水线设备：将臭氧水置于容器中后，在低温流水线输送带上初步成型。此外，也可以采用普通的冰柜进行冷冻。一旦臭氧水达到初步成型的要求，便可将初级臭氧冰转移到定型步骤的冷冻设备中进行定型，而成型步骤所用的冷冻设备便可空置出来，以进行下一批次的成型，周转灵活。
本发明步骤(4)中的冷冻定型可为一次，也可为多于一次，根据实际生产中是否需要对臭氧冰进行进一步的处理而调整：如果有进一步的脱模或包装等步骤，则需要在这些步骤后进行再次定型。定型的温度可根据所需要的生产速率进行具体的配置。如果希望在较短的时间内得到成品，则可降低定型温度。步骤(4)所使用的冷冻设备优选为冰柜。
优选地，步骤(1)中所使用的水为达到饮用水标准的水。臭氧水的稳定性受水中所含杂质的影响较大。水中如果含有机物，将消耗溶于水中的臭氧；水中如果有某些金属离子存在，臭氧容易迅速分解为氧气。因此，优选地对所使用 的水进行过滤等预处理，使其达到如国家颁布的GB5749-2006《生活饮用水卫生标准》中所要求的水质。
优选地，在步骤(1)中，使用温度在线监控传感器对所述的水的温度进行监控，并根据所述的温度在线监控传感器的反馈信号控制所述的水与臭氧的混合。通过对与臭氧混合的低温水的温度进行精确的控制，可使臭氧水的臭氧浓度保持稳定。在一个优选的实施方案中，步骤(1)中的水在冷冻装置中进行降温，该冷冻装置直接与步骤(2)的气液混合装置相连。当冷冻装置的水达到温度在线监控传感器所预设的温度时，气液混合装置的进水阀门打开，低温水由冷冻装置进入气液混合装置中，并与臭氧混合；当冷冻装置中的水温高于或低于传感器预设的温度时，进水阀门关闭。
优选地，在步骤(3)中，可先将臭氧水输入尺寸和形状不同的模具中，再进行初步冷冻。
优选地，步骤(4)中所述的成品臭氧冰的臭氧浓度为0.05～14ppm。
使用本发明的方法进行臭氧冰的大批量生产时，每条生产线的日产量可达到40吨以上，年产量达到1.44万吨以上。当所生产的臭氧冰重量在1～50000g之间时，可以通过更换冰槽模具实现规格转换，转换效率为2h/次。当单块臭氧冰重量超过50000g时，可通过更换冷冻装置实现规格转换，转换效率为8h/次。
本发明的技术方案具有以下的优点：
1.可以针对不同的使用目的，调整臭氧水中臭氧的浓度，从而生产不同臭氧浓度的臭氧冰；
2.对臭氧水中的臭氧浓度和温度进行实时监控，避免了现有技术中同一批次臭氧冰所含的臭氧浓度不均衡的弊端；
3.优化了现有的生产流程和工艺，使其能够适用于工业大批量生产，生产效率高；
4.采用二次降温的方法对臭氧水进行冻结，提高了生产的灵活性，降低了生产成本和能耗。
具体实施方式
以下列举具体实施例对本发明进行说明。需要指出的是，实施例只用于对本发明做进一步说明，不代表本发明的保护范围，其他人根据本发明作出的非本质的修改与调整，仍属于本发明的保护范围。
在下述的实施例中，所使用的自来水过滤器优选为天宇水处理设备(赣州)有限公司所生产的活性碳过滤器；所使用的自来水冷却设备优选为广州傲雪制冷设备有限公司生产的型号为HWX-195的多功能台式恒温箱；所使用的PSA工业制氧装置优选为广州创环臭氧电器设备有限公司所生产的PSA工业制氧机；所使用的臭氧发生器优选为广州创环臭氧电器设备有限公司所生产的小型立式臭氧发生器(CH-WZQ)；所使用的气液混合装置优选为广州创环臭氧电器设备有限公司所生产的CH-QY-B2臭氧水加压混合器；所使用的臭氧浓度在线监控传感器优选为购自淄博爱迪尔测控技术有限公司的ATI Q45H/64溶解臭氧分析仪；初步成型步骤所使用的冷冻设备优选为广州创环臭氧电器设备有限公司所生产的CH-SD-B1流水线式快速冷冻装置或CH-SD-B2低温冰柜；冷冻定型步骤所使用的冷冻设备优选为深圳市富达冷冻设备有限公司生产的型号为BKDB-100L-135或BKDW-318L-65的低温冰柜；所使用的温度在线监控传感器优选为深圳市泰士特科技股份有限公司生产的无线温度传感器。除上述列举的之外，本领域技术人员根据常规选择，也可以选择其它具有与本发明列举的上述产品具有相似性能的产品，均可以实现本发明的目的。
实施例1
(1)使用自来水过滤器过滤自来水，并在冷却设备中将其降温至3℃；
(2)使用PSA工业制氧装置制备纯度在89～90％的氧气，再将其通入臭氧发生器；
(3)将步骤(1)所得的低温水以2t/h的速率输入气液混合装置；将步骤(2)所得的臭氧以20g/h的速率输入该气液混合装置，并与低温水在0.3MPa的压力下充分混合为臭氧水。使用臭氧浓度在线监控传感器监控该臭氧水中的臭氧浓度，并反馈信号至臭氧发生器，从而对该臭氧发生器的驱动电流和驱动频率进行 调整，以调整臭氧发生器所产生的混合气体中臭氧的浓度，使臭氧水中的臭氧浓度保持在8ppm～9ppm之间；
(4)将所述的臭氧水在-35℃的温度下进行初步成型。臭氧冰的表面在30s内形成臭氧冰膜，冻结成初级臭氧冰；所述的臭氧冰膜的体积占臭氧水总体积的5％；
(5)将步骤(3)所得的初级臭氧冰通过输送带，输送入冷冻设备中，并于-12℃的温度下进行一次冷冻定型，8小时后形成成品臭氧冰。该臭氧冰中的臭氧浓度为0.6ppm～0.7ppm。
实施例2
(1)使用自来水过滤器过滤自来水，并在冷却设备中将其降温至5℃；
(2)使用PSA工业制氧装置制备纯度在89～90％的氧气，再将其通入臭氧发生器；
(3)将步骤(1)所得的低温水以2t/h的速率输入气液混合装置；将步骤(2)所得的臭氧以20g/h的速率输入该气液混合装置，并与低温水在0.2MPa的压力下充分混合为臭氧水。使用臭氧浓度在线监控传感器监控该臭氧水中的臭氧浓度，并反馈信号至臭氧发生器，从而对该臭氧发生器的驱动电流和驱动频率进行调整，以调整臭氧发生器所产生的混合气体中臭氧的浓度，使臭氧水中的臭氧浓度保持在12ppm～13ppm之间；
(4)将所述的臭氧水在-30℃的温度下进行初步成型。臭氧冰的表面在30s内形成臭氧冰膜，冻结成初级臭氧冰；所述的臭氧冰膜的体积占臭氧水总体积的2％；
(5)将步骤(3)所得的初级臭氧冰通过输送带，输送入冷冻设备中，并于-20℃的温度下进行一次冷冻定型，6小时后形成成品臭氧冰。该臭氧冰中的臭氧浓度为0.9ppm～1ppm。
实施例3
(1)在冷却设备中将自来水降温至3℃；使用温度在线监控传感器对所述的水的温度进行监控，并根据所述的温度在线监控传感器的反馈信号控制是否将所得的低温水输入气液混合装置；
(2)使用PSA工业制氧装置制备纯度在89～90％的氧气，再将其通入臭氧发生器；
(3)将步骤(1)所得的4℃的低温水以2t/h的速率输入气液混合装置；将步骤(2)所得的臭氧以20g/h的速率输入该气液混合装置，并与低温水在0.1MPa的压力下充分混合为臭氧水。使用臭氧浓度在线监控传感器监控该臭氧水中的臭氧浓度，并反馈信号至臭氧发生器，从而对该臭氧发生器的驱动电流和驱动频率进行调整，以调整臭氧发生器所产生的混合气体中臭氧的浓度，使臭氧水中的臭氧浓度保持在0.1ppm～1ppm之间；
(4)将所得的臭氧水输入正方体模具中，并在-60℃的温度下进行初步成型。臭氧冰的表面在120s内形成臭氧冰膜，冻结成初级臭氧冰；所述的臭氧冰膜的体积占臭氧水总体积的30％；
(5)将步骤(3)所得的初级臭氧冰通过输送带，输送入冷冻设备中，-5℃的温度下冷冻5小时，待初步定型后进行脱模；然后，再在-10℃下冷冻10小时，得到正方体臭氧冰。该臭氧冰中的臭氧浓度为0.05～0.2ppm。
实施例4
(1)使用自来水过滤器过滤自来水，并在冷却设备中将其降温至3℃；
(2)使用PSA工业制氧装置制备纯度在89～90％的氧气，再将其通入臭氧发生器；
(3)将步骤(1)所得的低温水以2t/h的速率输入气液混合装置；将步骤(2)所得的臭氧以40g/h的速率输入该气液混合装置，并与低温水在0.45MPa的压力下充分混合为臭氧水。使用臭氧浓度在线监控传感器监控该臭氧水中的臭氧浓度，并反馈信号至臭氧发生器，从而对该臭氧发生器的驱动电流和驱动频率进行 调整，以调整臭氧发生器所产生的混合气体中臭氧的浓度，使臭氧水中的臭氧浓度保持在149ppm～150ppm之间；
(4)将所得的臭氧水输入长方体模具中，并在-10℃的温度下进行初步成型。臭氧冰的表面在120s内形成臭氧冰膜，冻结成初级臭氧冰；所述的臭氧冰膜的体积占臭氧水总体积的3％；
(5)将步骤(3)所得的初级臭氧冰通过输送带，输送入冷冻设备中，-20℃下冷冻2小时，初步定型后进行脱模；然后在-25℃下冷冻1小时，进行包装；最后，在-30℃下冷冻5小时后形成长方体臭氧冰。该臭氧冰中的臭氧浓度为13ppm～14ppm。
实施例5
(1)使用自来水过滤器过滤自来水，并在冷却设备中将其降温至4℃；
(2)使用PSA工业制氧装置制备纯度在89～90％的氧气，再将其通入臭氧发生器；
(3)将步骤(1)所得的低温水以2t/h的速率输入气液混合装置；将步骤(2)所得的臭氧以30g/h的速率输入该气液混合装置，并与低温水在0.35MPa的压力下充分混合为臭氧水。使用臭氧浓度在线监控传感器监控该臭氧水中的臭氧浓度，并反馈信号至臭氧发生器，从而对该臭氧发生器的驱动电流和驱动频率进行调整，以调整臭氧发生器所产生的混合气体中臭氧的浓度，使臭氧水中的臭氧浓度保持在99ppm～100ppm之间；
(4)将所述的臭氧水在-40℃的温度下进行初步成型。臭氧冰的表面在120s内形成臭氧冰膜，冻结成初级臭氧冰；所述的臭氧冰膜的体积占臭氧水总体积的23％；
(5)将步骤(3)所得的初级臭氧冰通过输送带，输送入冷冻设备中，-120℃的温度下进行一次冷冻定型，0.5小时后形成成品臭氧冰。该臭氧冰中的臭氧浓度为7ppm～8ppm

Claims (9)

  1. 一种工业化生产臭氧冰的方法，其特征在于包括以下步骤：
    (1)制备低温水：将水降温至3～5℃；
    (2)制备臭氧水：将步骤(1)所得的低温水和由臭氧发生装置生产的臭氧在压力容器中加压混合为臭氧水；使用臭氧浓度在线监控传感器对所述的臭氧水中的臭氧浓度进行监控，以使所述的臭氧水中的臭氧浓度保持在臭氧浓度在线监控传感器的臭氧浓度设定值，所述臭氧浓度设定值在0.1～150ppm的范围内；
    (3)初步冷冻：将所述的臭氧水在温度≤-10℃的冷冻设备中进行初步成型，使其表面快速形成臭氧冰膜，冻结成初级臭氧冰；所述的臭氧冰膜的体积占臭氧水总体积的2～30％；
    (4)冷冻定型：将步骤(3)所得的初级臭氧冰输送至另一冷冻设备中，在＜0℃的温度下进行至少一次冷冻定型，形成成品臭氧冰。
  2. 根据权利要求1所述的工业化生产臭氧冰的方法，其特征在于：步骤(1)中的压力容器所施加的压力在0.1～0.45Mpa的范围内。
  3. 根据权利要求1或2所述的工业化生产臭氧冰的方法，其特征在于：步骤(3)所使用的冷冻设备为低温流水线设备。
  4. 根据权利要求1或2所述的工业化生产臭氧冰的方法，其特征在于：步骤(3)所使用的冷冻设备为冰柜。
  5. 根据权利要求3所述的工业化生产臭氧冰的方法，其特征在于：步骤(4)所使用的冷冻设备优选为冰柜。
  6. 根据权利要求5所述的工业化生产臭氧冰的方法，其特征在于：步骤(1)中所使用的水为达到饮用水标准的水。
  7. 根据权利要求6所述的工业化生产臭氧冰的方法，其特征在于：在步骤(1)中使用温度在线监控传感器对所述的水的温度进行监控，并根据所述的温度在线监控传感器的反馈信号控制所述的水与臭氧的混合。
  8. 根据权利要求7所述的工业化生产臭氧冰的方法，其特征在于：在步骤(3)中，可先将臭氧水输入尺寸和形状不同的模具中，再进行初步冷冻。
  9. 根据权利要求8所述的工业化生产臭氧冰的方法，其特征在于：步骤(4)中所述的成品臭氧冰的臭氧浓度为0.6～14ppm。
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021201959A1 (en) * 2020-04-03 2021-10-07 Venmill Industries, Inc. Ice machine cleaning apparatus

Families Citing this family (4)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1920449A (zh) * 2005-08-26 2007-02-28 周桂梅 含臭氧的低菌冰块及其制造方法
JP2007170714A (ja) * 2005-12-20 2007-07-05 Noboru Sakano 有用ガス含有氷の製造装置
CN105299993A (zh) * 2015-10-30 2016-02-03 张旭 一种工业化生产臭氧冰的方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10267476A (ja) * 1997-03-26 1998-10-09 Kobe Steel Ltd オゾン含有氷の製造方法
KR20020029708A (ko) * 2000-10-13 2002-04-19 변점수 오존 아이스 및 그 제조 방법
KR20110122918A (ko) * 2010-05-06 2011-11-14 조기원 고농도의 오존수로 제조된 살균얼음 및 그의 제조방법

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1920449A (zh) * 2005-08-26 2007-02-28 周桂梅 含臭氧的低菌冰块及其制造方法
JP2007170714A (ja) * 2005-12-20 2007-07-05 Noboru Sakano 有用ガス含有氷の製造装置
CN105299993A (zh) * 2015-10-30 2016-02-03 张旭 一种工业化生产臭氧冰的方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021201959A1 (en) * 2020-04-03 2021-10-07 Venmill Industries, Inc. Ice machine cleaning apparatus

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