Process for hydrogen production by adsorption catalysis of crude synthetic gas and device thereof

Abstract

The invention discloses a process for hydrogen production by adsorption catalysis of crude synthetic gas and a device thereof. The process comprises the following steps: 1) mixing water vapor and the crude synthetic gas according to a water-carbon mol ratio of 2 to 6, adding a reduced reforming catalyst with an adsorption function, and carrying out a reforming hydrogen-producing reaction in a fluidized state; 2) oxidizing the reforming catalyst after a high-temperature combustion reaction so as to remove carbon deposit and sulfur-containing components on the reforming catalyst, and heating the reforming catalyst so as to release CO2 and realize regeneration; and 3) subjecting the regenerated reforming catalyst to in-situ reduction at 400 to 900 DEG C, subjecting the reduced reforming catalyst to circulating production of hydrogen, i.e., a product. According to the invention, the crude synthetic gas containing coal tar and sulfur can be further converted into hydrogen, so sulfur removal and coal tar separation of the crude synthetic gas are saved, and the selection range of hydrogen-producing raw gases is greatly broadened; through in-situ reduction of the reforming catalyst, a reduction procedure is not needed to be additionally arranged; and the device provided by the invention saves the use of auxiliary equipment like a degassing tank and a reduction reactor, so procedures are greatly simplified.

Description

technical field [0001] The invention relates to hydrogen preparation technology, in particular to a crude synthesis gas adsorption and catalytic hydrogen production process and its equipment. Background technique [0002] Hydrogen is not only a recognized clean energy, but also an important gas raw material in chemical, metallurgical and oil refining industries. At present, most of the hydrogen used in industrial production at home and abroad is made from natural gas through steam reforming reaction (also known as steam reforming reaction) in a fixed bed reactor. This process has the following disadvantages: 1) The concentration of hydrogen is low, there are many reaction steps and purification steps, and the process is long; 2) The catalyst particles used in the fixed bed reactor are large, and there is a gradient in heat transfer inside the reactor, and the catalyst is prone to carbon deposition, resulting in a decrease in conversion rate. , and the service life becomes s...

AI Technical Summary

Problems solved by technology

This process has the following disadvantages: 1) The concentration of hydrogen is low, there are many reaction steps and purification steps, and the process is long; 2) The catalyst particles used in the fixed bed reactor are large, and there is a gradient in heat transfer inside the reactor, and the catalyst is prone to carbon deposition, resulting in a decrease in conversion rate. , the service life becomes shorter; 3) Catalyst replacement, regeneration and continuous production are difficult

[0003] In order to solve the above problems, relevant personnel have done a lot of research. Chinese patent CN101054161A discloses a process of using a circulating fluidized bed for steam reforming of methane to produce hydrogen. This process realizes the recovery and regeneration of catalysts, but the process Does not improve the effect of carbon dioxide produced by the reaction on the reduction in reaction conversion

Chinese patent CN102730636A discloses a composite reactor steam reforming hydrogen production method, which uses a fixed bed reforming reactor and a riser adsorption reactor in series to realize the strengthening of the reforming reaction by the adsorption reaction, because of this In the method, the reforming reaction and the adsorption reaction are carried out in two reactors respectively, so the promotion of the reforming reaction by the adsorption reaction cannot be well realized.

Chinese patent CN101559924A provides a methane-steam reforming hydrogen production process, which realizes reforming reaction and adsorption reaction at the same time by putting adsorbent and reforming catalyst into the same reactor, so as to remove carbon dioxide in time, The purpose of improving the reaction efficiency, and at the same time, the recycling of the adsorbent after regeneration maximizes the use efficiency of the adsorption, but this process only realizes the recycling of the adsorbent, and there is a problem that the reforming catalyst and the adsorbent are difficult to effectively separate

Chinese patent CN102464299 discloses a method for hydrogen production by steam reforming of fluidized bed methane, which provides an effective solution to the separation of adsorbent and reforming catalyst when used in the same reactor, that is, using density Differential use of low-density adsorbents to achieve the separation of adsorbent and catalyst particles, this method provides a better solution to the separation of adsorbent and catalyst, but it does not solve the regeneration and recycling of catalysts, which will still bring The problem of catalyst replacement and continuous production, in addition, the process also puts forward requirements on the operating range of the reactor, which increases the difficulty of the process and operation

Chinese patent CN1935634A provides an adsorption-enhanced methane steam reforming hydrogen production process and device using a circulating fluidized bed. This process realizes the adsorption reaction and reforming reaction by using a composite catalyst with dual functions of adsorption and catalytic reforming Simultaneously, because there is no problem that the adsorbent and the catalyst need to be separated, the process is simplified and the difficulty of operation is reduced. This process has the problem that the regenerated catalyst recycled after separation needs to be reduced separately and then enter the reactor for reaction. This undoubtedly affects the process. and continuity of operations present challenges

Chinese patent CN103373706A discloses a method and device for hydrogen production by methane reforming. In this method, hydrogen is used to reduce the composite adsorbent with dual functions of adsorption and catalysis at the bottom of the fluidized bed reactor and then enter the upper part of the reactor for hydrogen production. Reaction, this method completes the reduction of the composite catalyst and the reforming hydrogen production reaction in the same reactor while realizing the recycling of the catalyst, but this method needs to continuously feed hydrogen to reduce the regenerated catalyst, from the overall point of view of the process From the point of view, this undoubtedly reduces the hydrogen production of the process

Since the crude synthesis gas contains H 2 , CO, CH 4 As well as other hydrocarbons, it has the potential to be converted into hydrogen for more valuable utilization. However, the sulfur components and tar in the crude synthesis gas are likely to cause catalyst poisoning, thereby reducing the life of the catalyst, which largely limits the use of crude synthesis gas. Applications in the field of hydrogen production

Images