CN103693616B - The method and system of methane non-catalytic partial oxidation and methane steam reforming co-production synthesis gas - Google Patents
The method and system of methane non-catalytic partial oxidation and methane steam reforming co-production synthesis gas Download PDFInfo
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 232
- 238000000034 method Methods 0.000 title claims abstract description 34
- 238000000629 steam reforming Methods 0.000 title claims abstract description 28
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 27
- 230000003647 oxidation Effects 0.000 title claims abstract description 27
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 27
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 12
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 239000007789 gas Substances 0.000 claims description 87
- 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
- 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
- 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
- 229910052799 carbon Inorganic materials 0.000 abstract description 4
- 238000002309 gasification Methods 0.000 abstract description 4
- 238000007599 discharging Methods 0.000 abstract description 3
- 238000004134 energy conservation Methods 0.000 abstract description 3
- 238000010304 firing Methods 0.000 abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 2
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000002918 waste heat Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 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
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-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
- 150000001335 aliphatic alkanes Chemical class 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
- 239000001257 hydrogen Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003345 natural gas Substances 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
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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- Hydrogen, Water And Hydrids (AREA)
Abstract
The invention provides a kind of method of methane non-catalytic partial oxidation and methane steam reforming co-production synthesis gas, the heat that methane steam reforming warm produces in utilizing methane non-catalytic partial oxidation to react, after producing the first synthetic gas, react with methane non-catalytic partial oxidation the second synthetic gas produced, mix; Apply beneficial effect of the present invention: employing present method can utilize the heat in gasification, reduces heat waste.Eliminate the Carbon emission that tube furnace produces because of gas-firing, really accomplish that low-carbon (LC) is produced.Interchanger in methane steam reforming system can be reduced, reduce the cost of investment of methane steam reforming system, 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.
Description
Technical field
The invention belongs to chemical industry novel technique and new energy development field, be specifically related to the method and system of a kind of methane non-catalytic partial oxidation and methane steam reforming co-production synthesis gas.
Background technology
Methane non-catalytic partial oxidation technique mainly undergoes technological transformation to the nozzle of Top Structure of Heavy Oil Aerification Furnace (Texaco stove), is that raw material straight burning in vapourizing furnace produces the product such as synthetic ammonia, urea, has good application at fertilizer industry with methane.Texaco gasifier is 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, temperature 1200-1400 DEG C, under pressure 2.0-3.5Mpa condition, generate CO+H
2available gas more than 95%.High-temperature gas fully contacts with the washing water adding quench chamber in quench chamber, sharply expands through vapourizing furnace trunnion, and temperature is down to less than 210 DEG C, simultaneously by steam-laden, generates gasification gas, in the process, causes 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 made up of unstripped gas process, steam reforming, CO conversion and hydrogen purification 4 big unit.Steam reforming exists at catalyzer and under 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 take Sweet natural gas as the tubular oven of raw material.Waste heat recovery measure do not taked by tubular oven, causes amount of heat to diffuse, and flue gas emptying temperature is generally at about 350 DEG C, and waste heat energy, causes environmental thermal pollution.Tubular oven burner adopts natural ventilation system configuration combustion air, and efficiency of combustion is lower.To the research of tubular oven waste gas Waste Heat Reuse, be only confined to the replacing of fuel to reduce costs, the utilization of used heat is reclaimed, and does not have 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, conservative control excess air coefficient etc.
Summary of the invention
Object of the present invention provides the method and system of a kind of methane non-catalytic partial oxidation and methane steam reforming co-production synthesis gas, the method by methane non-catalytic partial oxidation technique together with methane steam reforming process integration, the heat utilizing methane non-catalytic partial oxidation technique to produce carries out pre-treatment to methane steam reforming process feed gas, reaches the object of energy-saving and emission-reduction.
The object of the invention is to be achieved through the following technical solutions:
A method for methane non-catalytic partial oxidation and methane steam reforming co-production synthesis gas, comprises the following steps:
1, by after pre-for methane thermally desulfurizing, send into vapourizing furnace, pass into oxygen-rich air simultaneously to vapourizing furnace, under hot conditions, the reaction of methane generation non-catalytic partial oxidation generates synthetic gas;
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, methane steam gas mixture, oxygen-rich air index in vapourizing furnace is adjusted, when the methane steam gas mixture that the steam methane outlet of vapourizing furnace is discharged reaches 500-700 DEG C, passed into gas converting heat formula convertor, methane and water vapor react generation reforming gas wherein, reforming gas are sent into oxygen enrichment convertor;
4, when the oxygen-rich air that the oxygen-rich air outlet of vapourizing furnace is discharged reaches 350-500 DEG C, pass into oxygen enrichment convertor, react under catalyst action with the reforming gas in step 3, formation reaction gas;
5, the reaction gas that generates of step 4 is successively through between the pipe of gas converting heat formula convertor, after methane heat exchanger, generate the second synthetic gas;
6, after being mixed with the second synthetic gas by the first synthetic gas, coproduction workshop section is sent;
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.
The system of a kind of methane non-catalytic partial oxidation and methane steam reforming 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 outlet connects 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 is semicircular tubulation structure, form by connecting several tubulation between two semi-rings, described semicircular tubulation is arranged between vapourizing furnace furnace wall and refractory brick 7, the gas entering system is distributed to each tubulation by half endless tube, flow out from diagonal angle semi-ring tubulation, 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, can produce a large amount of heat in production process, and thermosteresis is comparatively large, and employing present method can utilize the heat in gasification, reduces heat waste.In addition, between vapourizing furnace furnace wall and refractory brick, increase tubulation, the usage quantity of refractory brick can be reduced, reduce the running cost of vapourizing furnace.
(2) by ring-type tubulation heating in vapourizing furnace, the heating installation tube furnace in alternative methane steam reforming system, eliminates the Carbon emission that tube furnace produces because of gas-firing, really accomplishes that low-carbon (LC) is produced.In addition, interchanger in methane steam reforming system can be reduced, reduce the cost of investment of methane steam reforming system.
(3) synthetic gas that methane non-catalytic partial oxidation system is produced can carry out proportional mixing according to its gas ingredients with the synthetic gas that methane steam reforming system is produced, thus reduce whole system in the investment of conversion section, also reduce 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 methane steam reforming 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 of methane heat exchanger-1 desulfurizer-2 vapourizing furnace-3
Gas converting heat formula convertor-5 oxygen enrichment convertor-6 refractory brick-7
Steam methane inlet tube-31 oxygen-rich air outlet pipe-32 steam methane outlet pipe-33
Oxygen-enriched inlet pipe-34
Embodiment
For better the present invention being described, 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 outlet connects 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 tubulation between two semi-rings, and the gas entering system is distributed to each tubulation by half endless tube, then flows out from diagonal angle half endless tube.Whole semicircular tubulation system comprises two cover semicircular tubulations, a set ofly passes into methane vapor mixed gas, another set ofly passes into oxygen-rich air, and 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, mainly utilizes process furnace principle, and vapourizing furnace instead of the effect of process furnace and interchanger in methane steam reforming technique, and the raw material for methane steam reforming technique provides sufficient heat.
Fig. 1 is methane non-catalytic partial oxidation of the present invention and methane steam reforming 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 methane steam reforming 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, and drops into methane desulphurization system, and methane, oxygen-rich air are dropped into semicircular tubulation system.The program that goes into operation of vapourizing furnace is undertaken by primitive nail alkane non-catalytic partial oxidation process system gasifier operation code, after vapourizing furnace produces 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 deposit 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 methane non-catalytic partial oxidation system is normally run, regulate methane steam gas mixture, oxygen-rich air index respectively, when methane steam mixture temperature reaches 500-700 DEG C, methane steam gas mixture is passed into gas converting heat formula convertor, in catalyst layer, methane and steam reaction generate CO and H
2, the transformation of synthetic gas that methane conversion institute heat requirement is come by the oxygen enrichment convertor of high temperature provides, and go out the reforming gas of Reforming exchanger, methane content about 30%, temperature about 700-800 DEG C, this reforming gas directly enters oxygen enrichment convertor.
When oxygen-rich air temperature reaches 350-500 DEG C, enter the abundant mixed firing of reforming gas of oxygen enrichment convertor and Reforming exchanger, and pyrolytic conversion in the presence of a nickel catalyst, methane content in reforming gas is reduced further, go out residual 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 after the conversion reaction in pipe provides heat, temperature is down to 500-600 DEG C, reclaim after heat through methane heat exchanger again, temperature is down to 300-400 DEG C, now generates the second synthetic gas.
In system two, mainly deposit 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 being mixed with the second synthetic gas by the first synthetic gas, coproduction workshop section is sent.
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 preferably embodiment, but protection scope of the present invention is not limited thereto, is anyly familiar with those skilled in the art in the technical scope that the present invention discloses; the change that can expect easily or replacement, all should be encompassed within 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. a method for methane non-catalytic partial oxidation and methane steam reforming co-production synthesis gas, is characterized in that, comprises the following steps:
(1) by after pre-for methane thermally desulfurizing, send into vapourizing furnace, pass into oxygen-rich air simultaneously to vapourizing furnace, under hot conditions, the reaction of methane generation non-catalytic partial oxidation generates synthetic gas;
(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) methane steam gas mixture, oxygen-rich air index in vapourizing furnace is adjusted, when the methane steam gas mixture that the steam methane outlet of vapourizing furnace is discharged reaches 500-700 DEG C, passed into gas converting heat formula convertor, methane and water vapor react generation reforming gas wherein, reforming gas are 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 DEG C, pass into oxygen enrichment convertor, react under catalyst action with the reforming gas in step 3, formation reaction gas;
(5) reaction gas that generates of step 4 is successively through between the pipe of gas converting heat formula convertor, after methane heat exchanger, generate the second synthetic gas;
(6), after being mixed with the second synthetic gas by the first synthetic gas, coproduction workshop section is sent;
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.
2. the method system for use in carrying of methane non-catalytic partial oxidation and methane steam reforming 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) successively with desulfurizer (2), vapourizing furnace (3), useless pot (4) connects, described useless pot (4) gas outlet successively with vapourizing furnace (3), gas converting heat formula convertor (5), oxygen enrichment convertor (6) connects.
3. the system of a kind of methane non-catalytic partial oxidation according to claim 2 and methane steam reforming 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), wherein said useless pot (4) gas outlet 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. the system of a kind of methane non-catalytic partial oxidation according to claim 2 and methane steam reforming co-production synthesis gas, it is characterized in that, described vapourizing furnace (3) inside is semicircular tubulation structure, form by connecting several tubulation between two semi-rings, described semicircular tubulation is arranged between vapourizing furnace furnace wall and refractory brick (7), the gas entering system is distributed to each tubulation by half endless tube, flow out from diagonal angle semi-ring tubulation, 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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| CN105293434B (en) * | 2015-11-25 | 2017-06-30 | 华东理工大学 | A kind of method that integrated form gaseous hydrocarbon heat exchange type steam conversion is combined production synthesis gas with non-catalytic partial oxidation |
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2013
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| EP1935847A1 (en) * | 2006-12-20 | 2008-06-25 | Bp Exploration Operating Company Limited | Process for producing synthesis gas |
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