CN106245050B - 一种超纯氧的制备方法 - Google Patents

一种超纯氧的制备方法 Download PDF

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CN106245050B
CN106245050B CN201610747423.9A CN201610747423A CN106245050B CN 106245050 B CN106245050 B CN 106245050B CN 201610747423 A CN201610747423 A CN 201610747423A CN 106245050 B CN106245050 B CN 106245050B
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徐大鹏
杨延河
师富良
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SHANDONG KUNDA BIOTECHNOLOGY CO Ltd
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SHANDONG HONGDA BIOTECHNOLOGY CO Ltd
Gunther Bio Tech Ltd Shandong
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    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00Electrolytic production of inorganic compounds or non-metals
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    • Y02E60/30Hydrogen technology
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Abstract

本发明公开了一种超纯氧的制备方法,本发明采用电解制氧工艺,对电解前的软化水进行预处理,将软化水进行加热,将其中溶解的N2、Ar等各种气体全部脱除,通入高纯氧保压,再经催化剂催化脱氢和分子筛脱水工艺,过滤除尘工艺,钢瓶烘干处理工艺,生产出符合“GBT 14599‑2008纯氧、高纯氧和超纯氧”要求超纯氢。本发明的有益效果:成功避开了空气分离制氧和普通电解制氧等方法得到氧气纯度低、杂质多的缺点,具有生产能耗低、流程效率高,工艺简单、生产稳定等特点。

Description

一种超纯氧的制备方法
技术领域
本发明涉及氧气的制备方法,具体地说是一种超纯氧的制备方法。
背景技术
空气是工业氧生产取之不尽的源泉,空气分离制氧可以采用四种方法,即低温精馏法、常温变压吸附法、膜分离法和高温碱性熔盐催化吸收法。由于空气主要是由氮、氧、氩、二氧化碳、甲烷、氧等组成,由空气分离法制取的工业氧组成复杂,特别是含有难于用常温分离法除去的氩、氮等杂质,用此类工业氧为原料来制备超纯氧的难度非常大。
水是工业氧生产另一种重要原料,用电解水法制得的氧气纯度比较高,输出纯度为99.2-99.8%,其杂质比较单纯,主要为氧、饱和水蒸气、微量氮和烃类(以甲烷为代表)。其中,微量氮和烃类杂质主要来自于电解装置所用的水原料,即来自于电解水原料中溶解的空气。传统电解水法制氧并副产氧的装置中,水中溶解的氮气和其它气体杂质随水进入电解槽,最终进入产品氧气中。
如何将工业氧、高纯氧中的氮和烃类杂质去除,是生产制造超纯氧的的瓶颈,目前尚无用电解水法制备超纯氧的专利。
发明内容
针对超纯氧生产工艺存在的空白,本发明采用电解制氧工艺,对电解前的软化水进行预处理,通入高纯氧保压,再利用催化脱氢和分子筛脱水工艺,过滤除尘,钢瓶烘干处理工艺,生产出的超纯氧纯度符合“GBT 14599-2008 纯氧、高纯氧和超氧氧”的要求,具有超纯氧产量高、投资少、生产稳定等特点。
本发明解决其技术问题所采取的技术方案是:
一种超纯氧的制备方法,包括以下步骤:
(1)预热:将软化水罐中的软化水进行预热;
(2)保压:向步骤(1)预热后的软化水罐中通入高纯氧气保压;
(3)电解:将步骤(2)中的软化水经冷却后通入水电解系统进行电解,产出电解氧;
(4)催化脱氢:将步骤(3)中产出的电解氧通过脱氢催化塔脱除氢和甲烷等杂质;
(5)脱水干燥:将步骤(4)除杂质后的电解氧经冷却器冷却后用汽水分离器脱除游离水,增压,增压后通过高压汽水分离器,进入分子筛塔除去水分和二氧化碳。
(6)过滤除尘:步骤(5)脱水干燥的电解氧经过滤器过滤,除去杂质,即得超纯氧。
所述步骤(1)中,预热温度优选95~100℃,在此温度范围内,Ar、N2、CO、CO2、H2、CH4和Cl2在水中的溶解度几乎为零(见表1、表2),优选预热时间为10~30min,将溶解在其中的Ar、N2、CO、CO2、H2、CH4和Cl2全部去除。
所述步骤(2)中预热软化水充高纯氧保压,保压压力优选0.02~0.04MPa,边保压边降温冷却,冷却温度优选0~40℃。由于高纯氧的保压作用,避免空气中Ar、N2、CO、CO2、H2、CH4和Cl2再次溶解在软化水中。
所述步骤(4)中采用脱氢催化塔,可降低催化脱氢反应的耗能,作为优化的,所述脱氢催化塔所用催化剂为中国科学院大连化学物理研究所研制的催化剂OC-2,能保证在有氧气氛下氧与杂质CH4、CO、H2反应生成CO2及H2O,所述脱氢催化塔工作温度优选180±20℃,通过该步骤可以进一步去除电解氧中的氢、烃类等杂质。
所述步骤(5)中采用高压汽水分离器和分子筛等设备,充分去除电解氧中的水分、二氧化碳等杂质,作为优化的,电解氧增压至15MPa,所述分子筛优选13XAPG分子筛,由两组组成,工作时一组使用,一组再生。
所述步骤(6)进一步对脱水干燥后的电解氧进行机械杂质的去除,使氧的纯度得到进一步的提高。通过步骤(6)获得的超纯氧在压缩充瓶前。对钢瓶进行特殊烘干处理,去除瓶内粉尘和水,烘干后水含量应低于0.3ppm,抽至真空后进行充装。
表1 气体在水中的溶解度
表2 氩气(Ar)在1体积水中的吸收系数
注:吸收系数,是指在气体分压等于101.325KPa时,被1体积水所吸收的该气体体积。
本发明的有益效果是:本发明研究出一种新型操作简单、行之有效的超纯氧制备方法,在对原料软化水进行预热处理时,N2、Ar等各种难于去除的杂质即被脱除,经电解后可得到超纯氧,区别于其他方法中将工业氧、高纯氧进行纯化的工艺路线,具有生产能耗低、流程效率高,工艺简单、成本低等特点。
具体实施方式
以下对本发明的优选实施例进行详细描述,优选实施例中未注明具体条件的实验方法,按照常规条件进行。
以下实施例使用的主要设备的信息为:2m3软化水罐,该软化水罐中设有加热盘管和冷凝装置;水电解制氧装置:型号:ZDQ-125/1.5,氧气额定产量:125Nm3/h;催化脱氢塔,该催化脱氢塔采用两组电加热装置来保证反应温度:干燥器:包括汽水分离器、高压汽水分离器和分子筛塔,其中2台分子筛在工作时一组工作,另一台再生。前述未标明具体型号的设备为工业常规设备,由市售购买所得。
实施例1
通过上述生产装置,按下述流程进行高纯氧的制备:
(1)预热:在常压下将2m3软化水罐中的软化水加热至100℃,加热时间为16min,将溶解在水中Ar、N2、CO、CO2、H2、CH4和Cl2全部除去;
(2)保压:向步骤(1)预热后的软化水罐中通入高纯氧气保压,保压压力为0.3MPa,边保压边降温冷却,冷却温度为30℃,由于高纯氧的保压作用,避免空气中Ar、N2、CO、CO2、H2、CH4和Cl2再次溶解在软化水中。
(3)电解:将步骤(2)中冷却至30℃的软化水通入水电解制氧装置进行电解,产出电解氧,经检测,其中还有水、二氧化碳等杂质。
(4)催化脱氢:将步骤(3)中产出的电解氧引入脱氢催化塔脱,在温度为180±20℃下,采用中国科学院大连化学物理研究所研制的催化剂OC-2进行催化,使电解氧中的杂质氧与氧反应生成水,得到含氧99.999%的电解氧。
(5)脱水干燥:将步骤(4)除杂后的电解氧经冷却器冷却后用汽水分离器脱除游离水,然后增压至15MPa后通过高压汽水分离器,随后进入分子筛塔进一步除去水分和二氧化碳,所述分子筛优选13XAPG分子筛,由两组组成,工作时一组使用,一组再生。
(6)过滤除尘:步骤(5)脱水干燥的电解氧经过滤器过滤,除去机械杂质,即得纯度为99.99995%的超纯氧,其各项指标详见表3。
在压缩充瓶前,盛装超纯氢的钢瓶经过特殊烘干处理,去除瓶内粉尘和水,抽至真空后进行充装,生产出瓶装超纯氢。
表3 实施例测试结果
上述具体实施方式仅是本发明的具体个案,本发明的专利保护范围包括但不限于上述具体实施方式的产品形态和式样,任何符合本发明权利要求书的一种超纯氧的制备方法且任何所属技术领域的普通技术人员对其所做的适当变化或修饰,皆应落入本发明的专利保护范围。

Claims (3)

1.一种超纯氧的制备方法,其特征在于,包括以下步骤:
(1)预热:将软化水罐中的软化水加热至95~100℃,预热时间为10~30min;
(2)保压:向步骤(1)预热后的软化水罐中通入高纯氧气保压,保压压力为0.02~0.04MPa,边保压边降温冷却,冷却温度为30℃;
(3)电解:将步骤(2)中的软化水经冷却后通入水电解系统进行电解,产出电解氧;
(4)催化脱氢:将步骤(3)中产出的电解氧通过脱氢催化塔脱除氢、甲烷,脱氢催化塔工作温度控制在160~200℃;
(5)脱水干燥:将步骤(4)除杂后的电解氧经冷却器冷却后用汽水分离器脱除游离水,增压至15MPa后通过高压汽水分离器,进入分子筛塔除去水分和二氧化碳,分子筛为13XAPG分子筛;
(6)过滤除尘:步骤(5)脱水干燥的电解氧经过滤器过滤,除去杂质,即得超纯氧。
2.根据权利要求1所述的一种超纯氧的制备方法,其特征在于:所述步骤(4)脱氢催化塔所用催化剂为中国科学院大连化学物理研究所研制的催化剂OC-2。
3.根据权利要求1所述的一种超纯氧的制备方法,其特征在于:所述步骤(6)获得的超纯氧在压缩充瓶前,对钢瓶进行烘干处理,去除钢瓶内粉尘和水,烘干后钢瓶水含量低于0.3ppm,抽真空灌装。
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