Hydrophilic emulsion catalyst and application thereof in preparation of hydrogen-promoting softened deionized water

Abstract

The invention discloses a hydrophilic emulsion catalyst and application thereof in preparation of hydrogen-promoting softened deionized water. The hydrophilic emulsion catalyst is formed by uniformly mixing a blended solution with ethanol which is 10 times of the volume of the blended solution at 40 DEG C, the blended solution is composed of an organic ester catalyst, S80, copper oxide powder and OP10, and the organic ester catalyst is composed of ethanol, acetic acid and polyethylene polyamine. The hydrogen-promoting softened deionized water is prepared by filtering and magnetizing 96.5% of fresh water, adding 3.5% of a hydrophilic emulsification catalyst for hydrophilic emulsification, sterilizing and catalyzing. Compared with traditional deionized water, the hydrogen-promoting softening deionized water prepared by the invention has the advantages that the hydrogen production amount can be increased by 3-19% and the hydrogen purity can be improved when hydrogen is produced from methanol.

Description

Technical Field

[0001] The present invention relates to the technical field of hydrogen production from methanol, and particularly to a hydrophilic emulsified catalyst and its application in the preparation of hydrogen-promoting softened deionized water. Background Art

[0002] The process flow of hydrogen production from methanol is simple, easy to operate and maintain. The main equipment is common chemical equipment and the technology is relatively mature. Therefore, it is an important hydrogen production method and has wide applications in the chemical industry. At present, partial oxidation of methanol, steam reforming of methanol and oxidative steam reforming of methanol are the main ways of hydrogen production from methanol.

[0003] The reaction principle of hydrogen production by steam reforming of methanol is that methanol and water vapor react under certain temperature, pressure conditions and the action of a catalyst to undergo methanol cracking reaction and carbon monoxide shift reaction, generating hydrogen and carbon dioxide. This is a multi-component, multi-reaction gas-solid catalytic reaction system. To optimize the process of hydrogen production by steam reforming of methanol and improve the hydrogen production efficiency, the current research direction mainly focuses on the improvement of the catalyst. Especially for copper-based catalysts, due to their advantages such as high activity and good selectivity, there have been many studies on copper-based catalysts at home and abroad. For example, some studies have shown that the gradient distribution of catalyst activity from low to high in the reactor can improve the conversion rate of methanol and the hydrogen content at the outlet; increasing the copper content in the catalyst can increase the catalyst activity; Cu / ZnO / Al 2 O 3 series catalysts have good low-temperature activity and high hydrogen selectivity for the reaction of hydrogen production by steam reforming of methanol, etc. Summary of the Invention

[0004] The object of the present invention is to provide a new idea for the problems existing in the prior art in the aspect of hydrogen production by steam reforming of methanol, such as low hydrogen production efficiency, low hydrogen purity, and the research idea being limited to the improvement of the catalyst used in the hydrogen production reaction. That is, starting from the water used as the hydrogen production raw material, the hydrogen production efficiency is improved by transforming the water.

[0005] Traditional methods for preparing deionized water mainly include distillation, reverse osmosis (RO), adsorption and exchange using ion exchange resins, electrolysis, and mixed bed methods that mix cation exchange resins and anion exchange resins. Deionized water has many advantages: 1. High purity and low impurity content. Deionized water removes various ionic impurities in water through techniques such as ion exchange, such as cations like calcium, magnesium, iron, sodium, and anions like chloride, sulfate, carbonate. The impurity content is extremely low, usually reaching a conductivity below 1 μS / cm or even lower. It is purer than ordinary tap water and other water qualities. 2. Good chemical stability and not prone to chemical reactions. Since most ions are removed, deionized water is not easily induced to have chemical reactions due to the ions in water when contacting other substances. In some experiments and production processes with strict requirements for chemical reaction conditions, it can provide a stable chemical environment to ensure the accuracy of experimental results and the stability of product quality. 3. Low conductivity and good insulation performance. Ions in water are the main medium for conduction. Deionized water removes a large number of ions, greatly reducing its conductivity and having good insulation performance. It can be used in fields with high requirements for insulation performance such as the electronics industry to avoid problems such as short circuits caused by the conductivity of water. 4. No residual substances and no traces after evaporation. Deionized water will not leave scale or other residual substances caused by impurities such as minerals after evaporation. This is very important in some occasions with extremely high cleanliness requirements, such as the cleaning of optical lenses and the manufacturing of precision instruments, ensuring that there is no impurity residue on the surface of the object being cleaned or processed. 5. High solubility and good solubility for many substances. Although ions are removed, deionized water still has good solubility for many non-ionic substances and can be used as an excellent solvent in industries such as chemical experiments and pharmaceuticals, helping with the dissolution, mixing, and reaction of substances.

[0006] Although deionized water prepared by traditional methods has the above-mentioned many advantages, these methods are all aimed at removing impurities and mineral ions in water. Currently, for the water used in methanol-to-hydrogen production, deionized water prepared by the above traditional methods is mainly used, and the microscopic structure and content components of the water have not been transformed.

[0007] The technical solution of the present invention is described in detail as follows: In the first aspect, the present invention provides a hydrophilic emulsified catalyst, which is formed by uniformly mixing a blend liquid with ethanol at 40 °C in a volume 10 times that of the blend liquid. The blend liquid is composed of the following raw materials by mass percentage: Organic fat catalyst 1‰, S80 2‰, Copper oxide powder 0.2‰, OP10 the balance; The organic fat catalyst is composed of ethanol, acetic acid, and polyethylenepolyamine in an equal volume ratio.

[0008] S80, that is, emulsifier Span 80, with the chemical name of sorbitan monooleate, or sorbitol anhydride monooleate. OP10, with the chemical name of alkylphenol polyoxyethylene ether, is a non-ionic surfactant formed by the condensation of alkylphenol and ethylene oxide. The copper oxide powder preferably uses a powder with a mesh size of more than 1000 meshes.

[0009] In a second aspect, the present invention provides the application of the above hydrophilic emulsifying catalyst in the preparation of hydrogen-promoting softened deionized water.

[0010] In a third aspect, the present invention provides a method for preparing hydrogen-promoting softened deionized water. Calculated by mass percentage, it is prepared by adding 3.5% of the above hydrophilic emulsifying catalyst to 96.5% of fresh water after filtration and magnetization for hydrophilic emulsification, and then through sterilization and catalysis. The specific method is as follows: (1) The fresh water is filtered through a three-stage membrane to obtain pure water; (2) The pure water is heated to 90 °C and then magnetized. The magnetized pure water is added with a hydrophilic emulsifying catalyst for hydrophilic emulsification to obtain emulsified water; (3) The emulsified water is sterilized and subjected to green light catalysis to obtain a hydrogen-promoting softened deionized water product.

[0011] The hydrogen-promoting softened deionized water refers to water that can promote the hydrogen production amount of methanol-to-hydrogen, remove mineral metal ions, and be softened. Green light refers to visible light with a wavelength range between 495 nm and 570 nm, and the central wavelength is about 550 nm.

[0012] Optionally or preferably, in the above method, the three-stage membrane filtration in step (1) is completed by a three-stage membrane filter, and a filtration system with a sand filter element, an RO membrane filter element, and an activated carbon filter element is used for filtration in sequence.

[0013] Optionally or preferably, in the above method, the magnetization in step (2) uses electric field magnetization, the magnetic field intensity is 3000 - 7000 Gs, the water flow gap is 3 - 8 mm, and the water flow rate in the gap is less than 3 m / s.

[0014] Optionally or preferably, in the above method, the emulsification in step (2) is completed by an ultrasonic oscillation emulsifier, and the emulsification condition is a high frequency of 40 kHz.

[0015] Optionally or preferably, in the above method, the sterilization in step (3) uses ultraviolet sterilization.

[0016] In a fourth aspect, the present invention provides the hydrogen-promoting softened deionized water prepared by any of the above methods.

[0017] In a fifth aspect, the present invention provides the application of the above hydrogen-promoting softened deionized water in methanol-to-hydrogen.

[0018] Compared with the prior art, the present invention has the following beneficial effects: 1. For the hydrophilic emulsifying catalyst of the present invention, when preparing hydrogen-promoting softened deionized water, S80 and OP10 as emulsifiers help to increase the water-oil compatibility. The organic fat catalyst can promote the hydrophilic emulsification process and at the same time promote the gas production of methanol hydrogen production. Copper oxide is used as a hydrogen-promoting catalyst in methanol hydrogen production to promote hydrogen generation, and ethanol can improve the activity of the hydrogen-promoting catalyst.

[0019] The components in the organic fat catalyst may have the following functions: (1) Ethanol Changing the reaction path or increasing the reaction complexity: Ethanol itself can undergo reactions such as reforming to produce hydrogen. When added to the methanol hydrogen production system, it may introduce new reaction paths. For example, ethanol may first dehydrogenate to form intermediate products such as acetaldehyde, and then acetaldehyde further reacts, making the entire reaction system more complex. For example, in the presence of a suitable catalyst, ethanol will undergo a reaction similar to methanol reforming to produce hydrogen and carbon dioxide.

[0020] Affecting the product distribution: It may cause products related to the reaction of ethanol, such as acetic acid, etc., in addition to hydrogen and carbon dioxide in the products. Under certain conditions, ethanol and methanol may undergo some coupling reactions, changing the production ratio of hydrogen and other products.

[0021] Potential for increasing hydrogen production: From the elemental composition, ethanol is also rich in hydrogen elements and can decompose to produce hydrogen under suitable conditions, which may help to increase the overall hydrogen production.

[0022] (2) Acetic acid Possible catalytic effects: In some reactions involving the conversion of hydrocarbons, acetic acid may have a certain catalytic or co-catalytic effect. It may affect the progress of certain intermediate steps in the methanol hydrogen production reaction, such as the activation of methanol, the breaking and formation of chemical bonds, etc., thus changing the reaction rate and product distribution.

[0023] Changing the acidity and alkalinity of the reaction system: Acetic acid is an acidic substance. After adding it, the acidity of the reaction system will increase, which may affect the activity and selectivity of the catalyst. For some catalysts sensitive to acidity and alkalinity, it may change the nature of the active sites on their surfaces, thereby affecting the progress of the methanol hydrogen production reaction.

[0024] Participating in side reactions: Acetic acid may undergo side reactions such as esterification with methanol or other intermediate products in the reaction, consuming methanol or affecting the purity and composition of the products.

[0025] (3) Polyethylene polyamine As a ligand or cocatalyst: Polyethylene polyamine has multiple amino groups and can form complexes with some metal ions. In methanol steam reforming for hydrogen production, in the presence of a metal catalyst, polyethylene polyamine may bind to the metal as a ligand, changing the electron cloud density and spatial structure of the metal catalyst, thereby regulating the activity and selectivity of the catalyst and contributing to an increase in the conversion rate of methanol and the yield of hydrogen.

[0026] Regulating the properties of the reaction system: Polyethylene polyamine can change the properties of the reaction system such as polarity and pH, affecting the existence state and reactivity of methanol molecules and other reactants and intermediates, and thus having an indirect impact on the methanol steam reforming for hydrogen production reaction.

[0027] Promoting product separation or suppressing side reactions: It may interact with certain by-products or impurities in the reaction, promoting product separation or suppressing the occurrence of some side reactions that are not conducive to hydrogen production, thereby improving the purity of hydrogen and the selectivity of the reaction.

[0028] 2. In the method for preparing deionized water of the present invention, most impurities and metal ions are first removed by filtration to obtain pure water, and then the water is heated to 90 °C to increase the water temperature and the coagulation state of the water is changed by magnetization to reduce the degree of coagulation, which is conducive to adding a hydrophilic emulsifying catalyst for hydrophilic emulsification. Heating to 90 °C not only adapts to the properties of the emulsifier to facilitate the emulsification process, but also because the water molecules move violently at high temperatures, which is conducive to further promoting the magnetization process. The small clusters of water molecules in the emulsified water are wrapped by an emulsifier film, and at the same time, copper oxide is evenly dispersed in the water. No additional catalyst needs to be added during subsequent methanol steam reforming for hydrogen production. Liquid water molecules are connected together by molecular chains, and these molecular chains can be broken after being irradiated by green light and are in a semi-closed state. Water in this state is more easily decomposed during methanol steam reforming for hydrogen production.

[0029] 3. Compared with the deionized water prepared by traditional methods, when the hydrogen-promoting soft deionized water prepared by the method of the present invention is mixed with methanol in the same proportion, the hydrogen production amount can be increased by 3% - 10% under the same energy consumption and raw material cost in the processes of methanol catalytic steam reforming for hydrogen production and reforming steam reforming for hydrogen production.

[0030] Under the condition of the same hydrogen production amount, using the hydrogen-promoting soft deionized water prepared by the method of the present invention can increase the mixing ratio of deionized water and methanol, correspondingly reduce the hydrogen production cost, and improve the purity of hydrogen. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 It is a on-site photo of the methanol steam reforming for hydrogen production experiment process in Example 2.

[0032] Figure 2 It is a photo of the methanol and water agent for methanol steam reforming for hydrogen production in Example 2.

[0033] Figure 3It is a photo of the experiment of heating water in a measuring cup with the hydrogen produced by methanol reforming for hydrogen production in Example 2. Detailed implementation manners

[0034] In order to enable those skilled in the art to better understand the solution of this application, the following will clearly and completely describe this application in combination with the embodiments and the accompanying drawings. Obviously, the described embodiments are only a part of the embodiments of this application, rather than all the embodiments. Based on the embodiments in this application, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of this application. The instruments and reagents used in the embodiments are all from commercial channels unless otherwise specified.

[0035] Example 1 Preparation of hydrogen-promoted softened deionized water By mass percentage, 96.5% of fresh water (tap water, underground and surface water are all acceptable), and 3.5% of the required hydrophilic emulsifying catalyst.

[0036] Preparation process: 1. Preparation of hydrophilic emulsifying catalyst It is composed of mixing the blend liquid with ethanol 10 times the volume of the blend liquid at 40°C and mixing evenly. The blend liquid is composed of the following raw materials by mass percentage: Organic fat catalyst 1‰, S80 2‰, Copper oxide powder 0.2‰, OP10 the balance; The organic fat catalyst is composed of ethanol, acetic acid, and polyethylenepolyamine in equal volume ratio.

[0037] 2. Preparation of hydrogen-promoted softened deionized water (1) Take fresh water and connect it to a three-stage membrane filter to obtain purified water; the filtration system of the three-stage membrane filter includes a sand filter element, a RO membrane filter element, and an activated carbon filter element.

[0038] (2) After heating the purified water to 90°C, pass it through an electric field magnetizer to magnetize the water. The magnetic field strength is 3000 - 7000 Gs, the water flow gap is 3 - 8 mm, and the flow rate of water in the gap is less than 3 m / s. The magnetized water is input into an ultrasonic vibration emulsifier, and at the same time, the hydrophilic emulsifying catalyst is added in proportion, and emulsification is carried out under the condition of high frequency 40 kHz in the emulsifier to obtain emulsified water.

[0039] (3) The emulsified water flows through the photocatalytic chamber to be sterilized under the action of ultraviolet light, and under the action of green light catalysis, the decomposition reaction of water is driven by green light to break the water molecular chain, and finally the production process is completed. After inspection, it is put into the storage tank and warehoused to obtain the finished product of hydrogen-promoted softened deionized water.

[0040] (4) Storage method and shelf life The hydrogen-promoted softened deionized water has a shelf life of three years when stored at -5°C to 90°C.

[0041] Example 2: Methanol steam reforming for hydrogen production using hydrogen-promoted softened deionized water Experimental purpose: To test the hydrogen production effects of hydrogen-promoted softened deionized water and ordinary purified water (deionized water prepared by traditional methods).

[0042] Experimental method: A methanol reforming hydrogen production machine was used, with the raw materials being 65% methanol mixed with 35% water (by volume percentage, the mixture is 30 mm). Stable hydrogen production started 3 minutes after starting the machine.

[0043] For the hydrogen production effect, the purity of hydrogen was roughly detected by listening to the sound of hydrogen bottle ignition, and the flame color discrimination method was used to further verify the hydrogen purity. Observe the flame color, measure the flame height with a steel ruler, and heat the water in a measuring cup with the flame to measure the rising temperature of the water within a certain period of time.

[0044] The combustion method was used to calculate the hydrogen purity. Hydrogen burns to form water. According to the volume change of the gas before and after combustion or the amount of water formed, etc., combined with the stoichiometric relationship, the hydrogen purity was calculated. The operation method is to completely burn a certain amount of hydrogen in a closed container with oxygen present, measure the volume change of the gas in the container before and after combustion, or measure the amount of water formed through an absorption device, and calculate the hydrogen purity based on the relevant formula.

[0045] Table 1 Hydrogen production conditions and effects of experimental examples and comparative examples For No. 1, the flame height of hydrogen bottle ignition is 6 cm, the bottom of the flame is blue and the upper part is orange-red, and the water temperature rises by 16.1°C after heating the water for 5 minutes. For No. 2, the flame height of hydrogen bottle ignition is 7 cm, and the water temperature rises by 21.8°C after heating the water for 5 minutes.

[0046] Based on the above comparative tests, an alcohol-water agent with hydrogen-promoted softened deionized water and methanol mixed in the same proportion was used for methanol steam reforming for hydrogen production, and two conclusions were drawn: 1. The purity is higher. By observing the flame color and the hydrogen content in the test tube hydrogen ignition test, the hydrogen content of No. 2 is above 99%, and the hydrogen purity of No. 1 is lower than 96%. Through the same dose of hydrogen production gas volume acting on the same dose of initial warm water in the measuring cup and heating for the same time, the temperature increased by more than 10%. This proves that both the hydrogen purity and hydrogen production volume of the test No. 2 have been greatly improved and increased. The conclusion is that the application of hydrogen-promoted softened deionized water in methanol steam reforming for hydrogen production projects has the effects of improving quality and efficiency and market value.

[0047] In this article, specific examples are used to elaborate on the inventive concept in detail. The description of the above embodiments is only used to help understand the core idea of the present invention. It should be noted that for those of ordinary skill in the art, any obvious modifications, equivalent substitutions or other improvements made without departing from the inventive concept shall be included within the protection scope of the present invention.

Claims

1. A hydrophilic emulsified catalyst, characterized in that: The mixed liquid is mixed with 40°C ethanol 10 times the volume of the mixed liquid and mixed evenly. The mixed liquid is composed of the following raw materials in percentage by mass: composition: Organic fat catalyst 1‰, S80 2‰， Copper oxide powder 0.2‰, OP10 margin; The organic fat catalyst is composed of ethanol, acetic acid, and polyethylene polyamine mixed in equal volume proportions.

2. Use of the hydrophilic emulsified catalyst according to claim 1 in the preparation of hydrogen-promoting softened deionized water.

3. A method for preparing hydrogen-promoting softened deionized water, characterized in that: According to the percentage by mass, 96.5% of fresh water is filtered and magnetized, and then 3.5% of the hydrophilic emulsification catalyst according to claim 1 is added to perform hydrophilic emulsification, followed by sterilization and catalysis. The specific method is as follows: (1) Fresh water is filtered through three-stage membranes to obtain pure water; (2) Pure water is heated to 90°C and then magnetized. A hydrophilic emulsification catalyst is added to the magnetized pure water to perform hydrophilic emulsification to obtain emulsified water; (3) Emulsified water is sterilized and green-light catalyzed to obtain hydrogen-promoting softened deionized water products.

4. The method according to claim 3, characterized in that The three-stage membrane filtration in step (1) is completed by a three-stage membrane filter, and a filtration system with a sand filter element, an RO membrane filter element and an activated carbon filter element is used in sequence for filtration.

5. The method according to claim 3, characterized in that: The magnetization in step (2) adopts electric field magnetization, the magnetic field strength is 3000-7000Gs, the water flow gap is 3-8mm, and the flow rate of water in the gap is less than 3m / s.

6. The method according to claim 3, characterized in that The emulsification in step (2) is carried out by using an ultrasonic oscillation emulsifier, and the emulsification condition is a high frequency of 40 kHz.

7. The method according to claim 3, characterized in that The sterilization in step (3) is carried out by ultraviolet sterilization.

8. Hydrogen-promoting softened deionized water prepared by the method according to any one of claims 3 to 7.

9. Use of the hydrogen-promoting softened deionized water according to claim 8 in hydrogen production from methanol.

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