CN85101360A - The self-heating production of synthesis gas - Google Patents

Abstract

Self-heating is produced the method and apparatus of hydrogen-rich synthetic gas body, makes combustion reactions fluid countercurrent flow in steam-hydrocarbon material gas mixture and this process, reacts by catalyzer.Reaction tubes is fixed in the heat exchange chamber of reactor, be suitable for catalyzer and mixture realization response, oxygen or oxygen-rich air are fed in the combustion chamber of reactor, to realize burning, the combustion reactions fluid carries out secondary reaction by second catalytic domain, outside by reaction tubes is subsequently realized and is finished heat exchange by the mixture of pipe.Offer the thermo-negative reaction that takes place in second catalytic domain in the reaction tubes from the incendiary exothermic heat of reaction.

Description

The self-heating production of synthesis gas

The present invention relates to produce the method and apparatus of hydrogen-rich synthetic gas, as ammonia synthesis gas.

Certainly, from the hydrocarbon feed air-flow,, well-known as the method for production of ammonia natural gas.Make hydrocarbon material G﹠W steam mixture through endothermic catalytic reaction, produce carbon monoxide and hydrogen.The so-called initial reformate of this reaction.Feeding nitrogen then, mainly is bubbling air, and to produce ammonia synthesis gas, this is called secondary reformed.

All in independent reactor, carry out as the early stage business-like ammonia synthesis, initial reformate and secondary reformed step 1.When factory needed for its kind purposes or wishes to produce steam, this production method was only fully and is suitable for gratifying.Therefore, in this process, the thermal response fluid that moves from secondary reformed is used to produce or the heating superheated vapour.Perhaps be used for other aspects of ammonia synthesis, perhaps drain.

Produce under the situation of steam not needing, can be other purpose and effectively utilize in the synthesis gas production process heat from the secondary reformed step.From the heat in the secondary reformed step, a kind of purposes is to provide necessary heat for initial reformate.Main purpose of the present invention provides and can realize this method and apparatus that efficiently utilizes heat.

The production of ammonia, and resemble the production of producing the other products of methyl alcohol and so on from hydro carbons, developed into quite advanced technology in recent years.Wherein mainly be to improve cost-effectiveness, but be difficult to realize,

In this viewpoint, if can be at same reactor, in finish initial and secondary reformed step, this is an ideal very, by reducing expensive reactor, and main relevant devices, can reduce total production cost fully.

People have done various effort for making gratifying reactor, but have also run into certain difficulty.For example, No. 3751228 patent of the U.S. just described a kind of reactor, wherein, the reformed gas product of heat is drained from reactor bottom, rather than be used for being the reforming reaction heat supply, otherwise, but ventilate to reactor from the external world, so that needed heat in the reforming step to be provided, No. 4127289 patent of the U.S. also described a kind of similar reactor.

No. 4071330 patent of the U.S. described a kind of reactor, and it is installed in the stove, utilizes the heat passage heat that necessity is provided for the heat absorption reforming reaction of reactor shell and stove.The housing of reactor is with making as the thermal conductive metallic material of high nickel chrome steel one class.

No. 3549335 patent of the U.S., with diagram a kind of autothermic reactor has been described, it comprises the chuck that is made of inner and outer shell, be annulus therebetween, hydrocarbon material gas and vapor mixing are therefrom passed through, again by the opening on the reactor lower part inner housing, and by being seated in the outer initial reformate catalytic bed of pipe.After this, gas contacts with combustion reaction products, discharges from reactor at last.This reaction process, owing to utilize air combustion, so can not effectively utilize the reaction liberated heat.This technology has very big hope in the competition of modern technique today.

As previously mentioned, the objective of the invention is to provide a kind of improved method and apparatus for the self-heating production of hydrogen-rich synthetic gas body such as ammonia synthesis gas.In the synthesis gas production process, effectively utilize the reaction liberated heat.

Method and apparatus of the present invention is to make that the countercurrent flow of combustion reactions fluid realizes initial reformate by catalytic bed in the mixture of steam and hydrocarbon material gas and the process.Gas mixture makes it contact with oxygen or oxygen-rich air then and finishes burning by the reaction tubes of initial reformate catalyzer is housed.The combustion reactions fluid carries out secondary reaction by second catalytic domain, i.e. secondary reformed reaction, and produce synthesis gas.The synthesis gas product utilizes the burning liberated heat to provide heat for initial and secondary reaction by the reaction tubes outside like this.

Accompanying drawing is the optimum device sectional view of autothermic reactor of the present invention.

1 expression autothermic reactor in the accompanying drawing, reactor comprise heat-exchanging chamber 2 and for importing steam and hydrocarbon material gas, such as first entrance 3 of the mixture of natural gas. In the heat-exchanging chamber between the pipe utmost point 5 and 6 a plurality of reaction tubes 4 are housed. (for clarity sake, only mark two at figure), set reaction tube can make initial catalytic fixed bed 7 can be fixed on the inside, and catalyst can be any catalyst that is applicable to reformation certainly, such as nickel, will select special catalyst for well in advanced technology.

As shown in the figure, collect chamber 10 with the taper shape of vertical opening pipe 11 and set on the contiguous tube sheet 6 that links to each other with reaction tube, the partial reaction reformed gas from reaction tube is passed in the combustion reaction chamber 12. Reative cell 12 is positioned at the bottom of reactor 1. And reative cell 10 be shaped as cone. Be understood that, also can adopt other shape.

Second inlet mouth 13 is positioned at reactor bottom, in order to import oxygen or the oxygen-rich air dividing plate 14 with the end of the contiguous vertical convergent divergent channel 11 of burning in the realization combustion chamber, combustion chamber 10 and heat exchange chamber 2 is separated.On dividing plate 14, have a plurality of holes 15, the combustion reactions fluid can be flow through from the hole, and enter second catalyst zone 16.Therefore, fluid carries out another time or secondary reformed by catalyst zone, produces needed synthesis gas.Moreover what reforming catalyst can be with among those typical cases is any, preferably selects the high material of those efficient.Also have, illustrate for clearly using figure, the sub-fraction of only having drawn catalyzer, but should be understood that the catalyzer of putting into q.s constitutes whole catalytic domain.

When the synthesis gas of producing was upwards mobile from second catalyst zone, baffle plate 20 guiding by means of reaction tubes 4 outsides made reaction tubes directly contact with hot-fluid.This operation scheme guarantees to effectively utilize the burning liberated heat and offers thermo-negative reaction in the reaction tubes 4.

Be provided with outlet 21 at adjacent entrance 3 places, can discharge synthesis gas and purify by exporting 21, or further processing ammonia.The reactor that (or other products, depend on specific reaction process) accompanying drawing is represented is provided with manhole 22, and is the same with normal conditions, is used for maintenance or maintenance.If desired, reactor also can be offered additional export and import, to its objective is in order shunting, or additional combustion gas, steam to be fed in the combustion chamber.

In fact conversion process of the present invention, when being used for the production of synthetic ammonia, the mixture of steam and Sweet natural gas or other hydrocarbon material gas is sent in the reactor 1 by inlet mouth 3 with about 900-1300 temperature, and mixed airflow is through the opening on the plate 5, and by reaction tubes 4, after from reaction chamber, discharging, enter cone-shaped collection chamber 10, fluidity pipe 11, then enter into the bottom of reactor 1, enter the combustion chamber with about 1100 °-1400 high-temperature gas.Oxygen or oxygen-rich air that temperature is approximately 100 are sent in the combustion chamber by inlet mouth 13, realize burning, and the temperature of the combustion reactions fluid that is produced approximately is 2500 °-3500 °F, by the hole on the dividing plate 14 15, upwards enter second catalytic domain 16, so far, secondary reformed can take place.

The syngas mixture temperature that secondary reformed produces approximately is 1500-2100 °F, upwards flow, as top explanation and description, directly contact with reaction tubes 4, therefore, the required heat exchange of wanting can take place, the steam in the heating tube 4-hydrocarbon material gas mixture, and the cooling down forming gas mixture, discharge from top outlet 21.This moment, the temperature of synthetic mixture roughly was 1000 °-1300 °F.

Pressure range in the reactor is the transfer pressure that atmosphere is pressed onto synthesis gas.Be approximately 1200psig(gauge pressure-pound/time in the prior art ²), decide with corresponding technological conditions.The pressure of producing synthetic ammonia is approximately 700psig.

If use method of the present invention and reactor to produce other products beyond the ammonia according to top description, as methyl alcohol, hydrogen, oxidation-ethanol, the perhaps synthetic hydrocarbon polymer of Fischer-Tropsch process must be an ideal very.Since it is identical with the production method of above-mentioned synthetic ammonia to produce the key step of other products, just needn't with synthesizing of these gases method of the present invention have been described again.

The successful operation of the inventive method, the important point are that oxygen or oxygen-rich air are fed realization burning in the combustion chamber, rather than the air in the atmosphere.Use oxygen-rich air to be meant (by volume to calculate) in the air mixture to contain and have an appointment 25% or more amount of oxygen.The content of oxygen can be according to concrete reaction process from 25% to 100%.In production of synthetic ammonia, containing oxygen and be can be from about 25% to 40%, perhaps more some more.No matter to ammonia or concerning reactor, the volume oxygen level is best about 35%.The cost of investment that is used for reactor of the present invention like this is starkly lower than standard burning reformer.In addition, the present invention can be used for high pressure at an easy rate and reform, and is well suited for part standard.In developing country or the utilization of coastal waters gas, this point is most important.Have again, shortened the starting time exactly, saved employed gas, when synthesis device utilizes gas efficiency to descend, also can reduce the setup time of reformer.The present invention and the modern multichannel of utilizing, the initial reformate device of multi-combustor is compared, and is more suitable in automatic starting and control.

Also be noted that the autothermic reactor that illustrates and describe here, though be to have the heat exchange chamber that is positioned on the secondary reformed catalytic bed and the vertical type reactor of combustion chamber.After having read this piece document, other structure formation of this reactor concerning those technical specialists of what, will be clearer and more definite.Just as here the diagram and as described in, optimised form of the present invention is to have adopted the reaction tubes with catalyzer.Here the technology contents that is disclosed will belong to modern technique, for improving the fluid circulation distance in the reactor, pass through this pipe by the secondary or the second reformation catalytic domain expellant gas product.And the steam-material gas mixture that feeds will flow through the outer catalytic bed of pipe.Certainly, just be considered to belong within the category of the present invention as long as possess the device of above-mentioned basic characteristics and principle.

Also should propose, the housing of reactor 1, outer wall is an internal insulation in other words, uses the material such as intensified ceramic one class, passes housing to reduce heat, this has just obtained the heat deposit, has protected reactor staff's safety on every side.Owing to used as the material of carbon steel one class and done housing, thereby reduced investment cost.In addition, shown in 25, the reaction tubes 4 between the tube sheet 5 and 6 is suspended in the reactor from reactor wall among the figure, and this just can adopt thin-walled tube, and the reduction expense, simultaneously than thick-walled tube good heat-transfer.Can experience the pulling force stronger by the what thin-walled tube,, they are fixed in the reaction vessel so utilize the way that hangs than compression.If other modes of employing, pipe will be out of shape, even breaks.

Claims (11)

1, producing by hydrocarbon material gas in the self-heating production method of synthesis gas, improvements comprise: make the mixture of steam and hydrocarbon material gas and the combustion reactions fluid countercurrent flow in this process, react by catalyzer, with the cooling reacting fluid, and to steam--the reaction of material gas mixture provides heat and aerating oxygen or nitrogen-rich air to form said combustion reactions fluid.

2, method according to claim 1 is characterized in that: synthesis gas is methyl alcohol, ammonia, hydrogen, oxo-ethanol or Fischer-Tropsch process synthetic hydrocarbon polymer.

3, method according to claim 1, it is characterized in that: said mixture is by being equipped with the pipe of catalyzer, contact with oxygen or oxygen-rich air then and realize burning, the combustion reactions fluid carries out secondary reaction by second catalyst zone, said gaseous reaction product makes the burning liberated heat offer the thermo-negative reaction that takes place in the pipe by the outside of pipe.

4, method according to claim 3 is characterized in that: synthesis gas refers to the gas of producing ammonia, and steam and material gas mixture are reformed during by pipe, further reform when the combustion reactions fluid is flowed through second catalyst zone.

5, from ammonia, methyl alcohol, hydrogen, choose the self-heating production method of synthesis gas in the production of the synthetic hydrocarbon polymer of oxo-ethanol and Fischer-Tropsch process, comprise: make combustion reactions fluid countercurrent flow in the mixture of steam-hydrocarbon material gas and this process, carry out initial reformate by catalyst bed, part reformed gas is contacted with oxygen or oxygen-rich air realize burning, when the combustion reactions fluid carries out another time reformation during by second catalytic domain, and produce said synthesis gas, subsequently, synthesis gas and said steam-hydrocarbon material gas mixture carries out heat exchange, thereby the release of heat of combustion reactions offers the thermo-negative reaction of steam-material gas mixture, and synthesis gas is cooled by heat exchange simultaneously.

6, from ammonia, methyl alcohol, hydrogen, the natural production method of oxo-ethanol and Fischer-Tropsch process synthesis gas, comprise: the opposite flow direction of combustion reactions direction of flow in the mixture that makes steam-hydrocarbon material gas and this process, by the reaction tubes of catalyst bed is housed, carry out initial reformate, then, said part reformed gas is contacted with oxygen or oxygen-rich air to realize burning, the combustion reactions fluid carries out secondary reformed by second catalyst zone, and produce said synthesis gas, make synthesis gas flow through the outside of reaction tubes subsequently, heat release in the combustion reactions can offer the thermo-negative reaction of steam-material gas mixture like this, and has cooled off synthesis gas by heat exchange.

7, a kind of natural reaction device of producing synthesis gas, its structure comprises: a heat exchange chamber, import steam and expect that gas enters first inlet mouth of heat exchange chamber, be contained in the heat exchange chamber, and the reaction tubes of realizing the initial reformate catalyst for reaction is housed, the device that is communicated with reaction tubes and combustion chamber, the 3rd inlet mouth of oxygen or oxygen-rich air importing combustion chamber, the dividing plate of separating heat exchange chamber and combustion chamber, have on this dividing plate to fill and permitted the through hole that the combustion reactions fluid passes through, and constitute second catalytic domain, therefore, the combustion reactions fluid can carry out secondary reformed by the dividing plate and second catalyst zone, and the generation synthesis gas, be positioned at the synthesis gas relief outlet that is close to first gas port, make synthesis gas outside by reaction tubes before discharging from outlet, be the reaction of the initial reformate in reaction tubes heat supply, cooling down forming gas simultaneously.

8, reactor according to claim 7 is characterized in: the baffle plate into the guiding of the combustion reactions fluid outside the reaction tubes is housed in heat exchange chamber.

9, reactor according to claim 7 is characterized in: the device that is communicated with reaction tubes is to be contained in the collecting chamber that closes on the reaction tubes bottom, and has convergent divergent channel vertically downward, therefore, enters in the combustion chamber by this part.

10, reactor according to claim 7 is characterized in: the wall of reactor is an internal insulation, to increase the utilization of heat.

11, reactor according to claim 7 is characterized in: reaction tubes is contained in the reactor in the mode that is suspended on the reactor wall.

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