CN104773708A - Hydrogen raw material production equipment and process for ammonia synthesis - Google Patents

Abstract

The invention discloses hydrogen raw material production equipment and a process for synthesizing ammonia, wherein the hydrogen raw material production equipment comprises a control device, a methanol water storage and conveying device and at least three groups of methanol water reforming hydrogen production modules, wherein the control device is electrically connected with the methanol water storage and conveying device and each group of methanol water reforming hydrogen production modules so as to control the working states of the methanol water storage and conveying device and each group of methanol water reforming hydrogen production modules; the hydrogen produced by each group of methanol-water reforming hydrogen production modules is directly transmitted to the synthetic ammonia system through a transmission pipeline, and the control device controls the operation of a proper number of methanol-water reforming hydrogen production modules according to the hydrogen raw material demand information of the synthetic ammonia system. The invention has the advantages of high modularization, small single module volume, quick start, no need of a hydrogen storage tank, capability of instantly producing hydrogen and quickly separating the hydrogen, good stability, high intellectualization, sensitive parameter control in the aspects of hydrogen production temperature, gas flow, gas pressure and the like, high safety and strong reliability.

Description

A hydrogen raw material production equipment and process for ammonia synthesis

technical field

The invention relates to the technical field of ammonia synthesis industry, in particular to a hydrogen raw material production equipment and process for ammonia synthesis.

Background technique

Ammonia is one of the most important basic chemical products, not only the main final product, but also an important intermediate. Synthetic ammonia is widely used in the production of chemical fertilizers, various ammonium salts, nitric acid, explosives, plastics, synthetic fibers, paints, photosensitive materials and other products. At present, China's annual output of synthetic ammonia is more than 50 million tons, accounting for about one-third of the world's output. The raw materials for the ammonia synthesis industry are nitrogen and hydrogen. Nitrogen is separated from the air. The two commonly used separation methods are liquefaction and fractional distillation. The boiling point of nitrogen in the air is lower than that of oxygen. First, the air is pressurized and cooled to a liquid state, and then heated to make the nitrogen first Nitrogen is obtained by evaporating from liquid air. There are two main sources of hydrogen: first, the vast majority of hydrogen is produced from petroleum, coal and natural gas. Among them, the reaction equation for producing hydrogen at high temperature by using coal is C+H ₂ O→CO+H ₂ , and using natural gas in The reaction equation for producing hydrogen under the action of high temperature and catalyst is CH ₄ + H ₂ O → CO + 3H _2. Such methods need to consume fossil fuels that are already in short supply, and this type of hydrogen production equipment is bulky, slow to start, low in intelligence, and safe. Second, a small part of hydrogen is produced by electrolyzing water, which consumes a lot of electric energy.

With the advancement of technology, the technology of hydrogen production by reforming methanol and water has been gradually developed, and the hydrogen produced by this reforming hydrogen production technology is gradually used as raw material gas in the ammonia synthesis industry. Referring to the Chinese invention application 201310340475.0 (applicant: Shanghai Hejide Dynamic Hydrogen Machine Co., Ltd.), this patent discloses a methanol water hydrogen production system, the reforming chamber of the methanol and steam reformer, at a temperature of 350-409 ℃ for 1 Under the pressure of -5MPa, the catalyst passes through the catalyst. Under the action of the catalyst, methanol cracking reaction and carbon monoxide conversion reaction occur to generate hydrogen and carbon dioxide. This is a multi-component, multi-reaction gas-solid catalytic reaction system. The reaction equation is as follows: (1) CH ₃ OH→CO+2H ₂ ; (2) H ₂ O+CO→CO ₂ +H ₂ ; (3) CH ₃ OH+H ₂ O→CO ₂ +3H ₂ , reforming The _H2 and _CO2 generated by the reaction are _separated by the palladium membrane separator in the separation chamber to obtain high-purity hydrogen _. Referring to the Chinese invention application 200910311040.7 (applicant: Sichuan Yalian High-tech Co., Ltd.), the patent discloses a methanol steam hydrogen production process using catalytic combustion as a heat source, using methanol steam reforming reactor to produce synthetic ammonia raw material gas , This process produces hydrogen with excellent environmental protection. However, in the existing methanol-water reforming hydrogen production technology in the ammonia synthesis industry, a single reformer is used, which is poor in intelligence, unable to be modularized, large in size, slow in start-up, serious waste of methanol raw materials, and low in safety. The whole process requires storage Hydrogen tanks, the stability of synthetic ammonia is difficult to guarantee.

Contents of the invention

The technical problem to be solved by the present invention is to provide a hydrogen raw material production equipment for ammonia synthesis, which has a high modularity, a single module with small volume, fast start-up, and no need for hydrogen storage. Tank, which can produce hydrogen in real time and quickly separate hydrogen, has good stability, high intelligence, sensitive control of parameters such as hydrogen production temperature, gas flow and air pressure, high safety and reliability. For this reason, the present invention also provides a production process of the hydrogen raw material production equipment for ammonia synthesis.

For solving above-mentioned first technical problem, technical scheme of the present invention is:

A hydrogen raw material production equipment for ammonia synthesis, including a control device, a methanol water storage and delivery device, and at least three sets of methanol water reforming hydrogen production modules, the control device and the methanol water storage and delivery device and each group of methanol water weight The entire hydrogen production modules are electrically connected to control the working status of the methanol water storage and delivery device and each group of methanol water reforming hydrogen production modules; the hydrogen produced by each group of methanol water reforming hydrogen production modules is transported The pipeline is directly transmitted to the ammonia synthesis system. During the ammonia synthesis process, the ammonia synthesis system feeds back the real-time hydrogen raw material demand to the control device, and the control device controls an appropriate amount of methanol water reforming hydrogen production module according to the hydrogen raw material demand information of the ammonia synthesis system. The group is running, and the methanol water storage and delivery device is controlled to deliver methanol and water raw materials to the running methanol water reforming hydrogen production module.

The methanol-water storage and delivery device includes a methanol-water storage container and a delivery pump, wherein liquid methanol and water raw materials are stored in the methanol-water storage container, and the delivery pump is used to transport the methanol and water raw materials in the methanol-water storage container To the methanol-water reforming hydrogen production module; the number of the delivery pumps matches the number of the methanol-water reforming hydrogen production module, and the number of the methanol-water storage containers is equal to or less than the number of delivery pumps.

The methanol-water reforming hydrogen production module includes a reformer, and the reformer is equipped with a reforming chamber and a hydrogen purification device. The temperature in the reforming chamber is 300-570°C. The hydrogen-containing gas is produced by reforming methanol and water in the reforming chamber with water to produce hydrogen. The reforming chamber is connected to the hydrogen purification device through a connecting pipeline. All or part of the connecting pipeline is set in the reforming chamber, which can pass The high temperature in the reforming chamber continues to heat the gas output from the reforming chamber; the connecting pipeline acts as a buffer between the reforming chamber and the hydrogen purification device, so that the temperature of the gas output from the reforming chamber is the same as that of the hydrogen purification device Or close to it, hydrogen is obtained from the gas production end of the hydrogen purification unit and supplied to the ammonia synthesis system.

The methanol water reforming hydrogen production module includes two preferred structural modes:

The preferred structure of the first methanol-water reforming hydrogen production module is: the methanol-water reforming hydrogen production module is integrated with a heat exchanger, and the heat exchanger is installed between the methanol water storage and delivery device and the reformer On the delivery pipeline between the low-temperature methanol and water raw materials in the heat exchanger, they exchange heat with the high-temperature gas output from the reforming chamber, and the temperature of the methanol and water raw materials rises and vaporizes; the reformer is equipped with an electric heater , the electric heater provides a temperature of 300-570° C. for the reforming chamber; the hydrogen gas output from the gas production end of the hydrogen purification device is reduced in temperature after passing through the heat exchanger, and then supplied to the ammonia synthesis system.

Further, a compensation vaporization device is provided between the heat exchanger and the reformer, and the compensation vaporization device is provided with an electric heater, and the methanol and water raw materials can be further vaporized after passing through the compensation vaporization device.

The preferred structure of the second methanol water reforming hydrogen production module is: the methanol water reforming hydrogen production module is integrated with a heat exchanger, and the heat exchanger is installed between the methanol water storage and delivery device and the reformer On the pipeline between the two, the low-temperature methanol and water raw materials exchange heat with the high-temperature gas output from the reforming chamber in the heat exchanger, and the temperature of the methanol and water raw materials rises and vaporizes; there is no vaporization chamber in the reformer , the methanol and water raw materials enter the vaporization chamber for vaporization after exchanging heat in the heat exchanger, and the vaporized methanol vapor and water vapor enter the reforming chamber. The temperature is 400-570°C; all or part of the connecting pipeline between the reforming chamber and the hydrogen purification device is set on the upper part of the reforming chamber; the hydrogen output from the gas-producing end of the hydrogen purification device is exchanged After the heater, the temperature is lowered, and then supplied to the ammonia synthesis system.

Further, a start-up device is installed at one end of the reformer, and the start-up device includes a cup holder, and a raw material input pipeline, a heating gasification pipeline, an ignition device and a temperature detection device are installed on the cup holder; the raw material input pipeline can input methanol and Water raw material, the raw material input pipeline is connected with the heating gasification pipeline, methanol and water raw materials enter the heating gasification pipeline through the raw material input pipeline, and then output from the end of the heating gasification pipeline; the position of the ignition device and the heating gasification pipeline The ends correspond to each other, and are used to ignite the methanol and water raw materials output from the heating gasification pipeline. The methanol and water raw materials are ignited by the ignition device and then burned, which can heat the heating gasification pipeline, so that the methanol and water in the heating gasification pipeline The water raw material is gasified to rapidly increase the combustion intensity, and then heat the reformer; the temperature detection device is used to detect the temperature next to the heating gasification pipeline; after the reformer starts hydrogen production, the reformer produced Part of the hydrogen or/and residual gas is burned to maintain the operation of the reformer.

Still further, the cup holder includes a mounting part and a liquid containing part above the mounting part, the raw material input pipeline, heating and gasification pipeline, ignition device and temperature detection device are all installed on the mounting part of the cup holder, and the liquid containing The upper part of the liquid storage part can accommodate methanol and water raw materials output from the end of the heating gasification pipeline. The upper end of the liquid containing part is also equipped with a liquid splash cover; the heating gasification pipeline includes a straight pipe section, a spiral pipe section and an upper arched pipe section in sequence. The methanol and water raw materials can be raised to the highest position through the straight-through pipe section, then spirally descend through the spiral pipe section, and then output through the upper arched pipe section; an air inlet cover is installed on the bottom side of the cup holder, and the air inlet cover An air duct is provided through which outside air can enter the reformer; a solenoid valve is provided on the raw material input pipeline to control the opening or closing of the raw material input pipeline.

In the above technical scheme, the hydrogen purification device is a membrane separation device, and the membrane separation device is a membrane separation device that vacuum-plates palladium-silver alloy on the surface of porous ceramics. The coating layer is palladium-silver alloy, and the mass percentage of palladium-silver alloy is palladium. 75%-78%, silver accounts for 22%-25%.

For solving above-mentioned second technical problem, technical scheme of the present invention is:

A production process for hydrogen raw material production equipment for ammonia synthesis, comprising the following steps:

(1) The ammonia synthesis system feeds back the real-time demand for hydrogen raw materials to the control device during the synthesis of ammonia from hydrogen and nitrogen;

(2) The control device controls the operation of an appropriate number of methanol-water reforming hydrogen production modules according to the real-time hydrogen raw material demand information, and controls the methanol-water storage and delivery device to deliver methanol and water raw materials to the operating methanol-water reforming hydrogen production modules; When the demand for instant hydrogen raw materials is small, control the operation of less methanol-water reforming hydrogen production modules; when the demand for instant hydrogen raw materials is large, control the operation of more methanol-water reforming hydrogen production modules;

(3) The control device detects the working status of each group of methanol water reforming hydrogen production modules in real time. When any group of methanol water reforming hydrogen production modules operates abnormally, the control device controls the abnormal methanol water reforming Stop the operation of the hydrogen production module, and control the operation of a methanol water reforming hydrogen production module in standby state, or control other operating methanol water reforming hydrogen production modules to speed up the hydrogen production speed to compensate for the abnormal methanol production. The amount of hydrogen produced due to the shutdown of the water reforming hydrogen production module.

The beneficial effects of the present invention are:

First, the present invention adopts at least three sets of methanol-water reforming hydrogen production modules, which have a high degree of modularization. A single methanol-water reforming hydrogen production module is small in size and quick to start, and the parameters of hydrogen production temperature, gas flow and air pressure are controlled. sensitive;

Second, the hydrogen produced by each group of methanol-water reforming hydrogen production modules in the present invention is directly transmitted to the ammonia synthesis system through the delivery pipeline, without the need for high-pressure containers such as hydrogen storage tanks, and can instantly produce hydrogen and quickly separate hydrogen, thereby eliminating the need for The cost of the hydrogen storage tank improves the safety of hydrogen transportation and avoids the hydrogen leakage or even the explosion of the hydrogen storage tank caused by the abnormality of the hydrogen storage tank;

Third, since the hydrogen production capacity of each group of methanol water reforming hydrogen production modules in the present invention is much smaller than that of a single methanol water reforming hydrogen production module in the prior art, for example, if the present invention sets 100 sets of methanol water reforming hydrogen production modules, then the hydrogen production capacity of each methanol water reforming hydrogen production module in the present invention only needs 1/ of the hydrogen production capacity of a single methanol water reforming hydrogen production module in the prior art 100; when the immediate demand for hydrogen raw materials is small, the control device only needs to control the operation of fewer methanol-water reforming hydrogen production modules (for example, 50 groups); therefore, the present invention adopts at least three sets of methanol-water reforming hydrogen production When the module is used as the main device for hydrogen production, it can greatly reduce the no-load, its overall energy consumption is small, the consumption of methanol and water raw materials is low, and the utilization rate is high;

Fourth, after the present invention adopts at least three sets of methanol water reforming hydrogen production modules, when a set of methanol water reforming hydrogen production modules fails, other methanol water reforming hydrogen production modules of the hydrogen raw material production equipment can still Normal operation, or it can replace the methanol water reforming hydrogen production module in the standby state. Therefore, it has good stability, reliability and high intelligence, which can prevent ammonia synthesis due to the paralysis of some methanol water reforming hydrogen production modules. Major abnormalities of the system;

Fifth, the methanol water reforming hydrogen production module with a small hydrogen production capacity has low noise, which is conducive to reducing noise pollution;

Sixth, the present invention adopts at least three sets of methanol-water reforming hydrogen-producing modules. When the number of methanol-water reforming hydrogen-producing modules is insufficient, it is convenient to increase the methanol-water reforming hydrogen-producing modules to increase the hydrogen production capacity, so that The number of methanol-water reforming hydrogen production modules of the present invention can be flexibly expanded with ease;

Seventh, after the present invention sets at least three sets of methanol-water reforming hydrogen production modules, the hydrogen delivery pipeline that a single methanol-water reforming hydrogen production module transmits to the ammonia synthesis system can be made very small, and this very small-diameter hydrogen delivery The pipeline can greatly improve its ability to bear pressure (the smaller the pipeline, the greater the pressure bearing capacity), thereby greatly improving the safety performance of the ammonia synthesis system.

Description of drawings

Fig. 1 is a schematic block diagram of the overall structure of the present invention.

Fig. 2 is a schematic structural block diagram of a methanol water storage and delivery device according to a preferred embodiment of the present invention.

Fig. 3 is a schematic structural block diagram of a methanol water storage and delivery device according to another preferred embodiment of the present invention.

Fig. 4 is a schematic structural block diagram of a methanol-water reforming hydrogen production module according to a preferred embodiment of the present invention.

Fig. 5 is a schematic structural block diagram of a methanol-water reforming hydrogen production module according to another preferred embodiment of the present invention.

FIG. 6 is a schematic diagram of the decentralized structure of the reformer in FIG. 5 .

FIG. 7 is a schematic structural diagram of the starting device for the reformer in FIG. 5 .

FIG. 8 is a schematic structural view of the cup holder part of the reformer starting device in FIG. 5 .

Figure 9 is a schematic block diagram of the overall structure of the ammonia synthesis system.

Detailed ways

The structural principle and working principle of the present invention will be further described in detail below in conjunction with the accompanying drawings.

As shown in Figure 9, it is a block diagram of the overall structure of the ammonia synthesis system. After hydrogen and nitrogen are mixed and compressed in the compressor 6, they enter the synthesis tower 8 after passing through the degreaser 7; the synthesis tower 8 contains electric heaters, catalysts and heat exchangers. device, in which the synthesis reaction N ₂ + 3H ₂ → 2NH ₃ occurs, and NH ₃ is in a high-temperature gaseous state at this time; then, the high-temperature gaseous ammonia and unreacted hydrogen and nitrogen are cooled by the cooling tower 9, and the ammonia turns into a liquid state; The device 10 is separated, the liquid ammonia enters the liquid ammonia storage tank, and the unreacted hydrogen and nitrogen are compressed by the circulating compressor 12 and then returned to the degreaser 7 to start the next ammonia synthesis reaction.

As shown in Figure 1, a hydrogen raw material production equipment for ammonia synthesis, including a control device 1, a methanol water storage and delivery device 2, and at least three sets of methanol water reforming hydrogen production modules 3, the control device 1 and methanol water The storage and delivery device 2 and each group of methanol-water reforming hydrogen production modules 3 are electrically connected to control the working status of the methanol-water storage and delivery device 2 and each group of methanol-water reforming hydrogen production modules 3; The hydrogen produced by the methanol-water reforming hydrogen production module 3 is directly sent to the ammonia synthesis system 4 through the delivery pipeline. The ammonia synthesis system 4 feeds back the immediate demand for hydrogen raw materials to the control device 1 during the ammonia synthesis process. The control device 1 is based on The hydrogen raw material demand information of the ammonia synthesis system 4 controls the operation of an appropriate number of methanol-water reforming hydrogen production modules 3 , and controls the methanol-water storage and delivery device 2 to deliver methanol and water raw materials to the operating methanol-water reforming hydrogen production modules 3 . In addition, the number of methanol-water reforming hydrogen production modules 3 of the present invention is preferably 10-120 groups, and more preferably 50-100 groups, so as to better ensure the hydrogen demand of the ammonia synthesis system.

After at least three sets of methanol-water reforming hydrogen production modules 3 are installed in the present invention, the hydrogen delivery pipeline for a single methanol-water reforming hydrogen production module 3 to be transmitted to the ammonia synthesis system can be made very small. The diameter of the hydrogen delivery pipeline of the present invention is 2-8mm stainless steel pipe, this diameter of hydrogen delivery pipeline can greatly improve its ability to withstand pressure (the smaller the pipeline, the greater the pressure bearing capacity), thus greatly improving the safety performance of the ammonia synthesis system. Further, the hydrogen delivery pipeline is preferably a stainless steel pipe with a diameter of 3-6 mm.

As shown in Figures 2 and 3, the methanol water storage and delivery device 2 includes a methanol water storage container 21 and a delivery pump 22, and liquid methanol and water raw materials are stored in the methanol water storage container 21, and the delivery pump 22 Used to transport the methanol and water raw materials in the methanol water storage container 21 to the methanol water reforming hydrogen production module 3; the number of the delivery pump 22 matches the number of the methanol water reforming hydrogen production module 3, and the The number of methanol water storage containers 21 is equal to or less than the number of delivery pumps 22 . In FIG. 2 , the quantity of the methanol-water storage container 21 is single, and in FIG. 3 , the quantity of the methanol-water storage vessel 21 matches the quantity of the delivery pump 22 .

As shown in Figure 4 and Figure 5, the methanol-water reforming hydrogen production module 3 includes a reformer 31 or 32, and the reformer 31 or 32 is provided with a reforming chamber 311 or 321 and a hydrogen purification device 312 or 322. The temperature in the reforming chamber is 300-570°C. There is a catalyst in the reforming chamber. In the reforming chamber, methanol and water vapor pass through the catalyst under the pressure of 1-5M Pa. Under the action of the catalyst, methanol is produced. Cracking reaction and conversion reaction of carbon monoxide to generate hydrogen and carbon dioxide. This is a multi-component, multi-reaction gas-solid catalytic reaction system. The reaction equation is: (1) CH ₃ OH→CO+2H ₂ , (2) H ₂ O+CO→CO ₂ +H ₂ , (3) CH ₃ OH+H ₂ O→CO ₂ +3H ₂ , H ₂ and CO ₂ generated by the reforming reaction; the reforming chamber is connected to the hydrogen purification device through a connecting pipeline , all or part of the connecting pipeline is arranged in the reforming chamber, and the high temperature in the reforming chamber can continue to heat the gas output from the reforming chamber; the connecting pipeline is used as a buffer between the reforming chamber and the hydrogen purification device, so that The temperature of the gas output from the reforming chamber is the same as or close to the temperature of the hydrogen purification device. The hydrogen is obtained from the gas production end of the hydrogen purification device and supplied to the ammonia synthesis system 4 . Each group of methanol-water reforming hydrogen production modules in the present invention adopts the method of reforming hydrogen production by reformer at a temperature of 300-570°C and under the action of a catalyst, the hydrogen production speed and efficiency are high, and the conversion efficiency and utilization of methanol water raw materials are high. High efficiency and good stability; since the temperature of the hydrogen purification device is the same or close to the temperature of the reforming chamber, it can significantly improve the efficiency of hydrogen purification and reduce the difficulty of hydrogen purification to achieve rapid membrane separation.

The methanol water reforming hydrogen production module 3 includes two preferred structural modes:

As shown in Figure 4, the preferred structure of the first methanol-water reforming hydrogen production module 3 is: the methanol-water reforming hydrogen production module 3 is integrated with a heat exchanger 33, and the heat exchanger 33 is installed on On the delivery pipeline between the methanol-water storage delivery device 2 and the reformer 31, the low-temperature methanol and water raw materials are in the heat exchanger 33, exchanging heat with the high-temperature gas output from the reforming chamber 31, and the temperature of the methanol and water raw materials rises. High, vaporization; the reformer 31 is provided with an electric heater 313, and the electric heater 313 provides a temperature of 300-570° C. for the reforming chamber 311; After the heater 33, the temperature is lowered, and then supplied to the ammonia synthesis system 4.

Further, a compensation vaporization device 34 is also provided between the heat exchanger 33 and the reformer 31, and the compensation vaporization device 34 is provided with an electric heater 341, and the methanol and water raw materials can be further vaporized after passing through the compensation vaporization device 34 .

As shown in Figure 5, the preferred structure of the second methanol water reforming hydrogen production module 3 is: the methanol water reforming hydrogen production module 3 is integrated with a heat exchanger 35, and the heat exchanger 35 is installed on On the delivery pipeline between the methanol-water storage and delivery device 2 and the reformer 321, the low-temperature methanol and water raw materials are in the heat exchanger 35, exchanging heat with the high-temperature gas output from the reforming chamber 321, and the temperature of the methanol and water raw materials rises. High, vaporization; there is no vaporization chamber (not shown in the figure) in the reformer 32, and the methanol and water raw materials enter the vaporization chamber for vaporization after exchanging heat in the heat exchanger 35, and the vaporized methanol vapor and water The steam enters the reforming chamber 321, the temperature of the lower and middle parts of the reforming chamber 321 is 300-420°C, and the temperature of the upper part of the reforming chamber 321 is 400-570°C; the connecting pipe between the reforming chamber 321 and the hydrogen purification device 322 The whole or part of the pipeline is set on the upper part of the reforming chamber; the hydrogen gas output from the gas production end of the hydrogen purification device 322 is supplied to the ammonia synthesis system 4 after passing through the heat exchanger 35 after the temperature is lowered.

Further, as shown in FIGS. 5-8 , one end of the reformer 32 is equipped with a starting device 5 , and the starting device 5 includes a cup holder 51 on which a raw material input pipeline 52 , a heating gasification pipeline 53 , Ignition device 54 and temperature detection device 55; the raw material input pipeline 52 can input methanol and water raw materials, the raw material input pipeline 52 is connected with the heating gasification pipeline 53, and the methanol and water raw materials enter the heating gasification pipeline 53 through the raw material input pipeline 52 After that, it is output from the end of the heating gasification pipeline 53; the position of the ignition device 54 corresponds to the end of the heating gasification pipeline 53, and is used to ignite the methanol and water raw materials output in the heating gasification pipeline 53, methanol and The water raw material is burned after being ignited by the ignition device 54, which can heat the heating gasification pipeline 53, so that the methanol and water raw material in the heating gasification pipeline 53 are gasified to rapidly increase the combustion intensity, and then heat the reformer 32; The temperature detection device 55 is used to detect the temperature next to the heating gasification pipeline 53; after the reformer 32 starts hydrogen production, part of the hydrogen or/and residual gas produced by the reformer 32 is used to maintain the operation of the reformer 32 through combustion . The reformer 32 uses the starting device 5 to heat the reformer 32, so that the reformer 32 is started, and then the reforming reaction occurs. The start-up time can be completed within 5 minutes, which is very fast. After the start-up is completed, the start-up device 5 off.

As shown in Figures 6-8, the cup holder 51 includes a mounting portion 511 and a liquid container 512 above the mounting portion, and the raw material input pipeline 52, heating and gasification pipeline 53, ignition device 54 and temperature detection device 55 Installed on the mounting part 511 of the cup holder, the liquid containing part 512 can contain the raw materials of methanol and water output from the end of the heating and vaporizing pipeline 53 , and the upper end of the liquid containing part 512 is also provided with a liquid splash-proof cover 513 . After the methanol and water raw materials are input into the raw material input pipeline 52, when they are output through the heating gasification pipeline 53, the excess methanol and water raw materials can be accommodated in the liquid holding part 512 of the cup holder. Of course, after the methanol and water raw materials are burned rapidly, the liquid Methanol and water raw materials in the container 512 will also be gasified and combusted. The liquid splash-proof cover 513 can prevent the methanol and water raw materials in the liquid container 512 from splashing around during gasification and combustion. The heating gasification pipeline 53 sequentially includes a straight-through pipe section 531, a spiral pipe section 532 and an upper arched pipe section 533. The methanol and water raw materials can be raised to the highest position through the straight-through pipe section 531, then descend spirally through the spiral pipe section 532, and then pass through Output after the upper arch pipe section 533. Like this, when starting device 5 starts working, methanol and water raw material enter heating gasification pipeline 53, under the effect of upper arched pipe section 533 of methanol and water raw material, methanol and water raw material can drop from upper arched pipe section 533 The end drips out so that the ignition device can ignite; after the ignition is successful, because the overall length of the spiral pipe section 532 is relatively long and the heating area is large, the methanol and water raw materials in the spiral pipe section 532 can be fully heated and vaporized.

As shown in Figures 6-8, an air inlet cover 56 is installed on the bottom side of the cup holder 51, and the air inlet cover is provided with an air duct 561 through which outside air can enter the reformer 32 , the outside air entering from the air duct 561 can provide oxygen for the starting device 5, and can also provide oxygen for the reformer 32. In order to increase the air intake, a fan (not shown in the figure) can be added outside the air duct 561; The raw material input pipeline 52 is provided with a solenoid valve to control the opening or closing of the raw material input pipeline 52 . The ignition device can be a high temperature resistant igniter on the market, such as an electronic pulse igniter.

In the above technical scheme, the hydrogen purification device 312 or 322 is a membrane separation device, which is a membrane separation device that vacuum-plates palladium-silver alloy on the surface of porous ceramics. The coating layer is palladium-silver alloy, and the quality of palladium-silver alloy is Percent palladium accounts for 75%-78%, and silver accounts for 22%-25%. The manufacturing process of the membrane separation device can refer to the invention patent 201210563913.5, the membrane separator of the methanol-water hydrogen production equipment and its preparation method, which was applied by the applicant Shanghai Hede Powerful Hydrogen Machinery Co., Ltd. on December 21, 2012.

The production process of hydrogen raw material production equipment for ammonia synthesis, comprising the following steps:

(1) The ammonia synthesis system feeds back the real-time demand for hydrogen raw materials to the control device during the synthesis of ammonia from hydrogen and nitrogen;

(2) The control device controls the operation of an appropriate number of methanol-water reforming hydrogen production modules according to the real-time hydrogen raw material demand information, and controls the methanol-water storage and delivery device to deliver methanol and water raw materials to the operating methanol-water reforming hydrogen production modules; When the demand for instant hydrogen raw materials is small, control the operation of less methanol-water reforming hydrogen production modules; when the demand for instant hydrogen raw materials is large, control the operation of more methanol-water reforming hydrogen production modules;

(3) The control device detects the working status of each group of methanol water reforming hydrogen production modules in real time. When any group of methanol water reforming hydrogen production modules operates abnormally, the control device controls the abnormal methanol water reforming Stop the operation of the hydrogen production module, and control the operation of a methanol water reforming hydrogen production module in standby state, or control other operating methanol water reforming hydrogen production modules to speed up the hydrogen production speed to compensate for the abnormal methanol production. The amount of hydrogen produced due to the shutdown of the water reforming hydrogen production module.

The above is only a preferred embodiment of the present invention, and any minor modifications, equivalent changes and modifications made to the above embodiments according to the technical solution of the present invention fall within the scope of the technical solution of the present invention.

Claims (10)

1. the hydrogen raw material production equipment for the synthesis of ammonia, it is characterized in that: comprise control device, methanol-water Storing and conveying device and at least three group methanol-water reformation hydrogen production modules, described control device and methanol-water Storing and conveying device and each organize methanol-water reformation hydrogen production module and be all electrically connected, to control the working order of methanol-water Storing and conveying device and each group methanol-water reformation hydrogen production module; The hydrogen that described each group of methanol-water reformation hydrogen production module obtains directly sends synthesis ammonia system to by transport pipe, this synthesis ammonia system is in the process of synthetic ammonia, instant hydrogen raw materials requirement amount is fed back to control device, this control device operates according to the methanol-water reformation hydrogen production module of the hydrogen raw materials requirement amount information Control proper amt of synthesis ammonia system, and controls the methanol-water reformation hydrogen production module conveying first alcohol and water raw material of methanol-water Storing and conveying device to running.

2. the hydrogen raw material production equipment for the synthesis of ammonia according to claim 1, it is characterized in that: described methanol-water Storing and conveying device comprises methanol-water storage vessel and transferpump, store liquid first alcohol and water raw material in described methanol-water storage vessel, described transferpump is used for the first alcohol and water feedstock transportation in methanol-water storage vessel to methanol-water reformation hydrogen production module; The quantity of described transferpump and the quantity of methanol-water reformation hydrogen production module match, and the quantity of described methanol-water storage vessel is equal to or less than the quantity of transferpump.

3. the hydrogen raw material production equipment for the synthesis of ammonia according to claim 1, it is characterized in that: described methanol-water reformation hydrogen production module comprises reformer, reformer chamber and hydrogen purification apparatus is provided with in this reformer, the temperature of reformer chamber is 300-570 DEG C of temperature, reformer chamber is provided with catalyzer, first alcohol and water is at the obtained hydrogen-containing gas of reformation hydrogen production reaction of reformer chamber generation first alcohol and water, reformer chamber is connected by connecting pipeline with hydrogen purification apparatus, the all or part of of connecting pipeline is arranged at reformer chamber, high temperature by reformer chamber continues the gas that heating exports from reformer chamber, described connecting pipeline, as the buffering between reformer chamber and hydrogen purification apparatus, makes the temperature of the gas exported from reformer chamber identical with the temperature of hydrogen purification apparatus or close, obtains hydrogen, be supplied to synthesis ammonia system from the aerogenesis end of hydrogen purification apparatus.

4. the hydrogen raw material production equipment for the synthesis of ammonia according to claim 3, it is characterized in that: described methanol-water reformation hydrogen production module is integrated with interchanger, described interchanger is installed on the transport pipe between methanol-water Storing and conveying device and reformer, the first alcohol and water raw material of low temperature is in interchanger, the high-temperature gas exported with reformer chamber carries out heat exchange, and first alcohol and water material temperature raises, vaporization; Described reformer is provided with electric heater, and this electric heater provides 300-570 DEG C of temperature for reformer chamber; The hydrogen of the aerogenesis end output of described hydrogen purification apparatus, after interchanger, temperature reduces, then is supplied to synthesis ammonia system.

5. the hydrogen raw material production equipment for the synthesis of ammonia according to claim 4, it is characterized in that: between described interchanger and reformer, be also provided with compensation vapourizing unit, this compensation vapourizing unit is provided with electric heater, and described first alcohol and water raw material can be vaporized further after compensating vapourizing unit.

6. the hydrogen raw material production equipment for the synthesis of ammonia according to claim 3, it is characterized in that: described methanol-water reformation hydrogen production module is integrated with interchanger, described interchanger is installed on the transport pipe between methanol-water Storing and conveying device and reformer, the first alcohol and water raw material of low temperature is in interchanger, the high-temperature gas exported with reformer chamber carries out heat exchange, and first alcohol and water material temperature raises, vaporization; Also vaporizing chamber is not had in described reformer, described first alcohol and water raw material enters vaporizing chamber vaporization in interchanger after heat exchange, methanol steam after vaporization and water vapor enter reformer chamber, and reformer chamber bottom and middle portion temperature are 300-420 DEG C, and the temperature on reformer chamber top is 400-570 DEG C; The all or part of top being arranged at reformer chamber of the connecting pipeline between described reformer chamber and hydrogen purification apparatus; The hydrogen of the aerogenesis end output of described hydrogen purification apparatus, after interchanger, temperature reduces, then is supplied to synthesis ammonia system; The hydrogen of the aerogenesis end output of described hydrogen purification apparatus, after interchanger, temperature reduces, then is supplied to synthesis ammonia system.

7. the hydrogen raw material production equipment for the synthesis of ammonia according to claim 6, it is characterized in that: described reformer one end is provided with starter gear, this starter gear comprises cup, cup is provided with raw material input channel, heating and gasifying pipeline, portfire and temperature detection device; Described raw material input channel can input first alcohol and water raw material, and raw material input channel is connected with heating and gasifying pipeline, and first alcohol and water raw material enters after heating and gasifying pipeline through raw material input channel, exports from the end of heating and gasifying pipeline; The position of described portfire is corresponding with the end of heating and gasifying pipeline, for lighting a fire to the first alcohol and water raw material exported in heating and gasifying pipeline, first alcohol and water raw material is through ignition device afterfire, can heat heating and gasifying pipeline, make heating and gasifying ducted first alcohol and water material gasification and strengthen rapidly intensity of combustion, and then being reformer heating; Described temperature detection device is for detecting the other temperature of heating and gasifying pipeline.

8. the hydrogen raw material production equipment for the synthesis of ammonia according to claim 7, it is characterized in that: described cup comprises the liquid containing portion above installation portion and installation portion, described raw material input channel, heating and gasifying pipeline, portfire and temperature detection device are all installed on the installation portion of cup, described liquid containing portion can hold the first alcohol and water raw material exported from heating and gasifying pipe end, and described liquid containing portion upper end is also provided with liquid Splashproof cover; Described heating and gasifying pipeline comprises straight-through pipeline section, pigtail and upper arch pipeline section successively, and described first alcohol and water raw material after straight-through pipeline section rises to extreme higher position, then can decline through pigtail spiral, then exports after upper arch pipeline section; The bottom side of described cup is provided with air intake cover plate, and this air intake cover plate is provided with air channel, and outside air can enter in reformer through this air channel; Described raw material input channel is provided with magnetic valve, opens or closes to control raw material input channel.

9. according to the hydrogen raw material production equipment for the synthesis of ammonia in claim 3 ~ 8 described in any one, it is characterized in that: described hydrogen purification apparatus is membrane separation unit, this membrane separation unit is the membrane separation unit at porous ceramic surface Vacuum Deposition palladium-silver alloy, coatings is palladium-silver alloy, the mass percent palladium of palladium-silver alloy accounts for 75%-78%, and silver accounts for 22%-25%.

10. the production technique of the hydrogen raw material production equipment for the synthesis of ammonia in claim 1 ~ 8 described in any one, is characterized in that, comprise the following steps:

(1) synthesis ammonia system is in the process of hydrogen and nitrogen synthetic ammonia, and instant hydrogen raw materials requirement amount is fed back to control device;

(2) control device operates according to the methanol-water reformation hydrogen production module of instant hydrogen raw materials requirement amount information Control proper amt, and controls the methanol-water reformation hydrogen production module conveying first alcohol and water raw material of methanol-water Storing and conveying device to running; When instant hydrogen raw materials requirement amount is less, control less methanol-water reformation hydrogen production module running, when instant hydrogen raw materials requirement amount is larger, control more methanol-water reformation hydrogen production module running;

(3) the work operational situation of each group methanol-water reformation hydrogen production module of control device detecting real-time, when any one group of methanol-water reformation hydrogen production module running is abnormal, the methanol-water reformation hydrogen production module that control device controls this exception shuts down, and control the methanol-water reformation hydrogen production module running that is in holding state, or the methanol-water reformation hydrogen production module controlled in other runnings accelerates hydrogen manufacturing speed, shut down with the methanol-water reformation hydrogen production module compensated because of this exception and the hydrogen manufacturing amount that reduces.