CN108102728A - The removal methods of organic sulfur in coke-stove gas - Google Patents
The removal methods of organic sulfur in coke-stove gas Download PDFInfo
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- CN108102728A CN108102728A CN201710590574.2A CN201710590574A CN108102728A CN 108102728 A CN108102728 A CN 108102728A CN 201710590574 A CN201710590574 A CN 201710590574A CN 108102728 A CN108102728 A CN 108102728A
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/002—Removal of contaminants
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/54—Nitrogen compounds
- B01D53/56—Nitrogen oxides
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/002—Removal of contaminants
- C10K1/003—Removal of contaminants of acid contaminants, e.g. acid gas removal
- C10K1/004—Sulfur containing contaminants, e.g. hydrogen sulfide
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/32—Purifying combustible gases containing carbon monoxide with selectively adsorptive solids, e.g. active carbon
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
- F02C—GAS-TURBINE PLANTS; AIR INTAKES FOR JET-PROPULSION PLANTS; CONTROLLING FUEL SUPPLY IN AIR-BREATHING JET-PROPULSION PLANTS
- F02C6/00—Plural gas-turbine plants; Combinations of gas-turbine plants with other apparatus; Adaptations of gas- turbine plants for special use
- F02C6/18—Plural gas-turbine plants; Combinations of gas-turbine plants with other apparatus; Adaptations of gas- turbine plants for special use using the waste heat of gas-turbine plants outside the plants themselves, e.g. gas-turbine power heat plants
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES
- F23J15/00—Arrangements of devices for treating smoke or fumes
- F23J15/02—Arrangements of devices for treating smoke or fumes of purifiers, e.g. for removing noxious material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/10—Inorganic adsorbents
- B01D2253/106—Silica or silicates
- B01D2253/108—Zeolites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/10—Inorganic adsorbents
- B01D2253/116—Molecular sieves other than zeolites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/30—Sulfur compounds
- B01D2257/306—Organic sulfur compounds, e.g. mercaptans
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/702—Hydrocarbons
- B01D2257/7027—Aromatic hydrocarbons
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES
- F23J2215/00—Preventing emissions
- F23J2215/10—Nitrogen; Compounds thereof
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Abstract
It the present invention relates to a kind of removal methods of organic sulfur in coke-stove gas, mainly solves in coke oven gas purification in the prior art that organic sulfur compound removing is not clean, causes the technical issues of sulfur dioxide (SO2) emissions are exceeded in tail gas after burning.Method of the present invention by removing organic sulfur in coke-stove gas, comprises the following steps：A. the coke-stove gas that coke oven comes out forms logistics I into slightly de- benzene unit after thick desulfurization；B. logistics I enters thick desulfurization unit, slightly forms logistics II after de- benzene；C. logistics II enters comprehensive purifying tower, and molecular sieve adsorbent is contained in the comprehensive purifying tower, while removes the aromatic hydrocarbons and organic sulfur compound in coal gas, forms logistics III；E. after logistics III enters compressor compresses, it is sent to gas turbine combustion and generates electricity, the technical solution of the tail gas emptying after gas turbine combustion preferably solves the problems, such as this, in the industrial production available for coke-stove gas power generation.
Description
Technical field
The present invention relates to a kind of removal methods of organic sulfur in coke-stove gas, the particularly coke-stove gas for fuel engine power generation
Purification method.
Background technology
At present, national requirements power plant carries out sulfur dioxide minimum discharge, and general requirement will reach two in every cubic metre of tail gas
Sulfur oxide content no more than 50 milligrams, compared by the minimum discharge for being reached sulfur dioxide using the power plant of coke-stove gas power generation at present
Difficulty, because not only containing hydrogen sulfide in coal gas, also containing substantial amounts of organic sulfur.
Coke-stove gas be mainly coke-oven plant's by-product containing hydro carbons, methane, hydrogen high thermal energy fuel gas, 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, ammonia carried in coal gas etc..
Existing fine purification technique for coke oven gas first removes the hydrogen sulfide in coke-stove gas, Ran Houyong with iron oxide adsorbent
Activated carbon removes naphthalene therein, removes benzene therein with activated carbon again, is then fed into fuel engine power generation, but remove hydrogen sulfide, benzene,
The effect of naphthalene is bad.
Also containing substantial amounts of organic sulfur in coal gas, the adsorbents such as existing iron oxide, activated carbon, coke, to organic sulfur not
Sensitivity, adsorption effect is more bad, causes coal gas in combustion engine after combustion power generation, and sulfur dioxide in tail gas content is exceeded.
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
Pipeline connects, and the bottom of towe outlet of tar recovery tower is connected with tar reclaimer, and bottom of towe outlet and the liquefied ammonia of liquefied ammonia recovery tower return
Receiving unit connects.The invention is by cooling down, being dehydrated, separating tar and ammonia, then through methanol washing process, removes the impurity in coal gas
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 to be connected on by four compressor filters from the first appendix that desulphurization system comes out；It is comprehensive using coal gas
The purification method of cleaning system is closed, is included the following steps：A, by coal gas desulfurization；B, by the coal gas filtered compressed obtained by step a；c、
By the isobaric heating of coal gas obtained by step b；D, by coal gas pre-filtering obtained by step c；E, by coal gas essence filtering obtained by step d, obtain
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 while desulfurization takes off benzene difference.
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
When compound solution impregnated carrier 2~6 is small, by 120 DEG C it is dry 2~4 it is small when, when 280~350 DEG C of roastings 4~6 are small after system
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 O2Wait 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 using the report of molecular sieve adsorbent purification coal gas, is not more disclosed and 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 the sordid technical problems of gas purification.
The content of the invention
The technical problems to be solved by the invention are organic sulfur compound, tar, benzene in coke oven gas purification in the prior art
It is unclean with naphthalene removing, the technical issues of compressor cooling pipe easily blocks, sulfur dioxide (SO2) emissions are exceeded in Combustion engine tail gas is caused,
The present invention provides a kind of removal methods of organic sulfur in new coke-stove gas.This method is used for the production using coke-stove gas power generation
In, remove the organic sulfur in coal gas, the advantages of gas purification is clean, and sulfur dioxide (SO2) emissions are low, and power generator is stable.
In order to solve the above technical problems, the technical solution adopted by the present invention is as follows：Organic sulfur is de- in a kind of coke-stove gas
Except method, comprise the following steps：
A. the coke-stove gas that coke oven comes out slightly forms logistics I into slightly de- benzene unit after de- benzene；
B. logistics I enters thick desulfurization unit, and logistics II is formed after thick desulfurization；
C. logistics II enters comprehensive purifying tower, and molecular sieve adsorbent is contained in the comprehensive purifying tower, while removes coal
Aromatic hydrocarbons and organic sulfur compound in gas form logistics III；
D. after logistics III enters compressor compresses, gas turbine combustion power generation is sent to, the flue gas after burning forms logistics IV；
E. logistics VI enters denitrating flue gas unit, removes the formation of the flue gas after nitrogen oxides logistics V and is vented.
In above-mentioned technical proposal, preferred technical solution is the logistics II into before comprehensive purifying tower, is entered
Moisture separator removes the moisture in coke-stove gas；In above-mentioned technical proposal, preferred technical solution uses for slightly de- benzene unit
Solvent-extracted method, thick desulfurization unit is using the desulfurization of at least one of organic amine, lime stone, calcium hydroxide or iron oxide
Agent.
In above-mentioned technical proposal, preferred technical solution is to contain molecular sieve or activated carbon in the moisture separator
At least one of.
In above-mentioned technical proposal, preferred technical solution is to contain cooling coil in the moisture separator, to passing through
Coal gas cool down.
In above-mentioned technical proposal, preferred technical solution enters back into tail gas desulfurization unit, scrubbing CO_2 for logistics V
Afterwards, it is vented.
In above-mentioned technical proposal, preferred technical solution is that the molecular sieve adsorbent is the absorption of hydrophobic type molecular sieve
Agent；Preferred technical solution in the molecular sieve adsorbent containing the Ith A in the periodic table of elements, II A, V A, I B, II B,
At least one of III B, IV B, V B, VI B, VII B or the VIIIth race's element 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；Molecular sieve is selected from X-type molecular sieve, Y type molecular sieve, A type molecular sieve, ZSM type molecules in the molecular sieve adsorbent
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/ modenite, ZSM-5/Magadiite, ZSM-5/ β zeolites/modenite, ZSM-5/ β boilings
At least one of stone/Y zeolites or ZSM-5/Y zeolites/modenite.
In above-mentioned technical proposal, preferred technical solution is that ZSM type molecular sieves include in the molecular sieve adsorbent
At least one of ZSM-5, ZSM-23, ZSM-11, ZSM-48, wherein the silica alumina ratio of the molecular sieve is more than 100.
In above-mentioned technical proposal, preferred technical solution removes the coke in coal gas for the molecular sieve adsorbent simultaneously
Oil, cyanide, ammonia；Aromatic hydrocarbons described in step c is benzene,toluene,xylene, in ethylbenzene, trimethylbenzene, naphthalene, anthracene, Kun at least
It is a kind of；Organic sulfur compound is at least one of mercaptan, thioether, thiophene, methyl mercaptan, Dimethyl sulfide.
In above-mentioned technical proposal, preferred technical solution be the molecular sieve adsorbent adsorption saturation after, at 100 DEG C
More than when regeneration 3 is small in above nitrogen or coal gas, after the completion of regeneration, reuse.
In above-mentioned technical proposal, preferred technical solution removes the coke in coal gas for the molecular sieve adsorbent simultaneously
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；Organic sulfur compound is mercaptan, thioether, thiophene, methyl mercaptan, in Dimethyl sulfide at least
It is a kind of.
In above-mentioned technical proposal, preferred technical solution removes hydrogen sulfide simultaneously for the molecular sieve adsorbent, and two
Sulfur oxide.
In above-mentioned technical proposal, preferred technical solution is that the molecular sieve adsorbent is regenerable sorbent.
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, it is necessary to shut down dredging, influences production efficiency, and the organic sulfur in coal gas cannot adsorb completely, power generation combustion engine burning
The sulfur dioxide in tail gas of discharge afterwards is exceeded.
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, in an adsorption tower, can be carried out at the same time comprehensive purifying process, so reduce the quantity of adsorption tower, reduce
Production cost.（3）Sulfur dioxide reaches minimum discharge in flue gas of power plants.
Technical solution using the present invention：The coke-stove gas that coke oven comes out enters into slightly de- benzene unit after thick desulfurization
Comprehensive purifying tower, purifying column is interior containing molecular sieve adsorbent, while removes the aromatic hydrocarbons and organic sulfur compound in coal gas, then into
After entering compressor compresses, gas turbine power generation is sent to.De- naphthalene tower exit hydrogen sulfide content is 1 mg/m3, naphthalene content is 1 mg/
m3, tar content 0, the organic sulfur carried in gas is also removed, and sulfur dioxide (SO2) emissions are in below 5mg, dress in combustion engine flue gas
It puts 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 be logistics III, and 5 be logistics IV.
I is de- crude benzol tower, and II is thick desulfurizing tower, and III is comprehensive purifying tower, and IV is gas compression pump, and V is fuel engine power generation
Machine.
Below by embodiment, the invention will be further elaborated, but is not limited only to the present embodiment.
Specific embodiment
【Embodiment 1】
As shown in Figure 1, the coke-stove gas that coke oven comes out slightly forms logistics I into slightly de- benzene unit after de- benzene, logistics I into
Enter thick desulfurization unit, logistics II is formed after thick desulfurization；Logistics II enters comprehensive purifying tower, contains in the comprehensive purifying tower and divides
Son sieve class adsorbent, while remove the aromatic hydrocarbons and organic sulfur compound in coal gas, form logistics III；Logistics III enters compressor pressure
It after contracting, is sent to gas turbine combustion and generates electricity, the tail gas after gas turbine combustion forms logistics IV, and logistics IV is vented.
Benzene concentration is in 1000~4000mg/m wherein in logistics II3Between, naphthalene concentration is in 200~500mg/m3Between, vulcanization
Hydrogen concentration is in 100~500mg/m3Between, organic sulfur concentration is in 50~200mg/m3Between；Logistics II enters comprehensive purifying tower, institute
It containing ZSM molecular sieve class adsorbent in the comprehensive purifying tower stated, while removes the aromatic hydrocarbons and sulfide in coal gas, forms logistics
III, benzene concentration is less than 50mg/m in logistics III3, naphthalene concentration is less than 4 mg/m3Between, concentration of hydrogen sulfide is less than 4mg/m3；Organic sulfur
Concentration is 1mg/m3, after logistics III enters compressor compresses, gas turbine power generation is sent to, device is continuously run 3 months or more, comprehensive
It closes purifying column exit benzene, naphthalene, concentration of hydrogen sulfide to stablize, gas compression pump does not occur plugging phenomenon, the exhaust emissions of combustion engine yet
In logistics IV in sulfur dioxide concentration be less than 5mg/m3。
【Embodiment 2】
The coke-stove gas that coke oven comes out slightly forms logistics I into benzene unit is slightly taken off after de- benzene, and logistics I enters thick desulfurization unit,
Logistics II is formed after thick desulfurization；Benzene concentration is in 1000~4000mg/m wherein in logistics II3Between, naphthalene concentration 200~
500mg/m3Between, concentration of hydrogen sulfide is in 100~500mg/m3Between, organic sulfur concentration, 100mg/m3；Logistics II enters synthesis
Purifying column, containing mordenite molecular sieve class adsorbent in the comprehensive purifying tower, while remove the aromatic hydrocarbons in coal gas and
Sulfide forms logistics III, and benzene concentration is less than 50mg/m in logistics III3, naphthalene concentration is less than 4 mg/m3Between, concentration of hydrogen sulfide is small
In 4mg/m3；After logistics III enters compressor compresses, gas turbine power generation is sent to, device is continuously run 3 months or more, comprehensive net
Hua Ta exits benzene, naphthalene, concentration of hydrogen sulfide are stablized, and gas compression pump does not occur plugging phenomenon, the object of the exhaust emissions of combustion engine yet
Sulfur dioxide concentration is less than 5mg/m in stream IV3。
【Embodiment 3】
The coke-stove gas that coke oven comes out slightly forms logistics I into benzene unit is slightly taken off after de- benzene, and logistics I enters thick desulfurization unit,
Logistics II is formed after thick desulfurization；Benzene concentration is in 1000~4000mg/m wherein in logistics II3Between, naphthalene concentration 200~
500mg/m3Between, concentration of hydrogen sulfide is in 100~500mg/m3Between, organic sulfur concentration is in 200mg/m3；Logistics II enters synthesis
Purifying column, the comprehensive purifying tower is interior containing Y zeolite molecular sieve class adsorbents, while removes the aromatic hydrocarbons in coal gas and vulcanization
Object forms logistics III, and benzene concentration is less than 50mg/m in logistics III3, naphthalene concentration is less than 4 mg/m3Between, concentration of hydrogen sulfide is less than
4mg/m3；Concentration in toluene, dimethylbenzene, ethylbenzene, trimethylbenzene, naphthalene, anthracene, Kun is less than 1 mg/m3Between；Sulfur dioxide, mercaptan,
Concentration in thioether, thiophene, methyl mercaptan, Dimethyl sulfide is less than 1 mg/m3Between.After logistics III enters compressor compresses, send
To gas turbine power generation, device is continuously run 3 months or more, and comprehensive purifying tower exit benzene, naphthalene, concentration of hydrogen sulfide are stablized, coal
Air compressor does not occur plugging phenomenon yet, and sulfur dioxide concentration is less than 5mg/m in the logistics IV of the exhaust emissions of combustion engine3。
【Embodiment 4】
The coke-stove gas that coke oven comes out slightly forms logistics I into benzene unit is slightly taken off after de- benzene, and logistics I enters thick desulfurization unit,
Logistics II is formed after thick desulfurization；Benzene concentration is in 1000~4000mg/m wherein in logistics II3Between, naphthalene concentration 200~
500mg/m3Between, concentration of hydrogen sulfide is in 100~500mg/m3Between, organic sulfur concentration is in 80mg/m3；Logistics II enters synthesis
Purifying column, the comprehensive purifying tower is interior containing rare earth modified Y molecular sieve class adsorbent, while removes the aromatic hydrocarbons in coal gas
And sulfide, logistics III is formed, benzene concentration is less than 50mg/m in logistics III3, naphthalene concentration is less than 4 mg/m3Between, organic sulfur concentration
In 1mg/m3, concentration of hydrogen sulfide is less than 4mg/m3；Concentration in toluene, dimethylbenzene, ethylbenzene, trimethylbenzene, naphthalene, anthracene, Kun is less than 1
mg/m3Between；Concentration in sulfur dioxide, mercaptan, thioether, thiophene, methyl mercaptan, Dimethyl sulfide is less than 1 mg/m3Between.Object
After stream III enters compressor compresses, gas turbine power generation is sent to, device is continuously run 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, dioxy in the logistics IV of the exhaust emissions of combustion engine yet
Change sulphur concentration and be less than 5mg/m3。
【Embodiment 5】
The coke-stove gas that coke oven comes out slightly forms logistics I into benzene unit is slightly taken off after de- benzene, and logistics I enters thick desulfurization unit,
Logistics II is formed after thick desulfurization；Benzene concentration is in 1000~4000mg/m wherein in logistics II3Between, naphthalene concentration 200~
500mg/m3Between, concentration of hydrogen sulfide is in 100~500mg/m3Between, organic sulfur concentration is in 150mg/m3Between；Logistics II into
Before entering comprehensive purifying tower, into moisture separator, the moisture in coke-stove gas is removed.Then logistics II enters comprehensive purifying
Tower, the interior ZSM-5 molecular sieve class adsorbent containing zinc modification of the comprehensive purifying tower, molecular sieve silica alumina ratio is 200, is taken off simultaneously
The aromatic hydrocarbons and organic sulfur compound in coal gas are removed, forms logistics III, benzene concentration is less than 50mg/m in logistics III3, naphthalene concentration is less than 4
mg/m3Between, concentration of hydrogen sulfide is less than 4mg/m3, organic sulfur concentration is in 1mg/m3；Toluene, dimethylbenzene, ethylbenzene, trimethylbenzene, naphthalene,
Concentration in anthracene, Kun is less than 1 mg/m3Between；It is dense in sulfur dioxide, mercaptan, thioether, thiophene, methyl mercaptan, Dimethyl sulfide
Degree is less than 1 mg/m3Between.Logistics III into after compressor compresses, being sent to gas turbine power generation, device continuously run 3 months with
On, comprehensive purifying tower exit benzene, naphthalene, concentration of hydrogen sulfide are stablized, and gas compression pump does not occur plugging phenomenon, the tail gas of combustion engine yet
Sulfur dioxide concentration is less than 5mg/m in the logistics IV of discharge3。
【Embodiment 6】
The coke-stove gas that coke oven comes out slightly forms logistics I into benzene unit is slightly taken off after de- benzene, and logistics I enters thick desulfurization unit,
Logistics II is formed after thick desulfurization；Benzene concentration is in 1000~4000mg/m wherein in logistics II3Between, naphthalene concentration 200~
500mg/m3Between, concentration of hydrogen sulfide is in 100~500mg/m3Between, organic sulfur concentration 60mg/m3；Logistics II is comprehensive in entrance
Before closing purifying column, into moisture separator, the moisture in coke-stove gas is removed；Then logistics II enters comprehensive purifying tower, institute
The Y molecular sieve class adsorbent of ZSM-5 molecular sieve and zinc modification containing copper modification in the comprehensive purifying tower stated, molecular sieve silica alumina ratio
It for 150, while removes the aromatic hydrocarbons and sulfide in coal gas, forms logistics III, benzene concentration is less than 50mg/m in logistics III3, naphthalene
Concentration is less than 4 mg/m3Between, concentration of hydrogen sulfide is less than 4mg/m3；In toluene, dimethylbenzene, ethylbenzene, trimethylbenzene, naphthalene, anthracene, Kun
Concentration is less than 1 mg/m3Between；Concentration in sulfur dioxide, mercaptan, thioether, thiophene, methyl mercaptan, Dimethyl sulfide is less than 1
mg/m3Between.After logistics III enters compressor compresses, gas turbine power generation is sent to, device is continuously run 3 months or more, comprehensive
Purifying column exit benzene, naphthalene, concentration of hydrogen sulfide are stablized, and gas compression pump does not occur plugging phenomenon yet, the exhaust emissions of combustion engine
Sulfur dioxide concentration is less than 5mg/m in logistics IV3。
After described molecular sieve adsorbent absorption aromatic hydrocarbons saturation, 150 DEG C with regeneration 10 is small in coal gas when, regeneration is completed
Afterwards, reuse.
【Embodiment 7】
The coke-stove gas that coke oven comes out slightly forms logistics I into benzene unit is slightly taken off after de- benzene, and logistics I enters thick desulfurization unit,
Logistics II is formed after thick desulfurization；Wherein, the method that slightly de- benzene unit uses methanol solvate extraction, thick desulfurization unit use hydroxide
Calcium desulfurizing agent, benzene concentration is in 1000~4000mg/m in logistics II3Between, naphthalene concentration is in 200~500mg/m3Between, hydrogen sulfide
Concentration is in 100~500mg/m3Between；Logistics II, into moisture separator, removes coke-oven coal before comprehensive purifying tower is entered
Moisture in gas；Then logistics II enters comprehensive purifying tower, the ZSM-5 molecular sieve being modified in the comprehensive purifying tower containing copper
With the Y molecular sieve class adsorbent of zinc modification, molecular sieve silica alumina ratio is 150, while removes the aromatic hydrocarbons and sulfide in coal gas, shape
Into logistics III, benzene concentration is less than 50mg/m in logistics III3, naphthalene concentration is less than 4 mg/m3Between, concentration of hydrogen sulfide is less than 4mg/m3；
Concentration in toluene, dimethylbenzene, ethylbenzene, trimethylbenzene, naphthalene, anthracene, Kun is less than 1 mg/m3Between；Sulfur dioxide, mercaptan, thioether, thiophene
Concentration in fen, methyl mercaptan, Dimethyl sulfide is less than 1 mg/m3Between.After logistics III enters compressor compresses, combustion gas wheel is sent to
Machine generates electricity, and device is continuously run 3 months or more, and 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 logistics IV of the exhaust emissions of combustion engine yet3.The molecular sieve
Class adsorbent absorption aromatic hydrocarbons saturation after, 150 DEG C in coal gas regeneration 10 it is small when, after the completion of regeneration, reuse.
【Embodiment 8】
The coke-stove gas that coke oven comes out slightly forms logistics I into benzene unit is slightly taken off after de- benzene, and logistics I enters thick desulfurization unit,
Logistics II is formed after thick desulfurization；Wherein, the method that slightly de- benzene unit uses methanol solvate extraction, thick desulfurization unit use hydroxide
Calcium desulfurizing agent, benzene concentration is in 1000~4000mg/m in logistics II3Between, naphthalene concentration is in 200~500mg/m3Between, hydrogen sulfide
Concentration is in 100~500mg/m3Between；Logistics II, into moisture separator, removes coke-oven coal before comprehensive purifying tower is entered
Moisture in gas；Then logistics II enters comprehensive purifying tower, the ZSM-5 molecular sieve being modified in the comprehensive purifying tower containing copper
With the Y molecular sieve class adsorbent of zinc modification, molecular sieve silica alumina ratio is 150, while removes the aromatic hydrocarbons and sulfide in coal gas, shape
Into logistics III, benzene concentration is less than 50mg/m in logistics III3, naphthalene concentration is less than 4 mg/m3Between, concentration of hydrogen sulfide is less than 4mg/m3；
Concentration in toluene, dimethylbenzene, ethylbenzene, trimethylbenzene, naphthalene, anthracene, Kun is less than 1 mg/m3Between；Sulfur dioxide, mercaptan, thioether, thiophene
Concentration in fen, methyl mercaptan, Dimethyl sulfide is less than 1 mg/m3Between.After logistics III enters compressor compresses, combustion gas wheel is sent to
Machine generates electricity, and the tail gas of formation enters back into flue gas desulfuration and denitrification unit；Then it is vented.Device continuously operation 3 months or more, it is comprehensive net
Hua Ta exits benzene, naphthalene, concentration of hydrogen sulfide are stablized, and gas compression pump does not occur plugging phenomenon, the object of the exhaust emissions of combustion engine yet
Sulfur dioxide concentration is less than 5mg/m in stream IV3.After described molecular sieve adsorbent absorption aromatic hydrocarbons saturation, at 150 DEG C with coal gas
It is middle regeneration 10 it is small when, after the completion of regeneration, reuse.
【Embodiment 9】
The coke-stove gas that coke oven comes out slightly forms logistics I into benzene unit is slightly taken off after de- benzene, and logistics I enters thick desulfurization unit,
Logistics II is formed after thick desulfurization；Wherein, the method that slightly de- benzene unit uses methanol solvate extraction, thick desulfurization unit use hydroxide
Calcium desulfurizing agent, benzene concentration is in 1000~4000mg/m in logistics II3Between, naphthalene concentration is in 200~500mg/m3Between, hydrogen sulfide
Concentration is in 100~500mg/m3Between, organic sulfur concentration is in 70mg/m3；Logistics II is before comprehensive purifying tower is entered, into water
Gas separating device removes the moisture in coke-stove gas；Then logistics II enters comprehensive purifying tower, contains in the comprehensive purifying tower
The ZSM-5 molecular sieve and the Y molecular sieve class adsorbent of zinc modification that copper is modified, molecular sieve silica alumina ratio is 150, while removes coal gas
In aromatic hydrocarbons and sulfide, formed logistics III, in logistics III benzene concentration be less than 50mg/m3, naphthalene concentration is less than 4 mg/m3Between, sulphur
Change hydrogen concentration and be less than 4mg/m3；Concentration in toluene, dimethylbenzene, ethylbenzene, trimethylbenzene, naphthalene, anthracene, Kun is less than 1 mg/m3Between；Two
Concentration in sulfur oxide, mercaptan, thioether, thiophene, methyl mercaptan, Dimethyl sulfide is less than 1 mg/m3Between.Logistics III enters compression
After machine compression, gas turbine power generation is sent to, the tail gas of formation enters back into flue gas desulfuration and denitrification unit；Then it is vented.Device is 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 yet and shows
As sulfur dioxide concentration is less than 5mg/m in the logistics IV of the exhaust emissions of combustion engine3.The molecular sieve adsorbent absorption virtue
After hydrocarbon saturation, using purified coal gas 180 DEG C or more coal gas regenerate, regeneration 5 it is small when after, the absorption property of adsorbent is steady
Fixed, benzene concentration is less than 50mg/m in logistics III3, naphthalene concentration is less than 2mg/m3Between, concentration of hydrogen sulfide is less than 2mg/m3。
【Embodiment 12】
The coke-stove gas that coke oven comes out slightly forms logistics I into benzene unit is slightly taken off after de- benzene, and logistics I enters thick desulfurization unit,
Logistics II is formed after thick desulfurization；Wherein, the method that slightly de- benzene unit uses methanol solvate extraction, thick desulfurization unit use hydroxide
Calcium desulfurizing agent, benzene concentration is in 1000~4000mg/m in logistics II3Between, naphthalene concentration is in 200~500mg/m3Between, hydrogen sulfide
Concentration is in 100~500mg/m3Between；Logistics II, into moisture separator, removes coke-oven coal before comprehensive purifying tower is entered
Moisture in gas；Then logistics II enters comprehensive purifying tower, the ZSM-5 molecular sieve being modified in the comprehensive purifying tower containing copper
With the Y molecular sieve class adsorbent of zinc modification, molecular sieve silica alumina ratio is 150, while removes the aromatic hydrocarbons and sulfide in coal gas, shape
Into logistics III, benzene concentration is less than 50mg/m in logistics III3, naphthalene concentration is less than 4 mg/m3Between, concentration of hydrogen sulfide is less than 4mg/m3；
Concentration in toluene, dimethylbenzene, ethylbenzene, trimethylbenzene, naphthalene, anthracene, Kun is less than 1 mg/m3Between；Sulfur dioxide, mercaptan, thioether, thiophene
Concentration in fen, methyl mercaptan, Dimethyl sulfide is less than 1 mg/m3Between.After logistics III enters compressor compresses, combustion gas wheel is sent to
Machine generates electricity, and the tail gas of formation enters back into flue gas desulfuration and denitrification unit；Then it is vented.Device continuously operation 3 months or more, it is comprehensive net
Hua Ta exits benzene, naphthalene, concentration of hydrogen sulfide are stablized, and gas compression pump does not occur plugging phenomenon, the object of the exhaust emissions of combustion engine yet
Sulfur dioxide concentration is less than 5mg/m in stream IV3.After described molecular sieve adsorbent absorption aromatic hydrocarbons saturation, at 150 DEG C with coal gas
It is middle regeneration 10 it is small when, after the completion of regeneration, reuse.
Wherein, the tar in logistics III, cyanide, ammonia concentration are less than 1mg/m3.Device continuously operation 4 months or more,
Comprehensive purifying tower exit benzene, naphthalene, concentration of hydrogen sulfide are stablized, and gas compression pump does not occur plugging phenomenon, the tail gas row of combustion engine yet
Middle sulfur dioxide concentration is put less than 5mg/m3。
【Comparative example 1】
According to the method described in embodiment 1, simply using acticarbon, after running 3 hours, the sampling point of logistics III
Analysis, benzene concentration 1500mg/m3, naphthalene concentration is 200mg/m3, concentration of hydrogen sulfide 300mg/m3, organic sulfur concentration 100mg/
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. the removal methods of organic sulfur, comprise the following steps in a kind of coke-stove gas：
A. the coke-stove gas that coke oven comes out slightly forms logistics I into slightly de- benzene unit after de- benzene；
B. logistics I enters thick desulfurization unit, and logistics II is formed after thick desulfurization；
C. logistics II enters comprehensive purifying tower, and molecular sieve adsorbent is contained in the comprehensive purifying tower, while removes coal
Aromatic hydrocarbons and organic sulfur compound in gas form logistics III；
D. after logistics III enters compressor compresses, gas turbine combustion power generation is sent to, the flue gas after burning forms logistics IV；
E. logistics VI enters denitrating flue gas unit, removes the formation of the flue gas after nitrogen oxides logistics V and is vented.
2. the removal methods of organic sulfur in coke-stove gas according to claim 1, it is characterised in that the logistics II exists
Into before comprehensive purifying tower, into moisture separator, the moisture in coke-stove gas is removed；Slightly de- benzene unit uses solvent extraction
Method, thick desulfurization unit is using at least one of organic amine, lime stone, calcium hydroxide or iron oxide desulfurizing agent.
3. the removal methods of organic sulfur in coke-stove gas according to claim 2, it is characterised in that the aqueous vapor separation
Contain at least one of molecular sieve or activated carbon in device.
4. the removal methods of organic sulfur in coke-stove gas according to claim 2, it is characterised in that the aqueous vapor separation
Contain cooling coil in device, cool down to the coal gas of process.
5. the removal methods of organic sulfur in coke-stove gas according to claim 1, it is characterised in that logistics V enters back into tail
Desulfurization unit, after scrubbing CO_2, emptying.
6. the removal methods of organic sulfur in coke-stove gas according to claim 1, it is characterised in that the molecular sieve
Adsorbent is hydrophobic type adsorbent of molecular sieve；Contain the Ith A, II A, V in the periodic table of elements in the molecular sieve adsorbent
A, at least one of I B, II B, III B, IV B, V B, VI B, VII B or the VIIIth race's element element.
7. the removal methods of organic sulfur in coke-stove gas according to claim 5, it is characterised in that the period of element
The IIth element A is selected from least one of magnesium and calcium in table；Ith B races element is selected from least one of copper, silver；IIIth B races member
Element is selected from least one of lanthanum, cerium, yttrium；Molecular sieve is selected from X-type molecular sieve, Y type molecules in the molecular sieve adsorbent
Sieve, A type molecular sieve, ZSM types molecular sieve, modenite, beta molecular sieve, SAPO types molecular sieve, MCM-22, MCM-49, MCM-
56th, ZSM-5/ modenites, ZSM-5/ β zeolites, ZSM-5/Y, MCM-22/ modenite, ZSM-5/Magadiite, ZSM-5/ β
At least one of zeolite/modenite, ZSM-5/ β zeolites/Y zeolites or ZSM-5/Y zeolites/modenite.
8. the removal methods of organic sulfur in coke-stove gas according to claim 1, it is characterised in that the molecular sieve
ZSM types molecular sieve includes at least one of ZSM-5, ZSM-23, ZSM-11, ZSM-48 in adsorbent, wherein the molecular sieve
Silica alumina ratio be more than 100.
9. the removal methods of organic sulfur in coke-stove gas according to claim 1, it is characterised in that the molecular sieve
Adsorbent removes tar, cyanide, ammonia in coal gas simultaneously；Aromatic hydrocarbons described in step c is benzene,toluene,xylene, second
At least one of benzene, trimethylbenzene, naphthalene, anthracene, Kun；Organic sulfur compound is mercaptan, in thioether, thiophene, methyl mercaptan, Dimethyl sulfide
At least one.
10. the removal methods of organic sulfur in coke-stove gas according to claim 1, it is characterised in that the molecular sieve
After adsorbent adsorption saturation, in 100 DEG C or more of nitrogen or coal gas regenerate 3 it is small when more than, after the completion of regeneration, repetition make
With.
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Cited By (2)
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| CN109513347A (en) * | 2018-12-07 | 2019-03-26 | 山东洲蓝环保科技有限公司 | Pelletizing flue gas low-temperature desulfurization denitration method |
| CN115999335A (en) * | 2023-03-25 | 2023-04-25 | 河北冀隅智能科技有限公司 | Flue gas desulfurizing agent and preparation method thereof |
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