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CN100453447C - Technological method of purifying hydrogen of hydrogen enriched gas source - Google Patents

Technological method of purifying hydrogen of hydrogen enriched gas source Download PDF

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CN100453447C
CN100453447C CN 200610021537 CN200610021537A CN100453447C CN 100453447 C CN100453447 C CN 100453447C CN 200610021537 CN200610021537 CN 200610021537 CN 200610021537 A CN200610021537 A CN 200610021537A CN 100453447 C CN100453447 C CN 100453447C
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hydrogen
technological
method
gas
purifying
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CN 200610021537
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CN1903703A (en )
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吴素娟
伟 周
席怡宏
王业勤
王才全
马建新
高振平
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同济大学;四川亚联高科技有限责任公司;上海焦化有限公司
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Abstract

本发明公开了一种富氢气源提纯氢气的工艺方法,解决现有采用膜分离和/或变压吸附工艺提纯氢气存在的对原料气成分要求严格、应用范围不广、工艺复杂、装置占地大的技术问题,包括如下工序:a.原料气压缩;b.脱碳脱水;c.膜分离;d.催化反应脱氧;e.变压吸附,脱碳脱水工序设置在原料气压缩的2~3级压缩机之间,使用两塔吸附装置,两塔交替工作,利用没有通过膜分离工序的“慢气”进行吸附剂的再生,经过上述工序提取的氢气中氮气、烃类、氩气总量的体积含量低至0.08%以下,氢气的体积含量达到99.99%以上;本发明可广泛适用于各类富氢气源进行提纯氢气。 The present invention discloses a process of a method for purification of hydrogen source hydrogen rich gas, to solve the conventional membrane separation and / or the presence of pressure swing adsorption process for purification of hydrogen gas feed composition demanding, not broad range of applications, complex process, covering means large technical problem, comprising the steps of: a compressed gas feed; B decarburization dehydration; C separation membrane; catalytic deoxygenation D; E pressure swing adsorption, feed disposed decarburization dehydration step 2 to the compressed gas.... 3 between the compressor stages, using two adsorption towers apparatus, the two towers work, no regeneration of the adsorbent by using the "slow gas" membrane separation step, after the step of extracting hydrogen in nitrogen, hydrocarbons, argon total low amount of volume content of 0.08% or less, by volume hydrogen content reached 99.99%; the present invention is widely applicable to all types of purified hydrogen rich source of hydrogen.

Description

一种富氢气源提纯氢气的工艺方法 A process for the purification method of a hydrogen source of hydrogen-rich

技术领域 FIELD

本发明涉及一种提纯氢气的工艺方法,特别涉及一种利用膜分离、变压吸附工艺的各自特点进行工序组合,达到提高氢气提取纯度和回收率的一种富氢气源提纯氢气的工艺方法。 The present invention relates to a process for the purification of hydrogen gas, and in particular relates to a membrane separation, pressure swing adsorption process characteristics of each composition step, the process to achieve a method to improve the hydrogen rich source of purity and recovery of hydrogen extraction purification of hydrogen. 背景技术 Background technique

氢气是一种应用广泛的原材料,工业上作为原料气、还原气、冷却气、保护气和燃烧气,在化工、石油化工、冶金、机械加工、电力、医药、食品、玻璃、尖端技术和科学研究领域,有着广泛的用途;同时作为一种高效、清洁的能源,成为燃料电池燃料的首选。 Hydrogen is a widely used raw material as the raw material gas, reducing gas, cooled industrial gas, shielding gas and combustion gas, in the chemical, petrochemical, metallurgical, mechanical processing, power, medicine, food, glass, cutting-edge technology and science research field, has a wide range of uses; at the same time as an efficient, clean energy, become the preferred fuel cell fuel.

当前,国内向市场供氢的主要制氢方法有:以煤为原料的水煤气、半水煤气和焦炉气制氢;天然气和石油产品转化制氢;各种工业尾气的回收或氯碱工厂的副产品制氢;化学裂解制氢以及水电解制氢等。 Currently, the main methods of producing hydrogen for hydrogen to domestic market: coal as raw material of the water-gas, coke oven gas and semi-water gas hydrogen; hydrogen production from natural gas and petroleum products; recovery of various industrial exhaust gas or a byproduct of chlor-alkali plants hydrogen; chemical cleavage hydrogen water electrolysis hydrogen and the like. 根据不同的氢气气源和不同用氢场合对氢气质量的技术要求,可采用吸收、吸附(变压吸附和变温吸附)、 膜分离、金属氢化物及其连用的分离提纯技术。 Depending on the source of the hydrogen gas and hydrogen occasions different technical requirements for the quality of hydrogen, can be absorption, adsorption (pressure swing adsorption and temperature swing adsorption), membrane separation, and a metal hydride conjunction separation and purification techniques. 其中,为了有效地从各种工业尾气中提出氢气,降低资源浪费,实现"变废为宝",目前多采用--种或几种气体提纯技术相结合,从富氢气体中提纯氢气。 Wherein, in order to effectively raise the hydrogen from a variety of industrial exhaust gas, reduce waste of resources, and "turning waste into treasure", currently used - one or several gas purification technology combined with purified hydrogen from the hydrogen-rich gas.

1. 欧洲专利局2004年6月18日发布的公告号为FR2848548-A1的发明专利-一通过对含氧烃类气体进行部分催化氧化生产受控含量的氢气和一氧化碳混合气的方法(Process for generation of a mixture of controlled content of hydrogen and carbon monoxide by partial catalytic oxidation of a hydrocarbon in the presence of an oxygen-containing gas)。 1. The European Patent Office on June 18, 2004 as Publication No. issued patents FR2848548-A1 - by a method partially oxygenated hydrocarbon gas hydrogen and carbon monoxide content of the gas mixture of the catalytic production of controlled oxidation (Process for generation of a mixture of controlled content of hydrogen and carbon monoxide by partial catalytic oxidation of a hydrocarbon in the presence of an oxygen-containing gas).

报道了采用含氢气体为原料气,经过催化氧化、变压吸附和膜分离生产氢气和—氧化碳混合气的工艺。 It reported the use of hydrogen-containing gas as the raw material gas, through a catalytic oxidation, membrane separation and pressure swing adsorption to produce hydrogen and - process carbon monoxide gas mixture. 这种工艺并没有从根本上解决从富氢气源中提纯氢气的目的,只能得到氢气和一氧化碳的混合气,为了得到纯度符合工业级标准的氢气还必须进行再-步的处理。 This process does not solve the underlying object of the purified hydrogen gas from the hydrogen rich source, only to give hydrogen and carbon monoxide mixed gas, in order to obtain hydrogen purity must meet the industry standards also re - process step.

2. 专利号为00110355.5的中国专利——以甲乙丙丁烷混合气为原料与二氧化碳及氧气反应制氢气的方法 2. Chinese patent No. 00110355.5 patent of - B and C in a mixed gas of butane feedstock to carbon dioxide and oxygen, the reaction of hydrogen

报道了--种以甲烷和(或)乙烷和(或)丙烷和(或)丁烷的混合气为原料'在稀土和碱金属修饰的Ni/Si—2或Ni/Y—^203催化剂上与二氧化碳及氧气催化氧化,反应产物经水蒸气变换反应,及变压吸附或膜分离制取氢气。 Reported - species and methane (or) ethane, and (or) propane and (or) butane mixed gas as a raw material 'rare earth and alkali metal modified Ni / Si-2 or Ni / Y- ^ 203 catalyst the catalytic oxidation to carbon dioxide and oxygen, the reaction product was steam shift reaction, and pressure swing adsorption or membrane separation to produce hydrogen. This

种工艺实际上是烃类气体在催化剂的作用下与氧气发生部分氧化反应,最后通过膜分离或变压吸附(简称为PSA)工艺得到纯氢。 Process is actually a kind of hydrocarbon gas partial oxidation reaction occurs with oxygen in the catalyst, the last process to obtain pure hydrogen by membrane separation or pressure swing adsorption (referred to as PSA). 这种方法适用于以甲烷、 This method is suitable for methane,

乙烷、丙烷和丁烷的混合气如炼厂干气、炼厂湿气、油田气等气源直接制取氢气,实际上就是在一定程度上对这种工艺的原料进行了限制,不适用于更广泛范闺内的工业尾气制取氢,且工艺复杂、装置占地大。 Ethane, propane and butane mixed gas as refinery dry gas, refinery moisture, air and the like gas oil to produce hydrogen directly, in fact, to a certain extent on the material of such a process has been restricted, NA in the broader range of industrial exhaust Gui Preparation hydrogen, and the process is complicated, it occupies a large apparatus. 发明内容 SUMMARY

本发明的目的是:解决现有采用膜分离和/或变压吸附工艺提纯氢气存在的对原料气成分要求严格、应用范围不广、工艺复杂、装置占地大的技术问题, 提供一种适用范围广、产品气品质高、生产效率高的通用型富氢气源提纯氢气的工艺方法。 Object of the present invention are: to solve the conventional membrane separation and / or the presence of hydrogen pressure swing adsorption purification process feed gas composition strict requirements, a wide range of applications not, process complexity, a large area means the technical problem to provide a suitable wide range of high quality product gas, high-efficiency process for producing a hydrogen rich gas source universal purified hydrogen.

本发明的目的是通过下述技术方案来实现的: Object of the present invention is achieved by the following technical solution:

一种富氢气源提纯氢气的工艺方法,所述工艺方法包括如下工序- Process A method for purification hydrogen rich source of hydrogen, said process comprising the steps of -

a. 原料气压縮 a. feed gas compression

b. 脱碳脱水 b. decarbonization dehydration

c. 膜分离 c. separating membrane

d. 催化反应脱氧(简称为脱氧工序) d. deoxy-catalytic reaction (referred to as a deoxidation step)

e. 变压吸附(简称为PSA工序) 膜分离工序前加入脱碳脱水工序,可有效降低整个装置中的二氧化碳和水 e. Pressure swing adsorption (referred to as PSA step) was added before the dehydration step decarburization membrane separation step, the entire device can effectively reduce the carbon dioxide and water

的含量,减少后续装置的工作负荷。 Content, reduce the load follow-up device.

所述脱碳脱水工序设置在原料气压缩的2〜3级压缩机之间。 The decarburization step is disposed between the dewatering feed gas compression stage of the compressor 2 or 3.

所述脱碳脱水工序使用的装置为两吸附塔,两塔交替工作,利用没有通过膜分离工序的"慢气"进行吸附剂的再生。 The apparatus used for the dehydration step decarburization two adsorption towers, the two towers work, no regeneration of the adsorbent by using the "slow gas" membrane separation step.

由于整个系统是一个封闭系统,无法被完全脱除干净的二氧化碳和水分会在装置内部循环中不断累计,造成"富集",会对装置的运行效率和寿命造成很严重的影响,所以在压縮工段之间加入用于脱碳脱水的两塔装置,在原料气进入膜分离工序前,先对原料气中的二氧化碳和水分进行预处理,降低这两种物质的含量,有效解决"富集"的问题。 Since the whole system is a closed system, and can not be removed completely clean carbon dioxide and moisture accumulation will continue, resulting in causing a very serious impact on operational efficiency and lifetime of "enriched", the device would be circulated inside the device, so the pressure Add condensing section between two dewatering tower apparatus for decarburization, the feed gas prior to entering the membrane separation step, the raw material gas to carbon dioxide and water pretreatment, reduce the content of these two substances, an effective solution "enriched "The problem.

膜分离工序的入口气体压力为5.0〜6.0Mpa,经过膜分离工序后的出口气体是压力为0.9〜l.lMPa的渗透气(粗氢气)和压力为5.0〜6.0MPa的非渗透气。 The inlet gas pressure of the membrane separation step is 5.0~6.0Mpa, through the gas outlet of the membrane separation step is a pressure 0.9~l.lMPa permeate gas (crude hydrogen gas) and a pressure of the non-permeate gas 5.0~6.0MPa.

经过膜分离工序后的出口气体中,氮气、烃类、氩气总量的体积含量低至 After the gas outlet of the membrane separation step, nitrogen, hydrocarbons, the volume of total amount of the argon gas up

0.08%以下,氢气体积含量大于90%。 0.08% or less, the hydrogen content of greater than 90% by volume.

催化反应脱氧工序的温度为200°C±10°C,经过催化反应脱氧工序的气体中氣气浓度小于等于0.5ppm,压力为0.9Mpa。 The reaction temperature of the catalytic deoxygenation step is 200 ° C ± 10 ° C, gas concentration in the air after the gas catalytic deoxygenation step is smaller than or equal 0.5ppm, pressure was 0.9Mpa.

经过催化反应脱氧工序的出口气体,经冷却、除水后输送至变压吸附工序, 变压吸附工序的出口的产品气中,氢气体积含量大于等于99.99%:杂质含量为:一氧化碳《lppm,氮气《10ppm,氩气《40ppm, 二氧化碳《lppm,甲垸《lppm,氧气《0.5ppm。 After the gas outlet of the catalytic deoxygenation step, cooled, sent to the pressure swing adsorption step in addition to the water outlet of the pressure swing adsorption step in the product gas, the hydrogen content of not less than 99.99% by volume: impurity content of: Carbon Monoxide "lppm, nitrogen "10ppm, argon" 40ppm, carbon dioxide "lppm, A embankment" lppm, oxygen "0.5ppm.

变压吸附工序出口的解吸气回输给原料气并与之进行混合后,再进入脱碳脱水工序。 After the pressure swing adsorption step outlet gas desorbed and returned to the raw material mixed therewith, and then enter the decarburization dehydration step.

本发明将膜分离工序、脱氧工序、变压吸附工序三种工艺有机地结合起来, 并在膜分离前加入脱碳脱水工序,降低整个装置中的二氧化碳和水的含量,减少后续装置的工作负荷,成为一种适用范围广、产品品质高、生产效率高的通用變氣气提纯工艺。 The present invention is a membrane separation step, a deoxidation step, pressure swing adsorption process organically combine three processes, and decarbonization was added before the dehydration step membrane separation, to reduce the content of the entire apparatus in carbon dioxide and water, to reduce the workload of the follow-up means become a wide application range, high product quality, high production efficiency of the gas purification process gas becomes universal.

本发明公开的工艺方法具有如下有益效果: The inventive process disclosed herein has the following advantages:

① 利用膜分离系统对氮气、烃类、氩气(即所谓"慢气")有极其优异的分离效果,而变压吸附对氮气、烃类、氩气的分离效果不明显的特点,将膜分离工序置于变压吸附工序前端,以便对氮气、烃类、氩气进行有效的分离,可严格控制进入变压吸附工序的氮气、烃类、氩气、 一氧化碳气体总量,通过膜分离工序可以得到体积含量大于90%的粗氢气,为变压吸附工序提供工艺条件 ① using a membrane separation system has a very excellent separation of nitrogen, hydrocarbons, argon (so-called "slow gas"), and the pressure swing adsorption separation of nitrogen, hydrocarbons, argon obvious characteristics of the film placed in a pressure swing adsorption separation process step the front end, for effective separation of nitrogen, hydrocarbons, argon, nitrogen can strictly control proceeds, hydrocarbons, argon, carbon monoxide gas, the total pressure swing adsorption process, by membrane separation step obtained crude hydrogen content of 90% by volume, to provide conditions for the pressure swing adsorption step of the process

较好的JT料气; JT preferred feed gas;

② 当原料气中的一氧化碳浓度较高时,变压吸附工序需要配备大量吸附剂,以牺牲氢气回收率为代价分离一氧化碳,而膜分离工艺可以在保证氢气回收率很高的前提下,对-一氧化碳进行有效的分离; ② When a high concentration of carbon monoxide in the feed gas, pressure swing adsorption process with a large amount of adsorbent required, at the expense of separating the hydrogen recovery at the expense of carbon monoxide, and the membrane separation process can ensure a high hydrogen recovery under the premise of the - effective separation of carbon monoxide;

③ 膜分离系统对二氧化碳的分离效果很差,不能分离出水,而变压吸附工序利用吸附剂可以很轻松地分离出水和二氧化碳; ③ membrane separation system for carbon dioxide separation is poor, water can not be separated, the pressure swing adsorption process using an adsorbent can be easily separated from water and carbon dioxide;

©在变压吸附工序前增加催化脱氧工序,可在原料气进入变压吸附工序前除去原料气中所含氧气,将氧气含量降低到0.5ppm以下,有效降低变压吸 © increase the pressure swing adsorption process prior to catalytic deoxygenation step may be to remove oxygen contained in the feed gas before the feed gas enters the pressure swing adsorption process, to reduce the oxygen content to 0.5ppm or less, reduce the pressure swing adsorption

附r序的负荷; R load attachment sequence;

⑤在原料气压縮工序中压縮机的2〜3级之间加入脱水脱碳工序,有效降低原料气中二氧化碳和水分的含量,避免造成二氧化碳和水分的在整个装置中 2 or 3 is added between in stage ⑤ compressor feed gas compression dehydration step decarburization step, effectively reduce the carbon dioxide content of the feed gas and water, to avoid carbon dioxide and moisture in the entire device

不断循环,造成这两种物质"富集"现象的发生; Continuous cycle, resulting in both substance "enrichment" phenomenon occurs;

⑥根据工序之间的相互配合与补充,可以得到氢气体积含量大于等于99.99%的纯氢产品气。 ⑥ The mutual cooperation between the complementary step, the volume content of hydrogen can be greater than or equal to 99.99% pure hydrogen product gas.

利用上述工序的联合工艺提纯氢气,不仅具有较广的氢源适应性(对于氢气体积含量从60%〜90%的富氢气源都可适用),而且对原料气的压力也具有^T的适应性(100〜4100kPa)。 Using the combined process of hydrogen purification step, not only has a wide adaptability of a hydrogen source (hydrogen volume content may be suitable for from 60% ~ 90% of the hydrogen rich source), and the pressure of the feed gas also has to adapt ^ T sex (100~4100kPa).

可见,采用上述工序和工艺的本发明,与背景技术中的工艺方法相比,有益效果明显,可广泛适用于富氢气源提纯氢气的工艺中。 Be seen, the present invention employs the above-described steps and processes, as compared with the background art process methods, the beneficial effect is obvious, and can be widely applied to a hydrogen-rich source of hydrogen purification process. 具体实施方式 detailed description

卜'面结合具体实施例对本发明作进一步的说明。 Bu 'plane in conjunction with specific embodiments of the present invention will be further described.

在列举具体实施例之前,先简单讲述膜分离工艺和变压吸附工艺的特点。 Before particular embodiments exemplified embodiment, the first membrane separation process briefly the pressure swing adsorption process and characteristics.

膜分离工艺的工作原理就是利用一种高分子聚合物薄膜来选择过滤原料气而达到气体分离的目的(膜材料通常是聚酰亚胺或聚砜)。 Working principle of membrane separation process is the use of a polymer of the polymer film is selected to achieve the purpose of filtering the raw material gas in gas separation (membrane material typically polyimide or polysulfone). 当两种或两种以上的气体混合物通过聚合物薄膜时,各气体组分在聚合物中的溶解扩散系数的菱异,导致其渗透通过膜壁的速率不同。 When two or more kinds of the gas mixture through the polymer film, the diffusion coefficient of each gas dissolved in the polymer components different Ling, resulting in its penetration rate by different membrane wall. 通常直径较小或极性较强的分子透过胺的渗透速率较快,称之为"快气",如C02、 H20、 H2、 He等;反之,称为"慢气",如N2、 Ar、 CH4或其他烃类等。 Generally small molecules or polar diameter amine faster rate of permeation, called "fast gas", such as C02, H20, H2, He and the like; the other hand, known as the "slow gas", such as N2, ar, CH4 or other hydrocarbons. 膜分离系统的核心部件是膜分离器, 其构造与管壳式换热器相类似,将数万根细小的中空纤维丝浇铸成管束而置于承压管壳内。 The core component membrane separation system is a membrane separator, which is configured with a shell and tube heat exchanger is similar to several tens of thousands of fine hollow filaments into a bundle and placed in casting pressure tubular housing. 当混合气进入分离器后,在驱动力(膜两侧相应组分压差)的作用下,沿纤维的一侧轴向流动,"快气"不断透过膜壁而在低压渗透侧富集, 通过渗透气出口排出,而"慢气"则在高压滞留侧富集,从与气体入口相对的另一端非渗透气出口排出。 When the gas mixture enters the separator, under the driving force (pressure difference across the membrane respective components), the axial flow along the side of the fiber, "fast gas" enriched continuously through the membrane wall in a low pressure permeate side , is discharged through permeate outlet, while the "slow gas" enriched retentate side of the high pressure, non-permeate gas from the outlet and inlet of the opposite end of the gas discharge.

变压吸附(PSA)工艺也广泛应用于工业气体的分离提纯,在分离过程中, 气体组分在升压时吸附,降压时解吸,不同组分由于其吸附和解吸的特征不同, 在压力周期性的变化过程中实现分离。 Pressure swing adsorption (PSA) processes are also widely used in industrial gas separation and purification, in the separation process, the gas components adsorbed on the boost, buck desorption characteristics because of its different components to different adsorption and desorption at a pressure periodic variation during separation. 变压吸附分离过程一般在中低压条件下进行,操作简单,自动化程度高,设备不需要特殊材料;原料气中的C02、H20、 CO、 CH4以及少量硫化物(硫含量低于50ppm)等工业上常见的有害组分可同对除去。 Pressure swing adsorption process is generally carried out under low pressure conditions, simple operation, high degree of automation, the device does not require special materials; feed gas C02, H20, CO, CH4 and small amounts of sulfur compounds (sulfur content below 50ppm) and other industrial the same may be common to remove harmful components.

实施例l:原料气成分及摩尔含量如表1所示,原料气的压力为100kPa, 温度为40 °C。 Embodiment Example l: molar composition and pressure of the feed gas contents as shown in Table 1 as the raw material gas 100 kPa, a temperature of 40 ° C. 原料气和变压吸附工序的尾气(即解吸气)在混合器内混合(初々站介段无解吸气),原料气源压力高低决定于混合器内压力的高低,有着较好的压力适应性。 Feed gas and the exhaust gas pressure swing adsorption processes (i.e., desorbed) mixing (First 々 station via the intake section no solution) in a mixer, the raw material gas supply pressure determines the level of the pressure level of the mixer, have better pressure adaptability. 将上述混合气输入压缩机进行压縮,为了达到需要的压力,压 The mixture gas input to the compressor is compressed to achieve the required pressure, pressure

缩机为多级,在2〜3级压縮机之间安装脱碳脱水吸附塔对原料气进行脱碳脱水。 Multistage compressor, mounted between the adsorber decarburization dewatering stage 2 or 3 to the compressor feed gas dehydration decarburization.

表1 实施例1的原料气成分及含量表 Table feed gas composition and content of Table 1 of Example 1

<table>table see original document page 7</column></row> <table>脱碳脱水工序采用两塔交替工作,其中一塔在工作时(即吸附二氧化碳和水份),另一塔利用膜分离工序的高压富集侧的"慢气"进行冲洗,将其中已经被吸附的二氧化碳和水份脱除,输送至低压瓦斯罐,同时已经被净化的原料气进入后续工序进行氢气的提纯,这套脱碳脱水装置保证进入膜分离工序的原 <Table> table see original document page 7 </ column> </ row> <table> dehydration step using the decarburization work two towers, one tower is in operation (i.e., adsorption of carbon dioxide and water), the other film Tully high pressure separation step is enriched "slow gas" side of the rinsing, which will have been adsorbed carbon dioxide and water removal, to a low pressure gas delivery tank, while the feed gas has been purified into the downstream processes for purification of hydrogen gas, which decarburization ensure that the original set of dewatering apparatus into the membrane separation step

枓气中二氧化碳的体积含量始终保持在3%左右,水份的含量始终保持在10ppm以下,避免二氧化碳和水份的"累积"。 Tu volume content of carbon dioxide gas is always maintained at around 3%, the moisture content is kept at 10ppm or less, carbon dioxide and moisture to avoid the "accumulation."

将混合气压力提升到5.5MPa后,输入膜分离器,对混合气进行膜分离处理,得到压力为0.9MPa的渗透气(粗氢气)和压力为5.8MPa的非渗透气(膜分离装置尾气),为减少进入变压吸附装置的氧含量,降低变压吸附装置的负荷,在粗氢气进入变压吸附装置制氢前,增加了一级催化反应脱氧装置,脱氧温度大约为200°C±10°C,经过脱氧装置后气体的氧含量约0.5ppm左右。 After the mixed gas pressure is raised to 5.5MPa, enter the membrane separator, the mixture gas membrane separation to give a pressure of 0.9MPa permeate gas (crude hydrogen gas) and a pressure of 5.8MPa non-permeate gas (off-gas membrane separation apparatus) , to reduce the oxygen content into the pressure swing adsorption apparatus, reduce the load on the pressure swing adsorption apparatus in the crude hydrogen gas before entering hydrogen pressure swing adsorption apparatus, an increase of catalytic deoxygenation apparatus deoxygenation temperature of about 200 ° C ± 10 ° C, the oxygen content after deoxidation means about the gas around 0.5ppm. 最后经过脱氧后的气体直接进入变压吸附装置进行下一步分离,可得到体积含量大子99.99%的纯氢气体。 Finally, after the deoxygenation gas directly into the next swing adsorption apparatus for separating, to obtain a large volume of sub-content 99.99% pure hydrogen gas.

脱轼工序设置在膜分离工序之后是基于两方面的考虑,尽管现在的脱氧催化剂町以耐CO,但是CO对其脱氧效果仍然是有影响的。 Shi removal step is provided after the membrane separation step is based on two considerations, although the present deoxygenation catalyst to resist cho CO, CO its deoxidizing effect but still influential. 一般情况下是采用提霜反应温度来解决这个问题;若将脱氧工序设置在膜分离工序之前,催化反应产生的水会在该工况条件下达到饱和,这将会影响膜分离工序的正常运行。 Generally the reaction temperature is the use of extract cream to solve this problem; If deoxidation step is provided before the membrane separation step, a catalytic reaction of water will reach saturation at the working conditions, which will affect the normal operation of the membrane separation step .

在本实施例中选择了膜分离工序在前,变压吸附.T序在后的工艺模式,并托膜分离工序和变压吸附工序之间加入了脱氧工序。 Membrane separation step preceding the selected process mode after the pressure swing adsorption sequence .T, care and pressure swing adsorption and membrane separation step is added between step deoxygenation step according to the present embodiment. 这种工艺模式能够充分发挥膜分离和变压吸附各自的特性优势,提高装置整体的性能指标。 Such a process model can give full play to pressure swing adsorption and membrane separation respective characteristics to improve its overall performance of the device. 膜分离的特点是:在渗透压差足够大的条件下,能够有效地除掉N2、烃类、Ar、 CO气体, 获得较高的氢气收率,而且N2、烃类、Ar、 CO这类气体对变压吸附而言,均为分离系数比较低的组分,用膜分离工艺可以将N2、烃类、Ar、 CO气体大部分除去,这无疑给变压吸附(PSA)提供了良好的气源组成条件。 Membrane separation is characterized by: a sufficiently large difference in osmotic pressure conditions, can be effectively removed N2, hydrocarbons, Ar, CO gas, to obtain a high yield of hydrogen, and N2, hydrocarbons, Ar, CO such for pressure swing adsorption gas, are relatively low separation factor component may be N2, hydrocarbons, Ar, CO gas is mostly removed by membrane separation process, no doubt to pressure swing adsorption (PSA) provides a good source gas composition conditions. 膜分离制氢 Hydrogen separation membrane

产品氢气的纯度一般不高,为86〜96%,这也是把它放在第一级的主要原因; 变压吸附的突出优点是产品纯度高,在气源条件达到变压吸附所要求的气源标 Purity hydrogen gas is generally not high, is 86~96%, which is mainly due to put it in a first stage; pressure swing adsorption outstanding advantages of high product purity, the gas source to achieve the required gas pressure swing adsorption source standard

准时,产品氢气的纯度可达99.9999% (体积含量),氢气的回收率为大于75 %,所以将变压吸附工序作为最终出产品的工序。 Time, the hydrogen purity of the product up to 99.9999% (volume fraction), the recovery of hydrogen is greater than 75%, so the final step of the pressure swing adsorption process as a product.

工序的位置设置也符合了原料气压力的合理分配。 Position setting step is also in line with a reasonable distribution of the feed gas pressure. 膜分离工序的工作压力比较高,为5.5MPa (在规定压力范围内),放在位置较前的工序,渗透降压和脱氧后的粗氢气的压力正好适合变压吸附工序的工作压力。 Membrane separation step operating pressure is relatively high, is 5.5MPa (within a predetermined pressure range), on the location of the previous step, the crude hydrogen gas pressure after penetration and deoxygenated blood pressure just right for the pressure swing adsorption step operating pressure. 操作压力的确定是从后往前,按照最经济的模式来确定。 The operating pressure is determined from the back, in accordance with the determined most economical mode.

变压吸附的任务是提纯氢气,因为对产品品质的要求很高,在本例中,采用了一次均压的变压吸附模式;从简单使用的角度出发,本例中吸附剂的再生选用了冲洗再生模式。 The pressure swing adsorption hydrogen purification task, because of the high demands on product quality, in the present embodiment, using a pressure swing adsorption mode of the pressure equalization time; from the perspective of easy use, regeneration of the adsorbent of the present embodiment selected rinse regeneration mode. 在这种模式下,合理的操作压力应在0.8〜1.2MPa之间, 考虑到此操作压力对膜分离操作压差和压比的影响,变压吸附操作压力确定为0.8MPa。 In this mode, a reasonable operating pressure should be between 0.8~1.2MPa, on consideration of this film influence the operating pressure and the operating pressure of the separation pressure ratio, pressure swing adsorption pressure determined 0.8MPa. 确定了工艺模式后,三塔吸附结构即可定型。 After determining the mode of the process, the structure can be shaped three adsorption. 所以本例中变压吸附工序釆用3-l-1.5/P (吸附塔数量为3个,其中l个塔吸附, 一均半,其中半次先均至中间罐,然后再均至吸附塔,冲洗再生)工艺,操作压力0.8MPa。 Therefore, in the present embodiment preclude the use of pressure swing adsorption process of 3-l-1.5 / P (the number of adsorption column 3, where l adsorption tower, are a half, half of which are secondary to the first tundish, and then through both adsorption column rinsing regeneration) process, the operating pressure of 0.8MPa. 确定变压吸附操作压力后,膜分离工序的渗透压力即可确定: After determining the pressure swing adsorption operation pressure, the osmotic pressure of the membrane separation step can be determined:

变压吸附操作压力+脱氧压力损失=0.8+0.1 =0.9MPa + Deoxygenation pressure swing adsorption operation pressure loss = 0.8 + 0.1 = 0.9MPa

为保证膜分离工序的运行效率(适当的分离效果和氢气回收率)膜入口原料压力应达到5.0〜6.0MPa。 To ensure the operation efficiency of the membrane separation step (suitable separation and recovery of hydrogen) film feed inlet pressure should reach 5.0~6.0MPa. 在本例中,原料气通过膜分离的压差AP-4.5〜 5.0MPa时,氢气回收率在90%上下,上限和下限相差3〜4个百分点。 In the present embodiment, the feed gas separation membrane when the pressure difference AP-4.5~ of 5.0 MPa, the hydrogen recovery of 90% up and down, upper and lower limits differ by 3 to 4 points. 如果膜入口原料气压力降低到4.0〜4.5MPa,氢气的回收率就会降低到85%以下,这对整体装置的生产指标影响就很大。 If the film inlet feed gas pressure is reduced to 4.0~4.5MPa, hydrogen recovery will be reduced to below 85%, which means the effect on the overall production index is enormous. 因此,本例中原料气压力压縮提升至5.5MPa。 Thus, in this example compressed feed air pressure up to 5.5MPa.

经过上述工序后,得到的产品成分及含量如表2所示,产品气的压力为800kPa,温度为40。 After the above step, the resulting product composition and pressure as the content shown in Table 2 is a product gas of 800 kPa, a temperature of 40. C。 C.

表2 实施例1的产品气成分及含量表 TABLE product gas composition and content of Table 2 of Example 1

<table>table see original document page 8</column></row> <table> <Table> table see original document page 8 </ column> </ row> <table>

实施例2:基本工艺方法如实施例l,其中原料气的成分与含量如表3所示,原料气的压力为100kPa,温度为40'C。 Example 2: process for basic ingredients of embodiment L, wherein the content of the feed gas pressure as shown in Table 3 as the feed gas 100 kPa, a temperature of 40'C.

将混合气压力提升到5.0MPa后,输入膜分离器,对混合气进行膜分离处理,得到压力为l.OMPa的渗透气(粗氢气)和压力为5.2MPa的非渗透气(膜 After the mixed gas of 5.0 MPa pressure is raised to, enter the membrane separator, the mixture gas membrane separation to give a pressure of l.OMPa permeate gas (crude hydrogen gas) and a pressure of 5.2MPa non-permeate gas (membrane

分离装置尾气),其它工艺参数与实施例l相同。 Off-gas separation means), other process parameters the same as Example l.

表3 实施例2的原料气成分及含量<table>table see original document page 9</column></row> <table>的产品气成分及含量如表6所示,产品气的压力为 Product gas composition and content of Table 3 Example 2 and the content of the feed gas composition <table> table see original document page 9 </ column> </ row> <table> pressure as shown in Table 6 for the product gas

经过h述工序得到800kPa,温度为40。 After said step h to give 800kPa, a temperature of 40. C。 C.

表6 实施例3的产品气成分及含量表<table>table see original document page 9</column></row> <table> Table 6 Example Product gas composition and content of Table <table> 3 of table see original document page 9 </ column> </ row> <table>

Claims (5)

1、一种富氢气源提纯氢气的工艺方法,其特征在于:所述工艺方法包括如下工序, a.原料气压缩b.脱碳脱水c.膜分离d.催化反应脱氧e.变压吸附所述脱碳脱水工序设置在原料气压缩的2~3级压缩机之间,以降低原料气中二氧化碳和水分的含量;所述脱碳脱水工序使用的装置为两吸附塔,两塔交替工作,利用没有通过膜分离工序的“慢气”进行吸附剂的再生; 所述膜分离工序的入口气体压力为5.0~6.0Mpa,经过膜分离工序后的出口气体是压力为0.9~1.1Mpa的渗透气和压力为5.0~6.0Mpa的非渗透气; 所述催化反应脱氧工序的温度为200℃±10℃,经过催化反应脱氧工序的气体中氧气浓度小于等于0.5ppm,压力为0.9Mpa。 1. A process for purification of hydrogen rich hydrogen source, wherein: said process comprising the steps of, A compressed feed gas separation membrane b c d decarburization dehydration reaction catalyzed deoxygenation of the pressure swing adsorption e..... decarburizing said dehydration step is provided between the compressed feed gas compressor 2 to 3, to reduce the carbon dioxide content of the feed gas and water; apparatus used in the dehydration step decarburization two adsorption towers, the two towers work, no regeneration of the adsorbent by using the "slow gas" membrane separation step; an inlet gas pressure of the membrane separation step is 5.0 ~ 6.0Mpa, through the gas outlet of the membrane separation step is a permeate pressure of 0.9 ~ 1.1Mpa and the non-permeate gas pressure is 5.0 ~ 6.0Mpa; and the reaction temperature of the catalytic deoxygenation step was 200 ℃ ± 10 ℃, the oxygen concentration in the gas after the catalytic deoxygenation step is smaller than or equal 0.5ppm, pressure was 0.9Mpa.
2、 如权利要求1所述的一种富氢气源提纯氢气的工艺方法,其特征在于: 经过膜分离工序后的出口气体中,氮气、烃类、氩气总量的体积含量低至0.08% 以下,氢气体积含量大于90%。 2. The one-rich process for the purification of a hydrogen source of hydrogen, characterized in that: the gas outlet through the membrane separation step, nitrogen, hydrocarbons, the volume content of the total amount of argon up to 0.08% hereinafter, the hydrogen content of greater than 90% by volume.
3、 如权利要求1所述的一种富氢气源提纯氢气的工艺方法,其特征在于: 经过催化反应脱氧工序的出口气体,经冷却、除水后输送至变压吸附工序,变压吸附工序的出口的产品气中,氢气体积含量大于等于99.99%。 3. The one source of hydrogen rich gas according to claim 1 of the process for purification of hydrogen gas, wherein: the gas through the outlet of the catalytic deoxygenation step, cooled, sent to the pressure swing adsorption step in addition to the water, pressure swing adsorption step product gas outlet, the volume of the hydrogen content of 99.99%.
4、 如权利要求3所述的一种富氢气源提纯氢气的工艺方法,其特征在于: 变压吸附工序出口处的产品气中,杂质含量为: 一氧化碳《lppm,氮气《 10ppm,氩气《40ppm, 二氧化碳《lppm,甲烷《lppm,氧气《0.5ppm。 4, one kind of hydrogen-rich gas as claimed in claim 3, wherein the source process for the purification of hydrogen, characterized in that: the product gas at the outlet of a pressure swing adsorption process, the impurity content of: Carbon Monoxide "lppm, nitrogen" 10 ppm, argon " 40ppm, carbon dioxide "lppm, methane" lppm, oxygen "0.5ppm.
5、 如权利要求1或2或3或4所述的一种富氢气源提纯氢气的工艺方法, 其特征在于:变压吸附工序出口的解吸气回输给原料气进行混合。 5. The one hydrogen rich source 1 or 2 or 3 or 4, wherein the process for purification of hydrogen gas, wherein: a pressure swing desorption step returned to the intake port feed gas mixture.
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