CN107236576A - Coke oven gas purification method for fuel engine power generation - Google Patents
Coke oven gas purification method for fuel engine power generation Download PDFInfo
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- CN107236576A CN107236576A CN201710590192.XA CN201710590192A CN107236576A CN 107236576 A CN107236576 A CN 107236576A CN 201710590192 A CN201710590192 A CN 201710590192A CN 107236576 A CN107236576 A CN 107236576A
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- logistics
- coke
- molecular sieve
- gas
- benzene
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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
-
- 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
-
- 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
-
- 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
Abstract
The present invention relates to a kind of purification method of the coke-stove gas for fuel engine power generation, mainly solve sulfide in coke oven gas purification in the prior art, tar, benzene and naphthalene removing unclean, cause the technical problem that compressor cooling pipe is easily blocked, Combustion engine tail gas sulfur dioxide (SO2) emissions are exceeded.The present invention is by using comprising the following steps：A. the coke-stove gas that coke oven comes out enters slightly de- benzene unit, slightly forms logistics I after de- benzene；B. logistics I enters thick desulfurization unit, and logistics II is formed after thick desulfurization；C. logistics II enters in comprehensive purifying tower, described comprehensive purifying tower and contains molecular sieve adsorbent, while the aromatic hydrocarbons and sulfide in coal gas are fallen in removing, forms logistics III；E. logistics III enters after compressor compresses, is sent to the tail gas after gas turbine combustion generating, gas turbine combustion, forms logistics IV, the technical scheme that logistics IV is vented preferably solves the problem, in the industrial production generated electricity available for coke-stove gas.
Description
Technical field
The present invention relates to a kind of purification method of the coke-stove gas for fuel engine power generation, particularly Jiao for fuel engine power generation
The purification method of producer gas.
Background technology
Coke-stove gas be mainly coke-oven plant's by-product containing hydro carbons, methane, hydrogen high heat energy fuel gas, generally as
Fuel gas generation is used.Because the thermal efficiency of fuel engine power generation is higher than steam turbine, the coke-stove gas of general coke-oven plant generates electricity from combustion
Machine generates electricity.But purity requirement of the fuel engine power generation to coal gas is higher, benzene,toluene,xylene in coke-stove gas, naphthalene, Jiao are removed
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, in order to prevent nitride exceeded, in addition it is also necessary to remove the ammonia in coke-stove gas.So before gas-fired generates electricity,
Need to be purified, aromatic hydrocarbons, tar, sulfide, ammonia carried in removing 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, with activated carbon removes benzene therein again, is then fed into fuel engine power generation, but abjection 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
Separate out and arranged outside tar liquid, being cooled to -30~-50 DEG C into liquefied ammonia recovery tower separates out row outside liquid ammonia, by Methanol Wash Column
Imurity-removal, clean coke-stove gas enters clean coal gas tank.The device of coke oven gas purification includes primary cooler, dehydrating tower, tar and reclaimed
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 is connected, 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 are returned
Receiving unit is connected.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
Coke-stove gas in method, gas turbine power generation coke-stove gas comprehensive purification system, 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 on the first appendix come out from desulphurization system；It is comprehensive using coal gas
The purification method of cleaning system is closed, is comprised 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 filtered, obtained
Meet the coal gas of combustion engine requirement.Present system sets four groups of dry desulfurizing towers on the basis of crude benzol purified treatment, newly, with the present invention
One it 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.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, by 120 DEG C dry 2~4 hours, 280~350 DEG C roasting 4~6 hours after i.e. make
Obtain the multifunctional purifying agent.The Multifunctional raw gas purifying agent is used for water-gas, semiwater gas, coke-stove gas or IGCC generating combustions
COS, CS are purified in gas unstripped gas2、HCN、SO2、SO3And O2Deng 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.
Prior art does not purify the report of coal gas using molecular sieve adsorbent, does not more disclose and uses molecular sieve adsorption
Agent, while removing the report of sulfide and aromatic hydrocarbons, gas purifying method of the present invention, completely removing sulfide and aromatic hydrocarbons are directed to
Solving for property presently, there are the sordid technical problem of gas purification.
The content of the invention
The technical problems to be solved by the invention are mainly to solve sulphur in coke oven gas purification in the prior art in the prior art
Compound, tar, benzene and naphthalene removing be not clean, causes compressor cooling pipe easily to block, titanium dioxide in the Combustion engine tail gas after generating
The exceeded technical problem of sulphur emissions, the present invention provides a kind of new coke oven gas purification method.This method is used to use coke-oven coal
In the production that gas generates electricity, gas purification is clean, and sulphur emissions are low, the stable advantage of TRT.
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, bag
Include following steps：
A. the coke-stove gas that coke oven comes out enters slightly de- benzene unit, slightly forms logistics I after de- benzene；
B. logistics I enters thick desulfurization unit, and logistics II is formed after thick desulfurization；
C. logistics II enters in comprehensive purifying tower, described comprehensive purifying tower and contains molecular sieve adsorbent, while coal is fallen in removing
Aromatic hydrocarbons and sulfide in gas, form logistics III；
E. logistics III enters after compressor compresses, is sent to the tail gas after gas turbine combustion generating, gas turbine combustion, is formed
Logistics IV, logistics IV is vented.
In above-mentioned technical proposal, preferred technical scheme is described logistics I before comprehensive purifying tower is entered, into water
Moisture in gas separating device, removing coke-stove gas.
In above-mentioned technical proposal, technical scheme preferably enters tail gas desulfurization and denitration unit for described logistics IV, takes off
After sulfur dioxide and nitride, emptying.
In above-mentioned technical proposal, technical scheme preferably is that described molecular sieve adsorbent is hydrophobic type molecular sieve adsorption
Agent.
In above-mentioned technical proposal, preferred technical scheme is to contain in the periodic table of elements in described molecular sieve adsorbent
At least one of 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 element.
In above-mentioned technical proposal, technical scheme preferably is selected from magnesium and calcium for the IIth element A in the described 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, technical scheme preferably is divided for molecular sieve in described molecular sieve adsorbent selected from X-type
Sub- 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/ modenite, ZSM-5/
In Magadiite, ZSM-5/ β zeolites/modenite, ZSM-5/ β zeolites/Y zeolites or ZSM-5/Y zeolites/modenite extremely
Few one kind.
In above-mentioned technical proposal, technical scheme preferably includes for ZSM type molecular sieves in described molecular sieve adsorbent
At least one of ZSM-5, ZSM-23, ZSM-11, ZSM-48.
In above-mentioned technical proposal, technical scheme preferably is more than 100 for the silica alumina ratio of the molecular sieve.
In above-mentioned technical proposal, technical scheme preferably is Jiao in described molecular sieve adsorbent simultaneously removing coal gas
Oil, cyanide, ammonia.
In above-mentioned technical proposal, technical scheme preferably is that described 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, technical scheme preferably is that described molecular sieve adsorbent is regenerable sorbent.
In above-mentioned technical proposal, after preferred technical scheme is described molecular sieve adsorbent adsorption saturation, at 100 DEG C
Regenerate more than 3 hours, after the completion of regeneration, reuse in nitrogen above or coal gas.
In above-mentioned technical proposal, technical scheme preferably uses solvent-extracted method, thick desulfurization list for slightly de- benzene unit
Member uses limestone desulfurizer.
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 with activated carbon take off naphthalene；Benzene is taken off with activated carbon using debenzolizing tower again；3 are used altogether
Absorbing unit, purifies coal gas successively.In plant running, 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.Using the method for the present invention, have the following advantages that：（1）Using point
Sub- sieve adsorbant, can thoroughly remove benzene, naphthalene and hydrogen sulfide, organic sulfur totally, the problem of solving line clogging.（2）Will
Adsorbent carries out multifunction, can be while desulfurization, de- benzene, de- naphthalene, in an adsorption tower, comprehensive purifying mistake can be carried out simultaneously
Journey, so reduces the quantity of adsorption tower, reduces production cost.
Using technical scheme：The coke-stove gas that coke oven comes out enters slightly de- benzene unit, slightly enters after de- benzene
Contain molecular sieve adsorbent in comprehensive purifying tower, purifying column, while the aromatic hydrocarbons and sulfide in coal gas are fallen in removing, enter back into pressure
After the compression of contracting machine, gas turbine power generation is sent to.De- naphthalene tower exit hydrogen sulfide content is less than 4mg/m3, naphthalene content is less than 4
mg/m3, tar content is 0, and the organic sulfur carried in gas is also removed, in combustion engine flue gas sulfur dioxide (SO2) emissions in below 7mg,
Plant running is stable, achieves preferable technique effect.
Accompanying drawing content
The coke oven gas purification schematic flow sheet of the present invention that Fig. 1 is.
In Fig. 1,1 is the coke-stove gas of coke oven, and 2 be logistics I, i.e., the coke-stove gas after thick 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.
Embodiment
【Embodiment 1】
As shown in Figure 1, the coke-stove gas that coke oven comes out enters slightly de- benzene unit, slightly forms logistics I after de- benzene, logistics I is entered
Enter thick desulfurization unit, logistics II is formed after thick desulfurization；Logistics II enters to contain in comprehensive purifying tower, described comprehensive purifying tower and divided
Son sieve class adsorbent, while the aromatic hydrocarbons and sulfide in coal gas are fallen in removing, forms logistics III；Logistics III enters compressor compresses
Afterwards, the tail gas after gas turbine combustion generating, gas turbine combustion is sent to, logistics IV is formed, 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；Logistics II enters in comprehensive purifying tower, described comprehensive purifying tower and contains ZSM molecules
Class adsorbent is sieved, while the aromatic hydrocarbons and sulfide in coal gas are fallen in removing, logistics III is formed, benzene concentration is less than 50mg/ in logistics III
m3, naphthalene concentration is less than 4 mg/m3Between, concentration of hydrogen sulfide is less than 4mg/m3；Logistics III enters after compressor compresses, is sent to combustion gas
Turbine is generated electricity, and device is continuously run more than 3 months, and comprehensive purifying tower exit benzene, naphthalene, concentration of hydrogen sulfide are stable, gas compression
Machine does not occur sulfur dioxide concentration in the logistics IV in plugging phenomenon, the exhaust emissions of combustion engine yet and is less than 5mg/m3。
【Embodiment 2】
The coke-stove gas that coke oven comes out enters slightly de- benzene unit, slightly forms logistics I after de- benzene, 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；Logistics II enters comprehensive purifying tower, described comprehensive purifying
Contain mordenite molecular sieve class adsorbent in tower, while the aromatic hydrocarbons and sulfide in coal gas are fallen in removing, form logistics III, logistics
Benzene concentration is less than 50mg/m in III3, naphthalene concentration is less than 4 mg/m3Between, concentration of hydrogen sulfide is less than 4mg/m3；Logistics III enters pressure
After the compression of contracting machine, gas turbine power generation is sent to, device is continuously run more than 3 months, comprehensive purifying tower exit benzene, naphthalene, vulcanization
Hydrogen concentration is stable, and gas compression pump does not occur plugging phenomenon yet, and sulfur dioxide concentration is small in the logistics IV of the exhaust emissions of combustion engine
In 5mg/m3。
【Embodiment 3】
The coke-stove gas that coke oven comes out enters slightly de- benzene unit, slightly forms logistics I after de- benzene, 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；Logistics II enters comprehensive purifying tower, described comprehensive purifying
Contain Y zeolite molecular sieve class adsorbents in tower, while the aromatic hydrocarbons and sulfide in coal gas are fallen in removing, form logistics III, logistics III
Middle benzene concentration is less than 50mg/m3, naphthalene concentration is less than 4 mg/m3Between, concentration of hydrogen sulfide is less than 4mg/m3；Toluene, dimethylbenzene, second
Concentration in benzene, trimethylbenzene, naphthalene, anthracene, Kun is less than 1 mg/m3Between；Sulfur dioxide, mercaptan, thioether, thiophene, methyl mercaptan, first
Concentration in base thioether is less than 1 mg/m3Between.Logistics III enters after compressor compresses, is sent to gas turbine power generation, and device connects
Reforwarding row more than 3 months, comprehensive purifying tower exit benzene, naphthalene, concentration of hydrogen sulfide are stable, and gas compression pump does not occur plugging yet and showed
As 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 enters slightly de- benzene unit, slightly forms logistics I after de- benzene, 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；Logistics II enters comprehensive purifying tower, described comprehensive purifying
Contain rare earth modified Y molecular sieve class adsorbent in tower, while the aromatic hydrocarbons and sulfide in coal gas are fallen in removing, form 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；Toluene, diformazan
Concentration in benzene, ethylbenzene, trimethylbenzene, naphthalene, anthracene, Kun is less than 1 mg/m3Between；Sulfur dioxide, mercaptan, thioether, thiophene, methyl sulphur
Concentration in alcohol, Dimethyl sulfide is less than 1 mg/m3Between.Logistics III enters after compressor compresses, is sent to gas turbine power generation, fills
Continuous operation more than 3 months is put, comprehensive purifying tower exit benzene, naphthalene, concentration of hydrogen sulfide are stable, gas compression pump is not also blocked up
Pipe phenomenon, sulfur dioxide concentration is less than 5mg/m in the logistics IV of the exhaust emissions of combustion engine3。
【Embodiment 5】
The coke-stove gas that coke oven comes out enters slightly de- benzene unit, slightly forms logistics I after de- benzene, 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；Logistics II is before comprehensive purifying tower is entered, into aqueous vapor
Moisture in separator, removing coke-stove gas.Then logistics II enters in comprehensive purifying tower, described comprehensive purifying tower and contains zinc
Modified ZSM-5 molecular sieve class adsorbent, molecular sieve silica alumina ratio is 200, while the aromatic hydrocarbons and sulfide in coal gas, shape are fallen in removing
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.Logistics III enters after compressor compresses, is sent to combustion gas wheel
Machine is generated electricity, and device is continuously run more than 3 months, and comprehensive purifying tower exit benzene, naphthalene, concentration of hydrogen sulfide are stable, 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。
【Embodiment 6】
The coke-stove gas that coke oven comes out enters slightly de- benzene unit, slightly forms logistics I after de- benzene, 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；Logistics II is before comprehensive purifying tower is entered, into aqueous vapor
Moisture in separator, removing coke-stove gas；Then logistics II enters in comprehensive purifying tower, described comprehensive purifying tower and contains copper
Modified ZSM-5 molecular sieve and the Y molecular sieve class adsorbent of zinc modification, molecular sieve silica alumina ratio are 150, while removing is fallen in coal gas
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, vulcanization
Hydrogen concentration is less than 4mg/m3；Concentration in toluene, dimethylbenzene, ethylbenzene, trimethylbenzene, naphthalene, anthracene, Kun is less than 1 mg/m3Between；Dioxy
The concentration changed in sulphur, mercaptan, thioether, thiophene, methyl mercaptan, Dimethyl sulfide is less than 1 mg/m3Between.Logistics III enters compressor
After compression, gas turbine power generation is sent to, device is continuously run more than 3 months, comprehensive purifying tower exit benzene, naphthalene, hydrogen sulfide are dense
Degree is stable, and gas compression pump does not occur plugging phenomenon yet, and sulfur dioxide concentration is less than in the logistics IV of the exhaust emissions of combustion engine
5mg/m3。
After described molecular sieve adsorbent absorption aromatic hydrocarbons saturation, regenerated 10 hours with coal gas at 150 DEG C, regeneration is completed
Afterwards, reuse.
【Embodiment 7】
The coke-stove gas that coke oven comes out enters slightly de- benzene unit, slightly forms logistics I after de- benzene, logistics I enters thick desulfurization unit,
Logistics II is formed after thick desulfurization；Wherein, thick de- benzene unit uses the method that methanol solvate is extracted, and thick desulfurization unit uses 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 is before comprehensive purifying tower is entered, into moisture separator, removes coke-oven coal
Moisture in gas；Then logistics II enters the ZSM-5 molecular sieve being modified in comprehensive purifying tower, described comprehensive purifying tower containing copper
With the Y molecular sieve class adsorbent of zinc modification, molecular sieve silica alumina ratio is 150, while the aromatic hydrocarbons and sulfide in coal gas, shape are fallen in removing
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.Logistics III enters after compressor compresses, is sent to combustion gas wheel
Machine is generated electricity, and device is continuously run more than 3 months, and comprehensive purifying tower exit benzene, naphthalene, concentration of hydrogen sulfide are stable, 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.Described molecular sieve
After class adsorbent absorption aromatic hydrocarbons saturation, regenerated 10 hours, after the completion of regeneration, reused with coal gas at 150 DEG C.
【Embodiment 8】
The coke-stove gas that coke oven comes out enters slightly de- benzene unit, slightly forms logistics I after de- benzene, logistics I enters thick desulfurization unit,
Logistics II is formed after thick desulfurization；Wherein, thick de- benzene unit uses the method that methanol solvate is extracted, and thick desulfurization unit uses 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 is before comprehensive purifying tower is entered, into moisture separator, removes coke-oven coal
Moisture in gas；Then logistics II enters the ZSM-5 molecular sieve being modified in comprehensive purifying tower, described comprehensive purifying tower containing copper
With the Y molecular sieve class adsorbent of zinc modification, molecular sieve silica alumina ratio is 150, while the aromatic hydrocarbons and sulfide in coal gas, shape are fallen in removing
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.Logistics III enters after compressor compresses, is sent to combustion gas wheel
Machine generates electricity, and the tail gas of formation enters back into flue gas desulfuration and denitrification unit；Then it is vented.Device is continuously run more than 3 months, comprehensive net
Hua Ta exits benzene, naphthalene, concentration of hydrogen sulfide are stable, and gas compression pump does not occur plugging phenomenon, the thing 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
Middle regeneration 10 hours, after the completion of regeneration, is reused.
【Embodiment 9】
The coke-stove gas that coke oven comes out enters slightly de- benzene unit, slightly forms logistics I after de- benzene, logistics I enters thick desulfurization unit,
Logistics II is formed after thick desulfurization；Wherein, thick de- benzene unit uses the method that methanol solvate is extracted, and thick desulfurization unit uses 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 is before comprehensive purifying tower is entered, into moisture separator, removes coke-oven coal
Moisture in gas；Then logistics II enters the ZSM-5 molecular sieve being modified in comprehensive purifying tower, described comprehensive purifying tower containing copper
With the Y molecular sieve class adsorbent of zinc modification, molecular sieve silica alumina ratio is 150, while the aromatic hydrocarbons and sulfide in coal gas, shape are fallen in removing
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.Logistics III enters after compressor compresses, is sent to combustion gas wheel
Machine generates electricity, and the tail gas of formation enters back into flue gas desulfuration and denitrification unit；Then it is vented.Device is continuously run more than 3 months, comprehensive net
Hua Ta exits benzene, naphthalene, concentration of hydrogen sulfide are stable, and gas compression pump does not occur plugging phenomenon, the thing 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, after purification
Coal gas regeneration of the coal gas more than 180 DEG C, after regenerating 5 hours, the absorption property of adsorbent is stable, and benzene concentration is less than in logistics III
50mg/m3, 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 enters slightly de- benzene unit, slightly forms logistics I after de- benzene, logistics I enters thick desulfurization unit,
Logistics II is formed after thick desulfurization；Wherein, thick de- benzene unit uses the method that methanol solvate is extracted, and thick desulfurization unit uses 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 is before comprehensive purifying tower is entered, into moisture separator, removes coke-oven coal
Moisture in gas；Then logistics II enters the ZSM-5 molecular sieve being modified in comprehensive purifying tower, described comprehensive purifying tower containing copper
With the Y molecular sieve class adsorbent of zinc modification, molecular sieve silica alumina ratio is 150, while the aromatic hydrocarbons and sulfide in coal gas, shape are fallen in removing
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.Logistics III enters after compressor compresses, is sent to combustion gas wheel
Machine generates electricity, and the tail gas of formation enters back into flue gas desulfuration and denitrification unit；Then it is vented.Device is continuously run more than 3 months, comprehensive net
Hua Ta exits benzene, naphthalene, concentration of hydrogen sulfide are stable, and gas compression pump does not occur plugging phenomenon, the thing 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
Middle regeneration 10 hours, after the completion of regeneration, is reused.
Wherein, in logistics III tar, cyanide, ammonia concentration is less than 1mg/m3.Device is continuously run more than 4 months,
Comprehensive purifying tower exit benzene, naphthalene, concentration of hydrogen sulfide are stable, 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 10 hours of operation, the sampling point of logistics III
Analysis, benzene concentration is in 1500mg/m3, naphthalene concentration is in 200mg/m3, concentration of hydrogen sulfide is in 300mg/m3。
Obviously, supplemented using the adsorbent of the present invention, 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
The coal gas demonstrate,proved after purification is clean, it is ensured that the normal operation of electricity generation system.
Claims (10)
1. a kind of purification method of coke-stove gas, comprises the following steps：
A. the coke-stove gas that coke oven comes out enters slightly de- benzene unit, slightly forms logistics I after de- benzene；
B. logistics I enters thick desulfurization unit, and logistics II is formed after thick desulfurization；
C. logistics II enters in comprehensive purifying tower, described comprehensive purifying tower and contains molecular sieve adsorbent, while coal is fallen in removing
Aromatic hydrocarbons and sulfide in gas, form logistics III；
E. logistics III enters after compressor compresses, is sent to the tail gas after gas turbine combustion generating, gas turbine combustion, is formed
Logistics IV, logistics IV is vented.
2. the purification method of coke-stove gas according to claim 1, it is characterised in that described logistics II is entering synthesis
Before purifying column, into moisture separator, the moisture in coke-stove gas is removed.
3. the purification method of coke-stove gas according to claim 1, it is characterised in that logistics IV enters tail gas desulfurization and de-
After nitre unit, scrubbing CO_2 and nitride, emptying.
4. the purification method of coke-stove gas according to claim 1, it is characterised in that described molecular sieve adsorbent is
Hydrophobic type adsorbent of molecular sieve；In described molecular sieve adsorbent contain the periodic table of elements in the Ith A, 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.
5. the purification method of coke-stove gas according to claim 4, it is characterised in that the IIth A in the described 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 purification method of coke-stove gas according to claim 1, it is characterised in that in described molecular sieve adsorbent
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 types
Molecular sieve, MCM-22, MCM-49, MCM-56, ZSM-5/ modenite, ZSM-5/ β zeolites, the boiling of ZSM-5/Y, MCM-22/ mercerising
Stone, ZSM-5/Magadiite, ZSM-5/ β zeolites/modenite, ZSM-5/ β zeolites/Y zeolites or ZSM-5/Y zeolites/mercerising boiling
At least one of stone.
7. the purification method of coke-stove gas according to claim 1, it is characterised in that in described molecular sieve adsorbent
ZSM types molecular sieve includes at least one of ZSM-5, ZSM-23, ZSM-11, ZSM-48, wherein the sial of the molecular sieve rubs
You are than being more than 100.
8. the purification method of coke-stove gas according to claim 1, it is characterised in that described molecular sieve adsorbent is same
When removing coal gas in tar, cyanide, ammonia；Aromatic hydrocarbons described in step c is benzene,toluene,xylene, ethylbenzene, trimethylbenzene,
At least one of naphthalene, anthracene, Kun；Sulfide is hydrogen sulfide, sulfur dioxide, mercaptan, thioether, thiophene, methyl mercaptan, Dimethyl sulfide
At least one of.
9. the purification method of coke-stove gas according to claim 1, it is characterised in that described molecular sieve adsorbent is inhaled
After attached saturation, regenerate more than 3 hours, after the completion of regeneration, reuse in the nitrogen or coal gas more than 100 DEG C.
10. the purification method of coke-stove gas according to claim 1, it is characterised in that slightly de- benzene unit uses solvent extraction
Method, thick desulfurization unit uses limestone desulfurizer.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109453649A (en) * | 2018-12-07 | 2019-03-12 | 铜陵泰富特种材料有限公司 | Boiler smoke low-temp desulfurization method of denitration |
| CN109813797A (en) * | 2019-04-13 | 2019-05-28 | 中国烟草总公司郑州烟草研究院 | The rapid detection method of sulphur compound in a kind of cigarette mainstream flue gas |
| CN109813797B (en) * | 2019-04-13 | 2021-07-06 | 中国烟草总公司郑州烟草研究院 | Rapid detection method for sulfur compounds in cigarette mainstream smoke |
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