CN104388138A - Method for co-producing natural gas and hydrogen by utilizing coke oven gas - Google Patents

Method for co-producing natural gas and hydrogen by utilizing coke oven gas Download PDF

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Publication number
CN104388138A
CN104388138A CN201410618203.7A CN201410618203A CN104388138A CN 104388138 A CN104388138 A CN 104388138A CN 201410618203 A CN201410618203 A CN 201410618203A CN 104388138 A CN104388138 A CN 104388138A
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CN
China
Prior art keywords
gas
hydrogen
coke
natural gas
oven gas
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CN201410618203.7A
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Chinese (zh)
Inventor
王拴虎
韩园元
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新奥能源贸易有限公司
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Priority to CN201410618203.7A priority Critical patent/CN104388138A/en
Publication of CN104388138A publication Critical patent/CN104388138A/en

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Abstract

The invention relates to a method for co-producing natural gas and hydrogen by utilizing coke oven gas, belonging to the field of comprehensive utilization of coke oven gas. The method comprises the following steps: pretreating the coke oven gas by virtue of a pretreatment system, and removing most of sulfur, tar, benzene and naphthalene; mixing the pretreated coke oven gas with water vapor so as to enter a sulfur-tolerant shift system, performing low-temperature sulfur-tolerant shift, converting most of CO in the coke oven gas into H2, and converting a large proportion of organic sulfur in the coke oven gas into inorganic sulfur; separating the converted coke oven gas by virtue of a pressure swing adsorption system or a film, and separating pure hydrogen products, crude methane and desorption waste gas; removing acidic gases and organic sulfur in the crude methane obtained by pressure swing adsorption by virtue of a purification system, thereby obtaining the natural gas product. The process flow has the advantages of simple process, low energy consumption, investment conservation, convenience in operation and capacity of producing lots of byproduct hydrogen, and finally, the aim of efficiently and comprehensively utilizing the coke-oven gas is achieved.

Description

Cog joint is utilized to produce the method for Sweet natural gas and hydrogen
Technical field
The present invention relates to a kind of method utilizing cog joint to produce Sweet natural gas and hydrogen, belong to coke-oven gas field of comprehensive utilization.
Background technology
Coke-oven gas refers to and is mixed with coking coal, a kind of inflammable gas obtained while high temperature carbonization output coke and tar products in pit kiln with several bituminous coal, and general dry coal per ton can commercial coke oven gas 300-350 standard cubic meter.Coke(oven)gas is mixture, and its productive rate and composition be difference to some extent because coking coal quality is different with coking condition, and its main component is H 2(55%-70%) and CH 4(15%-30%), CO (5%-9%), CO 2(2%-5%), N 2(2%-6%), in addition also containing other a small amount of composition.
Current coking industry, for reducing environmental pollution, increasing economic efficiency, more and more payes attention to the comprehensive utilization of coke-oven gas.Except supplying traditional utilization ways such as gas, generating, synthetic ammonia, methanol, coke-oven gas preparing natural gas (or natural gas liquids) more and more attracts widespread attention in recent years.The methane that gas employing methanation of coke oven preparing natural gas obtains is more, but the most of hydrogen consumed in coal gas, what can not meet hydrogenation unit such as the construction of large-scale coal chemical enterprise hydrogenation of tar, carbolineum hydrogenation etc. uses hydrogen demand, and the methane that the direct separation of methane of coke-oven gas obtains is less, and energy expenditure is higher, the carbon monoxide in coal gas is difficult to carry out chemical utilization again.
Summary of the invention
The object of the invention is in conjunction with China's coking industry actual, propose a kind of technique utilizing cog joint to produce Sweet natural gas and hydrogen.
Utilize cog joint to produce a method for Sweet natural gas and hydrogen, comprise the steps:
(1) first coke-oven gas is carried out pre-treatment through pretreatment system, remove the impurity such as most sulphur, tar, benzene and naphthalene;
(2) coke-oven gas after pretreatment and water vapour are mixed into sulfur-resisting transformation system, and through low temperature sulfur tolerant shift, in coke-oven gas, most CO is converted into H 2, the large part of organosulfur simultaneously in coke(oven)gas is converted into inorganic sulfur;
(3) coke-oven gas after conversion, through pressure swing adsorption system or membrane sepn, isolates pure hydrogen product, thick methane gas and desorb waste gas;
(4) the thick methane gas obtained after pressure-variable adsorption, through purification system, removes CO 2and H 2the sour gas such as S and organosulfur, obtain gas product.
Described pretreatment system comprises screw-type compressor or through roots blower, temperature swing absorption unit and reciprocation compressor.Coke-oven gas first through screw-type compressor or after roots blower pressurization, enters temperature swing absorption unit, the sorbent material that in coke-oven gas, the impurity such as most sulphur, tar, benzene, naphthalene is attracted in adsorption tower removes, then is pressurizeed by reciprocation compressor.Coke-oven gas is compressed to 0.1 ~ 1MPa through screw-type compressor, or is compressed to 0.01 ~ 0.1MPa through roots blower; Coke-oven gas is compressed to 1.5 ~ 3MPa by reciprocation compressor.
Described sulfur-resisting transformation system comprises preheater, process furnace, shift converter and separating tank, and contacted by pipeline between preheater, process furnace, shift converter, shift converter is connected with separating tank after preheater again, and shift converter can be 1 ~ 3 and is connected in series.The temperature of described low temperature sulfur tolerant shift is 200 ~ 500 DEG C.Shift converter is fixed-bed reactor, and 2 ~ 4 sections of conversion catalyst are housed, and every section of catalyst bed is provided with de-salted water spray equipment.Most CO reacts with water vapour and is converted into H under the effect of low temperature sulfur tolerant shift catalyst wherein 2, the organosulfur simultaneously in coke(oven)gas is also converted into inorganic sulfur greatly.
Described pressure swing adsorption system comprises at least two psa units, and each psa unit is by multiple stage surge tank and multiple stage adsorption tower composition.
Described purification system comprises absorption tower and regenerator column and auxiliary facility thereof, selects tetramethylene sulfone, compound MDEA equal solvent in described absorption tower according to the situation of gaseous fraction, absorbs CO 2, H 2the sour gas such as S and organosulfur, regenerator column is used for the cyclic regeneration of solvent.
The present invention adopt coke-oven gas be raw material mass-producing produce Sweet natural gas and hydrogen two kinds of products; the gas product finally obtained meets Sweet natural gas GB (GB17820) class technical specification; directly can send into pipe network or sell compressed natural gas (CNG); or produce natural gas liquids (LNG) through dehydration, demercuration and deep cooling again, the byproduct hydrogen obtained in pilot process can for coal chemical enterprise hydrogenation unit.
The more existing various coke-oven gas of this technological process produces natural gas process process, have that flow process is simple, energy consumption is low, reduced investment, easy to operate, can the advantage of by-product hydrogen in a large number, finally reach the object of high-efficiency comprehensive utilization coke(oven)gas.
Accompanying drawing explanation
Fig. 1 is process flow diagram of the present invention.
Main Reference Numerals:
1 pretreatment system 2 sulfur-resisting transformation system
3 pressure swing adsorption system 4 purification systems
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in further detail, but the mode provided only exemplarily and not should be construed as limiting the scope of the invention.
As shown in Figure 1, the present invention utilizes cog joint to produce the method for Sweet natural gas and hydrogen, comprises the steps:
(1) first coke-oven gas is carried out pre-treatment through pretreatment system 1, remove the impurity such as most sulphur, tar, benzene and naphthalene.Pretreatment system 1 comprises screw-type compressor or through roots blower, temperature swing absorption unit and reciprocation compressor.Coke-oven gas first through screw-type compressor or after roots blower pressurization, is entered temperature swing absorption unit, then is pressurizeed by reciprocation compressor.
Coke-oven gas after being purified coke-oven plant is compressed to 0.1 ~ 1MPa through screw-type compressor, or be compressed to 0.01 ~ 0.1MPa through roots blower, enter temperature swing absorption unit, the sorbent material that in coke(oven)gas, the impurity such as most sulphur, tar, benzene, naphthalene is attracted in adsorption tower removes, then is compressed to 1.5 ~ 3MPa by reciprocation compressor.
(2) coke-oven gas after pretreatment enters sulfur-resisting transformation system 2 after mixing with water vapour, DEG C enter one to three shift converter through heat exchange to 200 ~ 500 and carry out sulfur-resisting transformation, in shift converter, most CO reacts with water vapour and is converted into H under the effect of low temperature sulfur tolerant shift catalyst 2, the organosulfur simultaneously in coke(oven)gas is also converted into inorganic sulfur greatly, the coke(oven)gas leaving shift converter reclaims heat through preheater, separating tank deliver to after being separated moisture after operation.
After coke(oven)gas after compression mixes with water vapour, through one to three section of low temperature sulfur tolerant shift, reaction: CO+H below occurring in shift converter 2o=H 2+ CO 2, in this process coke(oven)gas, most CO is converted into H 2, the organosulfur simultaneously in coke(oven)gas is converted into inorganic sulfur greatly.Sulfur-resisting transformation system 2 comprises preheater, process furnace, shift converter and separating tank, and contacted by pipeline between preheater, process furnace, shift converter, shift converter is connected with separating tank after preheater again.Shift converter can be 1 ~ 3 and is connected in series, and the temperature of low temperature sulfur tolerant shift is 200 ~ 500 DEG C.Shift converter is fixed-bed reactor, and 2 ~ 4 sections of conversion catalyst are housed, and every section of catalyst bed is provided with de-salted water spray equipment.Most CO reacts with water vapour and is converted into H under the effect of low temperature sulfur tolerant shift catalyst wherein 2, the organosulfur simultaneously in coke(oven)gas is also converted into inorganic sulfur greatly.
(3) coke-oven gas after conversion, through pressure swing adsorption system 3 or membrane sepn, isolates pure hydrogen product, thick methane gas and desorb waste gas; Pressure swing adsorption system 3 comprises at least two psa units, and each psa unit is by surge tank and multiple stage adsorption tower composition.
Coke(oven)gas after conversion, through pressure swing adsorption system 3, first isolates raw hydrogen, and extracts thick methane gas out, carries out pressure-variable adsorption separation more afterwards to raw hydrogen, obtains the pure hydrogen product of purity more than 99.9% and desorb waste gas.Each psa unit, by multiple stage surge tank and multiple stage adsorption tower composition, utilizes the difference of gas with various adsorption rate on the sorbent, and by not stopping to carry out Adsorption and desorption to adsorption tower, the switching of reproduced state realizes to gas separation.
(4) the thick methane gas obtained after pressure-variable adsorption, through purification system 4 solvent absorbing, removes CO wherein 2, H 2the sour gas such as S and organosulfur, finally obtain the gas product of purity more than 98%.
The thick methane gas of extracting out from adsorption tower enters absorption tower after compression, selects tetramethylene sulfone, compound MDEA equal solvent according to the situation of gaseous fraction, absorbs CO wherein 2, H 2the sour gas such as S and organosulfur, Sweet natural gas GB (GB17820) one class specification requirements can be met after the methane gas obtained isolates moisture, the gas product of purity more than 98%, absorbs the solvent after sour gas and organosulfur and uses through regenerator column regeneration Posterior circle.
The present invention can summarize with other specific forms without prejudice to the present invention's spirit and principal character.Therefore, above-mentioned embodiment of the present invention can only be thought explanation of the present invention and can not limit the present invention, and claims indicate scope of the present invention.Person skilled obviously can change or change apparatus and method of the present invention and combine not departing from spirit of the present invention, content and scope, realizes the technology of the present invention.Special needs to be pointed out is, all similar replacements and change apparent to those skilled in the art, they are all deemed to be included in spirit of the present invention, content and scope.

Claims (10)

1. utilize cog joint to produce a method for Sweet natural gas and hydrogen, it is characterized in that the method comprises the steps:
(1) first coke-oven gas is carried out pre-treatment through pretreatment system, remove most sulphur, tar, benzene and naphthalene;
(2) coke-oven gas after pretreatment and water vapour are mixed into sulfur-resisting transformation system, and through low temperature sulfur tolerant shift, in coke-oven gas, most CO is converted into H 2, the large part of organosulfur simultaneously in coke(oven)gas is converted into inorganic sulfur;
(3) coke-oven gas after conversion, through pressure swing adsorption system or membrane sepn, isolates pure hydrogen product, thick methane gas and desorb waste gas;
(4) the thick methane gas obtained after pressure-variable adsorption, through purification system, removes sour gas and organosulfur, obtains gas product.
2. utilize cog joint to produce the method for Sweet natural gas and hydrogen as claimed in claim 1, it is characterized in that: described pretreatment system comprises screw-type compressor or through roots blower, temperature swing absorption unit and reciprocation compressor.
3. utilize cog joint to produce the method for Sweet natural gas and hydrogen as claimed in claim 2, it is characterized in that: coke-oven gas first through screw-type compressor or after roots blower pressurization, is entered temperature swing absorption unit, then pressurizeed by reciprocation compressor.
4. utilize cog joint to produce the method for Sweet natural gas and hydrogen as claimed in claim 3, it is characterized in that: coke-oven gas is compressed to 0.1 ~ 1MPa through screw-type compressor, or be compressed to 0.01 ~ 0.1MPa through roots blower; Coke-oven gas is compressed to 1.5 ~ 3MPa by reciprocation compressor.
5. utilize cog joint to produce the method for Sweet natural gas and hydrogen as claimed in claim 1, it is characterized in that: described sulfur-resisting transformation system comprises preheater, process furnace, shift converter and separating tank, contacted by pipeline between preheater, process furnace, shift converter, shift converter is connected with separating tank after preheater again.
6. utilize cog joint to produce the method for Sweet natural gas and hydrogen as claimed in claim 1, it is characterized in that: the temperature of described low temperature sulfur tolerant shift is 200 ~ 500 DEG C.
7. utilize cog joint to produce the method for Sweet natural gas and hydrogen as claimed in claim 5, it is characterized in that: described shift converter is 1 ~ 3 and is connected in series.
8. utilize cog joint to produce the method for Sweet natural gas and hydrogen as claimed in claim 5, it is characterized in that: described shift converter is fixed-bed reactor, 2 ~ 4 sections of conversion catalyst are housed, and every section of catalyst bed is provided with de-salted water spray equipment.
9. utilize cog joint to produce the method for Sweet natural gas and hydrogen as claimed in claim 1, it is characterized in that: described pressure swing adsorption system comprises at least two psa units, described psa unit is made up of surge tank and multiple stage adsorption tower.
10. utilize cog joint to produce the method for Sweet natural gas and hydrogen as claimed in claim 1, it is characterized in that: described purification system comprises absorption tower and regenerator column, described absorption tower adopts tetramethylene sulfone and/or compound MDEA solvent absorbing sour gas and organosulfur.
CN201410618203.7A 2014-11-05 2014-11-05 Method for co-producing natural gas and hydrogen by utilizing coke oven gas CN104388138A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104946327A (en) * 2015-06-04 2015-09-30 成都同创伟业新能源科技有限公司 Coal gas utilization method realized by coal-tar fraction hydro-upgrading and LNG manufacturing combination
CN105110291A (en) * 2015-07-21 2015-12-02 河南环宇石化装备科技股份有限公司 Method for preparation of LNG from recovered coke oven gas and co-production of synthetic ammonia
CN106276795A (en) * 2016-08-03 2017-01-04 西南化工研究设计院有限公司 A kind of group technology utilizing coke-stove gas extraction metallurgy reducing gases
CN106902614A (en) * 2017-03-27 2017-06-30 山东钢铁集团日照有限公司 A kind of method of organic sulfur in removing coke-stove gas

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101157442A (en) * 2007-04-27 2008-04-09 中国石化集团宁波工程有限公司 Waste heat reclaiming process for CO transformation
CN101434879A (en) * 2008-12-15 2009-05-20 四川天一科技股份有限公司 Method for preparing methyl alcohol synthesis gas and compressed natural gas from coke oven gas and coal
CN103275777A (en) * 2013-06-08 2013-09-04 华电重工股份有限公司 Method for preparing hydrogen and liquefied natural gas through using gas retort raw gas

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101157442A (en) * 2007-04-27 2008-04-09 中国石化集团宁波工程有限公司 Waste heat reclaiming process for CO transformation
CN101434879A (en) * 2008-12-15 2009-05-20 四川天一科技股份有限公司 Method for preparing methyl alcohol synthesis gas and compressed natural gas from coke oven gas and coal
CN103275777A (en) * 2013-06-08 2013-09-04 华电重工股份有限公司 Method for preparing hydrogen and liquefied natural gas through using gas retort raw gas

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104946327A (en) * 2015-06-04 2015-09-30 成都同创伟业新能源科技有限公司 Coal gas utilization method realized by coal-tar fraction hydro-upgrading and LNG manufacturing combination
CN105110291A (en) * 2015-07-21 2015-12-02 河南环宇石化装备科技股份有限公司 Method for preparation of LNG from recovered coke oven gas and co-production of synthetic ammonia
CN106276795A (en) * 2016-08-03 2017-01-04 西南化工研究设计院有限公司 A kind of group technology utilizing coke-stove gas extraction metallurgy reducing gases
CN106902614A (en) * 2017-03-27 2017-06-30 山东钢铁集团日照有限公司 A kind of method of organic sulfur in removing coke-stove gas
CN106902614B (en) * 2017-03-27 2019-10-18 山东钢铁集团日照有限公司 A kind of method of organic sulfur in removing coke-stove gas

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