CN108559549A - The electricity-generating method of coke-stove gas - Google Patents

The electricity-generating method of coke-stove gas Download PDF

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Publication number
CN108559549A
CN108559549A CN201710590823.8A CN201710590823A CN108559549A CN 108559549 A CN108559549 A CN 108559549A CN 201710590823 A CN201710590823 A CN 201710590823A CN 108559549 A CN108559549 A CN 108559549A
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China
Prior art keywords
logistics
molecular sieve
coke
gas
concentration
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Inventor
彭继荣
马海洋
李建
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Hubei Shen Tan Environmental Protection New Material Co Ltd
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Hubei Shen Tan Environmental Protection New Material Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10KPURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00Purifying combustible gases containing carbon monoxide
    • C10K1/002Removal of contaminants
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10KPURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00Purifying combustible gases containing carbon monoxide
    • C10K1/002Removal of contaminants
    • C10K1/003Removal of contaminants of acid contaminants, e.g. acid gas removal
    • C10K1/004Sulfur containing contaminants, e.g. hydrogen sulfide
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10KPURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00Purifying combustible gases containing carbon monoxide
    • C10K1/20Purifying combustible gases containing carbon monoxide by treating with solids; Regenerating spent purifying masses
    • C10K1/205Methods and apparatus for treating the purifying masses without their regeneration

Abstract

The present invention relates to a kind of electricity-generating method of coke-stove gas, mainly solves sulfide in coke oven gas purification in the prior art, tar, benzene and naphthalene removing not exclusively, cause the susceptible to plugging technical problem of compressor cooling pipe.The present invention is by using including the following steps:Coke-stove gas enters thick desulfurization unit, and slightly de- benzene unit, slightly forms logistics II after de- benzene;Logistics II enters moisture separator, forms logistics III;Logistics III enters comprehensive purifying tower, forms logistics IV;After logistics IV enters compressor compresses, it is sent to gas turbine combustion power generation, the tail gas after gas turbine combustion forms logistics V;Logistics V enters tail gas desulfurization denitration unit, and after scrubbing CO_2 and nitride, tail gas forms the technical solution that logistics VI is vented, and preferably solves the problems, such as this, can be used in the industrial production of coke-stove gas power generation.

Description

The electricity-generating method of coke-stove gas
Technical field
The present invention relates to a kind of electricity-generating methods of coke-stove gas, are especially used for the power generation side of the coke-stove gas of fuel engine power generation Method.
Background technology
Coke-stove gas is mainly the high thermal energy fuel gas containing hydro carbons, methane, hydrogen of coke-oven plant's by-product, generally as Fuel gas generation uses.Since the thermal efficiency of fuel engine power generation is higher than steam turbine, combustion is selected in the coke-stove gas power generation of general coke-oven plant Machine generates electricity.But fuel engine power generation is higher to the purity requirement of coal gas, to remove benzene,toluene,xylene, naphthalene, coke in coke-stove gas The organic matters such as oil prevent from blocking combustion engine nozzle, also to remove the sulfide in coke-stove gas, prevent the flue gas titanium dioxide after burning Sulphur emissions are exceeded, and nitride is exceeded in order to prevent, it is also necessary to remove the ammonia in coke-stove gas.So before gas-fired power generation, It is purified, removes aromatic hydrocarbons, tar, sulfide, the ammonia etc. carried in coal gas.
Existing fine purification technique for coke oven gas first removes the hydrogen sulfide in coke-stove gas with iron oxide adsorbent, then uses Activated carbon removes naphthalene therein, with activated carbon removes benzene therein again, is then fed into fuel engine power generation, but deviate from hydrogen sulfide, benzene, The effect of naphthalene is bad.
Document CN201410651179.7 discloses a kind of method of coke oven gas purification, and process is:Coke-stove gas passes through Primary cooler is cooled to 300~500 DEG C with water indirectly, and dehydrating tower, which is dehydrated to 5~10ppm of water content, enters tar recovery tower, condensation It is precipitated outside tar liquid and arranges, be cooled to outside -30~-50 DEG C of precipitation liquid ammonias and arrange into liquefied ammonia recovery tower, by Methanol Wash Column Imurity-removal, clean coke-stove gas is into clean coal gas tank.The device of coke oven gas purification includes primary cooler, dehydrating tower, tar recycling Tower, liquefied ammonia recovery tower and Methanol Wash Column are simultaneously sequentially connected.Tar recovery tower and liquefied ammonia recovery tower respectively with liquid carbon dioxide The bottom of tower outlet of piping connection, tar recovery tower is connect with tar reclaimer, and bottom of tower outlet and the liquefied ammonia of liquefied ammonia recovery tower return Receiving unit connects.The invention removes the impurity in coal gas by cooling, dehydration, separating tar and ammonia, then through methanol washing process And harmful substance, without reference to using adsorbent purifying coke oven gas.
Document CN201210012179.3 is related to a kind of gas turbine power generation coke-stove gas comprehensive purification system and its purification Method, gas turbine power generation coke-stove gas comprehensive purification system, the coke-stove gas in gas pipe is successively through desulphurization system, compressor Filtration system and gas filtering system enter in gas turbine, and desulphurization system is that four groups of dry desulfurizing towers are connected in parallel on gas pipe, pressure Contracting machine filtration system is connected on from the first appendix that desulphurization system comes out by four compressor filters;It is comprehensive using coal gas The purification method for closing purification system, includes the following steps:A, by coal gas desulfurization;B, by the coal gas filtered compressed obtained by step a;c、 By coal gas equipressure heating obtained by step b;D, by coal gas pre-filtering obtained by step c;E, coal gas essence obtained by step d is filtered, is obtained Meet the coal gas of combustion engine requirement.Present system newly sets four groups of dry desulfurizing towers, with the present invention on the basis of crude benzol purified treatment One is tower and meanwhile desulfurization to take off benzene different.
Document CN201110250178.8 reports a kind of Multifunctional raw gas purifying agent and its methods for making and using same.It should Multifunctional raw gas purifying agent using activated alumina as carrier, load ammonium molybdate, while load copper acetate, zinc acetate, lead acetate, 1~2 kind in nickel oxalate, ammonium metavanadate, while the one kind being also loaded in magnesium chloride, potassium carbonate, sodium carbonate is made, this is multi-functional The former composition of raw material gas purifying agent is in terms of carrier quality, and the ammonium molybdate of load is the 1%~10% of carrier quality, other 2~3 kinds Metallic compound total amount is the 10%~25% of carrier quality.The preparation method of the Multifunctional raw gas purifying agent is first to use metal Compound solution impregnated carrier 2~6 hours, 2~4 hours dry by 120 DEG C, 280~350 DEG C of roastings are made after 4~6 hours Obtain the multifunctional purifying agent.The Multifunctional raw gas purifying agent is for water-gas, semiwater gas, coke-stove gas or IGCC power generation combustions COS, CS are purified in gas unstripped gas2、HCN、SO2、SO3And O2Equal impurity, wherein COS, CS2、HCN、SO2、SO3Conversion ratio >= 90%, O2Removal efficiency >=95%.The document does not have been reported that cleanser has suction-operated to aromatic hydrocarbons.
The prior art does not use the report of molecular sieve adsorbent purification coal gas, does not more disclose and is adsorbed using molecular sieve Agent, while the report of sulfide and aromatic hydrocarbons is removed, gas purifying method of the present invention removes sulfide and aromatic hydrocarbons, is directed to completely Property solves that presently, there are purify sordid technical problem when coal gas generates electricity.
Invention content
When the technical problem to be solved by the present invention is to use coke-stove gas power generation in the prior art, in coke oven gas purification Sulfide, tar, benzene and naphthalene removing be not clean, causes the technology that compressor cooling pipe easily blocks, sulfur dioxide (SO2) emissions are exceeded Problem, the present invention provide a kind of new coke oven gas purification method.In production of this method for coke-stove gas power generation, coal gas is net Change totally, sulphur emissions are low, the stable advantage of power generator.
In order to solve the above technical problems, the technical solution adopted by the present invention is as follows:A kind of purification method of coke-stove gas, packet Include following steps:
A. the coke-stove gas that coke oven comes out enters slightly de- benzene unit, slightly forms logistics I, wherein benzene concentration in logistics I after de- benzene In 1000~4000mg/m3Between, naphthalene concentration is in 100~500mg/m3Between;
B. logistics I enters thick desulfurization unit, and logistics II is formed after thick desulfurization, wherein in logistics II concentration of hydrogen sulfide 100~ 500mg/m3Between;
C. logistics II enters moisture separator, after removing the operative liquid moisture in coke-stove gas, forms logistics III;
D. logistics III enters comprehensive purifying tower, molecular sieve adsorbent A is contained in the comprehensive purifying tower, while removing Aromatic hydrocarbons in coal gas and sulfide form logistics IV, and benzene concentration is less than 100mg/m wherein in logistics IV3, naphthalene concentration is less than 4 mg/m3Between, concentration of hydrogen sulfide is less than 4mg/m3
E. after logistics IV enters compressor compresses, it is sent to gas turbine combustion power generation, the tail gas after gas turbine combustion is formed Logistics V, wherein a concentration of of sulfur dioxide is less than 50mg/m in logistics V3
F. logistics V enters tail gas desulfurization, denitration unit, and after scrubbing CO_2 and nitride, tail gas forms logistics VI, puts It is empty, wherein a concentration of of sulfur dioxide is less than 10mg/m in logistics VI3, the adsorbent of molecular sieve B of tail gas desulfurization use.
In above-mentioned technical proposal, preferred technical solution is that the thick de- benzene unit uses solvent-extracted method, is taken off Except the benzene of part in coal gas, thick desulfurization unit removes the hydrogen sulfide of part in coal gas using limestone desulfurizer.
In above-mentioned technical proposal, preferred technical solution is that the molecular sieve adsorbent is the absorption of hydrophobic type molecular sieve Agent.
In above-mentioned technical proposal, preferred technical solution is to be filled in molecular sieve or activated carbon in moisture separator It is at least one.
In above-mentioned technical proposal, preferred technical solution is to contain in the adsorbent of molecular sieve A and adsorbent of molecular sieve B There are at least one of the Ith A, II A, V A, I B, II B, III B, IV B, V B, VI B, VII B or the VIIIth race's element in the periodic table of elements Element.
In above-mentioned technical proposal, preferred technical solution is that the IIth element A is selected from magnesium and calcium in the periodic table of elements At least one of;Ith B races element is selected from least one of copper, silver;IIIth B races element in lanthanum, cerium, yttrium at least It is a kind of.
In above-mentioned technical proposal, preferred technical solution is the molecular sieve adsorbent A and molecular sieve adsorbent B Middle molecular sieve is selected from X-type molecular sieve, Y type molecular sieve, A type molecular sieve, ZSM types molecular sieve, modenite, beta molecular sieve, SAPO Type molecular sieve, MCM-22, MCM-49, MCM-56, ZSM-5/ modenite, ZSM-5/ β zeolites, ZSM-5/Y, MCM-22/ mercerising Zeolite, ZSM-5/Magadiite, ZSM-5/ β zeolites/modenite, ZSM-5/ β zeolites/Y zeolites or ZSM-5/Y zeolites/mercerising At least one of zeolite.
In above-mentioned technical proposal, preferred technical solution is that ZSM type molecular sieves include in the molecular sieve adsorbent A At least one of ZSM-5, ZSM-23, ZSM-11, ZSM-48.
In above-mentioned technical proposal, preferred technical solution is the molecular sieve adsorbent while removing the coke in coal gas Oil, cyanide, ammonia.
In above-mentioned technical proposal, preferred technical solution is that the aromatic hydrocarbons is benzene,toluene,xylene, ethylbenzene, front three At least one of benzene, naphthalene, anthracene, Kun;Sulfide is hydrogen sulfide, sulfur dioxide, mercaptan, thioether, thiophene, methyl mercaptan, methyl At least one of thioether.
In above-mentioned technical proposal, preferred technical solution is that the molecular sieve adsorbent is regenerable sorbent;Institute The adsorbent of molecular sieve A and adsorbent of molecular sieve B stated is continuing with after being regenerated 3 ~ 60 hours at 100 ~ 600 DEG C.
It is known in the art, during gas purification process, coal gas is purified using traditional handicraft, using desulfurizing tower again It is middle to use iron oxide desulfurization;Using in de- naphthalene tower naphthalene is taken off with activated carbon;Benzene is taken off with activated carbon using debenzolizing tower again;3 are used altogether Absorbing unit purifies coal gas successively.In device operation, device exit hydrogen sulfide, benzene and naphthalene are dense, compressor cooling tube Road is frequently occluded, and is needed to shut down and be dredged, influences production efficiency.
Method using the present invention, has the following advantages that:(1)Using adsorbent of molecular sieve, can by benzene, naphthalene and hydrogen sulfide, Organic sulfur can be removed thoroughly totally, solve the problems, such as line clogging.(2)Adsorbent is subjected to multifunction, can simultaneously desulfurization, De- benzene, de- naphthalene can be carried out at the same time comprehensive purifying process, reduce the quantity of adsorption tower in this way, reduce in an adsorption tower Production cost.
Technical solution using the present invention:The coke-stove gas that coke oven comes out enters slightly de- benzene unit, slightly enters after de- benzene Dewatering unit, dewatered coal gas enter comprehensive purifying tower, molecular sieve adsorbent are contained in purifying column, while removing coal gas In aromatic hydrocarbons and sulfide, after entering back into compressor compresses, be sent to gas turbine power generation.Taking off naphthalene tower exit hydrogen sulfide content is 0 mg/m3, naphthalene content is 0 mg/m3, tar content 0, the organic sulfur carried in gas is also removed, dioxy in combustion engine flue gas Change sulphur emissions in 10m hereinafter, device is stable, achieves preferable technique effect.
Description of the drawings
The coke oven gas purification flow diagram of the present invention that Fig. 1 is.
In Fig. 1,1 for coke oven coke-stove gas, 2 be logistics I, i.e. the slightly coke-stove gas after de- benzene, and 3 be logistics II;4 It is logistics IV for logistics III, 5,6 be compressed coal gas, and 7 be logistics V, and 8 be logistics VI;
In Fig. 1, I is de- crude benzol tower, and II is thick desulfurizing tower, and III is moisture separator, and IV is comprehensive purifying tower, and V is gas compression Machine, VI is fuel engine power generation machine, and VII is tail gas desulfurization denitration unit.
The present invention will be further described below by way of examples, but is not limited only to the present embodiment.
Specific implementation mode
【Embodiment 1】
As shown in Fig. 1, the electricity-generating method of coke-stove gas, includes the following steps:A. the coke-stove gas that coke oven comes out enters thick De- benzene unit slightly forms logistics I after de- benzene, and benzene concentration is in 2000mg/m wherein in logistics I3Between, naphthalene concentration is in 1300mg/m3 Between;B. logistics I enters thick desulfurization unit, logistics II is formed after thick desulfurization, wherein concentration of hydrogen sulfide exists in logistics II 300mg/m3Between;C. logistics II enters moisture separator, after removing the operative liquid moisture in coke-stove gas, forms logistics Ⅲ;D. logistics III enters comprehensive purifying tower, and the interior adsorbent containing ZSM-5 molecular sieve of the comprehensive purifying tower removes simultaneously Fall the aromatic hydrocarbons and sulfide in coal gas, form logistics IV, benzene concentration is less than 100mg/m wherein in logistics IV3, naphthalene concentration is less than 4 mg/m3Between, concentration of hydrogen sulfide is less than 4mg/m3;E. after logistics IV enters compressor compresses, it is sent to gas turbine combustion power generation, Tail gas after gas turbine combustion forms logistics V, wherein a concentration of of sulfur dioxide is less than 50mg/m in logistics V3;f. Logistics V enters tail gas desulfurization, denitration unit, and after scrubbing CO_2 and nitride, tail gas forms logistics VI, emptying, wherein The a concentration of of sulfur dioxide is less than 10mg/m in logistics VI3, the Y molecular sieve adsorbent of tail gas desulfurization use.Device continuous operation 3 A month or more, comprehensive purifying tower exit benzene, naphthalene, concentration of hydrogen sulfide were stablized, and gas compression pump does not occur plugging phenomenon, combustion engine yet Exhaust emissions in sulfur dioxide concentration be less than 5mg/m3
【Embodiment 2】
The electricity-generating method of coke-stove gas, includes the following steps:A. the coke-stove gas that coke oven comes out enters slightly de- benzene unit, slightly Logistics I is formed after de- benzene, benzene concentration is in 1000mg/m wherein in logistics I3Between, naphthalene concentration is in 800mg/m3Between;B. logistics I Into thick desulfurization unit, logistics II is formed after thick desulfurization, wherein concentration of hydrogen sulfide is in 200mg/m in logistics II3Between;C. object Stream II enters moisture separator, after removing the operative liquid moisture in coke-stove gas, forms logistics III;D. logistics III enters comprehensive Purifying column, the adsorbent for the ZSM-5 molecular sieve being modified containing copper in the comprehensive purifying tower are closed, while removing in coal gas Aromatic hydrocarbons and sulfide form logistics IV, and benzene concentration is less than 100mg/m wherein in logistics IV3, naphthalene concentration is less than 4 mg/m3Between, Concentration of hydrogen sulfide is less than 4mg/m3;E. after logistics IV enters compressor compresses, gas turbine combustion power generation, gas turbine are sent to Tail gas after burning forms logistics V, wherein a concentration of of sulfur dioxide is less than 50mg/m in logistics V3;F. logistics V into Enter tail gas desulfurization, denitration unit, after scrubbing CO_2 and nitride, tail gas forms logistics VI, emptying, wherein in logistics VI The a concentration of of sulfur dioxide is less than 10mg/m3, the rare earth modified Y molecular sieve adsorbent of tail gas desulfurization use.Device is continuously transported Row 3 months or more, comprehensive purifying tower exit benzene, naphthalene, concentration of hydrogen sulfide are stablized, and gas compression pump does not occur plugging phenomenon yet, Sulfur dioxide concentration is less than 7mg/m in the exhaust emissions of combustion engine3
【Embodiment 3】
The coke-stove gas that coke oven comes out enters slightly de- benzene unit, slightly forms logistics I after de- benzene, wherein benzene concentration exists in logistics I 3000mg/m3Between, naphthalene concentration is in 400mg/m3Between;Logistics I enters thick desulfurization unit, and logistics II is formed after thick desulfurization, wherein II concentration of hydrogen sulfide of logistics is in 400mg/m3Between;Logistics II enters moisture separator, removes the operative liquid in coke-stove gas After moisture, logistics III is formed;Logistics III enters comprehensive purifying tower, contains copper and zinc modification ZSM-5 in the comprehensive purifying tower Molecular sieve adsorbent, while removing aromatic hydrocarbons and sulfide in coal gas, form logistics IV, wherein benzene concentration in logistics IV Less than 100mg/m3, naphthalene concentration is less than 4 mg/m3Between, concentration of hydrogen sulfide is less than 4mg/m3;Logistics IV enters compressor compresses Afterwards, it is sent to gas turbine combustion power generation, the tail gas after gas turbine combustion forms logistics V;The entrance of logistics V tail gas desulfurization, After denitration unit, scrubbing CO_2 and nitride, tail gas forms logistics VI and is vented, the rare earth that the tungsten that tail gas desulfurization uses is modified Y molecular sieve adsorbent.
The aromatic hydrocarbons and sulfide in coal gas, toluene, dimethylbenzene, ethylbenzene, three are fallen in removing simultaneously in above-mentioned comprehensive purifying tower Concentration in toluene, naphthalene, anthracene, Kun is less than 1 mg/m3Between;Hydrogen sulfide, sulfur dioxide, mercaptan, thioether, thiophene, methyl mercaptan, Concentration in Dimethyl sulfide is less than 1 mg/m3Between.
Device continuous operation 3 months or more, comprehensive purifying tower exit benzene, naphthalene, concentration of hydrogen sulfide are stablized, gas compression pump Do not occur plugging phenomenon, sulfur dioxide concentration is less than 5mg/m in the exhaust emissions of combustion engine yet3
【Embodiment 4】
According to the purification method of embodiment 1, the Y molecular sieve class adsorbent being modified containing copper is contained in the comprehensive purifying tower, The aromatic hydrocarbons and sulfide in coal gas are fallen in removing simultaneously, and benzene concentration is less than 50mg/m in logistics herein3, naphthalene concentration is less than 2mg/m3It Between, concentration of hydrogen sulfide is less than 2mg/m3;After purified coal gas enters compressor compresses, it is sent to gas turbine power generation, combustion gas wheel Tail gas after machine burning enters tail gas desulfurization, denitration unit, after scrubbing CO_2 and nitride, tail gas emptying, and tail gas desulfurization The copper of use and the rare-earth Y molecular sieve adsorbent of zinc modification.Device continuous operation 3 months or more, comprehensive purifying tower exit benzene, Naphthalene, concentration of hydrogen sulfide are stablized, and gas compression pump does not occur plugging phenomenon yet, and sulfur dioxide concentration is less than in the exhaust emissions of combustion engine 7mg/m3
【Embodiment 5】
According to the purification method of embodiment 1, wherein benzene concentration is less than 100mg/m in logistics IV3, naphthalene concentration is less than 4 mg/m3 Between, concentration of hydrogen sulfide is less than 4mg/m3;After logistics IV enters compressor compresses, it is sent to gas turbine combustion power generation, combustion gas wheel Tail gas after machine burning, forms logistics V;Logistics V enters tail gas desulfurization, denitration unit, scrubbing CO_2 and nitride Afterwards, tail gas forms logistics VI and is vented, the rare-earth Y molecular sieve adsorbent that the vanadium and tungsten that tail gas desulfurization uses are modified.
ZSM-5 molecular sieve class adsorbent containing zinc modification in above-mentioned comprehensive purifying tower, molecular sieve silica alumina ratio are 600, while removing aromatic hydrocarbons and sulfide in coal gas, the concentration in toluene, dimethylbenzene, ethylbenzene, trimethylbenzene, naphthalene, anthracene, Kun is small In 1 mg/m3Between;Concentration in hydrogen sulfide, sulfur dioxide, mercaptan, thioether, thiophene, methyl mercaptan, Dimethyl sulfide is less than 1 mg/m3Between.Device continuous operation 3 months or more, comprehensive purifying tower exit benzene, naphthalene, concentration of hydrogen sulfide are stablized, gas compression Machine does not occur plugging phenomenon yet, and sulfur dioxide concentration is less than 5mg/m in the exhaust emissions of combustion engine3
【Embodiment 6】
The coke-stove gas that coke oven comes out enters slightly de- benzene unit, slightly forms logistics I after de- benzene, wherein benzene concentration exists in logistics I 1000~3500mg/m3Between, naphthalene concentration is in 200~500mg/m3Between, concentration of hydrogen sulfide is in 100~500mg/m3Between;Object Stream I enters comprehensive purifying tower, the Y molecular sieve of the ZSM-5 molecular sieve and zinc modification that are modified containing copper in the comprehensive purifying tower Class adsorbent, while removing aromatic hydrocarbons and sulfide in coal gas, logistics II is formed, benzene concentration is less than 60mg/m in logistics II3, Naphthalene concentration is less than 1 mg/m3Between, concentration of hydrogen sulfide is less than 1mg/m3;After logistics II enters compressor compresses, it is sent to gas turbine Power generation, device continuous operation 3 months or more, comprehensive purifying tower exit benzene, naphthalene, concentration of hydrogen sulfide are stablized, gas compression pump Do not occur plugging phenomenon, sulfur dioxide concentration is less than 5mg/m in the exhaust emissions of combustion engine3
【Embodiment 7】
The coke-stove gas that coke oven comes out enters slightly de- benzene unit, subsequently into thick desulfurization unit, slightly logistics after the thick desulfurization of de- benzene Middle benzene concentration is in 1000~3000mg/m3Between, naphthalene concentration is in 200~400mg/m3Between, concentration of hydrogen sulfide 100~ 400mg/m3Between;Logistics enters moisture separator, after removing the operative liquid moisture in coke-stove gas, into comprehensive purifying Tower, the Y molecular sieve class adsorbent of the interior ZSM-5 molecular sieve and zinc modification being modified containing copper of the comprehensive purifying tower, wherein The silica alumina ratio of the silica alumina ratio 400 of ZSM-5 molecular sieve, Y molecular sieve is more than 100.Adsorbent removes in coal gas simultaneously Aromatic hydrocarbons and sulfide, herein in logistics benzene concentration be less than 50mg/m3, naphthalene concentration is less than 2mg/m3Between, concentration of hydrogen sulfide is less than 2mg/m3;After purified coal gas enters compressor compresses, it is sent to gas turbine power generation, the tail gas after gas turbine combustion enters Tail gas desulfurization, denitration unit, after scrubbing CO_2 and nitride, tail gas emptying.Device continuous operation 3 months or more, it is comprehensive Purifying column exit benzene, naphthalene, concentration of hydrogen sulfide are stablized, and gas compression pump does not occur plugging phenomenon yet, in the exhaust emissions of combustion engine Sulfur dioxide concentration is less than 5mg/m3
【Embodiment 8】
The coke-stove gas that coke oven comes out enters slightly de- benzene unit, and logistics I is slightly formed after de- benzene, and the thick de- benzene unit uses The method of methanol solvate extraction, removes the benzene of part in coal gas, benzene concentration is in 1000~4000mg/m wherein in logistics I3Between, Naphthalene concentration is in 200~500mg/m3Between;Logistics I enters thick desulfurization unit, and thick desulfurization unit is removed using limestone desulfurizer The hydrogen sulfide of part in coal gas forms logistics II after thick desulfurization, wherein II concentration of hydrogen sulfide of logistics is in 100~500mg/m3It Between;Logistics II enters moisture separator, after removing the operative liquid moisture in coke-stove gas, forms logistics III;Logistics III enters Comprehensive purifying tower contains ZSM-5 molecular sieve class adsorbent in the comprehensive purifying tower, at the same remove the aromatic hydrocarbons in coal gas and Sulfide forms logistics IV, wherein benzene concentration is less than 100mg/m in logistics IV3, naphthalene concentration is less than 4 mg/m3Between, hydrogen sulfide Concentration is less than 4mg/m3;After logistics IV enters compressor compresses, it is sent to gas turbine combustion power generation, the tail after gas turbine combustion Gas forms logistics V;Logistics V enters tail gas desulfurization, denitration unit, after scrubbing CO_2 and nitride, tail gas formation VI emptying of stream.
In above-mentioned comprehensive purifying tower and tail gas desulfurization unit uses the ZSM-5 molecular sieve class adsorbent containing zinc modification, Molecular sieve silica alumina ratio be 600, while remove fall coal gas in aromatic hydrocarbons and sulfide, toluene, dimethylbenzene, ethylbenzene, trimethylbenzene, Concentration in naphthalene, anthracene, Kun is less than 1 mg/m3Between;Hydrogen sulfide, sulfur dioxide, mercaptan, thioether, thiophene, methyl mercaptan, methyl Concentration in thioether is less than 1 mg/m3Between.Device continuous operation 3 months or more, comprehensive purifying tower exit benzene, naphthalene, vulcanization Hydrogen concentration is stablized, and gas compression pump does not occur plugging phenomenon yet, and sulfur dioxide concentration is less than 5mg/m in the exhaust emissions of combustion engine3
【Embodiment 9】
The coke-stove gas that coke oven comes out enters slightly de- benzene unit, subsequently into thick desulfurization unit, slightly logistics after the thick desulfurization of de- benzene Middle benzene concentration is in 1000~3000mg/m3Between, naphthalene concentration is in 200~400mg/m3Between, concentration of hydrogen sulfide 100~ 400mg/m3Between;Logistics enters moisture separator, after removing the operative liquid moisture in coke-stove gas, into comprehensive purifying Tower, the Y molecular sieve class adsorbent of the interior ZSM-5 molecular sieve and zinc modification being modified containing copper of the comprehensive purifying tower, wherein The silica alumina ratio of the silica alumina ratio 400 of ZSM-5 molecular sieve, Y molecular sieve is more than 100.Adsorbent removes in coal gas simultaneously Aromatic hydrocarbons and sulfide, herein in logistics benzene concentration be less than 50mg/m3, naphthalene concentration is less than 2mg/m3Between, concentration of hydrogen sulfide is less than 2mg/m3;After purified coal gas enters compressor compresses, it is sent to gas turbine power generation, the tail gas after gas turbine combustion enters Tail gas desulfurization, denitration unit, after scrubbing CO_2 and nitride, tail gas emptying, above-mentioned tail gas desulfurization unit is changed using copper The Y molecular sieve class adsorbent of the ZSM-5 molecular sieve and zinc modification of property.Device continuous operation 3 months or more, the outlet of comprehensive purifying tower Locate benzene, naphthalene, concentration of hydrogen sulfide to stablize, gas compression pump does not occur plugging phenomenon yet, and sulfur dioxide is dense in the exhaust emissions of combustion engine Degree is less than 5mg/m3
It after adsorbent in comprehensive adsorption tower adsorbs a week, is regenerated at 170 DEG C using purified coal gas, regeneration 12 is small Shi Hou, cold blowing to room temperature, is continuing with, and the absorption property of adsorbent is stablized, and benzene concentration is less than 50mg/m in logistics II3, naphthalene is dense Degree is less than 2mg/m3Between, concentration of hydrogen sulfide is less than 2mg/m3
【Comparative example 1】
According to method described in embodiment 1, acticarbon is only used, after running 10 hours, the sampling point of logistics II Analysis, benzene concentration is in 2000mg/m3, naphthalene concentration is in 200mg/m3, concentration of hydrogen sulfide is in 300mg/m3
Obviously, adsorbent supplement using the present invention, has effectively adsorbed benzene, naphthalene, hydrogen sulfide, ammonia, tar, hydrogen cyanide, first Benzene, dimethylbenzene, ethylbenzene, trimethylbenzene, naphthalene, anthracene, Kun, sulfur dioxide, mercaptan, thioether, thiophene, methyl mercaptan, first and base thioether are protected It has demonstrate,proved that purified coal gas is clean, ensure that the normal operation of electricity generation system.

Claims (10)

1. a kind of electricity-generating method of coke-stove gas, includes the following steps:
A. the coke-stove gas that coke oven comes out enters slightly de- benzene unit, slightly forms logistics I, wherein benzene concentration in logistics I after de- benzene In 1000~4000mg/m3Between, naphthalene concentration is in 100~500mg/m3Between;
B. logistics I enters thick desulfurization unit, and logistics II is formed after thick desulfurization, wherein in logistics II concentration of hydrogen sulfide 100~ 500mg/m3Between;
C. logistics II enters moisture separator, after removing the operative liquid moisture in coke-stove gas, forms logistics III;
D. logistics III enters comprehensive purifying tower, molecular sieve adsorbent A is contained in the comprehensive purifying tower, while removing Aromatic hydrocarbons in coal gas and sulfide form logistics IV, and benzene concentration is less than 100mg/m wherein in logistics IV3, naphthalene concentration is less than 4 mg/m3Between, concentration of hydrogen sulfide is less than 4mg/m3
E. after logistics IV enters compressor compresses, it is sent to gas turbine combustion power generation, the tail gas after gas turbine combustion is formed Logistics V, wherein a concentration of of sulfur dioxide is less than 50mg/m in logistics V3
F. logistics V enters tail gas desulfurization, denitration unit, and after scrubbing CO_2 and nitride, tail gas forms logistics VI, puts It is empty, wherein a concentration of of sulfur dioxide is less than 10mg/m in logistics VI3, the adsorbent of molecular sieve B of tail gas desulfurization use.
2. the electricity-generating method of coke-stove gas according to claim 1, it is characterised in that the thick de- benzene unit is using molten The method of agent extraction removes the benzene in coal gas, and solvent is selected from organic amine, and either the thick desulfurization unit of alcohols uses lime stone or has Machine amine.
3. the electricity-generating method of coke-stove gas according to claim 1, it is characterised in that be filled with molecule in moisture separator At least one of sieve or activated carbon.
4. the electricity-generating method of coke-stove gas according to claim 1, it is characterised in that the molecular sieve adsorbent A is Hydrophobic type adsorbent of molecular sieve;In the adsorbent of molecular sieve A and adsorbent of molecular sieve B containing the Ith A in the periodic table of elements, At least one of II A, V A, I B, II B, III B, IV B, V B, VI B, VII B or the VIIIth race's element element.
5. the electricity-generating method of coke-stove gas according to claim 4, it is characterised in that the IIth A in the periodic table of elements Element is selected from least one of magnesium and calcium;Ith B races element is selected from least one of copper, silver;IIIth B races element be selected from lanthanum, At least one of cerium, yttrium.
6. the electricity-generating method of coke-stove gas according to claim 1, it is characterised in that the molecular sieve adsorbent A and In adsorbent of molecular sieve B, molecular sieve be selected from X-type molecular sieve, Y type molecular sieve, A type molecular sieve, ZSM types molecular sieve, modenite, Beta molecular sieve, SAPO types molecular sieve, MCM-22, MCM-49, MCM-56, ZSM-5/ modenite, ZSM-5/ β zeolites, ZSM-5/ Y, MCM-22/ modenites, ZSM-5/Magadiite, ZSM-5/ β zeolites/modenite, ZSM-5/ β zeolites/Y zeolites or At least one of ZSM-5/Y zeolites/modenite.
7. the electricity-generating method of coke-stove gas according to claim 1, it is characterised in that the adsorbent of molecular sieve A and point In sub- sieve adsorbant B, ZSM type molecular sieves include at least one of ZSM-5, ZSM-23, ZSM-11, ZSM-48, wherein described The silica alumina ratio of molecular sieve is more than 100.
8. the electricity-generating method of coke-stove gas according to claim 1, it is characterised in that the molecular sieve adsorbent is same When removing coal gas in tar, cyanide, ammonia.
9. the electricity-generating method of coke-stove gas according to claim 1, it is characterised in that the aromatic hydrocarbons is benzene, toluene, two At least one of toluene, ethylbenzene, trimethylbenzene, naphthalene, anthracene, Kun;Sulfide be hydrogen sulfide, sulfur dioxide, mercaptan, thioether, thiophene, At least one of methyl mercaptan, Dimethyl sulfide.
10. the electricity-generating method of coke-stove gas according to claim 1, it is characterised in that the adsorbent of molecular sieve A and Adsorbent of molecular sieve B is regenerable sorbent, is continuing with after being regenerated 3 ~ 60 hours at 100 ~ 600 DEG C.
CN201710590823.8A 2017-07-19 2017-07-19 The electricity-generating method of coke-stove gas Pending CN108559549A (en)

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1277245A (en) * 2000-04-20 2000-12-20 江苏苏钢集团有限公司 Coke-oven gas desulfurizing and decyanating process
CN1880413A (en) * 2005-06-13 2006-12-20 成都华西化工研究所 Method for simultaneously removing multiple harmful impurity from coal gas
CN1919985A (en) * 2006-09-13 2007-02-28 西南化工研究设计院 Method of preparing synthetic natural gas by coke oven gas
CN101280235A (en) * 2008-05-21 2008-10-08 太原理工天成科技股份有限公司 Method for preparing liquefied natural gas from coke oven gas
JP2010024264A (en) * 2008-07-15 2010-02-04 Ihi Corp Tar removal method and apparatus
CN102250658A (en) * 2010-05-19 2011-11-23 上海标氢气体技术有限公司 Method for preparing liquefied natural gas by converting raw materials of coke oven gas and blast furnace gas
CN104557388A (en) * 2013-10-23 2015-04-29 中国石油化工股份有限公司 Deep desulfurization method of refinery C4
US9486782B2 (en) * 2010-09-13 2016-11-08 Lummus Technology Inc. Low temperature sulfur tolerant tar and sulfur removal with concomitant synthesis gas conditioning

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1277245A (en) * 2000-04-20 2000-12-20 江苏苏钢集团有限公司 Coke-oven gas desulfurizing and decyanating process
CN1880413A (en) * 2005-06-13 2006-12-20 成都华西化工研究所 Method for simultaneously removing multiple harmful impurity from coal gas
CN1919985A (en) * 2006-09-13 2007-02-28 西南化工研究设计院 Method of preparing synthetic natural gas by coke oven gas
CN101280235A (en) * 2008-05-21 2008-10-08 太原理工天成科技股份有限公司 Method for preparing liquefied natural gas from coke oven gas
JP2010024264A (en) * 2008-07-15 2010-02-04 Ihi Corp Tar removal method and apparatus
CN102250658A (en) * 2010-05-19 2011-11-23 上海标氢气体技术有限公司 Method for preparing liquefied natural gas by converting raw materials of coke oven gas and blast furnace gas
US9486782B2 (en) * 2010-09-13 2016-11-08 Lummus Technology Inc. Low temperature sulfur tolerant tar and sulfur removal with concomitant synthesis gas conditioning
CN104557388A (en) * 2013-10-23 2015-04-29 中国石油化工股份有限公司 Deep desulfurization method of refinery C4

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
吴晓东等编著: "《稀土催化材料》", 30 June 2017, 北京:中国铁道出版社 *

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