CN100562486C - Technology of oxidation preparing synthetic gas by coke loven coal gas local strong oxidation part - Google Patents
Technology of oxidation preparing synthetic gas by coke loven coal gas local strong oxidation part Download PDFInfo
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- CN100562486C CN100562486C CNB200610102293XA CN200610102293A CN100562486C CN 100562486 C CN100562486 C CN 100562486C CN B200610102293X A CNB200610102293X A CN B200610102293XA CN 200610102293 A CN200610102293 A CN 200610102293A CN 100562486 C CN100562486 C CN 100562486C
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- coke
- oxidation
- local strong
- strong oxidation
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Abstract
The invention discloses a kind of technology of oxidation preparing synthetic gas by coke loven coal gas local strong oxidation part, it is characterized in that coke-oven gas is with whirlwind-type, oxygen is with the direct injection of speaking out of turn, the two non-method for pre mixing sprays into reactor, and formation local strong oxidation district, local temperature in the local strong oxidation district is higher than 1700 ℃, and medial temperature is carried out the thermal transition of methane and thiophenic sulfur under 1150 ℃～1300 ℃ condition.The raw materials used gas of the present invention is loose, does not need deep desulfuration and decoking wet goods foreign material, by Pintsch process with all alkane, alkene and aromatic compound all cracking change into C and H
2, under the situation of catalyst-free, technological process is simple, and it is few to efflux off-gas, and technology combined coefficient height has not only utilized resource but also protected environment.
Description
Technical field
The present invention relates to a kind of preparation method of synthetic gas, especially a kind of preparing synthesis gas from coke oven gas promptly is the coke-oven gas on-catalytic local strong oxidation portion oxidation synthesis gas technology of the mixed gas of main component with hydrogen, carbon monoxide and carbonic acid gas.
Background technology
Coke-oven gas and Sweet natural gas, coal-seam gas, biogas etc. are similar to be a kind of CH of being rich in
4The main resource of gas.Present CH
4Conversion process can be divided into catalytic steam conversion, catalyzing part oxidation and non-catalytic partial oxidation method.
Catalytic steam transforms and is meant under the nickel catalyzator effect, passes through CH
4-H
2The O reforming reaction transforms CH
4Become CO and H
2Technology.Its principal reaction is as (1～4) formula.The product synthetic gas is CO, H
2And CO
2Mixture, three's balance depends on reaction formula (4).The principal reaction of steam reforming (1～3) is a strong endothermic reaction.
CH
4+H
2O＝CO+3H
2 ΔH298＝206.4kJ/mol (1)
CH
4+2H
2O＝CO
2+4H
2 ΔH298＝165.4kJ/mol (2)
CH4+CO2＝2CO+2H2 ΔH298＝247.4kJ/mol (3)
CO+H2O＝CO2+H2 ΔH298＝-41.0kJ/mol (4)
It is the catalytic steam conversion process that Sweet natural gas intermittently transforms process for preparing synthetic gas.This technology investment is low, and is simple to operate.China is this technologies of the many employings of the little synthesis ammonia plant of raw material in early days with the Sweet natural gas.Its main drawback is the energy consumption height, production intensity is low, catalyst life is short.Therefore, batch technology is eliminated gradually, also is not suitable for coke-oven gas and transforms.
Catalyzing part oxidation.The disclosed heat exchange type coke-oven gas of Chinese invention patent CN1385501A pressurized catalysis partial oxidation process is produced the synthetic gas technology and is belonged to this class technology.
In the disclosed technology of Chinese invention patent CN1385501A, with the nickel compound containing is catalyzer, at 2.07MPa pressure, under 950 ℃～1150 ℃ temperature, the burned heat energy that provides of part hydrogen in the coke-oven gas, methane and water vapour generation scission reaction generate CO and H in the combustion gas
2This technology than conventional methane steam reforming economize in raw materials, the energy and investment, have the advantage of safe operation and protection nickel catalyzator.Have the use catalyzer but compare it with the on-catalytic technology, the desulfurizing and purifying system that palpus is complicated consumes a large amount of problems such as steam.The catalyzing part oxidation technology is to the strictness of unstripped gas S content requirement, and product gas H
2The content height is used for methyl alcohol when synthetic, and the hydrogen resource utilization is lower.
The non-catalytic partial oxidation method.It is the thermodynamic control process that the coke-oven gas non-catalytic partial oxidation transforms, and improves reaction with temperature of reaction and quickens.For example, it to steam/hydrocarbons ratio 2 steam methane gas mixture, react 6h down at 700 ℃ and 750 ℃, remaining methane content is respectively 86% and 72% in the dried reforming gas, transformation efficiency only reaches 3%～8% of equilibrium conversion, heat 2h down when temperature rises to 950 ℃ and 1050 ℃, methane conversion reaches 68% and 86% of equilibrium conversion.When the non-catalytic partial oxidation service temperature reaches 1300 ℃～1500 ℃, CH
4Could transform fast, process just has the industrialization meaning.The advantage of on-catalytic method is that 1. loose to the unstripped gas requirement, coke(oven)gas does not need deep desulfuration to purify catalyst-free poisoning problem; 2. by Pintsch process with all alkane, alkene and aromatic compound all cracking change into C and H
2, no carbon distribution poisoning problem.But it exists conversion operation temperature and energy consumption higher; 3. there is carbon black to generate in the product gas, needs deficiencies such as purification system.
Summary of the invention
Coke-oven gas transforms preparing synthetic gas, and essence is high H
2Under the content condition, CH in the coke-oven gas
4-H
2O is converted into CO and H by reforming reaction
2Process.CH
4-H
2The O reforming reaction has two kinds of approach, 1. under the effect of Ni catalyst series, transforms the promptly common catalyzed conversion of saying in lower temperature of reaction (1150 ℃～960 ℃); 2. the thermal transition under the catalyst-free condition, i.e. (more than 1300 ℃) CH under hot conditions
4-H
2The O conversion of reforming, promptly on-catalytic transforms.The present invention is directed to (1) use catalyzer that above-mentioned catalyzed conversion exists; (2) must be furnished with complicated desulfurizing and purifying system; (3) consume problem such as a large amount of steam and conventional on-catalytic transforms the temperature of reaction that exists and oxygen consumption is high and require high shortcoming to launch work to equipment material, the local strong oxidation partial oxidation new invention principle that the present invention proposes, select excellent, structure of reactor to select excellent, flow field and temperature field to distribute by nozzle arrangements and select excellent research, develop and does not a kind ofly use catalyzer, investment is low, energy consumption is low, simply and the coke-oven gas thermal transition novel process of easy handling.
Ultimate principle of the present invention is under the certain temperature condition, CH
4Can with water vapor or CO
2Reforming reaction takes place, CH
4+ H
2O=CO+3H
2+ 206KJ/mol, CH
4+ CO
2=2CO+2H
2+ 247KJ/mol generates synthetic gas, i.e. CO and H
2CH
4Reforming reaction speed and temperature correlation.Under the condition that has catalyzer to exist, above-mentioned reaction can be finished at 950 ℃～1050 ℃.Do not have under the condition of catalyzer, above-mentioned reaction needed is being carried out more than 1400 ℃, just can embody the value of industrial applications.Therefore,, rationally improve temperature of reaction, become and improve CH no matter be that catalyzed conversion or on-catalytic transform
4Transformation efficiency and the key of amplifying reactor.But, improve temperature of reaction, can cause that oxygen consumption increases, thermo-efficiency reduces and to problems such as material requirements strictnesses.On-catalytic local strong oxidation reaction theory of the present invention provides does not increase the oxygen consumption, but makes CH by the approach that forms localized hyperthermia in oxidation zone
4High-level efficiency transforms.
There is notable difference in temperature field in on-catalytic local strong oxidation reactor temperature field and catalyzing part oxidation conversion and the conventional non-catalytic partial oxidation conversion reactor.The temperature field that Fig. 2 and Fig. 3 have provided in on-catalytic local strong oxidation conversion reactor and the conventional on-catalytic conversion reactor distributes.
The strong oxidation technology in this part has formed the localized hyperthermia district.Each kinds of oxidation reaction is carried out fast in this high-temperature zone, with H
2Be converted into example, active center concentration is big not enough during beginning, thus speed of response is slower and the ordinary combustion reacting phase seemingly, formed sensitive period.It carries out fast with following chain reaction speed, until reaching maximum value.
1) generation of chain: H
2+ O
2→ 2OH (5)
H
2+M→2H+M (6)
O
2+O
2→O
3+O (7)
2) continuation of chain and branching: H+O
2→ OH+O (5)
OH+H
2→H
2O (6)
O+H
2→OH+H (7)
3) wall chain rupture: H+ wall → 1/2H
2(5)
OH+ wall → 1/2 (H
2O
2) (6)
O+ wall → 1/2O
2(7)
4) space chain rupture: H+O
2+ M → HO
2+ M* (5)
O+O
2+M→O
2+M* (6)
O+H
2+M→H
2O+M* (7)
Because H
2And O
2Thorough mixing in non-catalytic partial oxidation and catalytic partial oxidation reactor, wherein main primitive reaction are the reactions of free atom and free radical, and almost the branching of chain all takes place each link.The circulation of 5,6,7 reactions is carried out, and causes the continuous increase of H atomicity, promptly
H+O
2→OH+O
2OH+2H
2→2H
2O+2H
From (8) formula as can be seen, a hydrogen atom has produced three hydrogen atoms, and three will produce nine ... thereby speed of response is more and more faster.In on-catalytic local strong oxidation reactor, infeed reactant continuously, H
2Oxidizing reaction is carried out with maximum reaction velocity.From reaction formula as can be seen, H
2The water that burning generates, many HO with ionic forms
-, O
-H with molecular conformation
2O also deposits.This is CH
4Conversion provides fabulous condition, makes CH
4Transform fast.Simulation shows, this conversion reaction concentrates on the outer rim border in sharp-pointed temperature field, at a large amount of CH in this zone
4Finish conversion, absorb a large amount of heat temperature of reaction is reduced rapidly, make the oxidation panel medial temperature reduce to about 1250 ℃ at the reactor hypomere, the residue CH
4Continue to transform with oxidation reaction product, temperature of reaction progressively reduces.Because the top oxidation panel shortens, provide long reduction space to reduction section, make CH
4Conversion reaction is more abundant.
As can be seen from the figure, temperature distribution Fig. 2 that the on-catalytic local strong oxidation transforms is more concentrated, and local temperature is more than 1700 ℃.
And the temperature distribution that conventional on-catalytic transforms is more even.This is because conversion product and O
2Cause with admixture.In the reactor that catalyzing part oxidation transforms and conventional non-catalytic partial oxidation transforms, unstripped gas and oxygen are pre-mixed before oxidizing reaction, have fulfiled the mixing process of molecule ahead of schedule.When oxidizing reaction is carried out, the species H that speed of response is fast
2A large amount of participation oxidations, and the slow species CH of speed of response
4The ratio that participates in oxidation is low.Because H
2With O
2Speed of response be higher than CH far away
4With CO and O
2Speed of response.Therefore, in catalyzing part oxidation conversion and conventional non-catalytic partial oxidation conversion reactor, the Primary Actor of oxidising process is H
2, because H in the system
2, CH
4, O
2Mix Deng, thus the bulk temperature homogeneous, more than 1300 ℃.Formed the service temperature height, O
2Problems such as consumption height.
Technological process of the present invention is normal pressure (or pressurization) reactive system.By the next normal pressure (0.6Mpa) in coke-oven plant, it is saturated to the coke-oven gas humidification that 25 ℃～55 ℃ coke-oven gas at first enters 35 ℃～55 ℃ saturated humidifiers of constant temperature, be sent to gas preheating device and the pyrolytic conversion gas heat exchange that comes by waste heat boiler then, saturated coke-oven gas is raised to about 35 ℃～300 ℃, then entering with coke-oven gas (or methanol synthetic discharged gas delayed) burning is the tube furnace of thermal source, after in tube furnace, being preheating to 35 ℃～600 ℃, coexist in the oxygen preheat device, high-temperature steam by waste heat boiler is preheating to the pure oxygen (or oxygen enrichment) about 25 ℃～300 ℃, spray into together in the coke-oven gas conversion reactor and transform, wherein, coke-oven gas is with whirlwind-type, oxygen is with the direct injection of speaking out of turn, the two non-method for pre mixing sprays into, and forms the local strong oxidation district, and the local temperature in the local strong oxidation district is higher than 1700 ℃, medial temperature is under 1150 ℃～1300 ℃ invert point, and coke-oven gas is converted into synthetic gas.Local strong oxidation high temperature also changes organosulfur complicated in the coke-oven gas simultaneously, exactly is effectively thiophenic sulfur all to be converted into H
2S or be easy to the forms such as COS of hydrolysis.
Finish high temperature (950 ℃～1000 ℃) gas (CH of conversion in the convertor
4≤ 3.0%), reforming gas outlet by the conversion reactor bottom is discharged, enter waste heat boiler then, part sensible heat recovery to pyrolytic conversion gas drops to about 500 ℃ its temperature, in the coke-oven gas preheater, continue the recovery part sensible heat then, the reforming gas temperature drops to about 200 ℃, cools off washing at the cooling washing tower then, is sent to purified synthesis gas workshop section at last.
Positively effect of the present invention is that this technology has the advantage of conventional on-catalytic method and catalysis method: 1. do not use catalyzer, catalyst-free poisoning problem, no carbon distribution poisoning problem has been saved the preceding sweetener of conversion reactor, technological process is oversimplified, saved investment, simplified operation; 2. unstripped gas is required loosely, coke(oven)gas does not need deep desulfuration and decoking wet goods foreign material, by Pintsch process with all alkane, alkene and aromatic compound all cracking change into C and H
23. in conversion process, reluctant organosulfur thiophene is converted into the sulphur that is easy to remove; 4. service temperature is lower, 1200 ℃～1300 ℃ of top of combustion chamber temperature, 960 ℃ of temperature outs; 5. be provided with the coal gas saturex before the gas preheating device, the saturated water of raw material coal gas has utilized reluctant high density to contain sewage such as phenol, has reduced sewage and has sent to some other department, has protected environment.6. H in its product gas
2/ CO=2.05 is the high-quality synthetic gas that is used for synthesizing methanol, building-up process efficient height, and it is few to efflux off-gas, the resource utilization height.
Description of drawings
Fig. 1 is that the coke-oven gas on-catalytic transforms local strong oxidation portion oxidation synthesis gas process flow diagram
Fig. 2 is the local temperature in the local strong oxidation reactor of the present invention
Fig. 3 is the temperature distribution in the conventional on-catalytic conversion reactor
Among the figure: 1: oxygen buffering voltage-stabilizing system 2: oxygen preheat device 3; Coal gas buffering voltage-stabilizing system 4: the saturated humidifier 5 of coal gas: gas preheating device 6: gas preheating stove 7: conversion reactor 8: waste heat boiler 9: cooling washing tower
Embodiment
Can be further detailed the present invention below in conjunction with drawings and Examples:
The normal pressure (0.6Mpa) that the present invention is come by the coke-oven plant, it is saturated to the coke-oven gas humidification that 25 ℃～55 ℃ coke-oven gas at first enters 35 ℃～55 ℃ saturated humidifiers of coal gas, be sent to gas preheating device and the pyrolytic conversion gas heat exchange that comes by waste heat boiler then, saturated coke-oven gas is raised to about 35 ℃～300 ℃, then entering with coke-oven gas (or methanol synthetic discharged gas delayed) burning is the tube furnace of thermal source, after in tube furnace, being preheating to 35 ℃～600 ℃, coexist in the oxygen preheat device, high-temperature steam by waste heat boiler is preheating to the pure oxygen (or oxygen enrichment) about 25 ℃～300 ℃, spray into together in the coke-oven gas conversion reactor and transform, wherein, coke-oven gas is with whirlwind-type, oxygen is with the direct injection of speaking out of turn, the two non-method for pre mixing sprays into, and forms the local strong oxidation district, and the local temperature in the local strong oxidation district is higher than 1700 ℃, medial temperature is under 1150 ℃～1300 ℃ invert point, and coke-oven gas is converted into synthetic gas.Local strong oxidation high temperature also changes organosulfur complicated in the coke-oven gas simultaneously, exactly is effectively thiophenic sulfur all to be converted into H
2S or be easy to the forms such as COS of hydrolysis.
Finish high temperature (950 ℃～1000 ℃) gas (CH of conversion in the convertor
4≤ 1.0%), reforming gas outlet by the conversion reactor bottom is discharged, enter waste heat boiler then, part sensible heat recovery to pyrolytic conversion gas drops to about 500 ℃ its temperature, in the coke-oven gas preheater, continue the recovery part sensible heat then, the reforming gas temperature drops to about 200 ℃, cools off washing at the cooling washing tower then, is sent to purified synthesis gas workshop section at last.
Table 1 has provided the composition of a group of enter the mouth moisture and dry gas.Data show in the table, and the main component of coke-oven gas is H
2, CO and CH
4
The composition (mol%) of table 1 inlet moisture and dry gas
* get 25 ℃ of following 1Nm
3Saturation moisture content in the dry gas is 0.02600kg/m
3(0.0323m
3/ m
3)
Table 2 has provided the composition of one group of local strong oxidation partial oxidation conversion reactor exit gas.
The composition (mol%) of table 2 conversion reactor exit gas
Claims (3)
1. technology of oxidation preparing synthetic gas by coke loven coal gas local strong oxidation part, it is characterized in that coke-oven gas is with whirlwind-type, oxygen is with the direct injection of speaking out of turn, the two non-method for pre mixing sprays into conversion reactor, and form the local strong oxidation district, in the local strong oxidation district, local temperature is higher than 1700 ℃, medial temperature methane and thiophenic sulfur under 1150 ℃～1300 ℃ condition carry out thermal transition, adopt the method for on-catalytic local strong oxidation partial oxidation that coke-oven gas is converted to synthetic gas.
2. technology of oxidation preparing synthetic gas by coke loven coal gas local strong oxidation part according to claim 1, it is saturated to it is characterized in that coke-oven gas at first carries out humidification, again with the heat exchange of pyrolytic conversion gas, make saturated coke-oven gas preheating and be warmed up to 35 ℃～600 ℃, spray in the conversion reactor and transform with being preheating to 25 ℃～300 ℃ pure oxygen or oxygen enrichment then.
3. technology of oxidation preparing synthetic gas by coke loven coal gas local strong oxidation part according to claim 1 and 2, after it is characterized in that 930 ℃～1100 ℃ of the high-temperature product gases that transform in the conversion reactor are discharged by conversion reactor, carry out that sensible heat reclaims, cooling cooling and purifying.
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|---|---|---|---|
| CNB200610102293XA CN100562486C (en) | 2006-12-22 | 2006-12-22 | Technology of oxidation preparing synthetic gas by coke loven coal gas local strong oxidation part |
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|---|---|---|---|
| CNB200610102293XA CN100562486C (en) | 2006-12-22 | 2006-12-22 | Technology of oxidation preparing synthetic gas by coke loven coal gas local strong oxidation part |
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| CN100562486C true CN100562486C (en) | 2009-11-25 |
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| JP5400505B2 (en) * | 2009-07-06 | 2014-01-29 | バブコック日立株式会社 | Coke oven gas non-catalytic reforming method and reformer |
| CN104593079B (en) * | 2015-01-15 | 2018-04-03 | 太原理工大学 | A kind of technique of broken coal production Clean synthesis gas |
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