Methanol hydrogen production system

Abstract

The system comprises a steam vaporization tank, a cracking reaction tank and a cooler which are connected in sequence, the steam vaporization tank comprises an outer container and an inner container arranged in the middle of the outer container in a sleeving mode, the inner container is used for containing a heating medium, and a heating pipe is arranged in the inner container; a methanol containing cavity is defined between the inner container and the outer container; and a steam outlet pipe is arranged at the top of the side wall of the outer container. The steam vaporization tank is of a double-layer structure, heat conduction oil is arranged in an inner container and is half-filled, methanol gas is arranged on the upper portion between the inner container and the outer container, liquid is arranged on the lower portion between the inner container and the outer container and is uniformly vaporized into methanol steam, gas on the upper portion is overheated and enters the cracking reaction tank, the cracking reaction tank is provided with a plurality of steel pipes filled with catalysts, and the methanol steam is long in gas path and is uniformly cracked into mixed hydrogen under the action of the catalysts.

Description

Technical Field

[0001] The invention belongs to the technical field of new energy hydrogen production, and specifically relates to a methanol hydrogen production system. Background Art

[0002] The statements herein merely provide background information related to the present invention and do not necessarily constitute prior art.

[0003] Hydrogen is a renewable energy source with a wide range of sources, including water, natural gas, methanol, ethanol, biomass, etc. Due to the energy depletion and environmental pollution caused by fossil fuels, people's desire for clean energy is becoming more and more obvious. Hydrogen has a high combustion calorific value and its products are pollution-free. It is a clean and sustainable energy source. The current methods of hydrogen production mainly include hydrogen production by reaction of steam and hydrogen production catalyst, hydrogen production by reforming of fossil fuels, hydrogen production by electrolysis of water, hydrogen production by photohydrolysis, hydrogen production by biomass, and hydrogen production by plasma.

[0004] At present, methanol is widely used to produce hydrogen. Methanol hydrogen production refers to the use of methanol solution as raw material under certain temperature and pressure conditions. The methanol solution produces methanol vapor after being heated, and then the methanol vapor undergoes a conversion reaction under the action of a hydrogen production catalyst, ultimately achieving the purpose of producing hydrogen.

[0005] In the prior art, the preparation method of methanol vapor mainly adopts electric heating tube to heat methanol solution to finally obtain methanol vapor; however, methanol is often mixed with methanol in gaseous and liquid states, so when methanol is heated by combustion catalysis, methanol will be heated unevenly, resulting in a decrease in vaporized methanol vapor; at the same time, the methanol vapor path in the cracking reaction is short, the catalyst is heated unevenly, and the cracking reaction is incomplete; in addition, during the heating process, the heat in the exhaust gas after combustion cannot be fully utilized, which ultimately reduces the efficiency of preparing mixed hydrogen and increases energy consumption. Summary of the invention

[0006] In view of the deficiencies in the prior art, an object of the present invention is to provide a methanol hydrogen production system.

[0007] In order to achieve the above object, the present invention is implemented through the following technical solutions:

[0008] The present invention provides a methanol hydrogen production system, comprising a steam vaporization tank, a cracking reaction tank and a cooler connected in sequence, wherein:

[0009] The steam vaporization tank comprises an outer tank and an inner tank which is sleeved in the middle of the outer tank, the inner tank is used to hold a heating medium, and a heating pipe is arranged inside the inner tank; a methanol holding chamber is formed between the inner tank and the outer tank; a methanol inlet pipe is arranged at the bottom of the side wall of the outer tank, and a steam outlet pipe is arranged at the top.

[0010] The steam vaporization tank in the present invention is provided with an inner tank and an outer tank, wherein the inner tank is arranged in the middle of the outer tank, a heating medium is contained in the inner tank, and a heating pipe is arranged, the heating medium is uniformly heated by the heating pipe, and the methanol between the inner tank and the outer tank can be heated.

[0011] Since the inner tank is arranged in the middle of the outer tank, the thickness of the methanol liquid layer surrounding the inner tank is uniform, thereby improving the uniformity of heating of the methanol.

[0012] In some embodiments, the inner liner and the outer liner are both cylindrical structures, and the inner liner covers the outer liner in the effective height direction.

[0013] Here, the effective height of the outer tank refers to the maximum height that the outer tank can hold methanol, that is, methanol always exists between the inner tank and the outer tank, and both the inner tank and the outer tank are cylindrical structures, thereby ensuring that the thickness of the methanol liquid layer is uniform, which can better ensure the uniformity of methanol heating.

[0014] In some embodiments, a first safety valve is disposed on the top of the outer container, the first safety valve is connected to the inside of the outer container, and the first safety valve is a one-way valve. When the pressure of the methanol vapor between the outer container and the inner container exceeds a preset pressure, the first safety valve opens to discharge part of the gas to ensure the safe operation of the vapor vaporizer.

[0015] Preferably, a first high temperature sensor is disposed on the top of the outer container, and a temperature measuring section of the first high temperature sensor extends into the interior between the outer container and the inner container, for measuring the internal temperature of the prepared methanol vapor to ensure the safe operation of the vapor vaporizer.

[0016] In some embodiments, the heating tube is an electric heating tube, which is vertically arranged at the bottom of the inner tank.

[0017] The electric heating tube is arranged at the bottom of the inner tank. During actual operation, the temperature of the heat transfer oil at the bottom of the inner tank is the highest, and the methanol inlet pipe is arranged at the bottom of the outer tank, that is, the temperature of the methanol at the bottom of the outer tank is the lowest. The heat transfer oil with the highest temperature heats the methanol with the lowest temperature, which can effectively improve the heating efficiency of the methanol.

[0018] In some embodiments, an oil-water separator is disposed on the top of the outer container, and the oil-water separator is connected to the interior of the inner container.

[0019] In some embodiments, a liquid level gauge is provided on the side wall of the outer container.

[0020] In some embodiments, the cracking reaction tank is a vertical structure, including a cylindrical shell, an upper cover and a lower cover, and the lower cover is supported by a support leg assembly;

[0021] A catalyst support plate is sandwiched between the lower cover and the cylindrical shell, a perforated plate is arranged between the upper cover and the cylindrical shell, through holes are evenly distributed on the catalyst support plate, and a steel pipe assembly is fixedly arranged between the catalyst support plate and the perforated plate through the through holes, and the steel pipe is filled with catalyst;

[0022] Both ends of each steel pipe are connected to the interior of the upper cover and the lower cover;

[0023] A baffle is arranged inside the lower cover to divide the cavity of the lower cover into a first part and a second part. The lower cover of the first part is provided with an air inlet connected to the steam outlet pipe of the steam vaporizer; the lower cover of the second part is provided with an air outlet.

[0024] By adopting the cracking reaction tank of the present invention, the flow path of methanol vapor during catalytic cracking is to flow through the steel pipe from bottom to top, and then bend and flow through the steel pipe from top to bottom, which can effectively extend the flow path length of the methanol vapor, thereby increasing the residence time of the catalytic cracking reaction of methanol, so as to effectively improve the conversion rate and efficiency of methanol.

[0025] The catalyst is filled in a steel pipe, and the steel pipe is assembled and fixed through a catalyst support plate and a perforated plate, and connected with an upper cover and a lower cover, so that all methanol vapor flows through the steel pipe and fully contacts with the catalyst, which can effectively increase the contact area between methanol vapor and the catalyst, thereby improving the catalytic cracking efficiency of methanol.

[0026] Preferably, the cracking reaction tank is provided with an oil inlet at the bottom and an oil outlet at the top. High-temperature heat transfer oil is introduced into the cracking reaction tank to heat the inside of the cracking reaction tank and provide the heat required for the methanol catalytic cracking reaction. Since the heat transfer oil flows evenly through each steel pipe, the catalyst and reaction gas in the steel pipe can be evenly heated to ensure the progress of the reaction.

[0027] Preferably, a heat transfer oil reflux tank is provided on the top of the cylindrical shell, and the heat transfer oil reflux tank is connected to the top of the cylindrical shell. The function of the heat transfer oil reflux tank is to collect the overflow of the heat transfer oil into the heat transfer oil reflux tank when the heat transfer oil is in an overheated state, so as to avoid the danger of volume expansion.

[0028] Preferably, a second high temperature sensor and a second safety valve are provided on the top of the upper cover.

[0029] In some embodiments, the cooler includes a first cooler and a second cooler arranged in series, the hydrogen inlet of the first cooler is connected to the gas outlet of the cracking reaction tank, the cooling medium of the first cooler is methanol, and the cooling medium of the second cooler is water.

[0030] The high-temperature hydrogen obtained by catalytic cracking of methanol is first exchanged with methanol. On the one hand, the hydrogen can be initially cooled down, and on the other hand, the methanol can be initially heated. The heated methanol is recovered to the steam vaporization tank, which can effectively save the energy of methanol vaporization.

[0031] Preferably, the second mixed hydrogen outlet of the second cooler is connected to a drainer. The mixed hydrogen is mixed with methanol vapor that has not had time to undergo catalytic cracking reaction and methanol that has not had time to vaporize. The methanol vapor is recovered after condensation, and the methanol is discharged through the drainer and can flow back into the methanol storage tank for reuse, while the hydrogen is purified.

[0032] The beneficial effects achieved by one or more embodiments of the present invention are as follows:

[0033] 1. The structure of the present invention integrates multiple processes into one, including preheating of methanol solution, vaporization, cracking, cooling, filtering and diverting methanol vapor, and reflux to a methanol storage tank, etc., with a high degree of automation.

[0034] 2. The steam vaporization tank of the present invention has a double-layer structure, with heat transfer oil in the inner tank, which is more than half filled, and methanol gas is on the upper side and liquid is on the lower side between the inner and outer tanks, which are uniformly vaporized into methanol vapor. The upper gas is overheated and enters the cracking reaction tank. The cracking reaction tank has multiple steel pipes filled with catalysts. The methanol vapor has a long gas path and is uniformly cracked into mixed hydrogen under the action of the catalyst.

[0035] 3. The heat transfer oil boiler adopts special-shaped heating tubes for heating. The heat transfer oil enters the cracking reaction tank for circulation, making the catalyst heated more evenly and the catalytic conversion efficiency higher.

[0036] By using the double cooler, the mixed hydrogen can both preheat the methanol solution and be cooled by water to room temperature gas, thus fully utilizing the energy of the gas exhaust. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] The accompanying drawings in the specification, which constitute a part of the present invention, are used to provide a further understanding of the present invention. The exemplary embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute improper limitations on the present invention.

[0038] Figure 1 Schematic diagram of the overall structure of a methanol hydrogen production system according to an embodiment of the present invention;

[0039] Figure 2 is a schematic structural diagram of a steam vaporization tank according to an embodiment of the present invention;

[0040] Figure 3 It is a structural schematic diagram of a cracking reaction tank according to an embodiment of the present invention;

[0041] Figure 4 2 is a schematic structural diagram of a cracking reaction tank baffle and a catalyst support plate according to an embodiment of the present invention;

[0042] Figure 5 Schematic diagram of the structure of a cooler according to an embodiment of the present invention.

[0043] In the figure: 1. Steam vaporizer; 1.1. Vaporizer body; 1.2. Electric heating tube; 1.3. Methanol inlet pipe; 1.4. Liquid level gauge; 1.5. Inner tank; 1.6. Outer tank; 1.7. Steam outlet pipe; 1.8. First safety valve; 1.9. First high temperature sensor; 1.10. Oil-water separator;

[0044] 2. Cracking reaction tank; 2.1. Cracking tank body; 2.2. Air inlet; 2.3. Baffle; 2.4. Oil inlet; 2.5. Steel pipe; 2.6. First heat transfer oil reflux tank; 2.7. Second high temperature sensor; 2.8. Upper cover; 2.9. Second safety valve; 2.10. Second heat transfer oil reflux cover; 2.11. Oil outlet; 2.12. Cracking tank cavity; 2.13. Catalyst support plate; 2.14. Air outlet;

[0045] 3. Thermal oil boiler;

[0046] 4. Cooler; 4.1. First cooler; 4.2. Second cooler; 4.1.1. Methanol inlet; 4.1.2. Methanol outlet; 4.1.3. First mixed hydrogen inlet; 4.1.4. First mixed hydrogen outlet; 4.2.1. Second mixed hydrogen inlet; 4.2.2. Second mixed hydrogen outlet; 4.2.3. Water inlet; 4.2.4. Water outlet;

[0047] 5. Drainer. DETAILED DESCRIPTION

[0048] It should be noted that the following detailed descriptions are illustrative and intended to provide further explanation of the present invention. Unless otherwise specified, all technical and scientific terms used in the present invention have the same meanings as those commonly understood by those skilled in the art to which the present invention belongs.

[0049] The present invention is further described below in conjunction with the embodiments and the accompanying drawings.

[0050] like Figure 1 As shown, a methanol hydrogen production system includes a steam vaporization tank 1, a cracking reaction tank 2, a thermal oil boiler 3, a cooler 4, and an automatic drainer 5.

[0051] The steam reactor 1 is a double-layer container with inner and outer layers, and more than half of the heat transfer oil is placed in the inner tank 1.5, which is used to prepare methanol vapor;

[0052] The cracking reaction tank 2 is arranged between the steam vaporization tank 1 and the thermal oil boiler 3, and has a plurality of steel pipes 2.5 filled with catalysts. Methanol vapor enters from the lower port and undergoes chemical reaction along the steel pipes 2.5 under the action of the hydrogen production catalyst to generate mixed hydrogen.

[0053] The special-shaped heating tube in the thermal oil boiler 3 heats the thermal oil, and the oil pump circulates and continuously supplies the thermal oil to the cracking reaction tank 2 to form a closed loop;

[0054] There are two coolers 4, into which methanol solution and water are introduced as cooling media respectively. The high-temperature mixed gas after the reaction is cooled in series in sequence and then returns to the automatic drainer 5.

[0055] The following is a brief description of the structure and performance of each component:

[0056] like Figure 2 As shown, the steam vaporizer 1 includes a vaporizer body 1.1, an electric heating pipe 1.2, a methanol inlet pipe 1.3, a liquid level gauge 1.4, an inner tank 1.5, an outer tank 1.6, a steam outlet pipe 1.7, a first safety valve 1.8, a first high temperature sensor 1.9, and an oil-water separator 1.10. The inner tank 1.5 is filled with more than half of the heat transfer oil, and a methanol solution is introduced between the inner and outer tanks 1.5 and the outer tank 1.6 to the scale of the liquid level gauge 1.4. The electric heating pipe 1.1 is arranged on the vaporizer body 1.1, and the methanol solution heated to the boiling point vaporizes into methanol vapor and flows out from the steam outlet pipe 1.7. The first high temperature sensor 1.9, the first safety valve 1.8, and the oil-water separator 1.10 are distributed on the upper part of the steam vaporizer 1. The first high temperature sensor 1.9 senses the maximum temperature set for the vaporizer cavity, and the first safety valve 1.8 is a one-way valve exhaust to ensure that the cavity is maintained at a suitable temperature. The oil-water separator 1.10 can remove oil impurities.

[0057] like Figure 3 and Figure 4 As shown, the cracking reaction tank 2 includes a cracking tank body 2.1, an air inlet 2.2, a baffle 2.3, an oil inlet 2.4, a steel pipe 2.5, a first heat transfer oil reflux tank 2.6, a second high temperature sensor 2.7, an upper cover 2.8, a second safety valve 2.9, a second heat transfer oil reflux tank 2.10, an oil outlet 2.11, a cracking tank cavity 2.12, a catalyst support plate 2.13, and an air outlet 2.14. The vaporized methanol vapor enters the The cracking tank body 2.1 has a lower cover which is isolated from an air inlet 2.2 and an air outlet 2.14 by a baffle 2.3. A plurality of steel pipes 2.5 are evenly distributed and fixed to the cracking tank body 2.1. The catalyst is built in and is arranged on a catalyst support plate 2.13. Methanol vapor passes upward from the inside of the steel pipe 2.5, passes through an upper cover 2.8, and then passes downward from the other side of the steel pipe 2.5 to undergo a conversion reaction into mixed hydrogen under the action of the hydrogen production catalyst.

[0058] The first heat transfer oil return cover 2.6 and the second heat transfer oil return cover 2.10 overflow the heat transfer oil in the cracking tank cavity 2.12 when the temperature is too high. The second high temperature sensor 2.7 senses the maximum temperature set in the cracking tank cavity 2.12, and the second safety valve 2.9 is a one-way valve exhaust to ensure that the cracking tank cavity 2.12 is maintained at a suitable temperature.

[0059] The thermal oil boiler 3 is provided with special-shaped heating tubes (such as straight single-end tubes, straight double-end tubes, U-shaped tubes, W-shaped tubes and special-shaped tubes, etc.) to heat the thermal oil. The oil pump injects oil into the oil inlet 2.4 of the cracking reaction tank 2, and the thermal oil flows back to the thermal oil boiler 3 through the oil outlet 2.11 of the cracking reaction tank 2. The thermal oil is circulated and continuously provided to form a closed loop, so that the heating is more uniform.

[0060] like Figure 5 As shown, the cooler 4 includes a first cooler 4.1 and a second cooler 4.2. Methanol solution is introduced into the first cooler 4.1, and water is introduced into the second cooler 4.2. The mixed hydrogen flowing out from the gas outlet 2.14 of the cracking reaction tank 2 first enters the first mixed hydrogen inlet 4.1.3, flows out through the first mixed hydrogen outlet 4.1.4, and then flows into the second cooler 4.2 through the second mixed hydrogen inlet 4.2.1. The prepared mixed hydrogen is subjected to dual cooling of the methanol solution and water, and flows into the automatic drainer 5 through the second mixed hydrogen outlet 4.2.2 of the second cooler 4.2.

[0061] Methanol inlet 4.1.1 is sucked from the methanol storage tank by a vortex pump, and then heated up by the transfer of hot tail gas mixed with hydrogen, and enters the methanol inlet pipe 1.3 of the steam vaporization tank 1 through the methanol outlet 4.1.2.

[0062] The cooled mixed hydrogen is introduced into the drainer (WBK-20 automatic drainer) 5 to filter out the methanol vapor that has not cracked and the methanol that has not been vaporized, so that the methanol flows back to the methanol storage tank, and then the dry mixed hydrogen goes to the burner.

[0063] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A methanol hydrogen production system, characterized in that: It includes a steam vaporization tank, a cracking reaction tank and a cooler connected in sequence, wherein: The steam vaporization tank comprises an outer tank and an inner tank which is sleeved in the middle of the outer tank, the inner tank is used to hold a heating medium, and a heating pipe is arranged inside the inner tank; a methanol holding chamber is formed between the inner tank and the outer tank; a methanol inlet pipe is arranged at the bottom of the side wall of the outer tank, and a steam outlet pipe is arranged at the top.

2. The methanol-to-hydrogen system according to claim 1, characterized in that: The inner liner and the outer liner are both cylindrical structures, and the inner liner covers the outer liner in the effective height direction.

3. The methanol-to-hydrogen system according to claim 2, characterized in that: A first safety valve is arranged on the top of the outer container, the first safety valve is connected to the inside of the outer container, and the first safety valve is a one-way valve; Preferably, a first high-temperature sensor is disposed on the top of the outer container, and a temperature measuring section of the first high-temperature sensor extends into the interior between the outer container and the inner container.

4. The methanol-to-hydrogen system according to claim 1, characterized in that: The heating tube is an electric heating tube, which is vertically arranged at the bottom of the inner tank.

5. The methanol-to-hydrogen system according to claim 1, characterized in that: An oil-water separator is arranged on the top of the outer container, and the oil-water separator is communicated with the interior of the inner container.

6. The methanol-to-hydrogen system according to claim 1, characterized in that: A liquid level gauge is arranged on the side wall of the outer container.

7. The methanol-to-hydrogen system according to claim 1, characterized in that: The cracking reaction tank is a vertical structure, comprising a cylindrical shell, an upper cover and a lower cover, wherein the lower cover is supported by a support leg assembly; A catalyst support plate is sandwiched between the lower cover and the cylindrical shell, a perforated plate is arranged between the upper cover and the cylindrical shell, through holes are evenly distributed on the catalyst support plate, and a steel pipe assembly is fixedly arranged between the catalyst support plate and the perforated plate through the through holes, and the steel pipe is filled with catalyst; Both ends of each steel pipe are connected to the interior of the upper cover and the lower cover; A baffle is arranged inside the lower cover to divide the cavity of the lower cover into a first part and a second part. The lower cover of the first part is provided with an air inlet, which is connected to the steam outlet pipe of the steam vaporization tank; the lower cover of the second part is provided with an air outlet; Preferably, the cracking reaction tank is provided with an oil inlet at the lower part and an oil outlet at the upper part; Preferably, a heat transfer oil reflux tank is provided at the top of the cylindrical shell, and the heat transfer oil reflux tank is communicated with the interior of the top of the cylindrical shell.

8. The methanol-to-hydrogen system according to claim 7, characterized in that: A second high temperature sensor and a second safety valve are arranged on the top of the upper cover.

9. The methanol-to-hydrogen system according to claim 1, characterized in that: The cooler comprises a first cooler and a second cooler which are arranged in series, the hydrogen inlet of the first cooler is connected to the gas outlet of the cracking reaction tank, the cooling medium of the first cooler is methanol, and the cooling medium of the second cooler is water.

10. The methanol-to-hydrogen system according to claim 1, characterized in that: The second mixed hydrogen outlet of the second cooler is connected to the drainer.

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