CN104773708A - Hydrogen raw material production equipment and process for ammonia synthesis - Google Patents
Hydrogen raw material production equipment and process for ammonia synthesis Download PDFInfo
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- CN104773708A CN104773708A CN201510180225.4A CN201510180225A CN104773708A CN 104773708 A CN104773708 A CN 104773708A CN 201510180225 A CN201510180225 A CN 201510180225A CN 104773708 A CN104773708 A CN 104773708A
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Abstract
The invention discloses hydrogen raw material production equipment and process for ammonia synthesis. The hydrogen raw material production equipment comprises a control device, a methanol water storage conveyer and at least three groups of methanol water-reforming hydrogen production modules, wherein the control device is electrically connected with the methanol water storage conveyer and each group of methanol water-reforming hydrogen production modules, so as to control the working states of the methanol water storage conveyer and the methanol water-reforming hydrogen production modules; hydrogen prepared by various methanol water-reforming hydrogen production modules is directly conveyed to an ammonia synthesis system through conveying pipelines; and the control device is used for controlling a proper number of methanol water-reforming hydrogen production modules to run according to the hydrogen raw material quantity demand information of the ammonia synthesis system. The hydrogen raw material production equipment is high in modularization; a single module is small in size and fast to start; the hydrogen can be immediately prepared without a hydrogen storage tank, and can be rapidly separated; and the hydrogen raw material production equipment is good in stability, high in intellectualization, sensitive in parameters control of hydrogen preparation temperature, gas flow and air pressure, high in safety and high in reliability.
Description
Technical field
The present invention relates to ammonia synthesizing industry technical field, particularly a kind of hydrogen raw material production instrument and supplies for the synthesis of ammonia.
Background technology
Ammonia is one of most important basic chemical industry product, is main the finished product, is again important intermediate.Synthetic ammonia is widely used in the products productions such as chemical fertilizer, various ammonium salt, nitric acid, explosive, plastics, synthon, paint, sensitive materials.Current Chinese synthetic ammonia annual production more than 5,000 ten thousand tons, accounts for 1/3rd of worldwide production.The raw material of ammonia synthesizing industry is nitrogen and hydrogen.Nitrogen is separated from air, and normally used two kinds of separation methods are liquefaction and fractionation, utilize the boiling point of nitrogen in air lower than the boiling point of oxygen, first air pressurized to be lowered the temperature liquefy, and then heat, first nitrogen is evaporated from liquid-air, thus obtains nitrogen.The source of hydrogen mainly contains two kinds: one, most hydrogen produce from oil, coal and Sweet natural gas, and wherein, the reaction equation adopting coal at high temperature hydrogen making is C+H
2o → CO+H
2, the reaction equation adopting Sweet natural gas hydrogen making under high temperature and catalyst action is CH
4+ H
2o → CO+3H
2these class methods need to consume mineral fuel natively very in short supply, and this kind of hydrogen producer volume is large, startup is slow, intellectuality is low, poor stability, energy consumption are high; Two, small portion hydrogen produces by the method for brine electrolysis, and it is large that this method consumes electric energy.
Along with the progress of technology, adopt the technology of first alcohol and water reformation hydrogen production to be developed gradually, the hydrogen obtained by this reforming hydrogen producing technology is used as the unstripped gas in ammonia synthesizing industry gradually.With reference to Chinese invention application 201310340475.0(applicant: Shanghai Hejide Dynamic Hydrogen Machine Co., Ltd.), which disclose a Methanol water hydrogen production system, the reformer chamber of methyl alcohol and steam reformer, at 350-409 DEG C of temperature 1-5M Pa pressure condition under pass through catalyzer, under the effect of catalyzer, the transformationreation of methanol decomposition reaction and carbon monoxide occurs, generates hydrogen and carbonic acid gas, this is the gas solid catalytic reaction system of component more than, many reactions.Reactional equation is as follows: (1) CH
3oH → CO+2H
2; (2) H
2o+CO → CO
2+ H
2; (3) CH
3oH+H
2o → CO
2+ 3H
2, the H that reforming reaction generates
2and CO
2, then the palladium membrane separation apparatus through separate chamber is by H
2and CO
2be separated, obtain high-purity hydrogen.With reference to Chinese invention application 200910311040.7(applicant: Sichuan Yalian High-tech Co., Ltd), which disclose the methanol steam hydrogen production technology of a kind of catalyticcombustion as thermal source, obtain syngas for synthetic ammonia by methanol steam reforming reactor, this manufacture technics hydrogen feature of environmental protection is excellent.But methanol-water reforming hydrogen producing technology all adopts single reformer in existing ammonia synthesizing industry, intelligent poor, cannot modularization, volume large, start slowly, methanol feedstock waste is serious, security is low, whole process need hydrogen-storage tank, and synthetic ammonia stability is difficult to ensure.
Summary of the invention
The technical problem to be solved in the present invention is for above-mentioned deficiency of the prior art, a kind of hydrogen raw material production equipment for the synthesis of ammonia is provided, this hydrogen raw material production EM equipment moduleization is high, single module volume is little, startup is quick, need not hydrogen-storage tank, instant hydrogen manufacturing and sharp separation can go out hydrogen, good stability, intelligent high, the aspect state modulator such as hydrogen manufacturing temperature, gas flow and air pressure are sensitive, and security is high, reliability is strong.For this reason, the present invention also will provide a kind of described production technique for the synthesis of the hydrogen raw material production equipment of ammonia.
For solving above-mentioned first technical problem, technical scheme of the present invention is:
A kind of hydrogen raw material production equipment for the synthesis of ammonia, 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.
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.
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, and all or part of of connecting pipeline is arranged at reformer chamber, and the 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.
Described methanol-water reformation hydrogen production module comprises two kinds of preferred structure modes:
The preferred structure mode of the first methanol-water reformation hydrogen production module is: 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.
Further, be also provided with compensation vapourizing unit between described interchanger and reformer, 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.
The preferred structure mode of the second methanol-water reformation hydrogen production module is: 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.
Further, described reformer one end is provided with starter gear, and 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; After described reformer starts hydrogen manufacturing, the hydrogen partial that reformer is obtained is or/and residual air is run by burning maintenance reformer.
Further again, 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.
In technique scheme, described hydrogen purification apparatus is membrane separation unit, and this membrane separation unit is the membrane separation unit at porous ceramic surface Vacuum Deposition palladium-silver alloy, and coatings is palladium-silver alloy, the mass percent palladium of palladium-silver alloy accounts for 75%-78%, and silver accounts for 22%-25%.
For solving above-mentioned second technical problem, technical scheme of the present invention is:
For the synthesis of a production technique for the hydrogen raw material production equipment of ammonia, 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.
The invention has the beneficial effects as follows:
One, the present invention adopt at least three group methanol-water reformation hydrogen production modules, and the degree of modularity is high, and single methanol-water reformation hydrogen production modular volume is little, startup is quick, and the aspect state modulator such as hydrogen manufacturing temperature, gas flow and air pressure are sensitive;
The hydrogen that two, the present invention respectively organizes methanol-water reformation hydrogen production module obtained directly sends synthesis ammonia system to by transport pipe, without the need to the contour pressurized vessel of hydrogen-storage tank, the instant hydrogen manufacturing of energy and sharp separation go out hydrogen, thus eliminate hydrogen-storage tank cost, improve the degree of safety of hydrogen conveying, avoid the hydrogen leak even problem of hydrogen-storage tank blast that cause because hydrogen-storage tank is abnormal;
Three, due to the present invention, often to organize the hydrogen manufacturing amount of methanol-water reformation hydrogen production module much smaller relative to the hydrogen manufacturing amount of methanol-water reformation hydrogen production module single in prior art, such as, if the present invention arranges 100 groups of methanol-water reformation hydrogen production modules, the hydrogen manufacturing amount that so the present invention often organizes methanol-water reformation hydrogen production module only needs 1/100 of the hydrogen manufacturing amount of single methanol-water reformation hydrogen production module in prior art; When instant hydrogen raw materials requirement amount is less, control device only needs to control less methanol-water reformation hydrogen production module (such as 50 groups) running; Therefore, when the present invention adopts at least three group methanol-water reformation hydrogen production modules as hydrogen manufacturing agent set, greatly can reduce zero load, its overall power consumption is less, and first alcohol and water raw material consumption is lower, utilization ratio is high;
After four, the present invention adopts at least three group methanol-water reformation hydrogen production modules, when one group of methanol-water reformation hydrogen production module breaks down, other methanol-water reformation hydrogen production modules of hydrogen raw material production equipment can also run well, or the methanol-water reformation hydrogen production module replacement work being in holding state can be made, therefore, its stability and reliability is good, intelligent high, can prevent the great exception causing synthesis ammonia system because of the paralysis of part methanol-water reformation hydrogen production module;
Five, the methanol-water reformation hydrogen production module noise of less hydrogen manufacturing amount is less, is conducive to reducing sound pollution;
Six, the present invention adopts at least three group methanol-water reformation hydrogen production modules, when methanol-water reformation hydrogen production module quantity is inadequate, methanol-water reformation hydrogen production module can be increased easily, improve hydrogen manufacturing amount, make methanol-water reformation hydrogen production module quantity of the present invention energy masterly ground resilient expansion;
After seven, the present invention arranges at least three group methanol-water reformation hydrogen production modules, the hydrogen delivery tube road that single methanol-water reformation hydrogen production module is sent to synthesis ammonia system can be accomplished very little, the hydrogen delivery tube road of this very minor diameter significantly can improve its ability of bearing pressure, and (pipeline is less, bearing capacity is larger), thus significantly improve the safety performance of synthesis ammonia system.
Accompanying drawing explanation
Fig. 1 is one-piece construction block diagram of the present invention.
Fig. 2 is the methanol-water Storing and conveying apparatus structure block diagram of one embodiment of the present invention.
Fig. 3 is the methanol-water Storing and conveying apparatus structure block diagram of another preferred embodiment of the present invention.
Fig. 4 is the methanol-water reformation hydrogen production modular structure block diagram of one embodiment of the present invention.
Fig. 5 is the methanol-water reformation hydrogen production modular structure block diagram of another preferred embodiment of the present invention.
Fig. 6 is the dispersed texture schematic diagram of reformer in Fig. 5.
Fig. 7 is the structural representation of reformer starter gear in Fig. 5.
Fig. 8 is the cup holder portion structural representation of reformer starter gear in Fig. 5.
Fig. 9 is the one-piece construction block diagram of synthesis ammonia system.
Embodiment
Below in conjunction with accompanying drawing, structural principle of the present invention and principle of work are described in further detail.
As shown in Figure 9, be the one-piece construction skeleton diagram of synthesis ammonia system, hydrogen and nitrogen enter synthetic tower 8 mix compression in compressor 6 after after oil eliminator 7; Containing electric heater in synthetic tower 8, wherein there is building-up reactions N in catalyst and heat exchanger
2+ 3H
2→ 2NH
3, now NH
3for high-temperature gas; Then, high-temperature gas ammonia and unreacted hydrogen and nitrogen cool through cooling tower 9, and ammonia transfers liquid state to; Again then, be separated through separator 10, liquid ammonia enters liquefied ammonia storage tank, and unreacted hydrogen and nitrogen are back to oil eliminator 7 after recycle compressor 12 compresses, and start ammonia synthesis reaction next time.
As shown in Figure 1, a kind of hydrogen raw material production equipment for the synthesis of ammonia, comprise control device 1, methanol-water Storing and conveying device 2 and at least three group methanol-water reformation hydrogen production modules 3, described control device 1 is organized methanol-water reformation hydrogen production module 3 with methanol-water Storing and conveying device 2 and each and is all electrically connected, to control the working order of methanol-water Storing and conveying device 2 and each group methanol-water reformation hydrogen production module 3; The hydrogen that described each group of methanol-water reformation hydrogen production module 3 obtains directly sends synthesis ammonia system 4 to by transport pipe, this synthesis ammonia system 4 is in the process of synthetic ammonia, instant hydrogen raw materials requirement amount is fed back to control device 1, this control device 1 operates according to the methanol-water reformation hydrogen production module 3 of the hydrogen raw materials requirement amount information Control proper amt of synthesis ammonia system 4, and control methanol-water Storing and conveying device 2 to running methanol-water reformation hydrogen production module 3 carry first alcohol and water raw material.In addition, the quantity of methanol-water reformation hydrogen production module 3 of the present invention is preferably 10 groups ~ 120 groups, more preferably 50 groups ~ 100 groups, can better ensure the hydrogen demand amount of synthesis ammonia system like this.
After the present invention arranges at least three group methanol-water reformation hydrogen production modules 3, the hydrogen delivery tube road that single methanol-water reformation hydrogen production module 3 is sent to synthesis ammonia system can be accomplished very little, hydrogen delivery tube road of the present invention adopts diameter to be the stainless steel tube of 2 ~ 8mm, the hydrogen delivery tube road of this diameter significantly can improve its ability of bearing pressure, and (pipeline is less, bearing capacity is larger), thus significantly improve the safety performance of synthesis ammonia system.Further, hydrogen delivery tube road is preferably and adopts diameter to be the stainless steel tube of 3 ~ 6mm.
As shown in Figures 2 and 3, described methanol-water Storing and conveying device 2 comprises methanol-water storage vessel 21 and transferpump 22, store liquid first alcohol and water raw material in described methanol-water storage vessel 21, described transferpump 22 for by the first alcohol and water feedstock transportation in methanol-water storage vessel 21 to methanol-water reformation hydrogen production module 3; The quantity of described transferpump 22 and the quantity of methanol-water reformation hydrogen production module 3 match, and the quantity of described methanol-water storage vessel 21 is equal to or less than the quantity of transferpump 22.In fig. 2, the quantity of methanol-water storage vessel 21 is independent 1, and the quantity of methanol-water storage vessel 21 and the quantity of transferpump 22 match in figure 3.
As shown in Figure 4 and Figure 5, described methanol-water reformation hydrogen production module 3 comprises reformer 31 or 32, reformer chamber 311 or 321 and hydrogen purification apparatus 312 or 322 is provided with in this reformer 31 or 32, the temperature of reformer chamber is 300-570 DEG C of temperature, reformer chamber is provided with catalyzer, in reformer chamber, methyl alcohol and water vapour pass through catalyzer under the pressure condition of 1-5M Pa, under the effect of catalyzer, there is the transformationreation of methanol decomposition reaction and carbon monoxide, generate hydrogen and carbonic acid gas, this is component more than, the gas solid catalytic reaction system of many reactions, reactional equation is: (1) CH
3oH → CO+2H
2, (2) H
2o+CO → CO
2+ H
2, (3) CH
3oH+H
2o → CO
2+ 3H
2, the H that reforming reaction generates
2and CO
2, reformer chamber is connected by connecting pipeline with hydrogen purification apparatus, and all or part of of connecting pipeline is arranged at reformer chamber, and the 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 4 from the aerogenesis end of hydrogen purification apparatus.The present invention respectively organizes the mode that methanol-water reformation hydrogen production module adopts reformer reformation hydrogen production at the temperature of 300-570 DEG C and under catalyst action, its hydrogen manufacturing speed and efficiency high, methanol-water feedstock conversion efficiency and utilization ratio high, good stability; Because the temperature of hydrogen purification apparatus is identical with reformer chamber temperature or close, therefore, hydrogen purification efficiency can be significantly improved and reduce hydrogen purification difficulty, realizing fast film and be separated.
Described methanol-water reformation hydrogen production module 3 comprises two kinds of preferred structure modes:
As shown in Figure 4, the preferred structure mode of the first methanol-water reformation hydrogen production module 3 is: described methanol-water reformation hydrogen production module 3 is integrated with interchanger 33, described interchanger 33 is installed on the transport pipe between methanol-water Storing and conveying device 2 and reformer 31, the first alcohol and water raw material of low temperature is in interchanger 33, the high-temperature gas exported with reformer chamber 31 carries out heat exchange, and first alcohol and water material temperature raises, vaporization; Described reformer 31 is provided with electric heater 313, and this electric heater 313 provides 300-570 DEG C of temperature for reformer chamber 311; The hydrogen of the aerogenesis end output of described hydrogen purification apparatus 312, after interchanger 33, temperature reduces, then is supplied to synthesis ammonia system 4.
Further, be also provided with between described interchanger 33 and reformer 31 and compensate vapourizing unit 34, this compensation vapourizing unit 34 is provided with electric heater 341, and described first alcohol and water raw material can be vaporized further after compensating vapourizing unit 34.
As shown in Figure 5, the preferred structure mode of the second methanol-water reformation hydrogen production module 3 is: described methanol-water reformation hydrogen production module 3 is integrated with interchanger 35, described interchanger 35 is installed on the transport pipe between methanol-water Storing and conveying device 2 and reformer 321, the first alcohol and water raw material of low temperature is in interchanger 35, the high-temperature gas exported with reformer chamber 321 carries out heat exchange, and first alcohol and water material temperature raises, vaporization; Vaporizing chamber (not shown) is not also had in described reformer 32, described first alcohol and water raw material enters vaporizing chamber vaporization in interchanger after 35 heat exchange, methanol steam after vaporization and water vapor enter reformer chamber 321, reformer chamber 321 bottom and middle portion temperature are 300-420 DEG C, and the temperature on reformer chamber 321 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 321 and hydrogen purification apparatus 322; The hydrogen of the aerogenesis end output of described hydrogen purification apparatus 322, after interchanger 35, temperature reduces, then is supplied to synthesis ammonia system 4.
Further, as shown in Figure 5-Figure 8, described reformer 32 one end is provided with starter gear 5, and this starter gear 5 comprises cup 51, cup 51 is provided with raw material input channel 52, heating and gasifying pipeline 53, portfire 54 and temperature detection device 55; Described raw material input channel 52 can input first alcohol and water raw material, and raw material input channel 52 is connected with heating and gasifying pipeline 53, and first alcohol and water raw material enters after heating and gasifying pipeline 53 through raw material input channel 52, exports from the end of heating and gasifying pipeline 53; The position of described portfire 54 is corresponding with the end of heating and gasifying pipeline 53, for lighting a fire to the first alcohol and water raw material exported in heating and gasifying pipeline 53, first alcohol and water raw material is through portfire 54 ignition, combustion, can heat heating and gasifying pipeline 53, make the first alcohol and water material gasification in heating and gasifying pipeline 53 and strengthen rapidly intensity of combustion, and then heating for reformer 32; Described temperature detection device 55 is for detecting the other temperature of heating and gasifying pipeline 53; After described reformer 32 starts hydrogen manufacturing, the hydrogen partial that reformer 32 is obtained is or/and residual air is run by burning maintenance reformer 32.Reformer 32 utilizes starter gear 5 to heat for reformer 32 just, just makes reformer 32 start, and then reforming reaction occurs, and start time can complete in 5 minutes, and very fast, after having started, starter gear 5 cuts out.
As Figure 6-Figure 8, described cup 51 comprises the liquid containing portion 512 above installation portion 511 and installation portion, described raw material input channel 52, heating and gasifying pipeline 53, portfire 54 and temperature detection device 55 are all installed on the installation portion 511 of cup, described liquid containing portion 512 can hold the first alcohol and water raw material exported from heating and gasifying pipeline 53 end, and described liquid containing portion 512 upper end is also provided with liquid Splashproof cover 513.After raw material input channel 52 inputs first alcohol and water raw material, when heating and gasifying pipeline 53 exports, unnecessary first alcohol and water raw material can be contained in the liquid containing portion 512 of cup, certainly, after first alcohol and water raw material burns rapidly, the first alcohol and water raw material in liquid containing portion 512 also can gasification, and combustion.Described liquid Splashproof cover 513 can prevent the first alcohol and water raw material splashes when gasification, and combustion in liquid containing portion 512.Described heating and gasifying pipeline 53 comprises straight-through pipeline section 531, pigtail 532 and upper arch pipeline section 533 successively, described first alcohol and water raw material can after straight-through pipeline section 531 rises to extreme higher position, decline through pigtail 532 spiral again, then export after upper arch pipeline section 533.Like this, when starter gear 5 is started working, first alcohol and water raw material enters heating and gasifying pipeline 53, and first alcohol and water raw material is under the effect of upper arch pipeline section 533, first alcohol and water raw material can ooze, so that portfire is lighted a fire from the end of upper arch pipeline section 533 in the mode of drippage; After lighting a fire successfully, because the entire length of pigtail 532 is long, heating surface area is large, and therefore, the first alcohol and water raw material in pigtail 532 can fully by thermal evaporation.
As Figure 6-Figure 8, the bottom side of described cup 51 is provided with air intake cover plate 56, this air intake cover plate is provided with air channel 561, outside air can enter in reformer 32 through this air channel, the outside air entered from this air channel 561 can be starter gear 5 provides oxygen, also can be reformer 32 and oxygen is provided, for improving air inlet, fan (not shown) can be increased outside air channel 561; Described raw material input channel 52 is provided with magnetic valve, opens or closes to control raw material input channel 52.Described portfire can adopt resistant to elevated temperatures lighter for ignition on market, such as polarity formula pulse type ignitor etc.
In technique scheme, described hydrogen purification apparatus 312 or 322 is membrane separation unit, and this membrane separation unit is the membrane separation unit at porous ceramic surface Vacuum Deposition palladium-silver alloy, and coatings is palladium-silver alloy, the mass percent palladium of palladium-silver alloy accounts for 75%-78%, and silver accounts for 22%-25%.The manufacturing process of membrane separation unit can refer to the patent of invention 201210563913.5 that the applicant Shanghai Hejide Dynamic Hydrogen Machine Co., Ltd. applied on December 21st, 2012, membrane separation apparatus of methanol-water hydrogen producer and preparation method thereof.
For the synthesis of the production technique of the hydrogen raw material production equipment of ammonia, 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.
The above is only better embodiment of the present invention, every above embodiment is done according to technical scheme of the present invention any trickle amendment, equivalent variations and modification, all belong in the scope of 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.
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Application publication date: 20150715 |