CN107903949A - A kind of coke oven gas desulfurization denitrogenation takes off the deep-purifying method of benzene hydrocarbon - Google Patents

A kind of coke oven gas desulfurization denitrogenation takes off the deep-purifying method of benzene hydrocarbon Download PDF

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CN107903949A
CN107903949A CN201711136521.XA CN201711136521A CN107903949A CN 107903949 A CN107903949 A CN 107903949A CN 201711136521 A CN201711136521 A CN 201711136521A CN 107903949 A CN107903949 A CN 107903949A
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coke
benzene
sulfur
tower
hydrogen
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CN107903949B (en
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秦志峰
靳永勇
苗茂谦
上官炬
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Taiyuan University of Technology
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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
    • 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
    • C10K1/002—Removal of contaminants
    • C10K1/003—Removal of contaminants of acid contaminants, e.g. acid gas removal
    • C10K1/005—Carbon dioxide
    • 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
    • C10K1/34—Purifying combustible gases containing carbon monoxide by catalytic conversion of impurities to more readily removable materials

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  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
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Abstract

The present invention relates to a kind of deep-purifying method of coke-oven coal qi exhaustion benzene hydrocarbon nitrogen and desulfurization, coke-stove gas is by coke-oven plant's tar removing, except naphthalene, desulfurization, except hydrogen cyanide, after deamination and the pretreatment of de- benzene process, pass through coarse-fine detar, naphthalene, benzene and thiophene, repeatedly absorb hydrogen sulfide, hydrogen cyanide, ammonia, benzene, naphthalene and thiophene reduce its concentration step by step, carbonyl sulfur and carbon disulfide absorb twice through hydrolysis twice, carbonyl sulfur, carbon disulfide and thiophene absorb twice through catalytic hydroconversion twice, finally pass through hyperfine de- benzene hydrocarbon, denitrogenation, it is de- that desulfurization reaches depth essence, finally obtain ultralow benzene hydrocarbon, sulphur, the coke-stove gas of nitrogen, through industrializing gas holder storage, used for industrial combustion gas and highly processed goods unstripped gas.

Description

A kind of coke oven gas desulfurization denitrogenation takes off the deep-purifying method of benzene hydrocarbon
Technical field
The present invention relates to the deep-purifying method that a kind of coke oven gas desulfurization denitrogenation takes off benzene hydrocarbon, belongs to coking of coal industry downstream Fuel gas purification techniques field.
Background technology
Coke-stove gas is a kind of byproduct of process of coking, contains multiple gases component in not purified coke-stove gas, Organic sulfur especially containing tar, naphthalene, hydrogen cyanide, hydrogen sulfide and various structures complexity etc., except effective in specific coke-stove gas Component H258~66%, CH421~25%, CO 5~8%, CmHn1.6~2.0%, CO21.9~2.3%, N22~6% Outside, also containing tar≤40mg/Nm3, naphthalene≤150mg/Nm3, benzene≤4000mg/Nm3, hydrogen cyanide≤50mg/Nm3, ammonia≤ 100mg/Nm3, hydrogen sulfide≤50mg/Nm3, carbonyl sulfur≤150mg/Nm3, carbon disulfide≤100mg/Nm3, thiophene≤50mg/Nm3 Deng impurity, these burn impurities can generate substantial amounts of nitrogen oxides, oxysulfide, unburnt dust and organic carbon hydrogenation Polymer particle, is directly discharged into air, causes the formation of the pollutants such as acid rain, haze, seriously pollutes environment, wastes money Source.For these impurity during coke-stove gas deep processing synthesizes ammonia, natural gas, methanol etc., impurity can cause catalyst poisoning, drop In the service life of low catalyst, catalyst change is frequent, increases the production cost of product while producing solid waste.
Coke oven gas purification method generally use plurality of impurities processing unit, is pre-processed, takes off naphthalene, de- benzene, takes off respectively The processes such as ammonia, desulfurization, purify coke-stove gas.At present, have some patent disclosures purification method of group technology, but Degree of purification is not high, and such as the patent of Application No. CN201110001580.2, the hydrogen sulfide after purification in coke-stove gas drops to 25ppm Hereinafter, Application No. CN201410470519.6《A kind of coke oven gas purification method》, hydrogen sulfide in coke oven after purification Content 17mg/m3, ammonia content 45mg/m3, hydrogen cyanide content 17mg/m3.And for example Application No. CN102061197A, CN102977932A, CN104789274A, CN103923706A etc., clean-up effect is general, and not to existing in coke-stove gas Vulcanisation hydrogen beyond carbonyl sulfur, carbon disulfide, thiophene etc. handled.It is and low by obtaining low benzene hydrocarbon after deep purifying The coke-stove gas of nitrogen low-sulfur, gas purity is good, quality is high, available for a variety of industrial fuel fields use and synthetic raw gas, Favourable condition is created for the sustainable development of enterprise while environmental protection, the present invention have found a kind of wide adaptation range, precision The method of the high de- purifying coke oven gas of depth essence, is the deep purifying of very good coke-oven coal qi exhaustion benzene hydrocarbon nitrogen and desulfurization Method.
The content of the invention
It is an object of the invention to provide the deep-purifying method that a kind of coke oven gas desulfurization denitrogenation takes off benzene hydrocarbon, coke oven For coal gas by coarse-fine detar, naphthalene, benzene and thiophene, repeatedly absorb hydrogen sulfide, hydrogen cyanide, ammonia, benzene, naphthalene and thiophene reduces it step by step Concentration, carbonyl sulfur and carbon disulfide through hydrolysis twice, absorb twice, and carbonyl sulfur, carbon disulfide and thiophene through being catalyzed twice Hydro-conversion, absorb twice, and finally reaching depth essence by hyperfine de- benzene hydrocarbon, denitrogenation, desulfurization takes off, and finally obtains ultralow benzene Race's hydrocarbon, sulphur, the coke-stove gas of nitrogen, the purification coal gas can produce directly through industrializing gas holder storage for industrial combustion gas and deep processing Product unstripped gas uses, to reduce pollution, environmental protection.
The present invention is achieved through the following technical solutions：
Thick detar and naphthalene：Tar removing, except naphthalene, desulfurization, except hydrogen cyanide, deamination and the de- pretreated coke-oven coal of benzene process The thick tar adsorption of gas active carbocoal and naphthalene, while remove a small amount of benzene and thiophene；
Smart detar and naphthalene：After the coke-stove gas supercharging after thick take off, through the first fine removing tower essence detar and naphthalene, take off at the same time Except a small amount of benzene and thiophene；
Thick depriving hydrogen sulphide, hydrogen cyanide, benzene and thiophene：To the coke-stove gas after smart detar and naphthalene, into the second fine removing tower Carry out thick depriving hydrogen sulphide, hydrogen cyanide, benzene and thiophene；
Carbonyl sulfur and carbon bisulfide hydrolytic essence are de-：To the coke-stove gas after thick depriving hydrogen sulphide, hydrogen cyanide, benzene and thiophene, warp After crossing a catalyzing hydrolysis carbonyl sulfur and carbon disulfide, the hydrogen sulfide after once hydrolyzing, then quadric catalysis hydrolyzing carbonyl sulfur are absorbed After carbon disulfide, the subtractive process of secondary hydrolysis after cure hydrogen is absorbed, reduces carbonyl sulfur and carbon disulfide in coke-stove gas Content；
Fine de-sulfur hydrogen, hydrogen cyanide, benzene and thiophene：The coke-stove gas after carbonyl sulfur and carbon disulfide is taken off to hydrolysis essence, into Enter the 3rd fine removing tower and carry out fine de-sulfur hydrogen, hydrogen cyanide, benzene and thiophene；
Organic sulfur hydrogenation essence is de-：To the coke-stove gas after fine de-sulfur hydrogen, hydrogen cyanide, benzene and thiophene, by being once hydrogenated with After catalyzed conversion, after stair oxidation zinc fine de-sulfur hydrogen, then after secondary hydrogenation catalyst conversion organic sulfur removal, secondary oxidation zinc essence Hydrogen sulfide removal process, smart removal of organic sulfur；
Hyperfine removing：Coke-stove gas after smart removal of organic sulfur enters super fine removing tower, and hyperfine removing changes work using metal Property carbon fiber filling, adsorb micro benzene hydrocarbon, nitrogen compound and sulfide, be finally reached the target of deep purifying coke-stove gas.
It is described it is thick de- after coke-stove gas enter before the first fine removing tower and be pressurized to 1-3MPa through twin compressor, the first essence is de- Activated carbon is loaded in tower, alkali modification activated carbon is loaded in the second fine removing tower and the 3rd fine removing tower, adsorption conditions are room temperature, pressure 1~3MPa, air speed 500h-1。
The carbonyl sulfur and the primary and secondary catalyzing hydrolysis of carbon disulfide are being filled with the one of titanium-based hydrolyst respectively Carried out in secondary and secondary hydrolysis tower, into the coke-stove gas before primary and secondary hydrolysis tower first through exchanging heat to 40~130 DEG C of temperature, 1000~1500h of air speed-1Under the conditions of, carbonyl sulfur and carbon bisulfide hydrolytic change into hydrogen sulfide, and conversion ratio is respectively greater than 90% He 80%.
Alkali modification activated carbon is loaded in 3rd fine removing tower, adsorption conditions are room temperature, 1~3MPa of pressure, air speed 500h-1。
The primary and secondary catalyzing hydrolysis after cure hydrogen removing carries out in primary and secondary hydrogen sulfide stripping tower respectively, Less than 40 DEG C are first cooled into the coke-stove gas before primary and secondary hydrogen sulfide stripping tower, alkali modification activated carbon is loaded in tower, Adsorption conditions are room temperature, 1~3MPa of pressure, air speed 500h-1。
Coke-stove gas after the carbonyl sulfur and carbon bisulfide hydrolytic essence are de-, enters after being heated to 250 DEG C and is once hydrogenated with Convert desulfurizing tower, titanium-based cobalt-molybdenum hydrogenation catalyst loaded in tower, reaction condition is 250~350 DEG C of temperature, 1~3MPa of pressure, 1000~2000h of air speed-1, carbonyl sulfur, carbon disulfide and thiophene be converted into hydrogen sulfide, conversion ratio is respectively greater than 85%, 95%, 30%.
Coke-stove gas after hydro-conversion enters stair oxidation zinc desulfurizing tower, and zinc oxide fine de-sulfur is loaded in tower Agent, adsorption conditions are 300~350 DEG C of temperature, 1~3MPa of pressure, 1000~1500h of air speed-1。
The secondary hydrogenation catalyst conversion of organic sulfur carries out in secondary hydro-conversion desulfurizing tower, into secondary hydro-conversion Coke-stove gas before desulfurizing tower will first be cooled to 320 DEG C, and titanium-based cobalt-molybdenum hydrogenation catalyst, reaction temperature 320-390 are loaded in tower DEG C, 1~3MPa of pressure, 1000~2000h of air speed-1, carbonyl sulfur, carbon disulfide and thiophene are converted into hydrogen sulfide, conversion ratio difference More than 90%, 98%, 80%.
The secondary oxidation zinc fine de-sulfur hydrogen process carries out in secondary oxidation zinc fine de-sulfur tower, and zinc oxide is loaded in tower Desulfurizing agent, 350-390 DEG C of reaction temperature, 1~3MPa of pressure, 1000~2000h of air speed-1。
The coke-stove gas after secondary oxidation zinc fine de-sulfur enters super fine removing tower, and superfinishing takes off changes activity using metal Carbon fiber, adsorbs micro benzene hydrocarbon, nitrogen compound and sulfide, outlet benzene hydrocarbon ＜ 0.1mg/Nm3, total nitrogen ＜ 0.1mg/Nm3With Total sulfur ＜ 0.02mg/Nm3。
Compared with prior art, the beneficial effects of the invention are as follows：
(1) process system desulfurization degree of the invention is high, of the invention into one in addition to removing the hydrogen sulfide in coke-stove gas Step absorbs the carbonyl sulfur in coke-stove gas and carbon disulfide through hydrolysis twice twice, carbonyl sulfur, carbon disulfide and thiophene Absorbed twice through catalytic hydroconversion twice, reduce the content of organic sulfur in coke-stove gas step by step, ensure that in coke-stove gas The abundant removing of sulphur.
(2) the every level-one basic activated carbon of the present invention complete hydrogen sulfide, hydrogen cyanide, ammonia, benzene, naphthalene all unadsorbed to previous stage Further absorbed with thiophene, by way of adsorbing layer by layer, reduce hydrogen sulfide in coke oven, hydrogen cyanide, ammonia, benzene, naphthalene step by step With the concentration of thiophene, reach the target of deep purifying.
(3) present invention has further carried out hyperfine removing, changes activated carbon fiber absorption using metal, final to obtain The coke-stove gas of the low benzene hydrocarbon of the low nitrogen of low-sulfur, draws wherein benzene hydrocarbon ＜ 0.1mg/Nm after testing3, total nitrogen ＜ 0.1mg/Nm3With it is total Sulphur ＜ 0.02mg/Nm3, clean-up effect is excellent.
(4) coke-stove gas of the present invention first carries out thick depriving hydrogen sulphide, cyaniding before carbonyl sulfur and carbon bisulfide hydrolytic is carried out Hydrogen, benzene and thiophene process, blocking of the influence and benzene that reduction hydrogen sulfide balances hydrolysis to hydrolyst duct, ensure The progress of purification in next step.Coke-stove gas of the present invention first carries out fine de-sulfur hydrogen, hydrogen cyanide, benzene before hydrodesulfurization tower is entered And thiophene, reduce the carbon distribution of the influence that is balanced to hydrogenation reaction of hydrogen sulfide and benzene to hydrogenation catalyst.
The coke-stove gas that the present invention finally obtains, ammonia, natural gas, first are used and synthesize available for a variety of industrial combustion gas fields The process such as alcohol unstripped gas uses, and the deep-purifying method of this coke-stove gas reduces pollution, protects environment, this purification method Advanced, step is rationally, the auxiliary material safety and stability that uses is reliable, the gas purity after deep purifying is good, quality is high, is very Preferable coke oven gas desulfurization denitrogenation takes off the deep-purifying method of benzene hydrocarbon.
Brief description of the drawings
Fig. 1 is the deep-purifying method process flow chart that coke oven gas desulfurization denitrogenation of the present invention takes off benzene hydrocarbon
Embodiment
Below in conjunction with attached drawing, technical scheme is described further.But protection scope of the present invention is not Be limited to these embodiments, every change or equivalent substitute without prejudice to present inventive concept be included in protection scope of the present invention it It is interior.
Coke-stove gas will carry out in purification process in strict accordance with technological process, additive, cooling agent, the catalyst used To be used in strict accordance with dosage is calculated, purify thick the removing impurities matter tar and naphthalene tower that use, compressor, smart removing impurities matter tar and naphthalene Tower, thick de-hydrogen sulfide column, primary and secondary hydrolysis tower, primary and secondary hydrogen sulfide stripping tower, primary and secondary hydro-conversion take off The equipment such as sulphur tower, zinc oxide desulfurization tower, super fine removing tower will run well, and parameter selection is reasonable, to ensure the continuous of building-up process Property, accuracy, so that purified coal gas obtains quality assurance.
The chemical substance material that the present embodiment uses is：Coke-stove gas, active carbocoal, activated carbon, alkali modification activated carbon, titanium Base hydrolyst, titanium-based iron-molybdenum hydrogenation catalyst, titanium-based cobalt-molybdenum hydrogenation catalyst, zinc oxide fine desulfurizer, metal change work Property carbon fiber, clean water.
Purification method is as follows：
(1) the rough detar of coke-oven coal and naphthalene
Tar removing, except naphthalene, desulfurization, except hydrogen cyanide, deamination and the de- pretreated coke-stove gas of benzene process, with 25000m3/ The speed of h enters rough removing tower, and active carbocoal 100m is loaded in tower3, room temperature, pressure 30KPa, air speed 250h-1Under the conditions of, tar, Naphthalene, benzene and thiophene are tightly held by activated carbon, and export tar≤5mg/Nm in coke-stove gas3, naphthalene≤10mg/Nm3, benzene≤1000mg/ Nm3With thiophene≤35mg/Nm3；
(2) coke-stove gas is pressurized
Coke-stove gas after the thick removing impurities matter tower of the producer gas that discharges of the coke is pressurized to 1~3MPa through reciprocating compressor, and it is de- to be sent to essence Impurity tar and naphthalene tower；
(3) detar of coke-stove gas essence and naphthalene
Coke-stove gas after compression, into the first fine removing tower, activated carbon 50m is loaded in tower3, room temperature, pressure 1MPa, air speed 500h-1Under the conditions of, tar, naphthalene, benzene and thiophene are tightly held by activated carbon, and export tar≤0.1mg/Nm in coke-stove gas3, naphthalene≤ 1mg/Nm3, benzene≤100mg/Nm3With thiophene≤10mg/Nm3；
(4) the rough depriving hydrogen sulphide of coke-oven coal, hydrogen cyanide, benzene and thiophene
Coke-stove gas is after the first fine removing tower essence is de-, and into the second fine removing tower, alkali modification activated carbon 50m is loaded in tower3, Room temperature, pressure 1MPa, air speed 500h-1Under the conditions of, hydrogen sulfide, hydrogen cyanide and ammonia by alkali modification activated carbon adsorption, while naphthalene, benzene and Thiophene is by alkali modification activated carbon adsorption, outlet hydrogen sulfide in coke oven≤1mg/Nm3, hydrogen cyanide≤2mg/Nm3, ammonia≤20mg/ Nm3, naphthalene≤0.1mg/Nm3, benzene≤10mg/Nm3With thiophene≤2mg/Nm3；
(5) catalyzing hydrolysis of carbonyl sulfur and carbon disulfide in coke-stove gas
Coke-stove gas is after the second fine removing tower essence is de-, through heat exchange to 130 DEG C of temperature, into filling 35000kg titanium-based water Solve a hydrolysis tower of catalyst, 1000~1500h of air speed-1Under the conditions of, carbonyl sulfur and carbon bisulfide hydrolytic change into hydrogen sulfide, Conversion ratio is respectively greater than 90% and 80%, exports hydrogen sulfide in coke oven≤150mg/Nm3, carbonyl sulfur≤15mg/Nm3With two Nitric sulfid≤20mg/Nm3；
(6) coke-stove gas carbonyl sulfur and carbon disulfide once hydrolyze the removing of after cure hydrogen
Coke-stove gas is cooled to less than 40 DEG C after once hydrolyzing, and into a hydrogen sulfide stripping tower, alkali is loaded in tower Modified activated carbon 50m3, room temperature, pressure 3MPa, air speed 500h-1Under the conditions of, hydrogen sulfide is by alkali modification activated carbon adsorption, while cyanogen Change hydrogen, ammonia, benzene and thiophene to continue, by alkali modification activated carbon adsorption, to export hydrogen sulfide in coke oven≤5mg/Nm3, hydrogen cyanide≤ 0.5mg/Nm3, ammonia≤5mg/Nm3, benzene≤2mg/Nm3With thiophene≤1mg/Nm3；
(7) carbonyl sulfur and the hydrolysis of carbon disulfide quadric catalysis in coke-stove gas
The coke-stove gas come out from a hydrogen sulfide stripping tower, through exchanging heat to 130 DEG C of temperature, into secondary hydrolysis tower, titanium Base hydrolyst loads 35000kg, 1000~1500h of air speed-1Under the conditions of, CS2With COS hydrolysis into hydrogen sulfide, convert Rate is respectively greater than 90% and 80%, exports hydrogen sulfide in coke oven≤20mg/Nm3, carbonyl sulfur≤2mg/Nm3And carbon disulfide ≤5mg/Nm3；
(8) coke-stove gas carbonyl sulfur and the secondary hydrolysis after cure hydrogen removing of carbon disulfide
Coke-stove gas is cooled to less than 40 DEG C after secondary hydrolysis, and into post-cure hydrogen removing tower, alkali is loaded in tower Modified activated carbon 50m3, room temperature, pressure 3MPa, air speed 500h-1Under the conditions of, hydrogen sulfide is by alkali modification activated carbon adsorption, while cyanogen Change hydrogen, ammonia, benzene and thiophene further by alkali modification activated carbon adsorption, export hydrogen sulfide in coke oven≤1mg/Nm3, hydrogen cyanide ≤0.05mg/Nm3, tar≤0.01mg/Nm3, naphthalene≤0.01mg/Nm3, benzene≤0.5mg/Nm3, ammonia≤0.05mg/Nm3And thiophene ≤0.5mg/Nm3；
(9) coke-stove gas fine de-sulfur hydrogen, hydrogen cyanide, benzene and thiophene
Coke-stove gas is after by carbonyl sulfur and carbon disulfide, hydrolysis absorbs twice twice, into the 3rd fine removing tower, tower Middle filling alkali modification activated carbon 50m3, room temperature, pressure 1MPa, air speed 500h-1Under the conditions of, hydrogen sulfide, hydrogen cyanide and ammonia are changed by alkali Property activated carbon adsorption, while naphthalene, benzene and thiophene export hydrogen sulfide in coke oven≤0.1mg/ by alkali modification activated carbon adsorption Nm3, hydrogen cyanide≤0.1mg/Nm3, ammonia≤0.1mg/Nm3, benzene≤0.1mg/Nm3With thiophene≤0.08mg/Nm3；
(10) hydrogenation catalyst conversion of organic sulfur in coke-stove gas
Coke-stove gas after the 3rd fine removing tower fine de-sulfur hydrogen, hydrogen cyanide, benzene and thiophene, after being heated to 250 DEG C, Into hydro-conversion desulfurizing tower of coke-stove gas, titanium-based iron-molybdenum hydrogenation catalyst 25000kg, reaction temperature 280~ 330 DEG C, pressure 3MPa, 1000~2000h of air speed-1Under the conditions of, carbonyl sulfur, carbon disulfide and thiophene are converted into hydrogen sulfide, conversion Rate is respectively greater than 80%, 90%, 20%, exports hydrogen sulfide≤10mg/Nm3, carbonyl sulfur≤0.6mg/Nm3, carbon disulfide≤ 0.5mg/Nm3With thiophene ＜ 0.07mg/Nm3；
(11) stair oxidation zinc fine de-sulfur hydrogen
After hydro-conversion of coke-stove gas, stair oxidation zinc desulfurizing tower is directly entered, loads zinc oxide fine desulfurizer 50000kg, in 350 DEG C of reaction temperature, pressure 3MPa, 1000~1500h of air speed-1Under the conditions of, hydrogen sulfide is gone out by oxidation zinc-iron alloy solution Mouth hydrogen sulfide≤0.1mg/Nm3；
(12) the secondary hydrogenation catalyst conversion of organic sulfur in coke-stove gas
Coke-stove gas after stair oxidation zinc desulfurizing tower desulfurization, it is secondary into coke-stove gas after cooling the temperature to 340 DEG C Hydro-conversion desulfurizing tower, titanium-based cobalt-molybdenum hydrogenation catalyst 25000kg, in 350~390 DEG C of reaction temperature, 1~3MPa of pressure, sky 1000~2000h of speed-1Under the conditions of, carbonyl sulfur, carbon disulfide and thiophene are converted into hydrogen sulfide, conversion ratio is respectively greater than 90%, 95%th, 85%, export hydrogen sulfide≤1mg/Nm3, carbonyl sulfur≤0.02mg/Nm3, carbon disulfide≤0.005mg/Nm3, thiophene ＜ 0.01mg/Nm3；
(13) secondary oxidation zinc fine de-sulfur hydrogen
Coke-stove gas is directly entered secondary oxidation zinc fine de-sulfur tower, zinc oxide fine desulfurizer after quadric catalysis is hydrogenated with 25000kg is loaded, in 330~360 DEG C of reaction temperature, pressure 1MPa, 1500~2000h of air speed-1Under the conditions of, hydrogen sulfide, carbonyl Sulphur, carbon disulfide are by oxidation zinc-iron alloy solution, outlet hydrogen sulfide≤0.01mg/Nm3, carbonyl sulfur≤0.018mg/Nm3, carbon disulfide≤ 0.005mg/Nm3, thiophene ＜ 0.01mg/Nm3, total sulfur≤0.045mg/Nm3；
(14) hyperfine removing
Coke-stove gas after organic sulfur three times hydrogenation catalyst conversion enters super fine removing tower, and superfinishing is taken off using filling 20m3 Metal changes activated carbon fiber, in 250~300 DEG C of reaction temperature, 1~3MPa of pressure, 1000~1500h of air speed-1Under the conditions of, absorption Micro benzene hydrocarbon, nitrogen compound and sulfide, outlet benzene hydrocarbon ＜ 0.01mg/Nm3, total nitrogen ＜ 0.01mg/Nm3With total sulfur ＜ 0.02mg/Nm3, it is finally reached the target of deep purifying coke-stove gas.
The above is the preferred embodiment of the present invention, and technical scheme is described further, but this hair Bright protection domain is not limited to these embodiments.Every change or equivalent substitute without prejudice to present inventive concept is included in this Within the protection domain of invention.

Claims (9)

1. a kind of coke oven gas desulfurization denitrogenation takes off the deep-purifying method of benzene hydrocarbon, it is characterised in that is carried out including next coming in order The step of：
Thick detar and naphthalene：Tar removing, use except naphthalene, desulfurization, except hydrogen cyanide, deamination and the pretreated coke-stove gas of de- benzene process The thick tar adsorption of active carbocoal and naphthalene, while remove a small amount of benzene and thiophene；
Smart detar and naphthalene：After the coke-stove gas supercharging after thick take off, through the first fine removing tower essence detar and naphthalene, while remove few Measure benzene and thiophene；
Thick depriving hydrogen sulphide, hydrogen cyanide, benzene and thiophene：To the coke-stove gas after smart detar and naphthalene, carried out into the second fine removing tower Thick depriving hydrogen sulphide, hydrogen cyanide, benzene and thiophene；
Carbonyl sulfur and carbon bisulfide hydrolytic essence are de-：To the coke-stove gas after thick depriving hydrogen sulphide, hydrogen cyanide, benzene and thiophene, by one After secondary catalyzing hydrolysis carbonyl sulfur and carbon disulfide, the hydrogen sulfide after once hydrolyzing, then quadric catalysis hydrolyzing carbonyl sulfur and two are absorbed After nitric sulfid, the subtractive process of secondary hydrolysis after cure hydrogen is absorbed, reduces carbonyl sulfur and carbon disulfide containing in coke-stove gas Amount；
Fine de-sulfur hydrogen, hydrogen cyanide, benzene and thiophene：To the coke-stove gas after the de- carbonyl sulfur of hydrolysis essence and carbon disulfide, into the Three fine removing towers carry out fine de-sulfur hydrogen, hydrogen cyanide, benzene and thiophene；
Organic sulfur hydrogenation essence is de-：To the coke-stove gas after fine de-sulfur hydrogen, hydrogen cyanide, benzene and thiophene, by a hydrogenation catalyst After conversion, after stair oxidation zinc fine de-sulfur hydrogen, then after secondary hydrogenation catalyst conversion organic sulfur removal, secondary oxidation zinc fine de-sulfur Change hydrogen process, smart removal of organic sulfur；
Hyperfine removing：Coke-stove gas after smart removal of organic sulfur enters super fine removing tower, and hyperfine removing changes activated carbon using metal Fiber loads, and adsorbs micro benzene hydrocarbon, nitrogen compound and sulfide, is finally reached the target of deep purifying coke-stove gas.
2. a kind of coke oven gas desulfurization denitrogenation according to claim 1 takes off the deep-purifying method of benzene hydrocarbon, its feature exists 1-3MPa is pressurized to before the coke-stove gas after thick take off enters the first fine removing tower, activated carbon, the second essence are loaded in the first fine removing tower Alkali modification activated carbon is loaded in de- tower and the 3rd fine removing tower, adsorption conditions are room temperature, 1~3MPa of pressure, air speed 500h-1。
3. a kind of coke oven gas desulfurization denitrogenation according to claim 1 takes off the deep-purifying method of benzene hydrocarbon, its feature exists In carbonyl sulfur and the primary and secondary catalyzing hydrolysis of carbon disulfide are being filled with the primary and secondary water of titanium-based hydrolyst respectively Xie Tazhong is carried out, into the coke-stove gas before primary and secondary hydrolysis tower first through heat exchange to 40~130 DEG C of temperature, air speed 1000~ 1500h-1Under the conditions of, carbonyl sulfur and carbon bisulfide hydrolytic change into hydrogen sulfide, and conversion ratio is respectively greater than 90% and 80%.
4. a kind of coke oven gas desulfurization denitrogenation according to claim 1 takes off the deep-purifying method of benzene hydrocarbon, its feature exists In primary and secondary catalyzing hydrolysis after cure hydrogen removing carries out in primary and secondary hydrogen sulfide stripping tower respectively, into once Less than 40 DEG C are first cooled to the coke-stove gas before post-cure hydrogen removing tower, alkali modification activated carbon, adsorption conditions are loaded in tower For room temperature, 1~3MPa of pressure, air speed 500h-1。
5. a kind of coke oven gas desulfurization denitrogenation according to claim 1 takes off the deep-purifying method of benzene hydrocarbon, its feature exists Coke-stove gas after carbonyl sulfur and carbon bisulfide hydrolytic essence are de-, enters a hydro-conversion desulfurizing tower after being heated to 250 DEG C, In tower load titanium-based cobalt-molybdenum hydrogenation catalyst, reaction condition for 250~350 DEG C of temperature, 1~3MPa of pressure, air speed 1000~ 2000h-1, carbonyl sulfur, carbon disulfide and thiophene be converted into hydrogen sulfide, and conversion ratio is respectively greater than 85%, 95%, 30%.
6. a kind of coke oven gas desulfurization denitrogenation according to claim 1 takes off the deep-purifying method of benzene hydrocarbon, its feature exists Coke-stove gas after a hydro-conversion enters stair oxidation zinc desulfurizing tower, and zinc oxide fine desulfurizer, adsorption bar are loaded in tower Part is 300~350 DEG C of temperature, 1~3MPa of pressure, 1000~1500h of air speed-1。
7. a kind of coke oven gas desulfurization denitrogenation according to claim 1 takes off the deep-purifying method of benzene hydrocarbon, its feature exists In the secondary hydrogenation catalyst conversion of organic sulfur carries out in secondary hydro-conversion desulfurizing tower, into before secondary hydro-conversion desulfurizing tower Coke-stove gas to be first cooled to 310-330 DEG C, load titanium-based cobalt-molybdenum hydrogenation catalyst in tower, 320-390 DEG C of reaction temperature, 1~3MPa of pressure, 1000~2000h of air speed-1, carbonyl sulfur, carbon disulfide and thiophene be converted into hydrogen sulfide, and conversion ratio is respectively greater than 90%th, 98%, 80%.
8. a kind of coke oven gas desulfurization denitrogenation according to claim 1 takes off the deep-purifying method of benzene hydrocarbon, its feature exists Carried out in secondary oxidation zinc fine de-sulfur hydrogen process in secondary oxidation zinc fine de-sulfur tower, zinc oxide fine desulfurizer loaded in tower, 350-390 DEG C of reaction temperature, 1~3MPa of pressure, 1000~2000h of air speed-1。
9. a kind of coke oven gas desulfurization denitrogenation according to claim 1 takes off the deep-purifying method of benzene hydrocarbon, its feature exists Enter super fine removing tower in the coke-stove gas after secondary oxidation zinc fine de-sulfur, hyperfine removing changes activated carbon fibre using metal Dimension, adsorbs micro benzene hydrocarbon, nitrogen compound and sulfide, outlet benzene hydrocarbon ＜ 0.1mg/Nm3, total nitrogen ＜ 0.1mg/Nm3And total sulfur ＜ 0.02mg/Nm3。
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