阅读说明：本技术 一种利用水蒸汽的硼氢化物水解制氢方法 (Hydrogen production method by hydrolysis of borohydride by using water vapor ) 是由 刘艺培 侯向理 叶龙 于 2019-10-17 设计创作，主要内容包括：本发明公开了一种利用水蒸汽的硼氢化物水解制氢方法,将硼氢化物、催化剂以及膨松剂粉末混合均匀,再将水或者含水物质加热,产生的水蒸汽通入固体混合物进行水解制氢。该方法利用水蒸汽供水,大大提高了储氢密度,增大了反应接触面积,提高了硼氢化物利用率；且可以通过调节水蒸汽的温度和供应量控制反应速率。通过向产氢物料中添加膨松剂,提高水蒸汽的渗透能力,使水蒸汽与固体混合物快速充分接触,并避免了副产物偏硼酸盐结晶导致的结块现象,有效提高了硼氢化物的反应效率。将水或者含水物质与固体混合物分开放置,便于储存和运输,便于产氢速率的控制。(The invention discloses a method for preparing hydrogen by hydrolyzing borohydride with water vapor, which comprises the steps of uniformly mixing borohydride, a catalyst and leavening agent powder, heating water or a water-containing substance, and introducing the generated water vapor into a solid mixture for preparing hydrogen by hydrolyzing. The method utilizes water vapor to supply water, greatly improves the hydrogen storage density, increases the reaction contact area and improves the utilization rate of borohydride; and the reaction rate can be controlled by adjusting the temperature and supply amount of the water vapor. The swelling agent is added into the hydrogen production material, so that the permeability of water vapor is improved, the water vapor is quickly and fully contacted with the solid mixture, the caking phenomenon caused by crystallization of a byproduct metaborate is avoided, and the reaction efficiency of borohydride is effectively improved. The water or the water-containing substance and the solid mixture are separately placed, so that the storage and the transportation are convenient, and the control of the hydrogen production rate is convenient.)

1. A method for preparing hydrogen by hydrolysis of borohydride by using water vapor is characterized by comprising the following steps:

s1: weighing borohydride, a catalyst and leavening agent powder, and uniformly mixing;

s2: weighing water or water-containing substances for later use;

s3: separately placing the mixed powder and the water/water-containing substance in a reaction vessel;

s4: heating the water/water-containing substance end, introducing the generated water vapor into the tail end of the mixed powder, and collecting the hydrogen generated by the reaction.

2. The method for producing hydrogen by hydrolysis of borohydride according to claim 1, wherein the mass ratio of the borohydride, the catalyst, the raising agent and the water or the water-containing substance is 1 (0.5 ~ 1) (0.3 ~ 0.5.5): (1 ~ 3).

3. The method for producing hydrogen by hydrolysis of borohydride with water vapor according to claim 1, wherein the method comprises: the swelling agent

Is one or more of activated carbon, vermiculite, molecular sieve and foam particles.

4. The method for producing hydrogen by hydrolysis of borohydride with water vapor according to claim 1, wherein the method comprises: the borohydride is one or more of sodium borohydride, potassium borohydride, lithium borohydride, magnesium borohydride and calcium borohydride.

5. The method for producing hydrogen by hydrolysis of borohydride with water vapor according to claim 1, wherein the method comprises: the catalyst is solid acid, strong acid and weak base salt or a mixture of the solid acid and the strong acid and the weak base salt.

6. The method for producing hydrogen by hydrolysis of borohydride with water vapor according to claim 1, wherein the method comprises: the water-containing substance is sodium carbonate decahydrate, water-absorbing molecular sieve or water-absorbing vermiculite.

7. The method for producing hydrogen by hydrolysis of borohydride according to claim 6, wherein the temperature for heating the water-containing substance is 80 ~ 150 ℃.

Technical Field

The invention relates to a hydrogen production technology, in particular to a method for producing hydrogen by hydrolyzing borohydride with water vapor.

Background

With the rapid development of economy, fossil energy is consumed in large quantities, causing shortage of non-renewable energy and serious environmental pollution. The hydrogen energy can be ideal energy in the future, can provide fuel for a fuel cell, has high energy density of the hydrogen gas and no pollution of products, and effectively solves the problems brought by the existing fossil fuel. There are many methods for producing hydrogen, such as catalytic reforming hydrogen production, biological hydrogen production, photocatalytic hydrolysis hydrogen production, electrolytic water hydrogen production, borohydride hydrolysis hydrogen production, and the like. Among them, hydrogen production by hydrolysis of borohydride is the most widely studied one at present, and industrial large-scale hydrogen production can be realized. The hydrogen prepared by hydrolyzing the borohydride has high purity and controllable hydrogen production rate, can solve the practical problems of storage, transportation and the like of the hydrogen, and provides a convenient and safe solution for the utilization of hydrogen energy.

In the existing hydrogen production schemes by hydrolysis of borohydride, borohydride is mostly prepared into alkaline solution, and then the alkaline solution reacts with a catalyst to produce hydrogen. For example, CN 108238586 a discloses a method for producing hydrogen from sodium borohydride, which comprises preparing sodium borohydride into an alkali solution, preparing an inorganic acid solution, sequentially adding the alkali solution and the acid solution into a hydrogen reactor through two liquid supply pipelines, and adjusting the liquid inlet amount to control the hydrogen production speed. According to the method, sodium borohydride and inorganic acid are respectively prepared into solutions and then are led to a reactor to realize hydrogen production, so that the whole system is complicated; the temperature is difficult to rapidly rise due to the form of double solutions, and the starting speed is slow; the increase in the amount of water lowers the hydrogen storage density of the entire system.

For example, CN 104649225A discloses a portable all-solid hydrogen production material and a preparation method and application thereof, the patent proposes that the solid substance reacting with water to release hydrogen and the water-containing solid substance are fully mixed and heated to the dehydration temperature of the water-containing substance to produce hydrogen, the hydrogen production method disclosed by the patent has the following defects that the dehydration temperature of ① water-containing compounds is low, crystal water is lost when the water-containing compounds are heated to 40 ℃, low-temperature environment is required to be provided for storage after the solid substances are mixed, otherwise, the hydrogen is possibly generated at any time to cause danger, and simultaneously, the dehydration temperature of some compounds is high, the water is required to be heated to hundreds of degrees to start dehydration, the storage and transportation of the solid mixture are convenient and safe, but the energy consumption in the reaction process is increased, ②, because all the raw materials are mixed together, the rate and the start-stop control of the reaction process are difficult, hysteresis exists, ③, the solid mixture is fully reacted, and the solid mixture is required to be uniformly mixed and heated to be uniform, the local osmotic temperature difference is reduced, otherwise, the crystal water production efficiency is easily influenced, and the internal and external caking reaction is increased.

Disclosure of Invention

In order to solve the problems, the invention provides a method for preparing hydrogen by hydrolysis of borohydride by using water vapor, which is characterized in that the water vapor is introduced into a solid mixture of the borohydride, a catalyst and a leavening agent to prepare the hydrogen by hydrolysis.

In order to achieve the purpose, the invention adopts the following specific technical scheme:

a method for preparing hydrogen by hydrolysis of borohydride by using water vapor comprises the following steps:

s1: weighing borohydride, a catalyst and leavening agent powder, and uniformly mixing;

s2: weighing water or water-containing substances for later use;

s3: separately placing the mixed powder and the water/water-containing substance in a reaction vessel;

s4: heating the water/water-containing substance end, introducing the generated water vapor into the tail end of the mixed powder, and collecting the hydrogen generated by the reaction.

Preferably, the mass ratio of the borohydride, the catalyst, the leavening agent and the water or the water-containing substance is 1 (0.5 ~ 1) to (0.3 ~ 0.5) to (1 ~ 3).

Preferably, the leavening agent is one or more of activated carbon, vermiculite, molecular sieve and foam particles.

Preferably, the borohydride is one or more of sodium borohydride, potassium borohydride, lithium borohydride, magnesium borohydride and calcium borohydride.

Preferably, the catalyst is a solid acid, a strong acid and weak base salt or a mixture of the two. The catalyst promotes the forward reaction, the solid acid is boric acid, and the strong acid weak base salt is anhydrous magnesium sulfate or anhydrous zinc sulfate.

Preferably, the water-containing substance is sodium carbonate decahydrate, a water-absorbing molecular sieve or water-absorbing vermiculite.

Further, the heating temperature of the aqueous substance was 80 ~ 150 ℃.

The method comprises the steps of firstly uniformly mixing borohydride, a catalyst and leavening agent powder, then heating water or a water-containing substance, introducing generated water vapor into a solid mixture for hydrolysis hydrogen production, placing the water or the water-containing substance and the solid mixture separately, supplying water by using the water vapor, facilitating storage and transportation, and effectively improving hydrogen storage density, compared with the method of directly mixing all solid raw materials for reaction, the contact area between the raw materials is greatly increased, the utilization rate of sodium borohydride is improved, and the reaction rate can be controlled by adjusting the temperature and the supply quantity of the water vapor during the reaction process, more specifically, the reaction efficiency of the water vapor and the solid mixture is optimized by adding the leavening agent, the gaps among the mixed powder particles can be increased by the leavening agent, on one hand, the resistance of the water vapor entering the solid mixture can be reduced, so that the water vapor fully permeates into the solid mixture, the hydrogen production can be rapidly and comprehensively generated, on the other hand, the leavening agent can maintain a certain degree of loose degree of the solid mixture during the reaction process, and the impact force applied by the water vapor on the solid mixture can be avoided, a large amount of partial condensation of the solid mixture is prevented from being condensed on the surface of the borohydride, the leavening agent, the solid mixture, the heat conductivity of the water is ensured, the vermiculite is further, the water absorption rate is improved by strictly controlled by strictly selecting 351, the water absorption of the water-containing substance, the water-absorbing catalyst is strictly controlled by strictly, the water-absorbing catalyst 3580, the water-absorbing catalyst is strictly controlled by strictly, the water-absorbing catalyst, the water-absorbing.

The invention has the following beneficial effects:

the solid mixture of water vapor, borohydride, a catalyst and a leavening agent is used for reaction, so that the hydrogen storage density is greatly improved, the reaction contact area is increased, and the borohydride utilization rate is improved; and the reaction rate can be controlled by adjusting the temperature and supply amount of the water vapor.

The swelling agent is added into the hydrogen production material, so that the permeability of water vapor is improved, the water vapor is quickly and fully contacted with the inside of the solid mixture, the caking phenomenon caused by crystallization of a byproduct metaborate is avoided, and the reaction efficiency of borohydride is effectively improved.

The solid borohydride, the catalyst and the leavening agent are mixed, and water or water-containing substances are independently placed, so that the storage and the transportation are convenient, and the control of the hydrogen production rate is convenient.

Detailed Description

The present invention will be further described with reference to the following examples.