CN111733427A - A kind of electrolysis seawater hydrogen production system and method thereof - Google Patents

A kind of electrolysis seawater hydrogen production system and method thereof Download PDF

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CN111733427A
CN111733427A CN202010649095.5A CN202010649095A CN111733427A CN 111733427 A CN111733427 A CN 111733427A CN 202010649095 A CN202010649095 A CN 202010649095A CN 111733427 A CN111733427 A CN 111733427A
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seawater
electrolysis
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tank
hydrogen
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苗鹤
户睿淦
袁金良
尹明明
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Ningbo University
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    • CCHEMISTRY; METALLURGY
    • 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
    • C25B1/01Products
    • C25B1/02Hydrogen or oxygen
    • C25B1/04Hydrogen or oxygen by electrolysis of water
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/36Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

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Abstract

本发明公开了一种电解海水制氢***,包括太阳能光伏发电单元,用于为电解海水单元提供电能;电解海水单元,用于电解海水制氢并副产甲酸盐;甘油滴加单元,用于向电解海水单元自动、定量地添加甘油,保证电解海水单元中的电解池中甘油浓度稳定;氢气收集单元,用于收集电解海水单元电解海水时产生的氢气;以及余液回收单元,用于回收电解海水单元电解海水时产生的甲酸盐。本发明的电解海水制氢***,一方面,具有能耗低,操作方便及耐腐蚀等优点,可满足在海水等恶劣条件下的长期稳定运行要求;另外一方面,可回收高价值甲酸盐副产物,具有良好的经济价值。

Figure 202010649095

The invention discloses a hydrogen production system by electrolysis of seawater, comprising a solar photovoltaic power generation unit for providing electric energy for the seawater electrolysis unit; an electrolysis seawater unit for producing hydrogen by electrolysis of seawater and by-producing formate; It is used to automatically and quantitatively add glycerol to the electrolysis seawater unit to ensure the stable concentration of glycerin in the electrolytic cell in the electrolysis seawater unit; the hydrogen collection unit is used to collect the hydrogen generated during the electrolysis of seawater in the electrolysis seawater unit; and the residual liquid recovery unit is used for Recovers formate produced during seawater electrolysis in the seawater electrolysis unit. On the one hand, the electrolysis seawater hydrogen production system of the present invention has the advantages of low energy consumption, convenient operation, corrosion resistance, etc., and can meet the requirements of long-term stable operation under harsh conditions such as seawater; on the other hand, high-value formate can be recovered By-products with good economic value.

Figure 202010649095

Description

一种电解海水制氢***及其方法A kind of electrolysis seawater hydrogen production system and method thereof

技术领域technical field

本发明涉及电解制氢的技术领域,具体的说涉及一种电解海水制氢***及其方法。The invention relates to the technical field of electrolysis of hydrogen production, in particular to a system and method of electrolysis of seawater for hydrogen production.

背景技术Background technique

氢气具备热值高,无污染,可再生性等特点,是最具有前景的新能源。电解水制氢技术是目前工业上获得氢气的一种方式,全球4%的氢气都来源于电解水,其原理是在电驱动下,电解池中的水在阴极还原成氢气,阳极氧化成氧气。电解水制氢技术已经非常成熟,但其现有技术仍具有一定的缺陷。第一,电解水制氢有很高的成本,消耗大量的电能,从而无法进行大规模的制备氢气来储能;第二,电解水制氢技术应用于大规模的工业,同时会造成淡水资源的缺乏问题。Hydrogen has the characteristics of high calorific value, no pollution and renewability, and is the most promising new energy source. Hydrogen production by electrolysis of water is a way to obtain hydrogen in industry. 4% of the world's hydrogen comes from electrolyzed water. . The technology of electrolysis of water for hydrogen production is very mature, but its existing technology still has certain defects. First, hydrogen production from water electrolysis has a high cost and consumes a lot of electric energy, so large-scale hydrogen production cannot be used for energy storage; lack of problems.

基于上述的技术缺陷,采用太阳能与电解海水制氢结合,利用太阳能降低成本,电解海水避免淡水资源的减少,可解决上述的技术缺陷。但同时引入了新的技术不足,电解海水阳极发生OER反应时,氯离子电解会同时产生氯气,氯气与其反应产物(次氯酸盐)会腐蚀电极,损坏***,降低了电解装置的使用寿命。Based on the above-mentioned technical defects, the above-mentioned technical defects can be solved by combining solar energy with electrolysis of seawater to produce hydrogen, using solar energy to reduce costs, and by electrolyzing seawater to avoid the reduction of freshwater resources. However, at the same time, the introduction of new technologies is insufficient. When the OER reaction occurs in the electrolytic seawater anode, the chloride ion electrolysis will simultaneously generate chlorine gas, and the chlorine gas and its reaction product (hypochlorite) will corrode the electrode, damage the system, and reduce the service life of the electrolysis device.

鉴于此,亟需提供一种电解海水制氢***,以防止电解过程产生氯气并腐蚀电极,从而造成电解***的损坏问题。In view of this, there is an urgent need to provide a system for producing hydrogen by electrolysis of seawater, so as to prevent chlorine gas from being generated during the electrolysis process and corrode electrodes, thereby causing damage to the electrolysis system.

发明内容SUMMARY OF THE INVENTION

鉴于以上现有技术的不足之处,本发明的主要目的在于提供一种电解海水制氢***,以解决现有制氢***能耗高,淡水资源消耗大及电解***易腐蚀等问题,从而使其满足诸如在海水等恶劣条件下的长期稳定运行要求。In view of the deficiencies of the above prior art, the main purpose of the present invention is to provide a kind of electrolysis seawater hydrogen production system, to solve the problems such as high energy consumption of the existing hydrogen production system, large consumption of fresh water resources and easy corrosion of the electrolysis system, thereby making It meets the requirements for long-term stable operation in harsh conditions such as seawater.

为达到以上目的,本发明采用的技术方案为:In order to achieve the above purpose, the technical scheme adopted in the present invention is:

一种电解海水制氢***,所述***包括:A system for producing hydrogen by electrolysis of seawater, the system comprising:

太阳能光伏发电单元,所述太阳能光伏发电单元与电解海水单元相连,用于为电解海水单元提供电能;a solar photovoltaic power generation unit, the solar photovoltaic power generation unit is connected to the seawater electrolysis unit, and is used for providing electrical energy for the seawater electrolysis unit;

电解海水单元,用于电解海水制氢并副产甲酸盐;Seawater electrolysis unit, used to electrolyze seawater to produce hydrogen and by-produce formate;

甘油滴加单元,所述甘油滴加单元与电解海水单元相连,用于向电解海水单元自动、定量地添加甘油,保证电解海水单元中的电解池中甘油浓度稳定;a glycerol dripping unit, the glycerol dripping unit is connected with the electrolysis seawater unit, and is used to automatically and quantitatively add glycerol to the electrolysis seawater unit, so as to ensure the stable glycerin concentration in the electrolytic cell in the electrolysis seawater unit;

氢气收集单元,所述氢气收集单元连接至电解海水单元的顶部,用于收集电解海水单元电解海水时产生的氢气;以及a hydrogen collecting unit, the hydrogen collecting unit is connected to the top of the seawater electrolysis unit, and is used for collecting hydrogen generated when the seawater electrolysis unit electrolyzes seawater; and

余液回收单元,所述余液回收单元连接至电解海水单元底部,用于回收电解海水单元电解海水时产生的甲酸盐。The residual liquid recovery unit, which is connected to the bottom of the electrolysis seawater unit, is used for recovering the formate produced during the electrolysis of seawater in the electrolysis seawater unit.

进一步地,所述太阳能光伏发电单元包括太阳能电池板、太阳能电源控制器、蓄电池和主控制板;所述太阳能电池板与太阳能电源控制器相连,用于接收太阳能的光照并转换为电能;所述蓄电池连接至太阳能电源控制器,用于电能的储存;所述主控制板输入端连接至太阳能电源控制器,用于接收太阳能电源控制器发出的控制信号,所述主控制板输出端连接至电解池中的阴极板和阳极板;所诉太阳能电源控制器,用于控制太阳能光伏发电单元信号的输入和输出。Further, the solar photovoltaic power generation unit includes a solar panel, a solar power controller, a storage battery and a main control panel; the solar panel is connected to the solar power controller, and is used for receiving solar light and converting it into electrical energy; the The battery is connected to the solar power controller for storage of electrical energy; the input end of the main control board is connected to the solar power controller for receiving the control signal sent by the solar power controller, and the output end of the main control board is connected to the electrolysis The cathode plate and the anode plate in the pool; the solar power controller is used to control the input and output of the signal of the solar photovoltaic power generation unit.

进一步地,所述电解海水单元包括电解池和电解液补充单元;所述电解液补充单元包括离心水泵、进水阀、高位水箱、第一控制阀和第二控制阀;所述进水阀设置在离心水泵和高位水箱之间的管路上,所述第一控制阀和第二控制阀设置在高位水箱和电解池之间的管路上,所述第一液位检测器设置在高位水箱内,所述第二液位检测器设置在电解池内。Further, the electrolytic seawater unit includes an electrolytic cell and an electrolyte replenishing unit; the electrolyte replenishing unit includes a centrifugal water pump, a water inlet valve, a high-level water tank, a first control valve and a second control valve; the water inlet valve is provided with On the pipeline between the centrifugal water pump and the high-level water tank, the first control valve and the second control valve are arranged on the pipeline between the high-level water tank and the electrolytic cell, and the first liquid level detector is arranged in the high-level water tank, so The second liquid level detector is arranged in the electrolytic cell.

进一步地,所述甘油滴加单元包括甘油储存箱、称重器、第一加料阀和第二加料阀;所述称重器设置在甘油储存箱的底部,所述第一加料阀设置在甘油储存箱和高位水箱之间的管路上,所述第二加料阀设置在甘油储存箱和电解池之间的管路上。Further, the glycerin dripping unit includes a glycerin storage tank, a weighing device, a first feeding valve and a second feeding valve; the weighing device is arranged at the bottom of the glycerin storage tank, and the first feeding valve is arranged at the glycerol storage tank. On the pipeline between the storage tank and the high-level water tank, the second feeding valve is arranged on the pipeline between the glycerin storage tank and the electrolytic cell.

进一步地,所述氢气收集单元包括洗涤器、干燥器和储气瓶;所述洗涤器和干燥器依次设置在电解池和储气瓶的连接管路上。Further, the hydrogen collection unit includes a scrubber, a dryer and a gas storage cylinder; the washer and the dryer are sequentially arranged on the connecting pipeline between the electrolytic cell and the gas storage cylinder.

进一步地,所述余液回收单元包括集液阀和余液容纳箱;所述集液阀设置在电解池和余液容纳箱的连接管路上。Further, the residual liquid recovery unit includes a liquid collecting valve and a residual liquid holding tank; the liquid collecting valve is arranged on the connecting pipeline between the electrolytic cell and the residual liquid holding tank.

进一步地,所述余液回收单元还包括蒸发罐、第一蒸馏罐和第二蒸馏罐;所述蒸发罐接收余液容纳箱中的余液,并进行水份的蒸发操作,所述蒸发罐内添加有无水乙醇,使蒸发残留物中的甲酸钠和甘油溶解其中,所述第一蒸馏罐接收蒸发罐中的甲酸钠、无水乙醇和甘油的混合物,并进行蒸馏操作,以使低沸点的无水乙醇从所述混合物中分离出来,并返回至蒸发罐中,所述第二蒸馏罐接收第一蒸馏罐中的剩余甘油和甲酸钠物质,并继续蒸馏操作。Further, the residual liquid recovery unit also includes an evaporation tank, a first distillation tank and a second distillation tank; the evaporation tank receives the residual liquid in the residual liquid holding box, and performs the evaporation operation of water content, and the evaporation tank Anhydrous ethanol is added to dissolve the sodium formate and glycerin in the evaporation residue, and the first distillation tank receives the mixture of sodium formate, anhydrous ethanol and glycerin in the evaporation tank, and conducts distillation operation to make the Absolute ethanol is separated from the mixture and returned to the evaporation tank, the second distillation tank receives the remaining glycerol and sodium formate species in the first distillation tank and continues the distillation operation.

主要功能如下:The main functions are as follows:

1.高位水箱上水功能:第一液位检测器检测高位水箱的水位为h1,0≤h1≤a;1. High-level water tank filling function: the first liquid level detector detects the water level of the high-level water tank as h1, 0≤h1≤a;

①0<h1<a时,不发生动作,即此时高位水箱液位处于合理范围,无需上水,不发生动作;①When 0<h1<a, no action occurs, that is, the liquid level of the high-level water tank is in a reasonable range at this time, and there is no need for water supply, and no action occurs;

②h1=0,关闭第一控制阀,打开进水阀,离心水泵动作,即高位水箱液位为零,此时进水阀和离心水泵动作,进行上水;②h1=0, close the first control valve, open the water inlet valve, and the centrifugal water pump will act, that is, the liquid level of the high-level water tank is zero. At this time, the water inlet valve and the centrifugal water pump will act to fill the water;

③h1=a,关闭进水阀,离心水泵停止,同时传递信号到主控制板,即高位水箱液位已满,停止离心水泵,关闭进水阀,同时传递信号到主板,启动甘油滴加功能,配置高位水箱中的甘油浓度;③h1=a, close the water inlet valve, the centrifugal water pump stops, and transmit a signal to the main control board at the same time, that is, the high water tank liquid level is full, stop the centrifugal water pump, close the water inlet valve, and transmit a signal to the main board at the same time, start the glycerin dripping function, Configure the glycerin concentration in the high water tank;

2.甘油滴加功能:2. Glycerol dripping function:

(1)每一高位水箱所需甘油质量为b g,主控制板10收到“高位水箱加满”信号后,将称重器当前值m设为c;(1) The mass of glycerin required for each high-level water tank is b g, and the main control board 10 sets the current value m of the scale to c after receiving the signal of "filling the high-level water tank";

①m>c-b时,第二加料阀打开;此时主控制板收到“高位水箱加满”信号后,甘油滴加功能启动,滴入所需甘油bg;①When m>c-b, the second feeding valve is opened; at this time, after the main control board receives the signal of "filling the high-level water tank", the glycerin dripping function is activated, and the required glycerin bg is dripped;

②m≤c-b时,第二加料阀关闭;此时甘油滴加bg完成,关闭阀门,完成甘油滴加工作;② When m≤c-b, the second feeding valve is closed; at this time, the dripping of glycerol bg is completed, and the valve is closed to complete the dripping of glycerin;

(2)电解池每5min消耗的甘油为dg,主控制板每过5min,将称重器当前值m设置为e;(2) The glycerol consumed by the electrolytic cell is dg every 5min, and the current value m of the scale is set to e every 5min of the main control board;

①m>e-d时,第一加料阀打开;周期性补充电解池中损耗的的甘油,每过5min,打开阀门,补充甘油dg;①When m>e-d, the first feeding valve is opened; the glycerol lost in the electrolytic cell is periodically replenished, and every 5min, the valve is opened to replenish glycerol dg;

②m≤e-d时,第一加料阀关闭;补充甘油dg完成,关闭阀门;②When m≤e-d, the first feeding valve is closed; when the supplement of glycerol dg is completed, the valve is closed;

3.电解池自动加电解质功能:第二液位检测器检测液位为h2,hmin≤h2≤hmax,hmin,hmax分别代表电解过程中设定液位上限值和下限值。3. The function of automatically adding electrolyte to the electrolytic cell: the liquid level detected by the second liquid level detector is h2, hmin≤h2≤hmax, hmin, hmax respectively represent the upper limit and lower limit of the liquid level set during the electrolysis process.

①hmin<h2<hmax,无动作;电解池中液位位于合理范围,无动作发生;①hmin<h2<hmax, no action; the liquid level in the electrolytic cell is within a reasonable range, and no action occurs;

②h2≤hmin,打开第一控制阀;电解池中液位低于合理范围,打开阀门,高位水箱向电解池中加入电解质;②h2≤hmin, open the first control valve; the liquid level in the electrolytic cell is lower than a reasonable range, open the valve, and the high-level water tank adds electrolyte to the electrolytic cell;

③hmax≤h2,关闭第一控制阀;电解池中液位高于合理范围,关闭阀门,停止加入电解质;③hmax≤h2, close the first control valve; if the liquid level in the electrolytic cell is higher than a reasonable range, close the valve and stop adding electrolyte;

④h2=0时,关闭集液阀,打开第二控制阀;甲酸盐回收功能完成,此时阀门动作,高位水箱向电解池中加入电解质,继续制氢;④When h2=0, close the liquid collecting valve and open the second control valve; the formate recovery function is completed, the valve is activated at this time, and the high-level water tank adds electrolyte to the electrolytic cell to continue hydrogen production;

4.甲酸盐回收功能:***运行时间t=T*N(T为回收周期设定值,N=1,2,3···)时,第二控制阀关闭,打开集液阀;每经过一个周期,阀门动作,进行甲酸盐的回收。4. Formate recovery function: When the system running time t=T*N (T is the set value of the recovery period, N=1, 2, 3...), the second control valve is closed and the liquid collecting valve is opened; After a cycle, the valve operates to recover formate.

相应地、一种电解海水制氢方法,所述方法包括以下步骤:Correspondingly, a method for producing hydrogen by electrolysis of seawater, the method comprises the following steps:

启动***开关,太阳能光伏发电单元首先启动,光照一段时间后,太阳能电源控制器9输出稳定电流,电解海水单元启动,开始进行电解海水操作,此时电解池阴极侧不断产出氢气,阳极侧副产甲酸钠物质;When the system switch is turned on, the solar photovoltaic power generation unit starts first. After lighting for a period of time, the solar power controller 9 outputs a stable current, the seawater electrolysis unit starts, and the seawater electrolysis operation begins. At this time, the cathode side of the electrolysis cell continuously produces hydrogen, and the anode side vice Sodium formate producing substances;

电解海水过程中,电解池液位降低至设定值下限,甘油滴加单元开始向电解池中滴加甘油,同时电解液补充单元中的高位水箱向电解池补充电解液,以维持电解池中甘油浓度的稳定,当电解池液位升高至设定值上限,完成电解液自动补充操作;During the electrolysis of seawater, the liquid level of the electrolytic cell drops to the lower limit of the set value, and the glycerol dripping unit begins to drip glycerol into the electrolytic cell. The glycerol concentration is stable. When the liquid level of the electrolytic cell rises to the upper limit of the set value, the automatic replenishment operation of the electrolyte is completed;

电解海水过程中,电解池阴极侧产出的氢气经过洗涤器和干燥器,以脱除氢气中所夹带的水份和杂质,然后通过回收管道进入氢气瓶中,进行氢气收集操作;以及During the electrolysis of seawater, the hydrogen produced on the cathode side of the electrolysis cell passes through a scrubber and a dryer to remove water and impurities entrained in the hydrogen, and then enters a hydrogen bottle through a recovery pipeline for hydrogen collection; and

电解海水一段时间后,停止电解海水操作,并将电解池中含有甲酸钠的余液排至余液容纳箱,余液排净后,电解池再次进行电解液自动补充操作,然后重新启动电解海水操作及后续的电解液自动补充操作和氢气收集操作。After the electrolysis of seawater for a period of time, the electrolysis of seawater is stopped, and the residual liquid containing sodium formate in the electrolytic cell is discharged to the residual liquid holding tank. After the residual liquid is drained, the electrolytic cell will perform the automatic replenishment operation of the electrolyte again, and then restart the electrolytic seawater operation. And the subsequent automatic replenishment operation of electrolyte and hydrogen collection operation.

进一步地,所述余液容纳箱中的余液输送至蒸发罐中,进行水份的蒸发操作,然后向所述蒸发罐内添加无水乙醇,搅拌使蒸发残留物中的甲酸钠和甘油溶解于无水乙醇中;再将甲酸钠、无水乙醇和甘油的混合物输送至第一蒸馏罐中,进行无水乙醇的蒸馏操作,以使低沸点的无水乙醇从所述混合物中分离出来;所述第一蒸馏罐中的剩余甘油和甲酸钠物质输送至第二蒸馏罐中,并继续蒸馏操作,所述第二蒸馏罐顶部出口为甘油,所述第二蒸馏罐底部得到甲酸钠副产物。Further, the residual liquid in the residual liquid holding box is transported to the evaporation tank, and the evaporation operation of water content is carried out, and then anhydrous ethanol is added to the evaporation tank, and the sodium formate and glycerin in the evaporation residue are dissolved in the evaporation residue by stirring. In dehydrated ethanol; then the mixture of sodium formate, dehydrated alcohol and glycerin is transported to the first distillation tank, and the distillation operation of dehydrated ethanol is carried out, so that the dehydrated alcohol with low boiling point is separated from the mixture; the The remaining glycerol and sodium formate substances in the first distillation tank are transported to the second distillation tank, and the distillation operation is continued. The top outlet of the second distillation tank is glycerol, and the bottom of the second distillation tank obtains the by-product of sodium formate.

进一步地,所述无水乙醇循环至蒸发罐,所述甘油循环至甘油储存箱。Further, the absolute ethanol is circulated to the evaporation tank, and the glycerol is circulated to the glycerol storage tank.

本发明的有益效果:Beneficial effects of the present invention:

本发明的电解海水制氢***,通过设置甘油滴加单元,将甘油与海水进行定量混合,配成一定浓度的电解质,以甘油的氧化反应来代替OER反应,降低了反应所需电压,避免了氯气的产生,从而避免了海水制氢过程中电极被氯气及其副产物腐蚀的问题。In the electrolysis seawater hydrogen production system of the present invention, by setting a glycerol dripping unit, glycerol and seawater are quantitatively mixed to form an electrolyte of a certain concentration, and the oxidation reaction of glycerol replaces the OER reaction, thereby reducing the voltage required for the reaction and avoiding the need for The generation of chlorine gas, thus avoiding the problem that the electrode is corroded by chlorine gas and its by-products in the process of hydrogen production from seawater.

本发明的电解海水制氢***,通过水泵、液位传感器、信号阀和称重器的联动控制,实现电解池中甘油的自动滴加补充,并维持电解池中甘油浓度的恒定。The electrolysis seawater hydrogen production system of the invention realizes the automatic dropwise addition of glycerin in the electrolytic cell and maintains the constant glycerin concentration in the electrolytic cell through the linkage control of the water pump, the liquid level sensor, the signal valve and the weighing device.

本发明的电解海水制氢***,通过余液回收单元对反应副产物甲酸盐进行高浓度富集,带来一定的经济价值。The electrolysis seawater hydrogen production system of the present invention carries out high-concentration enrichment of the reaction by-product formate through the residual liquid recovery unit, which brings certain economic value.

本发明的电解海水制氢***,通过设置太阳能光伏发电单元,将太阳能与电解海水结合,节约了淡水资源,同时解决了电解水成本高的问题。The electrolysis seawater hydrogen production system of the present invention combines solar energy with electrolyzed seawater by arranging a solar photovoltaic power generation unit, which saves fresh water resources and solves the problem of high cost of electrolyzed water.

附图说明Description of drawings

图1为本发明实施例1电解海水制氢***的示意图;1 is a schematic diagram of a hydrogen production system by electrolysis of seawater in Example 1 of the present invention;

图2为本发明实施例2电解海水制氢***的示意图;Fig. 2 is the schematic diagram of the hydrogen production system of electrolysis seawater in embodiment 2 of the present invention;

其中,称重器1、甘油储存箱2、水泵3、进水阀4、第一液位检测器5、高位水箱6、第二加料阀7、太阳能电池板8、太阳能电源控制器9、主控制板10、蓄电池11、第一控制阀12、第二控制阀13、第二液位检测器14、第一加料阀15、集液阀16、电解池17、余液容纳箱18、洗涤器19、干燥器20、储气瓶21、蒸发罐22、第一蒸馏罐23、第二蒸馏罐24、海高位水箱25。Among them, the weighing device 1, the glycerin storage tank 2, the water pump 3, the water inlet valve 4, the first liquid level detector 5, the high-level water tank 6, the second feeding valve 7, the solar panel 8, the solar power controller 9, the main Control board 10, battery 11, first control valve 12, second control valve 13, second liquid level detector 14, first feeding valve 15, liquid collecting valve 16, electrolytic cell 17, residual liquid holding tank 18, scrubber 19. The dryer 20, the gas cylinder 21, the evaporation tank 22, the first distillation tank 23, the second distillation tank 24, and the sea high water tank 25.

具体实施方式Detailed ways

以下描述用于揭露本发明以使本领域技术人员能够实现本发明。以下描述中的优选实施例只作为举例,本领域技术人员可以想到其他显而易见的变型。The following description serves to disclose the invention to enable those skilled in the art to practice the invention. The preferred embodiments described below are given by way of example only, and other obvious modifications will occur to those skilled in the art.

实施例1Example 1

如图1所示,一种电解海水制氢***,所述***包括:As shown in Figure 1, an electrolysis seawater hydrogen production system, the system includes:

太阳能光伏发电单元,所述太阳能光伏发电单元与电解海水单元相连,用于为电解海水单元提供电能;所述太阳能光伏发电单元包括太阳能电池板8、太阳能电源控制器9、蓄电池11和主控制板10;所述太阳能电池板8与太阳能电源控制器9相连,用于接收太阳能的光照并转换为电能;所述蓄电池11连接至太阳能电源控制器9,用于电能的储存;所述主控制板10输入端连接至太阳能电源控制器9,用于接收太阳能电源控制器9发出的控制信号,所述主控制板10输出端连接至电解池17中的阴极板和阳极板;所诉太阳能电源控制器9,用于控制太阳能光伏发电单元信号的输入和输出;The solar photovoltaic power generation unit, which is connected with the seawater electrolysis unit, is used to provide electrical energy for the seawater electrolysis unit; the solar photovoltaic power generation unit includes a solar panel 8, a solar power controller 9, a battery 11 and a main control board 10; the solar panel 8 is connected to the solar power controller 9 for receiving solar light and converts it into electrical energy; the battery 11 is connected to the solar power controller 9 for storage of electrical energy; the main control board 10 The input end is connected to the solar power controller 9 for receiving the control signal sent by the solar power controller 9, and the output end of the main control board 10 is connected to the cathode plate and the anode plate in the electrolytic cell 17; The device 9 is used to control the input and output of the signal of the solar photovoltaic power generation unit;

电解海水单元,用于电解海水制氢并副产甲酸盐;所述电解海水单元包括电解池17和电解液补充单元;所述电解液补充单元包括离心水泵3、进水阀4、高位水箱6、第一控制阀12和第二控制阀13;所述进水阀4设置在离心水泵3和高位水箱6之间的管路上,所述第一控制阀12和第二控制阀13设置在高位水箱6和电解池17之间的管路上,所述第一液位检测器5设置在高位水箱6内,所述第二液位检测器14设置在电解池17内;The electrolysis seawater unit is used to electrolyze seawater to produce hydrogen and by-produce formate; the electrolysis seawater unit includes an electrolytic cell 17 and an electrolyte replenishing unit; the electrolyte replenishing unit includes a centrifugal pump 3, a water inlet valve 4, and a high-level water tank 6. The first control valve 12 and the second control valve 13; the water inlet valve 4 is arranged on the pipeline between the centrifugal water pump 3 and the high-level water tank 6, and the first control valve 12 and the second control valve 13 are arranged at On the pipeline between the high-level water tank 6 and the electrolytic cell 17, the first liquid level detector 5 is arranged in the high-level water tank 6, and the second liquid level detector 14 is arranged in the electrolytic cell 17;

甘油滴加单元,所述甘油滴加单元与电解海水单元相连,用于向电解海水单元自动、定量地添加甘油,保证电解海水单元中的电解池17中甘油浓度稳定;所述甘油滴加单元包括甘油储存箱2、称重器1、第一加料阀15和第二加料阀7;所述称重器1设置在甘油储存箱2的底部,所述第一加料阀15设置在甘油储存箱2和高位水箱6之间的管路上,所述第二加料阀7设置在甘油储存箱2和电解池17之间的管路上;The glycerol dripping unit, which is connected with the electrolysis seawater unit, is used to automatically and quantitatively add glycerol to the electrolysis seawater unit to ensure that the concentration of glycerin in the electrolytic cell 17 in the electrolysis seawater unit is stable; the glycerol dripping unit Including a glycerin storage tank 2, a weighing device 1, a first feeding valve 15 and a second feeding valve 7; the weighing device 1 is arranged at the bottom of the glycerin storage tank 2, and the first feeding valve 15 is arranged in the glycerin storage tank 2 and the pipeline between the high-level water tank 6, the second feeding valve 7 is arranged on the pipeline between the glycerin storage tank 2 and the electrolytic cell 17;

氢气收集单元,所述氢气收集单元连接至电解海水单元的顶部,用于收集电解海水单元电解海水时产生的氢气;所述氢气收集单元包括洗涤器19、干燥器20和储气瓶21;所述洗涤器19和干燥器20依次设置在电解池17和储气瓶21的连接管路上;以及a hydrogen collection unit, the hydrogen collection unit is connected to the top of the seawater electrolysis unit, and is used to collect the hydrogen generated when the seawater electrolysis unit electrolyzes seawater; the hydrogen collection unit includes a scrubber 19, a dryer 20 and a gas storage bottle 21; The scrubber 19 and the dryer 20 are sequentially arranged on the connecting pipeline of the electrolytic cell 17 and the gas cylinder 21; and

余液回收单元,所述余液回收单元连接至电解海水单元底部,用于回收电解海水单元电解海水时产生的甲酸盐;所述余液回收单元包括集液阀16和余液容纳箱18;所述集液阀16设置在电解池17和余液容纳箱18的连接管路上。The residual liquid recovery unit, which is connected to the bottom of the electrolysis seawater unit, is used to recover the formate produced when the electrolytic seawater unit electrolyzes seawater; the residual liquid recovery unit includes a liquid collecting valve 16 and a residual liquid holding tank 18 ; The liquid collecting valve 16 is arranged on the connecting pipeline of the electrolytic cell 17 and the residual liquid holding tank 18 .

电解池17的阴极板和阳极板均采用Pt电极,甘油在阳极被氧化生成甲酸盐、碳酸盐和水,水在阴极被还原生成氢气。阳极水的产生大于阴极水的消耗,甘油浓度逐渐降低。需在电解过程中不断补充甘油浓度,防止甘油浓度低于0.05mol/L,导致氧化反应迟缓。Both the cathode plate and the anode plate of the electrolytic cell 17 use Pt electrodes, glycerol is oxidized at the anode to generate formate, carbonate and water, and water is reduced at the cathode to generate hydrogen. The production of anode water is greater than the consumption of cathode water, and the glycerol concentration gradually decreases. It is necessary to continuously replenish the glycerol concentration during the electrolysis process to prevent the glycerol concentration from being lower than 0.05mol/L, resulting in slow oxidation reaction.

高位水箱6尺寸为0.5m*0.5m*0.5m,所需甘油的浓度为0.1mol/L。The size of the high-level water tank 6 is 0.5m*0.5m*0.5m, and the required concentration of glycerin is 0.1mol/L.

设置参数:高位水箱6的水位值a=0.5m,每一高位水箱6所需甘油的质量b=体积*浓度*相对分子质量=1.15Kg,电解每5min消耗的甘油为25g,电解池17的hmin=10cm,hmax=20cm,回收周期设置为12h。Setting parameters: the water level value of the high-level water tank 6 a=0.5m, the mass of glycerin required by each high-level water tank 6 b=volume*concentration*relative molecular mass=1.15Kg, the glycerol consumed by electrolysis every 5min is 25g, the hmin=10cm, hmax=20cm, and the recovery period is set to 12h.

相应地电解海水制氢方法,所述方法包括以下步骤:Correspondingly, a method for producing hydrogen by electrolysis of seawater, the method comprises the following steps:

高位水箱6初始水位为0.2m,电解池17水位为15cm,启动***开关,太阳能光伏发电单元首先启动,太阳能电池板8将光能转化为直流电,光照一段时间后,太阳能电源控制器9输出稳定电流,电解海水单元启动,开始进行电解海水操作,此时电解池17阴极侧不断产出氢气,阳极侧副产甲酸钠物质,初始状态所有阀门关闭;在电流的作用下,电解池17阳极发生甘油氧化反应,无气体生成,阴极发生HER反应产生氢气;多余的电能储存于蓄电池11中;The initial water level of the high water tank 6 is 0.2m, the water level of the electrolytic cell 17 is 15cm, the system switch is turned on, the solar photovoltaic power generation unit starts first, and the solar panel 8 converts the light energy into direct current. After a period of illumination, the output of the solar power controller 9 is stable. Electric current, the seawater electrolysis unit is started, and the seawater electrolysis operation begins. At this time, the cathode side of the electrolytic cell 17 continuously produces hydrogen, and the anode side produces sodium formate by-product, and all valves are closed in the initial state; under the action of the current, the anode of the electrolytic cell 17 produces glycerin. Oxidation reaction, no gas is generated, HER reaction occurs at the cathode to generate hydrogen; excess electrical energy is stored in the battery 11;

电解海水过程中,打开第二加料阀7,每间隔5min,甘油滴加单元向电解池17中滴加25g甘油,当第二液位检测器14检测到电解池17中的液位降低至设定值下限10cm,打开第一控制阀12和第二控制阀13,电解液补充单元中的高位水箱6向电解池17补充电解液,以维持电解池17中甘油浓度的稳定,当电解池17液位升高至设定值上限20cm,关闭第一控制阀12,完成电解液自动补充操作;运行一段时间后,在向电解池17中加液过程中,高位水箱6的液位变为0,此时打开进水阀4,启动离心水泵3,将海高位水箱25中的海水泵3入高位水箱6,高位水箱6的液位不断上升,高位水箱6液位上升至0.5m,离心水泵3停止,进水阀4关闭,第一进料阀打开,注入甘油1.15kg,第一进料阀关闭,完成高位水箱6电解质的配置;During the electrolysis of seawater, the second feeding valve 7 was opened, and the glycerol dripping unit dripped 25 g of glycerol into the electrolytic cell 17 at every interval of 5 min. The lower limit of the fixed value is 10cm, the first control valve 12 and the second control valve 13 are opened, and the high-level water tank 6 in the electrolyte replenishing unit replenishes the electrolyte to the electrolytic cell 17 to maintain the stability of the glycerin concentration in the electrolytic cell 17. When the electrolytic cell 17 The liquid level rises to the upper limit of 20cm of the set value, and the first control valve 12 is closed to complete the automatic replenishment operation of electrolyte; , at this time, open the water inlet valve 4, start the centrifugal water pump 3, and put the sea water pump 3 in the high-level water tank 25 into the high-level water tank 6. The liquid level of the high-level water tank 6 continues to rise, and the liquid level of the high-level water tank 6 rises to 0.5m. 3 stop, the water inlet valve 4 is closed, the first feeding valve is opened, 1.15kg of glycerol is injected, the first feeding valve is closed, and the configuration of the electrolyte in the high-level water tank 6 is completed;

电解海水过程中,电解池17阴极侧产出的氢气经过洗涤器19和干燥器20,以脱除氢气中所夹带的水份和杂质,然后通过回收管道进入氢气瓶中,进行氢气收集操作;以及In the process of electrolysis of seawater, the hydrogen produced on the cathode side of the electrolytic cell 17 passes through the scrubber 19 and the dryer 20 to remove the water and impurities entrained in the hydrogen, and then enters the hydrogen bottle through the recovery pipeline to carry out the hydrogen collection operation; as well as

电解海水一段时间后(***启动12h),电解池17中甲酸盐浓度很高,停止电解海水操作,关闭第二控制阀13,打开集液阀16,并将电解池17中含有甲酸钠的余液排至余液容纳箱18,余液排净后,关闭集液阀16,打开第一控制阀12和第二控制阀13,电解池17再次进行电解液自动补充操作,然后重新启动电解海水操作及后续的电解液自动补充操作和氢气收集操作。After electrolyzing seawater for a period of time (12h after the system was started), the concentration of formate in the electrolytic cell 17 was very high, so the electrolysis of seawater was stopped, the second control valve 13 was closed, the liquid collecting valve 16 was opened, and the remainder of the electrolytic cell 17 containing sodium formate was removed. The liquid is discharged to the residual liquid holding tank 18. After the residual liquid is drained, the liquid collecting valve 16 is closed, the first control valve 12 and the second control valve 13 are opened, and the electrolytic cell 17 is again automatically replenished. operation and subsequent automatic electrolyte replenishment operation and hydrogen collection operation.

实施例2Example 2

如图2所示,一种电解海水制氢***,所述***包括:As shown in Figure 2, an electrolysis seawater hydrogen production system, the system includes:

太阳能光伏发电单元,所述太阳能光伏发电单元与电解海水单元相连,用于为电解海水单元提供电能;所述太阳能光伏发电单元包括太阳能电池板8、太阳能电源控制器9、蓄电池11和主控制板10;所述太阳能电池板8与太阳能电源控制器9相连,用于接收太阳能的光照并转换为电能;所述蓄电池11连接至太阳能电源控制器9,用于电能的储存;所述主控制板10输入端连接至太阳能电源控制器9,用于接收太阳能电源控制器9发出的控制信号,所述主控制板10输出端连接至电解池17中的阴极板和阳极板;所诉太阳能电源控制器9,用于控制太阳能光伏发电单元信号的输入和输出;The solar photovoltaic power generation unit, which is connected with the seawater electrolysis unit, is used to provide electrical energy for the seawater electrolysis unit; the solar photovoltaic power generation unit includes a solar panel 8, a solar power controller 9, a battery 11 and a main control board 10; the solar panel 8 is connected to the solar power controller 9 for receiving solar light and converts it into electrical energy; the battery 11 is connected to the solar power controller 9 for storage of electrical energy; the main control board 10 The input end is connected to the solar power controller 9 for receiving the control signal sent by the solar power controller 9, and the output end of the main control board 10 is connected to the cathode plate and the anode plate in the electrolytic cell 17; The device 9 is used to control the input and output of the signal of the solar photovoltaic power generation unit;

电解海水单元,用于电解海水制氢并副产甲酸盐;所述电解海水单元包括电解池17和电解液补充单元;所述电解液补充单元包括离心水泵3、进水阀4、高位水箱6、第一控制阀12和第二控制阀13;所述进水阀4设置在离心水泵3和高位水箱6之间的管路上,所述第一控制阀12和第二控制阀13设置在高位水箱6和电解池17之间的管路上,所述第一液位检测器5设置在高位水箱6内,所述第二液位检测器14设置在电解池17内;The electrolysis seawater unit is used to electrolyze seawater to produce hydrogen and by-produce formate; the electrolysis seawater unit includes an electrolytic cell 17 and an electrolyte replenishing unit; the electrolyte replenishing unit includes a centrifugal pump 3, a water inlet valve 4, and a high-level water tank 6. The first control valve 12 and the second control valve 13; the water inlet valve 4 is arranged on the pipeline between the centrifugal water pump 3 and the high-level water tank 6, and the first control valve 12 and the second control valve 13 are arranged at On the pipeline between the high-level water tank 6 and the electrolytic cell 17, the first liquid level detector 5 is arranged in the high-level water tank 6, and the second liquid level detector 14 is arranged in the electrolytic cell 17;

甘油滴加单元,所述甘油滴加单元与电解海水单元相连,用于向电解海水单元自动、定量地添加甘油,保证电解海水单元中的电解池17中甘油浓度稳定;所述甘油滴加单元包括甘油储存箱2、称重器1、第一加料阀15和第二加料阀7;所述称重器1设置在甘油储存箱2的底部,所述第一加料阀15设置在甘油储存箱2和高位水箱6之间的管路上,所述第二加料阀7设置在甘油储存箱2和电解池17之间的管路上;The glycerol dripping unit, which is connected with the electrolysis seawater unit, is used to automatically and quantitatively add glycerol to the electrolysis seawater unit to ensure that the concentration of glycerin in the electrolytic cell 17 in the electrolysis seawater unit is stable; the glycerol dripping unit Including a glycerin storage tank 2, a weighing device 1, a first feeding valve 15 and a second feeding valve 7; the weighing device 1 is arranged at the bottom of the glycerin storage tank 2, and the first feeding valve 15 is arranged in the glycerin storage tank 2 and the pipeline between the high-level water tank 6, the second feeding valve 7 is arranged on the pipeline between the glycerin storage tank 2 and the electrolytic cell 17;

氢气收集单元,所述氢气收集单元连接至电解海水单元的顶部,用于收集电解海水单元电解海水时产生的氢气;所述氢气收集单元包括洗涤器19、干燥器20和储气瓶21;所述洗涤器19和干燥器20依次设置在电解池17和储气瓶21的连接管路上;以及a hydrogen collection unit, the hydrogen collection unit is connected to the top of the seawater electrolysis unit, and is used to collect the hydrogen generated when the seawater electrolysis unit electrolyzes seawater; the hydrogen collection unit includes a scrubber 19, a dryer 20 and a gas storage bottle 21; The scrubber 19 and the dryer 20 are sequentially arranged on the connecting pipeline of the electrolytic cell 17 and the gas cylinder 21; and

余液回收单元,所述余液回收单元连接至电解海水单元底部,用于回收电解海水单元电解海水时产生的甲酸盐;所述余液回收单元包括集液阀16和余液容纳箱18;所述集液阀16设置在电解池17和余液容纳箱18的连接管路上。The residual liquid recovery unit, which is connected to the bottom of the electrolysis seawater unit, is used to recover the formate produced when the electrolytic seawater unit electrolyzes seawater; the residual liquid recovery unit includes a liquid collecting valve 16 and a residual liquid holding tank 18 ; The liquid collecting valve 16 is arranged on the connecting pipeline of the electrolytic cell 17 and the residual liquid holding tank 18 .

所述余液回收单元还包括蒸发罐22、第一蒸馏罐23和第二蒸馏罐24;所述蒸发罐22接收余液容纳箱18中的余液,并进行水份的蒸发操作,所述蒸发罐22内添加有无水乙醇,使蒸发残留物中的甲酸钠和甘油溶解其中,所述第一蒸馏罐23接收蒸发罐22中的甲酸钠、无水乙醇和甘油的混合物,并进行蒸馏操作,以使低沸点的无水乙醇从所述混合物中分离出来,并返回至蒸发罐22中,所述第二蒸馏罐24接收第一蒸馏罐23中的剩余甘油和甲酸钠物质,并继续蒸馏操作。The residual liquid recovery unit also includes an evaporation tank 22, a first distillation tank 23 and a second distillation tank 24; the evaporation tank 22 receives the residual liquid in the residual liquid holding tank 18, and performs an evaporation operation for water content, the Anhydrous ethanol is added in the evaporation tank 22 to dissolve the sodium formate and glycerin in the evaporation residue, and the first distillation tank 23 receives the mixture of sodium formate, anhydrous ethanol and glycerin in the evaporation tank 22, and carries out a distillation operation, In order to separate the low boiling point absolute ethanol from the mixture and return it to the evaporation tank 22, the second distillation tank 24 receives the remaining glycerol and sodium formate substances in the first distillation tank 23 and continues the distillation operation.

电解池17的阴极板和阳极板均采用Pt电极,甘油在阳极被氧化生成甲酸盐、碳酸盐和水,水在阴极被还原生成氢气。阳极水的产生大于阴极水的消耗,甘油浓度逐渐降低。需在电解过程中不断补充甘油浓度,防止甘油浓度低于0.05mol/L,导致氧化反应迟缓。Both the cathode plate and the anode plate of the electrolytic cell 17 use Pt electrodes, glycerol is oxidized at the anode to generate formate, carbonate and water, and water is reduced at the cathode to generate hydrogen. The production of anode water is greater than the consumption of cathode water, and the glycerol concentration gradually decreases. It is necessary to continuously replenish the glycerol concentration during the electrolysis process to prevent the glycerol concentration from being lower than 0.05mol/L, resulting in slow oxidation reaction.

高位水箱6尺寸为0.5m*0.5m*0.5m,所需甘油的浓度为0.2mol/L。The size of the high-level water tank 6 is 0.5m*0.5m*0.5m, and the required concentration of glycerin is 0.2mol/L.

设置参数:高位水箱6的水位值a=0.5m,每一高位水箱所需甘油的质量b=体积*浓度*相对分子质量=2.3Kg,电解每5min消耗的甘油为25g,电解池17的hmin=10cm,hmax=20cm,回收周期设置为12h。Setting parameters: the water level value of the high-level water tank 6 a=0.5m, the mass of glycerin required by each high-level water tank b=volume*concentration*relative molecular mass=2.3Kg, the glycerol consumed by electrolysis every 5min is 25g, the hmin of the electrolytic cell 17 =10cm, hmax=20cm, and the recovery period is set to 12h.

本实施例的电解海水制氢方法,包括以下步骤:The method for producing hydrogen by electrolysis of seawater of the present embodiment comprises the following steps:

高位水箱6初始水位为0.2m,电解池17水位为15cm,启动***开关,太阳能光伏发电单元首先启动,太阳能电池板8将光能转化为直流电,光照一段时间后,太阳能电源控制器9输出稳定电流,电解海水单元启动,开始进行电解海水操作,此时电解池17阴极侧不断产出氢气,阳极侧副产甲酸钠物质;在电流的作用下,电解池17阳极发生甘油氧化反应,无气体生成,阴极发生HER反应产生氢气;多余的电能储存于蓄电池11中;The initial water level of the high water tank 6 is 0.2m, the water level of the electrolytic cell 17 is 15cm, the system switch is turned on, the solar photovoltaic power generation unit starts first, and the solar panel 8 converts the light energy into direct current. After a period of illumination, the output of the solar power controller 9 is stable. Electric current, the electrolysis seawater unit starts, and starts the electrolysis of seawater operation. At this time, the cathode side of the electrolytic cell 17 continuously produces hydrogen, and the anode side produces sodium formate by-product; , the HER reaction occurs at the cathode to generate hydrogen; the excess electric energy is stored in the battery 11;

电解海水过程中,打开第二加料阀7,每间隔5min,甘油滴加单元向电解池17中滴加25g甘油,当第二液位检测器14检测到电解池17中的液位降低至设定值下限10cm,打开第一控制阀12和第二控制阀13,电解液补充单元中的高位水箱6向电解池17补充电解液,以维持电解池17中甘油浓度的稳定,当电解池17液位升高至设定值上限20cm,关闭第一控制阀12,完成电解液自动补充操作;运行一段时间后,在向电解池17中加液过程中,高位水箱6的液位变为0,此时打开进水阀4,启动离心水泵3,将海高位水箱25中的海水泵3入高位水箱6,高位水箱6的液位不断上升,高位水箱液位上升至0.5m,离心水泵3停止,进水阀4关闭,第一进料阀打开,注入甘油2.3kg;,第一进料阀关闭,完成高位水箱6电解质的配置;During the electrolysis of seawater, the second feeding valve 7 was opened, and the glycerol dripping unit dripped 25 g of glycerol into the electrolytic cell 17 at every interval of 5 min. The lower limit of the fixed value is 10cm, the first control valve 12 and the second control valve 13 are opened, and the high-level water tank 6 in the electrolyte replenishing unit replenishes the electrolyte to the electrolytic cell 17 to maintain the stability of the glycerin concentration in the electrolytic cell 17. When the electrolytic cell 17 The liquid level rises to the upper limit of 20cm of the set value, and the first control valve 12 is closed to complete the automatic replenishment operation of electrolyte; , at this time, open the water inlet valve 4, start the centrifugal water pump 3, and put the sea water pump 3 in the high-level water tank 25 into the high-level water tank 6. The liquid level of the high-level water tank 6 continues to rise, and the liquid level of the high-level water tank rises to 0.5m. The centrifugal pump 3 Stop, the water inlet valve 4 is closed, the first feeding valve is opened, and 2.3 kg of glycerol is injected; the first feeding valve is closed, and the configuration of the electrolyte in the high-level water tank 6 is completed;

电解海水过程中,电解池17阴极侧产出的氢气经过洗涤器19和干燥器20,以脱除氢气中所夹带的水份和杂质,然后通过回收管道进入氢气瓶中,进行氢气收集操作;以及In the process of electrolysis of seawater, the hydrogen produced on the cathode side of the electrolytic cell 17 passes through the scrubber 19 and the dryer 20 to remove the water and impurities entrained in the hydrogen, and then enters the hydrogen bottle through the recovery pipeline to carry out the hydrogen collection operation; as well as

电解海水一段时间后(***启动12h),电解池17中甲酸盐浓度很高,停止电解海水操作,关闭第二控制阀13,打开集液阀16,并将电解池17中含有甲酸钠的余液排至余液容纳箱18,余液排净后,关闭集液阀16,打开第一控制阀12和第二控制阀13,电解池17再次进行电解液自动补充操作,然后重新启动电解海水操作及后续的电解液自动补充操作和氢气收集操作。After electrolyzing seawater for a period of time (12h after the system was started), the concentration of formate in the electrolytic cell 17 was very high, so the electrolysis of seawater was stopped, the second control valve 13 was closed, the liquid collecting valve 16 was opened, and the remainder of the electrolytic cell 17 containing sodium formate was removed. The liquid is discharged to the residual liquid holding tank 18. After the residual liquid is drained, the liquid collecting valve 16 is closed, the first control valve 12 and the second control valve 13 are opened, and the electrolytic cell 17 is again automatically replenished. operation and subsequent automatic electrolyte replenishment operation and hydrogen collection operation.

所述余液容纳箱18中的余液输送至蒸发罐22中,进行水份的蒸发操作,设置恒温150℃,蒸发时间设置为5h,得到固相NaCl、Na2CO3、HCOONa和液相甘油的混合物,然后向所述蒸发罐22内添加150kg无水乙醇,搅拌使蒸发残留物中的甲酸钠和甘油溶解于无水乙醇中;过滤后再将包括甲酸钠、无水乙醇和甘油的滤液输送至第一蒸馏罐23中,设置温度为150℃,设置蒸馏时间5h,进行无水乙醇的蒸馏操作,以使低沸点的无水乙醇从所述混合物中分离出来;所述第一蒸馏罐23中的剩余甘油和甲酸钠物质输送至第二蒸馏罐24中,设置温度为320℃,设置蒸馏时间为0.5h,并继续蒸馏操作,所述第二蒸馏罐24顶部出口为甘油,所述第二蒸馏罐24底部得到甲酸钠副产物。The residual liquid in the residual liquid holding box 18 is transported to the evaporation tank 22, and the evaporation operation of water content is carried out, the constant temperature is set to 150 ° C, and the evaporation time is set to 5 h to obtain a mixture of solid-phase NaCl, Na CO , HCOONa and liquid-phase glycerin , then add 150kg dehydrated alcohol in described evaporation tank 22, stir to dissolve sodium formate and glycerin in the evaporation residue in dehydrated alcohol; after filtration, the filtrate comprising sodium formate, dehydrated alcohol and glycerin is transported to the first In the distillation tank 23, the set temperature is 150°C, and the distillation time is set to 5h, and the distillation operation of absolute ethanol is carried out, so that the low-boiling point absolute ethanol is separated from the mixture; the remainder in the first distillation tank 23 The glycerol and sodium formate substances are transported to the second distillation tank 24, the temperature is set to 320°C, the distillation time is set to 0.5h, and the distillation operation is continued. The top outlet of the second distillation tank 24 is glycerol, and the second distillation tank 24 Sodium formate by-product is obtained at the bottom.

所述无水乙醇循环至蒸发罐22,所述甘油循环至甘油储存箱2。The absolute ethanol is circulated to the evaporation tank 22 , and the glycerol is circulated to the glycerol storage tank 2 .

以上显示和描述了本发明的基本原理、主要特征和本发明的优点。本行业的技术人员应该了解,本发明不受上述实施例的限制,上述实施例和说明书中描述的只是本发明的原理,在不脱离本发明精神和范围的前提下本发明还会有各种变化和改进,这些变化和改进都落入要求保护的本发明的范围内。本发明要求的保护范围由所附的权利要求书及其等同物界定。The foregoing has shown and described the basic principles, main features and advantages of the present invention. It should be understood by those skilled in the art that the present invention is not limited by the above-mentioned embodiments. The above-mentioned embodiments and descriptions describe only the principles of the present invention. Without departing from the spirit and scope of the present invention, there are various Variations and improvements are intended to fall within the scope of the claimed invention. The scope of protection claimed by the present invention is defined by the appended claims and their equivalents.

Claims (10)

1.一种电解海水制氢***,其特征在于,所述***包括:1. an electrolysis seawater hydrogen production system, is characterized in that, described system comprises: 太阳能光伏发电单元,所述太阳能光伏发电单元与电解海水单元相连,用于为电解海水单元提供电能;a solar photovoltaic power generation unit, the solar photovoltaic power generation unit is connected to the seawater electrolysis unit, and is used for providing electrical energy for the seawater electrolysis unit; 电解海水单元,用于电解海水制氢并副产甲酸盐;Seawater electrolysis unit, used to electrolyze seawater to produce hydrogen and by-produce formate; 甘油滴加单元,所述甘油滴加单元与电解海水单元相连,用于向电解海水单元自动、定量地添加甘油,保证电解海水单元中的电解池中甘油浓度稳定;a glycerol dripping unit, the glycerol dripping unit is connected with the electrolysis seawater unit, and is used to automatically and quantitatively add glycerol to the electrolysis seawater unit, so as to ensure the stable glycerin concentration in the electrolytic cell in the electrolysis seawater unit; 氢气收集单元,所述氢气收集单元连接至电解海水单元的顶部,用于收集电解海水单元电解海水时产生的氢气;以及a hydrogen collecting unit, the hydrogen collecting unit is connected to the top of the seawater electrolysis unit, and is used for collecting hydrogen generated when the seawater electrolysis unit electrolyzes seawater; and 余液回收单元,所述余液回收单元连接至电解海水单元底部,用于回收电解海水单元电解海水时产生的甲酸盐。The residual liquid recovery unit, which is connected to the bottom of the electrolysis seawater unit, is used for recovering the formate produced during the electrolysis of seawater in the electrolysis seawater unit. 2.如权利要求1所述的电解海水制氢***,其特征在于,所述太阳能光伏发电单元包括太阳能电池板、太阳能电源控制器、蓄电池和主控制板;所述太阳能电池板与太阳能电源控制器相连,用于接收太阳能的光照并转换为电能;所述蓄电池连接至太阳能电源控制器,用于电能的储存;所述主控制板输入端连接至太阳能电源控制器,用于接收太阳能电源控制器发出的控制信号,所述主控制板输出端连接至电解池中的阴极板和阳极板;所诉太阳能电源控制器,用于控制太阳能光伏发电单元信号的输入和输出。2. The electrolysis seawater hydrogen production system according to claim 1, wherein the solar photovoltaic power generation unit comprises a solar panel, a solar power controller, a storage battery and a main control panel; the solar panel and the solar power control The battery is connected to the solar power controller for receiving solar energy and converts it into electrical energy; the battery is connected to the solar power source controller for storing electrical energy; the input end of the main control board is connected to the solar power source controller for receiving solar power source control. The output end of the main control board is connected to the cathode plate and the anode plate in the electrolytic cell; the solar power controller is used to control the input and output of the signal of the solar photovoltaic power generation unit. 3.如权利要求1所述的电解海水制氢***,其特征在于,所述电解海水单元包括电解池和电解液补充单元;所述电解液补充单元包括离心水泵、进水阀、高位水箱、第一控制阀和第二控制阀;所述进水阀设置在离心水泵和高位水箱之间的管路上,所述第一控制阀和第二控制阀设置在高位水箱和电解池之间的管路上,所述第一液位检测器设置在高位水箱内,所述第二液位检测器设置在电解池内。3. The electrolysis seawater hydrogen production system as claimed in claim 1, wherein the electrolysis seawater unit comprises an electrolytic cell and an electrolyte replenishing unit; the electrolyte replenishing unit comprises a centrifugal water pump, a water inlet valve, a high-level water tank, The first control valve and the second control valve; the water inlet valve is arranged on the pipeline between the centrifugal water pump and the high-level water tank, and the first control valve and the second control valve are arranged on the pipeline between the high-level water tank and the electrolytic cell , the first liquid level detector is arranged in the high-level water tank, and the second liquid level detector is arranged in the electrolytic cell. 4.如权利要求1所述的电解海水制氢***,其特征在于,所述甘油滴加单元包括甘油储存箱、称重器、第一加料阀和第二加料阀;所述称重器设置在甘油储存箱的底部,所述第一加料阀设置在甘油储存箱和高位水箱之间的管路上,所述第二加料阀设置在甘油储存箱和电解池之间的管路上。4. The electrolysis seawater hydrogen production system according to claim 1, wherein the glycerin dripping unit comprises a glycerin storage tank, a weighing device, a first feeding valve and a second feeding valve; the weighing device is provided with At the bottom of the glycerin storage tank, the first feed valve is arranged on the pipeline between the glycerol storage tank and the high-level water tank, and the second feed valve is arranged on the pipeline between the glycerol storage tank and the electrolytic cell. 5.如权利要求1所述的电解海水制氢***,其特征在于,所述氢气收集单元包括洗涤器、干燥器和储气瓶;所述洗涤器和干燥器依次设置在电解池和储气瓶的连接管路上。5. The electrolysis seawater hydrogen production system according to claim 1, wherein the hydrogen collection unit comprises a scrubber, a dryer and a gas storage cylinder; the scrubber and the dryer are sequentially arranged in the electrolytic cell and the gas storage on the connecting line of the bottle. 6.如权利要求1所述的电解海水制氢***,其特征在于,所述余液回收单元包括集液阀和余液容纳箱;所述集液阀设置在电解池和余液容纳箱的连接管路上。6. The electrolysis seawater hydrogen production system according to claim 1, wherein the residual liquid recovery unit comprises a liquid collecting valve and a residual liquid holding tank; on the connecting line. 7.如权利要求1所述的电解海水制氢***,其特征在于,所述余液回收单元还包括蒸发罐、第一蒸馏罐和第二蒸馏罐;所述蒸发罐接收余液容纳箱中的余液,并进行水份的蒸发操作,所述蒸发罐内添加有无水乙醇,使蒸发残留物中的甲酸钠和甘油溶解其中,所述第一蒸馏罐接收蒸发罐中的甲酸钠、无水乙醇和甘油的混合物,并进行蒸馏操作,以使低沸点的无水乙醇从所述混合物中分离出来,并返回至蒸发罐中,所述第二蒸馏罐接收第一蒸馏罐中的剩余甘油和甲酸钠物质,并继续蒸馏操作。7. The electrolysis seawater hydrogen production system according to claim 1, wherein the residual liquid recovery unit further comprises an evaporation tank, a first distillation tank and a second distillation tank; The residual liquid is evaporated, and the evaporation operation of water content is carried out. Anhydrous ethanol is added in the evaporation tank to dissolve the sodium formate and glycerin in the evaporation residue. The first distillation tank receives the sodium formate and anhydrous in the evaporation tank. A mixture of ethanol and glycerol, and a distillation operation is carried out to separate the low-boiling absolute ethanol from the mixture and return it to the evaporation tank, the second distillation tank receiving the remaining glycerol in the first distillation tank and sodium formate material and continue the distillation operation. 8.一种如权利要求1~7任一项所述的电解海水制氢方法,其特征在于,所述方法包括以下步骤:8. A method for producing hydrogen by electrolysis of seawater as claimed in any one of claims 1 to 7, wherein the method comprises the following steps: 启动***开关,太阳能光伏发电单元首先启动,光照一段时间后,太阳能电源控制器9输出稳定电流,电解海水单元启动,开始进行电解海水操作,此时电解池阴极侧不断产出氢气,阳极侧副产甲酸钠物质;When the system switch is turned on, the solar photovoltaic power generation unit starts first. After lighting for a period of time, the solar power controller 9 outputs a stable current, the seawater electrolysis unit starts, and the seawater electrolysis operation begins. At this time, the cathode side of the electrolysis cell continuously produces hydrogen, and the anode side vice Sodium formate producing substances; 电解海水过程中,电解池液位降低至设定值下限,甘油滴加单元开始向电解池中滴加甘油,同时电解液补充单元中的高位水箱向电解池补充电解液,以维持电解池中甘油浓度的稳定,当电解池液位升高至设定值上限,完成电解液自动补充操作;During the electrolysis of seawater, the liquid level of the electrolytic cell drops to the lower limit of the set value, and the glycerol dripping unit begins to drip glycerol into the electrolytic cell. The glycerol concentration is stable. When the liquid level of the electrolytic cell rises to the upper limit of the set value, the automatic replenishment operation of the electrolyte is completed; 电解海水过程中,电解池阴极侧产出的氢气经过洗涤器和干燥器,以脱除氢气中所夹带的水份和杂质,然后通过回收管道进入氢气瓶中,进行氢气收集操作;以及During the electrolysis of seawater, the hydrogen produced on the cathode side of the electrolysis cell passes through a scrubber and a dryer to remove water and impurities entrained in the hydrogen, and then enters a hydrogen bottle through a recovery pipeline for hydrogen collection; and 电解海水一段时间后,停止电解海水操作,并将电解池中含有甲酸钠的余液排至余液容纳箱,余液排净后,电解池再次进行电解液自动补充操作,然后重新启动电解海水操作及后续的电解液自动补充操作和氢气收集操作。After the electrolysis of seawater for a period of time, the electrolysis of seawater is stopped, and the residual liquid containing sodium formate in the electrolytic cell is discharged to the residual liquid holding tank. After the residual liquid is drained, the electrolytic cell will perform the automatic replenishment operation of the electrolyte again, and then restart the electrolytic seawater operation. And the subsequent automatic replenishment operation of electrolyte and hydrogen collection operation. 9.如权利要求8所述的电解海水制氢方法,其特征在于,所述余液容纳箱中的余液输送至蒸发罐中,进行水份的蒸发操作,然后向所述蒸发罐内添加无水乙醇,搅拌使蒸发残留物中的甲酸钠和甘油溶解于无水乙醇中;再将甲酸钠、无水乙醇和甘油的混合物输送至第一蒸馏罐中,进行无水乙醇的蒸馏操作,以使低沸点的无水乙醇从所述混合物中分离出来;所述第一蒸馏罐中的剩余甘油和甲酸钠物质输送至第二蒸馏罐中,并继续蒸馏操作,所述第二蒸馏罐顶部出口为甘油,所述第二蒸馏罐底部得到甲酸钠副产物。9. The method for producing hydrogen by electrolysis of seawater as claimed in claim 8, wherein the residual liquid in the residual liquid holding tank is transported to the evaporation tank, the evaporation operation of water content is carried out, and then the residual liquid in the evaporation tank is added Absolute ethanol, stir to dissolve the sodium formate and glycerin in the evaporation residue in the absolute ethanol; then transfer the mixture of sodium formate, anhydrous ethanol and glycerol to the first distillation tank, and carry out the distillation operation of the anhydrous ethanol to make The low-boiling absolute ethanol is separated from the mixture; the remaining glycerol and sodium formate in the first distillation tank are transported to the second distillation tank, and the distillation operation is continued, and the top outlet of the second distillation tank is glycerol , the sodium formate by-product is obtained at the bottom of the second distillation tank. 10.如权利要求9所述的电解海水制氢方法,其特征在于,所述无水乙醇循环至蒸发罐,所述甘油循环至甘油储存箱。10 . The method for producing hydrogen by electrolysis of seawater according to claim 9 , wherein the absolute ethanol is circulated to the evaporation tank, and the glycerol is circulated to the glycerol storage tank. 11 .
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112481656A (en) * 2020-11-30 2021-03-12 华南理工大学 Bifunctional catalyst for high-selectivity electrocatalysis of glycerin oxidation conversion to produce formic acid and high-efficiency electrolysis of water to produce hydrogen, preparation method and application thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101275233A (en) * 2007-12-27 2008-10-01 复旦大学 A method for producing hydrogen using alcohols as raw material
CN203976930U (en) * 2014-08-11 2014-12-03 厦门大学 Sun power electrolysis seawater device for producing hydrogen
CN205295485U (en) * 2015-12-31 2016-06-08 王学福 A system for producing hydrogen and oxygen by solar electrolysis of seawater
CN106967996A (en) * 2017-04-18 2017-07-21 碧海舟(北京)节能环保装备有限公司 The hydrogen manufacturing of clean energy resource seawater and sodium hypochlorite system
CN110205642A (en) * 2019-04-30 2019-09-06 上海海事大学 A kind of solar energy equipment
CN110820007A (en) * 2019-11-14 2020-02-21 深圳大学 A PBI proton exchange membrane electrolysis module and seawater electrolysis hydrogen production device

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101275233A (en) * 2007-12-27 2008-10-01 复旦大学 A method for producing hydrogen using alcohols as raw material
CN203976930U (en) * 2014-08-11 2014-12-03 厦门大学 Sun power electrolysis seawater device for producing hydrogen
CN205295485U (en) * 2015-12-31 2016-06-08 王学福 A system for producing hydrogen and oxygen by solar electrolysis of seawater
CN106967996A (en) * 2017-04-18 2017-07-21 碧海舟(北京)节能环保装备有限公司 The hydrogen manufacturing of clean energy resource seawater and sodium hypochlorite system
CN110205642A (en) * 2019-04-30 2019-09-06 上海海事大学 A kind of solar energy equipment
CN110820007A (en) * 2019-11-14 2020-02-21 深圳大学 A PBI proton exchange membrane electrolysis module and seawater electrolysis hydrogen production device

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
高丹等: "乙二醇作电子给体的Pt/TiO_2光催化海水制氢反应", 《南昌大学学报(理科版)》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112481656A (en) * 2020-11-30 2021-03-12 华南理工大学 Bifunctional catalyst for high-selectivity electrocatalysis of glycerin oxidation conversion to produce formic acid and high-efficiency electrolysis of water to produce hydrogen, preparation method and application thereof
CN112481656B (en) * 2020-11-30 2021-08-10 华南理工大学 Bifunctional catalyst for high-selectivity electrocatalysis of glycerin oxidation conversion to produce formic acid and high-efficiency electrolysis of water to produce hydrogen, preparation method and application thereof

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