CN1008350B - Autothermal production of synthesis gas - Google Patents
Autothermal production of synthesis gasInfo
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- CN1008350B CN1008350B CN 85101360 CN85101360A CN1008350B CN 1008350 B CN1008350 B CN 1008350B CN 85101360 CN85101360 CN 85101360 CN 85101360 A CN85101360 A CN 85101360A CN 1008350 B CN1008350 B CN 1008350B
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Abstract
The present invention relates to a self-heat method for producing hydrogen-enriched synthesis gas and a device. The gaseous mixture of steam and hydrocarbon materials and combustion reaction fluid in the process reversely flow, and reaction is carried out through catalysts. A reaction pipe is fixed in a heat exchange chamber of a reactor and is suitable for realizing the reaction of the catalysts and the mixture, oxygen or oxygen-enriched air is led in a combustion chamber of the reactor for realizing combustion, the combustion reaction fluid carries out secondary reaction through a second catalytic area and passes through the outer part of a reaction pipe subsequently, and the heat exchange of the combustion reaction fluid and the mixture passing through the reaction pipe is realized. Reaction heat release from combustion is supplied for endothermic reaction generated in the second catalytic in the reaction pipe.
Description
The present invention relates to produce method and apparatus such as the hydrogen-rich synthetic gas of the hydrocarbon of ammonia, methyl alcohol, hydrogen, oxo alcohol or Fischer-Tropsch process.
Certainly, for instance from the hydrocarbon feed air-flow,, well-known as the method for production of ammonia natural gas.So, make nytron material G﹠W steam mixture through endothermic catalytic reaction, produce carbon monoxide and hydrogen, the so-called initial reformate of this reaction.Must feed nitrogen then, be typically bubbling air, to produce required ammonia synthesis gas, this is called secondary reformed.
All in independent reactor, carry out as the existing industrialized 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.
Do not needing to produce under the situation of steam, for other purpose utilizes in the synthesis gas production process heat from the secondary reformed step comparatively favourable.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 view of this viewpoint, if can finish initial in same reactor and the secondary reformed step, this is an ideal very, by reducing the reactor of costliness, 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 from the external world to the logical hot gas of reactor, so that needed heat in the reforming step to be provided, No. 4127389 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., for example and described a kind of autothermic reactor, it comprises the chuck that is made of inner housing, 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 placed on 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, but it also need emit excessive nitrogen or regulate the ratio of product in follow-up phase, and in addition, efficient is very low.
As previously mentioned, the objective of the invention is provides a kind of improved method and apparatus for the self-heating production of the synthetic gas of hydrogen-rich synthetic gas body such as ammonia or methyl alcohol, hydrogen, oxo alcohol or hydrocarbon (using Fischer-Tropsch process), effectively utilizes the reaction liberated heat in the synthesis gas production process.
In method and apparatus of the present invention, the countercurrent flow of combustion reactions fluid realizes initial reformate by catalytic bed in mixture by making 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 exchange chamber 2 and for importing steam and hydrocarbon material gas, as first inlet 3 of the mixture of Sweet natural gas.A plurality of reaction tubess 4 are housed in the heat exchange chamber between tube sheet 5 and 6.(for clarity sake, only on figure, mark two), set reaction tubes can make initial catalytic fixed bed 7 can be fixed on the inside, and catalyzer can be any catalyzer that is applicable to reformation certainly, as nickel, and concrete selection of catalysts is that present technique field professional knows.
As shown in the figure, the conical collecting chamber 10 that has vertical convergent divergent channel 11 is contained on the contiguous tube sheet 6 that links to each other with reaction tubes, and the partial reaction reformed gas from reaction tubes is passed in the combustion reactions chamber 12.Reaction chamber 12 is positioned at the bottom of reactor 1.And reaction chamber 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 oxygen-rich air to realize the burning in the combustion chamber.The dividing plate 14 of the end of contiguous vertical convergent divergent channel 11 separates combustion chamber 10 and heat exchange chamber 2.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, it is secondary reformed that fluid carries out another time by catalyst zone, produces needed synthesis gas.Moreover what reforming catalyst can be with among those typical cases is any, the material of preferably selecting those present technique fields professional to know.Also have, illustrate for clearly using figure, a part of catalyzer that only drawn, 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 that synthesis gas purifies and further processing ammonia by exporting 21.The reactor that (or other products, depend on specific reaction process) accompanying drawing is represented is provided with hand-hole 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.
Carrying out 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, send in the reactor 1 by inlet mouth 3 with about 900-1300 temperature, opening on the mixed airflow process tube sheet 5, and by reaction tubes 4, after from reaction chamber, discharging, enter cone-shaped collection chamber 10, by managing 11, then enter into the bottom of reactor 1, enter the combustion chamber with about 1100 °-1400 high-temperature gas.Is temperature that room temperature is sent in the combustion chamber by inlet mouth 13 to the oxygen or the oxygen-rich air that are about 100, realize burning, 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, needed heat exchange 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 syngas mixture roughly was 1000 °-1300 °F.
Pressure range in the reactor is pressed onto the transfer pressure of synthesis gas basically from atmosphere.Be approximately 1200psig(gauge pressure-pound/inch in the prior art
2), decide with corresponding technological conditions.The typical 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, hydroxyl synthol, 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 especially method of the present invention have been described with the synthetic of these gases 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.Oxygen-rich air is meant and contains the 25%(volume of having an appointment) or the air mixture of 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.Concerning most of ammonia synthesis gas processing condition, with oxygen level at the 35%(volume) about be the best.On the other hand, in the production methanol process, used 100% oxygen substantially.According to the technology contents that this paper gave, this area professional can determine suitable ratio at least and whether should use oxygen or oxygen-rich air.
Air with oxygen-rich air generation provides many important advantages.Thereby, owing to can control the ratio of oxygen and nitrogen in the mixture, the nitrogen content of combustible fluid can be controlled better.The control nitrogen content is very important for the present invention, and this is because nitrogen is often taken away heat from reactor, thereby technology is lost with a large amount of hot-fluid that combustion reactions obtains.Therefore, by the control nitrogen content, this technology has avoided utilizing the unnecessary loss of heat, and in technology, can make existing high enthalpy with use to greatest extent consistent.In addition, reduce or eliminate the needs of denitrogenating or regulating the product ratio in the downstream, prevented poor efficiency again.
Present technique field professional is appreciated that steam also can be incorporated into the combustion chamber with oxygen-rich air.Like this, can introduce further steam component, the consumption that the initial reformate reaction is brought is compensated.It can also be used to control temperature of combustion, and ensures the normal running of upstream oxygen-rich air preliminary heating device.
The present technique field professional can also see, compares with reactor with existing technology, and technology of the present invention and equipment have significant further advantage.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.Gas utilization on this developing country or near the coastal sea, this point is most important.Have again, shortened the starting time exactly, saved employed gas, when synthesis device descends with gas efficiency, 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 for those technical specialists, 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 environment 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 shown among the figure 8, 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.Because thin-walled tube can be experienced the pulling force stronger than compression, so utilize the way that hangs, they is fixed in the reaction vessel.If other modes of employing, pipe will be out of shape, even breaks.
Claims (11)
1, a kind of autothermic process by initial reformate, partial combustion and secondary reformed production synthesis gas, its feature comprises the steps:
But provide fuel gas and steam mixture to an independent reaction vessel;
Make said mixture in the first part of reactor, realize the initial reformate of heat absorption by heating, and make these mixtures produce part reformed gas by first catalyst zone;
In the second section of reactor, introduce part reformed gas and oxygen-rich air, comprise part fuel gas in the second section but make part reformed gas burning from first part produce combustion flow;
Reform the second time that combustion flow from second section is implemented in by third part in the third part of catalyzer;
The reactant of secondary reformed is guided in the first part of reactor;
Wherein the incendiary thermopositive reaction provides enough heats to the initial reformate of heat absorption.
2, produce the autothermal process of synthesis gas, this method comprises the steps:
Carry a kind of flammable feed gas and steam mixture to a reactor;
By heating this mixture and making it pass through first catalyzer, in the first area of reactor, make mixture carry out the self-heating initial reformate, to produce a kind of part reformed gas;
Transport portion reformed gas and oxygen-rich air in the second area of reactor make from the part reformed gas of first area and carry out partial combustion, but to produce a kind of combustion reactions fluid that contains part fuel gas at second area;
By making combustion reactions fluid from second area pass the 3rd zone and existing in the 3rd zone under the situation of catalyzer, make the combustion reactions fluid in the 3rd zone of reactor, carry out secondary reformed;
Secondary reformed reacting fluid mixture is imported the first area of reactor;
Wherein enough heats are provided to the heat absorption initial reformate from the incendiary exothermic heat of reaction.
3, method according to claim 1 is characterized in that: synthesis gas is methyl alcohol, ammonia, hydrogen, oxo alcohol or Fischer-Tropsch process synthetic hydrocarbon polymer.
4, 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, and said gaseous reaction product is by the outside of pipe.Make the burning liberated heat that the thermo-negative reaction that takes place in the pipe is provided.
5, a kind of autothermal process of producing synthetic gas, be used to produce at least a product that is selected from ammonia, methyl alcohol, hydrogen, the pure and mild Fischer-Tropsch process hydrocarbon of oxo process, it is characterized in that passing through catalyzer by the secondary reformed reacting fluid countercurrent flow of mixture and described process, make steam and hydrocarbon material gas in a container, carry out initial reformate, production part reformed gas; Afterwards, make described part reformed gas contact oxygen or oxygen-rich air to burn; Make the combustion reactions fluid by second catalytic domain further reformation to be provided and to produce described synthetic gas; Feed described synthetic gas with the relation that is heat exchange with described steam-hydrocarbon material gas mixture subsequently, thereby be cooled because of heat exchange from the thermo-negative reaction heat supply and the described synthetic gas of described combustion reactions liberated heat to described mixture.
6, a kind of autothermal process of producing synthetic gas, be used to produce at least a product that is selected from ammonia, methyl alcohol, hydrogen, the pure and mild Fischer-Tropsch process hydrocarbon of oxo process, it is characterized in that making the secondary reformed reacting fluid countercurrent flow of described mixture and described process by one or more reaction tubess that contain fixed bed catalyst, thereby make steam and hydrocarbon material gas in a container, carry out initial reformate, produce a part of reformed gas; Afterwards, make described part reformed gas contact oxygen or oxygen-rich air, burn; Make the combustion reactions fluid by second catalytic domain further reformation to be provided and to produce described synthetic gas; Pass through described synthetic gas in the outside of described reaction tubes subsequently, thereby make described combustion reactions liberated heat supply with the mixture of described thermo-negative reaction, and described synthetic gas is cooled because of heat exchange.
7, a kind of autothermic reactor of producing synthetic gas, wherein initial reformate and secondary reformed can both be finished efficiently, it is characterized in that this reactor comprises an independent reactor with heat exchange chamber of first part and second section, one links to each other with described heat exchange chamber, be used for first inlet with steam and material gas introducing heat exchange chamber, a plurality of reaction tubess that are installed in the described heat exchange chamber first part, its position and described first inlet are longitudinally-spaced, and communicate and be non-concentric relation with described first inlet, provide runner by described a plurality of reaction tubess for steam and the material gas that described first inlet comes, described a plurality of reaction tubes all contains catalyzer in each to carry out first reforming reaction and to be positioned at the position of described relatively first inlet, like this, steam and the material air-flow introduced by first inlet will be distributed in a plurality of reaction tubess, the combustion chamber, link up the device of described reaction tubes, make the gas that reacts thus from reaction tubes feed described combustion reactions chamber, described device is from described reaction tubes longitudinal extension and extend to described combustion reactions chamber always, second inlet connects described combustion reactions chamber so that oxygen or oxygen-rich air are introduced described combustion reactions chamber, described second inlet is nonconcentric(al) relation with described combustion chamber, and this device defines second catalytic domain of the second section that is positioned at described heat exchange chamber, a dividing plate separates described heat exchange chamber and described combustion reactions chamber, include device in the described dividing plate so that the combustion reactions fluid passes through described second catalytic domain, wherein said second catalytic domain comprises that one is supported on catalyst bed on the described dividing plate to carry out secondary reformed, thereby, the combustion reactions fluid can carry out once more reforming reaction and produce synthetic gas by described dividing plate and described second catalytic domain, and by being arranged in the synthetic gas relief outlet of described reactor, and described outlet almost is non-concentric relation adjacent to described first inlet and with described first inlet and described reaction tubes, like this, synthetic gas in described reaction tubes circumferential flux mistake, provides heat and has cooled off synthetic gas for carrying out described initial reformate reaction in the described reaction tubes before discharging by described outlet.
8, the reactor of claim 7 comprises that further the fluid baffles that is arranged in the described heat exchange chamber first part flows into described reaction tubes with guiding combustion reactions fluid.
9, the reactor of claim 7, the described device of wherein linking up described reaction tubes are collectors adjacent with the exit end of described reaction tubes, and one of them pipe passes described dividing plate straight down and enters the combustion chamber.
10, the reactor of claim 7 further comprises the suspension system that is used for described a plurality of reaction tubess are connected to described reactor.
11, a kind of autothermic process of producing synthesis gas from hydrocarbon flow, it is characterized in that: only in a container, carry out initial reformate and secondary reformed, described initial reformate is described mixture and secondary reformed reacting fluid adverse current to be reacted with cooling secondary reformed reacting fluid and to the initial reformate of described mixture by first catalyzer heat is provided, thereby makes the mixture reaction of steam and hydrocarbon material gas; And secondary reformed is to make the combustion reactions fluid of introducing oxygen or oxygen-rich air generation flow through second catalyzer in the fluid of described initial reformate reaction, to produce described secondary reformed reacting fluid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 85101360 CN1008350B (en) | 1985-04-01 | 1985-04-01 | Autothermal production of synthesis gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 85101360 CN1008350B (en) | 1985-04-01 | 1985-04-01 | Autothermal production of synthesis gas |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN85101360A CN85101360A (en) | 1987-01-31 |
| CN1008350B true CN1008350B (en) | 1990-06-13 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 85101360 Expired CN1008350B (en) | 1985-04-01 | 1985-04-01 | Autothermal production of synthesis gas |
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| CN (1) | CN1008350B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| BRPI0919324A2 (en) * | 2008-09-05 | 2015-12-29 | Intercat Equipment Inc | material removal device and material stocking method in one or more units |
| CN111871336A (en) * | 2020-08-21 | 2020-11-03 | 中国海洋石油集团有限公司 | Low-carbon alkane reforming reaction device and synthesis gas equipment |
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1985
- 1985-04-01 CN CN 85101360 patent/CN1008350B/en not_active Expired
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| Publication number | Publication date |
|---|---|
| CN85101360A (en) | 1987-01-31 |
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