CN102489222A - Reaction device for synthesizing methane, and method for synthesizing methane - Google Patents

Reaction device for synthesizing methane, and method for synthesizing methane Download PDF

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CN102489222A
CN102489222A CN2011103976159A CN201110397615A CN102489222A CN 102489222 A CN102489222 A CN 102489222A CN 2011103976159 A CN2011103976159 A CN 2011103976159A CN 201110397615 A CN201110397615 A CN 201110397615A CN 102489222 A CN102489222 A CN 102489222A
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beds
methane
downstream
ceramic balls
inert ceramic
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刘雪飞
赵海龙
刘鹏翔
王志彬
张建祥
常俊石
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Xindi Energy Engineering Technology Co Ltd
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Xindi Energy Engineering Technology Co Ltd
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Abstract

The invention discloses a device and a method for synthesizing methane. The device for synthesizing methane comprises a raw material air inlet, a middle catalyst bed layer, and a downstream reaction product outlet; the upstream of the catalyst bed layer is provided with a primary air distribution system; and the downstream of the catalyst bed layer is provided with a secondary air distribution system. The device for synthesizing methane also comprises a waste heat boiler which is directly connected with the downstream reaction product outlet. The device for synthesizing methane has a simple structure and improved energy saving performance and economy, and is easy to manufacture; and by using the device, the reaction can be performed continuously.

Description

Be used for methane synthetic reaction unit and methane synthetic method
Technical field
The present invention relates to the synthetic field of methane, particularly a kind of synthetic reaction device of oven gas system methane.
Background technology
The methane synthetic reaction is at high temperature and CO, CO in the gas is arranged under the situation of catalyst existence 2And H 2React, generate CH 4And H 2O.The methane synthetic reaction is a strong exothermal reaction, and the enthalpy change of each reaction is as follows:
CO+3H 2→CH 4+H 2O，
Figure BDA0000116093030000011
CO 2+4H 2→CH 4+2H 2O，
Methanator is general to adopt axial flow fixed bed adiabatic reactor, the fluid in the bed to distribute directly to influence heat transfer, mass transfer and catalyst and the utilization ratio of reactor in the bed.And methanation reaction is a violent exothermic reaction, in the reactor of thermal insulation, when the fluid skewness, can cause serious hot-spot, not only influences selection of catalysts property and conversion ratio, and life of catalyst is obviously descended.Conventional method is at the fluid inlet place of fixed bed reactors fluid distributor to be set, and described in CN2075277U, CN2705231Y, its advantage is to make fluid get into beds comparatively uniformly.But the structure more complicated of distributor goes out beds the direct fluid distribution apparatus is not set, and fluid is evenly distributed in the whole beds.
Reaction back high-temperature gas connects waste-heat recovery device through fairlead usually; This method is under the condition of high pressure, high-temperature, to carry out; This strengthens the difficulty that manufactures and designs that connects pipeline; The steam grade and the output of waste heat system recoveries are descended, thereby not only influence the energy-conservation of system, and the economy of device is obviously descended.
Summary of the invention
Technical problem to be solved by this invention be to above-mentioned prior art present situation and propose a kind of have rational in infrastructure, easily manufactured, successive reaction, energy-conservation oven gas system methane synthesizer.
The technical scheme that technical problem to be solved by this invention adopts is:
In one embodiment; Methane synthesizer of the present invention has the beds at raw material gas inlet, middle part and the reacting product outlet in downstream thereof; The upper reaches of beds are provided with the one-level gas distributed system, and the downstream of beds are provided with the secondary gas compartment system.
In another embodiment, methane synthesizer of the present invention also comprises waste heat boiler.Preferably, said waste heat boiler directly is connected with the reacting product outlet in downstream through flange or welding without pipeline, constitutes the methane synthesizer of equipment as a whole.
The type of feed of catalyst is in the said apparatus: lay several layers inert ceramic balls layer on brick vault top, catalyst is seated in this porcelain ball layer upper reaches, and re-lays the inert ceramic balls layer of several layers different-grain diameter at the catalyst upstream portion.
In methane was synthetic, the temperature range of pyroreaction gas was 250～800 ℃, and pressure is 0～3.0MPa, and byproduct steam is pressed the saturated vapor of 1.0～4.5MPa.
The present invention has the following advantages:
1, the novel distribution of gas structure of the inner employing of methane synthesizer.This distribution device in gas-fluid is by the raw material gas inlet impingement baffle, and the inert ceramic balls layer of catalyst upstream and downstream and brick vault constitute.The inert ceramic balls layer at the upper reaches of import impingement baffle and catalyst is formed the one-level compartment system, and unstripped gas is tentatively distributed; The secondary compartment system is formed in the inert ceramic balls layer in catalyst downstream and the duct on the brick vault, and interacts with the one-level compartment system, in beds, forms the uniform air flow passage, makes unstripped gas more even distribution in bed.Reduce the risk of bed hot-spot, increased activity of such catalysts, prolonged life of catalyst.
Above-mentioned distribution device in gas-fluid, unstripped gas charging impingement baffle is made up of a disk and many suspension rods, and wherein the diameter of disk is 0.5～1.5 times of raw material gas inlet internal diameter, is preferably 1～1.2 times.The upper surface of length of boom and beds upper reaches inert ceramic balls layer than being 0.2～1, is preferably 0.4～0.7 to the distance of disk.The quantity of suspension rod is advisable with fixed disc stably, and can in the embodiment of this paper, adopt 4 suspension rods for more than 2, but the invention is not restricted to this.
The catalyst upstream and downstream all is provided with the multilayer inert ceramic balls, 2～3 layers at the preferred upper reaches, 2～4 layers in downstream; It highly is between 50～300mm, between preferred 80～160mm that each layer laid; The particle diameter of inert ceramic balls is between φ 1～φ 80mm, and between preferred φ 10～φ 60mm, the particle diameter of the every layer of porcelain ball of laying can be identical or different.Porcelain ball size, the number of plies also need be mated with corresponding reactor with the selection of height, if mate improperly, then or make bed pressure drop excessive, perhaps makes distribution of gas inhomogeneous.
The radian of brick vault is between 60～150 °, between preferred 80～130 °.The vault centre of sphere is all roughly pointed in the axle center, duct of vault perforate, and the percent opening with arch section of brick vault is 1%～20% of an arch area, and preferred 8%～15%.The vault radian should be interrelated with the vault percent opening, and the proportioning mistake can make vault carry the incessantly weight of catalyst, causes subsiding of vault.
2, waste heat boiler is in particular horizontal waste heat boiler.Preferred waste heat boiler directly is connected with the fixed bed adiabatic reactor bottom through flange or welding, thereby saves the high pressure-temperature fairlead that tradition is used, and reduces the cost of equipment investment, avoids the thermal loss of transport process, can produce more high-grade steam.
Description of drawings
Fig. 1 is vertical sectional structure chart of one embodiment of the invention;
Fig. 2 is the structure chart of the raw material gas inlet impingement baffle of one embodiment of the invention;
Among the figure, the brick vault 9-of the inert ceramic balls layer 8-fire resistant heat preserving liner 10-reaction gas in the inert ceramic balls layer 6-beds 7-catalyst downstream at the horizontal waste heat boiler 3-of 1-fixed bed adiabatic reactor 2-raw material gas inlet 4-raw material gas inlet impingement baffle 5-catalyst upper reaches outlet 11-suspension rod 12-disk
Fig. 3 inside reactor point for measuring temperature horizontal plane distribution map
9 groups of points for measuring temperature are represented in T1 among the figure～9.
The vertical distribution map of Fig. 4 inside reactor point for measuring temperature
TXa～f among the figure, vertical distribution of 9 groups of points for measuring temperature in the representative graph 3.
The specific embodiment
To the detailed description of the invention, below be merely preferred embodiment of the present invention below in conjunction with accompanying drawing, can not limit scope of the present invention with this.The equalization of promptly doing according to claim of the present invention generally changes and modifies, and all should belong to the scope that the present invention is contained.
Embodiment 1
This reaction unit is used for oven gas system methane, and the saturated vapor of by-product 4.0MPa.300 ℃ of unstripped gas temperature, pressure 2.0MPa, the component molar content is respectively: CO 6.5%, CO 22.4%, N 22.8%, CH 425%, H 248%, CnHn 2.5%, H 2O 12.8%, and the loading height of catalyst is 2.5m, reactor diameter 1.8m.
As shown in Figure 1, horizontal waste heat boiler directly links to each other with the bottom of fixed bed adiabatic reactor through welding.The diameter of raw material gas inlet impingement baffle is 1.2 times of raw material gas inlet internal diameter; The upper surface of length of boom and beds upper reaches inert ceramic balls layer to the distance of disk than being 0.6; Two-layer inert ceramic balls is laid at the catalyst upper reaches, and one deck is φ 60mm inert ceramic balls (the prosperous vitrification worker's filler of Pingxiang City Co., Ltd, specification φ 60mm); Loading highly is 120mm; One deck is φ 20mm inert ceramic balls (the prosperous vitrification worker's filler of Pingxiang City Co., Ltd, specification φ 20mm), and loading highly is 80mm; Two layers of inert ceramic balls are laid in the catalyst downstream; One deck is φ 25mm inert ceramic balls (the prosperous vitrification worker's filler of a Pingxiang City Co., Ltd; Specification φ 25mm), loading highly is 100mm, and one deck is φ 50mm inert ceramic balls (the prosperous vitrification worker's filler of a Pingxiang City Co., Ltd; Specification φ 50mm), loading highly is 100mm; Brick vault radian is 120 °, and percent opening is 10%.
Reaction bed temperature distributes as shown in table 1, can find out that by table 1 the entire reaction bed temperature is evenly distributed, no hot localised points.Explain that reacting gas has obtained good distribution in reactor.
Table 1
1 2 3 4 5 6 7 8 9
a 300 300 300 300 300 300 300 300 300
b 651 650 651 650 650 650 651 650 651
c 651 650 651 650 651 650 651 650 651
d 650 650 650 650 650 650 650 650 650
e 649 650 650 650 650 650 650 649 649
f 649 649 650 650 650 650 650 649 649
The unit of temperature is degree centigrade in the table.
Embodiment 2
Reacting gas composition and operating condition are identical with embodiment 1.
Horizontal waste heat boiler connects through flange and directly links to each other with the bottom of fixed bed adiabatic reactor.The diameter of raw material gas inlet impingement baffle is 1 times of raw material gas inlet internal diameter; The upper surface of length of boom and beds upper reaches inert ceramic balls layer to the distance of disk than being 0.4; Two-layer inert ceramic balls is laid at the catalyst upper reaches, and one deck is φ 50mm inert ceramic balls (the prosperous vitrification worker's filler of Pingxiang City Co., Ltd, specification φ 50mm); Loading highly is 100mm; One deck is φ 40mm inert ceramic balls (the prosperous vitrification worker's filler of Pingxiang City Co., Ltd, specification φ 40mm), and loading highly is 120mm; Three layers of inert ceramic balls are laid in the catalyst downstream, and one deck is φ 10mm inert ceramic balls (the prosperous vitrification worker's filler of Pingxiang City Co., Ltd, specification φ 10mm); Loading highly is 50mm, and one deck is φ 25mm inert ceramic balls (the prosperous vitrification worker's filler of Pingxiang City Co., Ltd, specification φ 25mm); Loading highly is 100mm; One deck is φ 50mm inert ceramic balls (the prosperous vitrification worker's filler of Pingxiang City Co., Ltd, specification φ 25mm), and loading highly is 100mm; Brick vault radian is 90 °, and percent opening is 14%.
Reaction bed temperature distributes as shown in table 2, can find out that by table 2 the entire reaction bed temperature is evenly distributed, no hot localised points.Explain that reacting gas has obtained good distribution in reactor.
Table 2
1 2 3 4 5 6 7 8 9
a 300 300 300 300 300 300 300 300 300
b 650 651 651 650 651 650 650 650 651
c 650 651 651 651 651 651 650 651 651
d 650 651 651 651 651 650 649 650 650
e 649 650 650 651 651 649 649 649 650
f 649 650 650 650 650 649 649 649 649
The unit of temperature is degree centigrade in the table.
Comparative example 1
Reacting gas composition and operating condition are identical with embodiment 1.
Adopt traditional gas distributor, the catalyst upper reaches are not provided with the porcelain ball, and vault construction (promptly go out beds the direct fluid distribution apparatus is not set) is not adopted in downstream, sieve plate directly is set is used to stack catalyst.Reaction bed temperature distributes as shown in table 3, can find out that from table 3 catalyst bed layer segment vertical passage temperature is too high, explains that reacting gas gets into the beds skewness, tangible channel occurred.
Table 3
1 2 3 4 5 6 7 8 9
a 300 300 300 300 300 300 300 300 300
b 634 630 661 635 640 658 642 638 657
c 642 635 660 651 645 658 648 642 657
d 650 651 655 659 651 657 649 657 653
e 649 650 653 659 656 654 649 656 650
f 649 650 653 657 656 649 649 655 649
The unit of temperature is degree centigrade in the table.
Comparative example 2
The condition of reacting gas composition, operating condition and reactor is identical with embodiment 1.Difference is that the catalyst upper reaches are not provided with distribution porcelain ball.Reaction bed temperature distributes as shown in table 4, can find out from table 4, gets into the bed initial stage at gas, and distribution of gas is inhomogeneous, and portion temperature is lower.Though the final distribution of gas is more even in the bed bottom, bed top catalyst utilization is lower.
Table 4
1 2 3 4 5 6 7 8 9
a 300 300 300 300 300 300 300 300 300
b 350 400 653 653 420 500 653 652 648
c 643 648 651 651 640 650 652 651 650
d 652 651 651 651 650 651 652 651 650
e 651 650 650 650 650 650 651 650 650
f 651 650 650 649 649 650 650 650 649
The unit of temperature is degree centigrade in the table.
Comparative example 3
The condition of reacting gas composition, operating condition and reactor is identical with embodiment 1.Difference is a length of boom with the upper surface of porcelain ball layer to the distance of disk than being 0.15.Reaction bed temperature distributes as shown in table 5, can find out from table 5, and reactor middle part bed temperature is lower, and the bed peripheral temperature is comparatively even.Reacting gas distributes lessly in the bed centre in explanation, and most gases pass bed from periphery.
Table 5
1 2 3 4 5 6 7 8 9
a 300 300 300 300 300 300 300 300 300
b 320 652 653 653 652 654 655 652 651
c 340 652 653 653 652 654 654 652 650
d 450 651 653 652 652 653 654 652 650
e 600 651 652 651 651 653 653 651 650
f 630 651 652 651 651 652 651 651 650
The unit of temperature is degree centigrade in the table.
Comparative example 4
The condition of reacting gas composition, operating condition and reactor is identical with embodiment 1.Difference is that the porcelain ball is not set between catalyst and the vault.Reaction bed temperature distributes as shown in table 6, can find out that from table 6 bed part vertical passage temperature is too high, and portion temperature is lower.Explain that the temperature distributing disproportionation of reacting gas in reactor is even, channel occurred, cause local longitudinal temperature high, the situation that local temperature is on the low side.
Table 6
1 2 3 4 5 6 7 8 9
a 300 300 300 300 300 300 300 300 300
b 542 604 612 654 421 550 578 655 530
c 630 642 648 654 510 632 649 655 621
d 655 650 652 635 654 651 650 650 654
e 655 649 652 632 653 650 650 649 654
f 654 649 651 630 653 650 649 649 653
The unit of temperature is degree centigrade in the table.

Claims (9)

1. methane synthesizer; Said methane synthesizer has the beds at raw material gas inlet, middle part and the reacting product outlet in downstream thereof; The upper reaches of said beds are provided with the one-level gas distributed system, and the downstream of said beds are provided with the secondary gas compartment system.
2. methane synthesizer according to claim 1, wherein, said one-level gas distributed system is provided with unstripped gas charging impingement baffle and the inert ceramic balls layer of being located at the upper reaches of beds.
3. methane synthesizer according to claim 1, wherein, said secondary gas compartment system is provided with the inert ceramic balls layer and the brick vault in beds downstream, and a plurality of ducts are arranged on the vault.
4. methane synthesizer according to claim 2, wherein, said unstripped gas charging impingement baffle is made up of a disk and a plurality of suspension rod, and the diameter of wherein said disk is 0.5～1.5 times of raw material gas inlet internal diameter, is preferably 1～1.2 times; Said length of boom is 0.2～1 with the ratio of the distance of upper surface to the disk of the inert ceramic balls layer at the said beds upper reaches, is preferably 0.4～0.7.
5. methane synthesizer according to claim 2, wherein, the radian of said brick vault is 60～150 °, preferred 80～130 °; The vault centre of sphere is all roughly pointed in the axle center in said duct, and the percent opening with arch section of said brick vault counts 1%～20% with area %, and preferred 8%～15%.
6. according to each described methane synthesizer in the claim 1 to 5; Wherein, The number of plies of the inert ceramic balls layer at the said beds upper reaches is 2～3 layers; The number of plies of the inert ceramic balls layer in said beds downstream is 2～4 layers, and every layer laying highly is 50～300mm, preferred 80～160mm; The particle diameter of said inert ceramic balls is φ 1～φ 80mm, preferred φ 10～φ 60mm.
7. according to each described methane synthesizer in the claim 1 to 6, said methane synthesizer also comprises the waste heat boiler that is connected with the reacting product outlet in said downstream.
8. methane synthesizer according to claim 7, wherein, said waste heat boiler is horizontal waste heat boiler, the reacting product outlet in said downstream directly is connected through flange or welding with said waste heat boiler.
9. the method for a synthesizing methane, said method are used and are carried out according to each described methane synthesizer in the claim 1 to 8.
CN2011103976159A 2011-12-05 2011-12-05 Reaction device for synthesizing methane, and method for synthesizing methane Pending CN102489222A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108751959A (en) * 2018-08-24 2018-11-06 宜兴瑞泰耐火材料有限公司 A kind of dehydrogenating propane device reaction device porous brick and preparation method thereof
CN111249999A (en) * 2018-11-30 2020-06-09 中国科学院大连化学物理研究所 Fixed bed reactor for catalytic reduction of hexavalent uranium by hydrazine nitrate and application

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10273678A (en) * 1997-03-28 1998-10-13 Sekiyu Sangyo Kasseika Center Heat exchange type reforming reactor
CN201454503U (en) * 2009-08-31 2010-05-12 中国石油化工股份有限公司 Axial flow fixed bed gas-solid catalytic reactor
CN102029129A (en) * 2009-09-25 2011-04-27 华东理工大学 Axial-radial flow gas-solid phase fixed bed catalytic reactor

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10273678A (en) * 1997-03-28 1998-10-13 Sekiyu Sangyo Kasseika Center Heat exchange type reforming reactor
CN201454503U (en) * 2009-08-31 2010-05-12 中国石油化工股份有限公司 Axial flow fixed bed gas-solid catalytic reactor
CN102029129A (en) * 2009-09-25 2011-04-27 华东理工大学 Axial-radial flow gas-solid phase fixed bed catalytic reactor

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108751959A (en) * 2018-08-24 2018-11-06 宜兴瑞泰耐火材料有限公司 A kind of dehydrogenating propane device reaction device porous brick and preparation method thereof
CN108751959B (en) * 2018-08-24 2023-05-23 宜兴瑞泰耐火材料有限公司 Porous brick for propane dehydrogenation device reactor and preparation method thereof
CN111249999A (en) * 2018-11-30 2020-06-09 中国科学院大连化学物理研究所 Fixed bed reactor for catalytic reduction of hexavalent uranium by hydrazine nitrate and application

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Application publication date: 20120613