CN106315510A - Coke oven gas hydrogen production technology - Google Patents
Coke oven gas hydrogen production technology Download PDFInfo
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- CN106315510A CN106315510A CN201510370412.9A CN201510370412A CN106315510A CN 106315510 A CN106315510 A CN 106315510A CN 201510370412 A CN201510370412 A CN 201510370412A CN 106315510 A CN106315510 A CN 106315510A
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Abstract
The invention provides a coke oven gas hydrogen production technology. The technology comprises the following steps: (1) pretreatment; (2) hydrogenation saturation; (3) light hydrocarbon conversion: converting light hydrocarbons into H2 and CO2; (4) medium temperature conversion: converting CO into CO2; (5) desorption to remove carbon; and (6) PSA hydrogen extraction. On the basis of a conventional coke oven gas hydrogen production technology, a light hydrocarbon conversion technology and a carbon monoxide medium temperature conversion technology are introduced into the conventional technology so that light hydrocarbons such as methane, ethane, and the like, and carbon monoxide in coke oven gas can participate in the hydrogen production reactions. The provided technology can reduce the consumption of feed gas, and the energy is reasonably utilized.
Description
Technical field
The present invention relates to chemical production technical field, particularly relate to a kind of unstripped gas and consume low hydrogen production from coke oven gas technique.
Background technology
Metallurgical coke producer gas is the industrial chemicals of high-quality.The plant hydrogen of purity more than 99.5%, normally used hydrogen gas in coke oven gas volume fraction about 60%, methane 18 ~ 24%, carbon monoxide 6 ~ 10%, Hydrocarbon C can be produced with coke-stove gas for unstripped gasnHmAbout 2 ~ 4%, the most often use PSA technique hydrogen manufacturing, using this coke-stove gas is unstripped gas, and its hydrogen feedstock gas consumption is usually every output 1 M3Plant hydrogen consumes 2M3Coke-stove gas.External-heat dry distillation gas is the one of coke-stove gas, and wherein hydrogen volume mark is about 20 ~ 30%, methane 20 ~ 30%, carbon monoxide 10 ~ 18%, Hydrocarbon CnHmAbout 2 ~ 8%, use conventional PSA process hydrogen manufacturing, unstripped gas consumption is usually every output 1 M3Plant hydrogen need to consume 3.5M3More than external-heat dry distillation gas.
Summary of the invention
The present invention is directed to deficiency of the prior art, it is provided that the hydrogen production from coke oven gas technique that a kind of unstripped gas consumption is low.
The present invention is achieved by the following technical solutions:
A kind of hydrogen production from coke oven gas technique, its step includes:
(1) pretreatment: coke-stove gas is boosted to 0.3 ~ 0.6
Mpa, carries out purifying pretreatment by one section of temp.-changing adsorption and one section of pressure-variable adsorption；Pretreatment can remove the benzene in coke-stove gas, naphthalene, tar, NH3、H2S and other heavy hydrocarbons impurity, output purifies unstripped gas.
(2) hydrotreating: purify unstripped gas and enter hydro-refining unit and carry out that alkene is saturated and fine de-sulfur processes, the unsaturated olefin in coke-stove gas is made to be converted into saturated alkane, removing organic sulfur and chloride simultaneously, the sulfide in coke oven substrate concentration to hydrotreating is less than or equal to 0.2
Ppm, volume fraction of olefins is less than or equal to 1%, and chloride concentration is less than or equal to 0.2ppm, i.e. output and converts unstripped gas；
(3) lighter hydrocarbons convert: convert unstripped gas elder generation through feed gas compressor by boost in pressure to 3 ~ 5
MPa, then enters reburner and converts, make light alkane transformations become H under the effect of reforming catalyst2And CO2Output converts gas；Lighter hydrocarbons convert the one that can select in steam transforming, oxygen-enriched conversion, pure oxygen reformation.
(4) middle temperature transformation: convert pneumatic transmission middle temperature transformation reactor, under the effect of transformation catalyst, major part CO is converted to CO2, to CO volume fraction less than or equal to 4%, changing the flow of QI-blood in output；
The dominant response occurred in this step is:
CO+H2O=CO2 +H2 △Ho298 =-41.4KJ/mol
(5) absorption decarburization: middle changing the flow of QI-blood enters absorption decarbonization process after being cooled to 30 DEG C-50 DEG C, to remaining CO2Volume integral quantity is less than 3%, output decarbonization gas；
(6) PSA puies forward hydrogen operation: decarbonization gas carries out pressure-variable adsorption and carries hydrogen.
What step (6) produced put forward a hydrogenolysis gassing part send pretreatment unit in step (1) to do adsorbent reactivation source of the gas, and after regenerative response, resolution gas processes through desulfurization, carries hydrogenolysis gassing with remainder and merges and send reburner described in step (3) to do fuel gas.
Impurity content is higher, cleanliness factor is poor for grade as coal-tar middle oil in coke-stove gas, can carry out activated carbon adsorption tar removing process before carrying out step (1) described pretreatment.Step (5) described absorption decarbonation process may select Vacuum Pressure Swing Adsorption (VPSA) or pressure-variable adsorption (PSA).
The process for making hydrogen of the present invention, on the basis of coke-stove gas pressure swing adsorption hydrogen production traditional handicraft, introduce light hydrocarbon to convert and Carbon Monoxide Shift Reaction technique, light hydrocarbon composition and the carbon monoxides etc. such as the methane in raw coke oven gas, ethane is made to both participate in hydrogen production reaction, by the enforcement of this technique, hydrogen feedstock gas consumption can be reduced, and the energy can Appropriate application.
More traditional coke-stove gas PSA process for making hydrogen, can be greatly reduced the raw material gas consumption of Unit of Hydrogen product.When wherein coke-oven plant's coke-stove gas does raw material, can be by the consumption of raw materials of Unit of Hydrogen product by 2Nm3Coal gas/Nm3Product hydrogen, is down to 1Nm3Coal gas/Nm3Product hydrogen；When external-heat dry distillation gas does raw material, can be by the consumption of raw materials of Unit of Hydrogen product by 3Nm3Coal gas/Nm3More than product hydrogen, it is down to 0.8Nm3Coal gas/Nm3Below product hydrogen.
Detailed description of the invention
The present invention is expanded on further below by the description of specific embodiment.
Embodiment
1
。
Raw material is coke-stove gas, and the most hydrogeneous volume fraction is 60%, and methane volumetric mark is 18%, and carbon monoxide volume fraction is 9%, and hydrocarbon volume mark is about 2%.Process coke-stove gas 25000Nm3/h。
Process for making hydrogen comprises the following steps successively:
(1) pretreatment: by 25000Nm3/h
, pressure is that the coke-stove gas of 7Kpa boosts to 0.35Mpa, sends into activated carbon adsorber and removes part tar, carries out purifying pretreatment by one section of temp.-changing adsorption and one section of pressure-variable adsorption the most again；One section of temp.-changing adsorption uses three TSA processors, one section of pressure-variable adsorption to use three PSA treating columns, the wherein benzene in removing coke-stove gas, naphthalene, tar, NH3、H2S and other heavy hydrocarbons impurity, output purifies unstripped gas.
(2) be hydrogenated with saturated: purify unstripped gas enter hydro-refining unit, hydro-refining unit is made up of an insulation hydrogen addition reactor and a zinc oxide desulfurization reactor, device portal temperature 380 DEG C, carry out that alkene is saturated and fine de-sulfur processes, make unsaturated olefin in coke-stove gas hydrogenated, it is largely converted into saturated alkane, simultaneously removing organic sulfur and chloride.
The dominant response of this step has:
Alkene is saturated:
C2H4+ H2
→C2H6；C3H6+ H2
→C3H8；C4H8 + H2
→C4H10；
Mercaptan: RSH+H2 →RH+H2S；
Thioether: R1SR2+2H2
→R1H+R2H+H2S；
Disulfide: R1SSR2+3H2
→R1H+R2H+2H2S；
Thiophene: C4H4S+4H2
→C4H10+H2S；
Carbonyl sulfide: COS+H2 →CO+H2S；
Carbon bisulfide: CS2+4H2 →CH4 +2H2S；
ZnO (Gu)+H2S=ZnS (Gu)+H2O △Ho
298 =-76.62kJ/mol
It is 0.1 ppm that coke-stove gas after hydrofinishing process i.e. converts sulfide concentration in unstripped gas, and volume fraction of olefins is 1%, and chloride concentration is 0.2ppm；
(3) lighter hydrocarbons convert: converting unstripped gas and boost to 4Mpa through feed gas compressor, enter reburner, carry out one section of steam transforming under the effect of reforming catalyst, the dominant response of generation has:
CnHm+nH2O =nCO+(n+m/2)H 2
CO+3H2 =CH4 +H2O △Ho298 =-206kJ/mol
CO+H2O=CO2 +H2 △Ho298 =-41kJ/mol
Lighter hydrocarbons are changed into H2And CO2Producing and convert gas, on reburner convection section, waste heat boiler is to converting gas cooling, and the temperature converting gas is down to 340 DEG C, the middle pressure steam of by-product 3.5 ~ 4.0MPa simultaneously.
(4) middle temperature transformation: 340 DEG C convert pneumatic transmission middle temperature transformation reactor, under the effect of transformation catalyst-chromium oxide, CO are converted to CO2, generate equimolar H simultaneously2.The dominant response occurred in this step is:
CO+H2O=CO2 +H2 △Ho298 =-41.4KJ/mol
After reaction, CO volume fraction is 3%, changing the flow of QI-blood in generation；Middle changing the flow of QI-blood temperature after heat exchange is down to 40 DEG C.
(5) absorption decarburization: the middle changing the flow of QI-blood of 40 DEG C enters vac sorb operation to carry out adsorbing decarburization, CO after vac sorb2Volume integral quantity is 2%, produces decarbonization gas；CO in decarburization resolution gas2Volume fraction about 92%, can directly be vented, and can be used for producing technical grade CO2, it is possible to it is used as to produce food-class CO2Unstripped gas.
(6) PSA puies forward hydrogen operation: decarbonization gas carries out pressure-variable adsorption and carries hydrogen, output plant hydrogen 24500Nm3/ h, purity is 99.95%.Every output 1 M3Plant hydrogen consumes 1.02 M3Coke-stove gas.Putting forward a hydrogenolysis gassing part send TSA/PSA pretreatment unit to do regenerative raw materials source of the gas, and after regenerative response, resolution gas processes through desulfurization, carries hydrogenolysis gassing with remainder and merges and send reburner described in step (3) to do fuel gas.
Embodiment
2
。
Raw material is external-heat dry distillation gas, and external-heat dry distillation gas is the one of coke-stove gas, and wherein hydrogen-containing gas fraction is 27%, and methane volumetric mark is 28%, and carbon monoxide volume fraction is 14%, and hydrocarbon volume mark is about 7.5%.Process external-heat dry distillation gas 13000Nm3/h。
Process for making hydrogen comprises the following steps successively:
(1) pretreatment: with embodiment 1；
(2) be hydrogenated with saturated: step is with embodiment 1；
In conversion unstripped gas after hydrotreating, sulfide concentration is 0.2 ppm, and volume fraction of olefins is 1%, and chloride concentration is 0.2ppm；
(3) lighter hydrocarbons convert: converting unstripped gas and boost to 3.8Mpa through feed gas compressor, enter reburner, carry out one section of steam transforming under the effect of reforming catalyst, the dominant response of generation is with embodiment 1.
Lighter hydrocarbons are changed into H2And CO2Producing and convert gas, on reburner convection section, waste heat boiler is to converting gas cooling, and the temperature converting gas is down to 400 DEG C, the middle pressure steam of by-product 3.8MPa simultaneously.
(4) middle temperature transformation: 400 DEG C convert pneumatic transmission middle temperature transformation reactor, under the effect of transformation catalyst-chromium oxide, CO are converted to CO2, generate equimolar H simultaneously2.The dominant response occurred in this step is:
CO+H2O=CO2 +H2 △Ho298 =-41.4KJ/mol
After reaction, CO volume fraction is 4%, changing the flow of QI-blood in generation；Middle changing the flow of QI-blood temperature after heat exchange is down to 40 DEG C.
(5) absorption decarburization: the middle changing the flow of QI-blood of 40 DEG C enters pressure-variable adsorption operation to carry out adsorbing decarburization, CO after vac sorb2Volume integral quantity is 2%, produces decarbonization gas；
(6) PSA puies forward hydrogen operation: decarbonization gas carries out pressure-variable adsorption and carries hydrogen, output plant hydrogen 17000Nm3/ h, purity is 99.95%., every output 1 M3Plant hydrogen about consumes 0.75M3External-heat dry distillation gas.Putting forward a hydrogenolysis gassing part send TSA/PSA pretreatment unit to do regenerative raw materials source of the gas, and after regenerative response, resolution gas processes through desulfurization, carries hydrogenolysis gassing with remainder and merges and send reburner described in step (3) to do fuel gas.
Claims (4)
1. a hydrogen production from coke oven gas technique, its step includes:
(1) pretreatment: coke-stove gas boosts to 0.3-0.6 Mpa, carries out purifying pretreatment by one section of temp.-changing adsorption and one section of pressure-variable adsorption, and output purifies unstripped gas；
(2) hydrotreating: purify unstripped gas entrance hydro-refining unit and carry out the process of alkene saturated fine de-sulfur, the unsaturated olefin in coke-stove gas is made to be converted into saturated alkane, removing organic sulfur and chloride simultaneously, sulfide in coke oven substrate concentration to hydrotreating is less than or equal to 0.2 ppm, volume fraction of olefins is less than or equal to 1%, chloride concentration is less than or equal to 0.2ppm, i.e. output and converts unstripped gas；
(3) lighter hydrocarbons convert: convert unstripped gas first through feed gas compressor by boost in pressure to 3-5 MPa, then enter reburner and convert, make light alkane transformations become H under the effect of reforming catalyst2And CO2Output converts gas；
(4) middle temperature transformation: convert pneumatic transmission middle temperature transformation reactor, under the effect of transformation catalyst, major part CO is converted to CO2, to CO volume fraction less than or equal to 4%, changing the flow of QI-blood in output；
The dominant response occurred in this step is:
CO+H2O=CO2 +H2 △Ho298 =-41.4KJ/mol
(5) absorption decarburization: middle changing the flow of QI-blood enters absorption decarbonization process after being cooled to 30 DEG C-50 DEG C, to remaining CO2Volume integral quantity is less than 3%, output decarbonization gas；
(6) PSA puies forward hydrogen operation: decarbonization gas carries out pressure-variable adsorption and carries hydrogen.
2. a kind of hydrogen production from coke oven gas technique as claimed in claim 1, it is characterized in that: what step (6) produced put forward a hydrogenolysis gassing part send pretreatment unit in step (1) to do adsorbent reactivation source of the gas, after regenerative response, resolution gas processes through desulfurization, carries hydrogenolysis gassing with remainder and merges and send reburner described in step (3) to do fuel gas.
3. a kind of hydrogen production from coke oven gas technique as claimed in claim 1 or 2, it is characterised in that: before carrying out described step (1) described pretreatment, coke-stove gas is carried out activated carbon adsorption tar removing process.
4. a kind of hydrogen production from coke oven gas technique as claimed in claim 1 or 2, it is characterised in that: step (5) described absorption decarbonation process is Vacuum Pressure Swing Adsorption or pressure-variable adsorption.
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Cited By (5)
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| CN108622856A (en) * | 2018-06-04 | 2018-10-09 | 新疆敦华石油技术股份有限公司 | Hydrogen making by natural gas reformation periodic off-gases retracting device and recovery method |
| CN110127613A (en) * | 2019-05-20 | 2019-08-16 | 广东国能中林实业有限公司 | A kind of efficiently advanced hydrogen production from coke oven gas technique |
| CN110182761A (en) * | 2019-05-05 | 2019-08-30 | 杨皓 | A kind of technique of oven gas conversion preparing synthetic gas |
| CN111320528A (en) * | 2020-03-24 | 2020-06-23 | 北京石油化工工程有限公司 | Method and system for preparing ethanol by comprehensively utilizing steel mill tail gas |
| CN113955717A (en) * | 2021-10-21 | 2022-01-21 | 福州大学 | System and method for producing hydrogen by desulfurizing tail gas generated in iron-making and steel-making |
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| CN104495749A (en) * | 2014-12-23 | 2015-04-08 | 东北大学 | Device and method for producing hydrogen by utilizing coke oven crude gas |
| CN104609369A (en) * | 2015-01-30 | 2015-05-13 | 山东益丰生化环保股份有限公司 | Method for converting desorbed waste gases from petroleum refinery to feed gases used in hydrogen production process |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108622856A (en) * | 2018-06-04 | 2018-10-09 | 新疆敦华石油技术股份有限公司 | Hydrogen making by natural gas reformation periodic off-gases retracting device and recovery method |
| CN110182761A (en) * | 2019-05-05 | 2019-08-30 | 杨皓 | A kind of technique of oven gas conversion preparing synthetic gas |
| CN110182761B (en) * | 2019-05-05 | 2023-03-21 | 杨皓 | Process for preparing synthesis gas by converting coke-oven gas |
| CN110127613A (en) * | 2019-05-20 | 2019-08-16 | 广东国能中林实业有限公司 | A kind of efficiently advanced hydrogen production from coke oven gas technique |
| CN111320528A (en) * | 2020-03-24 | 2020-06-23 | 北京石油化工工程有限公司 | Method and system for preparing ethanol by comprehensively utilizing steel mill tail gas |
| CN113955717A (en) * | 2021-10-21 | 2022-01-21 | 福州大学 | System and method for producing hydrogen by desulfurizing tail gas generated in iron-making and steel-making |
| CN113955717B (en) * | 2021-10-21 | 2023-12-22 | 中琉科技有限公司 | System and method for producing hydrogen by desulfurizing tail gas from iron making and steel making |
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