Desulfurization purifier and its application method for coke-stove gas
Technical field
The present invention relates to the chemical cleaning method fields for the sulphur compound component for removing known structure, specially a kind of to be used for coke oven
The desulfurization purifier and its application method of coal gas.
Background technology
The purposes of coke-stove gas produces the products such as methanol, coke oven typically as fuel gas or as industrial chemicals
Contain H in coal gas2S, the objectionable impurities such as HCN need to remove objectionable impurities before use, such as directly use unprocessed
Coke-stove gas, SO can be generated after burning2、SO3、NOXEtc. atmosphere pollutions influence air matter with being discharged in air outside flue gas
Amount, it is serious to form acid rain, plant growth is affected, building is endangered, impairs health.Coke oven when smelting iron and steel
Output and usage amount are all very big, and with the increasingly raising of environmental consciousness and environmental requirement, to sulfur content in coke-stove gas
Requirement it is increasingly strict, it would be desirable to slough the element sulphur in coke-stove gas as thoroughly as possible, smelting quality can not only be improved,
It can reduce environmental pollution, moreover it is possible to produce industrial widely used sulfuric acid using byproduct, therefore, there are many sulfur removal technologies at present
Applied to coke-stove gas, such as HPF methods, this method is using the ammonia in coke-stove gas as alkali source, using by hydroquinone, bicyclic phthalein cyanogen
Buy the quinone ferro-cobalt class composite catalyst that six ichthyodins and ferrous sulfate etc. are separately formed containing a small amount of co-catalyst, have it is with good investment,
Good, the stable advantage of desulfurization effect, still, the waste liquid of generation have very strong corrosivity and toxicity, are also easy to produce new dirt
Dye source, and sulfur content is not high in byproduct, and which limits the uses of sulfur removal technology.
Invention content
In order to overcome the deficiencies of existing technologies, provide a kind of desulfuration efficiency is high, investment is low, stable, operation flexibly, it is raw
Sulphur compound separation equipment at low cost, that effect on environment is small is produced, the invention discloses a kind of desulfurization for coke-stove gas is net
Makeup is set and its application method.
The present invention reaches goal of the invention by following technical solution:
The top of a kind of desulfurization purifier for coke-stove gas, including desulfurizing tower and spray head, desulfurizing tower is equipped with coke
Producer gas exports, and the both sides of desulfurizing tower lower part are respectively equipped with coke-stove gas entrance and mother liquor outlet, and the top inside desulfurizing tower is set
There are spray head, spray head to spray mother liquor downwards, it is characterized in that:Further include regenerator, gas wash tower, cooling tower, deentrainment tower, drying
Tower, converter, absorption tower, discharge tower, dehydration slot, pre- heat channel, mother liquid tank, heat exchanger, incinerator, waste heat boiler, liquid pump and
Air pump,
Regenerator is set to the side of desulfurizing tower, and the both sides on regenerator top are respectively equipped with mother liquor primary outlet and mother liquor pair goes out
Mouthful, the lower part of regenerator is equipped with air intake and mother liquor entrance, and the mother liquor sub-outlet of regenerator is dehydrated the mother of slot by being in series with
Liquid pipe is connected with the spray head of desulfurizing tower inner upper, the mother liquor outlet of desulfurizing tower lower part by be in series with liquid pump mother liquor pipe and
The mother liquor entrance on regenerator top connects, and the air outlet slit of air pump connects the air intake of regenerator lower part by appendix;
Pre- heat channel is set to the other side of regenerator, and the upper and lower part of pre- heat channel is respectively equipped with mother liquor entrance and mother liquor goes out
Mouthful, it is equipped with heat exchanger in pre- heat channel, the mother liquor entrance that the mother liquor primary outlet on regenerator top passes through mother liquor pipe and pre- heat channel top
Connection, heat exchanger input high-temperature steam to pre- heat channel, high-temperature steam and mother liquor occur high-temperature steam after heat exchange be cooled into it is cold
Simultaneously pre- heat channel is discharged through heat exchanger in condensate;
Mother liquid tank is set to the other side of pre- heat channel, and the upper and lower part of mother liquid tank is respectively equipped with mother liquor entrance and mother liquor
Outlet, the mother liquor outlet of pre- heat channel lower part are connected by being in series with the mother liquor pipe of liquid pump with the mother liquor entrance on mother liquid tank top;
Incinerator is set to the other side of mother liquid tank, and one end of incinerator is equipped with air intake and mother liquor entrance, incinerator
The other end be equipped with offgas outlet, the mother liquor outlet of mother liquid tank lower part is by being in series with mother liquor pipe and incinerator one end of liquid pump
The connection of mother liquor entrance, the air outlet slit of air pump passes through the air intake that appendix connects incinerator one end;
Waste heat boiler is set to the top of incinerator, and the steam pipe of waste heat boiler is coiled in outside the furnace wall of incinerator;
Gas wash tower, cooling tower, deentrainment tower, drying tower, converter, absorption tower and discharge tower are sequentially arranged in the another of incinerator
Side;The upper and lower part of gas wash tower is respectively equipped with gas inlet and offgas outlet;Cooling tower, deentrainment tower, drying tower, converter,
The lower part and top of absorption tower and discharge tower are all respectively equipped with gas inlet and offgas outlet;The offgas outlet of the incinerator other end
The gas inlet on gas wash tower top is connected by offgas duct, the tail gas of the offgas outlet connection cooling tower lower part of gas wash tower lower part enters
Mouthful;The offgas outlet on cooling tower top connects the gas inlet of deentrainment tower lower part by offgas duct, and the tail gas on deentrainment tower top goes out
The gas inlet of mouth connection drying tower lower part;The offgas outlet on drying tower top connects the tail gas of converter lower part by offgas duct
Entrance, the gas inlet of the offgas outlet connection absorption tower lower part on converter top;The offgas outlet on absorption tower top passes through tail
The gas inlet of tracheae connection discharge tower lower part, the exhaust port for discharging tower are set up.
The desulfurization purifier for coke-stove gas, it is characterized in that:Converter is set there are two gas inlet and two
A offgas outlet, absorption tower have two, and the offgas outlet on drying tower top is entered by the first tail gas of offgas duct connection converter
Mouthful, the first offgas outlet of converter connects the gas inlet of the first absorption tower lower part, the offgas outlet on the first absorption tower top
The second gas inlet of converter is connected by offgas duct, the second offgas outlet connection second absorption tower lower part of converter
Gas inlet, the offgas outlet on second absorption tower top connect the gas inlet of discharge tower lower part by offgas duct.
The application method of the desulfurization purifier for coke-stove gas, including catalytic desulfurization and burning, feature
It is:Further include oxidation regeneration, catalysis oxidation and absorption, carries out successively as follows:
Catalytic desulfurization:Coke-stove gas is cooled to after 25 DEG C~35 DEG C the input desulfurization of the coke-stove gas entrance through desulfurizing tower lower part
In tower, coke-stove gas is spread from bottom to top in desulfurizing tower, and the spray head out of desulfurizing tower is sprayed downwardly out mother liquor, coke-stove gas
After mother liquor counter current contacting, the H in coke-stove gas2S, oxidized under the catalysis of catalyst of the impurity such as HCN in mother liquor-reduction
Reaction be converted into S,WithAnd be dissolved in mother liquor, catalyst selects bicyclic phthalein cyanogen to buy the alkali metal salt of sulfonic acid, wherein
Reaction equation related with S elements is:2H2S+O2=2H2O+2S ↓, the H after catalytic desulfurization in coke-stove gas2S contents
Less than 200mg/m3[mark], HCN contents are less than 300mg/m3[mark], coke-oven coal of the subsequent coke-stove gas through desulfurizing tower (11) top
Gas outlet output;
Oxidation regeneration:Dissolved the mother liquor of impurity under the driving of liquid pump from the mother liquor outlet of desulfurizing tower lower part through regenerator
In the mother liquor entrance input regenerator of lower part, while air intake of the compressed air through regenerator lower part is inputted regenerator by air pump
It is interior, it is regenerated under oxygen-enriched atmosphere of the catalyst in regenerator in mother liquor, catalyst and fraction mother liquor are from regenerator
The mother liquor sub-outlet in portion inputs the spray head of desulfurizing tower inner upper through being dehydrated slot;
Burning:The mother liquor entrance input preheating on the preheated slot top of mother liquor primary outlet on most of mother liquor from regenerator top
In slot, heat exchanger inputs high-temperature steam to pre- heat channel, and heat exchange occurs for high-temperature steam and mother liquor, and high-temperature steam is cooled into condensation
Simultaneously pre- heat channel is discharged through heat exchanger in water, and mother liquor is preheated and from the mother liquor outlet of pre- heat channel lower part through the mother liquor on mother liquid tank top
Entrance inputs in mother liquid tank,
Mother liquor is inlet fogging through the mother liquor of incinerator one end from the mother liquor outlet of mother liquid tank lower part under the driving of liquid pump
It sprays into incinerator, while air pump, by air intake input incinerator of the compressed air through incinerator one end, mother liquor is burning
It burns under oxygen-enriched atmosphere in stove, the S in mother liquor is oxidized to SO2, neutralizing the related reaction equation of S elements is:S+O2=
SO2, mother liquor, which becomes, contains SO2Tail gas, waste heat boiler absorption mother liquor burning release heat simultaneously generate high-temperature steam;
Catalysis oxidation:Contain SO2Tail gas from the offgas outlet of the incinerator other end output after, removed successively through gas wash tower
Dust is cooled to 100 DEG C or less through cooling tower, removes fog through deentrainment tower, and the tail gas dustiness exported from deentrainment tower is less than
0.002g/m3[mark], water content are less than 0.03g/m3[mark], arsenic content are less than 0.001g/m3[mark], tail gas is heated through drying tower
It is dry to be inputted in converter to 420 DEG C, then from the gas inlet of converter lower part, the SO in tail gas2Under the effect of the catalyst
By O2It is oxidized to SO3, catalyst selection vanadic anhydride, neutralizing the related reaction equation of S elements is:2SO2+O2=
2SO3。SO2It is converted to SO3Ratio be not less than 99.5%;
It absorbs:Contain SO3Tail gas input and inhale from the gas inlet of the offgas outlet on converter top through absorption tower lower part
It receives in tower, SO3H is become by water or sulfuric acid absorption2SO4, neutralizing the related reaction equation of S elements is:SO3+H2O=H2SO4,
H2SO4It send to product slot, remaining tail gas inputs discharge from the offgas outlet on absorption tower top through discharging the gas inlet of tower lower part
Tower, tail gas are washed to up to standard with ammonia process and are discharged to air outside afterwards, and extra waste liquid containing ammonia salt can be sent to sulphur ammonium saturator or relieving haperacidity system
System.
The application method of the desulfurization purifier for coke-stove gas, it is characterized in that:
When absorption, contain SO3Tail gas from the gas inlet input of the first offgas outlet of converter through the first absorption tower
In first absorption tower, SO3H is become by water or sulfuric acid absorption2SO4, H2SO4It send to product slot, remaining tail gas is from the first absorption tower
Second gas inlet of the inverted tower of offgas outlet on top inputs in converter again, the SO in tail gas2In the work of catalyst
With lower by O2It is oxidized to SO3, contain SO3Tail gas enter from tail gas of second offgas outlet through second absorption tower of converter (17)
In mouth input second absorption tower, SO3H is become by water or sulfuric acid absorption2SO4, H2SO4It send to product slot, remaining tail gas is from second
The offgas outlet on absorption tower top discharges tower through discharging the gas inlet input of tower lower part, and tail gas is washed with ammonia process to up to standard rear outer
It is discharged to air, extra waste liquid containing ammonia salt can be sent to sulphur ammonium saturator or acid making system.
The beneficial effects of the invention are as follows:Desulfurization effect is good, and desulfurization waste liquor amount is low disposable, and stable operation is flexible, and saving is set
Standby investment, reduces operating cost.
Description of the drawings
Fig. 1 is the structural schematic diagram of the present invention;
Fig. 2 is the structural schematic diagram using the present invention on two absorption towers.
Specific implementation mode
It is further illustrated the present invention below by way of specific embodiment.
Embodiment 1
A kind of desulfurization purifier for coke-stove gas, including desulfurizing tower 11, spray head 2, regenerator 12, gas wash tower
13, cooling tower 14, deentrainment tower 15, drying tower 16, converter 17, absorption tower 18, discharge tower 19, dehydration slot 31, pre- heat channel 32, mother
Liquid storage tank 33, heat exchanger 41, incinerator 42, waste heat boiler 43, liquid pump 51 and air pump 52, as shown in Figure 1, concrete structure is:
The top of desulfurizing tower 11 is exported equipped with coke-stove gas, and the both sides of 11 lower part of desulfurizing tower are respectively equipped with coke-stove gas entrance
And mother liquor outlet, the top inside desulfurizing tower 11 are equipped with spray head 2, the sprinkling mother liquor downwards of spray head 2;
Regenerator 12 is set to the side of desulfurizing tower 11, and the both sides on 12 top of regenerator are respectively equipped with mother liquor primary outlet and mother
The lower part of liquid sub-outlet, regenerator 12 is equipped with air intake and mother liquor entrance, and the mother liquor sub-outlet of regenerator 12 is by being in series with
The spray head 2 for being dehydrated 11 inner upper of mother liquor pipe and desulfurizing tower of slot 31 connects, and the mother liquor outlet of 11 lower part of desulfurizing tower passes through string
The mother liquor pipe for being associated with liquid pump 51 is connected with the mother liquor entrance on 12 top of regenerator, and the air outlet slit of air pump 52 is connected by appendix
The air intake of 12 lower part of regenerator;
Pre- heat channel 32 is set to the other side of regenerator 12, and the upper and lower part of pre- heat channel 32 is respectively equipped with mother liquor entrance and mother
Liquid exports, and heat exchanger 41 is equipped in pre- heat channel 32, and the mother liquor primary outlet on 12 top of regenerator passes through on mother liquor pipe and pre- heat channel 32
The mother liquor entrance in portion connects, and heat exchanger 41 inputs high-temperature steam to pre- heat channel 32, and height after heat exchange occurs for high-temperature steam and mother liquor
Warm steam is cooled into condensed water and pre- heat channel 32 is discharged through heat exchanger 41:
Mother liquid tank 33 is set to the other side of pre- heat channel 32, and the upper and lower part of mother liquid tank 33 is respectively equipped with mother liquor entrance
And mother liquor outlet, the mother liquor outlet of 32 lower part of pre- heat channel is by being in series with the mother on 33 top of mother liquor pipe and mother liquid tank of liquid pump 51
Liquid entrance connects;
Incinerator 42 is set to the other side of mother liquid tank 33, and one end of incinerator 42 is equipped with air intake and mother liquor entrance,
The other end of incinerator 42 is equipped with offgas outlet, and the mother liquor outlet of 33 lower part of mother liquid tank is by being in series with the mother liquor pipe of liquid pump 51
It is connected with the mother liquor entrance of 42 one end of incinerator, the air outlet slit of air pump 52 connects the air of 42 one end of incinerator by appendix
Entrance;
Waste heat boiler 43 is set to the top of incinerator 42, and the steam pipe of waste heat boiler 43 is coiled in the furnace wall of incinerator 42
Outside;
Gas wash tower 13, cooling tower 14, deentrainment tower 15, drying tower 16, converter 17, absorption tower 18 and discharge tower 19 are set successively
In the other side of incinerator 42;The upper and lower part of gas wash tower 13 is respectively equipped with gas inlet and offgas outlet;Cooling tower 14 removes
Mist tower 15, drying tower 16, converter 17, absorption tower 18 and discharge tower 19 lower part and top be all respectively equipped with gas inlet and tail
Gas exports;The offgas outlet of 42 other end of incinerator connects the gas inlet on 13 top of gas wash tower, gas wash tower 13 by offgas duct
The gas inlet of 14 lower part of offgas outlet connection cooling tower of lower part;The offgas outlet on 14 top of cooling tower is connected by offgas duct
The gas inlet of 15 lower part of deentrainment tower, the gas inlet of 16 lower part of offgas outlet connection drying tower on 15 top of deentrainment tower;It is dry
The offgas outlet on 16 top of tower connects the gas inlet of 17 lower part of converter, the offgas outlet on 17 top of converter by offgas duct
Connect the gas inlet of 18 lower part of absorption tower;The offgas outlet on 18 top of absorption tower connects 19 lower part of discharge tower by offgas duct
The exhaust port of gas inlet, discharge tower 19 is set up.
The present embodiment by a. catalytic desulfurizations, b. oxidation regenerations, c. burnings, d. catalysis oxidations and e. in use, absorb this 5
Step carries out successively:
A. catalytic desulfurization:Coke-stove gas is cooled to after 25 DEG C~35 DEG C the input of the coke-stove gas entrance through 11 lower part of desulfurizing tower
In desulfurizing tower 11, as shown in fig. 1A, coke-stove gas is spread from bottom to top in desulfurizing tower 11, the spray out of desulfurizing tower 11
First 2 are sprayed downwardly out mother liquor, after coke-stove gas and mother liquor counter current contacting, the H in coke-stove gas2S, the impurity such as HCN are in mother liquor
Catalyst catalysis under oxidized-reduction reaction be converted into S,WithAnd be dissolved in mother liquor, catalyst is selected double
Ring phthalein cyanogen buys the alkali metal salt of sulfonic acid, such as bicyclic phthalein cyanogen buys sodium sulfonate, bicyclic phthalein cyanogen buys potassium sulfonate, burnt after catalytic desulfurization
H in producer gas2S contents are less than 200mg/m3[mark], HCN contents are less than 300mg/m3[mark], subsequent coke-stove gas is through desulfurizing tower
The coke-stove gas outlet output on 11 tops, as shown in fig. ib;
B. oxidation regeneration:The mother liquor for having dissolved impurity passes through under the driving of liquid pump 51 from the mother liquor outlet of 11 lower part of desulfurizing tower
In the mother liquor entrance input regenerator 12 of 12 lower part of regenerator, while air pump 52 is by air of the compressed air through 12 lower part of regenerator
Entrance inputs in regenerator 12, is regenerated under oxygen-enriched atmosphere of the catalyst in regenerator 12 in mother liquor, catalyst and small
Partial mother liquid inputs the spray head 2 of 11 inner upper of desulfurizing tower from the mother liquor sub-outlet on 12 top of regenerator through being dehydrated slot 31;
C. it burns:The mother liquor entrance on preheated 32 top of slot of mother liquor primary outlet on most of mother liquor from 12 top of regenerator is defeated
Enter in pre- heat channel 32, heat exchanger 41 inputs high-temperature steam to pre- heat channel 32, and heat exchange, high-temperature steam occur for high-temperature steam and mother liquor
It is cooled into condensed water and pre- heat channel 32 is discharged through heat exchanger 41, mother liquor is preheated and is passed through from the mother liquor outlet of 32 lower part of pre- heat channel
In the mother liquor entrance input mother liquid tank 33 on 33 top of mother liquid tank,
Mother liquor enters under the driving of liquid pump 51 from mother liquor of the mother liquor outlet of 33 lower part of mother liquid tank through 42 one end of incinerator
Mouth atomization sprays into incinerator 42, while air intake of the compressed air through 42 one end of incinerator is inputted incinerator 42 by air pump 52
Interior, mother liquor burns under the oxygen-enriched atmosphere in incinerator 42, and the S in mother liquor is oxidized to SO2, mother liquor, which becomes, contains SO2Tail
Gas, the heat of 43 absorption mother liquor of waste heat boiler burning releasing simultaneously generate high-temperature steam;
D. catalysis oxidation:Contain SO2Tail gas from the offgas outlet of 42 other end of incinerator output after, successively through gas wash tower
13 are cooled to 100 DEG C or less except dust, through cooling tower 14, remove fog through deentrainment tower 15, the tail gas exported from deentrainment tower 15
Dustiness is less than 0.002g/m3[mark], water content are less than 0.03g/m3[mark], arsenic content are less than 0.001g/m3[mark], tail gas warp
16 heat drying of drying tower is inputted to 420 DEG C, then from the gas inlet of 17 lower part of converter in converter 17, the SO in tail gas2
Under the effect of the catalyst by O2It is oxidized to SO3, catalyst selection vanadic anhydride, SO2It is converted to SO3Ratio be not less than
99.5%;
E. it absorbs:Contain SO3Tail gas from the gas inlet of the offgas outlet through 18 lower part of absorption tower on 17 top of converter
It inputs in absorption tower 18, SO3H is become by water or sulfuric acid absorption2SO4, H2SO4It send to product slot, remaining tail gas is from absorption tower 18
The offgas outlet on top discharges tower 19 through discharging the gas inlet input of 19 lower part of tower, and tail gas is washed with ammonia process to rear outer row up to standard
To air, extra waste liquid containing ammonia salt can be sent to sulphur ammonium saturator or acid making system.
Embodiment 2
A kind of desulfurization purifier for coke-stove gas, including desulfurizing tower 11, spray head 2, regenerator 12, gas wash tower
13, cooling tower 14, deentrainment tower 15, drying tower 16, converter 17, absorption tower 18, discharge tower 19, dehydration slot 31, pre- heat channel 32, mother
Liquid storage tank 33, heat exchanger 41, incinerator 42, waste heat boiler 43, liquid pump 51 and air pump 52, as shown in Fig. 2, concrete structure is:Turn
Change tower 17 to set there are two gas inlet and two offgas outlets, absorption tower 18 there are two, and the offgas outlet on 16 top of drying tower is logical
The first gas inlet of offgas duct connection converter 17 is crossed, the first offgas outlet of converter 17 connects 18 lower part of the first absorption tower
Gas inlet, the offgas outlet on 18 top of the first absorption tower connected the second gas inlet of converter 17 by offgas duct, turned
Change the gas inlet of 18 lower part of the second offgas outlet connection second absorption tower of tower 17, the offgas outlet on 18 top of second absorption tower
The gas inlet of 19 lower part of discharge tower is connected by offgas duct.Other structures are all same with embodiment 1.
The present embodiment by a. catalytic desulfurizations, b. oxidation regenerations, c. burnings, e. catalysis oxidations and e. in use, absorb this 5
Step carries out successively:
When e. absorbing, contain SO3Tail gas enter from the first offgas outlet of converter 17 through the tail gas on the first absorption tower 18
In the first absorption tower 18 of mouth input, SO3H is become by water or sulfuric acid absorption2SO4, H2SO4It send to product slot, remaining tail gas is from
Second gas inlet of the inverted tower of the offgas outlet on one absorption tower, 18 top 17 is inputted again in converter 17, in tail gas
SO2Under the effect of the catalyst by O2It is oxidized to SO3, contain SO3Tail gas inhaled from the second offgas outlet of converter 17 through second
It receives in the gas inlet input second absorption tower 18 of tower 18, SO3H is become by water or sulfuric acid absorption2SO4, H2SO4It send to product slot,
Remaining tail gas discharges tower 19, tail from the offgas outlet on 18 top of second absorption tower through discharging the gas inlet input of 19 lower part of tower
Gas is washed to up to standard with ammonia process and is discharged to air outside afterwards, and extra waste liquid containing ammonia salt can be sent to sulphur ammonium saturator or acid making system.
Other steps are all same with embodiment 1.