CN103693616A - Method and system for coproduction of synthesis gas employing methane non-catalytic part oxidation and methane steam transformation - Google Patents
Method and system for coproduction of synthesis gas employing methane non-catalytic part oxidation and methane steam transformation Download PDFInfo
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- CN103693616A CN103693616A CN201310670181.4A CN201310670181A CN103693616A CN 103693616 A CN103693616 A CN 103693616A CN 201310670181 A CN201310670181 A CN 201310670181A CN 103693616 A CN103693616 A CN 103693616A
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 236
- 238000000034 method Methods 0.000 title claims abstract description 40
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 27
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 27
- 230000003647 oxidation Effects 0.000 title claims abstract description 25
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 16
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 16
- 230000009466 transformation Effects 0.000 title abstract description 8
- 239000007789 gas Substances 0.000 claims abstract description 92
- 238000004519 manufacturing process Methods 0.000 claims abstract description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 52
- 239000001301 oxygen Substances 0.000 claims description 52
- 229910052760 oxygen Inorganic materials 0.000 claims description 52
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 238000002407 reforming Methods 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 8
- 239000011449 brick Substances 0.000 claims description 6
- 239000012495 reaction gas Substances 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 230000003009 desulfurizing effect Effects 0.000 claims description 2
- 238000005755 formation reaction Methods 0.000 claims description 2
- 238000002309 gasification Methods 0.000 abstract description 4
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- 238000002485 combustion reaction Methods 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 239000003345 natural gas Substances 0.000 abstract description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract 2
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract 1
- 239000001569 carbon dioxide Substances 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000000629 steam reforming Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000004134 energy conservation Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 239000002918 waste heat Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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Abstract
The invention provides a method and a system for coproduction of synthesis gas employing methane non-catalytic part oxidation and methane steam transformation. Heat generated in oxidation reaction of methane non-catalytic part is utilized to generate first synthesis gas in a methane steam transformation preheating process, and then the first synthesis gas is mixed with second synthesis gas generated in oxidation reaction of the methane non-catalytic part. The method and the system have the beneficial effects that the heat in the gasification process can be utilized by adopting the method, so that heat loss is reduced; the release of carbon dioxide caused by combustion of a natural gas of a tube furnace is removed, so that low-carbon production is really achieved. The number of heat exchangers in a methane steam transformation system can be reduced, and the investment cost of the methane steam transformation system is reduced. Coproduction of the synthesis gas employing methane transformation is carried out by using the method, so that the targets of saving energy, reducing consumption, reducing emission and reducing the cost can be achieved, and the method and the system have certain economic values.
Description
Technical field
The invention belongs to chemical industry novel technique and new energy development field, be specifically related to the method and system that a kind of methane non-catalytic partial oxidation and steam methane transform co-production synthesis gas.
Background technology
Methane non-catalytic partial oxidation technique is mainly that the nozzle of Top Structure of Heavy Oil Aerification Furnace (Texaco stove) is undergone technological transformation, and take methane as raw material straight products such as producing synthetic ammonia, urea that burns in vapourizing furnace, at fertilizer industry, has good application.Texaco gasifier is that its refractory liner of hot wall stove is refractory brick, its gasifying process principle is: methane, oxygen enter vapourizing furnace respectively after the inside and outside passage of gasifying furnace nozzle fully mixes, 1200-1400 ℃ of temperature, under pressure 2.0-3.5Mpa condition, generate CO+H
2at more than 95% available gas.High-temperature gas fully contacts with adding the washing water of quench chamber in quench chamber, through vapourizing furnace trunnion, sharply expands, and temperature is down to below 210 ℃, simultaneously by steam-laden, generates gasification gas, in this process, has caused a large amount of thermosteresis.Accompanying drawing 1 is shown in the technical process of methane non-catalytic partial oxidation.
Methane steam reforming main technique technology provider has Technip (KTI), Uhde, Linde, Foster Wheeler, Top soe, Hpwe Baker etc.Its typical process flow is roughly the same, and whole technical process is comprised of unstripped gas processing, steam reforming, CO conversion and hydrogen purification 4 big units.Steam reforming is under catalyzer existence and hot conditions, makes methane and steam reaction, generates H
2, the gas mixture such as CO, this reaction is strong endothermic reaction, needs extraneous heat supply.Its heat-supplying mode is to take the tubular oven that Sweet natural gas is raw material.Tubular oven is not taked waste heat recovery measure, causes amount of heat to diffuse, and flue gas emptying temperature is generally 350 ℃ of left and right, and waste heat energy, causes environmental thermal pollution.Tubular oven burner adopts natural ventilation system configuration combustion air, and efficiency of combustion is lower.The research that tubular oven waste gas used heat is utilized, is only confined to the replacing of fuel to reduce costs, and the utilization of used heat is reclaimed, and there is no the extension outside technology.Energy-saving Method For Pipe Heater and measure mainly contain the heat-exchange system of optimization device, reduce funnel temperature, improve air charging temperature, rationally control excess air coefficient etc.
Summary of the invention
Object of the present invention provides a kind of methane non-catalytic partial oxidation and steam methane to transform the method and system of co-production synthesis gas, the method combines methane non-catalytic partial oxidation technique and steam methane conversion process, the heat that utilizes methane non-catalytic partial oxidation technique to produce carries out pre-treatment to steam methane conversion process unstripped gas, reaches the object of energy-saving and emission-reduction.
The object of the invention is to be achieved through the following technical solutions:
Methane non-catalytic partial oxidation and steam methane transform a method for co-production synthesis gas, comprise the following steps:
1, by after the pre-thermally desulfurizing of methane, send into vapourizing furnace, to vapourizing furnace, pass into oxygen-rich air simultaneously, under hot conditions, the anti-synthetic gas that generates of methane generation non-catalytic partial oxidation;
2, synthetic gas is dropped into useless pot system, generate the first synthetic gas and middle pressure steam, middle pressure steam drops into the methane inlet duct of vapourizing furnace;
3, adjust methane steam gas mixture, oxygen-rich air index in vapourizing furnace, when the methane steam gas mixture of discharging when the steam methane outlet of vapourizing furnace reaches 500-700 ℃, passed into gas converting heat formula convertor, methane and water vapor react generation reforming gas therein, and reforming gas is sent into oxygen enrichment convertor;
When the oxygen-rich air that 4, the outlet of the oxygen-rich air of vapourizing furnace is discharged reaches 350-500 ℃, pass into oxygen enrichment convertor, under catalyst action, react formation reaction gas with the reforming gas in step 3;
5, the reaction gas that step 4 generates, successively through between the pipe of gas converting heat formula convertor, after methane heat exchanger, generates the second synthetic gas;
6, after the first synthetic gas is mixed with the second synthetic gas, send coproduction workshop section;
The reaction gas that wherein said step 4 generates provides heat to the reaction in pipe between the pipe of gas converting heat formula convertor.
A kind of methane non-catalytic partial oxidation and steam methane transform the system of co-production synthesis gas, comprise methane heat exchanger 1, desulfurizer 2, vapourizing furnace 3, useless pot 4, gas converting heat formula convertor 5 and oxygen enrichment convertor 6, wherein said methane heat exchanger 1 is connected with desulfurizer 2, vapourizing furnace 3, useless pot 4 successively, and the gas outlet of described useless pot 4 is connected with vapourizing furnace 3, gas converting heat formula convertor 5, oxygen enrichment convertor 6 successively.
Described vapourizing furnace 3 also comprises steam methane inlet tube 31, oxygen-rich air outlet pipe 32, steam methane outlet pipe 33, oxygen-enriched inlet pipe 34, wherein said useless pot 4 gas outlets connect steam methane inlet tube 31, steam methane outlet pipe 33, gas converting heat formula convertor 5 and oxygen enrichment convertor 6 successively, and described oxygen-enriched inlet pipe 34 connects oxygen-rich air outlet pipe 32, oxygen enrichment convertor 6, gas converting heat formula convertor 5 and methane heat exchanger 1 successively.
Described vapourizing furnace 3 inside are semicircular tubulation structure, by connecting several tubulations between two semi-rings, form, described semicircular tubulation is arranged between vapourizing furnace furnace wall and refractory brick 7, the gas that enters system is distributed to each tubulation by half endless tube, from diagonal angle semi-ring tubulation, flow out, wherein said steam methane inlet tube 31 is communicated with steam methane outlet pipe 33, and described oxygen-enriched inlet pipe 34 is communicated with oxygen-rich air outlet pipe 32.
Apply beneficial effect of the present invention:
(1) methane non-catalytic partial oxidation gasification furnace is hot wall stove, in production process, can produce a large amount of heat, and thermosteresis is larger, adopts present method can utilize the heat in gasification, reduces heat waste.In addition, between vapourizing furnace furnace wall and refractory brick, increase tubulation, can reduce the usage quantity of refractory brick, reduce the running cost of vapourizing furnace.
(2) by ring-type tubulation in vapourizing furnace, heat, the heating installation tube furnace in alternative steam methane conversion system, eliminates the Carbon emission that tube furnace produces because of gas-firing, really accomplishes low-carbon (LC) production.In addition, can reduce interchanger in steam methane conversion system, reduce the cost of investment of steam methane conversion system.
(3) synthetic gas that the synthetic gas that methane non-catalytic partial oxidation system is produced is produced with steam methane conversion system can carry out proportional mixing according to its gas ingredients, thereby reduce whole system in the investment of conversion section, also reduced the investment of downstream pressure-variable adsorption denitrogenation workshop section simultaneously.
(4) utilize present method to carry out the coproduction of methane conversion synthetic gas, can accomplish energy-conservation, lower consumption, reduce discharging, reduce costs, there is certain economic worth.
Accompanying drawing explanation
Fig. 1: methane non-catalytic partial oxidation of the present invention and steam methane transform co-production synthesis gas system flowchart
Fig. 2: vapourizing furnace sectional view
Fig. 3: loop pipe system vertical view
Fig. 4: loop pipe sectional view
The useless pot-4 in vapourizing furnace-3, desulfurizer-2, methane heat exchanger-1
Refractory brick-7, oxygen enrichment convertor-6, gas converting heat formula convertor-5
Steam methane outlet pipe-33, oxygen-rich air outlet pipe-32, steam methane inlet tube-31
Oxygen-enriched inlet pipe-34
Embodiment
For better explanation the present invention, below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is clearly and completely described.
As Fig. 1, shown in 2, comprising of this system: methane heat exchanger 1, desulfurizer 2, vapourizing furnace 3, useless pot 4, gas converting heat formula convertor 5 and oxygen enrichment convertor 6, wherein methane heat exchanger 1 successively with desulfurizer 2, vapourizing furnace 3, useless pot 4 connects, described vapourizing furnace 3 also comprises steam methane inlet tube 31, oxygen-rich air outlet pipe 32, steam methane outlet pipe 33, oxygen-enriched inlet pipe 34, wherein useless pot 4 gas outlets connect steam methane inlet tube 31 successively, steam methane outlet pipe 33, gas converting heat formula convertor 5, oxygen enrichment convertor 6, described oxygen-enriched inlet pipe 34 connects oxygen-rich air outlet pipe 32 successively, oxygen enrichment convertor 6, gas converting heat formula convertor 5 and methane heat exchanger 1.
Fig. 3,4 is semicircular tubulation system architecture in vapourizing furnace, and described semicircular tubulation forms by connecting several tubulations between two semi-rings, and the gas that enters system is distributed to each tubulation by half endless tube, and then from diagonal angle, half endless tube flows out.Whole semicircular tubulation system comprises two cover semicircular tubulations, a set of methane vapor mixed gas that passes into, and the another set of oxygen-rich air that passes into, subtend enters semicircular tubulation, and subtend flows out.
Semicircular tubulation is arranged between vapourizing furnace furnace wall and refractory brick 7, as Fig. 2.Described semicircular tubulation is installed in vapourizing furnace, is mainly to utilize process furnace principle, and vapourizing furnace has replaced the effect of process furnace and interchanger in steam methane conversion process, for the raw material of steam methane conversion process provides sufficient heat.
Fig. 1 is that methane non-catalytic partial oxidation of the present invention and steam methane transform joint process schema.
Technical process mainly comprises two systems, and system one is methane non-catalytic partial oxidation process system, comprises methane heat exchanger, desulfurizer, vapourizing furnace, useless pot etc.; System two is steam methane conversion process systems, comprises methane heat exchanger, desulfurizer, vapourizing furnace, useless pot, gas converting heat formula convertor, oxygen enrichment convertor etc.
(1) system one is driven: before methane non-catalytic partial oxidation system goes into operation, drop into methane desulphurization system, methane, oxygen-rich air are dropped into semicircular tubulation system.The program that goes into operation of vapourizing furnace is undertaken by former methane non-catalytic partial oxidation process system vapourizing furnace working specification, vapourizing furnace is produced after qualified synthetic gas, drop into useless pot system, generate the first synthetic gas and middle pressure steam, middle pressure steam is dropped into the methane gas pipeline of semicircular tubulation system.In system one, mainly depositing following primitive reaction:
CH
4+O
2→CO
2+H
2O
CH
4+H
2O→CO+H
2
CH
4+O
2→CO+H
2
(2) system two is driven: after the normal operation of methane non-catalytic partial oxidation system, regulate respectively methane steam gas mixture, oxygen-rich air index, when methane steam mixture temperature reaches 500-700 ℃, methane steam gas mixture is passed into gas converting heat formula convertor, in catalyst layer, methane and steam reaction generate CO and H
2, methane conversion institute heat requirement is provided by the next transformation of synthetic gas of the oxygen enrichment convertor of high temperature, goes out the reforming gas of Reforming exchanger, methane content approximately 30%, and approximately 700-800 ℃ of temperature, this reforming gas directly enters oxygen enrichment convertor.
When oxygen-rich air temperature reaches 350-500 ℃, enter the abundant mixed firing of reforming gas that oxygen enrichment convertor and Reforming exchanger come, and pyrolytic conversion under nickel catalyzator exists, methane content in reforming gas is further reduced, go out remaining methane content in the gas of oxygen enrichment convertor and be about 0.5%, this reforming gas through between the pipe of Reforming exchanger for the conversion reaction in pipe provides after heat, temperature is down to 500-600 ℃, again after methane heat exchanger reclaims heat, temperature is down to 300-400 ℃, now generates the second synthetic gas.
In system two, mainly depositing following primitive reaction:
CH
4+H
2O→CO+H
2
CH
4+O
2→CO+H
2
CO+H
2O→CO
2+H
2
CO+O
2→CO
2
(3) after the first synthetic gas is mixed with the second synthetic gas, send coproduction workshop section.
Utilize present method to carry out the coproduction of methane conversion synthetic gas, can accomplish energy-conservation, lower consumption, reduce discharging, reduce costs, there is certain economic worth.
The above; be only the present invention's embodiment preferably, but protection scope of the present invention is not limited to this, is anyly familiar with in technical scope that those skilled in the art disclose in the present invention; the variation that can expect easily or replacement, within all should being encompassed in protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection domain of claims.
Claims (4)
1. methane non-catalytic partial oxidation and steam methane transform a method for co-production synthesis gas, it is characterized in that, comprise the following steps:
(1) by after the pre-thermally desulfurizing of methane, send into vapourizing furnace, to vapourizing furnace, pass into oxygen-rich air simultaneously, under hot conditions, the anti-synthetic gas that generates of methane generation non-catalytic partial oxidation;
(2) synthetic gas is dropped into useless pot system, generate the first synthetic gas and middle pressure steam, middle pressure steam drops into the methane inlet duct of vapourizing furnace;
(3) adjust methane steam gas mixture, oxygen-rich air index in vapourizing furnace, when the methane steam gas mixture of discharging when the steam methane outlet of vapourizing furnace reaches 500-700 ℃, passed into gas converting heat formula convertor, methane and water vapor react generation reforming gas therein, and reforming gas is sent into oxygen enrichment convertor;
(4) when the oxygen-rich air that the outlet of vapourizing furnace oxygen-rich air is discharged reaches 350-500 ℃, pass into oxygen enrichment convertor, under catalyst action, react formation reaction gas with the reforming gas in step 3;
(5) reaction gas that step 4 generates, successively through between the pipe of gas converting heat formula convertor, after methane heat exchanger, generates the second synthetic gas;
(6) after the first synthetic gas is mixed with the second synthetic gas, send coproduction workshop section;
The reaction gas that wherein said step 4 generates provides heat to the reaction in pipe between the pipe of gas converting heat formula convertor.
One kind methane non-catalytic partial oxidation and steam methane transform the method system for use in carrying of co-production synthesis gas according to claim 1, it is characterized in that, comprise methane heat exchanger (1), desulfurizer (2), vapourizing furnace (3), useless pot (4), gas converting heat formula convertor (5) and oxygen enrichment convertor (6), wherein said methane heat exchanger (1) is connected with desulfurizer (2), vapourizing furnace (3), useless pot (4) successively, and the gas outlet of described useless pot (4) is connected with vapourizing furnace (3), gas converting heat formula convertor (5), oxygen enrichment convertor (6) successively.
3. a kind of methane non-catalytic partial oxidation according to claim 2 and steam methane transform the system of co-production synthesis gas, it is characterized in that, described vapourizing furnace (3) also comprises steam methane inlet tube (31), oxygen-rich air outlet pipe (32), steam methane outlet pipe (33), oxygen-enriched inlet pipe (34), the outlet of wherein said useless pot (4) gas connects steam methane inlet tube (31) successively, steam methane outlet pipe (33), gas converting heat formula convertor (5) and oxygen enrichment convertor (6), described oxygen-enriched inlet pipe (34) connects oxygen-rich air outlet pipe (32) successively, oxygen enrichment convertor (6), gas converting heat formula convertor (5) and methane heat exchanger (1).
4. a kind of methane non-catalytic partial oxidation according to claim 2 and steam methane transform the system of co-production synthesis gas, it is characterized in that, described vapourizing furnace (3) inside is semicircular tubulation structure, by connecting several tubulations between two semi-rings, form, described semicircular tubulation is arranged between vapourizing furnace furnace wall and refractory brick (7), the gas that enters system is distributed to each tubulation by half endless tube, from diagonal angle semi-ring tubulation, flow out, wherein said steam methane inlet tube (31) is communicated with steam methane outlet pipe (33), described oxygen-enriched inlet pipe (34) is communicated with oxygen-rich air outlet pipe (32).
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| CN105984842A (en) * | 2015-02-26 | 2016-10-05 | 福建三钢闽光股份有限公司 | Atmospheric-pressure oxygen-enriched non-catalytic conversion technological process for coke oven gas |
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| CN105293434A (en) * | 2015-11-25 | 2016-02-03 | 华东理工大学 | Method for producing synthetic gas through combination of integrated gas-state hydrocarbon heat exchange type steam conversion and non-catalytic part oxidation |
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