CN201626829U - Heat coupling fixed bed device for gas synthesis by natural gas - Google Patents
Heat coupling fixed bed device for gas synthesis by natural gas Download PDFInfo
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- CN201626829U CN201626829U CN2009202934072U CN200920293407U CN201626829U CN 201626829 U CN201626829 U CN 201626829U CN 2009202934072 U CN2009202934072 U CN 2009202934072U CN 200920293407 U CN200920293407 U CN 200920293407U CN 201626829 U CN201626829 U CN 201626829U
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Abstract
The utility model provides a heat coupling fixed bed device used for gas synthesis by natural gas, which comprises a heat exchanging zone, an oxidizing zone, a reforming zone, a nozzle, a heat insulating layer and a high-pressure resistant metal outer casing. The integral device mainly adopts a concentric structure, the oxidizing zone is positioned inside an inner pipe, the reforming zone is positioned in a gap between the inner pipe and an outer pipe or on the lower portion of the oxidizing zone of the inner pipe, the heat insulating layer is arranged outside the outer pipe, the high-pressure resistant metal outer casing is arranged outside the heat insulating layer, and the heat exchanging zone is arranged on the upper portion of the device. Raw material gas exchanges heat with a product in a reverse-flow indirect manner, enters from the top of the oxidizing zone via the nozzle to have rapid oxidization reaction, and flows into the reforming zone to obtain produced synthesis gas. Diversion ceramic and high-temperature resistant catalytic partial oxidizing catalysts are arranged in the oxidizing zone and capable of eliminating hotspots of a bed layer, relieving deposited carbon, further increasing the producing proportion of the synthesis gas, lowering material temperature to reaction temperature permitted by reforming catalysts, reducing heat needed by subsequent reforming reaction, leading reforming reaction temperature to reach more than 1000 DEG C and improving use rates of materials and energy.
Description
Technical field
The utility model provides a kind of thermal coupling fixed bed device, and it particularly is to belong to Sweet natural gas catalyzing part oxidation preparing synthetic gas autothermal reaction device for being used for the reaction unit of Sweet natural gas (methane) preparing synthetic gas.
Background technology
At present, 90% gas chemical industry utilization realizes by the Sweet natural gas synthetic gas production process in the world.Therefore, gas chemical industry's key problem in technology is the preparation of synthetic gas.From catalysis technique, reaction process and engineering many-side different combinations is carried out in the principal reaction (comprising steam reformation, CO 2 reformation, catalysis and non-catalytic complete oxidation and partial oxidation) of Sweet natural gas preparing synthetic gas, coupling and comprehensive utilization by energy, developed and the diversified forms of association reforming process, its core objective is realized the utilization of Sweet natural gas synthetic gas production process energy optimization exactly, thus the productive expense of the process of reduction.Representative technology has: the self-heating recapitalization technology (ATR) of the associating self-heating recapitalization technology (CAR) of heat exchange/reforming process of Kellogg (KRES), Uhde, the gas heating reforming process (GHR) of ICI, Topsoe, the catalyzing part oxidation (CPO) of ExxonMobil etc.
The something in common of above-mentioned various associating reforming process technology is, traditional steam reformation or steam reformation one self-heating recapitalization two-section joint reforming process are reformed and reformed, make the oxidizing reaction of the reforming reaction of heat absorption and heat release logistics, can be able to sufficient coupling by stream, thereby the material consumption and the energy consumption of the process of reduction.The development of these processes shows, the Sweet natural gas synthetic gas production process just gradually from water be the steam reformation of one of main raw material to being that the burning-reformation of one of main raw material and partial oxidation change with oxygen, its core technology feature is with the CPO process of gentle heat release and the steam reformation PROCESS COUPLING of strong heat absorption.Therefore, the successful exploitation of coupling process in fact also just becomes the key of high-efficiency and energy-saving type synthesis gas preparation process development.
In order to adapt to the higher working pressure in most of downstreams and to consider from the economy of whole process, synthetic gas production process need high pressure (＞carry out under 2MPa).Yet under high pressure, be subjected to the restriction of thermodynamic(al)equilibrium, expect comparatively ideal methane conversion and synthetic gas selectivity, goal response (reforming reaction) temperature must be above 1000 ℃.At present traditional reforming process temperature of reaction is lower, generally about 900 ℃, can not satisfy the demands.Obviously, obtain higher synthetic gas yield down, must solve following problems on the engineering in order to realize high temperature, high pressure:
(1) mixed problem of pyroreaction raw material.Consider the difficulty of the outside heat supply of process, have only by improving the material inlet temperature to guarantee that follow-up reforming reaction temperature reaches more than 1000 ℃ that calculation of thermodynamics shows that the preheating temperature of reaction raw materials need reach more than 600 ℃.Under so high preheating temperature, if Sweet natural gas enters reactor after being pre-mixed with oxygen again, because there is limits of explosion in mixture, the security of will certainly influence process operating.Therefore, raw material just can enter reactor after the preheating respectively and carries out contact reacts.
(2) coupling of thermopositive reaction and thermo-negative reaction fast.If raw material enters remix behind the reactor, then in the reactor content ingress, complete oxidation will take place earlier with Sweet natural gas in oxygen, generate carbonic acid gas and water, and emit a large amount of heats, the reforming reaction of heat absorption takes place in unreacted Sweet natural gas again with carbonic acid gas and water, generate synthetic gas.Because the speed of reaction of methane complete oxidation is higher than the speed of reforming reaction far away, therefore, two districts will inevitably occur in reactor: i.e. the strong heat absorption reforming reaction district at reactor forward strong exothermal reaction district and reactor rear portion.In heat release zone, can not in time shift as a large amount of reaction heat, high temperature hotspot will appear, cause unreacted methane generation cracking, cause the serious carbon distribution of catalyzer; In strong heat absorption district, if the required heat of postreaction in time, temperature of reaction will reduce fast, be difficult to obtain ideal methane conversion and synthetic gas selectivity.
As can be seen from the above analysis, be to obtain ideal methane conversion and synthetic gas selectivity, the partial oxidation reaction of the gentle heat release of generation that oxidation zone will be as much as possible, and make temperature of charge drop to the temperature of reaction that follow-up reforming catalyst is allowed; Reformer section should maintain under the high as far as possible temperature reacts.How to regulate and control this two reaction zones, just become formation that suppresses high temperature hotspot and the key that improves the synthetic gas productive rate.
The utility model content
The utility model provides a kind of novel fixed bed device that is used for the Sweet natural gas preparing synthetic gas, especially a kind of reaction unit that is applicable to self-heating, this device effectively the be coupled oxidizing reaction of strong heat release and the reforming reaction of strong heat absorption, simultaneously, unstripped gas preheating and synthetic gas cooling two portions have been coupled, greatly reduce the bed hot(test)-spot temperature, alleviated the generation of carbon distribution, and can make full use of the oxidizing reaction liberated heat, the reforming reaction temperature out is reached more than 1000 ℃, improved the matter and energy utilization ratio.
The purpose of this utility model is to provide a kind of thermal coupling fixed bed device that is used for the Sweet natural gas preparing synthetic gas, by means of this device, make Sweet natural gas and oxygen be injected to oxidation zone generation oxidizing reaction by nozzle through after the heat transfer zone, product together enters reformer section generation reforming reaction together with unreacted Sweet natural gas and generates synthetic gas, at last, synthetic gas is discharged after the quick heat exchange of heat transfer zone, the coupling of oxidizing reaction and reforming reaction has guaranteed that the self-heating of reaction carries out, heat transfer zone the fast cooling that has guaranteed reaction product is set, avoided synthetic gas to generate the generation of the reversed reaction of methane after leaving beds, the application of nozzle has guaranteed the mixed effect of unstripped gas.
The purpose of this utility model can be achieved through the following technical solutions.
This thermal coupling device that the utility model provides comprises heat transfer zone, oxidation zone, reformer section, nozzle, thermal insulation layer and high pressure resistant metal shell, described fixed bed device has adopted the concentric type structure, oxidation zone is positioned at pipe, reformer section is positioned at inner and outer pipes gap or oxidation zone bottom, outer tube is outward a thermal insulation layer, thermal insulation layer is outward high pressure resistant metal shell, and described heat transfer zone is positioned at the top of device, and nozzle is positioned at the oxidation zone top; Unstripped gas is injected to oxidation zone by nozzle after the heat transfer zone heating, and generation complete oxidation and partial oxidation reaction, emit a large amount of heats, wherein, the outer reformer section of pipe in part heat is delivered to by tube wall, it has not only reduced the heat surplus of oxidation zone, but also replenished the shortage of heat of follow-up reforming reaction, and most of heat makes material reach very high temperature, but generate the increase of ratio along with synthetic gas, temperature of charge will reduce, after reaching the temperature of reaction that reforming reaction allows, flow into reformer section, reforming reaction takes place under the effect of reforming catalyst generate synthetic gas, last, the product synthetic gas is discharged by the synthetic gas air outlet after heat transfer zone is cooled off fast.
The utility model oxidation zone is filled with different catalyzer with reformer section, because the oxidation zone temperature is very high, so be filled with pottery and high temperature resistant catalytic partial oxidation catalyst, the oxidation zone epimere mainly loads the water conservancy diversion pottery, its main effect is the quick uniform mixing of intensified response thing, eliminate the bed high temperature hotspot, alleviate carbon distribution; The oxidation zone hypomere mainly loads high temperature resistant catalytic partial oxidation catalyst, accelerate partial oxidation reaction speed, increase the synthetic gas proportion of production, the increase that generates ratio along with synthetic gas had both reduced temperature of charge, solved of the restriction of follow-up reforming catalyst to temperature of reaction, reduced the requirement of follow-up reforming reaction to temperature again, guaranteed that the temperature out of reforming reaction maintains more than 1000 ℃, this loaded catalyst should be able to guarantee that temperature of charge is reduced to the desired temperature of reaction of reforming catalyst; Reformer section is loaded high temperature resistant reforming catalyst, and its effect is to accelerate reforming reaction speed, further improves the synthetic gas yield.This type of feed has realized oxidation zone heat surplus and the heat coupling of reformer section shortage of heat, has improved the matter and energy utilization ratio.
The utility model is taked the mode by nozzle material-feeding.Sweet natural gas after preheating and oxygen is by the top air inlet of nozzle from reactor, avoided the uneven problem of mixing that is caused by charging respectively.
The used nozzle of the utility model adopts outer blended form, complete oxidation and partial oxidation reaction be from taking place after the ejection of duct in two kinds of gases separately immediately, the tempering problem of having avoided the blast problem that in the past caused with the air inlet of pre-mixing mode and interior hybrid mode to cause.
The used outer mix type nozzle of the utility model is divided into a plurality of series (shown in Figure 2 just wherein a kind of), at least two kinds of fluids can be injected to the reactor oxidation zone.
The utility model adopts the concentric type structure, and oxidation zone can be for cylindric, also can be for round table-like.Oxidation zone generation oxidizing reaction is emitted a large amount of heats, wherein, and the outer reformer section of pipe in a part directly is delivered to by the reactor partition, and major part will realize the heat coupling of oxidation zone and reformer section by the conversion of matter and energy.In this way, greatly reduce heat demand, be reflected under the adiabatic condition and operate, need not add heat substantially, realized autothermal reaction the outside.
The utility model synthetic gas air outlet is arranged on reactor top, and the inlet pipe of unstripped gas is passed from the atmosphere of synthetic gas, forms the adverse current indirect heat exchanger, and this is heat transfer zone.Because the synthetic gas temperature height that generates, and the temperature of Sweet natural gas and oxygen is low, so the heat that synthetic gas had can fully pass to Sweet natural gas and oxygen, plays the effect of preheating, and reduced the synthetic gas temperature, avoided generating the generation of the reversed reaction of methane.
The utility model reformer section is set to thermal insulation layer outward.Make whole reactor be in an approximate adiabatic state, reduce the thermosteresis of energy.
The utility model has adopted high pressure resistant metal shell, can guarantee to be reflected under the high pressure of 5MPa to carry out, and preferably is provided with explosion trap simultaneously, and this explosion trap can the overvoltage releasing pressure automatically, the safety of assurance device.
The utility model device solves the beds high temperature hotspot problem brought of Sweet natural gas complete oxidation, alleviate the generation of carbon distribution, and made full use of the energy that oxidizing reaction is emitted, do not needed external heat source, can realize adiabatic operation, not only save energy but also avoided the danger of blast.
Description of drawings
Fig. 1: Sweet natural gas preparing synthetic gas thermal coupling reaction unit 1 structural representation;
Fig. 2: thermal coupling reaction unit nozzle sectional view;
Fig. 3: thermal coupling reaction unit nozzle vertical view;
Fig. 4: Sweet natural gas preparing synthetic gas thermal coupling reaction unit 2 structural representations.
Drawing reference numeral:
1-Sweet natural gas inlet mouth 2-serpentine tube 3-nozzle
The high temperature resistant reforming catalyst of 4-oxidation zone 5-
The high temperature resistant catalytic partial oxidation catalyst of 6-
7-outer tube 8-synthetic gas air outlet 9-oxygen inlet mouth
Pipe in the 10-heat transfer zone 11-pottery 12-
The high pressure resistant metal shell of 13-reformer section 14-thermal insulation layer 15-
17-Sweet natural gas air outlet, 16-oxygen air outlet
Embodiment
Describe the utility model in detail below in conjunction with accompanying drawing, but do not limit practical range of the present utility model.
Embodiment one:
As Fig. 1, Fig. 2 and shown in Figure 3, present embodiment is thermal coupling device and the nozzle that is used for the Sweet natural gas preparing synthetic gas, and concrete structure is as follows:
This device comprises oxidation zone 4, inside is filled with high temperature resistant catalytic partial oxidation catalyst 6 and pottery 11, its effect is to provide the place for Sweet natural gas and oxygen generation oxidizing reaction, outside the following and interior pipe 12 of oxidation zone 4 is reformer section 13, reformer section 13 inside are filled with high temperature resistant reforming catalyst 5, and the effect of reformer section 13 is in order to make Sweet natural gas, water vapour and carbonic acid gas generation reforming reaction.The top of oxidation zone 4 is heat transfer zone 10, this heat transfer zone 10 is the temperature that are used for preheating Sweet natural gas and oxygen and reduce synthetic gas fast, prevent that synthetic gas high temperature from the reversed reaction of methane taking place to generate, Sweet natural gas inlet pipe and oxygen intake pipe all are serpentine tubes 2 in the heat transfer zone 10, the purpose of serpentine tube 2 is to increase heat interchanging area, be beneficial to sufficient heat exchange, heat transfer zone 10 tops are Sweet natural gas inlet mouths 1, oxygen inlet mouth 9 and synthetic gas air outlet 8, heat transfer zone 10 bottoms, oxidation zone 4 tops are nozzles of air supply 3, nozzle 3 adopts the charging of outer blended form, oxygen outlet 16 is 24 wedge shape mouths, and oxygen outlet and horizontal plane have certain included angle, is convenient to the thorough mixing of two kinds of gases.Outside the reformer section 13 is thermal insulation layer 14, and the inside is filled with lagging material, and being provided with of it kept reaction to be in an approximate adiabatic state, is high pressure resistant metal shell 15 outside the thermal insulation layer 14, and reformer section 13 catalyzer tops and reactor bottom are filled with pottery 11.
Sweet natural gas and oxygen enter into heat transfer zone 10 through inlet mouth 1 and 9 respectively and carry out preheating, reach more than 600 ℃, be injected to the oxidation zone 4 rapid complete oxidation and the partial oxidation reactions of taking place of reactor then through nozzle 3, emit a large amount of heats, beds---reformer section 13 in a part of heat is delivered to by interior pipe 12 partitions simultaneously between pipe 12 and the outer tube 7, provide required heat to reforming reaction, most of heat makes material obtain bigger temperature rise, material is under the effect of oxidation zone 4 catalyzer 6, the increase temperature that generates ratio along with synthetic gas reduces, after the temperature of reaction that follow-up reforming reaction is allowed, flow into reformer section 13, under the effect of reforming catalyst, reforming reaction takes place, further generate synthetic gas, afterwards, the high-temperature synthesis gas that reaction generates is flowed out by air outlet 8 by heat transfer zone 10 backs, unstripped gas (Sweet natural gas and oxygen) and synthetic gas reach the purpose of preheating material gas and quick cooling syngas in heat transfer zone 10 countercurrent flows.
Embodiment two:
As shown in Figure 4, be the another kind of structure iron of the thermal coupling fixed bed reaction unit of Sweet natural gas preparing synthetic gas.Adopted round table-like, such structure can effectively avoid the appearance in " dead band " (we are referred to as the dead band to mix uneven place), the probability of dwindling high temperature hotspot and methane cracking with the different structures of oxidation zone 4 that are of Fig. 1.In addition, reformer section 13 is not arranged between the concentric type annular space, but be positioned at the bottom of oxidation zone 4, the gas of being convenient to take place after the oxidizing reaction directly enters reformer section 13, the synthetic gas that the same water vapour of Sweet natural gas, carbonic acid gas generation reforming reaction generate enters heat transfer zone 10 through the concentric type annular space, shorten the time of unstripped gas generation oxidizing reaction, can make full use of the heat of oxidizing reaction.But reasonably oxidation zone 4 and reformer section 13 structures are necessary.
The effect of utilizing this thermal coupling fixed bed device to reach is:
(1) adopts this thermal coupling fixed bed device can realize effective utilization of heat, reduced energy consumption, substantially realized the self-heating operation.
(2) thermal coupling between zoneofoxidation heat surplus and the reformer section shortage of heat, reduced hot(test)-spot temperature, alleviated simultaneously the formation of low temperature " cold spot ", and make whole reactor be in a lower operation of temperature (＞1000 ℃) that the conventional reforming reaction device of ratio is high 100 ℃, improved the yield of synthesis gas.
(3) through the running of long period, catalyst surface and zoneofoxidation carbon deposition quantity are seldom.
(4) experimental result shows, methane conversion is that 92.2%, CO selectively is 92.3%, H2Selectively be 83.3%, substantially near the thermodynamical equilibrium level.
Claims (10)
1. the fixed bed device of a thermal coupling Sweet natural gas preparing synthetic gas, it is characterized in that: this thermal coupling device comprises heat transfer zone (10), oxidation zone (4), reformer section (13), nozzle (3), thermal insulation layer (14) and high pressure resistant metal shell (15), described fixed bed device has adopted the concentric type structure, oxidation zone (4) is positioned at pipe (12), reformer section (13) is positioned at inner and outer pipes gap or pipe (12) oxidation zone (4) bottom, outer tube (7) is outer to be thermal insulation layer (14), and thermal insulation layer (14) is outer to be high pressure resistant metal shell (15); Described heat transfer zone (10) is positioned at the top of device, and nozzle (3) is positioned at oxidation zone (4) top; Unstripped gas is injected to oxidation zone (4) by nozzle (3) after heat transfer zone (10) heating, take place to flow into reformer section (13) behind complete oxidation and the partial oxidation reaction, the final product synthetic gas is discharged by synthetic gas air outlet (8) after the cooling fast through heat transfer zone (10).
2. the fixed bed device of thermal coupling Sweet natural gas preparing synthetic gas as claimed in claim 1, it is characterized in that: the catalyzer of whole reactor filling is different, oxidation zone (4) epimere mainly loads water conservancy diversion pottery (11), oxidation zone (4) hypomere mainly loads high temperature resistant catalytic partial oxidation catalyst (6), and reformer section (13) is then loaded high temperature resistant reforming catalyst (5).
3. the fixed bed device of thermal coupling Sweet natural gas preparing synthetic gas as claimed in claim 1, it is characterized in that: synthetic gas air outlet (8) are positioned at reactor head, Sweet natural gas inlet pipe and oxygen intake pipe pass from the synthetic gas atmosphere, form an adverse current indirect heat exchange district (10), realize Sweet natural gas and the preheating of oxygen and the fast cooling of synthetic gas.
4. the fixed bed device of thermal coupling Sweet natural gas preparing synthetic gas as claimed in claim 1, it is characterized in that: unstripped gas adopts the mode of nozzle (3) charging, and Sweet natural gas after preheating and oxygen are passed through the oxidation zone (4) of nozzle (3) back jetting device respectively by Sweet natural gas inlet pipe and oxygen intake pipe.
5. the fixed bed device of thermal coupling Sweet natural gas preparing synthetic gas as claimed in claim 1 is characterized in that: nozzle (3) is outer mixed type, can be double flow duct, also can be the multithread road, and adopt special high temperature material to make.
6. the fixed bed device of thermal coupling Sweet natural gas preparing synthetic gas as claimed in claim 1 is characterized in that: Sweet natural gas inlet pipe and oxygen intake pipe are serpentine tube (2).
7. the fixed bed device of thermal coupling Sweet natural gas preparing synthetic gas as claimed in claim 1, it is characterized in that: natural gas feed can be Sweet natural gas and mixture of steam, oxygen feeding also can be oxygen and mixture of steam, perhaps adopts three-channel nozzle (3) that three kinds of gases are added respectively.
8. the fixed bed device of thermal coupling Sweet natural gas preparing synthetic gas as claimed in claim 1 is characterized in that: the structure of oxidation zone (4) can be for cylindric, also can be for round table-like, and internal surface is covered with protective layer, as stupalith or refractory materials.
9. the fixed bed device of thermal coupling Sweet natural gas preparing synthetic gas as claimed in claim 1 is characterized in that: oxidation zone is provided with portfire in (4).
10. the fixed bed device of thermal coupling Sweet natural gas preparing synthetic gas as claimed in claim 1 is characterized in that: whole device has adopted high pressure resistant metal shell (15).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009202934072U CN201626829U (en) | 2009-12-16 | 2009-12-16 | Heat coupling fixed bed device for gas synthesis by natural gas |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009202934072U CN201626829U (en) | 2009-12-16 | 2009-12-16 | Heat coupling fixed bed device for gas synthesis by natural gas |
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| Publication Number | Publication Date |
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| CN201626829U true CN201626829U (en) | 2010-11-10 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN2009202934072U Expired - Fee Related CN201626829U (en) | 2009-12-16 | 2009-12-16 | Heat coupling fixed bed device for gas synthesis by natural gas |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| GB2618076A (en) * | 2022-04-25 | 2023-11-01 | Zelp Ltd | Methane oxidation device |
-
2009
- 2009-12-16 CN CN2009202934072U patent/CN201626829U/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| GB2618076A (en) * | 2022-04-25 | 2023-11-01 | Zelp Ltd | Methane oxidation device |
| WO2023209351A1 (en) * | 2022-04-25 | 2023-11-02 | Zelp Limited | Methane oxidation device |
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Legal Events
| Date | Code | Title | Description |
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| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20101110 Termination date: 20111216 |